SYNTHETIC APPLICATION OF LITHIATED TRIS(METHYLTHIO)METHANE - PREPARATION OF ALIPHATIC METHYL THIOLCARBOXYLATES FROM THE CORRESPONDING HALIDES - CONVENIENT SYNTHESIS OF TRIS(METHYLTHIO)METHANE

被引:12
作者
BARBERO, M [1 ]
CADAMURO, S [1 ]
DEGANI, I [1 ]
DUGHERA, S [1 ]
FOCHI, R [1 ]
机构
[1] UNIV TURIN,IST CHIM ORGAN,VIA P GIURIA 7,I-10125 TURIN,ITALY
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1993年 / 17期
关键词
D O I
10.1039/p19930002075
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A thorough study directed towards the synthesis of methyl thiolcarboxylates was made on the basis of the following steps: (i) conversion of alkyl halides into the corresponding trimethyl trithioortho-carboxylates by using tris(methylthio) methyllithium in THF at -78-degrees-C; (ii) selective hydrolysis of the intermediates to methyl thiolcarboxylates by using 35% aq. HBF4 in DMSO or, in some cases, in THF. The overall yields of the two stages are, usually, between 70 and 88%. By this procedure it is also possible to incorporate O-18 in the carbonyl group of thiol esters (approximately 98% isotopic purity). Furthermore, a new, convenient method for the preparation of tris(methylthio)methane as the precursor of tris(methylthio)methyllithium was developed.
引用
收藏
页码:2075 / 2080
页数:6
相关论文
共 22 条
[1]  
ADACHI A, 1982, YAKUGAKU, V31, P549
[2]  
BARBERO M, 1988, SYNTHESIS-STUTTGART, P300
[3]  
BARBERO M, 1988, SYNTHESIS-STUTTGART, P22
[4]  
BATES RB, 1983, CARBANION CHEM, V17, pCH4
[5]  
BAUER W, 1985, HOUBENWEYL E, V5, P849
[6]   SYNTHESIS OF A MODEL FOR THE BCE RING-SYSTEM OF BRUCEANTIN - CAVEAT ON THE CYCLOHEXENE -] TRANS DIAXIAL DIOL CONVERSION [J].
DAILEY, OD ;
FUCHS, PL .
JOURNAL OF ORGANIC CHEMISTRY, 1980, 45 (02) :216-236
[7]  
DEGANI I, 1979, SYNTHESIS-STUTTGART, P178
[8]   INTRAMOLECULAR AROMATIC-SUBSTITUTION WITH BISTHIOCARBOCATIONS - VARIATIONS OF LEWIS ACID, SOLVENT AND ORTHOTHIO SUBSTITUENTS [J].
GAMAGE, SA ;
SMITH, RAJ .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1990, 43 (05) :815-824
[9]   HALOGENATED EPOXIDES .9. REACTION OF TRANS-2,3-DICHLOROOXIRANE WITH DIMETHYL SULFIDE [J].
GRIESBAUM, K ;
SCARIA, PM ;
DOHLING, T .
JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (08) :1302-1305
[10]  
GROBEL BT, 1977, SYNTHESIS-STUTTGART, P357