19900-84-6Relevant articles and documents
Tert -Butoxide-Assisted Structural Transformation of 2-Aza-1,3,5-trienes: Fast Track to 5-Ethynyl-2-vinyl- and 2,5-Divinyl-1,3-thiazoles
Nedolya, Nina A.,Tarasova, Olga A.,Albanov, Alexander I.,Trofimov, Boris A.
, p. 4313 - 4324 (2018)
Treatment of 2-aza-1,3,5-trienes, methyl N -[2-alkoxy-1-(prop-2-ynylsulfanyl)buta-1,3-dienyl]- and methyl N -[1-(allylsulfanyl)-2-alkoxybuta-1,3-dienyl]iminoformates, which are easily obtained from lithiated alkoxyallenes, methoxymethyl isothiocyanate, and propargyl or allyl bromide, with t -BuOK or t -BuONa in DMSO-THF results in the formation of 5-ethynyl-2-vinyl- and 2,5-divinyl-1,3-thiazoles. The reactions are realized under mild conditions at ca. -30 °C for 30 minutes. An unprecedented structural transformation of the (prop-2-ynylsulfanyl)- and (allylsulfanyl)-substituted 2-aza-1,3,5-trienes into 1,3-thiazoles presumably occurs via α-deprotonation of the substituent at the sulfur atom (on the SCH 2 group) followed by intramolecular [1,5]-cyclization at the imine group and aromatization (with elimination of MeOH).
Process for preparing cephalosporin derivatives
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, (2008/06/13)
A process for the manufacture of a cephalosporin derivative of the formula I STR1 in which X is sulphur, oxygen or sulphinyl; R1 is any one of the C-3 substituents from antibacterially-active cephalosporins known in the art; R2 is hydrogen or 1-6C alkyl; R3 is hydrogen or 1-6C alkyl; and the pharmaceutically-acceptable acid-addition and base-addition salts thereof, characterized by cyclization of a compound of the formula II: STR2 or a derivative thereof in which the carbonyl group is masked, or an acid-addition salt thereof, in which R4 and R5 individually have one of the values for R2 and R3, R6 is a nitrogen-protecting group and R7 is hydrogen or any one of the cephalosporin 3-carboxylic acid protecting groups known in the art; whereafter when the product from the cyclization retains the protecting group R7 (when R7 is other than hydrogen) the protecting group R7 is replaced by hydrogen by conventional means; and whereafter when the compound of the formula I is obtained in the form of the free base or salt, and a pharmaceutically-acceptable salt or free base respectively is required, any necessary conversion between free base and salt is carried out by conventional means.