STUDIES IN THE WAGNER-MEERWEIN REARRANGEMENT. PART I

1956 ◽  
Vol 34 (7) ◽  
pp. 991-1005 ◽  
Author(s):  
F. A. L. Anet ◽  
P. M. G. Bavin
Keyword(s):  
Formic Acid ◽  
Polyphosphoric Acid ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Ester Group ◽  
Lithium Aluminum ◽  
Methyl Ethyl ◽  
Mild Conditions ◽  
Convenient Route ◽  
Simultaneous Loss

The preparation by a convenient route of 9-methyl, ethyl, isopropyl, l-butyl, and benzyl phenanthrenes is described. This consists of the alkylation of methyl fluorene-9-carboxylate under mild conditions, reduction of the ester group with lithium aluminum hydride, and then tosylation of the carbinol. The tosyl esters so prepared rearrange to alkylphenanthrenes with simultaneous loss of the elements of toluenesulphonic acid, when heated alone or in formic acid. Dehydration of the carbinols at 160 ° with polyphosphoric acid also promotes rearrangement.

THE STRUCTURE OF MITRAPHYLLINE

1958 ◽  
Vol 36 (7) ◽  
pp. 1031-1038 ◽  
Author(s):  
J. C. Seaton ◽  
R. Tondeur ◽  
Léo Marion
Keyword(s):  
Double Bond ◽  
Experimental Evidence ◽  
Aromatic Amine ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Mineral Acid ◽  
Lithium Aluminum ◽  
Spectroscopic Evidence ◽  
Mild Conditions ◽  
Total Structure

Mitraphylline (C21H24O4N2) contains a carbomethoxyl group, and on hydrolysis gives rise to mitraphyllic acid. Spectroscopic evidence shows that the alkaloid contains two chromophores, one characteristic of an oxindole and one corresponding to the grouping CH3OOC—Ć==CH.OR. On treatment with dilute mineral acid the alkaloid gives rise to mitraphyllal (C19H24O3N2), which is a hemiacetal that no longer contains the isolated double bond and the carbomethoxyl group originally present in the alkaloid. Reduction of mitraphyllal by the Wolff–Kishner reaction gives mitraphyllane (C19H26O2N2). The dehydrogenation of mitraphyllal produced 3,4-diethylpyridine and 3-ethyloxindole. The action of lithium aluminum hydride on mitraphylline under mild conditions gave rise to mitraphyllol by reduction of the carbomethoxyl group, and under more vigorous conditions to dihydrodesoxy-mitraphyllol by reduction of the oxindole carbonyl as well. This last product has the properties of an aromatic amine. On the basis of the new experimental evidence, a total structure of mitraphylline is derived.

ANTINEOPLASTIC AGENTS: XI. N-BIS(2-BROMOETHYL)AMINES

1964 ◽  
Vol 42 (7) ◽  
pp. 1699-1706 ◽  
Author(s):  
George R. Pettit ◽  
Maurice R. Chamberland ◽  
David S. Blonda ◽  
Martyn A. Vickers
Keyword(s):  
Exchange Reaction ◽  
Antineoplastic Agents ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Efficient Synthesis ◽  
Nitrogen Mustards ◽  
Hydride Reduction ◽  
Halogen Exchange ◽  
Convenient Route

A novel halogen exchange reaction was found to accompany condensation of an acyl chloride with N-bis(2-bromoethyl)amine. Reaction between an acyl bromide and N-bis(2-bromoethyl)amine, however, gave the expected N-bis(2-bromoethyl)amide. A number of N-alkyl-N-bis(2-bromoethyl)amines were prepared by lithium aluminum hydride reduction of the corresponding N-bis(2-bromoethyl)amides. The overall transformation from N-bis(2-bromoethyl)amine presents a convenient route to certain bromo nitrogen mustards. An efficient synthesis of N-bis(2-iodoethyl)amine hydroiodide is also described.

ANTINEOPLASTIC AGENTS: X. N-BIS(2-FLUOROETHYL)AMINES

1964 ◽  
Vol 42 (3) ◽  
pp. 572-578 ◽  
Author(s):  
George R. Pettit ◽  
Robert L. Smith
Keyword(s):  
Aluminum Chloride ◽  
Antineoplastic Agents ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Potassium Fluoride ◽  
Lithium Aluminum ◽  
Nitrogen Mustards ◽  
Convenient Route

Successive conversion of N-bis(2-hydroxyethyl)-p-toluenesulphonamide (Ib) to respective dimethanesulphonate and difluoro derivatives (IIa, IIIa, and IIIc) was found to provide a convenient route to N-bis(2-fluoroethyl)amine. Reaction of N-bis(2-methanesulphonyl-oxyethyl)-p-toluenesulphonamide (IIIa) with limited quantities of potassium fluoride, in several pro tic solvents, was shown to yield N-(p-toluenesulphonyl)morpholine (IV). Utility of N-bis(2-fluoroethyl)amine as a precursor of fluoro-nitrogen mustards was illustrated by synthesis of two N-bis(2-fluoroethyl)benzylamines (IXb and Xa). Application of an aluminum chloride – lithium aluminum hydride reagent for hydrogenolysis of carbon–fluorine bonds was also suggested.

SYNTHESIS IN THE FIELD OF THE ERYTHRINA ALKALOIDS: PART I. THE SYNTHESIS OF HEXAHYDROAPOERYSOTRINE

1957 ◽  
Vol 35 (7) ◽  
pp. 651-662 ◽  
Author(s):  
B. Belleau
Keyword(s):  
Reaction Mechanisms ◽  
Polyphosphoric Acid ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Ring System ◽  
Ring Closure ◽  
Lithium Aluminum ◽  
Natural Origin ◽  
Erythrina Alkaloids ◽  
Acid Reduction

The synthesis of the complete ring system of the aromatic class of Erythrina alkaloids is described. The basic sequence involves reaction of hexahydroindole (whose preparation was studied in some detail) with phenylacetyl chloride to give the ketoamide (VII) which suffered ring closure to the desired ring system (XI) when treated with polyphosphoric acid. Reduction of XI with lithium aluminum hydride gave the corresponding base (XIII). Evidence in support of structure XI is presented. Application of the same sequence with homoveratroyl chloride as starting material led ultimately to the spiroamine (XIV) which proved identical with a sample of natural origin. The stereochemistry of the spiroamines is discussed and the reaction mechanisms involved are critically examined. The new cyclization reaction was successfully applied to the system phenylacetamide–cyclohexanone in an effort to explore its scope.

Preparation of Precocene 2 and 3,4-Epoxyprecocene 2 Deuterated Analogues at C-3, C-4 and C-3, C-4

1985 ◽  
Vol 40 (4) ◽  
pp. 556-558 ◽  
Author(s):  
F. Camps ◽  
A. Conchillo ◽  
A. Messeguer
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Deuterated Analogue ◽  
Convenient Route ◽  
Derivatives Of

A convenient route for the preparation of title compounds from benzopyran-4-one (1) and its corresponding 3,3-2H2 deuterated analogue (2) is reported. Treatment of 1 or 2 with lithium aluminum deuteride followed by dehydration afforded, respectively, 4-2H precocene (3c) or 3,4-2H2 precocene (3b). Likewise, reduction of 2 with lithium aluminum hydride and subsequent dehydration led to the formation of 3-2H precocene (3d). Finally, the corresponding 3,4-epoxy derivatives of all these compounds were prepared in good yields by conventional procedures.

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