The synthesis of meso-Hexoestrol[3,4-D2] and some related specifically deuterated compounds

1974 ◽  
Vol 27 (8) ◽  
pp. 1743 ◽  
Author(s):  
DJ Collins ◽  
JJ Hobbs
Keyword(s):  
Methyl Ketone ◽  
Sodium Hydride ◽  
Dimethyl Sulphoxide ◽  
Reduction Sequence ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Methylmagnesium Iodide ◽  
High Yields ◽  
Unsaturated Nitrile ◽  
Hofmann Elimination

Condensation of p-methoxyphenylacetonitrile with p-methoxypropiophenone in the presence of sodium hydride in dimethyl sulphoxide at 65� gave (Z)-(23%) and (E)-2,3-bis(p-methoxyphenyl)pent-2-enenitrile(16%). The reduction of this α,β-unsaturated nitrile with lithium aluminium deuteride in tetrahydrofuran, and workup with D2O or with H2O, gave high yields of erythro-2,3-bis(p-methoxy-phenyl)valeronitrile[2,3-D2], or -[3-D], respectively. Conversion of the dideuteronitrile into the corresponding methyl ketone with methylmagnesium iodide, followed by a hydride reduction-tosylation-hydride reduction sequence, then demethylation, afforded meso-hexoestrol[3,4-D2]. Dehydration of (3RS,4SR)-3,4-bis(p-methoxyphenyl)hexan-2ξ-ol[3,4-D2] with phosphoryl trichloride in pyridine gave 3,4-bis(p-methoxyphenyl)hex-2-ene[4-D]. Reduction of erythro-2,3-bis(p-methoxy- phenyl)valeronitrile[3-D] to the corresponding amine followed by quaternization and Hofmann elimination afforded 2,3-bis(p-methoxypheny1)pent-1-ene[3-D].

Enolic Ortho Esters. III. Preparation of a Keto Acetal by Hydride Reduction of an Enolic Ortho Ester

1989 ◽  
Vol 42 (9) ◽  
pp. 1617 ◽  
Author(s):  
DJ Collins ◽  
LM Downes ◽  
M Kyriakou
Keyword(s):  
Lithium Aluminium Hydride ◽  
Ortho Ester ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
High Yields ◽  
Ortho Esters

Lithium aluminium hydride reduction of the enolic ortho ester 4′,4′-dimethyl-3,4,5,8-tetra-hydrospiro [2H-l-benzopyran-2,21-[1,3]dioxolan] (8) in the absence of solvent gave 6-[21-(4″,4″- dimethyl-1″,3″-dioxolan-2″-yl)ethyl]cyclohex-3-en-1-one (11) which was isomerized to the α'β-unsaturated keto acetal (10). Similarly, hydride reduction of the phenolic ortho ester 4′-methyl-3,4-dihydrospiro[2H-1-benzopyran-2,2′-[1,3]dioxolan] (12a) and the 4′,4′-dimethyl analogue (12b), afforded the corresponding phenolic acetals (14a) and (14b) respectively, in high yields.′

Cyclization of 2-(2-bromoethoxy)-acetophenones and 5-(ω-haloalkoxy)-1,5-dihydro-2H-pyrrol-2-ones – Formation of five- to eight-membered oxygen-containing heterocycles via intramolecular alkylation

2004 ◽  
Vol 82 (5) ◽  
pp. 571-578 ◽  
Author(s):  
Kirill V Nikitin ◽  
Nonna P Andryukhova
Keyword(s):  
Sodium Hydride ◽  
Spiro Compounds ◽  
Lithium Diisopropylamide ◽  
Intramolecular Alkylation ◽  
High Yields

Under basic conditions (lithium diisopropylamide or sodium hydride in THF) 2-(2-bromoethoxy)-acetophenones were transformed to 3,4-dihydro[1]benzoxepin-5(2H)-ones (homochromanones) in high yields. The preparation of novel tetrahydropyrano[2,3-b]pyrrol-6(2H)-ones and 3,4-dihydro-2H-pyrrolo[2,1-b][1,3]oxazin-6(8aH)-ones and spiro compounds was performed using similar cyclization in moderate to good yields.Key words: cyclization, lithiation, spiro heterocycles.

Chemistry of the Podocarpaceae. XXXIV. Some oxidation products of (13R)-Labda-8(17),14-dien-13-ol (Manool)

1971 ◽  
Vol 24 (11) ◽  
pp. 2365 ◽  
Author(s):  
RC Cambie ◽  
KN Joblin ◽  
AF Preston
Keyword(s):  
Nucleophilic Substitution ◽  
Potassium Permanganate ◽  
Hydroxy Acid ◽  
Methyl Ketone ◽  
Major Product ◽  
Oxidation Products ◽  
Lithium Aluminium Hydride ◽  
Methyl Ketones ◽  
Sodium Dichromate ◽  
Lithium Aluminium

Some products from the oxidation of manool (3) are examined. Potassium permanganate gives, inter alia, the hitherto unreported compound (16) while sodium dichromate gives the methyl ketone (5) and, as the major product, a mixture of (Z)- and (E)-α,β-unsaturated aldehydes (21). Hypoiodite oxidation of the methyl ketone (5) gives the α-hydroxy acid (26) in addition to the expected acid (6). Products of nucleophilic substitution have also been obtained from the hypoiodite oxidation of the methyl ketones (9) and (37). Peracid oxidation of the methyl ketone (5) gives the epoxy acetate (41) which, on reduction with lithium aluminium hydride, affords the diol (7), from which the odoriferous oxide (30) can be prepared. Oxidations leading to formation of the dione (10) are investigated.

Synthesis of 3-(4′-Methoxyphenyl)-2,2,4,4-Tetramethylpentane and Some Cyclic Analogs

1986 ◽  
Vol 39 (12) ◽  
pp. 2095 ◽  
Author(s):  
DJ Collins ◽  
HA Jacobs
Keyword(s):  
Methanesulfonic Acid ◽  
Similar Reaction ◽  
Reaction Sequence ◽  
Quinone Methides ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Clemmensen Reduction ◽  
Analogous Manner ◽  
Hydrolysis Of ◽  
Zinc Iodide

Reaction of 1-methoxy-2-methyl-1-trimethylsilyloxyprop-1-ene (8) with 1-acetoxy-1-(4′-methoxyphenyl)-2,2-dimethylpropane (7b) in the presence of zinc iodide gave 84% of methyl 3-(4′methoxyphenyl)-2,2,4,4- tetramethylpentanoate (9a), which was reduced with lithium aluminium hydride to 3-(4′-methoxyphenyl)-2,2,4,4-tetramethylpentan-1-ol(12a). Hydride reduction of the derived tosylate (12b) afforded 3-(4′-methoxyphenyl )-2,2,4,4-tetramethylpentane (5b) which upon demethylation yielded the corresponding phenol (10a). In an analogous manner, 1-acetoxy-1-(4′-methoxyphenyl)-2-methylpropane (7d) was converted into 3- (4′-hydroxyphenyl)-2,2,4-trimethylpentane (10b). By a similar reaction sequence, 6-methoxy-2,2-dimethyl-3,4- dihydronaphthalen-1(2H)-one (14) was transformed into 6-hydroxy-2,2- dimethyl-1-(1′,1′-dimethylethyl)-1,2,3,4-tetrahydronaphthalene (16b). Hydrolysis of the ester (9a) and cyclization of the resulting carboxylic acid (19) by treatment with methanesulfonic acid at 20° for 18 h afforded 3-(1′, 1′-dimethylethyl)-6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-one (20). Clemmensen reduction of this followed by demethylation yielded 1-(1′,1′-dimethylethyl)-2,2-dimethyl-2,3-dihydro-1H-inden-5-ol (21b). Attempts to oxidize the phenols (10a), (10b), (16b) and (21b) to the corresponding quinone methides by conventional methods failed.

Lithium aluminium hydride reduction of some organo-sulphur compounds.

1967 ◽  
Vol 8 (11) ◽  
pp. 971-974 ◽  
Author(s):  
Kazi Abdul Latif ◽  
Paritosh Kumar Chakraborty
Keyword(s):  
Lithium Aluminium Hydride ◽  
Sulphur Compounds ◽  
Hydride Reduction ◽  
Lithium Aluminium
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