Part III B. Ultraviolet Spectral Data for Ninety Narcotics and Related Compounds

Sections

INTRODUCTION
THE ABSCISSA OF THE SPECTRAL GRAPH
THE ORDINATE OF THE SPECTRAL GRAPH
INTERCONVERSION OF VARIOUS ORDINATE VALUES
PREPARATION OF MATERIALS
APPARATUS
SOLVENTS
PROCEDURE
RESULTS
GENERAL DISCUSSION OF RESULTS1
PYRAN SPECTRA
ARYL SPECTRA
ISOQUINOLINE SPECTRA
PHENANTHRENE SPECTRA
ATLAS OF ULTRAVIOLET ABSORPTION SPECTRA OF NARCOTICS AND RELATED ALKALOIDS
Indexes

Details

Author: P.M. Oestreicher , Charles G Farmilo , Leo Levi
Pages: 42 to 70
Creation Date: 1954/01/01

Part III B. Ultraviolet Spectral Data for Ninety Narcotics and Related Compounds

P.M. Oestreicher Food and Drug Laboratories, Ottawa
Charles G Farmilo Food and Drug Laboratories, Ottawa
Leo Levi Food and Drug Laboratories, Ottawa

INTRODUCTION

The purpose of this paper is to present the experimental results of a survey of narcotics by means of ultraviolet spectrophotometry, consisting of summaries of ultraviolet absorption data, tables of maxima, minima and molecular extinction coefficients and spectra for ninety narcotics and related compounds for use in identification.

RÉSUMÉ OF METHODS OF PRESENTATION OF SPECTRAL DATA

There are various ways of recording ultraviolet spectral data. They are often presented in tabular form showing simply the value of the absorption maxima, or as a table of maxima and minima. Some tables include intensity values expressed either as E 1% 1 cm or as ? or as absorbence referred to a concentration, at the corresponding maximum and minimum wave-lengths. A table listing maxima and minima and intensity values is most valuable because it permits the construction of a rough graph of the actual spectral curve.

There are a few conventions to be noted in the presentation of spectral data in graphic form. Spectral data are always plotted so that, in the final graph, the abscissae represent either the wave-lengths expressed as millimicrons or angstroms, or the frequencies expressed as sec. -1 or fresnels, or the wave numbers expressed as cm. -1 or mm. -1. Wave-length values are usually plotted increasing to the right. The ordinates represent values for the intensity of absorption which may be expressed in several ways, either as absorbence, transmittance, specific extinction coefficients, K, or E 1% 1 cm, molecular extinction coefficient, ?, or as a log function of any of these values.

A variety of curves may be obtained for the ultraviolet spectra of a compound depending on the different units used for plotting abscissae and ordinates.

THE ABSCISSA OF THE SPECTRAL GRAPH

The abscissa of a spectral graph may be expressed in terms of wave-length, frequency and wave number. These are discussed under sections ( a), ( b), ( c) below and illustrated in plates I and II.

(a) Wave-length

Most ultraviolet spectrophotometers are now calibrated to give wave-length readings directly. It is convenient to express the abscissa as such in graphing these readings. The wave-length readings commonly used in graphs of spectra are as follows:

1 ? (angstrom)=10 -8cm.=10 -10m.

1 mµ (millimicron) = 10 ? = 10 -7cm.

1 µ (micron)=10,000 ? =l,000 mµ.

These wave-length units were used in plates I and II, parts (A), (D), (E), (F), and (G), as illustrations of the different possible plots.

(b) Frequency of oscillation of the wave (v, sec -1)

Frequency is an expression of the number of waves per unit of time, usually per second. Corresponding to each point of the spectrum there is a characteristic frequency or number of vibrations per second. This is a more fundamental unit than wave-length and is used for theoretical studies. For ordinary purposes the relationship between frequency and wave-length may be expressed by the formula v=c/?, where ? is the wavelength in cm., c is the speed of light in cm. in the medium. Another unit, the fresnel, is also used to express the frequency of oscillation of the wave. Its relationship to v, sec. -1 is shown in the following formulae:

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1 fresnel (f) = 10 12 vibrations per second

1 fresnel=frequency, sec. -1 x 10 -12 f, since it is smaller than v sec. -1 is sometimes used for convenience. The frequency plot is illustrated in plate I (C).

(c) Wave number (v cm -1 and v mm -1)

The wave number expresses the number of waves per unit length, either one centimetre or one millimetre, of the light path in vacuo. Wave number is related to wave-length according to the following equation:

?v=10 -8,where ? = ?, v = cm -1 v cm -1= 1/? in cm.

Wave numbers, like frequencies, are more fundamental than wave-lengths. The wave number plot is illustrated in plate I (B).

THE ORDINATE OF THE SPECTRAL GRAPH

Intensities, as ordinate values expressed as different units, may be plotted in two ways, A and B.

A. The absorption curve in which the high intensity values define the band maxima

(a) Absorbence (A), formerly called optical density or - log T, referred to a specific concentration

The absorbence data obtained from a Beckman instrument may be plotted directly on a graph. One disadvantage of such an absorbence plot is that in plate I (D). A single curve does not usually result, since a separate curve is obtained with each appreciable change in concentration.

(b) Specific extinction coefficient, (K) expressed in g. per l.

The formula used for calculating K is as follows:

K=A/c, where A=absorbence and c=concentration, g./1. The K plot results in a single curve over the entire concentration range.

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(c) Extinction coefficient for a one per cent solution referred to a one centimetre cell

(E 1% 1cm.)

E 1% 1 cm. = 10K. The spectra of unknown materials from natural sources are usually plotted as E1% 1 cm. since no knowledge of molecular weight is necessary and a single curve results. The type of curve obtained is illustrated in plate II (E).

(d) Molecular extinction coefficient (?)

In addition to yielding a single curve, the plotting of ? values may. allow some grouping of the spectra of structurally related compounds. The molecular weight appears as a factor in the calculation, making it possible to compare the spectra of compounds of different molecular weights. The molecular extinction coefficient plot is illustrated in plate II (F).

(e) The logarithm (to the base 10) of any of the intensity values, K, ?, E 1% 1cm.

Log ? is the most commonly employed intensity function. It serves the same purpose as the ? plot and has several additional advantages. The log ? plot expands the weaker absorption bands which are often obscured in the ? plot. When plotting spectra where the ? max. values are very high and the ? min. values are very low, a change in scale is often required. When studying the spectra of a large number of compounds these changes are undesirable. The log ? plot overcomes this difficulty. Illustrations of the log ? plot are shown in plate I (A), plate I (B) and plate I (C).

B. The absorption curve in which the low intensity values define the band maxima

(a) Transmittance or per cent transmission

Transmittance is inversely proportional to absorbence, as can be seen by comparing plate I (D) with plate II (G). The advantages and disadvantages of the absorbence plot also apply to the transmittance plot.

(b) Equivalent thickness of the absorption solution layer in mm. or cm.

This method of plotting intensity is now obsolete, but was used in the early literature. See figure 2, curve 1, and figure 9, part III A (1).

INTERCONVERSION OF VARIOUS ORDINATE VALUES

The following scheme of conversion was given by Friedel & Orchin ([2] ) for comparing literature spectra plotted with different intensity units.

Operation

Literature Value

Unknown Spectra

Operation

 
Log ?
Log ?
take log
take antilog
?
?
multiply by M
divide by M
K
K
divide by b.c.
multiply by b.c.
A
A
(measured)

where:

M= molecular weight of the compound

c= concentration of solution in g./1.

b= thickness of absorption cell in centimetres.

PREPARATION OF MATERIALS

The preparation of materials used in this paper has been dealt with in part I B ([3] ).

APPARATUS

The Beckman DU model ultraviolet spectrophotometer was used with one centimetre silica absorption cells.

SOLVENTS

The solvent used in the preparation of solutions for the ultraviolet absorption spectra of the free narcotic bases was in most cases reagent grade absolute ethanol. Since cryptopine base and pseudomorphine base were both insoluble in absolute ethanol, in these cases 0.02 N HCl was used as solvent. Distilled water was used to prepare solutions of the narcotic salts. A solution of mescaline sulphate was also prepared using 80 per cent ethanol as solvent. Two solutions of cotarnine base were prepared using absolute ethanol and water. These solutions were later acidified with a few drops of concentrated HCl. Distilled water was used to prepare a solution of morphine-N-oxide. All the solvents used were found to be spectrally pure and no further purification was necessary.

PROCEDURE

As a routine, for compounds whose spectral characteristics were unknown, the following procedure was used. Approximately 12.5 mg. of the compound were accurately weighed, placed in a 25 ml. volumetric flask and "made to volume" with the appropriate solvent. This stock solution (0.5 g. per 1.) was accurately diluted to yield a 1:5 solution (0.1 g. per 1.). The spectrum of the 1:5 solution was then rapidly obtained in the region 205-340 m µ. at intervals of 10-20 m µ. to determine if the 1:5 concentration was suitable, i.e., if the corresponding absorbence values at the maxima lie in the range 0.250-0.600. If the 1:5 dilution allowed the maximum absorbence to fall within these limits, the curve was more exactly determined from 205 m µ. using another portion of the 1:5 solution. Absorbence readings were taken every 2 mµ. for the major portion of the curve and every 1-0.5 m µ. in the regions of maximum and minimum absorption. When the preliminary determination of the spectrum showed the absorbance values of the maxima to be above 0.600, a portion of the 1:5 solution was further accurately diluted and a more exact determination was made. If the preliminary determination of the spectrum showed the absorbence values at the maxima to be below 0.250, a new solution was prepared from the stock solution and a more exact determination of the spectrum was made. In most cases, another dilution was necessary for measuring absorbences in the region 200-240 m µ. One concentration of solution however could be used to obtain the entire spectrum in the cases of meconic acid, opianic acid, thebenine HCl and cotarnine.

For the purpose of plotting the spectral curves, absorbence values were converted to molecular extinction coefficients, ?, according to the formula:

 
absorbance x molecular weight
(1) ?=
------------------------------
 
concentration (grams per liter)

The molecular weights of narcotics shown in table I, part I B (4), used to calculate ?, include the total molecular weight of water added to the anhydrous molecular weight of the narcotic. The measured absorbence and concentration values were used in formula 1. An extinction value for each absorbence reading was thus obtained.

The ? values were then plotted as ordinates on semilog paper against the wave-length in millimicrons as abscissae. This graph was then traced onto an ozalid grid.

The ozalid grid showed log ? as ordinates and wave-length in millicrons as abscissae. ? values of 10, 100, 1000, etc., correspond in position on the ozalid grid to log ? values of 1, 2, 3, etc. This method of graphing on previously prepared grids eliminated the need to convert each ? value to its log ? equivalent before plotting. The structural formula and the chemical or common name of the narcotic base was then mounted on the grid along with the chemical formula of the substance studied. The solvent employed was also shown. The legend on the spectra in most cases," Base (B) ethanol", indicates that the spectra are that of the base, symbolized by the letter "B". The legend, " BHCl water", indicates the spectra of the salt dissolved in water. In cases where a single graph was given a heavy line may indicate the compound BHCl or other salt, e.g., B 2H 2SO 4, etc.

RESULTS

Table I shows U.V. maxima in increasing order of wave-lengths. This table is intended to serve as a reference for the ultraviolet absorption analyses of unknown narcotics and related compounds and to illustrate the spectral relationships present in the compounds studied. All the wave-lengths of maximum absorption of each compound are included.

Table II shows spectral data arranged according to chemical families. The compounds in this table are arranged according to the main chemical classification shown in part I A (5). The table includes wave-lengths of maximum and minimum absorption and corresponding ? values and concentrations in g./1. The number following the name of the compound refers to the number of the spectrum.

The spectra of the ninety compounds studied are given in fifty-six graphs. The spectra are arranged and numbered according to the chemical classification given in part I A ([6] ).

GENERAL DISCUSSION OF RESULTS1

Certain correlations between structure and ultraviolet spectra are discussed in the following paragraphs. A number of the main chemical groupings including examples from each family are discussed first, followed with comments on the important spectral characteristics related to the structure.

PYRAN SPECTRA

Two compounds, meconic acid and pyrahexyl, are included in the pyran group. Meconic acid contains two carboxyl groups and a ketocarboxyl group and is a single ring substituted pyran. Pyrahexyl contains a phenolic OH group and is a dibenzopyran.

The spectra of meconic acid figure 1 and pyrahexyl (figure 2) are distinctly different. The meconic acid spectrum is irregular with three main peaks. The pyrahexyl spectrum is a smooth curve with two maxima. Like the spectrum of phenanthrene [(7)] the pyrahexyl spectrum has a peak at about 280 m µ., but unlike the phenanthrene spectrum, it has much higher ? values.

Table I

SPECTRAL DATA SHOWING ABSORPTION MAXIMA IN INCREASING ORDER OF WAVE-LENGTHS

Maxima wave.length ? m?.

Compound

Maxima wave.length ? m?.

Compound

208
narceine HCl
255
cotarnine base-
208-209
ethylnarceine HCl
 
water + HCl
209
morphine HCl
255-256
cotarnine base-
 
narcotine base
 
ethanol
 
opianic acid
257
thebenine HCl
 
morphine-N-oxide
 
alphaprodine HCl
209-210
N-allylnormorphine
 
betaprodine HCl
 
HCl
 
pethidine HCl
210-211
meconic acid
 
ethylpethidine HCl
211
morphine H 2SO 4
258
alphaprodine base
 
apomorphine HCl
 
pethidine base
 
narcotine HCl
 
pipidone HCl
 
ethylmorphine HCl
 
d-?-methadyl acetate
211-212
codeine base
 
HCl
212
codeine H 3PO 4
 
d-?-methadyl acetate
213
benzylmorphine HCl
 
HCl
217
morphothebaine HCl
 
l-a-methadyl acetate
217-218
thebenine HCl
 
HCl
218
dextromethorphan
258-259
cotarnine base-
 
HBr
 
ethanol + HCl
218-219
ecgonine
 
isomethadone HCl
219
racemethorphan HBr
 
isomethadone base
 
racemorphan base
259
dl-methadone base
 
(Dromoran® base)
 
dl-methadone HCl
219-220
levomethorphan HBr
 
d-methadone base
220-221
racemethorphan base
 
d-methadone HCl
229
pseudomorphine base
 
l-methadone base
 
pyrahexyl base
 
l-methadone HCl
230
opianic acid
 
pipidone base
 
cocaine base
 
phenadoxone HCl
233
cocaine HCl
259-260
phenadoxone base
234
cryptopine base
263
alphaprodine HCl
 
meconic acid
 
betaprodine HCl
239
papaverine base
 
pethidine HCl
244-245
phenacetin
 
ethylpethidine HCl
249
hydrastinine C1
264
pethidine base
249-250
papaverine HCl
 
pipidone HCl
251
alphaprodine HCl
 
alphaprodine base
 
ethylpethidine HCl
 
isomethadone HCl
     
dl-methadone HCl
251-252
pethidine HCl
 
l-methadone HCl
252
pethidine base
265
d-methadone HCl
 
alphaprodine base
 
isomethadone base
 
betaprodine HCl
 
pipidone base
 
dioxyline H 3PO 4
 
phenadoxone HCl
253
dl-methadone HCl
 
sinomenine HCl
 
d-methadone HCl
268
morphothebaine HCl
 
l-methadone HCl
269
mescaline H 2SO 4
 
dl-?-methadyl acetate
 
water
 
HCl
 
mescaline H 2SO 4
 
d?-methadyl acetate
 
80% ethanol
 
HCl
 
trichocereine HCl
 
d-?-methadyl acetate
270
narceine base
 
HCl
 
acetoxyketobemidone
 
phenadoxone HCl
 
HCl
    272
acetoxyketobemidone
254-255
cotarnine base-
 
HCl
 
water
 
apomorphine HCl
273
caffeine base
285
morphine H 2SO 4
273-274
acetylsalicylic acid
 
morphine HCl
274
cocaine base
 
morphine HI
 
cocaine HCl
 
morphine-N-oxide
274-275
ecgonine base
 
N-allylnormorphine
275
Bemidone HCl
 
HCl
276
morphothebaine HCl
 
thebaine base
276-277
pyrahexyl base
285-286
benzylmorphine base
277
Bemidone base
286
cryptopine base
 
narceine HCl
 
ethylmorphine base
 
ethylnarceine HCl
 
dihydromorphine
278
racemethorphan HBr
 
base
 
dextromethorphan
 
codeine base
 
HBr
287
morphine base
 
levomethorphan HBr
 
?-monoacetyl-
 
diacetylmorphine
 
morphine base
 
HCl
 
acetoxyketobemidone
279
levorphan tartrate
 
HCl
 
( l-Dromoran®
   
 
tartrate)
289
racemethorphan base
279-280
papaverine base
289-290
cotarnine base
 
racemorphan HBr
290-291
protopine base
 
(Dromoran® HBr)
291
narcotine base
280
Acedicon® HCl
 
narcotine HCl
 
Dicodid® bitartrate
292
dl-methadone HCl
 
Dilaudid® HCl
 
d-methadone HCl
 
Eukodal® HCl
 
1-methadone HCl
 
ketobemidone HCl
 
phenadoxone HCl
 
methylketobemidone
295-296
dl-methadone base
 
HCl
 
d-methadone base
281
racemethorphan base
 
1-methadone base
 
diacetylmorphine
296
isomethadone HCl
 
base
 
pipidone HCl
 
papaverine HCl
 
phenadoxone base
 
cocaine base
298
morphothebaine HCl
 
ketobemidone base
299
isomethadone base
 
propylketobemidone
 
pipidone base
 
base
300
thebenine HCl
281-282
methylketobemidone
303
meconic acid
 
base
307
hydrastinine C1
282
metopon HCl
309-310
dioxyline H 3PO 4
282-283
Dicodid® base
 
narcotine base
 
Dilaudid® base
311
papaverine HCl
283
Eukodal® base
313
narcotine HCl
 
laudanine base
314
papaverine base
 
opianic acid
319-320
thebenine HCl
 
racemorphan base
327
papaverine base
 
( dl-Dromoran®
329-330
thebenine HCl
 
base)
331
cotarnine base-
283-284
ethylmorphine HCl
 
water
 
benzylmorphine HCl
 
cotarnine base-
284
neopine HBr
 
water + HCl
 
codeine H 3PO 4
332-335
cotarnine base-
284-285
dihydrocodeine base
 
ethanol + HCl
 
metopon base
335
dioxyline H 3PO 4
 
Paveril® H 3PO 4
335-336
cotarnine base-
     
ethanol

ARYL SPECTRA

A. Aryl carboxylic acids

Two examples of this group were studied. Opianic acid is a substituted benzoic acid containing, in addition to the COOH group, a formyl and two methoxy groups.

The spectra of benzoic acid (figure 3) and its derivatives, opianic acid (figure 4) and o-acetoxybenzoic acid (aspirin) ([8] ), are different in most respects. However, both opianic and benzoic acids have spectra with a peak at 230 mµ while o-acetoxybenzoic acid and benzoic acid both have a peak at 275 m µ. It should be noted that the spectrum of cocaine base (figure 5) is identical with that of benzoic acid, which in other words is the chromophore of the alkaloid.

B. Aryl piperidines

There were eleven compounds in this subgroup whose spectra were obtained. These compounds can be combined into three main sub-subgroups. The first contains cocaine and ecgonine which are quite different chemically from the remaining compounds. Ecgonine is a non-aryl modified piperidine which forms part of the cocaine molecule. The second subgroup contains the piperidine carboxylates; pethidine, ethyl pethidine, ?and ?prodine and hydroxypethidine, which unlike all others carries a phenol hydroxyl. This subgroup can be further chemically divided into pethidines which are esters of isonipecotic acid, and ?and ?prodines which are piperidol esters of propionic acid. The third group contains four compounds, all arylpiperidylalkanones, i.e., ketobemidones. The ketobemidones are structurally related, the variation being in the alkyl portion of the ketone, e.g., methyl-, ethyl- and propyl-ketobemidones. Acetoxyketobemidone, in addition to being an ethyl ketone, contains an acetoxy substituent on the aryl ring. The important change in this compound is from a phenol to an ester.

The spectra fall into three groups which relate to the structures in the chemical classes. The spectra of ecgonine (figure 6) and cocaine (figure 5) show maxima at 274 m ?. but are not otherwise closely related. The spectrum of cocaine base has one more peak than the spectrum of the HCl salt, resembling the curve of benzoic acid (figure 3) more than that of ecgonine ( loc. cit.). The spectra of the aryl piperidine esters, e.g., pethidine (figure 7) and prodine (figures 9 and 10), are characterized by one absorption region consisting of fine structure between 253-264 m ?. and by very low ? values. The spectra of compounds in this group most closely resemble that of benzene ([9] ), with the exception of pethidine (figure 11). The spectrum of this compound is closely related to that of o-cyclohexylphenol ([10] ) and to the spectra of methyl-, ethyl- and propylketobemidone

(figures 12, 13, 14) which are all phenols. These compounds have one absorption band showing a maximum in the range 277-280 m ?. The spectrum of acetoxyketobemidone (figure 15) is entirely different from the spectrum of the parent compound, with two maxima at 271 m ?.and 286 m ?.

C. Diarylalkoneamines

There were four compounds studied in this group which may be further subdivided into hexanone amines, e.g. pipidone and isomethadone, and heptoneamines, e.g. methadone and phenadoxone. Another compound, ?-methadyl acetate, was included. Except for the latter, they are all ketones, ?-methadyl acetate being an acetyl ester derived from methadone. All the compounds in this class have two phenyl groups and a variety of substituted amino groups, e.g. dimethylamino, piperidino, and morpholino.

The spectra of the diarylalkoneamines fall into two groups. The first, including isomethadone (figure 16), pipidone (figure 17), methadone (figure 18) and phenadoxone (figure 19) is characterized by two regions of absorption : fine structure between 253-264 m ?and a large single band between 292-299 m ?. The heptanone bases absorb at 299 m ?. and their HCl salts at 296 m ?. The hexanone bases absorb between 295-296 m ?. and their HCl salts at 292 m ?. The dand l optical isomers of methadone have spectra similar to that of the dl form. The ? values of the salts are lower than those of the bases and range from 510-600 for the salts and from 610-880 for the bases at the maximum wave-length of 259 m ?. The second group includes isomers of ?-methadyl acetate (figure 20). The spectra of the isomers of ?-methadyl acetate (figure 20). The spectra of the d-, l- and dl-isomers are similar-. Slight but probably insignificant differences in ? maximum of the three isomers are noted. Fine structure in the region 253-264 m ?. (like the first group) was observed. The large single band, observed in the first group between 292-299 m ?., was not obtained in the second group. The spectrum of ?-methadyl acetate resembles that of pethidine (figure 7) in this respect, having two peaks and a shoulder in the fine structure region compared with the three definite peaks occurring in the pethidine spectra. The ? values at about 259 m ?. for the methadyl acetates are intermediate between those for pethidine and methadone. The ? range for pethidine is 200-217, for ?-methadyl acetate is 422-434, for methadone is 510-600.

D. Arylethylamines

There are four compounds in this group, two of which are trimethoxyphenylethylamines, and two of which are aryl-phenyleneethylamines. The latter contain a ketone and carboxylate attached to the aryl ring and also a methylenedioxy substituent on the phenylene ring.

The spectra of these arylethylamines divide into two groups corresponding to the chemical classification. All five spectra (including narceine HCl-figure 23) show a single absorption maxima at 270 m ?. The narceine spectra (figure 23) have a broad band compared with a narrower band for the mescaline spectra (figure 21). The ? values for the two groups are completely different; that of mescaline base appears to be about 750 and that of narceine base about 9620 at the maxima 270 m ?. The solvent and pH appear to have considerable effect on the spectra of these compounds. The spectrum of mescaline sulphate in 80 per cent ethanol obtained by Salomon and Bina ([11] ) does not compare with ours (figure 21).

ISOQUINOLINE SPECTRA

There are three main subdivisions in this group, dihydro-, phthalide-, and benzylisoquinolines.

A. Dihydroisoquinolines

There were two compounds studied in this subgroup, cotarnine and hydrastinine, which differ only in the presence of a methoxyl group on the benzene ring in cotarnine. For a discussion of the structure of these two compounds, see Small ([12] ).

The spectra of these compounds are of the same shape, (comparing the cotarnine base in water + HCl (figure 25) and the hydrastinine chloride in water (figure 26) with two main bands whose maxima are at 255 m ?. and 331 m ?. for cotarnine and 249 m ?and 307 m ?. for hydrastinine chloride. The hypsochromic shift should be noted. The ? values are higher for hydrastinine at the first maxima and higher for cotarnine at the second maxima. The spectra of cotarnine vary with different solvents and pH conditions.

B. Phthalideisoquinolines

Only narcotine and narcotine HCl were studied. These compounds are also of the dihydroisoquinoline type, but contain in addition a phthalide substituent.

The spectrum of narcotine and its HCl salt (figure 27) are different from those of the previous group. The spectrum of the HCl salt shows higher E values than that of the base, both having peaks at approximately 209 m ?. , 291 m ?. and 309-310 m ?.

C. Benzylisoquinolines

There are three distinct sub-groups represented in the six compounds studied in this series; papaverine, papaverine. HCl and dioxyline-H 3PO 4represent the true benzylisoquinolines. Laudanine differs in that the nitrogen containing ring is saturated and there is an OH group on the benzene ring. Cryptopine and protopine are distinctly different and belong in a group by themselves as they contain ten membered rings. The chemistry of cryptopine and protopine has been discussed by Small ([13] ). Dioxyline has an ethoxyl group on the benzyl ring and a methyl group on the isoquinoline ring, while papaverine has a methoxyl group on the benzyl ring. Cryptopine and protopine differ only in that the former has a dimethoxy and the latter a methylenedioxy group substituted on the phenyl ring.

The spectra of the benzylisoquinoline compounds divide into three distinctly different groups. Those of papaverine (figure 28) and dioxyline (figure 29) are similar in shape and in position of maxima and ? values. The spectrum of laudanine (figure 30) is quite different to that of papaverine, resembling that of ketobemidone (figure 13), with a single peak at 283 m ?. and lack of fine structure. The spectra of cryptopine (figure 31) and protopine (figure 32) are different from each other except that both have a peak about 290 m ?. The ? values are 5880 and 9270 for cryptopine and protopine respectively.

PHENANTHRENE SPECTRA

A. Phenanthroisoquinolines

The two compounds studied having the phenanthroisoquinoline nucleus were apomorphine HCI and morphothebaine HCl. The former has two phenol groups on one benzene ring. The latter has two phenolic hydroxyl groups on non-adjacent benzene rings and also a methoxyl group adjacent to one of the phenol hydroxyls. The 8-9 carbon bond in the phenanthrene ring system is saturated. Both compounds have an iminoethano ring.

The spectra of apomorphine HCl (figure 33) and morphothebaine HCl (figure 34) are similar, having absorption maxima in the region 272-276 m ?. The morphothebaine HCl spectrum has two peaks, one at 268 m?. and the other at 276 m ?. The spectrum of apomorphine HCl shows a single maximum at 272 m ?. The morphothebaine spectrum has a peak at 298 m ?. In this region the apomorphine spectrum is a plateau. The literature spectra reported by Elvidge ([14] ) and Kitasato ([15] ) for apomorphine in this region show fine structure (probably accounted for by an instrument with higher dispersion, e.g., Hilger).

B. Phenanthroethanoamines

Thebenine is the only true phenanthrene derivative in this homologous series, the remaining compounds being more fully hydrogenated. It has in addition on the A ring an OCH 3group and a phenolic hydroxyl in ortho position, and on the C ring a phenolic hydroxide in a position para to the ethylmethylamine group.

The spectrum of thebenine HCl (figure 35) resembles the phenanthrene spectrum (16) more closely than any of the other phenanthrene type narcotic spectra. It has five peaks compared with eleven for phenanthrene. The major peak in the phenanthrene spectrum occurs at 252 m ?. compared with 251 m ?. in the thebenine HCl spectrum. The fine structure in the region 300-350 m ?. is modified in the thebenine HCl spectrum.

C. Iminoethanophenanthrenes

This group consists of eight compounds, seven of which are optical isomers or derivatives of morphan. The remaining compound, sinomenine, is closely related in basic structure; however it has considerably more unsaturation and substituents, e.g. methoxyl, hydroxyl, and carbonyl groups. The methorphans have a methoxy in place of the hydroxyl of the morphans. Compared with sinomenine, the morphinan homologues (i.e., 3-hydroxy- and 3-methoxy-N-methylmorphinans) have completely saturated B and C rings.

The spectra divide into two groups corresponding to the chemical classification. The morphinan spectra (figures 36 and 37) are characterized by one main band extending from 250 m ?. to 290 m ?. and a definite peak occurring in the region extending from 278 m ?. to 283 m ?. The spectrum of racemethorphan base (figure 37) reveals a peak at 281 m ?. and 289 m ?. respectively. It is characterized by low ? values at the minima. The ? values of the minima in this series vary between isomers and are the lowest observed for any narcotic. The highest absorption of the spectra of these compounds is of the order of 9,000 while the lowest is around 20. The second type of spectrum in this group was obtained from a study of sinomenine HCl (figure 38). The spectrum does not appear to be related to any other obtained in this study.

D. Iminoethanophenanthrofurans

The majority of common opium alkaloids and their derivatives fall into this group. Eighteen compounds were studied and these can be further chemically subdivided into five groups, depending on the basic structures which are shown in the following diagrams.

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In group I : thebaine

group II : neopine

group III : morphine, ethyl-, benzyl-N-allyl-nor-, diacetyl-, ?-monoacetylmorphine, pseudomorphine, morphine-N-oxide and codeine

group IV : Acedicone®

group V : dihydromorphine, dihydrocodeine, dihydromorphinone, dihydrocodeinone, methyldihydromorphinone, dihydrohydroxy- codeinone

Some of the main structural differences in group III and V are of interest from the spectral point of view. In group III the basic morphine struc ture is modified by ether or ester formation in cases of ethyl- and benzyl-morphine and diamorphine and ?-monoacetyl morphine respectively. In N-allyl normorphine and morphine-N-oxide the methyl group associated with the N-atom in morphine has been substituted by an allyl group or an oxygen atom respectively. Pseudomorphine is believed to be a dimer of morphine. Group V compounds are divided into two groups; the dihydro-morphine and codeine and the keto containing morphine derivatives.

The spectra of the compounds in the five groups will be discussed by comparing the spectra of various members in each groups. Thebaine shows hyperconjugation in the C ring system which affects the absorption of light. The spectrum of thebaine (figure 42) is characterized by a higher ? maximum value than morphine (about five times greater) or dihydromorphine. The spectra of neopine (figure 41), codeine (figure 40) and morphine (figure 39) are almost identical in respect to the position of the absorption maxima and corresponding ? values, as well as in the general shape of the curve. The spectra of morphine salts (figure 39) are similar, except that the absorption of morphine sulphate is double that of the other salts or that of the base because of the presence of two moles of morphine per mole of morphine sulfate. There is no inflection point in the spectra of morphine HI, whereas other morphine salts show this characteristic in the region 230-240 m ?. The spectra of dihydromorphine (figure 43) and dihydrocodeine (figure 44) show absorption from 285-286 m ?. with ? values of 1700, while other morphine derivatives absorb in the same region with ? values of only 1500. The spectra of the ethers of morphine, e.g. ethyl- and benzyl-morphine (figures 49 and 50), are similar to the spectra of codeine and neopine except that the ? values have increased from 1500 to 1600 and 1800 respectively. The spectra of esters of morphine, e.g. mono- and diacetyl morphine (figures 51 and 52) are different. The former spectrum has a maxima at 287 with an ? value of about 1600, while the latter spectrum exhibits a hypsochromic shift to 281 m ?. with an ? value of 1300. The additional acetyl substituent on the alcoholic OH appears to have brought about both a hypo- and hypso-chromic effect.

The spectra of N-allyl-normorphine (figure 55) and morphine-N-oxide resemble the morphine spectrum. The spectrum of pseudo-morphine (figure 56) is very different from that of morphine, with a broad absorption band showing a maximum at 229 m?; and an ? value of about 37,000. There are two inflection points located at 260 m?. and 282 m ?. The spectrum of Acedicone®HCl (figure 53) is similar to that of morphine except that a slight hypsochromic shift has occurred, locating the maximum of absorption at 280 m ?. The spectra of the group V compounds are characterized by a slight hypo and hypsochromic effect compared with the spectrum of morphine. The absorption maxima of the salts occur in the region 280-282 m ?. and have corresponding ? values of 1210 to 1250. The spectra all have inflection points in the region 230-240 m ?.

ATLAS OF ULTRAVIOLET ABSORPTION SPECTRA OF NARCOTICS AND RELATED ALKALOIDS

FIGURES 1-4

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FIGURES 5-8

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FIGURES 9-12

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FIGURES 13-16

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FIGURES 17-20

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FIGURES 21-24

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FIGURES 25-28

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FIGURES 29-32

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FIGURES 33-36

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FIGURES 37-40

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FIGURES 41-44

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FIGURES 45-48

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FIGURES 49-52

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FIGURES 53-56

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Table II

SPECTRAL DATA FOR NARCOTIC IDENTIFICATLON ARRANGED ACCORDING TO CHEMICAL FAMILIES

Compound

No.

?Max. (m ?)

?Max

Conc (g /l.)

?Min (m ?)

?Min

Conc. (g./l.)

1. PYRANS
 
 
 
 
 
 
 
meconic acid
1
210-211
15,500 0.0107 224 12,800 0.0107
 
 
234 14,300 0.0107 261 5,000 0.0107
 
 
303 8,810 0.0107      
pyrahexyl
2 229 26,200 0.0057 249 710 0.0204
 
 
276-277
10,200 0.0204      
2. ARYLS
 
           
(a) Aryl carboxylic acids
 
           
opianic acid
4 209 15,400 0.0101 225 11,500 0.0101
 
 
229-231
12,300 0.0101 250 2,580 0.0101
 
 
282-284
13,800 0.0101      
(b) Aryl piperidines
 
           
cocaine
5 230 15,600 0.0103 216 8,390 0.0103
 
 
274 977 0.1032 261 720 0.1032
 
 
281 794 0.1032 279 760 0.1032
cocaine. HCl
5 233 12,400 0.0101 211 4,200 0.0101
 
 
274 1,060 0.2515 261 790 0.2515
ecgonine
6
218-219
5,610 0.0186 247 1,500 0.0372
 
 
274-275
2,800 0.0372      
pethidine
7 252 176 0.5080 250 152 0.5080
 
 
258 210 0.5080 255 142 0.5080
 
 
264 157 0.5080 262 120 0.5080
pethidine. HCl
7
251-252
176 0.5080 248 147 0.5080
 
 
257 217 0.5080 254 160 0.5080
 
 
263 174 0.5080 261 160 0.5080
ethylpethidine. HCl
8 251 165 0.5120 235 83 0.5120
 
 
257 201 0.5120 254 148 0.5120
 
 
263 152 0.5120 261 132 0.5120
dl-?-prodine
9 252 171 0.5400 240 105 0.5400
 
 
258 207 0.5400 255 142 0.5400
 
 
264 154 0.5400 262 118 0.5400
dl-?-prodine. HCl
9 251 168 0.4960 236 92 0.4960
 
 
257 203 0.4960 254 142 0.4960
 
 
263 151 0.4960 261 130 0.4960
dl-?-prodine. HCl
10 252 175 0.5200 237 97 0.5200
 
 
257 212 0.5200 254 162 0.5200
 
 
263 172 0.5200 261 158 0.5200
hydroxypethidine
11 277 2,260 0.0527 248 132 0.0527
hydroxypethidine. HCl
11 275 1,960 0.1010 247 172 0.1010
methylketobemidone
12
281-282
2,350 0.0496 252 250 0.0496
methylketobemidone. HCl
12 280 2,070 0.1016 250 355 0.1016
ketobemidone
13 281 2,370 0.0500 250 285 0.0500
ketobemidone. HCl
13 280 2,270 0.1016 251 435 0.1016
propylketobemidone
14
280-282
2,320 0.0512 252 260 0.0512
acetoxyketobemidone. HCl
15 271 482 0.2468 247 217 0.2468
 
 
285-286
465 0.2468 278 439 0.2468
(c) Diarylalkoneamines
 
           
isomethadone
16 259 608 0.2800 256 562 0.2800
 
 
265 561 0.2800 263 540 0.2800
 
 
299 620 0.2800 277 380 0.2800
isomethadone. HCl
16
258-259
569 0.2500 256 558 0.2500
 
 
264 565 0.2500 261 560 0.2500
 
 
296 751 0.2500 274 470 0.2500
pipidone
17 259 697 0.2240 256 679 0.2240
 
 
265 612 0.2240 264 600 0.2240
 
 
299 587 0.2240 278 390 0.2240
pipidone. HCl
17 258 599 0.2505 256 590 0.2505
 
 
264 585 0.2505 262 570 0.2505
 
 
296 759 0.2505 274 490 0.2505
dl-methadone
18 259 883 0.2032 258 860 0.2032
 
 
295-296
486 0.2032 279 419 0.2032
dl-methadone. HCl
18 253 499 0.5080 251 480 0.5080
 
 
259 542 0.5080 256 492 0.5080
 
 
264 513 0.5080 263 500 0.5080
 
 
292 557 0.5080 274 390 0.5080
d-methadone
18 259 861 0.2112 258 840 0.2112
 
 
295-296
474 0.2112 279 405 0.2112
d-methadone. HCl
18 253 478 0.5050 251 465 0.5050
 
 
259 529 0.5050 256 468 0.5050
 
 
265 505 0.5050 263 490 0.5050
 
 
292 553 0.5050 274 379 0.5050
l-methadone
18 259 866 0.2224 258 870 0.2224
 
 
295-296
478 0.2224 280 425 0.2224
l-methadone HCl
18 253 491 0.5040 250 480 0.5040
 
 
259 540 0.5040 256 480 0.5040
 
 
264 521 0.5040 262 500 0.5040
 
 
292 557 0.5040 275 380 0.5040
phenadoxone
19
259-260
861 0.2032 258 850 0.2032
 
 
296 570 0.2032 279 462 0.2032
phenadoxone HCl
19 253 465 0.2580 251 448 0.2580
 
 
259 513 0.2580 256 448 0.2580
 
 
265 495 0.2580 263 485 0.2580
 
 
292 581 0.2560 275 378 0.2580
dl-?-methadyl acetate HCl
20 253 363 0.5240 237 150 0.5240
 
 
258 432 0.5240 255 350 0.5240
d-?-methadyl acetate HCl
20 253 365 0.5000 238 155 0.5000
 
 
258 434 0.5000 255 350 0.5000
l-?-methadyl acetate HCl
20 253 355 0.4920 238 158 0.4920
 
 
258 422 0.4920 255 345 0.4920
(d) Arylethylamines
 
           
mescaline.H2SO4 - water
21 269 1,470 0.2240 252 680 0.2240
80 per cent ethanol
21 269 1,480 0.1300 254 739 0.1300
trichocereine HCl
22 269 756 0.2780 253 365 0.2780
narceine
23 270 9,620 0.0203 252 7,300 0.0203
narceine HCl
23 208 56,900 0.0040 250 4,530 0.0203
 
 
277 15,500 0.0203      
ethylnarceine HCl
24
208-209
51,100 0.0041 250 5,800 0.0202
 
 
277-278
15,500 0.0198      
3. ISOQUINOLINES
 
           
(a) Dihydroisoquinolines
 
           
cotarnine - water
25
254-255
11,400 0.0094 237 7,700 0.0094
 
 
331 8,460 0.0094 294 3,100 0.0094
I00 per cent ethanol
25
255-256
7,450 0.0206 246 6,800 0.0206
 
 
289-290
3,830 0.0206 279 3,250 0.0206
 
 
335-336
5,690 0.0206 304 2,820 0.0206
water+HCl
25 255 12,100 0.0094 236 6,900 0.0094
 
 
330-332
8,490 0.0094 287 2,150 0.0094
100 per cent ethanol+HCl
25
258-259
6,220 0.0206 240 3,850 0.0206
 
 
332-335
4,040 0.0206 292 1,150 0.0206
hydrastinine chloride
26 249 20,500 0.0042 225 6,100 0.0042
 
 
307 6,690 0.0208 270 760 0.0208
 
 
323 2,920 0.0208      
(b) Phthalideisoquinolines
 
           
narcotine
27 209 73,500 0.0020 263 1,800 0.0758
 
 
291 4,020 0.0758 294 3,900 0.0758
 
 
309-310
4,910 0.0758      
narcotine.HCl
27 211 58,000 0.0051 268 1,450 0.0510
 
 
291 2,520 0.0510 294 2,420 0.0510
 
 
313 3,510 0.0510      
(c) Benzylisoquinolines
 
           
papaverine
28 239 68,200 0.0047 215 21,000 0.0047
 
 
279-280
7,170 0.0311 261 5,900 0.0311
 
 
314 3,990 0.0311 305 2,650 0.0311
 
 
327 4,720 0.0311 319 3,450 0.0311
papaverine.HCl
28
249-250
48,900 0.0067 214 17,900 0.0067
 
 
280-282
6,360 0.0134 269 5,500 0.0134
 
 
311 6,590 0.0134 294 5,420 0.0134
dioxyline.H 3PO 4
29 252 56,400 0.0040 215 19,000 0.0040
 
 
284-285
6,470 0.0202 270 5,350 0.0202
 
 
309-310
7,950 0.0202 292 6,180 0.0202
 
 
335 6,230 0.0202 327 5,800 0.0202
dl-laudanine
30 283 6,800 0.0240 255 900 0.0240
cryptopine
31 234 10,700 0.0166 222 8,800 0.0166
 
 
286 5,880 0.0416 258 1,180 0.0416
protopine
32( 1)
290-291
9,270 0.0204 272 7,320 0.0204
 
( 2)
290-291
10,100 0.0200 266 7,080
0.0200
4. PHENANTHRENES
 
           
(a) Phenanthroisoquinolines
 
           
apomorphine.HCl
33 211 32,400 0.0042 247 6,200 0.0105
 
 
272 16,300 0.0105      
morphothebaine.HCl
34 217 34,200 0.0042 249 5,300 0.0208
 
 
268 13,600 0.0208 271 13,200 0.0208
 
 
276 14,300 0.0208 289 6,850 0.0208
 
 
298 7,650        
(a) Phenanthroethanoamines
 
           
thebenine.HCl
35
217-218
21,500 0.0102 231 16,000 0.0102
 
 
257 37,500 0.0102 279 9,400 0.0102
 
 
300 13,400 0.0102 312 11,000 0.0102
 
 
319-320
11,400 0.0102 324 11,000 0.0102
 
 
329-330
11,400 0.0102      
(c) Iminoethanophenanthrenes
 
           
racemorphan
36 219 9,000 0.0109 218 9,200 0.0109
 
 
283 2,350 0.0544 251 212 0.0544
racemorphan.HBr
36
279-280
1,900 0.1022 245 23.5 0.1022
levorphan.C 4H 6O 6
36 279 2,000 0.1064 244 32.0 0.1064
racemethorphan
37
220-221
7,510 0.0206 218 7,420 0.0206
 
 
281 2,320 0.1032 248 158 0.1032
 
 
289 2,110 0.1032 287 2,050 0.1032
racemethorphan.HBr
37 219 7,740 0.0103 216 7,600 0.0103
 
 
278 2,000 0.1032 245 100 0.1032
dextromethorphan.HBr
37 218 7,560 0.0106 215 7,400 0.0102
 
 
278 2,040 0.1016 246 135 0.1016
levomethorphan.HBr
37
219-220
7,960 0.0106 217 7,850 0.0102
 
 
278 2,010 0.1016 246 192 0.1016
sinomenine.HCl
38 265 5,230 0.0416 248 4,500 0.0416
(d) Iminoethanophenanthrofurans
 
           
morphine
39 287 1,510 0.1046 263 465 0.1046
morphine. HCl
39 209 26,200 0.0103 261 490 0.1030
 
 
285 1,540 0.1030      
morphine. HI
39 285 1,510 0.1056 262 515 0.1056
(morphine) 3H 3SO 4
39 211 46,400 0.0107 261 930 0.1068
 
 
285 3,000 0.1068      
codeine
40
211-212
24,000 0.0107 263 535 0.1072
 
 
286 1,550 0.1072      
codeine. H 3PO 4
40 212 25,500 0.0102 261 442 0.1010
 
 
284 1,650 0.1010      
neopine.HBr
41 284 1,490 0.1000 258 380 0.1000
thebaine
42 285 7,330 0.0205 256 3,200 0.0205,
dihydromorphine
43 286 1,700 0.1008 258 295 0.1008
dihydrocodeine
44
284-285
1,720 0.1016 258 515 0.1016
dihydromorphinone
45
282-283
1,230 0.0976 265 790 0.0976
dihydromorphinone.HCl
45 280 1,220 0.1002 261 625 0.1002
dihydrocodeinone
46
282-283
1,270 0.1040 264 725 0.1040
dihydrocodeinone.C 4H 6O 6
46 280 1,220 0.1006 261 582 0.1006
methyldihydromorphinone
47
284-285
1,280 0.0984 267 760 0.0984
methyldihydromorphinone.HCl.
47 282 1,250 0.1006 262 670 0.1006
dihydrohydroxycodeinone
48 283 1,250 0.1008 265 730 0.1008
dihydrohydroxycodeinone.HCl
48 280 1,210 0.1010 263 670 0.1010
ethylmorphine
49 286 1,680 0.1000 265 542 0.1000
ethylmorphine.HCl
49 211 26,800 0.0103 208 25,400 0.0103
 
 
283-284
1,610 0.1002 261 530 0.1002
benzylmorphine
50
285-286
1,820 0.1008 265 880 0.1008
benzylmorphine.HCl
50 213 31,600 0.0102 262 950 0.1002
 
 
283-284
1,860 0.1002      
?-monoacetylmorphine
51 287 1,660 0.1008 262 705 0.1008
diamorphine (diacetyl-morphine)
52 281 1,820 0.1080 255 400 0.1000
diamorphine.HCl
52 278 1,800 0.1080 252 430 0.1000
Acedicon®.HCl
53 280 1,410 0.1006 258 485 0.1006
morphine-N-oxide
54 209 27,700 0.0052 260 570 0.0516
 
 
285 1,630 0.0516      
N-allyl-normorphine.HCl
55
209-211
24,200 0.0101 260 483 0.1010
 
 
285 1,520 0.1010      
pseudomorphine
56
222-20
36,700
0.085
-
-
-

Indexes

(a) Name index for ultraviolet spectra of narcotics and related compounds

This index includes alphabetically the common names and the chemical names of the compounds studied. The number following the name refers to the number of its spectrum. More than one common name is given for some compounds. The chemical name is listed showing the fundamental structure first, followed by the substitu ents, thus 5,6-dimethoxy-2-formylbenzoic acid is listed under b; benzoic acid, 5,6-dimethoxy-2-formyl.

NAME INDEX FOR ULTRAVIOLET SPECTRA OF NARCOTICS AND RELATED COMPOUNDS

Acedicon®, HCl, 53

dl-?-acetyl methadol, HCl, 20

d-?-acetyl methadol, HCl, 20

l-?-acetyl methadol, HCl, 20

dl-amidone, 18

dl-amidone, HCl, 18

d-amidone, 18 d-amidone, HCl, 18

l-amidone, 18

l-amidone, HCl, 18

apomorphine, HCl, 33

Bemidone, 11

Bemidone, HCl, 11

benzoic acid, 3

benzoic acid, 5,6-dimethoxy-2-formyl, 4

cocaine, 5

cocaine, HCl, 5

codeine, 40

codeine, H 3PO 4, 40

codeine, dihydro, 44

codeinone, dihydro, 46

codeinone, dihydro, C 4H 6O 6, 46

codeinone, dihydro, enol acetate, HCl, 53

codeinone, dihydrohydroxy, 48

codeinone, dihydrohydroxy, HCl, 48

cotarnine, 25

cryptopine, 31

Demerol®, 7

Demerol®, HCl, 7

dextromethorphan, HBr, 37

diamorphine, 52

Dicodid®, 46

Dicodid®, C4H6O6, 46

Dilaudid®, 45

Dilaudid®, HCl, 45

Dionin, 49

Dionin, HCl, 49 dioxyline, 11/2H3PO4, 29

Dromoran®, 36

Dromoran®, HBr, 36

l-Dromoran®, C 4H 6O 6, 36

ecgonine, 6

ecgonine, benzoyl methyl, 5

ecgonine, benzoyl methyl, HCl, 5

Eukodal®, 48

Eukodal®, HCl, 48

Genomorphine, 54

Heptalgin, 19

Heptalgin, HCl, 19

dl-3-heptanone,6-dimethylamino-4,4-diphenyl,18

dl-3-heptanone,6-dimethylamino-4,4-diphenyl, HCl, 18

d-3-heptanone,6-dimethylamino-4,4-diphenyl, 18

d-3-heptanone,6-dimethylamino-4,4-diphenyl, HCl, 18

l-3-heptanone,6-dimethylamino-4,4-diphenyl, 18

l-3-heptanone,6-dimethylamino-4,4-diphenyl,HCl, 18

3-heptanone,6- ( N-morpholino ) -4,4-diphenyl, 19

3-heptanone,6-(N-morpholino)-4,4-diphenyl, HCl, 19

dl-?-3-heptanylacetate,6-dimethylamino-4,4-diphenyl, HCl, 20

d-?-3-heptanylacetate,6-dimethylamino-4,4-diphenyl, HCl, 20

l-?-3-heptanylacetate,6-dimethylamino-4,4-diphenyl, HCl, 20

Heroin, 52

Heroin, HC1, 52 dl-3-hexanone,6-dimethylamino-4,4-diphenyl-5-methyl, 16

dl-3-hexanone,6-dimethylamino-4,4-diphenyl-5-methyl, HCl, 16

3-hexanone,6-piperidino-4,4-diphenyl-5-methyl, 17

3-hexanone,6-piperidino-4,4-diphenyl-5-methyl, HCl, 17

hydrastinine, Cl, 26

hydrocodone, 46

hydrocodone, C 4H 6O 6, 46

isoamidone, 16

isoamidone, HCl, 16

isomethadone, 16

isomethadone, HCl, 16

isoquinoline,6,7-dimethoxy-1- (4'-ethoxy-3'-methoxy benzyl ) 3-methyl, 1?H 3PO 4, 29

isoquinoline,6,7-dimethoxy-l-veratryl, 28

isoquinoline,6,7-dimethoxy-l-veratryl, HCl, 28

ketobemidone, 13

ketobemidone, HCl, 13

ketobemidone, acetoxy, HCl, 15

ketobemidone, methyl, 12

ketobemidone, methyl, HCl, 12

ketobemidone, propyl, 14

dl-laudanine, 30

levomethorphan, HBr, 37

levorphan, C 4H 6O 6, 36

meconic acid, 1

mescaline, H 2SO 4, 21

dl-methadone, 18

dl-methadone, HCl, 18

d-methadone, 18

d-methadone, HC1, 18

l-methadone, 18

l-methadone, HCl, 18

dl- ?-methadyl acetate, HCl, 20

d- ?-methadyl acetate, HCl, 20

l- ?-methadyl acetate, HCl, 20

dl-methorphan base, 37

dl-methorphan, HCl, 37

d-methorphan, HCl, 37

l-methorphan, HCl, 37

dl-methorphinan, 36

dl-methorphinan, HBr, 36

metopon, 47

metopon, HCl, 47

dl-morphan base, 36

dl-morphan, HBr, 36

l-morphan, C 4H 6O 6, 36

dl-morphinan, 3-hydroxy-N-methyl, 36

dl-morphinan, 3-hydroxy-N-methyl, HBr, 36

l-morphinan, 3-hydroxy-N-methyl, C 4H 6O 6, 36

dl-morphinan, 3-methoxy-N-methyl, 37

dl-morphinan, 3-methoxy-N-methyl, HBr, 37

d-morphinan, 3-methoxy-N-methyl, HBr, 37

l-morphinan, 3-methoxy-N-methyl, HBr, 37

morphine, 39

morphine, HCl, 39

morphine, HI, 39

morphine, H 2SO 4, 39

morphine, benzyl, 50

morphine, benzyl, HCl, 50

morphine, diacetyl, 52

morphine, diacetyl, HCl, 52

morphine, dihydro, 43

morphine, ethyl, 49

morphine, ethyl, HC1, 49

morphine, ?-monocetyl, 51

morphine-N-oxide, 54

morphinone, dihydro, 45

morphinone, dihydro, HCl, 45

morphinone, methyl dihydro, 47

morphothebaine, HCl, 34

nalorphine, HCl, 55

narceine, 23

narceine, HCl, 23

narceine, ethyl, HCl, 24

narcotine, 27

narcotine, HCl, 27

neopine, HBr, 41

Nisentil®, 9

Nisentil®, HCl, 9

?-Nisentil®, HCl, 10

normorphine, N-allyl, HCl, 55

opianic acid, 4

oxycodone, 48

oxycodone, HCl, 48

papaverine, 28

papaverine, HCl, 28

Paveril®, 1?H 3PO 4, 29

pethidine, 7

pethidine, HCl, 7

pethidine, ethyl, HCl, 8

pethidine, hydroxy, 11

pethidine, hydroxy, HCl, 11

phenadoxone, 19 phenadoxone, HCl, 19

phenethylamine,-3,4,5-trimethoxy, H 2SO 4, 21

?-phenethylamine, 3,4,5-trimethoxy-N-dimethyl, HCl, 22

dl-?-( cis ) piperidine, 1,3-dimethyl-4-phenyl-4-propionoxy, 9

dl-?-(cis)piperidine, 1,3-dimethyl-4-phenyl-4-propionoxy, HCl, 9

dl-?-(trans) piperidine, 1, 3-dimethyl-4-phenyl-4-propionoxy, HCl, 10

piperidine, ethyl-1-methyl-4-phenyl-4-carboxylate, 7

piperidine, ethyl-1-methyl-4-phenyl-4-carboxylate, HCl, 7

piperidine, ethyl-1-methyl-3-ethyl-4-phenyl-4-carboxylate, HCl, 8

piperidine, ethyl-1-methyl-4-(m-hydroxyphenyl)-4-carboxylate, 11

piperidine, ethyl-1-methyl-4-(m-hydroxyphenyl)-4-carboxylate, HC1, 11

4-piperidyl ethyl ketone, 4-(m-acetoxyphenyl)-l-methyl, HCl, 15

4-piperidyl ethyl ketone, 4-(m-hydroxyphenyl)-l-methyl, 13

4-piperidyl ethyl ketone, 4-(m-hydroxyphenyl) -1-methyl, HCl, 13

4-piperidyl methyl ketone-4-(m-hydroxyphenyl)-l-methyl, 12

4-piperidyl methyl ketone-4-(m-hydroxyphenyl)-1-methyl, HCl, 12

4-piperidyl propyl ketone-4- (m-hydroxyphenyl) -1-methyl, 14

pipidone, 17

pipidone, HCl. 17

dl-?-prodine, 9

dl-?-prodine, HCl, 9

dl-?-prodine, HCl, 10

protopine, 32

pseudomorphine, 56

parahexyl, 2

pyran, 1-hydroxy-3-n-hexyl-6,6,9-trimethyl-7,8,9,10-tetrahydro-6-dibenzo, 2

1,4-pyran,3-hydroxy-4-oxo-2,6-dicarboxylic acid, 1

racemethorphan, 37

racemethorphan, HBr, 37

racemorphan, 36

racemorphan, HBr, 36

sinomenine, HCl, 38

synhexyl, 2

thebaine, 42

thebaine, acetyl, demethyldihydro, HCl, 53

thebenine, HCl, 35

trichocereine, HCl, 22

2-tropane,3-hydroxy, carboxylic acid, 6

(b) Formula index for spectra

The formulae are listed in increasing order of C atoms, followed in turn by increasing order of H, N, and O atoms. The number of the spectrum is listed after the chemical name.

FORMULA INDEX FOR SPECTRA

C 7H 4O 7.3H 2O (?)
3-hydroxy-4-oxo-1,4-pyran-2, 6-dicarboxylic acid trihydrate (?) 1.
C 9H 15NO 3
3-hydroxy-2-tropane carboxylic acid, 6.
C 10H 10O 5
5,6-dimethoxy-2-formylbenzoic acid, 4. hydrastinine chloride monohydrate, 26.
C 11H 12NO 2C1.H 2O
hydrastinine chloride monohydrate, 26.
(C 11H 17 NO 3 2H 2SO 4 2H 2O
3,4,5-trimethoxyphenethylamine sulphate dihydrate, 21. cotarnine (anhy?), 25.
C 12H 15NO 4 (anhy ?)
4-(m-hydroxyphenyl)-1-methyl-4-piperidyl methyl ketone, 12.
C 13H 21NO 3. HCl
4-(m-hydroxyphenyl)-1-methyl-4-piperidyl methyl ketone hydrochloride, 12.
C 14H 19NO 2
ethyl-1-methyl-4-phenylpiperidine-4-carboxylate, 7.
C 14H 19NO 2.HCl
4-(m-hydroxyphenyl)-1-methyl-4-piperidyl ethyl ketone, 13.
C 15H 21NO 2
ethyl-1-methyl-4-phenylpiperidine-4-carboxylate hydrochloride, 7.
C 15H 21NO 2
4-(m-hydroxyphenyl)-1-methyl-4-piperidyl ethyl ketone, 13.
C 15H 21NO 2.HCl
ethyl-1-methyl-4-phenylpiperidine-4-carboxylate hydrochloride, 7.
C 15H 21NO 2.HCl
4-(m-hydroxyphenyl)-1-methyl-4-piperidyl ethyl ketone hydrochloride, 13
C 15H 21NO 3
ethyl-1-methyl-4-(m-hydroxyphenyl)-piperidine-4-carboxylate, 11.
C 15H 21NO 3.HCl
ethyl-1-methyl-4-(m-hydroxyphenyl)-piperidine-4-carboxylate hydrochloride, 11.
C 16H 23NO 2
(cis)- dl-?-1,3-dimethyl-4-phenyl-4-propionoxy piperidine, 9.
C 16H 23NO 2
4-(m-hydroxyphenyl)-1-methyl-4-piperidyl propyl ketone, 14.
C 16H 23NO 2.HCl
(cis)- dl-?-1,3-dimethyl-4-phenyl-4-propionoxy piperidine hydrochloride, 9.
C 16H 23NO 2.HCl
(trans)- dl-?-1,3-dimethyl-4-phenyl-4-propionoxy piperidine hydrochloride, 10.
C 17H 17NO 2.HCl 1/2H 2O
apomorphine hydrochloride hemihydrate, 33.
C 17H 19,NO 3
dihydromorphinone, 45
C 17H 19NO 3.H 2O
morphine monohydrate, 39.
C 17H 19NO 3.HCl.3H 2O
morphine hydrochloride trihydrate, 39.
C 17H 19NO 3.HCl
dihydromorphinone hydrochloride, 45.
C 17H 19NO 3.HI.2H 2O
morphine hydroiodide dihydrate, 39.
(C 17H 19NO 3) 2.H 2SO 4.5H 2O
morphine sulphate pentahydrate, 39.
C 17H 19NO 4
morphine-N-oxide, 54.
C 17H 21NO 3.H 2O
dihydromorphine monohydrate, 43.
C 17H 21NO 4
benzoylmethyl ecgonine, 5.
C 17H 21NO 4.HCl
benzoylmethyl ecgonine hydrochloride, 5.
C 17H 23NO
dl-3-hydroxy-N-methylmorphinan, 36.
C 17H 32NO.HBr 1/2H 2O
dl-3-hydroxy-N-methylmorphinan hydrobromide hemihydrate, 36.
C 17H 23NO.C 4H 6O 6.2H 2O
l-3-hydroxy-N-methylmorphinan tartrate dihydrate, 36.
C 17H 23NO 3.HCl
4-(m-acetoxyphenyl)-1-methyl-4-piperidyl ethyl ketone hydrochloride, 15.
C 17H 25NO 2.HCl
ethyl-1-methyl-3-ethyl-4-phenylpiperidine-4-carboxylate hydrochloride, 8.
C 18H 19NO 3.HCl
morphothebaine, hydrochloride, 34.
C 18H 19NO 3.HCl.H 2O
thebenine hydrochloride monohydrate, 35.
C 18H 21NO 3
codeine, 40
C 18H 21NO 3
dihydrocodeinone, 46.
C 18H 21NO 3.HBr
neopine hydrobromide, 41.
C 18H 21NO 3.2H2O(?)
methyldihydromorphinone dihydrate (?), 47.
C 18H 21NO 3.HCl
methyldihydromorphinone hydrochloride, 47.
C 18H 21NO 3.H 3PO 4.XH 2O
codeine phosphate mixture of hydrates, 40.
C 18H 21NO 3 C 4H 6O 6.2H 2O(?)
dihydrocodeinone bitartrate dihydrate (?), 46.
C 18H 21NO 4
dihydrohydroxycodeinone, 48.
C 18H 21NO 4.HCl.H 2O(?)
dihydrohydroxycodeinone hydrochloride monohydrate (?), 48.
C 18H 23NO 3
dihydrocodeine, 44.
C 18H 25NO
dl-3-methoxy-N-methylmorphinan, 37.
C 18H 25NO.HBr.H 2O
l-3-methoxy-N-methylmorphinan hydrobromide monohydrate, 37.
C 18H 25NO.HBr.H 2O
d-3-methoxy-N-methylmorphinan hydrobromide monohydrate, 37.
C 18H 25NO.HBr.2H 2O
dl-3-methoxy-N-methylmorphinan hydrobromide dihydrate, 37.
C 19H 21NO 3
thebaine, 42.
C 19H 21NO 3. HCl
N-allylnormorphine hydrochloride, 55.
C 19H 21NO 4
?-monoacetyl morphine, 51.
C 19H 23NO 3.H 2O
ethylmorphine monohydrate, 49
C 19H 23NO 3.HCl.2H 2O
ethylmorphine hydrochloride dihydrate, 49.
C 19H 23NO 4.HCl.2H 2O
sinomenine hydrochloride dihydrate, 38.
C 20H 19NO5
protopine, 32.
C 20H 21NO 4
6,7-dimethoxy-1-veratryl isoquinoline, 28.
C 20H 21NO 4.HCl
6,7-dimethoxy-1-veratryl isoquinoline hydrochloride, 28.
C 20H 23NO 4.HCl
dihydrocodeinone enol acetate hydrochloride, 53.
C 20H 25NO 4
dl-laudanine, 30.
C 21H 23NO 5
cryptopine, 31.
C 21H 23NO 5
diacetylmorphine, 52.
C 21H 23NO 5.HCl.H 2O
diacetylmorphine hydrochloride monohydrate, 52.
C 21H 27NO
dl-6-dimethylamino-4,4-diphenyl-3-heptanone, 18.
C 21H 27NO
d-6-dimethylamino-4,4-diphenyl-3-heptanone, 18.
C 21H 27NO
l-6-dimethylamino-4,4-diphenyl-3-heptanone, 18.
C 21H 27NO
dl-6-dimethylamino-4,4-diphenyl-5-methyl-3-hexanone, 16.
C 21H 27NO.HCl
dl-6-dimethylamino-4,4-diphenyl-3-heptanone hydrochloride, 18.
C 21H 27NO.HCl
d-6-dimethylamino-4,4-diphenyl-3-heptanone hydrochloride, 18.
C 21H 27NO.HCl
l-6-dimethylamino-4,4-diphenyl-3-heptanone hydrochloride, 18.
C 21H 27NO.HCl.H 2O
dl-6-dimethylamino-4,4-diphenyl-5-methyl-3-hexanone hydrochloride monohydrate, 16.
C 22H 23NO 7
narcotine, 27.
C 22H 23NO 7.HCl 1/2H 2O
narcotine hydrochloride hemihydrate, 27.
C 22H 25NO 4.1 1/2H 3PO 4.1/2H 2O
6,7-dimethoxy-1- (4'-ethoxy-3'-methoxybenzyl)-3-methylisoquinoline phosphate hemihydrate, 29.
C 22H 32O 2
1-hydroxy-3-n-hexyl-6,6,9-trimethyl-7,8,9,10-tetrahydro-6-dibenzopyran, 2.
C 23H 27NO 8.2H 2O(?)
narceine dihydrate (?), 23
C 23H 27NO 8.HCl
narceine hydrochloride, 23.
C 23H 29NO 2
dl-6- ( N-morpholino)-4,4-diphenyl-3-heptanone, 19.
C 23H 29NO 2.HCl
dl-6-(N-morpholino)-4,4-diphenyl-3-heptanone hydrochloride, 19.
C 23H 31NO 2.HCl
dl-?-6-dimethylamino-4,4-diphenyl-3-heptanyl acetate hydrochloride, 20.
C 23H 31NO 2 HCl.1/2H 2O(?)
d--?6-dimethylamino-4,4-diphenyl-3-heptanyl acetate hydrochloride hemihydrate (?), 20.
C 23H 31NO 2HCl.1/2H 2O(?)
l-?-6-dimethylamino-4,4-diphenyl-3-heptanyl acetate hydrochloride hemihydrate (?), 20.
C 24H 25NO 3
benzylmorphine, 50.
C 24H 25NO 3.HCl
benzylmorphine hydrochloride, 50.
C 24H 31NO
dl-6-piperidino-4,4-diphenyl-5-methyl-3-hexanone, 17.
C 24H 31NO.HCl
dl-6-piperidino-4,4-diphenyl-5-methyl-3-hexanone hydrochloride, 17.
C 25H 31NO 3.HCl
ethylnarceine hydrochloride, 24.
C 34H 36N 2O 6.3H 2O(?)
pseudomorphine trihydrate (?), 56.
1

The figure numbers in the "General discussion of results" refer to spectra figures 1 to 56 inclusive.

REFERENCES

001

FARMILO, C G. "Part IIIA. The Ultraviolet Spectrophotometric Method", Bulletin on Narcotics, vol. VI, No. 3-4, p 18.

002

FRIEDEL, R. A. and ORCHIN, M. Ultraviolet Spectra of Aromatic Compounds , John Wiley & Sons, Inc., New York, and Chapman & Hall, Limited, London (1953) 8.

003

FARMILO, C G, OESTREICHER, P. M., LEVI, L. "Part IB. The Common Physical Constants for Identification of Ninety Narcotics and Related Compounds," Bulletin on Narcotics, vol. VI, No 1, pp. 7-19.

004

Ibid Table I, Part IB, pp 12-17.

005

FARMILO, C. G. and LEVI, L. "Part IA, Introduction to Identification of Narcotics by Physical Methods," Bulletin on Narcotics , vol. V, No. 4, p. 20.

006

Ibid. p. 24.

007

See reference 1, spectrum 341.

008

EDWARDS, L. J. "The Hydrolyses of Aspirin. A Determination of the Thermodynamic Dissociation Constant and a Study of the Reaction Kinetics by Ultraviolet Spectrophotometry," Transactions of the Faraday Society, 46, 723-728 (1950).

009

See reference 2, spectrum 7.

010

Ibid., spectrum 47.

011

SALOMON, K. and BINA, A. F. "Ultraviolet Absorption Spectra of Mescaline Sulfate and ?-Phenethylamine Sulfate," Journal of the American Chemical Society, 68, 2402 (1946).

012

SMALL, L. F. and LUTZ, R. E. Chemistry of the Opium Alkaloids, Supplement No. 103 to the Public Health Reports, Washington (1932) 49-59.

013

Ibid., 100-131.

014

ELVIDGE, W. F. "Absorption Spectrophotometry in Pharmaceutical Analyses. Part II," Quarterly Journal of Pharmacy and Pharmacology, XIII, No. 3, 219-236 (1940).

015

KITASATO, Zenjiro "Beitrage zur Kenntnis der Isochinolin- Alkaloid," Acta Phytochimica, 3, No. 2, 175-257 (1927).

016

See reference 5.