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ANTIMONY (ULTRA-VIOLET SPARK SPECTRUM)-continued.

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ANTIMONY (ULTRA-VIOLET SPARK SPECTRUM)-continued.

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ANTIMONY (ULTRA-VIOLET SPARK SPECTRUM)—continued.

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ARSENIC (SPARK SPECTRUM).

Exner and Haschek, Sitzungsber. kais. Akad. Wissensch. Wien,' cx. 1901.

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Absorption Spectra and Chemical Constitution of Organic Substances.Fifth Interim Report of the Committee, consisting of Professor W. NOEL HARTLEY (Chairman and Secretary), Professor F. R. JAPP, Professor J. J. DOBBIE, and Mr. ALEXANDER LAUDER, appointed to investigate the Relation between the Absorption Spectra and Chemical Constitution of Organic Substances.

THE work of two of the members of the Committee, Dr. Dobbie and Mr. Lauder, has been exclusively devoted to the investigation of certain alkaloids, and the connection between their chemical constitution and their absorption spectra, and the results they have obtained since the last meeting at Belfast constitute the substance of this report.1

NOTE. AS Sometimes the nitrates of the alkaloids are well-crystallised salts, the examination has been in certain cases made with nitrates. It is necessary to observe, however, that unlike chlorides, sulphates, and acetates, which are very diactinic and exert only a general absorption, nitric acid and the nitrates give characteristic absorption bands.2 This does not affect the spectra here referred to, but it might happen that if the effect of the nitric acid were not taken into account, erroneous conclusions could be drawn from the absorption band of the nitric acid being attributed to the organic base.

In a paper communicated to the Royal Society eighteen years ago by Hartley, it was proved that the principal alkaloids give highly characteristic absorption spectra which can be used for their identification and for ascertaining their purity. Furthermore, that alkaloids closely related to one another, like quinine and quinidine, cinchonine and cinchonidine, all contained a similar nucleus, which was probably formed by the conjugation of four pyridine or two quinoline groups, and that the opium alkaloids had also a characteristically constituted nucleus which is either a benzene or a pyridine derivative. The effect of alkyl and acetyl substitutions on the curve of absorption was demonstrated, the increased intensity of absorption of the apo-derivatives was shown and accounted for, and the occurrence of several oxidised radicals-hydroxyl, methoxyl, carbonyl, or carboxyl-in the constitution of an alkaloid was shown to be capable of causing remarkable differences in the absorption curves of the original nucleus. At the time at which this paper was published, however, little progress had been made with the investigation of the alkaloids, and it was not possible, therefore, to trace any closer connection between their structure and their spectra. In this connection, however, the relationship of the absorption curves to the differences in constitution of quinoline, dihydroquinoline, and tetrahydroquinoline, was determined by Hartley.

The Absorption Spectra of Corydaline, Berberine, and the Opium Alkaloids. The constitution of the principal members of the group of alkaloids to which corydaline and berberine belong-namely, papaverine, hydrastine,

Dobbie and Lauder, Chem. Soc. Trans., 1903, 83, pp. 605, 626.

2 Hartley, Chem. Soc. Trans., 1902, 81, and 1903, 83.

3 Phil. Trans., 1885, Part II., p. 471.

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