51447-08-6Relevant articles and documents
METHOD FOR PRODUCING COMPOUND HAVING CONJUGATED DIENE STRUCTURE
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Paragraph 0043, (2019/08/12)
PROBLEM TO BE SOLVED: To provide a method capable of industrially producing a conjugated diene or a conjugated triene in a short process from a raw material which is easy to obtain and handle. SOLUTION: A conjugated diene is produced from a 3-alkenal via reactions of the following first step, second step, and third step in this order: the first step of reacting a Grignard reagent with the 3-alkenal to obtain a homoallylic alcohol; a second step of reacting an esterification reagent or a halogenation reagent with the homoallylic alcohol to obtain a sulfonic ester or a halogenated product; and a third step of having a base act on the sulfinic acid ester or the halogenated product to cause an elimination reaction. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
Synthesis of naturally occurring diene and trienes by Te/Li exchange on (1Z,3Z)-butyltelluro-4-methoxy-1,3-butadiene
Dabdoub, Miguel J.,Dabdoub, Vania B.,Baroni, Adriano C.M.,Hurtado, Gabriela R.,Barbosa, Sandro L.
experimental part, p. 1666 - 1670 (2010/05/19)
(1Z,3Z)-Butyltelluro-4-methoxy-1,3-butadiene 2 was obtained by the hydrotelluration of (Z)-1-methoxy-but-1-en-3-ynes 1. The butadienyllithium 3 obtained by the Te/Li exchange reaction in the (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2 reacted with aldehydes to form the corresponding alcohols 4a-d with total retention of configuration. The alcohols formed undergo hydrolysis, resulting in the α,β,γ,δ-unsaturated aldehydes of (E,E) configuration, which are precursors of trienes obtained from natural sources. The products of this reaction were employed in the synthesis of methyl-(2E,4E)-decadienoate 7, which is a component of the flavor principles of ripe Bartlett pears. Performing the Wittig reaction of the methyl triphenylphosphorane with the deca-(2E,4E)-dienal 5a, we were able to synthesize the undeca-(1,3E,5E)-triene 6a. This compound is a sex-pheromone component of the marine brown algae Fucus serratus, Dictyopteris plagiograma, and Dictyopteris australis. Performing the Wittig reaction of methyl triphenylphosphorane with the octa-(2E,4E)-dienal 5c, the nona-(1,3E,5E)-triene 6b was synthesized. The compound obtained is a sex-pheromone component of the marine brown alga Sargassum horneri. The octa-(1,3E,5E)-triene 6c was easily obtained from hepta-(2E,4E)-dienal 5d by the Wittig reaction with methyl triphenylphophorane. This compound is a sex-pheromone component of the marine brown alga Fucus serratus.
Bridging the final gap in stereocontrolled Wittig reactions: Methoxymethoxy-armed allylic phosphorus ylides affording conjugated dienes with high cis selectivity
Wang, Qian,El Khoury, Mirella,Schlosser, Manfred
, p. 420 - 426 (2007/10/03)
After treatment with an appropriate base (butyllithium or sodium amide), 2-alkenyltris(2-methoxymethoxyphenyl)phosphonium salts carrying an allyl, crotyl, or prenyl (3-methyl-2-butenyl) side chain condense with saturated or unsaturated aldehydes to give conjugated dienes with Z/E ratios ranging from 90:10 to >99:1 and averaging 96:4. Owing to steric congestion, yields are only moderate (on average 41%; extremes 10-79%). The nonvolatile tris(2- methoxymethoxyphenyl)phosphine oxide by-product can be readily isolated and reduced to recover the phosphane starting material, or it may be hydrolyzed to the water-soluble tris(2-hydroxyphenyl)phosphine oxide.
