Studies of the optically active compounds of Anacardiaceae Exudates. IV. The structures of the rearrangement products from the long chain alicyclic ketoalocohol of Tigaso oil in Alkali

1958 ◽  
Vol 11 (4) ◽  
pp. 538
Author(s):  
JA Lamberton
Keyword(s):  
Methyl Ether ◽  
Active Compound ◽  
Monomethyl Ether ◽  
Optically Active ◽  
Side Chain ◽  
Lithium Aluminium Hydride ◽  
Active Compounds ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Long Chain

The structure IIIa previously proposed for the β-diketone with an unsaturated side chain, obtained by the action of alkali on the optically active compound of Tigaso oil, is confirmed by the formation of methyl stearyl ketone and resorcinol monomethyl ether in the pyrolysis of the methyl ether (IV). An anomalous lithium aluminium hydride reduction of the methyl ether (IV) and other reactions are discussed. Unsuccessful attempts have been made to synthesize the tribasic acid resulting from sodium hypobromite oxidation of the β-diketone (IIIb).

Chemistry of the Podocarpaceae. XXXVII. Oxidative degradations of phyllocladene and isophyllocladene : conversion of isophyllocladene into (+)-Podocarp-8(14)-en-13-one

1972 ◽  
Vol 25 (5) ◽  
pp. 959 ◽  
Author(s):  
RC Cambie ◽  
RC Hayward
Keyword(s):  
Chromium Trioxide ◽  
Optically Active ◽  
Oxidative Decarboxylation ◽  
Lithium Aluminium Hydride ◽  
Keto Acid ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Villiger Oxidation

The ozonolysis of phyllocladene (2) and isophyllocladene (12) has been carried out under a number of different conditions and the ozonide (34) of isophyllocladene has been isolated and characterized. Conversion of phyllocladene (2) into the diacid (20) has been accomplished by several routes from the norketone (3). Isophyllocladene (12) has been converted into (+)-podocarp-8(14)-en-13-one (1), an optically active relay which is useful in synthesis. The route involves ozonolysis of isophyllocladene, Baeyer-Villiger oxidation of the keto aldehyde (25), lithium aluminium hydride reduction of the ester (27), and chromium trioxide-pyridine oxidation of the resulting keto aldehyde (32) which gives the keto acid (30) in 26% overall yield. Oxidative decarboxylation then affords the enone (1) in 14% yield.

SYNTHESIS OF 8-AZA-D-HOMO-18-NORESTRONE METHYL ETHER

1965 ◽  
Vol 43 (5) ◽  
pp. 1323-1328 ◽  
Author(s):  
Norman A. Nelson ◽  
Yasumitsu Tamura
Keyword(s):  
Acid Hydrolysis ◽  
Methyl Ether ◽  
Potassium Salt ◽  
Lithium Aluminium Hydride ◽  
Enol Ether ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Similar Series

Alkylation of the potassium salt of 1,4-dihydro-2,6-dimethoxybenzene with 2-(2-bromoethyl)piperidine yielded the bis-enol ether I, which, on acid hydrolysis, afforded the crystalline vinylogous amide II. Lithium aluminium hydride reduction of II gave two isomers of 1,2,3,4,4a,5,6,6a,8,9,10,10a-dodecahydro-7H-benzo[c]quinolizin-7-one (III). A similar series of reactions starting with 1-(2-chloroethyl)-6-methoxy-1,2,3,4-tetrahydroisoquinoline hydrochloride (V) gave two isomers of 2,3,4,4a, 6,7,11b,12,13,13a-decahydro-9-methoxy-1H-di-benzo[a,f]quinolizin-1-one (8-aza-D-homo-18-norestrone methyl ether) (IX).

Attempted Enantioselective Synthesis of Terbutaline. Unexpected Partial Racemization During Lithium Aluminum Hydride Reduction of a Secondary Amide

1995 ◽  
Vol 48 (10) ◽  
pp. 1741 ◽  
Author(s):  
AC Donohue ◽  
WR Jackson
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Optically Active ◽  
Enantioselective Synthesis ◽  
Lithium Aluminum ◽  
Secondary Amide ◽  
Lithium Aluminium Hydride ◽  
Hydride Reduction ◽  
Lithium Aluminium

Syntheses leading to compounds related to the bronchodilator (–)- terbutaline via optically active cyanohydrins suffered unexpected partial racemization during lithium aluminium hydride reduction of key amide intermediates.

Studies of the optically active compounds of Anacardiaceae exudates. III. The long-chain Alicyclic Keto Alcohols from the exudate of Campnosperma auriculata Hook. F

1958 ◽  
Vol 11 (1) ◽  
pp. 73 ◽  
Author(s):  
JA Lamberton
Keyword(s):  
Catalytic Hydrogenation ◽  
Active Component ◽  
General Structure ◽  
Optically Active ◽  
Side Chain ◽  
Active Compounds ◽  
Aliphatic Side Chain ◽  
Active Substances ◽  
Optically Active Substances ◽  
Long Chain

Terentang oil, the exudate from the Malayan tree Campnosperma auriculata Hook. f., contains optically active substances closely related to the optically active component of Tigaso oil. These substances are assigned the general structure I and differ among themselves only in the amount and location of unsaturation in the C19 aliphatic side chain. All of them by heating with ethanolic alkali and subsequent hydrogenation give a product which is mainly 3-nonadecyl phenol. Catalytic hydrogenation alone produces (+)-3-hydroxy-3-nonadecylcyclohexanone and thence by dehydration 3-nonadecylcyclohex-2-enone. Hydrocampnospermonol is a convenient starting material for the preparation of the reference substances 3-nonadecyl phenol and 3-nonadecylcyclohexanone.

Studies on epoxides. Part II. Abnormal lithium aluminium hydride reduction of cis 3,4-epoxy-5-hydroxycholestanes

1967 ◽  
Vol 8 (52) ◽  
pp. 5261-5263 ◽  
Author(s):  
E. Glotter ◽  
S. Greenfield ◽  
D. Lavie
Keyword(s):  
Lithium Aluminium Hydride ◽  
Hydride Reduction ◽  
Lithium Aluminium

A Novel Synthesis of 1-Aryl-9-alkyl-2, 3, 3a, 4, 9, 9a-hexahydro-1H-pyrrolo[2, 3-b] quinoxalines by lithium aluminium hydride reduction of N-phenyl-1-benzimidazolyl-succinimides

1973 ◽  
Vol 56 (5) ◽  
pp. 1646-1655 ◽  
Author(s):  
Quazi Ahmed ◽  
Theodor Wagner-Jauregg ◽  
Ernst Pretsch ◽  
Josef Seibl
Keyword(s):  
Lithium Aluminium Hydride ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Novel Synthesis

Studies of the optically active compounds of Anacardiaceae exudates. II. The action of Alkali on the long-chain alicyclic Keto Alcohol of Tigaso Oil

1958 ◽  
Vol 11 (1) ◽  
pp. 64 ◽  
Author(s):  
LK Dalton ◽  
JA Lamberton
Keyword(s):  
Optical Activity ◽  
Active Compound ◽  
Optical Rotation ◽  
Large Change ◽  
Optically Active ◽  
Bicyclic Compound ◽  
Compound I ◽  
Alcoholic Alkali ◽  
Rapid Reaction ◽  
Long Chain

In cold alcoholic alkali the optically active compound I from Tigaso oil undergoes a rapid reaction which involves loss of its conjugated carbonyl system, and a large change, with inversion, of its optical rotation. The reaction is interpreted as a cyclization and the product is provisionally formulated as a bicyclononane derivative IIa. In hot alcoholic alkali, IIa is not the final product ; the bicyclic compound undergoes further reaction to give a mixture in which the unsaturated monocyclic triketone VII (R=C16H31) appears to predominate, but which probably consists of a mixture of VII and VIII (R=C16H31). These can be hydrogenated to a mixture of saturated monocyclic triketones VII and VIII (R =C16H33). The same hydrogenated triketones are obtained if IIa is first hydrogenated and then heated with alcoholic alkali. These triketones are optically active and by oxidation with hypobromite, or with permanganate and then hypobromite, yield bromoform and the chemically homogeneous tribasic acid IX, which still retains optical activity. The isolation of the saturated hydroxydiketone IIb in 4 per cent, yield from hydrogenated Tigaso oil suggests that 11% is present to that extent in the original oil.

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