Documente Academic
Documente Profesional
Documente Cultură
00/O
Printedin Great Britain.All rightsreserved Copyright 0 1982 Pergamon Press Ltd
SPECTROPHOTOMETRIC DETERMINATION OF
ATROPINE, PILOCARPINE AND STRYCHNINE
WITH CHLORANILIC ACID
M. ABDEL-HADY ELSAYED and SURAI P. AGARWAL*
Summary-In dioxan-chloroform medium the acceptor chloranilic acid forms 1: 1 molecular complexes
with the alkaloids atropine, pilocarpine and strychnine, with maximum absorption at 535, 527.5 and
535 nm respectively. Conformity with Beer’s law allows the use of the complexes for the assay of these
drugs.
Molecular complexes are formed by interaction Chloranilic acid solution. p-Chloranilic acid dissolved in
between electron donors and electron acceptors.’ 1,4_dioxan to give 0.005M and 0.2% solutions, which were
kept in the dark when not in use and under these con-
Donors fall into two major categories, lone-pair
ditions were stable for up to 6 weeks.
donors such as amines (including alkaloids), alcohols, Other reagents and solvents were analytical grade and
sulphoxides etc., and x-donors such as aromatics, par- used as such.
ticularly polycyclic systems. Some compounds such
as azoaromatics and aromatic amines may behave as Standard solutions
lone-pair donors towards some acceptors and A- Atropine and strychnine bases. An accurately weighed
amount of the base was dissolved in chloroform to give
donors towards others. Acceptors may be of Q- and of
0.2% and 5.0 x lo-“M solutions.
x-type. The former include iodine, recently employed Pilocarpine hydrochloride. An accurately weighed amount
in the assay of alkaloids’-’ and antihistamines.” K- (0.1173 g) was dissolved in about 15 ml of water in a
Acceptors are aromatic systems containing electron- 100-m] separatory funnel. The solution was alkalinized to
withdrawing substituents such as nitro, cyano or litmus with a few drops of dilute ammonia solution and
extracted with 15, 10, 10 and lo-ml portions of chloroform,
halogen groups, e.g., p-benzoquinone,g dichlorobenzo- each extract being washed with the same 15 ml of water in
quinone,” fluoranil,” chloranil,” tetracyano-pbenzo- another separatory funnel. The washed extracts were fil-
quinone13 and 7,7’,8,8’-tetracyanoquinodimethane. l4 tered through anhydrous sodium sulphate in a filter paper
p-Chloranilic acid has been largely used in the deter- in a small funnel, into a 50-m] standard flask. The funnel
and paper were washed with l-2 ml of chloroform and the
mination of metal ions,15,‘6 but not hitherto in the
volume was made up with the same solvent to 50 ml.
assay of alkaloids. A 5.0 x 10e3M solution of pilocarpine base in chloro-
The present work describes the spectrophotometric form was similarly prepared from 0.2447g of pilocarpine
determination of atropine, pilocarpine and strychnine hydrochloride, with final dilution to 200 ml.
by complefation with chloranilic acid. These alka- Preparation of assay solutions
loids are usually present in pharmaceutical dosage
Atropine sulphate, pilocarpine hydrochloride and strychnine
forms in very small amounts (1 mg or less per unit hydrochloride powders. About 0.12 g, accurately weighed,
dose). Such small amounts preclude the use of many was dissolved in about 15 ml of water in a lOO-ml separa-
methods for assay of these alkaloids. tory funnel and alkalinized. The bases were extracted with
chloroform and collected in a 50-ml standard flask as
described for pilocarpine hydrochloride.
EXPERIMENTAL Atropine sulphate eye-drops. A 5.0-m] portion was trans-
ferred into a lOO-ml separatory funnel containing 10 ml of
Reagents water and alkalinized. The base was extracted with chloro-
Alkaloids. Atropine base (BDH), atropine sulphate
form and collected in a 50-ml standard flask as above.
Atropine sulphate ampoules. The contents of 12 ampoules
(Merck), pilocarpine hydrochloride (Merck), strychnine
base (Merck), strychnine hydrochloride (Sigma). were pooled in a dry 20-ml conical flask, and mixed; 10.0
Alkaloid dosage forms. Atropine sulphate eye-drops, 1%
ml were measured into a 50-ml separatory funnel, alkalin-
solution containing 0.002’A phenylmercuric nitrate (Evans ized to litmus with ammonia and extracted with 4, 2, 2 and
Medical). Atropine sulphate injections B.P., 0.1% 2 ml of chloroform, the extracts being collected in a lo-ml
(E.G.Y.T.) and atropine sulphate injections B.P., 0.06% standard flask.
(Evans Medical). General procedure
An aliquot of assay solution was transferred into a 20-m]
* Author to whom reprint requests should be addressed. standard flask, 15 ml of 0.2% chloranilic acid solution were
535
536 SHORT COMMUNICATIONS
sented in Table 2. The recovery values are based on 6. H. Abdine, M. A. Elsayed and Y. M. Elsayed, Analyst,
the amounts found and those calculated to be present 1978.103.354.
7. M. A. Elsayed, Pharmazie, 1979, 34, 115.
from the nominal concentration of the preparations.
8. M. A. Elsayed and M. A. Abdel-Salam, Acta Pharm.
The reproducibility was rather poorer than that for Jugosl., 1978, UI, 75.
the pure salts. 9. T. Okan and K. Uekoma, Yakugaku Zasshi, 1967, 87,
1231; Chem. Abstr., 1968,68,591826.
Interferences 10. H. Abdine, M. A. Elsayed, I. Chaaban and M. E.
Abdel-Hamid, Analyst, 1978, 103, 1227.
Substances having no basic centre are not expected 11. N. M. D. Brown, R. Foster and C. A. Fyfe, J. Chem.
to interfere, since extraction of the alkaloid base pre- Sot. (B), 1967,406.
cedes the colour reaction. However, the method will 12. S. F. Belal, M. A. Elsayed, M. E. Abdel-Hamid and H.
not differentiate between the alkaloids investigated, Abdine, Analyst, 1980,~105,774.
13. K. Wallenfels. G. Bachman. D. Hofmann and R. Kern.
and amines will interfere. Nevertheless, the method is Tetrahedron, 1965, 21, 2239.
useful for routine analysis and quality control, and 14. A. Taha and J. Rticker, Arch Pharm. Weinheim, 1977,
the non-specificity could be overcome by using a 310, 485.
preliminary chromatographic separation. 15. D. D. Perrin, Organic Complexing Reagents, p. 189.
As the acceptor, chloranilic acid is superior to Interscience, New York, 1964.
16. J. F. Verchere, J. Chem. Research (S), 1978, 178.
chloranil, reaction with which is s~ow*~-~~ and gives 17. M. A. Slitkin, B. M. Smith and R. H. Walmsley,
complexes which are stable only for about 2 hr. Spectrochim. Acta, 1969,25A, 1479.
whereas chloranilic acid gives immediate formation of 18. G. Schwarzenbach and H. Suter, He/u. Chem. Acta,
a colour which is stable for at least 24 hr. 1941.24.617.
19. J. Bolard, J. Chim. Phys., 1969. 66, 221.
Acknowledgemenrs-The authors are grateful to Professor 20. H. J. Shine and R. D. Goodwin, J. Org. Chem., 1970,
P. Iwe Akubue, Dean of the Faculty, for providing facili- 35, 949.
ties, to Mr. C. U. Ogbuehi, Chief Pharmacist, University 21. P. G. Farrell and R. K. Wojtowski, J. Chem. Sot. C.,
Medical Centre, for providing dosage forms used in the 1970, 1394.
analysis, and to Senate Research Grants Committee, Uni- 22. J. Lascombe, J. Devanre and M. L. Josien, J. Chim.
versity of Nigeria, Nsukka, for funds (Grant No. 00354/79). Phys., 1964, 61, 1271.
23. M. D. Johnston, F. P. Gasparro and T. D. Kuntz, J.
Am. Chem. Sot., 1969, 91, 5715.
REFERENCES 24. P. Job, Ann. Chim., Paris, 1928, 9, 113; 1936, 16, 97.
25. J. H. Yoe and A. L. Jones, Ind. Eng. Chem., Anal. Ed.,
1. R. S. Mulliken, J. Chim. Phys., 1964, 61, 20. 1944, 16, 111.
2. A. M. Taha, A. K. S. Ahmad, C. S. Gomaa and H. 26. T. S. Al-Gabsha, S. A. Rahim and A. Townshend, Anal.
El-Fatatry, J. Pharm. Sci., 1974, 63, 1853. Chim. Acta, 1976,85, 189.
3. C. Gomaa and A. Taha, ibid., 1975,64, 1398. 27. Y. Tashima, H. Hasegawa H. Yaki and K. Takuira,
4. A. M. Taha and C. S. Gomaa, ibid., 1976, 65, 986. Bunseki Kagaku, 1970, 19, 43.
5. M. A. Elsayed, M. A. Abdel-Salam, N. A. Abdel-Salam 28. F. Alsulimany and A. Townshend, Anal. Chim. Acta,
and Y. A. Mohamed, Planta Medica, 1978, 34,430. 1973,66, 195.