Some Micro-Chemical Tests for Alkaloids

Transcription

S O M E
M I C R O - C H E M I C A L
T E S T S
F O E
A L K A L O I D S
CHAELES H. STEPHENSON
SCIENTIFIC ASSISTANT
BFEEAU OF CHBMISTEY, UNITED STATES DEPARTMENT OF AGEXOUtTURH,
WASHINGTON, D. O.
INCLUDING
C H E M I C A L
TESTS
A L K A L O I D S
O F
T H E
U S E D
C. E . P A R K E R
ASSISTANT CHEMIST
BUBEAU OF CHEMI3TBY, T7NITBD STATES DBPABTMSNT OF AQRICULTXJEB,
WASHINGTON, D. O.
With Tv/enty-seven Plates (162 Photomicrographs) and a
Folding Table of Reactions.
L O N D O N
CHARLES
GRIFFIN
& COMPANY,
12 E X E T E R STREET, STRAND,
1921
LIMITED
W.C.2
CONTENTS
PAGE
INTRODUCTION
1
MLCROCHEMICAL T E S T S FOR ALKALOIDS DESCRIBED BY OTHERS
3
CONCENTRATIONS OF ALKALOIDAL SOLUTIONS
7
REAGENTS U S E D
8
METHOD U S E D IN MAKING T E S T S
11
SCHEME FOR IDENTIFICATION OF ALKALOIDS
13
TABLE SHOWING B E S T TESTS FOR EACH ALKALOID
15
DETAILED DESCRIPTION OF T E S T S
16
CHEMICAL EXAMINATIONS
84
INDEX TO PLATES
107
PLATES
Ill
TABLE OF REACTIONS
FOLLOWS PLATES
S O M E
T E S T S
M I C R O C H E M I C A L
F O R
A L K A L O I D S
INTRODUCTION
T H I S work on microchemical tests for alkaloids was
begun in December, 1907, in order t o obtain microchemical
tests for the detection of cocaine. F r o m this b e g i n n i n g
work was done on other alkaloids u n t i l a total of sixty-four
had been tested. Thirteen of these alkaloids w e r e of doubtful purity, a n d therefore the results obtained o n these are
not recorded here.
T w o preliminary papers h a v e been p r e s e n t e d o n this
work before the Association of Official A g r i c u l t u r a l Chemists, the first i n 1908, published i n B u l l e t i n N o . 122,
B u r e a u of Chemistry, p . 9 7 , 1 9 0 9 , a n d the s e c o n d i n 1910,
published in B u l l e t i n N o . 137, B u r e a u of C h e m i s t r y , p.
189,1911.
I n this work no claim at all is m a d e for originality in
a p p l y i n g the microchemical t e s t s for alkaloids, as the
methods have been in use for m a n y years. M a s t of the
tests were worked out between t h e years 1907 a n d 1910,
and since that time several of the m o r e important contributions on the subject b y other authors have b e e n made.
References t o color reactions o n l y have, i n the m a i n , been
purposely omitted, since they w e r e considered of m i n o r importance for this work.
W e have endeavored to g i v e due credit for a l l micro*chemical tests which have been previously p u b l i s h e d and
£
SOME MICROCHEMICAL TESTS FOR ALKALOIDS
w h i c h are described i n this work, by referring in the t e x t t o
t e s t s a l r e a d y described b y others.
W h i l e t h e results in some cases are n o t all that m i g h t
b e d e s i r e d , y e t some v e r y sensitive and characteristic tests
h a v e b e e n w o r k e d out. N o tests whatever were obtained
o n t h r e e o f t h e fifty-one alkaloids described. Tests on the
o t h e r f o r t y - e i g h t alkaloids were, in m o s t cases, quite satisfactory.
P h o t o m i c r o g r a p h s of all the more important
c r y s t a l l i n e precipitates obtained were made, and the most
c h a r a c t e r i s t i c ones are g i v e n on plates.
F u n g o u s g r o w t h takes place in m a n y solutions of alkal o i d s a f t e r a time, a n especially heavy g r o w t h occurring in
b r u c i n e solutions. A l l of our work, however, was carried
o u t o n f r e s h l y prepared solutions.
T h e alkaloids w i t h which the greatest number of cryst a l l i n e p r e c i p i t a t e s w e r e obtained, u s i n g the standard alkal o i d a l r e a g e n t s , w e r e strychnine, berberine, tropacocaine
and brucine.
T h e a l k a l o i d s w i t h which no crystalline precipitates
w e r e o b t a i n e d were apocodeine, colchicine and solanine.
T h e f o l l o w i n g thirteen alkaloids w e r e discarded bec a u s e t h e r e w a s a serious doubt as t o their p u r i t y :
B e b e e r i n e , cephaline, coroutine, delphinine, duboisine, emet i n e , g e l s e m i n i n e , Iupinidine, pelletierine, sabadine, sabad i n i n e , s a n g u i n a r i n e and veratrine.
T h e a u t h o r desires f u l l y to acknowledge the assistance
r e c e i v e d f r o m M r . B . J . H o w a r d , Microscopist in charge
of t h e M i c r o c h e m i c a l Laboratory, not o n l y for the m a n y
v a l u a b l e s u g g e s t i o n s m a d e , but also for the taking of m a n y
of t h e p h o t o m i c r o g r a p h s herewith published.
MICROCHEMICAL TESTS FOR ALKALOIDS
DESCRIBED BY O T H E R S
T h e f o l l o w i n g authors describe crystalline p r e c i p i t a t e s
w i t h alkaloids, which precipitates have also been investig a t e d in this w o r k :
1. T . G . W o r m l e y , " M i c r o - c h e m i s t r y of P o i s o n s / '
1869. S e c o n d edition 1885. This is t h e most e x h a u s t i v e
work in E n g l i s h which w e have f o u n d o n t h e subject* I t
gives microchemical tests for a g r e a t number of p o i s o n s
other than alkaloids and deals with t w e l v e alkaloids, describing crystalline precipitates for n i n e of them. I t c o n tains m a n y fine p l a t e s showing the f o r m s of the v a r i o u s
crystalline precipitates. I n the 1 8 8 5 edition microchemical tests f o r g e l s e m i n e are given in addition to t h o s e d e scribed i n t h e first edition.
2. J . W . Griffin and A r t h u r H e n f r e y , " T h e M i c r o graphic D i c t i o n a r y , a guide t o the e x a m i n a t i o n of t h e
structure a n d nature of microscopic o b j e c t s , " 1 8 8 3 , vol. i,
p . 30. D e s c r i b e s five crystalline precipitates w h i c h w e
have w o r k e d o n .
3. A . W . B l y t h , " P o i s o n s : Their E f f e c t a n d D e t e c tion," 1885. T h e following crystalline precipitates are d e scribed: S t r y c h n i n e with potassium chromate; w i t h p o t a s sium t h i o c y a n a t e ; w i t h platinum chloride; with p a l l a d o u s
chloride; a n d w i t h g o l d chloride.
4. A . IB. L y o n s , " N o t e s on t h e A l k a l o i d s o f C o c a
L e a v e s , " The Am. Journ. Pharm., Oct., 1885, p . 3 0 . D e scribes the crystalline precipitates with cocaine a n d t h e following r e a g e n t s : P i c r i c acid; g o l d chloride; p l a t i n u m chloride; p o t a s s i u m h y d r o x i d e ; and sodium carbonate. G i v e s
4
sketches of the g o l d chloride a n d p l a t i n u m chloride reactions.
5. F . Giesel, " Ubermangansaures Kali zur P r i i f u n g
des Cocains," Pharm. Zeit., F e b . 2 7 , 1 8 8 6 . Describes the
crystalline precipitate with cocaine and potassium permanganate.
6. Popoff, " E m p l o i de l'acide Picrique pour la determination des alcaloides v e g e t a u x en toxicologie," Annales
d'Hygiene
publique et de mddecine Ugole, 3e Serie 26,
1 8 9 1 , p . 81. The author describes crystalline precipitates
w i t h picric acid and gives sketches of the crystals produced.
E i g h t of the crystalline precipitates described by him are
f o r m e d in solutions of greater concentration than 1 : 5 0 ,
a n d hence we do not describe them.
7. T . G. W o r m l e y , " N o t e s o n S o m e of the Chemical
P r o p e r t i e s of the Mydriatic Alkaloids," Amer.
Jowrn.
Pharm.j Nov., 1894, p. 513. Crystalline precipitates with
t h e following reagents are described: H y o s c i n e and g o l d
chloride; atropine and hyoscyamine a n d also hyoscine with
picric acid. W e did not obtain any crystalline precipitates
w i t h the two latter except in very concentrated solutions,
a n d w e have avoided, as a rule, describing the crystals
f o r m e d in solutions more concentrated than 1: 50.
8. H . Behrens, " A n l e i t u n g zur Mikrochemischen
A n a l y s e , " vol. iii, 1st Edition, 1896. Three editions of this
w o r k have appeared. This is the m o s t extensive work on
microchemical analysis which has been published.
9. W . R. D u n s t a n and F . H . Carr, " Contributions
t o O u r Knowledge of the A c o n i t e Alkaloids," The
Pharm. Journ., F e b . 15, 1896, p . 1 2 2 . T h e authors describe the crystalline precipitate w i t h aconitine and
p o t a s s i u m permanganate a n d that with cocaine and
p o t a s s i u m permanganate.
TESTS FOR ALKALOIDS DESCEIBED B Y OTHERS
5
10. M . V a d a m , " Differenciation d e s alcaloides a u
m o y e n de leurs precipites microcristallins," Journ.
de
Pharm. et de chimie, 6 serie, 1897, ii, p . 1 0 0 . D e s c r i b e s
t w e n t y - t h r e e different crystalline precipitates w h i c h w e
have studied.
11. B . Zenetti, " D e n mikrochemischen N a c h w e i s d e r
A l k a l o i d e mittelst Pikrinsaure ( F e s t s c h r i f t z u r S t r a s s burger V e r s a m m l u n g des D . A p . - V . ) . " R e f e r e n c e t o
above in Pharm.
Zeit.j N o v . 3 , 1897, vol. xlii, p . 7 5 2 .
D e s c r i b e s c r y s t a l s formed with picric acid a n d t h e
f o l l o w i n g alkaloids: A t r o p i n e , cocaine, n i c o t i n e , brucine,
a n d strychnine.
12. W . H . W a r r e n and R. S. W e i s s , " T h e P i c r o l o n a t e s of Certain A l k a l o i d s / ' Journ. of Biol. Chem., 3 , p .
3 2 7 , 1 9 0 7 . D e s c r i b e s crystals formed w i t h picric acid a n d
alcoholic solutions of nicotine, strychnine a n d brucine.
13. W a l t e r J . D i l l i n g , " Coniine, C o n h y d r i n e , P s e u d o conhydrine, Coniceine, and a N e w Coniine I s o m e r .
A
S u m m a r y o f T h e i r Cjhemicajl R e a c t i o n s , " The
Pharm.
Journ. and Pharmacist,
J u l y 17, 1909, p . 1 0 2 . D e s c r i p tion of five crystalline precipitates w i t h coniine, w h i c h
w e describe.
14. E . A b d e r h a l d e n , " H a n d b u c h des biochemischen
A r b e i t s m e t h o d e n , " 1910, vol. ii, p . 9 0 4 .
15. A l i d e Grutterink, " Beitrage zur mikrodhemischen
A n a l y s e E i n i g e r A l k a l o i d e und D r o g e n m i t b e s o n d e r e r
B e r i i c k s i c h t i g u n g der M e t h o d e n v o n H . B e h r e n s , " 1 9 1 0 .
T h e author gives a table showing reactions of f o r t y - t w o
alkaloids a n d bases w i t h sixty-nine r e a g e n t s , a n d describes
m o r e fully reactions for sixteen alkaloids. I n n o other
w o r k which w e have been able to locate h a v e microchemical
tests for so g r e a t a number of different alkaloids b e e n
6
given, a l t h o u g h t h e r e a r e o n l y sixteen of t h e t o t a l f o r t y t w o alkaloids for w h i c h t h e r e a r e sketches a n d m o r e comp l e t e descriptions of t h e p r e c i p i t a t e s .
16. L . R o s e n t h a l e r a n d P . G o e r n e r , " A r o m a t i c N i t r o
D e r i v a t i v e s , E s p e c i a l l y N i t r o p h e n o l s , as A l k a l o i d a l P r e c i p i t a n t s , " Z . Anal. Chem., 4 9 , 1910, p . 340. D e s c r i b e s
t h r e e crystalline p r e c i p i t a t e s w i t h p i c r i c acid which w e
h a v e described.
17. A . B o l l a n d , " M i k r o c h e m i s c h e S t u d i e n , " M o n a t shefte fiir Chemie 2 9 , 1 9 0 8 , p . 9 9 1 ; 32, 1 9 1 1 , p . 117. D e scribes m a n y c r y s t a l l i n e p r e c i p i t a t e s .
18. E . B . P u t t , " M i c r o c h e m i c a l T e s t s for t h e I d e n t i fication of Some of t h e A l k a l o i d s , " J. Ind. Eng.
Chem.,
vol. iv, p . 5 0 8 - 5 1 2 , 1 9 1 2 . D e s c r i b e s seven crystalline p r e cipitates t h a t w e h a v e w o r k e d o n . F o u r t e e n p h o t o m i c r o g r a p h s a r e given.
CONCENTRATIONS OF ALKALOIDAL
SOLUTIONS
I N t e s t i n g the alkaloids, aqueous solutions of from
1 : 1 0 0 0 to 1: 5 0 were used. I n one ease, however, a more
concentrated solution than 1 : 5 0 w a s used, a n d that w a s
with the alkaloid quinine, in which case a concentration of
1 : 3 5 was unetL T h i s m o r e concentrated solution w a s used
on account of the lack of .satisfactory crystal formation in
more dilute solutions. W h e n the alkaloid or alkaloidal salt
w a s not c o m p l e t e l y soluble in water, j u s t sufficient 10 per
cent, hydrochloric a d d wan a d d e d t o dissolve it. I n one or
t w o cases o n l y wits an alcoholic solution of the alkaloid
used, because the alkaloid w a s not soluble in w a t e r or in the
10 per cent, hydrochloric acid.
T h e s e solutions of alkaloids w e r e tested with different
reagents a n d t h e character of the precipitates, w h e n
formed, w a s noted under the microscope. A f t e r s o m e time
those r e a g e n t s which were f o u n d t o be u n s a t i s f a c t o r y as
alkaloiclaf precipitates were abandoned, a n d d u r i n g the remainder of the work o n l y those r e a g e n t s which a p p e a r e d
of value were retained.
T h e final revised list of reagents which w e r e f o u n d o f
value for tents n u m b e r s about forty.
REAGENTS USED
T h e following reagents were used in 5 per cent, aqueous
solutions: sodium carbonate; sodium nitroprusside; sodium
phosphate; sodium benzoate; sodium phosphomolybdate;
potassium hydroxide; potassium acetate; potassium iodide;
potassium iodate; potassium chromate; potassium ferrocyanide and ferricyanide; potassium cyanide; potassium
permanganate; saccharin; silver nitrate; ammonium molybdate; chromic acid; the chlorides of gold, platinum, palladium,* mercury, iron and zinc; a 10 per cent, solution of
barium nitrate; a saturated, aqueous solution of picric acid
and the following reagents for which w e give the formula:
Marine's r e a g e n t — C a d m i u m iodide
P o t a s s i u m iodide
D i s t i l l e d water
30 g m s .
60 g m s .
180 c.c.
Mayer's reagents—1:100 mercuric chloride in water
and add j u s t sufficient potassium iodide t o redissolve the
scarlet precipitate first produced.
Millon's reagent—dissolve metallic mercury in an
equal weight of concentrated nitric acid and dilute with an
equal volume of water.
Zinc-chlor-iodide—Zinc chloride
100 g m s .
Water
60 c.c.
20 g m s .
Iodine crystals
6 gms.
•Mr. E. B. Putt of this Bureau informs me that it is difficult to obtain
a 5 peT cent, aqueous solution of palladous chloride in a soluble form. What
is ordinarily supplied as palladous chloride is either palladous-ammonium
chloride or is a brown partially soluble powder that acts very much as if
it contained considerable basic salt. If such a salt is encountered, it can be
used only after being subjected to treatment with chlorine.
REAGENTS USED
Wagner's reagent—Iodine
Water
9
5(ty
1 0 0 0 c.c.
P h o s p h o m o l y b d i c acid—sodium p h o s p h o m o l y b d a t e i n
10 times its w e i g h t of a m i x t u r e of 1 p a r t of s t r o n g nitric
acid t o 10. p a r t s of water*
P h o s p h o t u n g s t i c acid—dissolve 1 0 0 p a r t s of sodium
t u n g s t a t e and 60 t o 80 p a r t s of sodium p h o s p h a t e in 500
parts of w a t e r a n d a d d nitric acid u n t i l t h e reaction is acid.
Silicotungstic a c i d — a 5 per cent, aqueous solution.
K r a u t ' s r e a g e n t — e i g h t y g r a m m e s bismuth nitrate i n
2 0 0 c.c. nitric acid of 1.18 sp. g r . D i s s o l v e 272 g r a m m e s
p o t a s s i u m iodide i n a little w a t e r a n d add t o above.
A m m o n i u m t h i o c y a n a t e — a 10 per cent, aqueous
solution.
A saturated aqueous solution of s o d i u m nitroprusside
w a s u s e d in addition t o the 10 per cent, solution, but reactions with both solutions appear to b e similar.
A 10 p e r cent, solution of picric acid i n alcohol w a s
u s e d i n addition t o t h e saturated aqueous solution. T h e
g r e a t e s t difference n o t e d w a s w i t h atropine, in which case
t h e alcoholic solution w a s m u c h m o r e sensitive in f o r m i n g
crystals t h a n the aqueous solution.
T h e f o l l o w i n g r e a g e n t s w e r e u s e d t o t e s t at least a p a r t
of t h e alkaloidal solutions, but t h e y w e r e n o t retained either
because t h e y r e a c t e d similarly t o s o m e r e a g e n t already on
t h e list or because t h e y did n o t f o r m crystalline precipit a t e s w i t h t h e alkaloids u n d e r the conditions u s e d i n
this w o r k :
A m m o n i u m h y d r o x i d e ; barium carbonate; barium
chloride; bismuth n i t r a t e ; bromine w a t e r ; c a d m i u m chlo-
10 SOME MICROCHEMICAL TESTS FOR ALKALOIDS
ride; chloral hydrate; citric acid; ferric sulphate; phenol;
phosphoric acid; potassium bromate; potassium bromide;
potassium chloride; potassium fluoride; picrolonic acid;
pyrogallic acid; sodium bicarbonate; sodium citrate;
sodium hydroxide; sodium hypochlorite; sodium nitrate;
sodium salicylate; sodium sulphite; sodium t u n g s t a t e ;
stannous chloride; strontium arsenate; strontium chromate; strontium nitrate; tannic acid; tartaric acid; uranium
acetate; uranium nitrate; zinc sulphide.
M E T H O D USED IN MAKING TESTS
T o prepare the residue for testing it is usually essential that the alkaloid be separated from the product in as
pure a form as possible by the usual chemical methods.
E x p e r i e n c e s with t h e tests have amply demonstrated the
importance of this operation preliminary to a p p l y i n g the
tests, and a considerable degree of purity is usually requisite
to the successful operation of the test.
T h e alkaloid or alkaloidal residue to be tested is dissolved in water, and if not completely soluble sufficient 10
per cent, hydrochloric acid is added drop by drop until it
is in solution. Care should be taken t o keep all solutions
to be tested as nearly neutral as possible, since t h e influence of free acid on the formation of crystalline alkaloidal
compounds tends t o break up or dissolve the crystals
first formed.
P l a c e one drop of the alkaloidal solution on a microscopic slide and add, b y means of a glass rod, one small
drop of the reagent. E x a m i n e for crystals under the microscope. Crystals are generally formed at once, though at
times the slide must stand for a few minutes. I n the latter
case do not place cover glass on the solution, as crystallization is often due to concentration b y evaporation.
B y rubbing the slide with a glass rod crystallization is
hastened, though t h e crystals are more likely to be abnorm a l when the solution is stirred. Precipitates which crystallize at all crystallize very quickly, as a rule, w h e n stirred
with a glass rod. I n a few cases, however, crystals are not
formed at all unless the solution be stirred. W h e n stirred,
the crystals are likely to be smaller and not so characteristic
as when the crystals form more slowly. W e recommend.
IS SOME MICROCHEMICAL TESTS FOR ALKALOIDS
that stirring with a glass rod be avoided as far as possible
on account of the abnormal crystal forms likely to be thus
obtained. H o w e v e r , stirring serves a useful purpose in
many cases a n d is often a desirable procedure.
Care should be taken that the glass rod used in m a k i n g
the test is properly cleaned between each test, otherwise it
serves t o carry at least a trace of crystalline matter from
one test over into the n e x t .
I t is desirable to make u p the alkaloid to be tested to
known strength, as the crystals formed show such variation
in many cases dependent u p o n concentration.
T h e amount of reagent used has usually great effect
upon the formation of crystals. Sometimes a very small
amount of reagent gives the best crystals, then again a considerable amount is needed in order to g e t crystal formation at all. N o r m a l l y an amorphous precipitate is formed
which soon crystallizes, though at times the crystals are
formed directly without the amorphous precipitate being
first thrown down.
W i t h some alkaloids, notably berberine and narcotine,
similar crystals are formed with a great number of different reagents, and it appears that the alkaloid is thrown out
of the solution by the addition of the reagent rather than
that a salt is formed.
L I M I T o r R E A C T I O N . — I n * every case where w e g e t
crystal formation in the 1 : 1 0 0 0 solution of the
alkaloid, a more dilute solution was used in order to
report the approximate greatest dilution with which crystals are formed. I t will be noted that i n some reactions,
cocaine with gold-chloride, for example, crystals are produced at dilutions of as great as 1: 20,000. S u c h a reaction is a very sensitive one and with it w e can identify mere
traces of alkaloid.
S C H E M E FOR IDENTIFICATION OF ALKALOIDS
T h e following outline m a y be of service i n i d e n t i f y i n g
t h e alkaloids, t h o u g h it h a s t h u s f a r been f o u n d impossible
t o m a k e o u t w h a t is considered a s a t i s f a c t o r y k e y for u s e i n
t h e i r identification.
I f a n y alkaloid is suspected, find it o n t h e list a n d u s e
t h e r e a g e n t u n d e r which it is placed. F o r e x a m p l e , i n testi n g for a t r o p i n e , u s e W a g n e r ' s r e a g e n t for cocaine, g o l d
chloride, e t c .
T h e a l k a l o i d s i n t h e following lists a r e n o t t h e o n l y
ones which f o r m c r y s t a l s w i t h t h e r e a g e n t s i n question, b u t
each alkaloid is listed u n d e r t h a t r e a g e n t w i t h which i t
f o r m s t h e m o s t s a t i s f a c t o r y c r y s t a l s for identification.
Characteristic crystalline precipitates are formed with
each r e a g e n t a n d alkaloids in the list following it.
WITH GOLD CHXOMDB SOLTJTIOX
1. Cocaine
2. Tropacocaine
3. Benzoyl-ecgonine
4. Strychnine
5. Caffeine
6. Quinidine
7. Quinoline
8. Apomorphine
9. Nicotine
10. Sparteine
11. Scopolamine
WITH KBATTT'S REAGEOT
1. Theobromine
2. Narceine
8. Anhalonine
4. Coniine
5. Arecoline
WITH POTASSIUM HXDBOXIDE SOLUTION
1. Thebaine
2. Papaverine
3. Narcotine
4. Hydrastine
5. Aspidospermine
6. Corydaline
7. Chelidonine
WITH WAGNEE'S REAGEOT
1. Homatropine
2. Hyoscyamine
8. Berberine
4. Atropine
5. ColcMdne
WITH PLATHHTM CHXORJDE SOLUTION
1. Calycanthine
2. Pilocarpine
3. Brucine
4. Cinchonidine
14. SOME MICROCHEMICAL TESTS FOR ALKALOIDS
WITH Yuotmunvvomc Acx»
1. Baaine
2. Pilocarpidinc
3. Pelleterine
WITH Mnrn« ( Vnumtm
*/ Ilrrnffie
J
- »>if»nlnf
WITH PII0»*I!0*OT.TWUT*
liyflm.»tJnJfir»
X. Choline
2. Ecgoninc
WITH MAEnr/i* R«A««}TT
Wrrii Mam'« 1Ci=***r%t
€>tl4nr
W
*»M Snwr* l*itf«riiATii
t Moiphlne
2. Codeine
WITH SODIUM CA»»OJ*ATIS
1. CInchoninc
2. Acoaltlne
W m t
TABLE S H O W I N G BEST T E S T S FOR
EACH
ALKALOID
i rrfrr t<i I'Ulrs, Arabic
(Roman
1. Aconititwr
Kraut'i H
KM lr*X»
iiuhi Chlnwh {h i)
KfAUl'* Hrfl^rlit
Vulnmium llyiiutt'ulr
10.
11.
I*.
1,1.
14.
Jii.
I*.
( xtinm
C aJ>i ftfjituftr
('hrhdkminr
( b*4»wr
< "*»* hf»j»if»r
<'bn»mir Atnl
I'lKMpbfttitnistir Atiil (XXIV, 4J
rklintirn < hl*m<lr <IV t)
Kr^u?'. Hraerttt < X ! U , f J
IfAlitiufti ( HlumJr <1V, JJj
Kraut's
(VI,
t
Arid
nni <
liiiri!
r
w.
(XV. 1)
I'Unnuin Chlorwir (IV, 1)
Cbrttmtr Ari«l
I'ivlM'Mia <h\ntUlr (VI. I)
W»tf«rr'. UrRgrnt (X, t>
lyrir And <XJX, l>
yWM M-And CXX.fi)
^
^
l
k
XI, i
(IV, 41
I. * *«« ^
*)
Afifl {XXIV\ fl)
*»!«••< «jm H
t
:t
(IV,
X
Wtfvtit (XVH, 4)
W«in#f« $U*ifnl
(XL h
U
Ummtk HMmttki CVHi. 4)
immiw&m
Arid (XXII,
CXI,«)
(V I)
ujm Amliil« (.XJI. 0)
mr ChUmdr fix, U
: M l (XXVl,0)
DETAILED DESCRIPTION O F T E S T S
I t will be noted that t h e alkaloids are treated i n alphabetical order. T h e descriptions are kept short, and m a n y
of t h e crystal forms produced can, at least, be b u t
poorly described.
Reference is made i n the t e x t to all crystal forms reproduced in the plates. M a n y of the precipitates photograph
very poorly, and for this reason some sensitive tests have
not been reproduced i n t h e plates.
ACONITINE.
F o u r crystalline a n d twenty-two non-crystalline p r e cipitates were obtained.
S O D I U M C A R B O N A T E . — T h i s is the m o s t sensitive test
for aconitine. Characteristic rosettes are usually slowly
formed i n great numbers! even in the 1 : 1 0 0 0 solution.
T h e y are usually formed more quickly i n the 1 : 5 0 0 solution than in the 1 : 2 0 0 solution. A m o r p h o u s precipitates
form in the t w o more concentrated solutions o n l y ( P l a t e
X I I I , Fig. 6).
POTASSIUM
PERMANGANATE.—The
precipitates
are
rather dense. T h e crystals are small, spherical, a n d form
very slowly in the t w o more dilute solutions. I n the 1 : 2 0 0
solution the crystals are rosettes and polarize; brightly.
T h e y are characteristic a n d of good size. N o t m a n y a r e
formed and they form slowly ( 9 ) .
POTASSIUM H Y D R O X I D E . — I n
the 1 : 2 0 0
solution t h e
amorphous precipitate crystallizes in rosettes of shortpointed rods. Crystals are often formed i n f e w numbers
only and very slowly.
DETAILED DESCRIPTION OF TESTS
17
P o t a s s i u m c y a n i d e gives results similar t o the above.
A m m o n i u m thiocyanate gives a v e r y slight precipitate
in the 1 : 50 solution only.
ANHALONINE
(MESCALINE)
T h e microchemical reactions of t w o samples, one
labeled " M e s c a l i n " a n d the other " A n h a l o n i n e , " were
identical. A t t e n t i o n is called to the m e l t i n g point obtained,
by Parker, 1 8 1 - 2 ° a s compared with Schmidt's figure recorded as 2 5 4 - 5 ° .
F o u r aqueous solutions of the alkaloid were used, viz.:
1 : 1 0 0 0 ; 1 : 5 0 0 ; 1 : 2 0 0 ; 1: 50.
N o n - c r y s t a l l i n e precipitates f o r m e d o n l y withzinc-chloriodide, phosphomolybdate, and silico-tungstic acid.
W i t h this alkaloid eleven crystalline precipitates were
obtained as f o l l o w s :
K R A U T ' S R E A G E N T . — T h i s i s the m o s t sensitive
test,
great numbers o f v e r y small crystals b e i n g formed even i n
a 1 : 3 0 0 0 solution. T h e y are too small, however, t o b e of
service as a test. T h e best concentration for crystal formation is about 1 : 2 0 0 . A t this concentration they are
often very l a r g e a n d moss-like i n appearance a n d polarize
only slightly. A n amorphous precipitate is thrown d o w n
first from w h i c h t h e crystals form quickly.
G O L D C H L O R I D E . — T h i s reagent does n o t form crystals
in the 1 : 1 0 0 0 solution, b u t small crystals, quickly g r o w i n g
to a g o o d size, are formed upon stirring t h e 1 : 5 0 0 solution.
V e r y l a r g e rods, i n a dense mass, f o r m in the 1 : 5 0
solution, a n d of g o o d size i n the 1 : 2 0 0 solution ( P l a t e
I,Fig.l) (17).
PLATINUM
CHLORIDE.—This
reagent
forms
small crystals o n stirring the 1 : 5 0 0 solution.
a
few
A dense
mass of large, fine needle rosettes w a s instantly formed in
the 1: 50 and 1: 200 solutions ( P l a t e I V , F i g . 1 ) ( 1 7 ) .
P i c n i c A C I D . — A n amorphous precipitate formed in
the 1 : 5 0 solution only, and this crystallizes very rapidly
into large, rough-appearing rods. L a r g e rods are also
formed in the 1: 200 solution, b u t without a first amorphous
precipitate. U p o n stirring the t w o more dilute solutions
we g e t a great number of small rods ( 1 7 ) .
WAGNER'S
REAGENT.—This
reagent
forms
heavy
amorphous precipitates i n the t w o more concentrated solutions which crystallize slowly into large, rough-appearing
rods of a bluish-black to black color. Their polarization is
slight T h e slight amorphous precipitate in t h e 1 : 5 0 0
solution does not crystallize, but upon stirring with a glass
rod great numbers of small rods are formed even i n the
1 : 1 0 0 0 solution if sufficient reagent be added ( 1 7 ) .
M E R C U R I C C H L O R I D E . — U p o n stirring the 1 : 50 solu-
tion great numbers of large, highly polarizing rosettes
either of plates or of rods are formed ( 1 7 ) .
POTASSIUM
PERMANGANATE.—This
reagent
forms
very short rods in the 1 : 50 solution only on stirring.
PALLADOUS C H L O R I D E . — C l e a r - c u t , h i g h l y
polarizing
crystals are formed i n the 1 : 5 0 solution o n stirring a n d a
very few in the 1 : 2 0 0 solution. T h e y axe normally fouror six-sided.
M A Y E R ' S R E A G E N T . — T h i s reagent forms
amorphous
precipitates in the t w o more concentrated solutions only.
Crystals form quickly and are rosettes o f rods or plates.
M A R M E ' S R E A G E N T . — L a r g e plates or rosettes of rods
formed in the 1 : 50 solution.
P H O S P H O T U N G S T I C A C I D . — T h i s r e a g e n t forms
crys-
tals slowly in all solutions from t h e amorphous precipitate.
19
T h e y are rosettes of short rods a n d i n t h e 1 : 5 0 solution
often v e r y l a r g e rods ( P l a t e X X I V , F i g , 3 ) . Froehde's
reagent gives a y e l l o w color.
APOCODEINE
ISTo crystalline precipitates were obtained whatever
with this alkaloid.
A l l of t h e c o m m o n alkaloidal reagents form heavy n o n crystalline precipitates.
APOMORPHINE
T h e solutions of this alkaloid take on a light, greenish
color within a f e w m i n u t e s and turn t o a dark blue after a
few hours.
T e n crystalline a n d twenty-five non-crystalline precipitates were obtained.
G O L D C H L O R I D E . — T h i s is t h e best t e s t for apomorphine.
H e a v y amorphous precipitates appear in all the solutions a t once a n d t h e y are of a deep, red-brown color. T h e
crystals are f o r m e d i n dense masses a n d do n o t polarize.
T h e y are small a n d very fine needles in all the solutions,
being somewhat larger in t h e more concentrated solutions a n d are occasionally rosettes.
This test is v e r y sensitive, as w e are able t o obtain fine
needles i n a 1 : 1 0 , 0 0 0 solution ( P l a t e I , F i g . 2 ) .
P L A T I N U M CHLORIDE.—Crystals formed from amor-
phous precipitate i n all solutions e x c e p t the 1 : 5 0 . T h e y
are characteristic, rather small rosettes, of a deep rose color.
C H R O M I C A C I D . — V e r y faint rose color in the 1 : 1 0 0 0
solution a n d precipitates i n t h e 1 : 5 0 0 a n d more concentrated solutions which are reddish-brown turning t o g r e e n
around t h e e d g e s .
€0 SOME MICROCHEMICA1 TESTS FOE ALKALOIDS
Crystals are small and formed in all solutions. T h e y
do not polarize. N o r m a l l y rosettes of short rods. The
crystals in the 1: 50 are considerably larger.
POTASSIUM IODIDE.—Amorphous precipitate in
the
1:50 solution only, and this crystallizes into small, highly
polarizing crystals which have sharp, clear-cut angles like
those of a diamond. T h e 1: 200 solution does not form
& precipitate.
Potassium iodide gives reactions similar to above.
Z I N C CHLOBJDE.—Small rods in rosettes instantly
formed in the 1: 50 solution only.
KRAUT'S R E A G E N T . — L a r g e rosettes of rods are formed
at once in the 1: 50 solution in addition t o the heavy brown
precipitate which does not crystallize.
PHOSPHOMOLYBDIC A C I D . — A dense mass of rod-like
crystals instantly formed in the 1 : 5 0 solution only.
HILXON'S REAGENT.—Rose-red precipitate forming
rods in the 1 : 5 0 solution and these are often i n rosettes.
N o crystals formed in the more dilute solutions.
Barium nitrate and silver nitrate give crystals similar
to those formed with this reagent and in the 1 : 5 0
solution only.
The following color reactions were noted:
Rose-red color with ferric sulphate and also with silver
nitrate and ammonium vanadate. R e d precipitate turning
to deep green with potassium chroniate and ferric chloride.
HlTDROBBOMIDE
F o u r crystalline and t e n non-crystalline precipitates
were obtained. O n l y one satisfactory test w a s worked out
for this alkaloid,
KJUTTT'S REAGENT.—Crystals are formed slowly from
21
the amorphous precipitates i n t h e t w o more concentrated
solutions, b u t are formed more quickly in t h e t w o dilute
solutions. T h e y are good-sized plates often i n rosettesT h e t e s t is sensitive, as great numbers of crystals are
formed i n t h e 1 : 1 0 0 0 solution ( P l a t e X I I I , F i g . 1 ) .
P I C R I C A C I D . — N o t a sensitive test and n o amorphous
precipitates a r e formed. A s the 1: 50 solution evaporates,
spherical crystals o r rosettes of short rods o f good size
are formed.
PALLADOXJS
CHXOBIDE.—After
t h e . 1 : 50
solution
stands f o r s o m e t i m e large irregular plates which polarize
well are f o r m e d . T h e s e plates are often i n rosettes ( P l a t e
VI, Fig. 1 ) .
MILLO^T'S S O L U T I O N . — I n t h e 1 : 50 solution only, small
needle-shaped crystals, often i n rosettes, are formed from.
the amorphous precipitate.
ASPIDOSPERMINE
E i g h t crystalline and twenty-four non-crystalline p r e cipitates w e r e obtained.
POTASSIUM
HYDEOXIDE.—A
fine
a n d sensitive
test.
F i n e l a r g e crystals a r e quickly formed from the amorphous precipitate. T h e y are a l o u t the same in appearance
in all solutions, though much larger i n t h e more concentrated solutions. T h e y form a dense mass of rosettes in
the 1 : 5 0 solution. Their appearance is similar t o that of
some forms o f seaweed ( P l a t e X V , Tig. 1 ) .
S m a l l rods formed in a 1: 3000 solution, which i s about
the limit o f reaction. Potassium chrornate, sodium carbonate, and potassium cyanide give crystals similar to above,
t h o u g h t h e y are not so sensitive.
WAGNER'S
REAGENT.—Yery
short,
pointed
rods
in
rosettes are formed i n the two more concentrated solutions
only. They are formed around the edges of the heavy
amorphous precipitates (Plate X , F i g . 1 ) .
Potassium iodide,' Mayer's reagent, and Marine's reagent all give results similar to the above.
The following color reactions were noted:
With ferric chloride a deep rose color i s developed in
addition to the amorphous precipitate.
With potassium iodate a faint pink color develops in
the 1: 50 solution on standing.
The amorphous precipitate with gold chloride takes on
a hlack color.
With chromic acid the amorphous precipitate takes on
a pink color.
ATKOPINE S U L P H A T E
Four crystalline and thirteen non-crjrstalline precipitates were obtained.
W A G N E R ' S R E A G E N T . — T h i s is a sensitive test and the
best one that we have for atropine. T h e crystals are normally small rods or triangular plates and are formed in
great numbers from the amorphous precipitate first thrown
down. They hare sharp angles and polarize poorly. A
1: 8000 solution forms great numbers of very small crystals.
T h e crystals in the 1 : 5 0 solution are of good size. This is
a satisfactory test, and though the crystals are never large,
they are characteristic ( P l a t e X , F i g s . 2 and 3) ( 1 8 ) .
Zinc-chlor-iodide or Kraut's reagent forms
similar to the above.
crystals
P I C R I C A C E D . — W e have a n amorphous precipitate but
n o crystals in solutions above 1 : 50. Crystals are obtained
with difficulty and only in the 1: 50 solution. T h e y are
23
normally large, plate-like and polarize brilliantly. Crystal
formation is so uncertain as t o make this reaction of n o
value as a test. This test is described b y W o r m l e y , he,
however, using an alcoholic solution of picric acid rather
than an aqueous solution ( 1 ) . T h e alcohoKc solution of
picric acid makes a very satisfactory reagent for this alkaloid, as u p o n stirring the 1 : 1 0 0 0 solution small plates are
formed and from the amorphous precipitates i n the other
solutions rosettes of plates are formed ( P l a t e X I X , F i g .
1) (6) ( 1 0 ) ( 1 1 ) .
P o t a s s i u m hydroxide forms a n amorphous precipitate
in the 1 : 5 0 solution but not in the 1 : 200 solution.
W o r m l e y describes a crystalline precipitate with potassium hydroxide, but w e have been unable t o confirm this ( 1 ) .
BENZOYL-ECGONINE
F i v e crystalline and nine non-crystalline precipitates
were obtained.
G O L D C H L O E I D E . — A m o r p h o u s precipitates are formed
in all solutions. This is the only sensitive test. Crystals
form from the amorphous precipitates rather quickly.
T h e y g r o w t o large size, are light greenish-yellow in color
and polarize brightly. T h e y are normally rosettes of l o n g
and rather narrow irregular plates. T h e y f o r m a dense
mass in t h e 1 : 50 solution. T h e photograph reproduced
was taken j u s t after t h e crystallization h a d started. Crystals of g o o d size are formed in a 1 : 3 0 0 0 solution after it
stands for some time ( P l a t e I , F i g . 3 ) .
W A G N E R ' S R E A G E N T . — H e a v y , amorphous precipitates
in all solutions, but crystals are formed only i n the t w o
more concentrated solutions. These crystals are large a n d
dense rosettes appearing like some form of seaweed. O n l y
U
a few crystals are formed in the 1 : 2 0 0 solution. T h e s e
crystals are of a light greenish color a n d polarize
fairly well.
Kraut's reagent reacts as above.
MAYER'S R E A G E N T . — V e r y l o n g , needle-like
crystals
are formed in the t w o more concentrated solutions only
and around the edges of the drops.
Palladous chloride forms a n amorphous precipitate in
the 1 : 5 0 solution only.
The amorphous precipitate with potassium permanganate and with mercuric chloride is very slight,
BEEBEBINE
A saturated aqueous solution, this being about 1 : 1 0 0 ,
also solutions of 1 : 5 0 0 and 1 : 1 0 0 0 were used. T h e solutions of this alkaloid are yellow.
U p o n addition of the following reagents t o a saturated
aqueous solution i n addition to a heavy amorphous precipitate, crystals are formed. T h e crystals show u p t o better
advantage if but little of the reagent be used.
The crystals are similar, if n o t identical, with all of t h e
reagents in the following list: Chromic acid; sodium nitroprusside; platinum chloride; palladous chloride; mercuric
chloride; zinc-chlor-iodide; W a g n e r ' s reagent; potassium
iodide; Kraut's reagent; Marine's reagent; jphosphomolybdic acid; saccharin; ammonium thiocyanate; potassium permanganate ( 2 ) ; picric acid; sulphuric acid; hydrochloric
acid; ferric chloride; zinc chloride; Millon's reagent; barium
and silver nitrate. T h e y are i n all cases moss-like or fine
needles, often in rosettes, and the greater part of the h e a v y
amorphous precipitate does n o t crystallize ( P l a t e X , F i g .
4, and P l a t e X X , F i g s . 5 and 6 ) ( 8 ) .
25
T h e r e a g e n t s with which no crystals were obtained are:
P o t a s s i u m cyanide; ammonium molybdate; g o l d chloride;
Mayer's r e a g e n t ; potassium ferrocyanide; potassium ferricyanide; silico-tungstic acid and phosphotungstic acid.
Berberine, u p o n evaporation of t h e aqueous solution,
crystallizes into yellow needles, often in rosettes.
B E T A I N E HYDROCHLORIDE
E i g h t crystalline and three non-crystalline precipitates
were obtained.
P H O S P H O T U N G S T I C A C I D . — T h i s is a fine, sensitive and
characteristic test. Crystals are formed at once in all solutions, a n d t h e y form a very dense mass in the t w o more
concentrated solutions. T h e crystals are of t w o kinds,
l o n g needles in rosettes and very short rods i n rosettes.
T h e limit of reaction is about 1 : 2 0 0 0 ( P l a t e X X I V ,
Fig. 4).
K R A U T ' S R E A G E N T . — A f e w needles are formed in the
1 : 1 0 0 0 solution. A m o r p h o u s precipitates in the three
more concentrated solutions o n l y a n d crystals are slowly
formed f r o m this unless the solutions are stirred, but if
stirred, t h e crystals are formed quickly, being needles usually in rosettes, though often six-sided crystals are formed.
P H O S P H O M O L Y B D I C A C I D . — T h e r e is n o precipitate in
the 1 : 1 0 0 0 solution.
Great numbers of small spherical crystals are formed
and also needles and often rods in the 1 : 5 0 0 solution. R e actions are best a t this dilution. L a r g e rosettes of needles
or rods are formed slowly i n t h e t w o more concentrated
solutions, the needles w i t h pointed ends a n d rods irregular
in outline. T h e amorphous precipitates are heavy in the
more concentrated solution ( P l a t e X X I V , F i g . 1 ) .
26
PICRIC ACID.—Crystals of rods and needles are formed
on stirring the 1: 50 solution only. This is not a t all sensitive as a test.
W i t h the alcoholic solution of picric acid they are
formed in the t w o more concentrated solutions.
W A G N E R ' S R E A G E N T . — O n l y in the 1 : 50 solution are
crystals formed on stirring.
in rosettes.
T h e y are characteristic plates
GOLD CHLORIDE.—Crystals are formed only o n stirring
the 1 : 5 0 solution. T h e y are usually regular rods a n d
sometimes there are a few plate-like forms.
They
polarize well.
SILICO-TUNGSTIC A C I D . — T h e amorphous precipitates
formed in the t w o more concentrated solutions o n l y crystallize. Crystals are very small and polarize b u t slightly.
They are normally short rods.
S O D I U M B E N Z O A T E . — C r y s t a l s are formed i n the 1 : 50
solution only and they are rosettes of plates and are exactly
like those formed when hydrochloric acid is added t o a
sodium benzoate solution.
The following color reaction was n o t e d :
Ammonium vanadate when added t o a little of the alkaloid gives a red color which fades quickly.
BRTJCINE
Twenty crystalline and nine non-crystalline precipitates were obtained.
POTASSIUM H Y D R O X I D E . — T u f t s of needle-shaped crys-
tals are formed in the 1 : 200 solution. This is t h e greatest
dilution that forms crystals at once and then only on stirring. V e r y large rosettes of needles are quickly formed
from the heavy amorphous precipitate in the 1 : 50 solu-
27
tion. These crystals g r o w t o large size a n d m a y easily be
seen without t h e aid of the microscope.
I n t h e more dilute solutions t u f t s of needle crystals are
formed from the amorphous precipitate only after some
time and as the solutions evaporate ( P l a t e X V , F i g . 2 )
(1) ( 8 ) .
Sodium carbonate gives results similar t o t h e above ( 8 ) .
SODIUM
NITRO-PRUSSIDE.—Spherical
crystals
are
formed in the 1: 2 0 0 solution on standing. T h e y are small
and show distinct polarization crosses. R o s e t t e s formed
from the amorphous precipitate in t h e 1 : 50 solution. N o
precipitate is formed i n the more dilute solutions ( P l a t e
I X , F i g .6 ) .
CHROMIC ACID.—Great
numbers
of
rods,
often
in
rosettes, are formed i n a 1 : 1 0 0 0 solution. T h e crystals
are large a n d i n a dense mass in t h e more concentrated solutions. A great number of small crystals were formed i n a
1: 4000 solution ( P l a t e X X I I , F i g . 1 ) .
Chrom-acetic acid gives crystals similar t o above, but
they are formed without an amorphous precipitate being
first thrown down.
P O T A S S I U M C H R O M A T E . — I n t h e three more
concen-
trated solutions rods often in rosettes are formed. Often
the rods have a twisted or spiral appearance ( 8 ) ( 1 0 ) .
P L A T I N U M C H L O R I D E . — T h i s is a v e r y sensitive test.
T h e 1 : 1 0 0 0 solution crystallizes o u t into a dense mass of
rods which are sometimes in rosettes. T h e crystals in the
1 : 5 0 solution are small, as it is t o o concentrated for best
results. A considerable number of small crystals are
formed i n a 1 : 2 0 , 0 0 0 solution ( P l a t e I V , F i g . 2 ) ( 1 )
(8) ( 1 0 ) .
P A L L A D O U S C H L O R I D E . — R o d s f o r m e d in all solutions
28 SOME MICEOCHEMICAL TESTS FOR ALEALOIDS
up to 1: 4000. A t the latter dilution w e g e t very few small
crystals. These rods are normally i n rosettes and formed
from an amorphous precipitate. I n the 1: 500 solution an
amorphous precipitate is first formed and the crystals are
not large and polarize poorly. The 1 : 5 0 solution is too
concentrated for best results and the crystals vary greatly
in size (Plate V I , F i g . 2 ) .
MERCXJEIC C H L O E I D E . — A light precipitate is obtained
in the 1:500 and 1 : 1 0 0 0 solution from which spherical or
rosette crystals are formed. T h e crystals are fine rosettes
of plates in the more concentrated solutions. T h e addition
of too great an amount of reagent hinders the formation of
crystals greatly ( 8 ) .
ZLNTC CHLOEIDE.—The crystals are clear-cut rods or
plates with sharp angles in rosettes, and the limit of reaction is about 1: 500 ( P l a t e X X V I , F i g . 5 ) .
ZDJC-CHLOR-IODIDE.—Limit of reaction is about 1:200.
Crystals are spherical or rosettes and like those obtained in
the zinc chloride reaction.
AMMONIUM
THIOCYANTATE.—The
slight
amorphous
precipitate in the 1 : 5 0 solution crystallizes quickly into
moss-like rosettes (Plate X X V , T i g . 1) ( 2 ) .
WAGDOB'S R E A G E N T . — H e a v y precipitates form in all
the solutions. Crystallization is slow a n d t h e crystals are
small rosettes except in more concentrated solutions, when
they are large rosettes or rods. T h e limit of reaction is
about 1: 2000 (Plate X , F i g . 5 ) .
POTASSIUM I O D I D E . — N o amorphous precipitates are
obtained with this reagent. Large, brightly polarizing
masses of plates, often i n rosettes, are forihed i n t h e t w o
more concentrated solutions i n great numbers. Crystals
are formed yery slowly in the 1: 500 solution. These crys-
tals have a characteristic appearance
Fig. 2 ) .
Plafe
K K A U T ' S R E A G E N T . — A dense precipitate but n o crys-
tals are formed in the 1 : 1 0 0 0 solution. A f e w good-sized
rosettes are formed in the 1 : 500 solution. T h e y appear t o
float at the surface. I n the more concentrated solutions
w e have another f o r m of crystals also present. T h e y are
smaller a n d darker a n d rosettes are formed slowly.
M A R M E ' S R E A G E N T . — V e r y dense, a m o r p h o u s precipi-
tates are obtained only in the three more dilute solutions.
Crystals form only i n the 1 : 5 0 solution. T h e y are the
same as those formed with potassium iodide; that is,
rosettes composed of rods.
POTASSIUM FERRICYANIDE.—Crystals
quickly f o r m i n
the 1: 50 solution o n l y from the dense, amorphous precipitate. T h e y are large rosettes of plates a n d polarize
brightly. M a n y of the crystals are needles a n d sometimes
a combination of needles and plates is obtained. T h e y are
very brilliant under polarized light ( 1 ) .
P O T A S S I U M C Y A N I D E . — C r y s t a l s f o r m in the t w o more
concentrated solutions only and in general outline look like
some form of grass in the 1 : 200 solution, a n d large rosettes
in the 1 : 5 0 solution. A dense, amorphous precipitate is
first formed i n t h e 1 : 5 0 solution ( P l a t e X X I , F i g . 1 ) .
S A C C H A R I N . — G r e a t numbers of small needles are
formed o n stirring the 1 : 2 0 0 solution a n d are slowly
formed in the 1 : 5 0 solution, i n which case w e have rosettes
of needles, or often of plates. N o crystals or precipitates
are obtained i n the t w o more dilute solutions ( P l a t e V ,
Fig. 6 ) .
P I C R I C A C I D . — T h i s is a poor test, as crystals form
slowly a n d often n o t at all, and then in concentrated solu-
tions only.
They are rosettes of needles ( 1 ) ( 6 ) ( 1 0 )
(11) ( 1 2 ) .
M I I X O N ' S R E A G E N T . — A slight precipitate is formed in
the 1 : 2 0 0 solution and it redissolves. There is a faint
rose-red color which forms rather slowly a n d starts around
the edge of the drop. O n standing, brilliant crystals are
formed. T h e crystals are rosettes of small plates and polarize well (Plate X X V I , F i g . 1 ) .
U p o n addition of water to some brucine crystals, they
change from irregular plates t o fine rosettes of needles a n d
these i n turn dissolve as more water is added.
The brucine solutions upon standing several weeks become a faint pink color.
The following color reaction was noted: A d d one drop
of chromic acid and then one drop of concentrated hydrochloric acid. A deep blood-red is then developed. Crystals are formed similar to those formed with a chromic
acid alone.
CAFFEINE
Six crystalline and t w o non-crystalline precipitates
were obtained.
KRAUT'S R E A G E N T — T h i s is the best test for caffeine.
I n t h e 1:1000 solution a heavy, amorphous precipitate
is formed which crystallizes quickly in dark, reddish-brown
rosettes of small size. T h e 1 : 5 0 0 and 1 : 200 solutions give
similar results. These crystals do n o t polarize.
The precipitate is so dense i n the 1 : 5 0 solution that it
hinders crystallization somewhat. M a n y of the crystals
are small rods. A 1 : 5000 solution forms some very small
crystals (Plate X I I I , F i g . 2 ) .
MERCURIC
CHLORIDE.—A
considerable
number
of
D E T A I L E D DESCRIPTION OF TESTS
31
needle-shaped crystals a r e formed i n all solutions. T h e y
f o r m a d e n s e m a s s i n t h e 1 : 50 s o l u t i o n a n d p o l a r i z e b r i l l i a n t l y . T h e l i m i t of r e a c t i o n is a b o u t 1 : 1 0 0 0 ( P l a t e
vin,Fig.i).
P A L L A D O U S C H L O R I D E . — T h e l i m i t of r e a c t i o n is a b o u t
1 : 200. T h e c r y s t a l s a r e s m a l l n e e d l e s a n d f o r m a dense
m a s s i n t h e 1 : 5 0 s o l u t i o n . T h e y p o l a r i z e b u t slightly.
GOLD CHLORIDE.—This
is n o t a s e n s i t i v e t e s t .
The
c r y s t a l s a r e n o r m a l l y n e e d l e s o r t u f t s of needles a n d f o r m
v e r y slowly. I n t h e 1 : 5 0 solution t u f t s o r r o s e t t e s of
fairly l a r g e r o d s o r n e e d l e s a r e f o r m e d o n s t a n d i n g ( P l a t e
I , F i g .4 ) ( 1 0 ) .
PHOSPHOMOLYBDIC
ACID.—Heavy,
amorphous
pre-
cipitates f o r m . C r y s t a l s a r e s m a l l r o d s u s u a l l y f o r m e d
around t h e edges. I n t h e 1 : 200 solution t h e crystals a r e
small a n d i n g r e a t n u m b e r s . T h e y d o n o t s t a n d o u t c l e a r l y
on a c c o u n t of b e i n g m a s s e d a n d o f t e n s u r r o u n d e d b y t h e
a m o r p h o u s p r e c i p i t a t e . I n t h e 1 : 5 0 solution t h e p r e c i p i t a t e is so d e n s e t h a t t h e c r y s t a l s f o r m slowly. T h e y a r e
normally rods.
SILICO-TUNGSTIC A C I D . — I n the two more concentrated
solutions t h e c r y s t a l s a r e v e r y s m a l l a n d t h e a m o r p h o u s p r e cipitates a r e d e n s e . T h e c r y s t a l s d o n o t p o l a r i z e b r i g h t l y .
CALYCANTHINE SULPHATE
T h i r t e e n c r y s t a l l i n e a n d fifteen n o n - c r y s t a l l i n e p r e cipitates w e r e o b t a i n e d .
PLATINUM
CHLORIDE.—This
is a s e n s i t i v e t e s t .
An
a m o r p h o u s p r e c i p i t a t e is f o r m e d which crystallizes a l m o s t
i n s t a n t l y i n t o cross-like c r y s t a l s i n all solutions.
They
a p p e a r especially well in t h e 1 : 5 0 solution ( P l a t e I V ,
Fig. 3 ) .
32 SOME MICEOCHEMICAL TESTS FOR ALKALOIDS
CHROMIC A C I D . — A m o r p h o u s p r e c i p i t a t e s appear
in
the three more concentrated solutions only. These precipitates crystallize on standing, forming fine, large rosettes
of needles or rods, especially large i n the 1 : 50 solution
(Plate X X I I , F i g . 2 ) .
PALLADOUS C H L O R I D E . — T h i s is a sensitive test.
Crys-
tals are quickly formed in all the solutions. T h e y are very
large and even in the 1 : 1 0 0 0 solution t h e y are of g o o d
size. Great numbers of small rods are formed o n stirring
the 1 : 2 0 0 0 solution (Plate V I , F i g . 3 ) .
ZINC-CHLOR-IODIDE.—Amorphous precipitates appear
in all the solutions. V e r y small crystals were noticed only
in the 1: 500 solution after it had stood for some time, but
most of the precipitate does not crystallize,
W A G N E R ' S R E A G E N T . — A m o r p h o u s precipitates formed
in all the solutions and crystals i n all but t h e 1 : 1 0 0 0 solution. Crystals are irregular plates often occurring in
rosettes. T h e y are very small in the 1 : 5 0 0 solution, but
form quickly a n d are of large size in the 1 : 5 0 solution.
A M M O N I U M T H I O C Y A N A T E . — A dense m a s s of rods is
formed in the 1 : 50 solution.
quick crystallization.
Stir the 1 : 5 0 0 solution for
P O T A S S I U M C Y A N I D E . — T h e crystals are small a n d tri-
angular in outline. T h e y are quickly formed in the t w o
more dilute solutions on stirring. T h e y are large and form
quickly from the precipitate in the 1 : 5 0 solution.
Potassium hydroxide or sodium carbonate gives results similar to those aboveKRAUT'S R E A G E N T . — V e r y large, d e e p , yellow, irregular plates are formed in the t w o more concentrated solutions only from the dense, amorphous precipitates.
P O T A S S I U M I O D I D E . — L a r g e rosettes of rods are formed
3S
instantly u p o n stirring the 1: 50 solution a n d in t h e 1 : 200
solution o n standing.
S O D I U M P H O S P H A T E . — C r y s t a l s are o n l y f o r m e d i n the
1: 50 solution. T h e y form slowly. T h e y are rather small,
clear-cut rosettes g r o w i n g t o g o o d size.
T h e following color reaction w a s n o t e d :
A m m o n i u m vanadate gives a blood-red color, which
quickly fades, i n the 1 : 50 solution.
SODIUM
NITROPRUSSIDE.—A
concentrated
aqueous
solution of the reagent w a s used.
T h e dense, amorphous precipitate quickly crystallizes
in the 1 : 5 0 solution only i n fine large rosettes of plates.
O n stirring the 1 : 5 0 0 solution small six-sided plates
are formed.
CHELIDONINE
T w e l v e crystalline a n d t w e n t y non-crystalline precipitates were obtained.
POTASSIUM
HYDROXIDE.—This
is
the
best
test
for
chelidonine.
T h e amorphous precipitate crystallizes quickly in all
solutions. T h e crystals i n the 1 : 1 0 0 0 solution are goodsized, irregular rods a n d polarize well. A 1 : 4 0 0 0 solution
forms numerous small crystals.
Other reagents which give crystals as above are sodium
carbonate; potassium chromate; potassium cyanide; sodium
phosphate a n d potassium acetate.
POTASSIUM
FERROCYANIDE.—The
light
amorphous
precipitates crystallize rather slowly i n small, highly p o l arizing crystals.
M a n y are formed even i n t h e
1 : 1 0 0 0 solution.
K R A U T ' S R E A G E N T . — C r y s t a l s f o r m e d in t h e t w o m o r e
3
dilute solutions from t h e amorphous precipitate are small
and black six-sided plates.
FERRIC
CHLORIDE.—The
amorphous
precipitate
is
slight. Small, highly polarizing crystals are formed in the
two more dilute solutions. T h e y appear like those formed
with zinc chloride.
Z I N C C H L O R I D E . — S m a l l , h i g h l y polarizing crystals are
formed i n the t w o more dilute solutions ( P l a t e X X V I I ,
Fig.l).
S O D I U M P H O S P H O M O L Y B D A T E . — P l a t e s of g o o d size are
formed in the t w o more dilute solutions.
SACCHARIN.—IsTo amorphous precipitate formed.
A
few small crystals are formed i n the t w o more dilute solutions. T h e y polarize well. Color reaction: W i t h a m monium vanadate added to d r y material a green color is
formed, gradually fading t o p i n k ; Froehde's reagent g a v e
a blue color.
CHOLINE
E i g h t crystalline a n d seven non-crystalline precipitates
were obtained.
P H O S P H O M O L Y B D I C A C I D . — T h i s is a sensitive t e s t for
choline. Amorphous precipitates a n d crystals are formed
in all the solutions. T h e y are small, as a rule. T h e best
concentration is 1 : 200, i n which solution great numbers of
needles, often in rosettes, axe formed. These crystals are
often in dense masses ( P l a t e X X I V , F i g . 2 ) .
SILICO-TUNGSTIC A C I D . — H e a v y precipitates f o r m in
all the solutions and the best crystals are formed i n the
1 : 5 0 0 solution. T h e crystals are rods or needles, often
curved, and normally have a peculiar granular appearance
on the surface.
35
PHOSPHOTXJNGSTIC A C I D . — H e a v y , amorphous precipi-
tates are f o r m e d w i t h this reagent a n d small crystals are
formed only i n t h e 1 : 5 0 solution. This is n o t a satisfactory
reagent t o u s e as a test for choline.
B A R I U M N I T R A T E . — G r e a t numbers of very small crystals are f o r m e d i n all solutions. T h e y appear t o be very
small rosettes.
MERCURIC CHLORIDE.—Heavy,
amorphous precipitate
formed in the 1 : 50 solution only. Crystals are formed i n
all the solutions, t h o u g h o n l y around edges i n t h e 1 : 1 0 0 0
solution. T h e y are small and polarize slightly a n d are
normally spherical.
KRAUT'S REAGENT.—Heavy,
amorphous
precipitates
appeared i n the three more concentrated solutions. I n the
1: 200 solution, a f e w l o n g and rather narrow, irregular
plates are formed around the edge of the drop only
Rosettes of small plates are formed a t once i n the 1 : 5 0
solution. T h e y are n o r m a l l y six-sided.
G O L D C H L O R I D E . — T h e limit of reaction is about 1 : 2 0 0 .
Rosettes of plate-like crystals in 1 : 5 0 solution are formed
from the amorphous precipitate. T h e y polarize fairly well.
MAYER'S R E A G E N T . — A n
amorphous precipitate
ap-
pears in t h e 1 : 5 0 solution only, and this crystallizes rapidly
into plates which are rather small a n d often triangular
in outline.
CINCHONINE SULPHATE
S i x crystalline precipitates and twenty-three non-crystalline precipitates were obtained.
S O D I U M C A R B O N A T E . — T h i s is a v e r y delicate a n d char-
acteristic test. T h e crystals are small rosettes a n d are
quickly formed i n g r e a t numbers in all the solutions. T h e y
36
are especially g o o d in the 1 : 1 0 0 0 solution. T h e y form
such a dense mass i n t h e more concentrated solutions that
they do not show u p so well as they d o i n t h e 1 : 1 0 0 0 solution. T h e y are dark i n appearance a n d d o n o t polarize
brightly ( P l a t e X I V , F i g s . 1 ( X 150) a n d 2 ( X 300) ( 8 ) .
Numbers of small needles are formed i n a 1 : 20,000
solution.
Other reagents forming crystals a s above alt h o u g h the tests are n o t so sensitive i n all cases, are as
follows: Potassium hydroxide; potassium chromate, a n d
potassium cyanide.
POTASSIUM P E R M A N G A N A T E . — N o t
a s a t i s f a c t o r y test,
as the amorphous precipitate frequently does n o t crystallize. T h e amorphous precipitate is v e r y dense in all t h e
solutions. T h e crystals form slowly a n d best i n t h e 1 : 2 0 0
solution. T h e y are small plates, usually p o i n t e d and often
in rosettes. T h e rosettes are often v e r y dense and are
found in great numbers as t h e solution stands.
P O T A S S I U M F E I I R O C Y A N I D E . — G r e a t n u m b e r s of small
rods in rosettes formed i n the 1 : 1 0 0 0 solution. M o s t of
the crystals in the 1 : 2 0 0 solution are spherical and show
distinct polarization crosses; others a r e rosettes of plates.
I n the 1 : 5 0 solution t h e amorphous precipitate is very
dense and the f e w crystals which form at first are like those
i n the 1: 2 0 0 solution. T h e precipitate does n o t crystallize
rapidly, however ( 8 ) ( 1 5 ) ,
CINCHONIDINE SULPHATE
N i n e crystalline a n d twenty-four non-crystalline p r e cipitates were obtained.
PLATINUM
CHLORIDE,—The
test
is
sensitive.
A
1 : 20,000 solution forms a number of small crystals. T h e
37
crystals are u s u a l l y rosettes of plates, sometimes of rods.
T h e y are clear-cut, but do n o t polarize highly. T h e 1 : 5 0
solution is t o o concentrated for best results ( P l a t e I V ,
Fig. 4) ( 8 ) .
SODIUM PHOSPHATE.—Dense
rosettes of n e e d l e s
are
quickly f o r m e d i n the t w o more concentrated solutions
only. T h e y show distinct polarization crosses ( P l a t e V I I ,
Fig. 5 ) .
POTASSIUM
CYANIDE.—On
standing
crystallization
takes place s l o w l y from t h e amorphous precipitate first
formed i n t h e three more concentrated solutions. T h e
crystals are dark, appearing in rosettes of needles o r
spherical a g g r e g a t e s .
S O D I U M B E N Z O A T E . — T h e very dense, amorphous p r e -
cipitate in t h e t w o more concentrated solutions crystallizes
out into large a n d dense rosettes of needles. T h e s e rosettes
grow t o a l a r g e size and can be plainly seen w i t h the n a k e d
eye. Stir t h e solution for quick results.
P I C R I C A C I D . — T h e crystals are very slowly formed
from the amorphous precipitate. T h e y are good-sized rods
in masses.
POTASSIUM
HYDROXIDE.—Spherical
crystals
are
quickly formed i n the 1 : 5 0 0 solution u p o n stirring*
A m o r p h o u s precipitates form in the 1 : 5 0 0 a n d more c o n centrated solutions. There is n o precipitate i n the 1 : 1 0 0 0
solution ( P l a t e X V , F i g . 3 ) .
P O T A S S I U M F E R R O C Y A N I D E . — T h i s is n o t so sensitive
as the above, b u t the crystals, when formed, are similar.
A n amorphous precipitate and crystals form in the 1 : 5 0
solution only.
Sodium carbonate reacts like t h e above ( 8 ) .
POTASSIUM
C H R O M A T E . — T h e light, a m o r p h o u s
pre-
38
cipitate first formed crystallizes into great numbers of rodshaped rosettes i n the 1 : 1 0 0 0 solution.
There is no
precipitate at greater dilutions.
COCAINE HYDROCHLORIDE
T e n crystalline a n d fourteen non-crystalline precipitates were formed.
T h e following observations w e r e n o t e d concerning the various reactions with cocaine i n which crystals
were produced.
G O L D C H L O R I D E . — T h i s is t h e m o s t sensitive reaction
for cocaine. A n amorphous precipitate is first produced in
all solutions. T h e crystals are characteristic a n d a few
small ones are produced i n a dilution of 1 : 2 0 , 0 0 0 . T h e
crystals can best be described b y photograph. T h e y are
normally delicate a n d characteristic rosettes.
When
formed slowly they are l o n g rods w i t h m a n y short arms
running out at nearly right angles from t h e m a i n axis.
Their shape varies greatly according t o t h e concentration
(Plate I , Figs. 5 and 6) (4) (8) ( 1 0 ) .
P L A T I N U M C H L O R I D E . — T h i s is also a v e r y sensitive
test for cocaine and a characteristic one. F e a t h e r y crystals
are formed u p to a dilution of about 1 : 4 0 0 0 ( P l a t e I V ,
Fig. 5) (8) (4) (10) ( 1 8 ) .
P I C R I C A C I D . — T h i s is a c o m p a r a t i v e l y p o o r reagent, as
the heavy, amorphous precipitates crystallize with difficulty a n d usually very slowly. Crystals formed in solutions u p t o about 1: 800, b u t t h e y are n o t very characteristic. T h e y are rosettes or sheaves of needles ( P l a t e X I X ,
Fig. 2) (4) (6) (10) ( 1 1 ) .
P O T A S S I U M P E R M A N G A N A T E . — S o l u t i o n s u p to about
1: 700 give purple-colored plates or a g g r e g a t e s of plates.
39
Vigorous stirring of t h e solution is often necessary t o start
crystallization, which then proceeds rapidly. T o obtain
this test readily, add only a very small amount of the reagent ( P l a t e X X I I I , F i g , 4 ) ( 5 ) ( 7 ) ( 1 5 ) .
P A L L A D O U S C H L O R I D E . — T h e crystals f o r m e d are char-
acteristic, but this reagent is not so sensitive as some of the
others mentioned above. T h e crystals v a r y much i n form
according t o the conditions of precipitation. O n e of the
most common forms is that obtained with a 1 : 1 0 0 solution, when feathery crystals are produced; 1 : 5 0 0 is about
the limit of reaction. F o r quick crystallization, a d d a drop
of chlorine water or a drop of dilute hydrochloric acid t o
the solution a n d then a d d the palladous chloride a n d stir
with a glass rod. This reaction is of interest, as it w a s the
first one w e used a n d w a s the starting-point of this investigation ( P l a t e V I , F i g . 4 ) .
C H R O M I C A C I D * — T h i s test is made b y adding a small
drop of chromic acid solution t o t h e test drop. A precipitate is formed which o n stirring disappears. A small drop
of strong hydrochloric acid is added a n d a yellowish deposit is produced, which after stirring o n t h e slide should
in a f e w minutes be transformed into loose, spherical
clusters of a n acicular crystal. This test appears t o be one
of the most uncertain because of t h e difficulty with which
crystals are produced ( P l a t e X X I I , F i g . 3 ) .
P o t a s s i u m dichromate m a y be substituted for the
chromic acid i n the above.
I n this test it w a s found that after once h a v i n g obtained
crystals n o difficulty w a s experienced thereafter, n o matter
how m a n y times the test w a s tried. There is always considerable difficulty in first obtaining crystals. A f t e r some
time the conclusion w a s arrived at that the glass rod used
in making the tests serves t o carry at least a trace of crystalline matter from one test t o the other, and that this trace
causes the whole drop t o crystallize out very quickly. This
fact is mentioned here t o call attention t o the necessity of
washing the stirring r o d thoroughly, since simply drying
on a towel will not clean it perfectly.
FERRIC C H L O R I D E . — T h e crystals
are a g g r e g a t e s
of
rather coarse, blade-like forms with chisel-shaped ends.
This is n o t a very sensitive test. Stir t o obtain quick results ( P l a t e I I I , F i g . 6 ) .
POTASSIUM
HYDROXIDE.—In
concentrated
solutions
this reagent produces a white, amorphous precipitate which
changes into crystals o n standing, or b y stirring with a glass
rod. T h e crystals are rod-shaped ( 4 ) .
Sodium carbonate gives results similar t o t h e above
(4) ( 8 ) . ^
Potassium cyanide forms l a r g e rods from t h e amorphous precipitate in t h e 1 : 5 0 solution slowly.
I n practical work the g o l d chloride a n d the platinum
chloride tests have been u s e d almost entirely, as they are
the most satisfactory.
Tests were performed t o determine the effect on the
gold chloride test of t h e presence of another alkaloid with
the following results: A s a rule, w h e n there is present
one-fifth as much of t h e other alkaloid as of cocaine, it has
no effect on the test; one-half t h e a m o u n t affects the crystals in more than half t h e combinations tried and twice the
amount destroys the test i n nearly every case.
Other alkaloids i n equal a m o u n t have a slight effect
only on the picric acid test, b u t change t h e form of crystals
with platinum chloride i n most cases.
41
T h e potassium permanganate test is destroyed in about
one-half of the cases, w h e n an equal amount of another
alkaloid is present.
T h e potassium hydroxide test is spoiled in only eight
out of forty cases when another alkaloid is present in
equal amount.
T h e effect of glycerine u p o n the different tests w a s tried
and it w a s found that glycerine, when present in o n e hundred times the amount of t h e alkaloid, d i d n o t interfere
w i t h the test i n a n y case.
Likewise granulated sugar present o n e hundred or
more times the amount of t h e cocaine does n o t interfere
with the tests.
Tannic acid, w h e n present in equal amount with t h e
cocaine, affects the test in all cases.
G u m arabic or lactose solutions do n o t affect the tests
for cocaine i n a n y case.
CODEINE
Solutions of codeine sulphate were used. T h e crystalline precipitates number nine; the non-crystalline eleven.
M A R M E ' S R E A G E N T . — T h i s , t h e best t e s t for morphine,
is also the best test for codeine. F i r s t w e have a n amorphous precipitate a n d from this great numbers of small,
silvery-appearing masses are formed at once, even in solutions as dilute as 1 : 2000. I n the more concentrated solutions, such as the 1 : 2 0 0 solution, for example, these masses
soon start t o crystallize a n d crystallization spreads rapidly
over the field a n d the crystals appear as small rods i n
masses. F i g . 1 shows first stages of crystallization, while
F i g . 2 shows very little of t h e precipitate which has n o t
crystallized. O n still f u r t h e r s t a n d i n g , r o s e t t e s of g o o d sized p l a t e s , n o r m a l l y v e r y i r r e g u l a r i n o u t l i n e , a r e f o r m e d ,
a l t h o u g h we often h a v e r o d s i n r o s e t t e s i n s t e a d of p l a t e s .
T h e s e changes a r e well s h o w n b y p h o t o g r a p h s ( P l a t e
X V I I , Figs. 1,2 and 3 ) .
R e a c t i o n s w i t h M a y e r ' s r e a g e n t a r e similar t o above
(10).
MILLON'S R E A G E N T . — T h i s reagent forms a precipitate
in t h e 1 : 1 0 0 0 solution, b u t n o c r y s t a l s w e r e n o t e d . I n t h e
1: 50 solution a p r e c i p i t a t e is f o r m e d first a n d it c r y s t a l lizes i n small, spherical c r y s t a l s . I n t h e 1 : 2 0 0 a n d m o r e
c o n c e n t r a t e d solutions t h e p r e c i p i t a t e t a k e s o n a yellow
color a n d t h e c r y s t a l s a r e still s m a l l a n d spherical. T h i s
reaction is of n o v a l u e a s a t e s t , t h e c r y s t a l s b e i n g t o o small
(Plate X X V I , F i g . 2 ) .
CHROMIC A C I D . — T h e amorphous precipitate
first
f o r m e d quickly c h a n g e s i n t o oil-like d r o p s . C r y s t a l s a r e
f o r m e d only i n t h e 1 : 5 0 solution. T h e y a r e characteristic,
d a r k i n a p p e a r a n c e , a n d a r e n o r m a l l y s p h e r i c a l , o r rosettes
of p l a t e s . S o m e t i m e s t h e y a r e m u c h l a r g e r a n d b u s h y i n
a p p e a r a n c e . F o r m a t i o n of c r y s t a l s t a k e s p l a c e slowly u n less t h e d r o p be s t i r r e d ( P l a t e X X I I , F i g . 4 ) .
P O T A S S I U M C H R O M A T E . — T h i s r e a g e n t is n o t sensitive
as a test. T h e 1 : 5 0 s o l u t i o n crystallizes o u t i n s t a n t l y i n t o
beautiful, l a r g e r o s e t t e s . T h e b r a n c h e s a r e b r o a d , p l a t e like, o r r o d s , a n d h a v e p o i n t e d e n d s ( P l a t e X X I ,
F i g . 4) ( 1 ) .
Z I N C - C H L O R - I O D I D E . — T h e l i m i t of r e a c t i o n for c r y s t a l s
is a b o u t 1 : 500, b u t t h e s o l u t i o n is t o o d i l u t e f o r good-sized
crystals. G r e a t n u m b e r s of r o s e t t e s a r e f o r m e d in t h e 1 : 5 0
solution, some b e i n g coarse, o t h e r s m a d e u p of needle-like
forms ( P l a t e X X V I I , F i g s . 2 a n d 3 ) .
43
P O T A S S I U M I O D I D E . — T h i s reagent forms long, needlelike crystals, often i n masses, in the 1 : 5 0 solution only.
Crystals are formed without a first amorphous precipitate
( P l a t e X V I I I , F i g .3 ) ( 1 ) .
W A G N E R ' S R E A G E N T . — T h i s r e a g e n t f o r m s precipitates
in all solutions, b u t crystals are formed o n l y i n t h e 1 : 5 0
and 1 : 2 0 0 solutions. T h e y are rosettes of plates, light
brown in color and usually of large size ( P l a t e X , Fig* 6 )
(8) (18) ( 1 ) .
A M M O N I U M T H I O C Y A N A T E . — L i m i t of reaction about
1 : 1 0 0 . L a r g e rosettes consisting of rods are formed in the
1 : 5 0 solution. T h e s e rods are pointed at t h e ends. T h e y
polarize brightly ( P l a t e X X V , F i g . 2 ) .
COLCHICINE
T h e aqueous solutions are yellow.
N o crystalline precipitates were obtained.
U p o n adding W a g n e r ' s reagent t o the 1 : 50 solution
of the alkaloid, a n amorphous precipitate is formed. S o m e
very fine needles are formed from this after it stands for
some time, but their formation is n o t always certain.
CONIINE
Seven crystalline a n d nine non-crystalline precipitates
were obtained.
P H O S P H O T U N G S T I C A C I D . — T h i s is a g o o d a n d sensitive
test. Short rods are instantly formed even in a 1 : 1 0 , 0 0 0
solution ( P l a t e X X I V , F i g . 5 ) ( 1 3 ) .
KRAUT'S REAGENT.—Heavy,
amorphous
precipitates
are first formed. T h e crystals are small, clear-cut plates
of a deep, reddish-brown color, and are often six-sided, but
44
are not all of the same shape. G r e a t numbers are formed
from the precipitate i n t h e 1 : 5 0 0 solution a n d all of the
1 : 1 0 0 0 solution crystallizes. Crystals were also obtained
in a 1: 3000 solution ( 8 ) ( 1 3 ) .
MARME'S REAGENT.—The
amorphous
precipitate
is
heavy in all cases. O n standing it takes o n a n appearance
similar to oil globules, a n d after some time crystals are
formed. T h e y are large a n d coarse in appearance a n d
form very slowly. T h e y are n o r m a l l y a bundle of rods
or plates.
T h e growth of the crystals m a y be v e r y clearly seen
under the microscope as the drops come i n contact with the
crystal. T h e 1: 200 and 1 : 5 0 0 solutions are best for crystal formation ( P l a t e X V I I , F i g . 4 ) ( 1 3 ) .
MAYER'S R E A G E N T . — A m o r p h o u s precipitates
formed
in all the solutions. Crystals are of good-sized rosettes of
irregular rods. Crystallization is slow a n d n o crystals are
formed in the 1 : 1 0 0 0 solution.
PHOSPHOMOLYBDIC
ACID.—Many
of
the
crystals
formed are small and spherical, others are plate-like,
sharply cut, and deep y e l l o w in color. T h e crystals are
formed rather quickly from t h e amorphous precipitate a n d
are best seen around the edges of t h e h e a v y amorphous precipitate and in the more concentrated solutions ( 1 3 ) .
PALLADOTJS C H L O R I D E . — O n l y
o n stirring do w e
get
crystals. These are small a n d f o r m o n l y as t h e solutions
become concentrated. T h e y are short rods, often i n rosettes.
B A R I U M N I T R A T E . — R o s e t t e s of small rods are formed
in all the solutions o n stirring ( 1 3 ) .
T h e heavy, amorphous precipitate w i t h g o l d chloride
takes on a violet color at once in t h e 1 : 5 0 solution.
45
CORYDALINE
S i x crystalline a n d twenty-seven non-crystalline p r e cipitates were obtained.
POTASSIUM H Y D R O X I D E . — A m o r p h o u s precipitates ap-
pear in all the solutions. Crystallization is slow. T h e
crystals are rosettes of rods i n the 1 : 50 solution. I n t h e
more dilute solutions, plates or rosettes of plates are formed.
A m m o n i u m hydroxide gives results similar t o the above.
SILVER N I T R A T E . — S h o r t
rods are f o r m e d
from
the
amorphous precipitate in t h e 1: 50 solution only.
AMMONIUM
THIOCYANATE.—Small
rosettes
are
formed in all the solutions quickly from t h e amorphous
precipitates.
P O T A S S I U M C H R O M A T E . — V e r y fine rods or needles i n
rosettes are formed
solutions only.
MERCURIC
in t h e t w o more
CHLORIDE.—Amorphous
concentrated
precipitates
ap-
pear i n all t h e solutions and t h e y all crystallize, t h o u g h n o t
rapidly. Rosettes of rods, polarizing fairly well, is t h e
normal form ( P l a t e V I I I , F i g . 2 ) .
M I L L O N ' S R E A G E N T . — I n the 1 : 50 solution, crystals in
rosettes of rods are formed from the amorphous precipitate.
The following color reactions were n o t e d : L i g h t blue
quickly changing to dark blue color with F r o e h d e ' s reagent in the 1 : 50 and 1: 200 solutions, and this color gradually fades out. A slight reddish or pink coloration formed
with ammonium vanadate i n all the solutions u p t o t h e
1 : 1 0 0 0 . I t is very faint in the 1 : 1 0 0 0 solution.
CYTISINE HYDROCHLORIDE
Nine crystalline and seven non-crystalline precipitates
were obtained.
MAYER'S R E A G E N T . — T h i s is the best t e s t for cytisine.
This is a very sensitive test, as good-sized rosettes of
rods are soon formed in a 1: 6000 solution. A very dense
crystalline precipitate is formed a t once i n all solutions.
They are moss-like, often turning to rods o n standing.
M A R M E ' S R E A G E N T . — T h e r e are n o precipitates in the
two more dilute solutions.
A n exceedingly dense mass of rods formed very
quickly from the amorphous precipitate i n t h e 1 : 50 solution. Stir the 1 : 2 0 0 solution for quick crystallization.
P L A T I N U M C H L O R I D E . — T h i s reagent f o r m s
crystals
only on stirring the 1 : 5 0 solution. T h e y are large and
dense rosettes of needles and do not polarize ( 8 ) .
PHOSPHOTUNGSTIC A C I D . — T h i s r e a g e n t forms heavy,
amorphous precipitates in all the solutions, a n d crystals i n
all except the 1: 50 solution are formed slowly* T h e y are
rosettes of plates and polarize but slightly.
WAGNER'S R E A G E N T . — T h i s is a sensitive test.
The
amorphous precipitate crystallizes in all the solutions used.
The crystals are normally l o n g rods, o f t e n in rosettes.
They do not polarize. T h e y are often leaf-like rosettes in
the 1 : 5 0 solution, and crystallization t a k e s place more
slowly in this solution than in the more dilute ones. T h e
crystals grow to a good size i n the 1 : 1 0 0 0 solution ( P l a t e
X I , Fig. 1 ) .
PICRIC A C I D . — N o crystals appear i n a n y solution more
dilute than 1: 200. O n stirring the 1: 2 0 0 solution w e g e t
great numbers of needles or often plates. T h e 1 : 50 solu-
47
tion crystallizes o u t slowly, forming very large,
rosettes of rods ( P l a t e X I X , F i g . 3 ) .
MERCURIC
CHLORIDE.—Fine
rosettes
of
dense
plates
are
formed in the t w o more concentrated solutions.
They
polarize well. O n l y a f e w small ones form o n stirring the
1: 5 0 0 solution ( P l a t e V I I I , F i g . 3 ) .
G O L D C H L O R I D E . — T h e best crystals with this reagent
are at a concentration of about 1 : 2 0 0 . T h e crystals are
t h e n large, somewhat leaf-like a n d characteristic.
They
do n o t polarize.
A great n u m b e r of very small crystals are formed o n
stirring the 1 : 1 0 0 0 solution ( P l a t e I I , F i g . 1) ( 8 ) .
T h e following color reaction w a s n o t e d :
T h e 1 : 50 solution takes on a deep reddish-brown color
w i t h ferric chloride.
DIONINE
(ETHYL-MORPHINE)
E i g h t crystalline a n d fourteen non-crystalline precipitates were obtained.
N o very sensitive tests for dionine were obtained.
WAGNER'S
REAGENT,—The
dense precipitate
in
the
1 : 5 0 and 1 : 2 0 0 solutions crystallize rather rapidly into
l a r g e rosettes of rods. Crystals were n o t obtained i n the
m o r e dilute solutions. T h e s e crystals are characteristic
(Plate X I , F i g . 2) ( 1 8 ) .
Kraut's reagent forms crystals similar t o t h e above, b u t
t h e reagent does n o t appear t o be so sensitive.
M A Y E R ' S R E A G E N T . — T h e crystals, f o r m e d in the t w o
m o r e concentrated solutions, are small. T h e y are silvery
in appearance a n d do n o t polarize. T h e y form slowly, as
a rule, and m o s t of t h e heavy, amorphous precipitate does
n o t crystallize.
Marine's reagent gives results as above.
ZINC-CHLOR-IODIDE.—This reagent forms a heavy p r e cipitate and in the 1 : 50 solution a f e w small crystals f o r m
around the edge. T h e y d o n o t polarize a n d might easily
be overlooked.
S O D I U M C A R B O N A T E . — S h o r t rods or rosettes of r o d s
are formed in the 1: 50 solution only and are formed s l o w l y
unless the drop be stirred. N o precipitate formed ( P l a t e
X I V , Fig. 3 ) .
Potassium hydroxide gives results as above.
MERCURIC C H L O R I D E . — N o precipitate appeared in t h e
two more dilute solutions. A n amorphous precipitate
formed i n the 1: 50 solution only. I n the 1 : 2 0 0 and m o r e
concentrated solutions, large rosettes of plates are the n o r mal form. Stir the 1: 200 solution i n order t o g e t quick
crystallization (Plate V I I I , F i g . 4 ) .
ECGONINE HYDROCHLORIDE
Three crystalline and four non-crystalline precipitates
were obtained.
PHOSPHOMOLYBDIC A C I D . — T h i s is a delicate and c h a r -
acteristic test. Crystalline precipitates are formed i n a l l
solutions up t o 1 : 4 0 0 0 . T h e y are best at a dilution o f
1:500. A l l of the amorphous precipitate i n the 1: 5 0 0
solution does not crystallize until it stands for some t i m e .
The crystals are dense rosettes of needles often of l a r g e
size. They do not polarize highly.
PHOSPHOTUNGSTIC A C I D . — T h e crystals are v e r y s m a l l
and indistinct rosettes and are best seen in the 1 : 1 0 0 0
solution. The amorphous precipitates in t h e more concentrated solutions do not crystallize.
K R A U T ' S R E A G E N T . — H e a v y , amorphous
precipitates
49
are formed. Crystals are formed i n t h e 1 : 2 0 0 a n d in the
1 : 5 0 0 solutions only. T h e y are six-sided a n d n o t very
large and are clear-cut plates ( P l a t e X I I I , F i g . 3 ) .
HEROINE (DIACETYL MORPHINE)
Seven crystalline a n d nineteen non-crystalline precipitates were obtained.
N o very sensitive tests were obtained o n heroine.
S O D I U M C A R B O N A T E . — A rather light, a m o r p h o u s pre-
cipitate is formed i n t h e 1 : 2 0 0 solution a n d it crystallizes
slowly. Crystals polarize very highly a n d are often fine
rosettes of p o i n t e d plates. There w a s n o precipitate i n t h e
dilute solution.
SODIUM
PHOSPHATE.—This
reagent
forms
rather
coarse rosettes of rods i n the 1 : 5 0 solution only, a n d n o
first amorphous precipitate appeared.
POTASSIUM HYDROXIDE.—No
precipitate a p p e a r s e x -
cept i n the 1 : 5 0 solution, a n d this soon crystallizes. T h e
crystals are rosettes of rods, often n o t well formed.
P L A T I N U M C H L O R I D E . — C r y s t a l s are formed o n l y f r o m
the heavy precipitate i n t h e t w o more concentrated solutions after some time. T h e y are spherical or often fine
rosettes of needles a n d do n o t polarize ( 1 8 ) .
M E R C U R I C C H L O R I D E . — N o precipitate a p p e a r s in the
dilute solutions. I n the 1 : 2 0 0 solution a f e w crystals are
slowly formed from the slight precipitate. T h e y do not
polarize brightly. I n t h e 1 : 5 0 solution w e have a dense
precipitate. Crystals are rather slowly formed, but they
g r o w into good-sized rosettes, sometimes of blade-like
forms. T h e reaction resembles that of morphine with this
reagent; hence, if it is obtained, a p p l y t h e tests for morphine, especially with Mayer's and Marine's reagents. T h e
4
50
amorphous precipitate appears like oil g l o b u l e s before it
crystallizes ( P l a t e V I I I , F i g . 5 ) .
POTASSIUM C Y A N I D E . — I n the 1 : 5 0 solution, a rather
dense precipitate crystallizes s l o w l y i n t o solid, j a g g e d appearing crystals, o f t e n rods or cubes. B e a u t i f u l rosettes
are often formed. B y stirring t h e 1 : 2 0 0 solution w e g e t
great numbers of p l a t e s polarizing v e r y brightly ( P l a t e
X X I , Fig. 2).
P I C R I C A C I D . — C r y s t a l s a p p e a r in t h e t w o m o r e c o n -
centrated solutions from the h e a v y a m o r p h o u s precipitates. T h e y are spherical or often small rosettes, a n d d o
n o t polarize brightly ( P l a t e X I X , F i g . 4 ) .
HOMATROPINE
F o u r crystalline a n d fourteen non-crystalline precipitates were obtained.
G O L D C H L O R I D E . — T h e limit of r e a c t i o n is a b o u t 1 : 5 0 0 ,
as the 1 : 1 0 0 0 solution forms neither crystals n o r amorphous precipitate. I n t h e 1 : 5 0 0 solution a slight amorphous precipitate is first formed. T h i s , o n standing, turns
into oil-like drops a n d from these crystals a r e formed.
T h e y form slowly, are of a greenish color, a n d polarize
brightly. T h e y are rosettes of plates. I n t h e 1 : 2 0 0 solution the amorphous precipitate is considerably heavier than
before a n d crystallization is slow. T h e crystals sometimes
appear t o be of a n orange color. E v e n in the 1 : 5 0 solution
crystallization is very slow ( P l a t e I I , F i g . 2 ) ( 1 7 ) •
WAGNER'S REAGENT.—This
is a s e n s i t i v e t e s t ,
as
a
number of very small crystals form i n a 1 : 4 0 0 0 solution
on standing, t h o u g h t h e y are t o o small t o be o f service
as a test.
DETAILED DESCRIFflON OF TESTS
51
T h e a m o r p h o u s precipitate in t h e 1 : 1 0 0 0 solution is
dense. T h e crystals form slowly. T h e y are n e a r l y all
small a n d dark-brown i n color a n d are m a i n l y six-sided.
A f e w are larger a n d consist of several r a d i a t i n g branches.
T h e y vary in color, b e i n g black, light or dark-brown, y e l l o w ,
and often o f a g r e e n color. T h e p h o t o g r a p h s s h o w t h e d e cided difference in the appearance of these crystals ( P l a t e
X I , Figs. 3 and 4) ( 1 7 ) .
K r a u t ' s r e a g e n t forms crystals quite similar t o above.
MILLON'S
REAGENT.—Small
spherical
crystals
are
formed in the 1 : 5 0 solution o n l y ( P l a t e X X V I , F i g . 3 ) .
HYDRASTINE
Thirty-three a m o r p h o u s precipitates w e r e obtained
with this alkaloid a n d o n l y o n e crystalline precipitate.
P O T A S S I U M H Y D R O X I D E . — U p o n a d d i n g a 25 per cent,
solution o f this r e a g e n t t o t h e 1 : 1 0 0 0 solution o f t h e alkaloid a n d stirring, crystals are produced from t h e amorphous precipitate. T h e y are clear-cut rosettes.
Crystal formation is much slower if t h e solution is n o t
stirred.
T h e crystals are similar but larger in more
concentrated solutions.
N o crystals were obtained with a 5 per cent, solution o f
potassium hydroxide, a n d it is often difficult t o obtain a n y
crystals a t all even with the 2 5 p e r cent, solution ( P l a t e
X V , F i g .4 ) .
T h e f o l l o w i n g color reaction w a s n o t e d : A m m o n i u m
vanadate g i v e s a pink color which is n o t p e r m a n e n t in t h e
1 : 5 0 solution.
A m m o n i u m thiocyanate g i v e s a n a m o r p h o u s precipitate in t h e 1 : 5 0 solution only.
5% SOME MICROCHEMICAL TESTS FOR ALKALOIDS
HYDRASTININE
A l l t h e solutions showed fluorescence, especially the
more dilute ones.
E i g h t non-crystalline a n d eleven crystalline precipitates were obtained.
POTASSIUM
PERMANGANATE.—The
crystals
formed
with this reagent are large a n d characteristic. T h e amorphous precipitate which is first formed does n o t ordinarily
crystallize i n t h e 1 : 1 0 0 0 solution. S o m e t i m e s w e g e t a
f e w rods and plates. I n the three m o r e concentrated solutions, however, w e g e t great numbers of large plates often
in rosettes. T h e y have saw-tooth edges or often appear
like some very deeply cut leaves ( P l a t e X X I I I , F i g .
5) ( 1 5 ) .
G O L D C H L O R I D E . — T h i s r e a g e n t f o r m s a m o r p h o u s pre-
cipitates i n all the solutions, a n d the t w o more concentrated
solutions crystallize o n l y o n stirring. T h e crystals formed
are rods, often pointed or notched at t h e ends a n d sometimes occurring in rosettes.
MERCURIC CHLORIDE.—On
stirring the 1 : 1 0 0 0
solu-
tion w e g e t a f e w small rods. R o d s , often pointed, a n d in
rosettes quickly formed o n stirring the 1 : 5 0 0 solution. A
dense mass of large rods instantly formed in t h e 1 : 2 0 0
solution. T h e 1 : 5 0 solution crystallizes o u t into one dense
mass of crystals ( 1 5 ) .
C H R O M I C A C I D . — T h i s test is characteristic but not very
sensitive, as no crystals are formed at greater dilutions than
1: 200. I n the more concentrated solutions w e g e t great
numbers of crystals. T h e y are normally dense rosettes of
rods of peculiar shape, often pointed. Variations i n the
appearance of t h e crystals are shown i n t h e photographs.
53
I n the 1 : 5 0 solution g r e a t numbers of large moss-like
rosettes are f o r m e d a t once from the amorphous precipitate ( P l a t e X X I I , F i g s . 5 a n d 6 ) .
P I C R I C A C I D . — P i c r i c acid f o r m s crystals in t h e t w o
more concentrated solutions only. T h e y are plates or
rosettes of p l a t e s . I n the 1 : 5 0 0 solution they are often
eight-sided; some a r e irregular in outline. T h e y are norm a l l y rosettes of l a r g e size i n the more concentrated solutions and polarize b r i g h t l y ( P l a t e X I X , F i g . 5 ) ( 1 6 ) .
ZINC-CHLOK-IODIDE.—Amorphous
precipitates
are
heavy a n d numbers of crystals are formed quickly, especially in t h e 1 : 1 0 0 0 solution if stirred. T h e crystals are
needles or rods u s u a l l y p o i n t e d a n d often i n rosettes.
PALLADOTJS C H L O R I D E . — N o precipitate appears i n the
1 : 1 0 0 0 solution.
N u m b e r s of rosettes are formed in the 1 : 5 0 0
solution. T h e y are composed of sharp-pointed needles
resembling thorns.
I n t h e 1 : 2 0 0 solution w e have large crystals in t w o
forms, needles i n rosettes a n d rosettes of plates. I n the
1: 5 0 solution w e g e t a dense mass of needle-shaped crystals. R o s e t t e s of plates are n o t so c o m m o n ( P l a t e V I ,
Fig. 5 ) .
P L A T I N U M C H L O B I D E . — C r y s t a l s f o r m o n l y o n stirring
in the 1 : 1 0 0 0 a n d 1 : 5 0 0 solutions, a n d t h e y are rosettes
of rods, as a rule. T h e dense precipitates in the other t w o
solutions crystallize quickly into large, bushy crystals
(Plate I V , F i g . 6 ) .
M A Y E R ' S R E A G E N T . — T h e precipitates are all
heavy
with this r e a g e n t a n d crystals are formed o n l y o n stirring.
T h e y are v e r y small i n all e x c e p t t h e 1 : 1 0 0 0 solution, and
in this solution t h e y are o f t e n good-sized rosettes of rods.
54
M A R M E ' S R E A G E N T . — A m o r p h o u s precipitates appear
which crystallize without stirring in all solutions- A dense
mass of crystals are obtained in the t w o more concentrated
solutions. T h e crystals in the 1 : 1 0 0 0 solution are large
and polarize highly. T h e y normally have cross arms a n d
j a g g e d edges.
A M M O N I U M M O L Y B D A T E . — H e a v y , a m o r p h o u s precipi-
tates a n d great numbers o f small needle-shaped crystals
are formed in all the solutions.
HYOSCYAMINE HYDROBROMIDE
A n alkaloidal salt labeled " D a t u r i n e S u l f a t e " g a v e
same results as t h e o n e labeled hyoscyamine hydrobromide,
and the chemical determinations were m a d e o n the former.
S i x crystalline a n d fifteen non-crystalline precipitates
were obtained.
KRAUT'S R E A G E N T . — T h e heavy, amorphous
precipi-
tate crystallizes s l o w l y into irregular rods in t h e 1 : 5 0 0 a n d
1 : 1 0 0 0 solutions. Crystals are larger a n d more quickly
formed in the more concentrated solutions. T h e y are often
in rosettes.
G O L D C H L O R I D E . — T h i s is n o t a sensitive test.
Amor-
p h o u s precipitates appear in all t h e solutions. C r y s t a l s of
pointed rods or irregular plates, often in rosettes, are
f o r m e d in t h e 1 : 5 0 solution after some time a n d o n stirring
{Plate I I , F i g . 3 ) .
MERCURIC
CHLORIDE.—An
amorphous
precipitate
forms in t h e 1 : 5 0 solution only.
Crystals appear only in the t w o more concentrated solutions. T h e y are large rosettes of rods polarizing brightly.
S t i r the 1 : 2 0 0 solution for quick results.
P I C R I C A C I D . — D e n s e r o s e t t e s o f n e e d l e s are
formed
slowly upon
solutions o n l y .
WAGNER'S
stirring
the
two
REAGENT.—Heavy,
more
65
concentrated
amorphous
precipi-
t a t e s in all t h e solutions a n d small crystals a r e q u i c k l y
formed. S o m e look like those formed w i t h atropine a n d
this reagent. T h e y are, as a rule, l a r g e r t h a n those f o r m e d
with atropine. I n t h e 1 : 5 0 solution, besides this form, w e
have l a r g e crystals of a l i g h t - g r e e n color a n d which a r e
dense rosettes u s u a l l y moss-like in g e n e r a l a p p e a r a n c e
( P l a t e X I , F i g . 5 ) . S m a l l crystals a r e f o r m e d in a
1 : 2 0 0 0 solution.
Z I N C - C H L O R - I O D I D E - — A g e l a t i n o u s precipitate f o r m e d
in a l l t h e solutions. T h e crystals are small p l a t e s a n d similar t o those formed w i t h atropine.
THE OPIUM
ALKALOIDS
T h e f o l l o w i n g o p i u m alkaloids w e r e s t u d i e d : M o r phine, codeine, apomorphine, apocodeine, n a r c o t i n e , n a r ceine, papaverine, thebaine, peronine, dionine a n d heroine.
Several o f these alkaloids have already been discussed*
MOBPHINE
F o u r aqueous solutions of m o r p h i n e hydrochloride
w e r e used, t h e alkaloid* being p r e s e n t o n e p a r t t o
1000, 5 0 0 , 2 0 0 , a n d 5 0 , respectively. E l e v e n n o n - c r y s talline a n d e l e v e n crystalline precipitates w e r e obtained
with these solutions.
M A B M E ' S R E A G E N T . — T h i s is t h e b e s t t e s t f o r m o r p h i n e .
I n all t h e solutions e x c e p t the 1 : 1 0 0 0 a g e l a t i n o u s precipitate is formed which crystallizes o u t quickly. T h i s precipi-
56
SOME MICROCHEMICAL TESTS, FOR ALKALOIDS
tate has a silvery appearance under the microscope. These
crystals are rosettes of v e r y fine needles a n d are characteristic. T h e y form a dense m a s s , especially so in the more
concentrated solutions. I n t h e 1 : 1 0 0 0 solution w e g e t n o
precipitate, but b y a d d i n g a drop of the reagent and allowi n g t o stand for a short time, l o n g needles form aroimd the
edge of the drop ( P l a t e X V I I , F i g . 5 ) .
WAGNER'S
REAGENT.—A
very
characteristic
test,
though n o t so sensitive as t h e one with Marine's reagent.
A heavy, amorphous precipitate i s formed in all solutions.
This precipitate forms reddish-brown drops before crystallization takes place, a n d from t h e precipitate crystallization
takes place very slowly.
I t is often necessary t o allow t h e solution t o stand several minutes before crystals are formed. T h e crystals are
large plates, reddish-brown i n color, a n d irregular in outline. O p t i m u m concentration is about 1 : 2 0 0 . W h i l e the
crystals are normally as described, y e t w e o f t e n obtain
rosettes of fine needles in t h e 1 : 5 0 solution, or sometimes
rods. These crystals are n o t dark-brown in color, b u t are
light in appearance a n d similar t o those formed b y the
potassium iodide solution. S t i r w i t h a g l a s s r o d about
thirty strokes as soon as reagent is added t o 1 : 50 solution
if quick crystallization be desired. T h e s e crystals are n o t
so large and are usually more regular in outline than when
they form more slowly ( P l a t e X I , F i g . 6 ) ( 1 8 ) .
SODIUM CARBONATE.—Great
n u m b e r s of s m a l l crys-
tals formed in the 1 : 2 0 0 solution, without t h e formation of
an amorphous precipitate. T h e s e crystals are characteristic, being sharply defined rods often i n rosettes. Crystals formed in more concentrated solutions t h a n this are
fine, clear-cut, a n d characteristic, t h o u g h n o t large. T h e
D E T A I L E D DESCRIPTION O F TESTS
57
solutions m u s t be stirred for quick crystallization. N o p r e c i p i t a t e o c c u r s in s o l u t i o n s m o r e d i l u t e t h a n t h e 1 : 2 0 0
( P l a t e X I V ,F i g .4 ) ( 8 ) .
MAYER'S R E A G E N T , — A gelatinous precipitate, with
a
s i l v e r y a p p e a r a n c e u n d e r t h e m i c r o s c o p e , is f o r m e d , b u t
since w e h a v e n o t b e e n a b l e t o p r o v e t h a t c r y s t a l s a r c
f o r m e d , t h e a p p e a r a n c e is b e s t d e s c r i b e d b y t h e p h o t o graph (Plate X V I , F i g . 3 ) .
Barium-mercuric-iodide
gives r e s u l t s s i m i l a r t o a b o v e .
A s t h e reactions with
codeine a r e q u i t e s i m i l a r t o t h i s , t h e s e r e a g e n t s a r e o n l y
of v a l u e i n d i s t i n g u i s h i n g m o r p h i n e a n d c o d e i n e f r o m
other alkaloids.
O T H E R T E S T S . — T h e other tests for m o r p h i n e a r e n o t
sensitive a n d h a v e n o t b e e n f o u n d o f p r a c t i c a l v a l u e . T h e y
a r e briefly a s f o l l o w s :
P o t a s s i u m c h r o m a t e f o r m s r o d s o r r o s e t t e s of r o d s o n l y
on stirring t h e 1 : 2 0 0 a n d more concentrated solutions.
T h i s r e a c t i o n is n o t a t a l l sensitive, a s it is o f t e n difficult
to obtain crystals on stirring t h e 1 : 2 0 0 solution ( P l a t e
X X I , Fig. 5) ( 4 ) .
Zinc-chlor-iodide forms a slight gelatinous precipitate,
but n o crystals in t h e 1 : 2 0 0solution, a n d a dense precipit a t e w h i c h c r y s t a l l i z e s i n s t a n t l y in t w o f o r m s of c r y s t a l s i n
the 1 : 50 solution. Yellow-brown, shiny crystals a r e u s u a l l y c o m m o n a n d t h e s e d o n o t p o l a r i s e . A d e n s e m a s s of
needle-like c r y s t a l s is a l s o f o r m e d a r o u n d t h e e d g e o f t h e
drop. These latter, j u d g i n g from their a p p e a r a n c e , a r e
f o r m e d b y t h e p o t a s s i u m iodide in t h e r e a g e n t .
Mercuric chloride forms large rosette-like crystals in
the 1 : 5 0 solution only a n d very quickly when stirred.
These crystals a r e formed without a n amorphous preeipi-
58
tate being thrown down first and are n o r m a l l y dense
rosettes of rods ( P l a t e V I I I , F i g . 6 ) ( 8 ) .
P o t a s s i u m iodide forms needles i n t h e 1 : 5 0 solution
only and slowly. These needles are normally l o n g a n d in
rosettes, and m a y often be easily seen without t h e aid of t h e
microscope ( P l a t e X V I I I , F i g . 4 ) .
Kraut's reagent forms very heavy, amorphous, brickred precipitates i n all solutions. Crystals are f o r m e d in
the 1 : 50 solution only, and a r e f e w a n d small a n d formed
from the precipitate, but only a very small part o f the p r e cipitate crystallizes. T h e crystals are very small rods a n d
so infrequently formed that this reagent is worthless a s a
test for morphine.
P o t a s s i u m permanganate. A dense mass of v e r y s m a l l
crystals noted i n more concentrated solutions o n l y a r o u n d
the edges of t h e heavy precipitate which is f o r m e d . T h e s e
crystals are irregular in outline and t o o small t o be of s e r vice as a test.
NABCEINE
Three solutions of narceine hydrochloride w e r e used i n
dilutions of 1 : 1 0 0 0 , 1 : 500, a n d 1 : 200.
N i n e crystalline and nineteen non-crystalline precipitates were obtained.
K R A U T ' S R E A G E N T . — V e r y dense, a m o r p h o u s
precipi-
tates are first formed. T h e crystals are beautiful l a r g e
rosettes of needles a n d are v e r y characteristic, a s t h e y a r e
deep-blue i n color. T h e test is n o t v e r y sensitive, a s t h e
1 : 5 0 0 solution forms crystals o n l y o n s t a n d i n g f o r s o m e
time. N o crystals were formed i n the 1 : 1 0 0 0 solution.
W a g n e r ' s r e a g e n t gives results similar t o t h e a b o v e
( P l a t e X I I , F i g . 1) ( 1 ) .
DETAILED DESCRIPTION OP TESTS
POTASSIUM
IODIDE.—The
crystals
are
rosettes
59
of
needles o f g o o d size, blue i n color a n d f o r m e d i n small
numbers i n the 1 : 5 0 0 solution, b u t m a n y are formed
in the m o r e concentrated solutions. T h e crystals are like
those f o r m e d w i t h K r a u t ' s solution o r w i t h W a g n e r ' s
reagent ( 8 ) .
Z I N C - C H L O R - I O D I D E . — H e a v y , a m o r p h o u s precipitates
a n d g r e a t n u m b e r s of fine, blue rosettes of needles are
formed i n a l l b u t t h e 1 : 1 0 0 0 solution.
PALLADOUS
CHLORIDE.—Amorphous
precipitates
formed i n t h e 1 : 2 0 0 solution o n l y .
S m a l l rosettes or
sheaves o f needles are s l o w l y f o r m e d i n all t h e solutions
(Plate V I , F i g -6 ) .
P L A T I N U M C H L O R I D E . — B e a u t i f u l f e a t h e r y r o s e t t e s are
formed f r o m t h e a m o r p h o u s precipitates in all solutions.
T h i s is a sensitive test ( P l a t e V , F i g , 1 ) ( 1 ) ( 1 0 ) .
POTASSIUM C H R O M A T E . — N o amorphous
precipitates
appeared. R o s e t t e s o f needles are f o r m e d in t h e more
concentrated solutions only. S t i r w i t h a g l a s s r o d for
quick crystallization ( 1 ) ( 1 0 ) .
P I C R I C A C I D . — T h e 10 p e r cent, alcoholic solution g a v e
heavy, a m o r p h o u s precipitates i n a l l t h e solutions a n d
rosettes o f small plates f o r m e d o n l y in t h e 1 : 5 0 solution.
GOLD CHLORIDE.—While
w e h a v e a p r e c i p i t a t e i n all
solutions, c r y s t a l s were o n l y obtained i n t h e 1 : 5 0 solution
after s t a n d i n g . T h e y are dense rosettes of needles. T h e
p h o t o g r a p h shows v e r y clearly t h e d r o p s i n process of crystallization ( P l a t e I I , F i g . 4 ) .
POTASSIUM HYDROXIDE.—There
were no
amorphous
precipitates, but rosettes of needles f o r m e d i n t h e 1 : 5 0
solution ( P l a t e X V , F i g . 6 ) .
NABCOTINE
Solutions of narcotine hydrochloride were usedE i g h t crystalline a n d t w e n t y - s i x non-crystalline p r e cipitates were obtained.
POTASSIUM H Y D R O X I D E . — I n
the 1 : 1 0 0 0
solution an
amorphous precipitate which is fairly h e a v y is formed and
crystals are slowly formed from this. T h e y are needles.
I n the 1: 5 0 0 solution the precipitate is dense and great
numbers of crystals are quickly formed. T h e y are normally rosettes of needles of g o o d size a n d d o n o t
polarize brightly.
I n the 1 : 2 0 0 solution t h e precipitate is very dense a n d
needles in rosettes, or m o r e often in sheaf-like bundles, are
formed- T h e whole precipitate crystallizes out o n standing.
I n the 1 : 5 0 solution t h e precipitate crystallizes t o a
dense mass of rosettes of needles o n standing.
The following reagents g i v e results practically the
same as the above, although there is some variation in sensitiveness of the reactions; potassium acetate ( P l a t e X I I ,
F i g . 5 ) ; potassium chromate; potassium cyanide; sodium
carbonate ( P l a t e X I V , F i g . 5 ) ; sodium phosphate, a n d
sodium phosphomolybdate ( 8 ) ( 2 ) .
T h e sodium carbonate a d d e d t o t h e alkaloid in a solution of 1 : 20,000 forms a number of very fine needle crystals.
W o r m l e y describes t h e crystals formed with potassium
hydroxide with potassium chromate a n d those formed with
potassium acetate, a n d g i v e s plates illustrating their
normal form.
NICOTINE
Seven crystalline a n d eleven non-crystalline precipitates were obtained.
61
G O L D C H L O R I D E . — A very h e a v y precipitate is formed
in the 1 : 1 0 0 0 solution, and this crystallizes quickly into
small spherical or sheaf-like crystals.
T h e y polarize
poorly. I n t h e 1 : 5 0 0 solution t h e precipitate a n d crystals
are as above. T h e crystals do n o t form as readily in the
1: 50 solution as they do at greater dilutions.
This test is sensitive, as a n aqueous solution of about
1 : 1 5 , 0 0 0 g i v e s considerable numbers of small and characteristic crystals ( P l a t e I I , F i g . 5 ) ( 8 ) .
M E R C U R I C C H L O R I D E . — T h e amorphous precipitate is
very slight in the 1 : 1000 solution a n d crystallization is
slow unless the solution be stirred, w h e n crystals are formed
at once. T h e y are small, clear-cut rosettes of plates and
polarize but slightly. I n the more concentrated solutions
the crystals are larger and form more rapidly.
A 1 : 4000 solution gives a number of small crystals on
stirring ( P l a t e I X , F i g . 1 ) ( 1 ) ( 8 ) .
K R A U T ' S R E A G E N T . — T h e amorphous precipitate crys-
tallizes at once i n needles, often i n rosettes, u p o n stirring
the 1 : 5 0 0 solution. N o crystals were obtained in the
1 : 1 0 0 0 solution.
I n the t w o more concentrated solutions, the crystals are
large rods, light-yellow in color a n d polarize brightly ( 8 ) .
W A G N E R ' S R E A G E N T . — C r y s t a l s are obtained with diffi-
culty from t h e heavy, amorphous precipitates, especially
if much of the reagent be used. N o crystals were obtained
in the 1 : 1 0 0 0 solution. U s e b u t a small amount of the
reagent for satisfactory results.
M A Y E R ' S R E A G E N T . — G r e a t n u m b e r s of small, spheri-
cal crystals are formed from the amorphous precipitate in
the t w o more concentrated solutions only. A light, amor-
plious precipitate is formed i n the 1 : 5 0 0 solution, but n o
crystals are formed at this dilution ( 1 0 ) .
P I C R I C A C I D . — T h i s is a sensitive test.
T h e crystals
are large and form instantly f r o m t h e heavy, amorphous
precipitate in all solutions. T h e precipitate first formed
immediately dissolves unless sufficient of t h e reagent be
used. S o m e crystals were obtained in the 1 : 4 0 0 0 solution
and this is about the limit of reaction ( 1 ) ( 6 ) ( 1 0 ) ( 1 1 )
(12) ( 1 6 ) .
B A R I U M N I T R A T E . — G r e a t n u m b e r s of small crystals
are formed at once and they polarize brightly.
dumb-bell shaped.
T h e y are
PAPAYERINE
Thirteen crystalline a n d t w e n t y - t w o
precipitates were obtained.
non-crystalline
P O T A S S I U M H Y D R O X I D E . — A m o r p h o u s precipitates a p -
pear in all the solutions a n d these precipitates all crystallize
o n standing and crystallization takes place more slowly i n
the more concentrated solutions. T h e crystals are small
rods or rosettes of rods often arranged i n the shape of a
fan. U p o n adding this r e a g e n t t o a 1 : 1 0 , 0 0 0 solution a n d
stirring, a considerable n u m b e r of small rods are formed
at once.
P o t a s s i u m chromate a n d also p o t a s s i u m acetate give
results similar t o the above ( P l a t e X V , F i g . 5 ) .
SODIUM
CARBONATE.—The
amorphous
precipitate
crystallizes slowly unless stirred.
O n standing, large
rosettes of rods are formed, while o n stirring the crystals
are i n small rods only.
S o d i u m phosphate gives crystals similar to the above.
63
Z I N C C H L O R I D E . — A l l the solutions crystallize at once.
T h e crystals are normally small rosettes of irregular plates.
This appears t o be a good test, a f e w small crystals b e i n g
formed in a 1 : 2 0 0 0 solution. A n amorphous precipitate
first formed i n the 1 : 5 0 solution only ( P l a t e X X V I ,
Fig. 6).
M E R C U R I C CHLORIDE.—Characteristic crystals, t h o u g h
not large ones, are formed with this reagent. T h e y a p p e a r
to be cubical with rounded edges, o r often rosettes of p l a t e s
in layers. A m o r p h o u s precipitates are f o r m e d i n all t h e
solutions a n d these crystallize o n stirring ( P l a t e I X ,
F i g . 2) ( 8 ) .
Other crystalline precipitates are briefly as f o l l o w s :
ZINC-CHLOR-IODIDE.—Crystals formed s l o w l y f r o m t h e
amorphous precipitate. T h e y are normally like c r y s t a l s
formed with zinc chloride.
P A L L A D O U S C H L O R I D E . — S m a l l , irregular crystals are
formed from the amorphous precipitate i n t h e 1 : 2 0 0 a n d
1: 50 solutions on standing ( P l a t e V I I , F i g . 1 ) .
MAYER'S
REAGENT.—The
amorphous
precipitate
is
very dense. T h e crystals are formed s l o w l y around t h e
edges of the drops and are not characteristic. T h e y are
small plates often i n dense masses.
M A R M E ' S R E A G E N T . — T h e amorphous precipitates are
all very dense a n d the crystals are small rosettes of p l a t e s
and do not form quickly. These crystals appear t o better
advantage after standing some time, as t h e y g r o w larger.
F E R R I C C H L O R I D E . — C r y s t a l s appear o n l y i n t h e t w o
more concentrated solutions. T h e y are rather quickly
formed i n great numbers from the amorphous precipitates
and appear almost square.
64
M I L L O N ' S R E A G E N T . — T h e crystals formed are identi-
cal with those formed b y t h e mercuric chloride solution,
but Millon's reagent is less sensitive.
P E R O N I N E ( B E N Z Y L M O R P H I N E HYDROCHLORIDE)
Three solutions o n l y w e r e used a n d they were aqueous
solutions of t h e f o l l o w i n g strengths: 1 : 1 0 0 0 , 1 : 5 0 0 ,
and 1 : 200.
POTASSIUM IODIDE.—This
is a sensitive a n d satisfac-
t o r y test.
L a r g e , dense rosettes of rods or needles are formed
from t h e amorphous precipitates at once. M a n y goodsized crystals are formed i n t h e 1 : 1 0 0 0 solution; a n o n crystalline precipitate is n o t formed first ( P l a t e X V I I I ,
F i g . 5).
HYDROCHLORIC
ACID.—Upon
adding
dilute
hydro-
chloric acid solution t o t h e 1 : 200 solution a n d stirring,
crystals of rods, often in rosettes, are formed. T h e rods
are usually notched a t t h e ends.
Ferric chloride gives crystals in the 1 : 2 0 0 solution
only, a n d t h e y appear like those above.
B A R I U M N I T R A T E . — A m o r p h o u s precipitates a n d then
crystals are formed in t h e 1 : 2 0 0 solution only, a n d they
are rods or needles, t h e rods o f t e n being notched at the ends.
Silver nitrate reacts in the same manner as this reagent.
MAYER'S R E A G E N T . — H e a v y ,
amorphous
precipitates
appear in all the solutions, b u t crystals are formed from
the precipitate o n l y i n t h e 1 : 2 0 0 solution. T h e y are
rosettes of rods, f o r m i n g slowly b u t g r o w i n g t o a large size.
AMMONIUM
THIOCYANATE.—Rosettes
of
rods
are
rather quickly formed from t h e heavy, amorphous precipitate in the 1 : 2 0 0 solution and o n stirring the 1 : 5 0 0 solution.
PHYSOSTIGMINE SULPHATE
65
(ESERHSTE)
T w o crystalline a n d sixteen non-crystalline precipitates
were obtained.
N o sensitive test for this alkaloid w a s obtained.
G O L D C H L O R I D E . — A m o r p h o u s precipitates a p p e a r in
all the solutions, but crystals o n l y in t h e 1: 5 0 solution.
The crystals are very small and dark in a p p e a r a n c e . T h e y
are formed i n great numbers from the heavy, dark-brown
precipitate first produced.
T h e f o l l o w i n g color reactions w e r e n o t e d :
P o t a s s i u m hydroxide g i v e s a d e e p - p i n k color i n all
the solutions.
A m m o n i u m vanadate g i v e s a red color i n the 1 : 50
solution and this fades o u t quickly. A p i n k color is obtained i n t h e 1 : 200 solution.
P o t a s s i u m cyanide gives a pink color in t h e solutions
on standing.
PlLOCARPIDINE
Three crystalline precipitates were obtained.
P H O S P H O T U N G S T I C A C I D . — T h i s is the best test for this
alkaloid. H e a v y , amorphous precipitates a n d o n stirring
great numbers of small rosettes or needle-like crystals are
formed. I f n o t stirred the crystals are f o r m e d o n l y around
the edges of the drops ( P l a t e X X I V , F i g . 6 ) .
P H O S P H O M O L Y B D I C A C I D . — V e r y h e a v y , amorphous
precipitates are formed i n all solutions. O n standing, small
spherical crystals are formed. E s p e c i a l l y g r e a t numbers
formed in the 1: 50 solution. T h e y do n o t polarize.
P L A T I N U M C H L O R I D E . — R o s e t t e s of l a r g e p l a t e s are
quickly formed i n the 1: 50 solution only. N o amorphous
precipitate or crystals formed in the 1 : 2 0 0 s o l u t i o n ( 1 7 ) .
5
66
PlLOCARPESTE HYDROCHLOUIDE
T w o crystalline a n d fourteen non-crystalline precipitates were obtained.
P L A T I N U M C H L O R I D E . — T h e m o s t characteristic crys-
tals were obtained w i t h this reagent. T h i s is not a very
sensitive test, as n o crystals were obtained i n more dilute
solutions than 1 : 2 0 0 . U p o n stirring t h e 1 : 2 0 0 solution,
w e g e t some crystals around t h e edges. T h e y are rosettes
of irregular plates. I n the 1 : 5 0 solution great numbers of
clear-cut plates are formed instantly ( P l a t e V , F i g . 2 ) ( 8 ) .
GOLD
CHLORIDE.—Heavy,
amorphous
precipitates
formed in all but t h e 1 : 1 0 0 0 solution, a n d these crystallize
u p o n stirring in plates or often in rosettes ( 1 0 ) .
PIPEEIJSTE
Solutions in 90 p e r cent, alcohol were used.
M a n y reagents are precipitated i n crystalline form
when added t o alcohol, a n d for this reason alcoholic solutions are not as satisfactory t o work with a s aqueous or
acid solutions.
T h e crystals formed were i n m o s t cases similar, being
rods of needles. T h e y were formed with all t h e following
reagents: Mercuric chloride; platinum chloride; sodium
nitro-prusside; potassium acetate; potassium ferricyanide;
saccharin; potassium iodide; Marine's reagent, a n d
ammonium molybdate.
THE
CINCHONA
ALKALOIDS
Microchenrical tests were worked o u t for t h e following
cinchona alkaloids: Q u i n i n e ; quinidine; cinchonine; cinchonidine, a n d quinoline. Cinchonine a n d cinchonidine
have already been discussed; see p p . 3 5 a n d 3 6 .
67
QUININE SULPHATE
F i v e crystalline precipitates a n d twenty-seven n o n crystalline precipitates were obtained.
N o sensitive tests f o r this alkaloid found.
S O D I U M P H O S P H A T E . — T h e r e w a s n o precipitate in the
two more dilute solutions.
G r e a t numbers of large, sheaf-like crystals are quickly
formed in t h e 1 : 2 0 0 solution. I n t h e 1 : 50 solution w e
have besides t h e sheaf-like crystals, another form. These
particles are rather small, silvery i n appearance, and are
present in great numbers. T h e y d o n o t polarize and are
probably non-crystalline, their appearance being similar t o
the particles formed w h e n M a y e r ' s reagent is added t o
morphine or t o codeine ( P l a t e V I I , F i g . 6 ) •
POTASSIUM
ACETATE.—Dense
masses
of
very
fine
needle crystals or rosettes of these are formed only in t h e
1: 50 solution ( P l a t e X I I , F i g . 6 ) .
P O T A S S I U M C H R O M A T E . — N o reaction in the two more
dilute solutions.
B y a d d i n g sufficient of this r e a g e n t a n d stirring, w e g e t
rosettes of needles at once i n t h e 1 : 2 0 0 solution. I n the
1: 50 solution t h e dense precipitate first formed crystallizes
rapidly into large rosettes of rods o n stirring ( P l a t e X X I ,
Fig. 6 ) .
WAGNER'S
REAGENT.—While
d e n s e precipitates
are
formed in all t h e solutions, n o crystals were obtained i n
any but t h e 1 : 5 0 solution. I n this solution crystallization
is slow. T h e crystals are, as a rule, n o t large and do n o t
polarize brightly. T h e y are n o t sharp i n outline.
M u c h of t h e precipitate takes o n a deep rose-red color,
this color b e i n g different from that obtained with any other
alkaloid tested w i t h this reagent ( P l a t e X I I , F i g . 2 ) .
68
Kraut's reagent gives reactions similar t o t h e above.
AMMONIUM THIOCYANATE.—The
amorphous precipi-
tate in the 1 : 50 solution crystallizes quickly i n large, dense,
moss-like crystals. T h e slight precipitate in the 1 : 2 0 0
solution forms small crystals o n stirring. T h e t w o photographs ( P l a t e X X V , F i g s . 4 and 5 ) show h o w widely the
crystals m a y vary in appearance.
QUINTDINE SULPHATE
S i x crystalline a n d t w e n t y - s i x non-crystalline precipitates were obtained.
P O T A S S I U M C H R O M A T E . — N o p r e c i p i t a t e s appeared in
the dilute solutions. I n t h e 1 : 50 solution a very dense,
amorphous precipitate is first thrown d o w n and crystals are
slowly formed. T h e y often exhibit a braided appearance.
GOLD
CHLORIDE.—In
the
1: 500
solution,
a
heavy,
amorphous precipitate crystallizes at once o n stirring or
slowly when n o t stirred into needles or rosettes of these.
These crystals are formed i n great numbers. N o crystals
appear in the 1 : 1 0 0 0 solution. Crystals do not form
quickly in the more concentrated solutions ( P l a t e I I ,
F i g . 6) ( 8 ) .
M E R C U R I C C H L O R I D E . — N o crystals are formed in a n y
solution more dilute than t h e 1 : 200. I n this solution fairsized rosettes are formed from the rather dense, amorphous precipitate. These crystals polarize brightly around
the edges, but n o t in the centre ( P l a t e I X , F i g . 3 ) .
POTASSIUM I O D I D E . — N o
amorphous
precipitate a p -
pears in the more dilute solutions. Crystals i n great n u m bers are formed at once o n stirring t h e 1 : 1 0 0 0 solution.
T h e y are normally triangular i n outline.
A f e w crystals were formed i n a 1 : 2 0 0 0 solution. I n
69
the more concentrated solutions the crystals are large and
form quickly. T h i s reagent does not form crystals with
any other of the cinchona alkaloids studied ( P l a t e X V I I I ,
F i g . 6) ( 8 ) .
P O T A S S I U M F E R R O C Y A N I D E . — G r e a t numbers of
rods
are formed quickly i n the more concentrated solutions.
Their appearance is best described b y the photograph.
N o precipitate appears i n t h e 1 : 1 0 0 0 solution ( P l a t e X X ,
Fig. 3) ( 8 ) .
A M M O N I U M T H I O C Y A N A T E . — S m a l l rosettes form on
stirring a 1 : 1 0 0 0 solution. V e r y large rosettes appear in
all the more concentrated solutions ( P l a t e X X V , F i g . 3 ) .
QUINOLISTE
E l e v e n crystalline a n d seventeen non-crystalline precipitates w e r e obtained.
C H R O M I C A C I D . — T h i s is n o t a sensitive test, as crystals
were obtained o n l y in t h e 1 : 5 0 solution. T h e y are rosettes
of leaf-like forms a n d polarize brightly. T h e amorphous
precipitate is light a n d crystallizes slowly ( P l a t e X X I I I ,
Fig. 1 ) .
G O L D C H L O R I D E . — T h i s is a sensitive test.
The 1:1000
solution crystallizes out quickly into a dense mass of crystals of a g r e e n color, appearing like some form of sea-weed.
T h e 1 : 5 0 0 solution is t o o concentrated t o give the best
results. S o m e fair-sized needles are formed in a 1 : 5000
solution ( P l a t e I I I , F i g . 1 ) .
P L A T I N U M C H L O R I D E . — N e e d l e - l i k e crystals, often in
rosettes, are obtained o n stirring t h e 1 : 1 0 0 0 solution. I n
the 1 : 5 0 solution t h e crystals are i n a dense mass and small
(Plate V , F i g . 3) ( 8 ) .
M E R C U R I C C H L O R I D E . — T h e crystals are dense rosettes
70
in all solutions e x c e p t t h e 1 : 1 0 0 0 , in which solution there is
no precipitate ( P l a t e I X , F i g . 4 ) ( 8 ) .
WAGNER'S
REAGENT.—Heavy,
amorphous
precipi-
tates and crystals are s l o w l y formed i n a l l t h e solutions.
T h e y are rods a n d v a r y f r o m brown or light yellowishbrown to a dark-bluish color ( P l a t e X I I , F i g . 3 ) .
K R A U T ' S R E A G E N T . — I n t h e 1 : 1 0 0 0 solution the amor-
phous precipitate crystallizes o u t quickly i n beautiful reddish-brown rosettes of needles. A 1 : 8000 solution g a v e a
few very small crystals. T h e more concentrated solutions
do n o t give a n y more satisfactory results t h a n the 1 : 1 0 0 0
solution ( P l a t e X I I I , F i g . 4 ) ( 8 ) .
P I C R I C A C I D . — T h i s is a sensitive t e s t for quinoline.
L a r g e crystals are formed instantly i n the 1 : 1000 solution, and a very dense mass of crystals in t h e more concentrated solutions. A f e w small crystals are formed i n a
1: 3000 solution ( P l a t e X I X , F i g . 6 ) .
MAYER'S R E A G E N T . — T h e
p r e c i p i t a t e i n the
1:1000
or 1 : 5 0 solution does n o t crystallize. T h e crystals are normally large rods in t h e other t w o solutions.
P O T A S S I U M F E R R O C Y A N I D E . — T h e c r y s t a l s are
small
rods or four-sided plates with sharp angles a n d formed
only in the t w o more concentrated solutions. T h e amorphous precipitate is very slight in the 1 : 5 0 0 solution ( P l a t e
X X , F i g .4) ( 8 ) .
P o t a s s i u m f errocyanide reacts like t h e above.
MILLON'S
REAGENT.—The
crystals
are
small,
dark
rosettes and formed in the t w o more concentrated solutions
only. T h e y have a light-pink color w h e n in masses and
this color is especially t o be seen i n the 1 : 5 0 solution ( P l a t e
X X V I , Fig. 4).
71
SCOPOLAMINE HYDROBROMIDE ( H Y O S C I N E
H YDROBROMIDE )
S a m p l e s marked either " H y o s c i n e " or " Scopolamin "
g i v e identical microchemical reactions. O n l y three crystalline precipitates were obtained. Thirteen non-crystalline precipitates were obtained.
G O L D C H L O R I D E . — T h i s is a sensitive test and the only
one, apparently, of practical value. T h e crystals are instantly formed o n stirring the solutions, otherwise they
f o r m slowly. N u m b e r s of small crystals are formed in a
1 : 4000 solution on stirring. T h e y are triangular in outline. T h e crystals g r o w t o a large size, especially i n the
1 : 2 0 0 solution. T h e y polarize brightly and are yellow i n
color and n o r m a l l y are rosettes of plates with coarse, sawtooth e d g e s . T h e y are characteristic. A m o r p h o u s precipitates a p p e a r i n all t h e solutions u p t o 1 : 5 0 0 ( P l a t e
III, Fig. 2) (7).
K R A U T ' S R E A G E N T . — T h e precipitates are all dense.
O n s t a n d i n g t h e y all crystallize. T h e y are noticed especially around t h e e d g e s a n d are usually rosettes of rods.
W A G N E R ' S R E A G E N T . — C r y s t a l s are very slowly formed
from the heavy, amorphous precipitates. O n stirring a
sticky m a s s is formed from the amorphous precipitate and
this on further stirring crystallizes rapidly into short rods,
sometimes i n rosettes ( P l a t e X I I , F i g . 4 ) .
SOLANINE
N o satisfactory test w a s obtained o n this substance.
T w e n t y - s e v e n amorphous precipitates were obtained.
SPARTEINE SULPHATE
S e v e n crystalline a n d fifteen non-crystalline precipitates were obtained.
n
G O L D C H L O R I D E . — T h e o n l y very sensitive test is that
with gold chloride. A great number of small, blade-like
crystals which polarize fairly w e l l are formed i n t h e 1 : 1 0 0 0
solution. T h e crystals are larger b u t similar in shape in
the 1: 500 solution. I n the t w o more concentrated solutions
the crystals vary greatly in shape a n d size a n d are often in
masses ( P l a t e I I I , F i g . 3 ) ( 1 0 ) .
Z I N O C H L O R - I O D I D E . — V e r y small crystals were formed
in all the solutions, but the greater part of t h e precipitate
does n o t crystallize. O n standing, the crystals i n t h e 1 : 1 0 0 0
solution g r o w t o a fair size. T h e y are v e r y irregular
in outline.
PALLADOUS
CHLORIDE.—No
amorphous
precipitates
appear. O n standing, fine, large, spherical crystals or
rosettes are formed i n t h e 1 : 5 0 solution a n d a f e w in the
1 : 2 0 0 solution. T h e y are of a deep, reddish-brown color
(Plate V I I , F i g .2 ) .
P O T A S S I U M F E R R I C Y A N I D E . — T h i s is n o t sensitive as a
reagent for sparteine. L a r g e plates a n d m a n y
square ones are formed in the 1 : 50 solution only.
MARME'S R E A G E N T . — T h e
dense, a m o r p h o u s
small
precipi-
tates crystallize slowly o n standing, great numbers of crystals being formed. T h e y are rather slender rods a n d of
good length.
FERRIC CHLORIDE.—Great
numbers
of
crystals
are
formed around the e d g e of t h e drop in the 1 : 50 solution
and a few in the 1 : 2 0 0 solution. T h e y float o n t h e liquid.
SILVER N I T R A T E . — C r y s t a l s are f o r m e d i n g r e a t n u m -
bers on stirring the 1 : 5 0 solution only.
small rods a n d polarize brightly.
T h e y are normally
73
STRYCHNINE SULPHATE
T w e n t y - s e v e n crystalline and five non-crystalline p r e cipitates were obtained with this alkaloid.
M a n y sensitive a n d characteristic tests were worked out.
POTASSIUM HYDROXIDE.—Rods
n o r m a l l y with a
V-
shaped recess i n each e n d are formed i n all the solutions.
A few small crystals are formed i n a 1 : 20,000 solution.
T h e crystals are large a n d rough i n appearance in the t w o
more concentrated solutions a n d are formed from the
amorphous precipitates first thrown down. Stir the more
dilute solutions for quick crystallization ( P l a t e X V I ,
F i g . 1) ( 8 ) ( 1 ) ;
Crystals similar t o t h e above are formed with ammonia
and also w i t h sodium carbonate ( P l a t e X I V , F i g . 6) ( 8 ) .
SODIUM
N I T R O - P R U S S I D E . — N o precipitates
were o b -
tained i n t h e t w o more dilute solutions.
A v e r y slight precipitate appeared in the 1 : 200 solution a n d this crystallized slowly. T h e crystals are spherical and show distinct polarization crosses. I n the 1: 50
solution t h e dense, amorphous precipitate crystallizes
quickly. M a n y of the crystals are spherical a n d others are
rosettes of p l a t e s ( 1 0 ) .
SODIUM
PHOSPHATE.—Small
rods
formed
in
the
1 : 1 0 0 0 solution o n stirring. I n t h e 1 : 2 0 0 solution cubical
or six-sided forms predominate. I n the 1 : 5 0 solution
there are m a n y sharp, clear-cut crystals formed at once.
T h e y are normally l o n g needles. L i m i t of reaction is
about 1 : 2 0 0 0 , b u t a t this dilution the crystals are
not characteristic.
AMMONIUM
T H I O C Y A N A T E . — S m a l l rods are
formed
on stirring t h e 1 : 1 0 0 0 solution a n d a very dense mass of
74
crystals appear in t h e more concentrated solution ( P L
X X V , F i g . 6) ( 2 ) ( 3 ) ( 8 ) .
C H R O M I C A C I D . — C r y s t a l s are quickly formed i n
solutions from the amorphous precipitates which i
thrown down in all but the 1 : 1 0 0 0 solution. T h e y a r e
two kinds, the m o s t c o m m o n being rectangular, h a v i
lines j o i n i n g the opposite corners. T h e y do not p o l a r i
T h e other crystalline f o r m is branching a n d does not pol;
ize. A t the 1: 200 dilution the last is the most comrn
form of crystals. A f e w small crystals are formed ir
1 : 5 0 0 0 solution. T h e reaction of potassium dichrom*
is similar to the above and w a s described by W o r m ]
(Plate X X I I I , F i g . 2) (8) ( 1 ) .
POTASSIUM
C H R O M A T E . — R o d s sometimes in r o s e t
are formed in solutions u p t o 1 : 500 ( 3 ) ( 1 0 ) .
G O L D C H L O B I D E . — A dense, amorphous p r e c i p i t a t e
thrown down u p o n a d d i n g the reagent. T h i s crystalli:
out rapidly. T h e crystals are dense rosettes. T h e y i
light-brown in color and do n o t polarize brilliantly.
These crystals g r o w t o a large size e v e n in a 1 : 1 0
solution. T h e w e i g h t of the cover g l a s s is sufficient
break the crystals.
T h e 1: 50 solution is t o o concentrated for satisfactc
results, as crystals are formed in a dense mass.
Some fairly large and characteristic crystals are f o r m
at a dilution of 1 : 2 0 , 0 0 0 ( P l a t e I I I , F i g . 4 ) ( 1 ) (
(8) (10).
P L A T I N U M C H L O E I D E . — C l e a r - c u t crystals are q u i d
formed from the amorphous precipitate i n all the solutioi
There is considerable variation in their appearance, t h o u
all are of the same general t y p e . T h e rosette clusters fii
formed break d o w n a n d assume i n m a n y instances t
75
form s h o w n i n p l a t e after three t o five m i n u t e s . I n a
1 : 1 5 , 0 0 0 solution g r e a t numbers of v e r y small crystals are
formed, b u t t h e y are n o t characteristic ( P l a t e V , F i g . 4 )
(1) (8) (10) ( 1 8 ) .
T h e above test, u s i n g dichloride of p l a t i n u m , w a s described b y W o r m l e y ( 4 ) .
P A I X A D O U S C H L O R I D E . — T h e c r y s t a l s are l a r g e rosettes,
the arms h a v i n g a m u c h curved a n d irregular shape. T h e r e
are also a n u m b e r of v e r y small crystals which float at the
surface of t h e drop. A f e w small crystals are formed in a
1 : 1 2 , 0 0 0 solution. W o r m l e y states t h a t these crystals are
similar t o those f o r m e d with p l a t i n u m chloride ( P l a t e V I I ,
Fig. 3) (1) ( 3 ) .
M E R C U R I C C H L O R I D E . — T h e c r y s t a l s are f a i r l y
large
a n d g r a c e f u l l y curved i n the 1 : 1 0 0 0 solution. T h e y polarize but slightly. I n t h e more concentrated solutions they
are dense rosettes. A f e w crystals are f o r m e d i n a 1 : 3 0 0 0
solution ( P l a t e I X , F i g . 5 ) ( 4 ) ( 8 ) .
F E R R I C C H L O R I D E . — C r y s t a l s are f o r m e d s l o w l y i n the
1 : 2 0 0 solution. T h e y are small a n d spherical. I n t h e
1 : 50 solution a dense m a s s of l a r g e needles are formed a t
once. T h e r e are also g r e a t n u m b e r s of small, spherical
crystals formed. T h e test is n o t sensitive.
Z I N C C H L O R I D E . — G o o d - s i z e d , sheaf-like c r y s t a l s
are
formed quickly i n t h e 1 : 2 0 0 solution. T h e y polarize brilliantly. N e e d l e s are formed b u t s l o w l y in t h e more dilute
solutions unless t h e solution be stirred.
Z I N C - C H L O R - I O D I D E . — G r e a t n u m b e r s of small, dark
crystals are formed in the 1 : 1 0 0 0 solution. T h e r e are t w o
forms o f crystals i n t h e 1 : 2 0 0 solution, o n e like that formed
with zinc chloride a n d t h e other spherical in appearance,
which does n o t polarize. I n t h e 1 : 5 0 solution these crys-
tals are fine rosettes. T h e limit of reaction is 1 : 1 0 , 0 0 0
(Plate X X V I I , Figs. 4 and 5 ) .
WAGNER'S REAGENT.—Dense
precipitates appear
in
all the solutions. There are t w o forms of crystals, o n e is
light in color a n d appears t o float a t t h e surface; t h e other
appears as large needles or rods i n masses i n the more concentrated solutions. T h e crystals formed i n a 1 : 2000 solution are small and n o t characteristic ( 1 ) .
Kraut's reagent gives reaction like ahove.
POTASSIUM IODIDE.—No
amorphous precipitates
are
formed. N e e d l e - s h a p e d crystals, often i n rosettes, are
formed i n the more dilute solutions, a n d these m u s t he
stirred for quick results.
D e n s e rosettes of plates are formed i n t h e 1 : 5 0
solution ( 1 ) .
M A R M E ' S R E A G E N T . — I n t h e 1 : 1 0 0 0 solution w e h a v e
first an amorphous precipitate which is n o t very dense, a n d
from this small, silvery-looking masses, possibly crystals,
are formed rather slowly.
W e also have a crystal formation w h e n the solution
stands for a short time. T h e s e crystals are quite different
from the other forms a n d are sharp-cut rosettes of small
plates. T h e y polarize brilliantly.
A 1 : 25,000 solution g i v e s a f e w small crystals, but t h e y
are not a t all characteristic. T h e 1 : 1 0 0 0 crystals are quite
normal i n appearance ( P l a t e X V I I , F i g . 6 ) .
M A Y E R ' S R E A G E N T . — A dense, amorphous
precipitate
and t w o forms of crystals are formed. T h e first f o r m o f
crystals floats o n the surface. T h e y are light in color, d o
not polarize, a n d are n o t clear-cut. T h e other f o r m is
darker, polarizes slightly a n d forms more slowly t h a n t h e
first. T h e y are rosettes of needles or rods in t h e more con-
77
centrated solutions. A good number of small crystals was
formed in a 1 : 2 0 , 0 0 0 solution ( P l a t e X V I , F i g s . 4 and 5)
(1) ( 1 0 ) .
POTASSIUM FERRICYANIDE.—Rosettes
of rods or plates
appeared i n t h e t w o more concentrated solutions only
(10) ( 1 5 ) ;
P o t a s s i u m ferrocyanide forms crystals similar t o above,
but the reaction is more sensitive ( 8 ) ( 1 0 ) .
P O T A S S I U M C Y A N I D E , — G r e a t numbers of rods often in
rosettes f o r m e d i n all the solutions. A f e w small crystals
were formed i n a 1 : 3000 solution. Stir the solutions for
quick results.
P H O S P H O M O L Y B D I C A C I D . — C r y s t a l s formed only in
the 1 : 5 0 solution.
T h e y are large rods of dense
masses a n d m u c h of the heavy, amorphous precipitate does
not crystallize.
S o d i u m phosphomolybdate gives results like the above.
S A C C H A R I N . — A f e w small crystals are formed on stirring a 1 : 2 0 0 solution. A very dense, amorphous precipitate is f o r m e d i n t h e 1 : 50 solution. T h i s turns into oillike drops which soon crystallize into plates in rosettes.
T h e y are f o r m e d slowly unless the solution be stirred.
P I C R I C A C I D . — T h e crystals are large, g r e e n rosettes
gracefully curved and are formed in all the solutions from
the amorphous precipitates. Crystals are formed on stirr i n g a 1 : 1 0 , 0 0 0 solution ( P l a t e X X , F i g . 1) ( 1 ) ( 6 )
(10) (11) ( 1 2 ) .
M I L L O N ' S R E A G E N T . — R o s e t t e s of needles appear in the
1 : 5 0 solution only. A few small crystals normally sixsided are sometimes formed in the 1 : 5 0 0 solution.
T h e f o l l o w i n g color reaction w a s noted. A m m o n i u m
vanadate p r o d u c e d a pink coloration in all the solutions.
THEBAISTE
F o u r crystalline and t w e n t y - s i x non-crystalline precipitates were obtained.
P O T A S S I U M H Y D R O X I D E . — G r e a t n u m b e r s of small rods
are formed i n the 1 : 1000 solution. T h e y polarize brightly.
I n the more concentrated solutions t h e crystals are
rosettes of plates or rods formed from t h e amorphous
precipitate.
T h e same crystal forms as above are g i v e n with sodium
carbonate or potassium cyanide ( P l a t e X V I , F i g . 2 ) ( 8 ) .
P L A T I N U M C H L O R I D E . — T h e best crystals are obtained
by using a very small amount of this reagent and in the
1 : 5 0 solution only. T h e y are fine needles i n rosettes or
sheaves. I n more dilute solutions crystallization is poor
and the crystals are small a n d spherical ( 1 0 ) .
THEOBROMINE
N o satisfactory microchemical tests were obtained.
N o t being soluble i n water or i n dilute hydrochloric
acid, a dilute solution i n 10 p e r cent, potassium hydroxide
was used, but i n order to obtain the f o l l o w i n g crystals t h e
drop of the solution m u s t be allowed t o d r y d o w n and thus
become more concentrated before a p p l y i n g t h e reagent.
G O L D C H L O R I D E . — A d e n s e m a s s of l i g h t - g r e e n , n e e d l e -
like crystals are formed.
KRAUT'S R E A G E N T . — A
dense m a s s of dark, reddish-
brown needles or small p l a t e s is formed. Sometimes t h e
crystals are small and spherical. A pink color is developed
around the edge of t h e drop.
P I C R I C A C I D . — W i t h alcoholic s o l u t i o n r o d crystals are
formed at once on stirring all solutions.
precipitates formed.
N o amorphous
DETAILED DESCRIPTION OP TESTS
79
TROPACOCAINE HYDROCHLORIDE
T w e n t y crystalline and only four non-crystalline precipitates were obtained.
C H R O M I C A C I D . — T h e limit of reaction is about 1: 2000.
A t this dilution a f e w small crystals are formed
on stirring.
Small, diamond-shaped crystals are formed o n stirring
the 1 : 1 0 0 0 solution. T h e y are very brilliant under polarized light. T h e t w o more concentrated solutions give beautiful large rosettes of plate-like forms.
Amorphous
precipitate formed i n the 1 : 5 0 solution only ( P l a t e
X X I I I , Fig. 3).
G O L D C H L O R I D E . — T h i s is a v e r y sensitive t e s t , as a con-
siderable number of small crystals are formed i n a 1: 30,000
solution o n stirring. Crystals form at once in t h e 1 : 1 0 0 0
solution. T h e y are fairly large and clear-cut. A f e w crystals float at the t o p of the drop. T h e y all have a rather
rough-appearing surface. T h e crystals are of the same
general form, but they are much larger w h e n the drop is
not stirred. T h e more concentrated solutions form dense
masses of crystals at once from the amorphous precipitate
(Plate I I I ,Fig. 5 ) ( 1 5 ) .
P L A T I N U M C H L O R I D E . — T h i s is a sensitive test.
Beau-
tiful large crystals are formed i n the more dilute solutions.
These crystals normally have cross-arms f o r m i n g an acute
angle one with another. T h e crystals are produced in such
masses that their form is n o t perfect i n more concentrated
solutions. A f e w very small crystals are formed i n a
1 : 2 0 , 0 0 0 solution ( P l a t e V , F i g . 5 ) ( 1 5 ) .
P A L L A D O U S C H L O R I D E . — T h i s is another sensitive test
for tropacocaine. Crystals formed in all t h e solutions vary
in shape. N o r m a l crystals have a very short cross-arm at
80
SOME MICROCHEMICAL TESTS FOE ALKALOIDS
an acute angle t o the m a i n axis. Solutions of 1 : 1 0 0 and
under are t o o concentrated f o r best results. N u m b e r s of
small crystals are f o r m e d i n a 1 : 4 0 0 0 solution ( P l a t e
VII, Fig.4).
MERCURIC
CHLORIDE.—Small,
jagged
crystals
are
formed o n stirring a 1 : 5000 solution. Solutions under
1: 100 are too concentrated a n d over 1 : 1 0 0 0 too dilute for
satisfactory crystal formation. I n t h e 1: 200 solution the
crystals are normally v e r y large a n d j a g g e d plates in
rosettes ( 5 ) .
F E R R I C C H L O R I D E . — C r y s t a l s a p p e a r in the t w o more
concentrated solutions only. I n a 1 : 100 solution an amorphous precipitate is formed which is at once redissolved,
but b y adding sufficient of the reagent the precipitate
finally does n o t dissolve b u t crystallizes out in moss-like
forms. T h e crystals are of the same general type, but
somewhat smaller o n stirring the solution.
Z I N C C H L O R I D E . — C r y s t a l s are f o r m e d in the more con-
centrated solutions only. T h e y are rods or are diamondshaped and formed in g r e a t numbers on stirring; 1 : 2 0 0 is
about the limit of reaction.
Z I N C - C H L O R - I O D I D E . — T h i s test is sensitive, crystals
being formed i n a 1 : 5 0 0 0 solution. T h e crystals are similar to those formed with zinc chloride ( P l a t e X X V I I ,
Fig. 6 ) .
W A G N E R ' S R E A G E N T . — T h i s is another sensitive test for
this alkaloid.
I n the 1 : 1 0 0 0 solution, a n amorphous precipitate is
formed which settles d o w n u p o n the slide and after a time
beautiful, clear-cut crystals of a light-yellow color are
formed. T h e y d o n o t f o r m rapidly i n all cases and vary
considerably i n shape. I n the 1 : 5 0 0 solution the crystals
DETAILED DESCBIPTTON OF TESTS
81
which form first float o n t o p of t h e drop, then darker crystals form which are usually a cluster of needles; 1 : 5 0 is
too concentrated for t h e best results. Great numbers of
crystals are formed in a 1 : 5000 solution.
Kraut's reagent gives results like the above ( P l a t e
X I I I , Fig. 5).
P O T A S S I U M I O D I D E . — M a n y p l a t e s are formed i n all t h e
solutions, but t h e y are small i n t h e 1 : 1 0 0 0 solution a n d
form slowly o n stirring.
M A R M E ' S R E A G E N T , — T h e c r y s t a l s are moss-like i n a p -
pearance. T h e test is sensitive, crystals being formed o n
stirring a 1 : 20,000 solution. I n t h e 1 : 1 0 0 0 solution the
dense, amorphous precipitate forms crystals slowly unless
the drop be stirred ( P l a t e X V I I I , F i g . 1 ) .
M A Y E R ' S R E A G E N T . — O n s t i r r i n g t h e 1 : 1 0 0 0 solution,
small crystals are formed in g r e a t numbers. T h e y are of
t w o kinds, t h e lighter colored ones float o n the surface; t h e
others are dark a n d appear as i n t h e photograph. T h e
limit of reaction is about 1 : 2 0 , 0 0 0 ( P l a t e X V I , F i g . 6 ) .
P O T A S S I U M F E R R I C Y A N I D E . — T h e limit of reaction is
about 1 : 2 0 0 . L a r g e plates are f o r m e d from the amorphous precipitate in this solution, b u t n o t quickly unless
stirred.
T h e s e crystals are v e r y brilliant
under
polarized light.
P O T A S S I U M F E R R O C Y A N I D E . — C r y s t a l s are formed o n l y
in the concentrated solutions. T h e y are normally clear-cut
rods or plates a n d polarize brilliantly.
POTASSIUM
PERMANGANATE.—Crystals
are
formed
quickly from the amorphous precipitate i n the 1 : 1 0 0 0 solution. T h e y are purple in color a n d appear t o be made u p
of a number of thin plates o n e u p o n t h e other ( P l a t e
X X I I I , F i g . 6 ) ( 1 5 ) . T h e crystals normally have a v e r y
82
graceful, wing-like appearance.
T h e crystals that are
formed when t h e solution is stirred are usually rectangular in form, often with a V - s h a p e d recess in either or both
ends; 1: 4000 appears t o be near t h e limit of reaction.
P I C R I C A C I D . — C r y s t a l s are quickly formed from the
amorphous precipitate i n the 1 : 1 0 0 0 solution. T h e y are
normally rosettes, but variations from the normal form
occur according t o t h e a m o u n t of r e a g e n t used,. T h e
weight of the cover-glass is sufficient t o break the crystals.
Crystals in the t w o more concentrated solutions form more
slowly. A f e w small crystals are f o r m e d i n a 1 : 8000 solution. W i t h a n alcoholic solution of this reagent a f e w
small needles are formed in a 1 : 2 0 , 0 0 0 solution ( P l a t e
X X , Fig. 2) ( 1 5 ) .
M I L L O N ' S R E A G E N T . — A dense, crystalline precipitate
is formed in a 1 : 5 0 solution. T h e y show m a n y colors and
polarize brightly.
B l a d e - l i k e rosettes are the normal
forms. N o crystals or precipitates form in the more
dilute solutions.
S O D I U M N I T R O - P R U S S I D E . — N o reaction i n the more
dilute solutions. L a r g e crystals are formed in a 1 : 1 0 0
solution. T h e s e crystals have a very rough-appearing surface and m a n y fine needles p r o j e c t i n g f r o m this give the
crystals a cactus-like appearance.
A M M O N I U M T H I O C Y A N A T E . — T h e slight,
amorphous
precipitate in the 1 : 50 solution crystallizes o n stirring at
once into fine plates often i n rosettes.
T w e n t y different tests for tropacocaine were tried on a
mixture of this alkaloid and some other alkaloid in equal
amounts. I n this w a y forty different alkaloids were tested
with tropacocaine. T h i s makes a total of eight hundred
tests. T h e results obtained were as follows: T h e test for
83
tropacocaine w a s n o t affected in 450, or 56 p e r cent., of the
cases; w a s slightly affected i n 84, or 15 p e r cent., and w a s
spoiled i n 266, or 2 9 p e r cent., of the total tests made.
S o m e reactions are n o t affected h y the presence of another alkaloid and others are v e r y easily spoiled. I f both
alkaloids i n a m i x t u r e precipitate with the reagent used,
the test is m o s t likely t o be spoiled.
I t appears that often the a m o u n t of r e a g e n t used has
more effect on the shape of the crystal t h a n the presence
of another alkaloid.
YOHIMBINE H Y D B O C H L O B I D E
One crystalline precipitate o n l y a n d twenty-eight
amorphous precipitates were obtained.
P O T A S S I U M C Y A N I D E . — R o s e t t e s of crystals of good
size are formed f r o m the amorphous precipitates, but they
form very slowly and in the 1 : 2 0 0 solution only. T h e y
show distinct polarization crosses ( P l a t e X X I , F i g . 3 ) .
T h e f o l l o w i n g color reactions were n o t e d :
Froehde's reagent g i v e s a deep-blue color i n the 1: 200
solution which, on standing, changes to green.
Millon's reagent gives a y e l l o w color on standing.
D I V I S I O N OF D R U G S
T h e following tests a n d observations bearing u p o n the
question of the authenticity a n d p u r i t y of the alkaloids used
in this work were m a d e . T h e authorities cited are :
A L L E N : " Commercial Organic A n a l y s i s " (fourth edition), 1909-14.
BRUHL,
HJELT
and A S C H A N :
"Die
Pflanzen-Alka-
loide," 1900.
H E N R Y : " T h e P l a n t Alkaloids," 1 9 1 3 .
P I C T E T - B I D D L E : " V e g e t a b l e Alkaloids," 1904.
R O S E N T H A L E R : " D e r N a c h w e i s Organischer V e r bindungen," 1 9 1 4 .
S C H M I D T : " Pharmaceutische Chemie " (fifth edition),
1911.
" U n i t e d S t a t e s P h a r m a c o p o e i a " (eighth edition, rev i s e d ) , 1905.
W I N T E R S T E I N A N D T R I E R : " D i e A l k a l o i d e , " 1910.
Reference is m a d e t o these works for the details of
pharmacopoeial tests a n d other w e l l - k n o w n tests a n d reagents. I t m a y be mentioned, however, that b y Mecke's
(Lafon's) reagent is understood a 0.5 p e r cent, solution of
selenious acid i n sulphuric acid.
T h e centigrade thermometer w a s u s e d in reading all
temperatures.
Aconitine, potent. Merck, crystals.
Crystalline powder presenting some rhomboidal and
prismatic fragments.
M . P . , 1 9 0 ° , heated rapidly t o 185°, t h e n 1° p e r minute.
84
85
( U . S . P . states M . P . 195° if rapidly heated, but 182°
with decomposition if slowly heated. H e n r y , 1 9 7 - 8 ° .
W i n t e r s t e i n a n d Trier, 1 9 7 - 8 ° . P i c t e t quotes D u n s t a n ,
1 8 9 - 1 9 0 ° and F r e u n d and Beck, 1 9 7 - 8 ° ; Briihl, when
rapidly heated, 1 9 7 - 8 ° ; Rosenthaler, 1 9 7 - 8 ° ; Schmidt
quotes E h r e n b e r g and P u r f u r s t , 1 9 4 ° . )
W i t h sulphuric acid and a m m o n i u m vanadate gave an
orange color. O n w a r m i n g with sulphuric acid the solution w a s at first colorless, carbonizing o n prolonged heating.
G a v e n o Vitali reaction.
W a s dextrorotatory; the hydrochloride w a s lsevorotatory.
T h e 1 : 1 0 0 0 solution of the sulphate g a v e with N / 1 0
potassium p e r m a n g a n a t e a precipitate barely perceptible
under t h e microscope.
A n h a l o n i n e H y d r o c h l o r i d e , Merck.
M . P . 181-2°.
(Schmidt, 2 5 4 - 5 ° . )
T h e nearly colorless solution i n sulphuric acid did not
become colored o n w a r m i n g .
Sulphuric acid with a trace of nitric acid produced a
violet-red color f a d i n g t o brown.
N i t r i c acid produced a reddish-purple color fading out
and not becoming blood-red, as stated b y Schmidt.
Apocodeine Hydrochloride, Merck.
M . b e t w e e n 150° a n d 1 6 0 ° ; not sharp.
( S c h m i d t states that its properties are similar to those
of apomorphine.)
I t s solution did not turn blue or black with ferrous
sulphate solution.
U p o n shaking its acetic acid solution with potassium
iodate and ether and diluting with water, the ether f o r m e d
a greenish layer.
On adding 10 per cent, solution of ferric chloride t o
the water solution it turned brown.
The substance with Marquis' reagent produced n o
color; Mecke's reagent produced a dirty-green color t u r n ing black; Froehde's reagent produced a dark-blue, becoming greenish-black.
Apomorphine Hydrochloride, Merck, Crystals.
M . 205-210°, decomposing with a dark color.
( U . S . P . decomposes between 200° and 210°.)
U . S . P . tests:
W h e n shaken with 100 parts of water, the latter
acquired no green color.
Conformed to the color tests of the U . S . P . except t h a t
with sulphuric acid and paraldehyde, the color was g r e e n ish-yellow rather than green. A l s o , dilute ferric chloride
solution gave not a red color, but violet, changing t o
purple. Ferric chloride, T . S . U . S . P . 8 , g a v e first a p u r p l e
and, as more was added, a deep-red color.
Arecoline Hydrobromide, Merck.
M . P . , 168-170°.
(Henry, 1 6 7 - 8 ° . Crystallized from alcohol. Schmidt,
1 6 7 - 8 ° ; crystallized from alcohol. Briihl, 1 6 7 - 8 ° ; crystallized from alcohol. Rosenthaler, 170°.)
Water solution g a v e no precipitate with tannic acid.
Aspidospermine, Merck.
Crystals according to Fraude.
M.P., 205-6°.
(Schmidt, 2 0 5 - 6 ° ; Pictet, 2 0 5 - 6 ° ; H e n r y , 2 0 5 - 6 ° ;
Briihl, 2 0 5 - 6 ° ; Winterstein, 2 0 5 - 6 ° ; Rosenthaler, 2 0 5 - 6 ° . )
The solution in dilute sulphuric acid being boiled w i t h
87
a small a m o u n t of potassium chlorate assumed a fuchsin
red color. O n evaporating with platinic chloride and hydrochloric acid, a violet-purple residue w a s left. O n triturating w i t h sulphuric acid and a little lead peroxide, the
mixture t u r n e d brown, then red.
A t r o p i n e Sulphate, Merck.
M.P., 189-190°.
D r i e d first at 1 2 0 ° , then over
sulphuric acid.
( U . S . P . , M . P . , about 189.9°. I f free f r o m hyoscyamine about 1 8 8 ° . H e n r y , about 189.9°. Schmidt, about
183°. Rosenthaler, about 180° dry.)
U . S . P . tests:
G a v e Vitali's reaction. T h e solution in water gave no
precipitate w i t h either platinic chloride or g o l d chloride,
but w h e n the alkaloid w a s extracted and converted into
the hydrochloride, its solution g a v e n o precipitate with
platinic chloride, but a copious one with g o l d chloride.
T h e chloraurate melted at 1 3 7 ° .
B e n z o y l E c g o n i n e , Merck.
Crystals appeared efflorescent.
M . P . , not sharp, about 1 7 5 ° . A f t e r drying, M . P . ,
1 9 1 - 2 ° , fairly sharp.
(Schmidt, 8 6 - 7 ° ; anhydrous, 1 9 5 ° ; H e n r y , 8 6 ° ; anhydrous, 1 9 5 ° ; B r u h l , 8 6 - 7 ° ; anhydrous, 1 9 5 ° ; Pictet, 9 2 ° ;
anhydrous, 1 9 5 ° ; W i n t e r s t e i n , anhydrous, 195°.)
Chloraurate, air-dry, m e l t e d 2 0 7 - 8 ° .
Berberine, K a h l b a u m .
G r a d u a l l y darkened above 150° to black, melting
above 2 0 0 ° .
( S c h m i d t about 1 4 0 ° ; B r u h l , 1 4 5 ° , decomposing above
150°. W i n t e r s t e i n , about 150°, dry. H e n r y , M . P . , indefinite, d e c o m p o s i n g above 1 1 0 ° , liquid o n l y at 160° with
decomposition. Pictet, melts at 120°, anhydrous. R o s e n thaler states that the base known in the solid form is not
berberine (hydroxide) but berberinal, M . P . , 144°.)
W a t e r solution neutral to litmus.
Formed with sulphuric acid a yellow solution becoming
olive-green, then brown.
Formed with nitric acid an orange solution immediately
becoming brown.
U p o n adding bromine water drop by drop to the water
solution of the alkaloid the precipitate first formed dissolved, on shaking, to a reddish-brown solution; further
addition of bromine water produced a brown precipitate,
dissolving on warming to a red solution.
The acetic and sulphuric acid solution of the alkaloid
on treatment with zinc was nearly decolorized. O n making this solution alkaline with ammonia and shaking out
with ether or chloroform the evaporation residue was
brownish-yellow, amorphous, and partly soluble in water.
Betaine Hydrochloride, Merck.
M . P . , about 235-6° with decomposition.
(Schmidt, with decomposition, 2 1 3 - 1 5 ° ; Rosenthaler,
with decomposition, 2 2 7 - 8 ° . )
The chloraurate, recrystallized with hot water, began
to soften about 190°, melted entirely with sudden evolution of gas at 2 4 5 - 8 ° .
(Schmidt, vol. ii, P a r t I , p . 450 [ 1 9 1 0 ] , states that
the chloraurate recrystallized from hot 1 per cent, hydrochloric acid, melts at 248°, from hot water, 209°.)
Brucine, Merck, R e a g e n t .
Softened at 173°. MJP., 1 7 6 - 7 ° . D r i e d at 110°.
(Henry, M . P . , anhydrous, 1 7 8 ° ; Pictet, M . P . , anhydrous, 178°; Schmidt, M . P . , anhydrous, 1 7 8 ° ; Briihl, M . P . ,
anhydrous, 178°; Rosenthaler, M . P . , anhydrous, 178°.)
89
W i t h nitric acid a blood-red color w a s p r o d u c e d gradually f a d i n g t o y e l l o w . O n a d d i n g stannous chloride it
became p u r p l e .
Caffeine.
M.P., 231-2°.
( U . S . P . , sublimes about 1 7 8 ° ; dried at 100° to constant weight, m e l t s at 2 3 6 - 8 ° . Schmidt, begins to sublime
a little about 1 0 0 ° , melts at 2 3 0 - 5 ° . W i n t e r s t e i n , sublimes at 2 2 1 ° , m e l t s d r y at 2 3 4 ° . H e n r y , sublimes at
176°, m e l t s d r y at 2 3 4 - 5 ° . P i c t e t , m e l t s dry 2 3 4 - 5 ° .
Rosenthaler, m e l t s dry 2 3 4 - 5 ° . )
D i s s o l v e d in sulphuric acid a n d in nitric acid without
production of a n y color.
M u r e x i d e test positive.
Sulphuric acid with potassium dichromate produced a
yellowish-green color, becoming green.
I t s solution w a s not precipitated b y M a y e r ' s reagent.
Calycanthine Sulphate.
M.P., 223-4°.
T h e substance w i t h nitric acid g a v e a g r e e n color. Sulphovanadic acid g a v e a blood-red color. Sulphuric acid
containing a little potassium dichromate g a v e a blood-red
color, finally b e c o m i n g greenish. Froehde's reagent g a v e
a yellow color, finally becoming red.
Chelidonine, Merck.
M . P - , 1 4 5 - 1 5 0 ° , not sharp.
(Henry, 135-6°.
Pictet, 1 3 5 - 6 ° .
Schmidt, 136°.
W i n t e r s t e i n , 1 3 6 ° . Rosenthaler, 1 3 5 - 6 ° . )
T h e solution i n w a r m alcohol, slightly acidified with
H C 1 , w a s precipitated w i t h gold chloride. B r o w n precipitate of microscopic prisms or needles. M . P . , 1 9 2 - 3 ° .
Sulphuric acid turned t h e p o w d e r black and the liquid
finally became faint violet.
Sulphuric acid with a trace of nitric acid g a v e a brown
color fading to yellow.
T h e mixture with sugar and
water, to which, after a few minutes, sulphuric acid was
added, turned purplish-brown.
Froehde's reagent g a v e a dirty-green color, becoming
grass-green, then dirty-green- Sulphovanadic acid g a v e a
light-green color, becoming dark-green, then dirty-green.
Cinchonidine Sulphate, Bullock and Crenshaw.
M.P., 205-6°.
( U . S . P . , loses water of crystallization at 1 0 0 ° , darkens
at 203°, melts 205.3°.)
U . S . P . tests:
T h e 1 : 1 0 0 0 solution in dilute sulphuric acid was very
slightly fluorescent. T h e substance treated with sulphuric
acid gave no color; on a d d i n g potassium chromate turned
yellowish-green, then green.
O n treating 0.5 g r a m with water and Rochelle salt
and filtering, the filtrate g a v e no precipitate with one
drop of ammonia water.
( N o excess of cinchonine or
quinidine sulphate.)
T h e aqueous solution w a s slightly alkaline to litmus,
lsevorotatory. I n the solution barium chloride produced a
precipitate insoluble in hydrochloric acid.
T h e base precipitated b y ammonia was o n l y slightly
soluble in ammonia, but quite so in ether.
Cinchonine Sulphate, F e i d t .
M.P., 198-9°.
U . S . P . — M . P . , 198.5°.
T h e 1 : 1 0 0 0 aqueous solution w a s slightly alkaline to
litmus, dextrorotatory, not perceptibly fluorescent, but be-
91
came so on addition of a f e w drops of sulphuric acid. T h e
aqueous solution w i t h barium chloride g a v e a white precipitate insoluble in hydrochloric acid. T h e substance was
nearly soluble i n 80 parts of chloroform a n d was not discolored by sulphuric acid.
Cocaine Hydrochloride.
M . R , 1 8 8 - 9 ° . ( U . S . P . , about 1 8 9 . 9 ° ; Briihl, 181.5°;
when quite pure, 2 0 1 - 2 ° ; H e n r y , 1 8 6 ° ; Rosenthaler, 1 8 3 ° ;
Schmidt, 1 8 6 ° , anhydrous.)
U . S . P . tests:
T h e aqueous solution g a v e with silver nitrate white precipitate insoluble in nitric acid.
O n a p p l y i n g the U . S . P . test for excess of isatropyl
cocaine, a crystalline precipitate was obtained, the supernatant liquid not appearing opalescent, but still not perfectly clear, o w i n g to some precipitate remaining
in suspension.
O n a p p l y i n g the test with potassium p e r m a n g a n a t e , the
color did n o t fade in one-half hour.
O n heating with sulphuric acid, vapors of benzoic
acid escaped.
Codeine S u l p h a t e Crystals, U . S . P . , Mallinckrodt.
B e g a n to t u r n brown about 2 1 5 - 2 2 0 ° . M . P . , 2 7 7 ° .
( U . S . P . , loses water of crystallization at 100°, decomposes above 2 0 0 ° , residue melts 2 7 8 ° ; H e n r y , M . P . ,
278° dec.)
U . S . P . tests:
T h e aqueous solution was neutral to l i t m u s ; with barium
chloride formed a white precipitate insoluble in H C 1 .
W i t h p o t a s s i u m ferricyanide and ferric chloride no
blue color a p p e a r e d at once.
O n a d d i n g t o the substance sulphuric acid, no color
92
appeared in the cold, on w a r m i n g the solution became
violet, and on further a d d i n g nitric acid, red.
Mecke's reagent produced a g r e e n color, turning blue
and then green. Marquis 5 reagent produced a violet color,
turning blue.
Colchicine.
D r i e d over sulphuric acid, n o sharp M . P . Softened at
135°, but was not in clear fusion at 160°.
( U . S . P . , dried over sulphuric acid, M . P . , 1 4 2 . 5 ° ;
Winterstein, no sharp M . P . , 1 4 3 - 7 ° ; P i c t e t , 1 4 5 ° ; Schmidt,
1 4 5 ° ; Briihl, quite dry, 1 4 3 - 7 ° ; H e n r y , dry, 1 4 3 - 7 ° ;
Rosenthaler, about 145°.)
U . S . P . tests:
T h e aqueous solution w a s yellow, neutral to litmus and
laevorotatory. T h e substance with sulphuric acid g a v e a
yellow solution which nitric acid turned greenish-blue, then
red, then yellow. O n adding excess of potassium hydroxide it became red.
T h e substance on boiling with hydrochloric acid and
ferric chloride formed a y e l l o w solution, becoming green,
which imparted a reddish color t o chloroform when shaken
with same.
Coniine, Merck, P u r e .
Light-brown, mobile liquid.
Dextrorotatory in alcoholic solution. T u r n e d litmus
paper blue, leaving n o f a t t y stain.
T o the alcoholic solution a little carbon bisulphide w a s
added and the mixture w a s w a r m e d . I n one portion of
this, copper sulphate 0.1 t o 0.2 per cent, solution produced
a brown precipitate, soluble in ether; in another portion
ferric chloride solution produced a brown color soluble in
ether; in another, uranium nitrate solution produced a red
color soluble in toluene.
93
A w a t e r solution of the hydrochloride on evaporation
left a residue of rush-like crystals.
O n a d d i n g to a solution of the same sodium hydroxide
solution a n d distilling with steam, an alkaline distillate,
with an odor of coniine, was obtained.
Corydaline Alkaloid, Merck.
M.P., 127°.
( S c h m i d t , 1 3 4 - 5 ° ; Pictet, Briihl, 1 3 4 - 5 ° ; Winterstein,
1 3 4 - 5 ° ; H e n r y , 135°.)
T h e alcohol solution was dextrorotatory.
Froehde's reagent g a v e a dark-blue color, becoming
dirty-green. Sulphovanadic acid g a v e a blue color, becomi n g bluish-gray.
Cytisine Hydrochloride, Merck.
M . P . n o t below 2 8 0 ° .
T h e aqueous solution was laevorotatory.
O n m a k i n g the solution alkaline with ammonia, shaking
out with chloroform and evaporating the chloroform in
several portions, the residue on adding ferric chloride
turned brown, becoming a dirty-blue on adding a few
drops of h y d r o g e n peroxide. O n warming on the water
bath this became yellow.
On w a r m i n g another portion of the residue with 2 c.c.
nitric acid, it turned yellow, and on dilution with water no
precipitate appeared.
D a t u r i n e Sulphate, Merck.
D r i e d at 100°, M . P . 2 0 0 ° ; dried at 120°, M . P . 2 0 4 - 5 ° .
( H e n r y states that the alkaloid from stramonium
fruits is identical with atropine; likewise Schmidt and
W i n t e r s t e i n . Briihl states that the identity, though questioned, is n o w admitted.)
G a v e Vitali's reaction. T h e aqueous solution was
94
laevorotatory. T h e solution with barium chloride g a v e a
white precipitate insoluble in hydrochloric acid. T h e properties indicate that this is hyoscyamine sulphate rather than
atropine sulphate.
Dionine, Merck.
M . P . , 1 2 3 - 5 ° . ( H e n r y , M . P . , 1 2 3 - 5 ° ; Rosenthaler,
begins to melt 110°, transparent 120°,)
G a v e Pellagri's reaction.
W i t h Froehde's reagent, yellowish-green color, becoming blue. Marquis' reagent, bluish-purple.
T h e aqueous solution u p o n addition of silver nitrate
gave a white precipitate, insoluble in nitric acid.
E c g o n i n e A c i d Hydrochloride, R h o m b s .
M.P., 245-250°.
H e n r y , E c g o n i n e hydrochloride, rhombs, 2 4 6 ° ; (d)
E c g o n i n e hydrochloride, rhombs, monoclinic prisms, 2 3 6 ° ;
(dl) E c g o n i n e hydrochloride, rhombs, slender needles; dry,
149° with dec.; Bruhl, rhombic tables, 2 4 6 ° ; (d) E c g o n i n e
hydrochloride, rhombs, 2 3 6 ° . )
A portion was dissolved in a m i n i m u m amount of water,
platinic chloride added and t h e n absolute alcohol and allowed to stand. T h e s c a n t y precipitate w a s washed three
times b y decantation with absolute alcohol and dried at
1 4 0 - 1 4 5 ° , and then over sulphuric acid in a desiccator for
several days. M . P . , 2 0 9 - 2 1 0 ° .
A l l e n , " Commercial O r g a n i c A n a l y s i s , " 1912, 6, 338,
states that B 2 H 2 P t C l 6 melts at 2 2 6 ° .
H e r o i n e ( D i a c e t y l m o r p h i n e H y d r o c h l o r i d e ) Mallinckrodt.
M . P . , 2 2 5 - 6 ° . ( S e e Schmidt £, P a r t 2, 1716.) T h e
substance with Froehde's reagent g a v e a purple color;
with Marquis' r e a g e n t a p u r p l e color; with Mecke's re-
95
agent a g r e e n color like morphine; w i t h nitric acid a yellow
color turning green.
O n w a r m i n g with sulphuric acid and alcohol the odor
of ethyl acetate w a s perceptible.
T h e aqueous solution with ferric chloride g a v e no blue
color; with silver nitrate a white precipitate insoluble in
nitric acid; barium chloride, n o precipitate.
H o m a t r o p i n e Hydrobromide,
Powers-WeightmanRosengarten.
M . P . , 2 0 9 - 2 1 0 ° . A sample of Mallinckrodt's, M . P . ,
2 0 8 - 9 ° . ( U . S . P . , 2 1 3 - 8 ° ; H e n r y , 213.8°.)
U . S . P . tests:
T h e aqueous solution was neutral to l i t m u s ; not precipitated b y tannic acid or platinic chloride. I n it iodine
solution produced a brown precipitate, silver nitrate a
white precipitate, insoluble in nitric acid. O n adding to it
chlorine water and shaking with chloroform, the latter was
colored brown b y free bromine.
T h e substance g a v e n o Vitali reaction. O n treating it
with sulphuric acid containing a trace of potassium dichromate a transient pink color appeared which w a s slowly
replaced by green.
O n m a k i n g the aqueous solution alkaline w i t h potassium hydroxide, shaking out with ether and evaporating
the latter, the residue was not crystalline, but rather semiliquid and sticky.
KTo M . P . of the free alkaloid
was obtainable.
T h e alkaloid turned yellow and then red on warming
with mercuric chloride solution, as stated by U . S . P .
Hydrastine Merck-Alkaloid-Highest Purity.
M . P . , 131°.
( U . S . P . , 131°; Winterstein, 132°;
96
Pictet, 1 3 2 ° ; Briihl, 1 3 2 ° ; Schmidt, 1 3 2 ° ; H e n r y , 1 3 2 ° ;
Rosenthaler, 132°.)
U . S . P . tests:
A l k a l i n e t o litmus. T h e chloroform solution was laevorotatory. Sulphuric acid produced a y e l l o w color, becomi n g purple on heating. Froehde's r e a g e n t produced a
green color, c h a n g i n g to b r o w n ; nitric acid produced a
reddish-yellow color; M e c k e ' s r e a g e n t produced a red,
changing to b r o w n ; sulphuric acid with potassium dichromate, a red color c h a n g i n g to brown.
T h e sulphuric acid solution on addition of potassium
permanganate acquired a blue fluorescence.
H y d r a s t i n i n e Hydrochloride, M e r c k .
M . P . , not sharp; softens about 1 9 3 ° ; M . P . , about 198°.
(Schmidt, 2 1 2 ° ; H e n r y , 2 1 2 ° ; Rosenthaler, 210°.)
U . S . P . tests:
T h e aqueous solution g a v e a blue fluorescence and was
slightly alkaline to l i t m u s ; w i t h bromine water g a v e a yellow precipitate soluble in ammonia.
P o t a s s i u m dichromate solution produced a precipitate
soluble on heating and crystallizing o u t a g a i n o n cooling.
A m m o n i a water produced no precipitate.
Sodium hydroxide produced a transient turbidity followed by a precipitate on standing.
T h e substance with sulphuric acid g a v e o n l y a faintyellow color; with nitric acid a yellowish color; with sulphuric and nitric acids a red color.
Sulphuric acid a n d a m m o n i u m vanadate produced an
orange color turning a dark-brown a n d then fading.
H y o s c i n e (see S c o p o l a m i n e ) .
H y o s c y a m i n e H y d r o b r o m i d e , M e r c k — f r o m Belladonna-Cryst.
97
M . P . , 1 4 7 - 8 ° . ( U . S . P . , 1 5 1 . 8 ° ; H e n r y , 151.8°.)
U . S . P . tests:
T h e chloraurate melted 1 5 9 - 1 6 0 ° . T h e aqueous solution w a s neutral t o litmus, laevorotatory; with silver nitrate
g a v e a precipitate insoluble in nitric acid, soluble in ammonia; with platinic chloride, no precipitate.
T h e solid substance g a v e Vitali's reaction; w i t h sulphuric acid n o color was produced, and the further addition of nitric acid produced no color.
Morphine A l k a l o i d .
M . P . , 2 5 3 - 4 ° . ( U . S . P . , w h e n rapidly heated, 2 5 4 ° ;
Briihl, with decomposition, about 2 3 0 ° ; Schmidt, cautiously heated, about 230°, without decomposition; above
230° or u p o n rapid heating it decomposes; P i c t e t , about
247° with decomposition; H e n r y , 254°, with decomposition; Rosenthaler, 230°.)
U . S . P . tests:
T h e aqueous solution was alkaline t o l i t m u s ; M a y e r ' s
reagent g a v e a gelatinous precipitate; sodium phosphomolybdate g a v e a yellow precipitate forming a blue solution u p o n addition of ammonia.
U p o n w a r m i n g with solutions of ferric chloride and
potassium ferricyanide, it turned blue. T h e neutral solution g a v e a blue color with ferric chloride and the acidified
solution g a v e no color.
Solid substance: with sulphuric acid, cold, g a v e no
color, but on heating a brownish-purple. W i t h sulphuric
acid and potassium iodate dark-brown color; with Mecke's
reagent, blue color becoming green and then b r o w n ; with
Froehde's reagent, reddish-purple color becoming blue;
with Marquis' reagent, purple color; with sulphuric acid
and potassium dichromate, colorless, then g r e e n ; with nitric
acid, orange color becoming yellow.
Narceine, Eimer and A m e n d .
M . P . , 1 6 5 - 6 ° ; dried at 1 0 5 - 1 1 0 ° , b e g a n to m e l t at
1 6 5 - 6 ° ; not entirely melted at 2 2 0 ° . ( H e n r y , 1 7 0 ° , or
140-145° dry; Pictet, 1 7 0 - 1 ° , or 145° d r y ; Schmidt,
162-5° air-dry; Briihl, 170°, dry at 100°, m e l t s 1 4 0 - 5 ° ;
Winterstein, with 3 H 2 O melts 170°, a n h y d r o u s 1 4 0 - 5 ° ;
Substance (see Schmidt, 2,1742).
W i t h F r o e h d e ' s reagent brown-green color not becoming r e d ; evaporated
with dilute sulphuric acid, red color—no v i o l e t streaks on
adding a trace of nitric acid; with s u l p h o v a n a d i c acid
brown color becoming yellow and then p a l e - r e d d i s h ; with
Marquis' reagent, brown color fading o u t ; w i t h Mecke's
reagent, brown to reddish color fading out.
Chlorine water and subsequent a d d i t i o n of ammonia
produced an evanescent red color not t u r n i n g blue u p o n
the addition of iodine solution.
Narcotine, E i m e r and A m e n d .
M . P . , 1 7 2 - 4 ° . ( H e n r y , 176°; Pictet, 1 7 6 ° ; Schmidt,
176°; Briihl, 176°; Rosenthaler, 176°.)
W i t h Froehde's reagent a green color; w i t h M e c k e ' s
reagent, pale-bluish; sulphovanadic acid, r e d ; Marquis' reagent, reddish color becoming yellow; s u l p h u r i c acid, y e l low color turning red on warming.
Nicotine, Merck, H i g h e s t Purity.
A brown liquid apparently s o m e w h a t decomposed.
T h e microchemical tests were, however, m a d e on a fresh
sample. Turned litmus paper blue and left a f a t t y - a p p e a r ing spot. T h e alcoholic solution was lsevorotatory; after
acidifying with H C 1 was dextrorotatory.
99
T h e above acid solution was m a d e alkaline
hydroxide and distilled with steam.
The
shaken out with chloroform and the latter " blasted off "
cold in the presence of dilute H C 1 . T h e residue g a v e precipitates with Meyer's, Kraut's, a n d Sonnenschein's reagents, and silicotungstic acid. T h e distillate was alkaline to litmus.
T o an ethereal solution of the alkaloid an ether solution
of iodine w a s added a n d the mixture allowed t o stand in a
corked tube. R e d needles formed but on inspection with
reflected light n o blue iridescence w a s apparent. U p o n
digesting one or t w o drops of the alkaloid with formaldehyde for some hours and then a d d i n g one or t w o drops of
nitric acid a red color was produced. T h e hydrochloride
solution u p o n evaporation left a non-crystalline residue.
Papaverine, Merck.
M . P . , 1 4 4 - 5 ° (softens 1 4 3 ° ) .
(Winterstein, 147°;
Pictet, 1 4 7 ° ; Schmidt, 1 4 7 ° ; H e n r y , 1 4 7 ° ; Briihl, 1 4 7 ° ;
Substance ( S c h m i d t 2, 1 7 3 1 ) . W i t h F r o e h d e ' s reagent g a v e violet-blue color t u r n i n g green, t h e n blue, then
g r e e n ; Marquis' reagent, reddish-violet color f a d i n g out.
Sulphovanadic acid, bluish-green color t u r n i n g blue;
Mecke's reagent a bluish-green color becoming blue and
then fading. Chlorine water g a v e a brownish-gray (not
green) solution. Precipitate produced b y ammonia had
about the same color; no reddish color.
Peronine, Merck.
M e l t e d above 2 6 0 ° . T h e substance g a v e Pellagri's
reaction.
W i t h Froehde's reagent a bluish-purple color becoming maroon, purplish-gray, then olive, c h a n g i n g rapidly at
first; Marquis' r e a g e n t , pink, becoming cherry color;
Mecke's reagent, light-green color becoming olive, then
greenish-brown; sulphovanadic acid, brownish color; sulphuric acid, cold, produced no color; on warming, a reddish
color; addition of a t r a c e of nitric acid turned the solution
dark brownish-red.
P h y s o s t i g m i n e Sulphate, Merck.
Melting-point, indeterminate; softened about 115°.
( U . S . P . , M . P . , about 1 4 0 ° ; softening at 1 3 0 ° ; H e n r y ,
deliquescent, m e l t s 1 4 0 ° . )
U . S . P . tests:
A q u e o u s solution faintly acid to litmus. W i t h barium
chloride gives a precipitate insoluble in hydrochloric acid.
W i t h ammonia an evanescent precipitate which redissolved,
the solution t u r n i n g p i n k ; with g o l d chloride a purple color
and turbidity; w i t h platinic chloride (in concentrated solution o n l y ) , yellowish precipitate.
T h e substance w i t h sulphuric acid g a v e a faint-yellow
color; with sulphuric acid and potassium iodate, lightpurple to reddish color.
F i v e m g . treated w i t h nitric acid g a v e a yellow color,
becoming red on w a r m i n g , and on evaporating the residue
became slightly greenish. T h e latter was not turned violet
by fumes of nitric a c i d ; addition of a drop of nitric acid
g a v e a red solution t u r n i n g greenish on dilution.
Pilocarpidine N i t r a t e , H a r n a c k - M e r c k .
M . P . , 132° ( S c h m i d t , 1 3 6 ° ; H e n r y , 1 3 3 ° ) . A p p l i e d
U . S . P . test for pilocarpine to 10 m g . with hydrogen peroxide, benzol, a n d potassium dichromate; result negative.
Violet color at first, but disappeared on shaking.
Pilocarpine Hydrochloride.
D r i e d in oven at 1 0 3 ° . M . P . , 1 9 6 - 7 ° . ( U . S . P . , dried
101
several hours at 1 0 0 ° ; melts 1 9 5 . 9 ° ; Schmidt, about 2 0 0 ° ;
Briihl, 2 0 0 ° ; Rosenthaler, about 2 0 0 ° ; H e n r y , 2 0 4 - 5 ° . )
U . S . P . tests:
H y d r o g e n peroxide, potassium dichromate and benzol
gave a violet color described as characteristic of pilocarpine.
T h e aqueous solution was faintly acid to litmus and
gave a white precipitate with silver nitrate insoluble in
dilute nitric acid.
T h e substance triturated with calomel turned black; on
addition of sulphuric acid evolved g a s ; addition of a particle
of potassium dichromate produced a green color.
Piperine, Merck.
M.P., 128-130°.
( U . S . P . , 1 3 0 ° ; H e n r y , 1 2 8 - 9 . 5 ° ; Pictet, 1 2 8 - 9 ° ;
Winterstein, 1 2 8 ° ; Briihl, 1 2 8 - 9 . 5 ° ; Schmidt, 1 2 8 - 9 ° ;
Substance with sulphuric acid produced at first brownish-red color, later becoming greenish; with nitric acid an
orange color.
Quinidine Sulphate, F e i d t & Co.
M . P . , 195°.
Tests (see Schmidt 2y 1 7 8 7 ) . W a r m e d 0.5 g. with
10 c.c. of water to 60°, added 0.5 g. potassium iodide,
stirred and let cool one hour, then filtered. I n filtrate one
drop 10 per cent, ammonia water produced n o precipitate.
Five-tenth g m . and 10 c.c. water acidified with sulphuric acid and 10 c.c. of ether were made alkaline with
ammonia and shaken. A l l the alkaloid was dissolved.
T h e solution acidified with sulphuric acid w a s fluorescent; gave the Thalleioquin test. T h e alcoholic solution of
the alkaloid was dextrorotatory.
Quinine Sulphate.
10£ SOME MICROCHEMICAL TESTS FOR ALKALOIDS
Dried at 115-120°.
Melting-point about 2 1 8 - 9 ° w i t h decomposition. D r i e d
over sulphuric acid, M . P . , 2 0 9 - 2 1 0 ° with decompositionN o t sharp. ( U . S . P . , dried over sulphuric acid, 2 0 5 ° ;
Schmidt, dried above 150° w i t h decomposition; H e n r y ,
dried over sulphuric acid, becomes anhydrous at 115%
melts at 205°.)
U . S . P . tests:
T h e aqueous solution w a s neutral t o l i t m u s ; w i t h
barium chloride gave a white precipitate insoluble in h y d r o chloric acid; gave the Thalleioquin t e s t ; w h e n acidified w i t h
sulphuric acid gave a blue fluorescence.
The ammonia test for other alkaloid g a v e a d e c i d e d
turbidity.
T h e substance with sulphuric acid acquired n o c o l o r ;
with nitric acid a faint-yellow color.
Quinoline, Merck, Pure.
Yellow, oily liquid having a slightly alkaline reaction t o
litmus paper and leaving a f a t t y stain thereon.
Boiling-point, 236° (determined in a capillary t u b e
containing a Scudder anti-bumping capillary a n d read on.
falling temperature at cessation of e b u l l i t i o n ) . D i f f i c u l t l y
soluble in water, readily soluble i n alcohol.
Scopolainine Hydrobromide, M e r c k . T r u e .
M . P . , 191°. (Dried t w o d a y s over sulphuric acid.)
U . S . P . , hyoscine hydrobromide.
Softens at 100°, melts a n d loses water of crystallization,
at 110°. D r i e d over sulphuric acid, M . P . , 1 9 1 - 2 ° .
(Schmidt, i-scopolamin-hydrobromid
dried,
180°;
H e n r y , i-scopolamin-hydrobromid dried, 1 8 0 ° ; Briihl, t h e
salt official in Germany dried a t 1 0 0 ° , M . P . , 1 8 7 - 1 9 1 ° ;
RosenthaJer, 1 9 0 - 2 ° . )
103
T h e chloraurate, M . P . , 1 9 7 ° ; the aqueous solution w a s
neutral to litmus, lasvorotatory, silver nitrate produced a
precipitate insoluble in nitric acid, b u t soluble in ammonia.
Chlorine water liberated bromine, i m p a r t i n g a brown
color to chloroform. Mayer's reagent w i t h hydrochloric
acid gave a precipitate; mercuric chloride, precipitate;
phosphotungstic acid, precipitate; picric acid, precipitate;
platinic chloride, precipitate.
T h e substance g a v e Vitali's reactions.
Solanine, Merck.
Softened at 250° with decomposition, n o t entirely
melted at 2 7 0 ° . ( H e n r y , 235° or 244° or 2 5 0 ° ; W i n t e r stein, 2 6 2 ° ; P i c t e t , 2 3 5 ° ; Bruhl, 2 4 4 ° ; Schmidt, 2 4 5 ° ;
Rosenthaler, 2 5 0 - 2 6 0 ° . ) ( S e e Schmidt 2, 1662.)
T h e substance with sulphuric acid g a v e an orange color
becoming violet; Froehde's reagent g a v e a y e l l o w color
becoming brown with purple streaks, purple and then
greenish; Mecke's reagent g a v e a brown color, then p u r p l e
streaks becoming greenish and then b r o w n ; sulphovanadic
acid, yellow color becoming brown, purple-violet a n d
then olive.
Sparteine Sulphate Crystals, E i m e r and A m e n d .
D r i e d at 110° in oven; melted in its water of crystallization a n d then solidified; was powdered and dried until
n o longer coherent; color became slightly yellowish-orange
when m e l t e d ; softened at 153°. M . P . , not sharp, 155-7°*
( U . S . P . , loses all water of crystallization at 110°, anhydrous, M . P . , 1 3 6 ° ; Rosenthaler, H e n r y and W i n t e r stein give lupinidine as a synonym of sparteine.)
U . S . P . tests:
T h e aqueous solution was acid to litmus. N o precipi-
tate in any dilution by p o t a s s i u m ferrocyanide 5 per
cent, solution.
Barium chloride gave a white precipitate insoluble in
H C L The ether-ammonia-iodine t e s t was positive. The
test for volatile alkaloid with potassium hydroxide and
litmus paper was positive. The substance treated with sulphuric acid did not carbonize.
Strychnine Hydrochloride, P o w e r s and W e i g h t m a n .
M . P . not below 260°.
T h e aqueous solution with silver nitrate g a v e a white
precipitate insoluble in nitric acid.
T h e substance treated with sulphuric acid containing a
trace of potassium dichromate g a v e the characteristic blueviolet color becoming purple, cherry and orange.
Sulphuric acid with ammonium vanadate g a v e a violet
color becoming purple, then cherry.
Sulphuric acid gave no color.
On adding potassium iodate a violet color becoming
reddish-purple appeared.
Nitric acid gave no color. O n evaporating and treating with ammonia became dark-yellow, and if treated with
alcoholic potassium hydroxide solution, orange-red color
changing to brown.
Thebaine, Eimer and A m e n d .
M.P., 191-2°.
( H e n r y , 193°; Pictet, 1 9 3 ° ; Briihl, 1 9 3 ° ; Schmidt,
193°; Rosenthaler, 193°.)
The substance with sulphuric acid g a v e a red color;
with Froehde's reagent a red color; with sulphovanadic
acid a red color.
Theobromine.
M . P . about 340°.
105
( S c h m i d t and Rosenthaler, suhlimes 290° without
melting; Winterstein, sublimes 2 9 0 - 5 ° without m e l t i n g ;
Pictet, sublimes 2 9 0 - 5 ° without m e l t i n g ; enclosed in a tube
melts 3 2 9 - 3 3 0 ° ; H e n r y , same as P i c t e t . )
Substance evaporated with chlorine water and the
residue exposed to the fumes of ammonia assumed a purple
color (murexide test p o s i t i v e ) .
Tropacocaine Hydrochloride, Merck.
(Benzoylpseudotropeine Hydrochloride.)
M . P . about 277° with decomposition.
(Briihl, 2 7 1 ° ; Rosenthaler, 2 7 1 ° ; H e n r y , 283° with decomposition; Schmidt (see Schmidt
2,1691).
One-tenth g m . dissolved in 5 c.c. of water and m i x e d
with three drops dilute sulphuric acid a n d five drops of
1 : 1 0 0 0 potassium permanganate solution g a v e violet color,
not diminishing much in one-half hour.
Yohimbine Hydrochloride, M e r c k (Quebrachine).
M . P . not sharp, 3 0 0 - 3 1 5 ° with decomposition.
( H e n r y , 2 9 5 - 3 0 0 ° with decomposition; Briihl, 2 8 7 ° ;
Rosenthaler, 2 8 5 - 2 9 0 ° ; Schmidt 2, 1845, about 300°.)
T h e aqueous solution was made alkaline with ammonia
and shaken out with chloroform and the chloroform evaporated. T h e alkaloidal residue dissolved in sulphuric acid
formed a colorless solution. I n this particles of potassium
dichromate produced grayish streaks not resembling those
characteristic of strychnine.
A portion of the alkaloidal residue was warmed in a
test-tube with ammoniacal silver nitrate solution. R e d u c tion indicated b y formation of a slight mirror.
T h e substance with sulphovanadic acid g a v e a blue,
turning wine color; with Froehde's reagent slowly developed a blue color turning green.
INDEX TO PLATES
Aconite with Sodium Carbonate
Ammonium Thiocyanate
Anhalonine with Gold Chloride
with Phosphotungstic Acid
with Platinum Chloride
Apomorphine with Gold Chloride
Arecoline with Kraut's Reagent
with Palladous Chloride
Aspidospermine with Potassium Hydroxide
with Wagner's Reagent
Atropine with Picric Acid
Benzoyl-ecgonine with Gold Chloride
Berberine with Hydrochloric Acid
with Sulphuric Acid
Betaine with Phosphomolybdic Acid
Brucine with Ammonium Thiocyanate
with Chromic Acid
with Millon's Reagent
with Potassium Cyanide
with Potassium Hydroxide
with Potassium Iodide
With Saccharin
with Sodium Nitropmsside
with Zinc Chloride
Caffeine with Gold Chloride
with Kraut's Reagent
with Mercuric Chloride
Calycanthine with Chromic Acid
Chelidonine with Zinc Chloride
Choline with Phosphomolybdic Acid
Chromic Acid
Cinchonine with Sodium Carbonate
Cinchonidine with Platinum Chloride
with Sodium Phosphate
Cocaine with Chromic Acid
with Ferric Chloride
with Gold Chloride
with Picric Acid
with Potassium Permanganate
PI. XIII, Fig. 6
PI. XXV
PL I, Fig. 1
PL XXIV, Fig. 3
PI. IV, Fig. 1
PL I, Fig. 2
PL XIII, Fig. 1
PL VI, Fig. 1
PL XV, Fig. 1
PL X, Fig. 1
PL XIX, Fig. 1
PL X, Figs. 2, 3
PL I, Fig. 3
PL XX, Fig. 5
PL XX, Fig. 6
PL X, Fig. 4
PL XXIV, Fig. 1
PL XXIV, Fig. 4
PL XXV, Fig. 1
PL XXII, Fig. 1
PL XXVI, Fig. 1
PL VI, Fig. 2
PL IV, Fig. 2
PL XXI, Fig. 1
PL XV, Fig. 2
PI. XVIII, Fig. 2
PL V, Fig. 6
PL IX, Fig. 6
PL X, Fig. 5
PL XXVI, Fig. 5
PL I, Fig. 4
.
PL XIII, Fig. 2
PL VIII, Fig. 1
PL XXII, Fig. 2
PL VI, Fig. 3
PL IV, Fig. 3
PL XXVII, Fig. 1
PL XXIV, Fig. 2
Pis. XXII and XXIII
PL XIV, Figs. 1, 2
PL IV, Fig. 4
PL XV, Fig. 3
.PL VII, Fig. 5
PL XXII, Fig. 3
PL III, Fig. 6
PL I, Figs. 5, 6
PL VI, Fig. 4
PL XIX, Fig. 2
PL IV, Fig. 5
PL XXIII, Fig. 4
107
Codeine with Ammonium Thiocyanate
with Chromic Acid
with Marine's Reagent
with Potassium Chromate
with Zinc-Chlor-Iodide
Coniine with Marine's Reagent
Corydalin© with Mercuric Chloride
Cytisine with Gold Chloride
with Picric Acid
Dionine with Mercuric Chloride
with Sodium Carbonate
Ecgonine with Kraut's Reagent
Ferric Chloride
Gold Chloride
Heroine with Mercuric Chloride
with Picric Acid
with Potassium Cyanide
Homatropine with Gold Chloride
Hydrastine with Potassium Hydroxide
Hydrastinine with Chromic Acid
with Picric Acid
Hydrochloric Acid
Hyoscyamine with Gold Chloride
Kraut's Reagent
Marine's Reagent
Mayer's Reagent
Mercuric Chloride
Millon's Reagent
Morphine with Marine's Reagent
with MayeT's Reagent
Narceine with Gold Chloride
Narcotine with Potassium Acetate
PI. XXV, Fig. 2
PL XXII, Fig. 4
PL XVII, Figs. 1, 2, 3
PI. XXVI, Fig. 2
PL XXI, Fig. 4
PL XVIII, Fig. 3
PL X, Fig. 6
PL XXVII, Figs. 2, 3
PL XVII, Fig. 4
PL XXIV, Fig. 5
*
PL VIII, Fig. 2
PL II, Fig. 1
PL VIII, Fig. 3
PL XIX, Fig. 3
PL XI, Fig. 1
PL VIII, Fig. 4
PL XIV, Fig. 3
„.,
PL XI, Fig. 2
PL XIII, Fig. 3
PL III
Pis. I, II, III
PL VIII, Fig. 5
PL XIX, Fig. 4
....PL XXI, Fig. 2
PL II, Fig. 2
PL XXVI, Fig. 3
JP1. XI, Figs. 3, 4
PL XV, Fig. 4
PL XXII, Figs. 5, 6
PL VI, Fig. 5
.PL XIX, Fig. 5
PL IV, Fig. 6
PL XIII, Fig. 5
„
..PL XX
PL II, Fig. 3
PL XI, Fig. 5
PL XIII
Pis. XVII, XVIII
PL XVI
Pis. VIII, IX
PL XXVI
PL XVII, Fig. 5
PL XVI, Fig. 3
PL VIII, Fig. 6
PL XXI, Fig. 5
PL XVIII, Fig. 4
PL XIV, Fig. 4
PL XI, Fig. 6
PL II, Fig. 4
PL VI, Fig. 6
PI. V, Fig. 1
PL XV, Fig. 6
PL XII, Fig. 1
PL XII, Fig. 5
PL XIV, Fig. 5
INDEX TO PLATES
Nicotine with Gold Chloride
Palladous Chloride
Papaverine with Mercuric Chloride
with Zinc Chloride
Peronine with Potassium Iodide
Phosphomolybdic Acid
Phosphotungstic Add
Picric Acid
Pilocarpidine with Phosphotungstic Add
Pilocarpine with Platinum Chloride
Platinum Chloride
Potassium Acetate
Potassium Chromate
Potassium Cyanide
Potassium Ferrocyanide
Potassium Hydroxide
Potassium Iodide
Potassium Permanganate
Quinine with Ammonium Thiocyanate
with Potassium Acetate
with Sodium Phosphate
Quinidine with Ammonium Thiocyanate
with Gold Chloride
with Potassium Ferrocyanide
Quinoline with Chromic Acid
with Gold Chloride
with Picric Add
with Potassium Ferrocyanide
Saccharin
Scopolamine with Gold Chloride
Sodium CaTbonate
Sodium Nitroprusside
Sodium Phosphate
Sparteine with Gold Chloride
Strychnine with Ammonium Thiocyanate
with Chromic Add
with Gold Chloride
with Mayer's Reagent
with Picric Add
109
PL n, Fig. 5
PL IX, Fig. 1
Pis. VI, VII
PL IX, Fig. 2
PL VII, Fig. 1
PL XV, Fig. 5
PI. XXVI, Fig. 6
PL XVIII, Fig. 5
PL XXIV
PL XXIV
Pis. XIX, XX
PL XXIV, Kg. 6
PL V, Fig. 2
Pis. IV, V
PL XII
PL XXI
PL XXI
n
PL XX
Pis. XV, XVI
PL XVIII
PL XXIII
PL XXV, Jigs. 4, 5
PL XII, Fig. 6
PL XXI, Fig. 6
PL VII, Fig. 6
PL XII, Fig. 2
PL XXV, Fig. 8
PL II, Fig. 6
PL IX, Fig. 8
PL XX, Fig. 8
PL XVIII, Fig. 6
PL XXIII, Fig. 1
PL III, Fig. 1
PL XIII, Fig. 4
PL IX, Fig. 4
PL XXVI, Fig. 4
PL XIX, Fig. 6
PL V, Fig. 8
PL XX, Fig. 4
PL XII, Fig. 3
PL V
PI. Ill, Fig. 2
PL XII, Fig. 4
Pis. XIII, XIV
PL IX
PL VII
PL III, Fig. 3
PL VII, Fig. 2
PL XXV, Fig. 6
PL XXIII, Fig. 2
PL III, Fig. 4
PL XVII, Fig. 6
PL XVI, Figs. 4, 5
PL VII, Fig. 3
Pi. V, Fig. 4
PL XX, Fig. 1
Strychnine with Potassium Hydroxide
with Mercuric Chloride ..
Sulphuric Acid
Thebaine with Potassium Hydroxide
Tropacocaine with Chromic Acid
with Gold Chloride
with Mayer's Reagent
with Picric Acid
Wagner's Reagent
Yohimbine with Potassium Cyanide
Zinc Chloride
Zinc-Chlor-Iodide
PL XVI, Fig. 1
PL IX, Fig. 5
.... PL XIV, Fig. 6
PL XXVII, Figs. 4, 5
PL XX
PL XVI, Fig. 2
PL XXIII, Fig. 3
PL III, Fig. 5
PL XIII, Fig. 5
PL XVIII, Fig. 1
PL XVI, Fig. 6
PL VII, Fig. 4
PL XX, Fig. 2
PL V, Fig. 5
PL XXIII, Fig. 6
.PL XXVII, Fig. 6
Pis. X, XI, XII
PL XXI, Fig. 8
Pis. XXVI, XXVII
PL XXVII
PLATE I.
FIG. 1.—An halo nine 1 : 200.
u
FIG.—
2. Apon
oripn
afie 1 :
FIG. 3—
. Benzoey-clgonie 1 : 50. FIG.—
4. Cn
aefie i : 50.
4r
FIG.—
5. Cocn
ariyesatsl1ofrm:ed500w
.h
-e.iC
-Xo1ca5ni0.e) 1 : 10O0.
ti godl cholrFdiIG
e. i^
PLATE II.
*>/*
Fn.. 1.—Cytisim.1 1 : 2u<).
\ "V "-,
FIG. 3.—Hyoscyanune 1 : 50.
Fi«. 5.—N'icotinc 1 : 100O.
Fu;. ii.—Quinitiine 1 : 2txi.
Crystals formed with cold chloride i Xlol!'.
ATE III.
Fie. 2.—Scopolaniine I :
FIG. 3.—Sparteine 1 : 20O.
FIG. 4.—Strychnine 1 : 500.
Crystals fcrmexi with gold chloride K X150 *.
4*
FIG. 5.—Tropacooiine 1 : l()O0, with gold Fit;, ti.—Cocaine 1 : 50. with ferric chloride
chloride (XI50).
t XI">*)).
PLATE IV.
-*/
-A"
,.'
V
Fiu. 1.—Anhaloiiine 1 : 20U.
FIG. I1.—Braciae 1 :
y
Fio. 3.—Calycanthine 1 : 1000.
•!
FIG. 4.—Cinchonidine 1 : 1000.
K
FIG. 5.—Cocaine 1 : 5O0.
FIG. t>.—Hydrastinine 1 : 5<.K).
Crystals formed with platinum chloride ( X150/.
\
PLATE V.
•chnine 1 : 500.
FIG. 3.—Quinoline 1 : 50O.
FIG. 4.—Strychnine
Crystals formed with platinum chloride i X15(Ji.
#
.FIG. 5.—Tropaeocaine 1 : 500, with platinum FIG. 6.—Brucine 1 : o<), with saccharine
chloride ( X150).
(X150».
PLATE VI.
FIG. 1.—Arecolino 1 : .50.
FIG. 2.—Brucinc- 1 : ,")O0.
FIG. o.—Hydrastininp 1 : W>.
FIG.ft.—Calyeanttdne1 : 1O0O.
Crystals formed with palladcms chloride ( XloO).
PLATE VII.
FIG. 1.—Papaverine 1 : ~>0.
FIG. 2.—Sparteine 1 : ~
. >a
&;fct.
FIG. 3.—Strychnine 1 : ,">(>0.
FIG. 4.—Tropaeocaine 1 : 100.
Crystals formed with palladous chloride ( X150>.
FIG. O.—Cinchonidine 1 : 2(X).
Fir,. 6.—Quinine 1 : 200.
Crystals formed with sodium phosphate 1 : 200.
PLATE VIII.
*
•
FG
I.—
1.n
C
eifaf1 : o)l.
J>,
FIG. 3—
. Cyn
site 1 : 50.
FG
I.—
4.D
n
oaei 1 : 50.
#•
*
Fi«.
5 . — H e r o i n e 1 : 2O0.
Crystals formed
•
with
>
TIG.
6.—Morphine
mercuric chloride ( X 150).
1 : 50.
PLATE IX.
FIG. S.—^uinidine 1 : 200.
FIG. 4.—Quinuline 1 : 2uu.
Crystals formed with mercaric chloride ( X150).
FIG. O.—Strychnine 1 : 500, with mercuric FIG. 6.—Bruciae 1 : 30, vrith sodiuai nitrochioride ( X150).
prusside.
PLATE X.
Pio. 1.—Aspidospcrrnine 1 : ~>0.
FIG. 2.—Atropine 1 : 500.
. .'i.—Atropine 1 : 500 {X'<i00)
FIG. 5.—Brueine 1 : 500.
FIG. 0.—Codeine 1 : 50.
Crystals formed with Wagner's reagent (X150}.
I'LATi: XI
FIG. 1.—Cytisiui' 1 : UI.
FIG. 3.—Homatropine 1 : ~A\)
FIG. 5.—ffyosevarciiii«> 1 : 50.
FKJ.fi.—MorphineI : 20CL
Crystals foriuei with Wagner's reajgent ( XlJi
i':..wi. MI.
Tic. 3.—Quinoline 1 : 2iN).
Fiu. 4.—Scopolarrui'e J : 50.
Crystals formed with ^'agner's reagen
Fro. 5.—Nareotine 1 : 2(K)
Fir, r,.—Qmrune 1 "15.
Crystals formed with potassium acetate Xl5»»
i'-LATL
*
*
*
*
*
*
«
FIG. 1.—ArtM'olinr 1 :.%4H)
Crystals fnrmed with Kraut's r»va*rf nt • Xl.V;
i
*
FG
I. —
5.reT
patcon
caieI 1X15CU
:.1000,w
h
ti Krausf"i F
iJT
.»-—
6. An
«f»in
ti 1 *>
i' w
h
agreon
U
.n
e • j
FIG. 3.—Dionine 1 :
u. 4. — M'..rpr;:n* 1 : "*•'
Pio. 5.—Narcotine 1 : 1000.
Fie »>. —Strychnin* 1 :
Crystals formed with sixiiuni carboaite H:1*H)
Fit;. 1.—Asjtu.ltjs'|>tiri!uiu' 1 : lt*tt»
FIG. T>.—Papavenuo 1 : 2tX>.
^ i</• ' -V-'*
Crystals formed with potassium hydr«->*nit» s . <•
%*
V
•4
Via l.—Stryfhnm«' 1 : ."»i*t
Crystals i'urim-if with p<
PLAiL XWL
FIG. 5.—Morphine I : 200.
Fi«. 6.— >tryrhmne 1
Crystals formed with Marine's reagent X !.*><!
Fin. i.—Tropaci »-.unv I : li«n>,\nth Mar
FIG. :i.—Codeine 1 : 50.
FIG. 5.—Peronine 1 : 200.
Fir? tf
Crystals formed -with potassiuni n.Mi.'ir- •
\;v.
FIG. 3.—Cvtisine 1 : 50.
*
Fir,. 6. —<)wn .line 1 : 1O«\
Fio. 5.—Hydrastinine 1 : 200.
13fV
Crystals formed with picric acid
r. \ . .;. V\
-K
X
%
*
*
*
4i
»%l*
*
Fie. 3—
.Q
.th
Cu
rn
yid
sitn
aisle of1rm:ed50w
i pntassFiu
irr.i.4ferr. >*>
• ;ir;t.*r'
i'LA 1L X.M
Fio. li.—Vohimbine I : 2(K), with potassium
cyanid*» ( X15W.
FIQ. 5.—Morphine 1 : 50.
Crystals formed with
Fin. 1.—C--*it'izit ]
-Kn
PLATE XXII.
m m - ••:
FIG. 1.—Brucine 1 : 500.
FIG. 3.—Cocaine ] : 200.
FIG. 2.—Calycanthine 1 : 50.
FIG. 5.—Hydrastinine 1 : 200.
FIG. 6.—Hydrastinine 1 : 200.
Crystals formed with chromic acid ( X150>.
PLATE XXIII.
FIG.
l.
.—
rytichniet1X5I0:*.500.
Iw
htiFG
cIhrom
c2i. nS
d
-8
*
.
-Tropacocaine
1 : 100, with chromic
FIG. 3.S—
Tropa«
4 -Cocaine 1 : 200, with potassium
t w. 4.-C perman2anate .
FtG
t
—
6
.
T
r
>
o
t
a
c
o
n
c
a
e
i
1
:
1
0
0
0
.
F
G
l
FG
I.—
5C
. ryH
y
d
n
r
v
i
a
e
t
s
1
:
5
0
0
.
r
«
*
.
».
astlom
fed w
hti pu
oatism pemanganeat( X150>.
PLATE XXIV.
.*»' n*
FIG. 1.—Betaine 11 :: 200.
200.
FIG.
1 : 200.
FIG. 2.—Choline
Ctl f
bdie
id { XlOi
Crystals formed with phosphomolybdie acid { XloOi.
***
V
s? :.
^
. •
* *r
*fc
"Hf..
PIG. 3.—Anhalonine 1 : 200.
FIG. 4.~Betaine 1 : 1000.
FIG. 5.—Coniine 1 : 200.
FIG. 6.—Piloearpidine 1 : 60
Crystals formed with phosphotungstic acid ( XI50).
PLATE XXV.
FIG. 1.—Brucine 1 : 50.
Fie. 3.—Ouinidine 1 : 2(M).
FIG. 2.—Codtine 1 : ">U.
FIG. 4.—Quinine 1 : 35.
FIG. 5.—Quinine 1 : 35.
FIG. 6.—Strychnine 1 : 500,
Crystals formed with ammonium thiocyanate ( X150^.
PLATE XXVI.
FIG. 1.—Bnicine 1 : 1UU0.
FIG. 2.—Codeine 1 : 5O.
• >
FIG. 3.—Homatropine 1 : 50.
Fio. 4.—Quinolme 1: 50.
Crystals formed with ZStillon's reagent ( X150).
•m.~
FIG. 6.—Papaverine
1 : 500.
FIG. 5.—Brucine
1 :: 50.
50.
cine
1
p
id (XlO)
C l f
Crystals formed with zinc chloride (XloO).
PLATE XXVII.
FIG. 1.—Chelidonine 1 : 500, with zinc
chloride (X150).
:
*
„ ^
c;.'6.—Codeine1 : 50.
V
Fio. 5.—Strychnine 1 : 50.
Fio. (J.—Tropacocy,Irio 1': ^Q
Crystals formed with zinc-chlor-iodide (X150),

Some Micro-Chemical Tests for Alkaloids

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