Codeine to Morphine Ratio of Illicit Heroin Hydrolysates

Sections

TABLE I: Morphine and codeine values of illicit heroin hydrolysates

Details

Author: Georges R. NAKAMURA , Tyunosin UKITA
Pages: 43 to 44
Creation Date: 1963/01/01

Codeine to Morphine Ratio of Illicit Heroin Hydrolysates

Georges R. NAKAMURA
Tyunosin UKITA *
Military Police Crime Laboratory APO 343, San Francisco, California, U.S.A.

In the light of heavy international traffic in illicit heroin, questions have been put to chemists concerning the origin of these narcotics. The senior author was therefore directed to inquire into a possible individual or group peculiarity of heroin preparations.

Paper chromatography study (1) of alkaline hydrolysates of different illicit heroin samples showed that all these hydrolysates contained codeine. From the determination of morphine and codeine in each hydrolysate, the ratio of these two alkaloids was calculated. A significant variation of this ratio among samples would indicate possible difference in the source of manufacture. Furthermore, when a high-percentage heroin is diluted in the clandestine market, its ratio will remain constant.

Method

The extraction procedure for morphine and codeine was a modified form of that described in (2) and (3). The strong alkali used in extraction (3) split off the acetyl groups of heroin in less than a minute, thus eliminating prior hydrolysis treatment described in (2). 10 to 50 mg of morphine and codeine could be recovered from 2 ml of 1 N NaOH without any appreciable loss. Most crude heroin contained brownish particles from plant sources which were removed in water by centrifuging at 4,000 rpm for 20 minutes. Final measurement was made by ultraviolet absorption spectrophotometry.

To 1 ml of aqueous solution containing 10 to 50 mg of heroin in a small separatory funnel was added an equal portion of 2 N NaOH and the mixture was allowed to stand 1 minute. The mixture was shaken 3 times with 10 volumes of CHCl 3 to extract codeine, passing the extracts through Celite (Johns Manville Co.) and filter paper or a pledget of cotton. The aqueous solution containing morphine was neutralized with HCl, adjusted to pH 8 with ammonia and shaken 3 times with ten volumes of 9:1 chloroform-ethanol. The residues obtained after evaporating the solvent from both extracts were dissolved in 0.5 N HCl for ultraviolet spectra reading in the Beckman DK-2 spectrophotometer. Morphine and codeine were determined using the extinction coefficient values listed by Oestreicher et al. (4) and base readings to account for small blanks. Results obtained from 20 different illicit heroin samples are shown in table I.

Professor, Faculty of Pharmaceutical Sciences, University of Tokyo, Tokyo, Japan.

Discussion

Preparations containing different percentages of heroin listed in table I had approximately the same percentage ratio of codeine to morphine after hydrolysis. However, a small variation was noted. Although most of these samples were confiscated in Korea (except 1, 2 and 3 from south-east Asia), there was no information as to whether these samples had a common source. Data on such ratios obtained from illicit heroin in other areas may be correlated with those presented here.

TABLE I: Morphine and codeine values of illicit heroin hydrolysates

Sample

Morphine %

Codine %

Codeine/morphine ratio

1 65.2 7.4
.11
2 60.0 7.0
.12
3 56.0 6.5
.12
4 55.0 7.0
.13
5 48.8 4.8
.10
6 46.7 4.5
.10
7 43.6 6.1
.14
8 42.7 5.7
.13
9 39.0 4.9
.13
10 36.7 3.8
.10
11 31.9 3.3
.10
12 30.8 3.2
.10
13 28.9 3.0
.10
14 27.2 2.7
.10
15 24.7 2.4
.10
16 20.6 2.0
.10
17 13.3 1.6
.12
18 11.8 1.3
.11
19 11.1 1.3
.12
20 8.4 0.9
.11

REFERENCES

001

NAKAMURA, G. R. & UKITA, T., "Heroin Hydrolysis Study by Paper Chromatography" (in preparation).

002

"The Analysis of Heroin ", Bulletin on Narcotics, V , No. 2, 1953, p. 31.

003

The Pharmacopoeia of the United States of America, XV , 1955, p. 445.

004

OESTREICHER, P. M., FARMILO, C. G. & LEVI, L., "Ultraviolet Spectra Data for Ninety Narcotics and Related Compounds ", Bulletin on Narcotics, VI , No. 3-4, 1954, p. 42.