THE HYDROGENOLYSIS OF 3-HYDROXYMETHYLINDOLE AND OTHER INDOLE DERIVATIVES WITH LITHIUM ALUMINUM HYDRIDE

1953 ◽  
Vol 31 (9) ◽  
pp. 775-784 ◽  
Author(s):  
Edward Leete ◽  
Léo Marion
Keyword(s):  
Carboxylic Acid ◽  
Sodium Hydroxide ◽  
Ethyl Ester ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Reduction Product ◽  
Alkaline Media ◽  
Lithium Aluminum ◽  
Indole Derivatives ◽  
Alkyl Ethers

Indole-3-aldehyde, indole-3-carboxylic acid and its ethyl ester were reduced by excess lithium aluminum hydride to skatole. The expected reduction product, 3-hydroxymethylindole, was obtained by the action of sodium hydroxide on gramine methiodide. It and its alkyl ethers were readily reduced to skatole. 3-Hydroxymethylindole underwent self-condensation to 3,3′-di-indolylmethane in neutral and alkaline media, and with acidic reagents was converted to an oxygen-free polymeric substance. The mechanism of these reactions and of the hydrogenolysis is discussed

PSEUDACONITINE, AND THE STEREOCHEMICAL RELATIONSHIP OF THE HIGHLY OXYGENATED ACONITE ALKALOIDS

1963 ◽  
Vol 41 (6) ◽  
pp. 1485-1489 ◽  
Author(s):  
Y. Tsuda ◽  
Léo Marion
Keyword(s):  
Acetic Acid ◽  
Absolute Configuration ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Reduction Product ◽  
Lithium Aluminum ◽  
Partial Hydrolysis ◽  
Previous Knowledge ◽  
Relationship Of ◽  
Hydrolysis Of

An alkaloid isolated from Aconitum spicatum Stapf has been found to be identical not only with the originally described pseudaconitine but also with 'α-pseudaconitine'. The product of the partial hydrolysis of the base, i.e., veratroylpseudaconine, is dextrorotatory, and not laevorotatory as recorded in the old literature. On heating, pseudaconitine undergoes pyrolysis, loses the elements of acetic acid, and gives rise to pyropseudaconitine. This substance, on treatment with lithium aluminum hydride, is converted to demethoxyisopyropseudaconine which is identical with the Wolff–Kishner reduction product of pyraconine. This correlation establishes that pseudaconitine and aconitine possess the same absolute configuration, which, in the light of previous knowledge, is extended also to indaconitine, delphinine, mesaconitine, and jesaconitine.

THE STRUCTURE AND STEREOISOMERISM OF THREE MITRAGYNA ALKALOIDS

1960 ◽  
Vol 38 (7) ◽  
pp. 1035-1042 ◽  
Author(s):  
J. C. Seaton ◽  
M. D. Nair ◽  
O. E. Edwards ◽  
Léo Marion
Keyword(s):  
Hydrochloric Acid ◽  
Dilute Hydrochloric Acid ◽  
Lithium Aluminum Hydride ◽  
Mercuric Acetate ◽  
Aluminum Hydride ◽  
Spectroscopic Properties ◽  
Membered Ring ◽  
Reduction Product ◽  
Lithium Aluminum ◽  
Lactam Carbonyl

Isorhyncophylline, the isomer into which rhyncophylline is convertible, has been found to occur in nature. Both bases are interconvertible. Isorhyncophylline on hydrolysis with dilute hydrochloric acid is converted to an aldehyde reducible to isorhyncophyllol. When the aldehyde is reduced in the Wolff–Kishner reaction, it is also isomerized and the product is isorhyncophyllane. This reduction product is oxidized by mercuric acetate to a neutral dilactam which still contains the oxindole carbonyl and further contains a new lactam carbonyl present in a six-membered ring. Reduction of the dilactam with lithium aluminum hydride gave a product having the spectroscopic properties of an indole. This confirms the assumption previously made that in rhyncophylline, ring C is five-membered. The isomerization of rhyncophylline, mitraphylline, and formosanine is described. Formosanine has been shown to be identical with uncarine-B and thus uncarine-A is the iso base derivable from formosanine.

Colorimetric and Volumetric Assays of Colchicine in Galenicals and in Pharmaceutical Preparations

1975 ◽  
Vol 58 (6) ◽  
pp. 1171-1173 ◽  
Author(s):  
Mohamed S Karawya ◽  
Aly M Diab
Keyword(s):  
Sodium Hydroxide ◽  
Secondary Amine ◽  
Perchloric Acid ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Pharmaceutical Preparations ◽  
Amide Group ◽  
Lithium Aluminum

Abstract In the method described the amide group in the colchicine molecule is reduced with lithium aluminum hydride to the corresponding secondary amine. The latter is extracted with chloroform and then determined either colorimetrically by the copper dithiocarbamate reaction or volumetrically by dissolving in acid and titrating with sodium hydroxide or perchloric acid. The results were comparable with those obtained by the Egyptian Pharmacopoeia spectrophotometry method.

Derivative Formation for the Confirmation of Endosulfan by Gas Chromatography

1969 ◽  
Vol 52 (6) ◽  
pp. 1240-1248
Author(s):  
A S Y Chal
Keyword(s):  
Gas Chromatography ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Reduction Product ◽  
Lithium Aluminum ◽  
Agricultural Crops ◽  
Sample Extract

Abstract Chemical conversions followed by GLC analysis are described for the confirmation of residues of α- and β-endosulfan in agricultural crops. Both isomers were reduced to the same diol by lithium aluminum hydride in tetrahydrofuran. Subsequent silylation to the disilyl ether can be used for the routine confirmation of both isomers down to a level of 0.02 p pm in a 10 g sample extract. Alternatively, the insecticide or its reduction product can be acetylated. By this procedure, 0.03 ppm or more of the parent insecticide can be identified in a 10 g sample extract.

REDUCTION OF STEROIDS USING LITHIUM ALUMINUM HYDRIDE

1949 ◽  
Vol 27b (12) ◽  
pp. 902-906 ◽  
Author(s):  
G. Papineau-Couture ◽  
Gordon A. Grant ◽  
E. M. Richardson
Keyword(s):  
Carbonyl Group ◽  
Phthalic Anhydride ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Selective Reduction ◽  
Reduction Product ◽  
Lithium Aluminum ◽  
Partial Reduction ◽  
Simultaneous Production

Lithium aluminum hydride has been used successfully in the partial reduction of phthalic anhydride to phthalide, in the selective reduction of the carbonyl group of dehydroisoandrosterone-3-acetate, and in the reduction of oestrone acetate to α-oestradiol without simultaneous production of the β-isomer. A new reduction product of Δ5-3(β)hydroxyetiobilienic acid, Δ9,14-2,13-dimethyl-7(β)hydroxy-2-hydroxymethyl-1-hydroxyethyl dodecahydrophenanthrene, is also described.

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