VALUE OF CATALOGUE OF NARCOTICS SPECTRA
EXPERIMENTAL PROCEDURES
ACKNOWLEDGMENTS
Author: Leo Levi, Charles E. Hubley, R. A. Hinge
Pages: 42 to 45
Creation Date: 1955/01/01
Within the last five years considerable efforts have been expended by a number of industrial and research laboratories to assemble the IR spectra of groups of chemical compounds for reference purposes and as a result of these survey projects several extensive collections of such data exist [1] . Unfortunately, none of these catalogues includes the narcotic drugs and closely related alkaloids and it is the purpose of this paper to present an atlas of such spectra.
The spectra presented in this atlas were recorded as mineral oil mulls and, where possible, as chloroform solutions. They should prove of particular value to the forensic chemist concerned with the identification and characterization of addiction-producing drugs seized in the illegal traffic or isolated from biological materials, and they will also be of considerable interest to the organic chemist faced with problems of structure elucidation. Eighty-five compounds have been included in this survey, and a detailed interpretation of the experimental data in terms of group frequencies and other structural correlations will form the subject of a subsequent paper in this series.
These spectra were obtained by grinding finely with an electric vibrator a few mg. of sample in mineral oil, placing the resultant smooth paste between two salt plates and measuring its absorption throughout the 2-16 micron range. Although mineral oil was used in the reference cell its absorption bands (3.5, 6.9 and 7.3 micron) were not completely compensated. All of the spectra were charted on a Baird Double Beam Recording IR Spectrophotometer equipped with rock salt optics and housed in an air-conditioned laboratory thermostated at 25°C.
From a series of media tried chloroform was considered the most suitable one because of its superiority as both an infrared and general solvent. The spectra were taken of approximately 1.4 per cent solutions, a pair of 0.455 mm. matched sodium chloride cells being used throughout the experiments. In cells of such thickness, required because of solubility limitations, chloroform shows relatively intense bands at 3.3, 4.18, 6.48, 7.0, 8.2, 9.6, 10.78 and beyond 12 microns. Hence, in these regions the inherent spectral characteristics of the compounds are either distorted or obscured, and because of the complete masking of sample absorption beyond 12 microns the spectra are shown up to this wavelength only. It would, therefore, be very desirable to supplement this altas with IR spectra of these alkaloids dissolved in other solvents having complementary absorption regions [1] .
SCOPE OF COLLECTION
The compounds included in this survey are shown in table I, which also lists many of their common synonyms and trade names1 under which they are marketed. Their authentication was reported in a previous paper of this series [2] and additional comments regarding their physico-chemical properties have been made by Oestreicher et al. [3] , Barnes and Sheppard [4] , and Barnes and Forsyth [5] . Thirteen of the compounds listed were not included in any of the previous projects and the infrared absorption spectra recorded in this atlas are the first absorption data to be published respecting those alkaloids. Other physical properties of these drugs are given in table II.
With the exception of 2-azabicyclo- (3,3,1) nonane hydrochloride, which compound was kindly supplied by Professor M. W. Cronyn of the University of California, Berkeley, Cal., all of the alkaloids shown in this table were obtained from T. and H. Smith, Ltd., Edinburgh, Scotland.
1Trade-marks registered in the United States Patent Office up to July-August 1951 are indicated in the alphabetical listing by the use of the symbol R enclosed in a circle.
The authors are grateful to the Defence Research Board, Ottawa, for permission to determine the spectra in their laboratories, and to both the Food and Drug Directorate of the Department of National Health and Welfare, Ottawa, and the Defence Research Board, Ottawa, for permission to publish these data. They are also indebted to Miss M. Smith, a summer student at the Defence Research Chemical Laboratories, and Mrs. P. O. Oestreicher of the Food and Drug Laboratories, Department of National Health and Welfare, for valuable technical assistance, and to Mr. C. A. Kerr, Chief Photographer of the Department of National Health and Welfare, for preparation of the illustrative material.
[Manuscripts Parts IVA and IVB received for review 1st December 1954]
Compound |
Empirical formula |
Melting point °C |
Observed |
Literature value |
Reference |
Per cent recovery (non-aqueous titration) (1) |
---|---|---|---|---|---|---|
Apomorphine Sulfate ........................ |
(C 17H 17O 2N) 2 H 2SO 4 |
230° |
sample starts decomposing and gradually becomes a black mass without melting |
- | - | 99.7 |
2-Azabicyclo-(3,3,1)nonane Hydrochloride |
C 8H 15N HCl |
205° |
sample starts softening |
300-302° |
(2) | 100 0 |
220° |
sample has sintered to a greyish-white mass |
288° |
(3) | - | ||
240° |
sample has become almost colourless |
- | - | - | ||
280° |
sample starts to darken |
- | - | - | ||
297-299° |
sample melts with decomposition |
- | - | - | ||
Codeine Hydrochloride |
C 18H 21O 3N HCl 2H 2O |
162-164° |
practically all of the sample melts to a |
264° |
(4) | 99.6 |
light yellow liquid |
287° |
(5) | - | |||
175° |
recrystallization sets in |
- | - | - | ||
258-263° |
sample melts with decomposition |
- | - | - | ||
Codeine Hydrobromide ...................... |
C 18H 21O 3N HBr 2H 2O |
158° |
sample starts to soften |
190-192° |
(4) | 99.8 |
164-167° |
sample melts partially |
- | - | - | ||
180° |
recrystallization occurs |
- | - | - | ||
253-258° |
sample melts with decomposition |
- | - | - | ||
Codeine Hydrogen Iodide .................... |
C 18H 21O 3N HI 2H 2O |
152-155° |
- |
266° |
(6) | 99.3 |
Codeine Sulfate ......................... |
(C 18H 21O 3N) 2 H 2SO 45H 2O |
266-269° |
(dec.) |
- |
- |
100.1 |
Cotarnine Chloride ....................... |
C 12H 14O 3N Cl 2H 2O |
186-188° |
(dec.) |
192° |
(7) | 100.7 |
Cotarnine Phthalate ........................ |
(C 12H 14O 3N) 2 C ?H 4(COO) 2 |
93.7-95.1° |
practically all of the sample is melted |
130° |
(8) | - |
98° |
recrystallization sets in |
- | - | - | ||
136-139° |
sample melts to a yellow liquid |
- | - | - | ||
Morphine Acetate ........................ |
C 17H 1?O?N C 2H 4O 2 3H?O |
95° |
sample begins to soften |
- | - | 99.7 |
104-108° |
sample melts almost completely |
- | - | - | ||
150° |
recrystallization starts |
- | - | - | ||
230° |
sample discolours to a brown mass |
- | - | - | ||
246-249° |
sample melts with decomposition |
- | - | - | ||
Morphine Meconate ....................... |
(C 17H 1?O 3N) 2 C 7H 4O 7 5H 2O |
187-189° |
(dec ) |
- |
- |
97.3 |
Narceine Sulfate ....................... |
C 23H 27O 8N H 2SO 4 10H 2O |
153-156° |
- | - | - | - |
Narcotine Sulfate ......................... |
(C 22H 23O 7N) 2 H 2SO 4 H 2O147-149° |
- | - | - | - | - |
Papaverine Sulfate .......................... |
C 20H 21O 4N H 2SO 4 |
120° |
sample starts to soften |
- | - | - |
125-133° |
sample melts partially |
- | - | - | ||
140° |
recrystallization sets in |
- | - | - | ||
202-206° |
sample melts with decomposition |
- | - | - |
References - Table
1. Levi, L., Oestreicher, P. M. and Farmilo, C. G. Bulletin on Narcotics, 5, 15 (1953).
2. Cronyn, M. W.: Jour. Org. Chem., 14, 1013 (1949)
3. Ginsburg, D.: Jour. Org. Chem, 15, 1003 (1950).
4. Martin,F.:Jpur. Pharm. Chim ., 26,(7), 176 (1922)
5. Wilson, D C.: Pharm Jour, 113, 688 (1924)
6. Small, L. F.: Chemistry of the Opium Alkaloids. United States Government Printing Office, Washington, 1932.
7. Dott, D. B.. Pharm Jour.. 113, 688 (1924)
8. Freund, M: U.S. Patent 892,414, July 7 (1908). Chem. Abstr., 2, 2847 (1908).
Hubley, C. E.; Levi, L.: The Infrared Spectroscopic Method, Bulletin on Narcotics, VII, 1 (1955).
002Farmilo, C. G.; Oestreicher, P. M.; Levi, L.: Common Physical Constants for Identification of Ninety-five Narcotics and Related Compounds, Bulletin on Narcotics, VI, 1 (1954).
003Oestreicher, P. M.; Farmilo, C. G.; Levi, L.: Ultraviolet Spectral Data for Eighty-six Narcotics, Bulletin on Narcotics, VI, 3 (1954).
004Barnes, W. H.; Sheppard, H. M.: X-Ray Diffraction Powder Data for Ninety Narcotics, Bulletin on Narcotics, VI, 2 (1954).
005Barnes, W. H.; Forsyth, W. J.: Unit Cell, Space Group, and Indexed X-Ray Diffraction Powder Data for Certain Narcotics, Canadian Journal of Chemistry, 32, 984 (1954).