• 대한화학회지
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• 제46권4호
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• pp.330-336
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• 2002

새로운 ${\alpha},{\beta}$-불포화Carboxanilide계열의 살균제를 개발을 목적으로 4-acetyl-3-methyl-N-phenyl-1,4-thiazine-2-Carboxamide(6)의 합성에 대하여 기술하였다. Dihydro-1,4-thiazine methyl ester 11을 산화하여 생성된 sulfoxide 7을 Pummerer 반응하여 $\alpha$-acetoxy dihydro-1,4-thiazine 10a를 얻었다. 반며에 Dihydro-1,4-thiazine Carboxanilide sulfoxide14는 동일한 반응조건 하에서 중간체 sulfonium ion의 carboxanilide기가 관여한 vinylogous Pummerer 반응의 전위에 의하여 중간체를 15를 통하여 acetoxymethyl dihydro-1,4-thiazine 18이 생성되었다. 1,4-Thiazine carboxanilide 6은 $\alpha$-acetoxy dihydro-1,4-thiazine 10a를 산촉매로 처리한 다음 생성된 21a를 가수분해하고 아닐린과 결합하여 합성하였다

• Bulletin of the Korean Chemical Society
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• 제16권7호
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• pp.609-613
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• 1995

The reaction of chloro(methylthio and arylthio)methanephosphonate (1) and Pummerer-type reaction of sulfinylmethanephosphonate (2) with nucleophiles such as aromatic compounds and thiols were examined. The direct chlorination of (methylthio and arylthio)methanephosphonate with N-chlorosuccinimide (NCS) led to the formation of monochlorinated phosphonates (1) in good yield. The reaction of 1 with aromatic compounds and thiols in the presence of stannic chloride afforded a variety of aryl(methylthio)methanephosphonates (3) and thioacetals of formylphosphonates (4), respectively. Phosphonates 3 and 4 were also obtained from the reaction of Pummerer intermediate, generated from sulfinylmethanephosphonate (2), with aromatic compounds and thiols, respectively. A versatile reaction conditions to generate Pummerer intermediate were examined. The best condition was the combination of trifluoroacetic anhydride with stannic chloride. All reactions may involve an initial formation of α-phosphoryl thiocarbocation and a subsequent nucleophilic attack of aromatic compounds and thiols.

• Archives of Pharmacal Research
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• 제26권12호
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• pp.985-989
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• 2003

An efficient synthesis of 5-chloro-3-[4-(3-diethylaminopropoxy)benzoyl]-2-(4-methoxyphenyl)benzofuran (8), a potent $\beta$-amyloid aggregation inhibitor, is described. 5-Chloro-2-(4-methoxyphenyl)benzofuran (3) was obtained by the one-pot synthesis of 4-chlorophenol with $\omega$(methylsulfinyl)-p-methoxyacetophenone (1) under Pummerer reaction conditions, and it was followed by the desulfurization of the resultant 5-chloro-3-methylthio-2-(4-methoxyphenyl)benzofuran (2e). Acylation of benzofuran 3 with 4-(3-bromopropoxy)benzoyl chloride (6) gave the ketone 7, which was converted into compound 8 by the treatment of diethylamine.