332011-48-0

Upstream product

• 123707-05-1 (3Z)-3,6-heptadienylidenetriphenylphosphonium iodide 
• 114802-11-8 ethyl 6-(7-formylheptyl)-2-methoxybenzoate 
• 50816-19-8 8-bromooctanol 
• 51732-22-0 acetaldehyde ethyl 6-chlorohexyl acetal 
• 188579-60-4 1-ethoxyethyl-13-tetradec-13-ene-7,10-dienyl ether 
• 188579-61-5 1-hydroxytetradec-13-ene-7,10-diyne 
• 188579-62-6 1-iodotetradec-13-ene-7,10-diyne 
• 188579-46-6 1-ethoxyethyl 7-octynyl ether 
• 6520-83-8 ethyl 2-methoxy-6-methylbenzoate 
• 55491-60-6 1-(1-Ethoxyethoxy)-6-bromohexane 
• 2009-83-8 6-chloro-1-hexanol 
• 332011-45-7 ethyl 6-(8-iodooctyl)-2-methoxybenzoate 
• 332011-43-5 ethyl 6-(8-chlorooctyl)salicylate 
• 332011-44-6 ethyl 6-(8-chlorooctyl)-2-methoxybenzoate 

Downstream Products

• 173446-84-9 ethyl [8(Z),11(Z),14-pentadecatrienyl]salicylate 
• 103904-73-0 6-(8(Z),11(Z),14-pentadecatrienyl)salicylic acid 

Relevant academic research and scientific papers

Synthesis of anacardic acids, 6-[8(Z),11(Z)-pentadecadienyl]salicylic acid and 6-[8(Z),11(Z),14-pentadecatrienyl]salicylic acid

11-Chloro-3-methoxy-2-undecenal was synthesized from 8-bromooctanol, and an annelation reaction with this aldehyde and ethyl acetoacetate proceeded to give the ethyl 6-(8-chlorooctyl)salicylate. Ethyl 6-(8-chlorooctyl)salicylate was converted to ethyl 6-(7-formylheptyl)-2-methoxybenzoate through the iodide after protection of the phenolic hydroxyl group. Finally, the Wittig reaction with the aldehyde and triphenylphosphonium iodides in the presence of BuLi gave the methoxybenzoates, and then treatments of these methoxybenzoates with BBr3 in CH2Cl2 and 10% NaOH in ethanol gave 6-[8(Z),11(Z)-pentadecadienyl]salicylic acid (anacardic acid 3) and 6-[8(Z),11(Z),14-pentadecatrienyl]salicylic acid (anacardic acid 4) which were isolated from plants of the anacardiaceae.

Synthesis of polyunsaturated constituents of phenolic lipids

The diene, (ZZ)-[(8,11)-pentadecadienyl]salicylic acid, (or 2-hydroxy-6-[(ZZ)-pentadeca-8,11-dienyl] acid), has been synthesised by two routes. In the first, the key intermediate methyl or ethyl 2-hydroxy-6-(7-bromoheptyl)benzoate has been converted to methyl or ethyl 2-hydroxy-6-(10-hydroxydec-8-ynyl)benzoate and thence by reaction of the corresponding bromide with 1-pentynylmagnesium bromide to methyl or ethyl 2-hydroxy-6-(pentadeca-8,11-diynyl)benzoate. Selective reduction afforded methyl or ethyl 2-hydroxy-6-[(ZZ)-pentadeca-8,11-dienyl]benzoate. An attempt to employ the Grignard reagent from methyl 2-methoxy-6-(non-8-ynyl)benzoate and reaction with 1-bromohex-2-yne was ineffective because of a side reaction of the former with ethylmagnesium bromide to give a ketone. In the third approach ethyl 2-methoxy-6-methylbenzoate was alkylated with 1-iodotetradeca-7,10-diyne and the product selectively reduced as before to the O-methyl ether ethyl ester. A variety of C14 intermediates has been prepared for the derivation of the 8(E),11(E), 8(E),11(Z) and 8(Z),11(E) stereoisomers by the alkylation procedure. A similar methodology of alkylation can be adopted for obtaining corresponding trienes in which some progress has been made commencing with the synthesis of the 8(Z),11(Z),14 compound.