Systematic Scheme of Identification TABLEI. IDPSTIFICA9
6
R
1 Ephedrine
-
2 3 4
Cocaine Procaine Colchicine 5 Cotarnine 6 Theobromine 7 Arecoline 8 Caffeipe 9 Nicotine 10 Piperine 11 Veratrine 12 Quinidine 13 Quinine 14 Heroine 15 Hyoscyamine 16 Atropine 17 Hashish 1s Codeine 19 Apomorphine
20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42
10
14 -
It br Y It br I’
G Or R
-
R
dk G dk R
Br br R y
-A G br R r Br -
Ro Br
Y
-
L
Y
-
T
P
PkAV dk R
OrR
It Or T 01 GAbr Y
-
-
-
-
YA YA It 1lc Or YAOr Y
v
dk G dk G
Yohimbine Berberine Strychnine Brucine Physostigmine Pilocarpine Dilaudid Hydrastine Papaverine Thebaine
13
d k br Y
L -
I t I A b l I’
PAdk G dty G P
-
O r RAY
R
PA01 G dk R VAOr R
Or
T
-
Or R P br R dty G dk br R br G
Or R Or R
Or
It Or YA Or R d b r br R
RABr
-
T
Or R
-
bd R Or R
-
Lupanine Lupinine Monolupine TriluDine Deltiline Narcotine Cinchonidine Emetine Scopolamine
B bd bl Br br ch Cr dk dkng dty
= = = = = = = = = =
Or R R
-
-
br R
blue blood bluish brown brownish cherry crimson dark darkening dirty
ein fl fd G gr
L
It 01 Or
Or R It Y It Or
Or R
Y
emerald fluorescence fading green greenish lavender light = olive = orange
= = = = = = =
C
Literature Cited
HERIICAL literature abounds with individual tests for alkaloids, but hitherto they have not been applied to all alkaloids and no systematic method for their identification has been available. The author has found that known reactions, modifications of known reactions, and new color reactions with simple reagents will enable one to identify forty-two of the more common alkaloids. The alkaloids in Table I are to be identified in the order given. I n all cases a few milligrams of each are treated a t room temperature, unless otherwise directed, with a fen cubic centimeters of the reagent shown in Table 11, so that effects of all reagents used on these alkaloids are now determined and disclosed. (For various confirmatory tests, see especially Mercks Reagenzien-T’erzeichnis, 1932.)
Acknowledgment The writer is greatly indebted to H. J. Snslinger of the Bureau of Sarcotics, J. F. Couch of the Bureau of Animal Industry, A. W. Ingersoll of Vanderbilt University, E. LaV. Jackson of Emory University, J. C. McManus of the U. S. Food and Drug Administration, and L. F. Small of the University of Virginia for providing some of the samples of alkaloids used in this work. 380
Allen, Merck Rept., 9, 112 (1900). Andr6, Chem. Zentr., 1904, 1180. Archetti, Z . anal. Chem., 40, 415 (1901). Armani and Barboni, Chem.-Ztg., 34, 448 (1910). Arnold, 2. anal. Chem., 23, 228-34 (1884). Biel, Ibid., 25, 452-3 (1886). Eiloart, Ibid., 25, 248-9 (1886). Ekkert, Pharm. ZentraZkalZe, 66, 36 (1925). Goldner, Pharm. Ztg., 34, 471 (1889). Johannson, Merck Rept., 10, 41 (1901). Kippenberger, Nachw. v. Gijtstofen, 1897, 104. Marchand, Chem. Zentr., 1849, 29. Martin, private correspondence. Miranda, Rev.jaarm. chilena, 1904, 317. Peset-Buendia, A n d e s SOC. espail. fis. guim., 14, 257-63 ( 1 9 i h . Richter, Apoth. Ztg., 24, 667 (1909). Robins, Pharm. Zentr., 17, 154 (1876). Schmidt, Arch. Pharm., 247, 141-9 (1909). Sonnenachein, 2. anal. Chem., 11, 440 (1872). Trapp, Canstatt’s Jahresber. (Vandenhoek & Ruprecht. Gottingen), 147 (1864). (21) Vitali, 2. anal. Chem., 20, 563 (1881). ( 2 2 ) Wagenaar, Pharm. lT’eebbZad, 65, 1213-16 (19281. (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20)
RECEIVED March 30. 1938
of Alkaloids TIOS OF
KIRBY E. JACKSON Georgia School of Technology. .Atlanta, Ga.
ALKALOIDS 17
23
21
20
19
- Adty G
PAdh GABr OrlOr R d k GAlt G Or RAol G TAOr R
Or Br Or P k l L
y Or It T + O r
gr TAdk
-
Or B r A R -
Pili G dk r BrAol G
O r R +it P K + B r ppf Or R + B r
YAbr Or r A g r Br
- I+ -
-AG VARlbr R ch R J o l G gr PAdty G
gr
T+ -
-
OT R + b I R T+Oi R It
-
G+ViBT
er B dkg dk gr B
dty G
P A r Br G qARAOr B P A r Br Or RAY Br Br dkng Or RAdk Br -AG -AG RAdk br R d k RAr Br -Aol G TAdk GABr PAbr R Or YAdk G
6 r K + p r B r + d k Or R -
It y
I t TAR + R
Or R R fd+Or T+Or R VAOr+Or R
YAlt G
OrAbr Or OrAbr Or TAol G r Br -A?
G
Or Br ch R qAy G
P = purple Pk = pink ppt = precipitate = quickly = red r = reddish R o = rose S c = scarlet
?!
T
It 1-
--It
I+tbd -
r Or+Pk
B r + l t Or T
-
-
-
-
It P k + Y +
-
-+Gilt Or R Y+T+Or P
6 r RAdk R
yBr+-+-
t b d = turbid V = violet W = white I’ = yellow v = vellowish - = colorless or odorless h = changing t o = after addition of remaining reagent or reagents t o complete test
-
TABLE11. REAGESTS 1 2
3
4 8 9 10 11
.iqueous solution of S a O H and KsFe C T l s 1 s ) Concentrated HrSOa ( 6 ) Eder’s reagent: Br, KBr, H20, 1:2:20 ( 2 2 ) THzOH.HC1 in excess KaOH ( 1 1 ) HCI, KCIO8, a n d ”3 (IC) 1% solution of (NH4)5TrOa in concentrated H2SO1 ( I O ) hqueous K O H and HaPO1.12Mo03 ( 4 ) D-HIPOI (A) 1 70solutio? of HzTiO, in concentrated H&On ( I 5 ) Fuming HhOa and NH3 ( 2 1 ) Aqueous NaOH and amyl alcohol ( 1 3 )
Bromine water, Hg(CN)z, and CaC03 ( 7 ) SazSnOs and concentrated H ~ S O I( 1 4 ) Concentrated H ~ S O containing A 1% HSOs. Pb02 ( 2 2 , 15 KaFe(CN)B in “ 0 3 (3) 16 2 % solution of Na?Fe(CN)sNO,S a O H , a n d HCl (8) 12 13 14
1; 18
19 20 21
22 23
HaP04.121loO~.then spot with NHa ( 2 0 ) Concentrated HAOI and a few mg. of MnO? (I) 10% FeCh solution Concentrated HnSOt and a few mp. of KzCrzOi ( 1 7 ) 2 % resorcinol in concentrated HzSO4 (0) C1, “I, and HCI ( 2 ) Concentrated HzSOPand a few mg. of Ce?Oa ( I 8 )
Ephedrine produces benzaldehyde. Heated cocaine with concentrated H ~ S O for I 1 t o 2 minutes in boiling water. cool, dilutes with water. Benzoic acid separates. White precipitate forms in presence of procaine. Colchicine produces a n orange coloration. Evaporate alkaloid with 3 drops of HCI and few crystals of KCIOa and spot with “3. Boil 1 t o 2 mg. of alkaloid with KOH for 2 t o 3 minutes, cool, add acid until white precipitate forms, add 50% K O H until precipitate just dissolves. Caffeine gives blue coloration. Heat with o-HaPO; for 10 minutes in boiling nater. Evaporate t o dryness a few mg. of alkaloid with fuming HSOa and spot with NHI. Add 95% E t O H t o alkaloid. shake, add few cc. of NaOH. shake, add 0.5 t o 1 C.C.of amyl alcohol, shake, add v a t e r until the amyl alcohol separates. I n presence of hashish the amyl alcohol is purple. Treat alkaloid with t h e acid mixLure, then add few mg. of PbOz. 1 cc. of a freshly prepared solution of Na?Fe(CN)aNO is added t o 1 cc. of the alkaloid HCI. 1 cc. of -V S a O H is added and then acidified with HC1. wine t o ruby-red colored in the presence of pilocarpine.
The liquid immediately becomes
Treat with C1, then with S H 3 . neutralize with HC1 and add in excess.
Colors develop.
