The regio- and stereoselectivity of the MCPBA-epoxidation of methyl dimorphecolate and derivatives

Methyl dimorphecolate (methyl 9(S)-hydroxy-10, 12-E,E-octadecadienoate) ( 1) was converted to resp. 9-methoxy ( 2), 9-trimethylsiloxy ( 3), 9-acetoxy ( 4), 9-chloroacetoxy ( 5) derivatives with reaction conditions optimized to high yields. The dienes were epoxidized with m-chloroperbenzoic acid to m...

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Published inIndustrial crops and products Vol. 3; no. 4; pp. 273 - 280
Main Authors Tassignon, P., de Waard, P., de Wit, D., De Buyck, L.
Format Journal Article
LanguageEnglish
Published Elsevier B.V 1995
Subjects
1H and 13C 2D NMR
9-Acyloxy
9-Methoxy
9-Trimethylsiloxy
Agrotechnological Research Institute
benzoic acid
Conjugated dienes
derivatives
Dimorphotheca sinuata
fatty acids
Instituut voor Agrotechnologisch Onderzoek
m-chloroperbenzoic acid
Mono-oxiranes
organochlorine compounds
oxidation
stereochemistry
structure
1H and 13C 2D NMR
Conjugated dienes
Mono-oxiranes
9-Acyloxy
9-Methoxy
9-Trimethylsiloxy
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Abstract Methyl dimorphecolate (methyl 9(S)-hydroxy-10, 12-E,E-octadecadienoate) ( 1) was converted to resp. 9-methoxy ( 2), 9-trimethylsiloxy ( 3), 9-acetoxy ( 4), 9-chloroacetoxy ( 5) derivatives with reaction conditions optimized to high yields. The dienes were epoxidized with m-chloroperbenzoic acid to mono-oxiranes with excellent conversion (ratio C10–C11 epoxy to C12–C13: 90:10 for 9-hydroxy; 12:88 for 9-methoxy; 26:74 for 9-siloxy; 16:84 for 9-acetoxy; 17:83 for 9-chloroacetoxy). Methanolysis of a mixture of 9-chloroacetoxy oxiranes gave the 9-hydroxy mixture with 19:81 proportions of isomers. Analysis was based on 1H and 13C NMR-spectrometry including 2D techniques.
AbstractList Methyl dimorphecolate (methyl 9(S)-hydroxy-10, 12-E,E-octadecadienoate) ( 1) was converted to resp. 9-methoxy ( 2), 9-trimethylsiloxy ( 3), 9-acetoxy ( 4), 9-chloroacetoxy ( 5) derivatives with reaction conditions optimized to high yields. The dienes were epoxidized with m-chloroperbenzoic acid to mono-oxiranes with excellent conversion (ratio C10–C11 epoxy to C12–C13: 90:10 for 9-hydroxy; 12:88 for 9-methoxy; 26:74 for 9-siloxy; 16:84 for 9-acetoxy; 17:83 for 9-chloroacetoxy). Methanolysis of a mixture of 9-chloroacetoxy oxiranes gave the 9-hydroxy mixture with 19:81 proportions of isomers. Analysis was based on 1H and 13C NMR-spectrometry including 2D techniques.
Methyl dimorphecolate (methyl 9(S)-hydroxy-10, 12-E,E-octadecadienoate) (1) was converted to resp. 9-methoxy (2), 9-trimethylsiloxy (3), 9-acetoxy (4), 9-chloroacetoxy (5) derivatives with reaction conditions optimized to high yields. The dienes were epoxidized with m-chloroperbenzoic acid to mono-oxiranes with excellent conversion (ratio C10-C11 epoxy to C12-C13: 90:10 for 9-hydroxy; 12:88 for 9-methoxy; 26:74 for 9-siloxy; 16:84 for 9-acetoxy; 17:83 for 9-chloroacetoxy). Methanolysis of a mixture of 9-chloroacetoxy oxiranes gave the 9-hydroxy mixture with 19:81 proportions of isomers. Analysis was based on 1H and 13C NMR-spectrometry including 2D techniques.
Author Tassignon, P.
De Buyck, L.
de Wit, D.
de Waard, P.
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Cites_doi 10.1016/S0021-9258(18)54151-X
10.1021/jo01280a032
10.1021/ja00231a081
10.1039/jr9570001958
10.1016/0009-3084(94)90070-1
10.1016/0009-3084(94)90109-0
10.1021/ja01491a034
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Issue 4
Keywords 1H and 13C 2D NMR
Conjugated dienes
Mono-oxiranes
9-Acyloxy
9-Methoxy
9-Trimethylsiloxy
Language English
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Tassignon (10.1016/0926-6690(95)00011-Z_BIB6) 1994; 71
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Snippet Methyl dimorphecolate (methyl 9(S)-hydroxy-10, 12-E,E-octadecadienoate) ( 1) was converted to resp. 9-methoxy ( 2), 9-trimethylsiloxy ( 3), 9-acetoxy ( 4),...
Methyl dimorphecolate (methyl 9(S)-hydroxy-10, 12-E,E-octadecadienoate) (1) was converted to resp. 9-methoxy (2), 9-trimethylsiloxy (3), 9-acetoxy (4),...
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StartPage 273
SubjectTerms 1H and 13C 2D NMR
9-Acyloxy
9-Methoxy
9-Trimethylsiloxy
Agrotechnological Research Institute
benzoic acid
Conjugated dienes
derivatives
Dimorphotheca sinuata
fatty acids
Instituut voor Agrotechnologisch Onderzoek
m-chloroperbenzoic acid
Mono-oxiranes
organochlorine compounds
oxidation
stereochemistry
structure
Title The regio- and stereoselectivity of the MCPBA-epoxidation of methyl dimorphecolate and derivatives
URI https://dx.doi.org/10.1016/0926-6690(95)00011-Z
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