合成路线:A new method for the synthesis of malotilate has been reported:The reaction of diisopropylmalonate (I) with carbon disulfide (II) by means of KOH in DMSO gives the dipotassium salt of diisopropyl dithiolylidene-malonate (III),which is then cyclized with 1,1,1-trichloroethane (IV) by means of KOH in the same solvent as before.
参考文献标题:Process for producing 1,3-dithiol-2-ylidene malonates
文献作者:Matsui,H.; Tanaka,H.; Yabutani,K.; Kurono,H.(Nihon Nohyaku Co.,Ltd.)
参考来源:US 4327223
合成路线:This compound can be obtained by several related ways:1) The reaction of 2-thioxo-1,3-dithiole-4,5-dicarboxylic acid (I) with methyl iodide in refluxing nitromethane gives 2-(methylsulfanyl)-1,3-dithiolium iodide (II),which is finally condensed with diisopropyl malonate (III),by means of NaH in refluxing THF.2) The cyclization of sodium acetylide (IV) with sulfur and carbon disulfide gives 1,3-dithiole-2-thione (V),which is treated first with dimethyl sulfate and then with sodium perchlorate yielding 2-(methylsulfanyl)-1,3-dithiolium perchlorate (V).Finally,this compound is condensed with diisopropyl malonate (III) by means of NaH as before.3) 1,3-Dithiole-2-thione (V) can also be obtained by cyclization of ethylene carbonate (VII) with carbon disulfide by means of K2CO3 and hexabutyldistannathiane.4) 1,3-Dithiole-2-thione (V) can also be obtained by cyclization of ethylene trithiocarbonate (VIII) with acetylene at 110-45 C,although with low yields.5) The selective hydrolysis of 2-(4-acetoxy-1,3-dithiol-2-ylidene)malonic acid diisopropyl ester (IX) gives the corresponding 4-hydroxy derivative (X),which is finally dehydrated with either,chlorosulfonic acid or sulfuric acid or thionyl chloride and DBU or phosphorous trichloride or phosphorous oxychloride.
参考文献标题:The preparation of cyclic dithia and thiaza compounds by the reaction of potassium carbonate with heterocumulenes and alkylene dibromides or carbonate catalyzed by organostannyl compounds
文献作者:Fujinami,T.; et al.
参考来源:Bull Chem Soc Jpn 1982,55(4),1174
合成路线:This compound can be obtained by several related ways:1) The reaction of 2-thioxo-1,3-dithiole-4,5-dicarboxylic acid (I) with methyl iodide in refluxing nitromethane gives 2-(methylsulfanyl)-1,3-dithiolium iodide (II),which is finally condensed with diisopropyl malonate (III),by means of NaH in refluxing THF.2) The cyclization of sodium acetylide (IV) with sulfur and carbon disulfide gives 1,3-dithiole-2-thione (V),which is treated first with dimethyl sulfate and then with sodium perchlorate yielding 2-(methylsulfanyl)-1,3-dithiolium perchlorate (V).Finally,this compound is condensed with diisopropyl malonate (III) by means of NaH as before.3) 1,3-Dithiole-2-thione (V) can also be obtained by cyclization of ethylene carbonate (VII) with carbon disulfide by means of K2CO3 and hexabutyldistannathiane.4) 1,3-Dithiole-2-thione (V) can also be obtained by cyclization of ethylene trithiocarbonate (VIII) with acetylene at 110-45 C,although with low yields.5) The selective hydrolysis of 2-(4-acetoxy-1,3-dithiol-2-ylidene)malonic acid diisopropyl ester (IX) gives the corresponding 4-hydroxy derivative (X),which is finally dehydrated with either,chlorosulfonic acid or sulfuric acid or thionyl chloride and DBU or phosphorous trichloride or phosphorous oxychloride.
参考文献标题:Reactions of ethylene di- and trithiocarbonates with acetylenes.Anomalous reaction with bromocyanoacetylene to give a thioacyl bromide
文献作者:Jones,F.N.; O'Connor,B.R.
参考来源:J Org Chem 1970,35(6),2002
合成路线:This compound can be obtained by several related ways:1) The reaction of 2-thioxo-1,3-dithiole-4,5-dicarboxylic acid (I) with methyl iodide in refluxing nitromethane gives 2-(methylsulfanyl)-1,3-dithiolium iodide (II),which is finally condensed with diisopropyl malonate (III),by means of NaH in refluxing THF.2) The cyclization of sodium acetylide (IV) with sulfur and carbon disulfide gives 1,3-dithiole-2-thione (V),which is treated first with dimethyl sulfate and then with sodium perchlorate yielding 2-(methylsulfanyl)-1,3-dithiolium perchlorate (V).Finally,this compound is condensed with diisopropyl malonate (III) by means of NaH as before.3) 1,3-Dithiole-2-thione (V) can also be obtained by cyclization of ethylene carbonate (VII) with carbon disulfide by means of K2CO3 and hexabutyldistannathiane.4) 1,3-Dithiole-2-thione (V) can also be obtained by cyclization of ethylene trithiocarbonate (VIII) with acetylene at 110-45 C,although with low yields.5) The selective hydrolysis of 2-(4-acetoxy-1,3-dithiol-2-ylidene)malonic acid diisopropyl ester (IX) gives the corresponding 4-hydroxy derivative (X),which is finally dehydrated with either,chlorosulfonic acid or sulfuric acid or thionyl chloride and DBU or phosphorous trichloride or phosphorous oxychloride.
参考文献标题:Synthesis of 1,3-dithiol-2-thiones (' Isotrithione')
文献作者:Mayer,R.; et al.
参考来源:Angew Chem.Int Ed Engl 1964,76(3),143
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