183144-25-4

Upstream product

• 6425-08-7 4,4'-(phenylmethylene)bismorpholine 
• 867-13-0 diethoxyphosphoryl-acetic acid ethyl ester 
• 104272-27-7 diethyl ester of 2,2-(diethylthio)ethylenephosphonic acid 
• 100-52-7 benzaldehyde 
• 183144-12-9 [2,2-Bis-ethylsulfanyl-1-(hydroxy-phenyl-methyl)-vinyl]-phosphonic acid diethyl ester 

Relevant academic research and scientific papers

Efficient synthesis of new phosphono-substituted dihydrothiopyrans via hetero Diels-Alder reaction, under thermal and high pressure conditions

New α-phosphono-β-aryl- or β-heteroaryl-substituted α,β-unsaturated dithioesters 2 were easily prepared from diethyl phosphonodithioacetate 1 and used as thiadienes in thermal or high pressure hetero Diels-Alder cycloadditions with enol and thioenol ethers. The resulting new phosphono 3,4-dihydro 2H-thiopyrans 3 were isolated in excellent yields and with a cis- or trans-diastereoselectivity depending on the conditions of the reaction as well as the structure of the reagents. Some of the thiopyrans 3 were also favourably synthesized via a domino Knoevenagel-hetero Diels-Alder sequence. (C) 2000 Elsevier Science Ltd.

Synthesis and synthetic application of phosphonoketene dithioacetals. New synthesis of dithioallenes and (α-dithiocarboxyvinyl)phosphonates

Phosphonoketene dithioacetals 3a-e were obtained in good yields by the reaction of ethyl phosphonoacetates 1a,b with 2-4 equiv of thiols 2a-c in the presence of an alkylaluminum dichloride or dialkylaluminum chlorides. Reaction of 2,2-dithio-1-phosphonovinyl anions with aldehydes afforded allylic alcohols 4-7, 11-18 in good to moderate yields. Treatment of the alcohols 4-6 with t-BuOK in THF led to symmetrical [2 + 2] cycloadducts 20-22 of 1,1-(ethylenedithio)allenes in moderate yields, while a similar reaction of the alcohols 11-13 produced a mixture of symmetrical and unsymmetrical [2 + 2] cycloadducts of 1,1-(trimethylenedithio)allenes, 23a-25a and 23b-25b, in 55-94% yields. The alcohol 15 on a similar treatment gave 3-tert-butyl-1,1-bis(ethylthio)allene (26) in quantitative yield. The structures of 20 and 23b were determined by X-ray analysis. Treatment of the alcohols 15 and 18 with trifluoromethanesulfonic acid/n-Bu4NX (X = Br, I) or triphenylphosphine/CBr4 in CH2Cl2 afforded α-phosphonodithioacryclic acid esters 34 and 35 in 25-52% yields. The tandem Michael-Wittig reaction of 35 with sodium salt of 2-pyrrolecarbaldehyde in DMF gave ethyl 3-phenyl-3H-cyclopenta[a]pyrrole-2-dithiocarboxylate (36) in 25% yield.