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:

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.

(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 RESULTS 1

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.

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

FIGURES 5-8

FIGURES 9-12

FIGURES 13-16

FIGURES 17-20

FIGURES 21-24

FIGURES 25-28

FIGURES 29-32

FIGURES 33-36

FIGURES 37-40

FIGURES 41-44

FIGURES 45-48

FIGURES 49-52

FIGURES 53-56

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.

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.