Ken'ichi Narita

Synthesis and properties of the first crystalline 1,4-ylide, 9-cyano-10-methyl-10-thiaanthracene☆

Thioxanthyliumperchlorat (I) reagiert mit KCN zu einem Addukt (II), das in Gegenwart von Silbersalzen zu den Thioxanthylium-Salzen (III) substituiert wird.

A novel 1,4-cycloaddition reaction of a stable 2-thianaphthalene derivative: formation and X-ray crystal structure of 3-benzoyl-1a,2-dimethoxy-carbonyl-1-methylthio-1a,7b-dihydrocyclopropa[α]naphthalene

Treatment of 1-benzoyl-2-methyl-2-thianaphthalene (1a) with dimethyl acetylenedicarboxylate leads to a novel 1, 4-cycloaddition resulting in the formation of 3-benzoyl-1a, 2-dimethoxycarbonyl-1-methvlthio-1a,7b-dihydrocyclopropa [a]naphthalene (2) whose structure has been confirmed by X-ray crystallography.

Synthesis and Properties of the First Crystalline 1,4-Ylide, 9-Cyano-10-methyl-10-thiaanthracene

Thioxanthyliumperchlorat (I) reagiert mit KCN zu einem Addukt (II), das in Gegenwart von Silbersalzen zu den Thioxanthylium-Salzen (III) substituiert wird.

Stable 2-thianaphthalenes: synthesis and reactions with electrophiles

The stable and crystalline 2-thianaphthalene derivatives 2-methyl-2-thianaphthalene-1-carbonitrile (8) and 1-benzoyl-2-methyl-2-thianaphthalene (9) have been synthesized in high yields by proton abstraction from the corresponding benzothiopyrylium salts (6) and (7) with triethylamine in ethanol. The ylidic nature of the 2-thianaphthalenes was established on the basis of spectral and chemical evidence. The reaction of the 2-thianaphthalene (8) with dimethyl acetylenedicarboxylate (DMAD) in ethanol afforded the naphthalene derivative (12), while the same reaction using benzene as a solvent although giving no naphthalene derivative, afforded the dihydrocyclopropa[a]naphthalene derivative (15) and the 5H-benzocycloheptene derivative (16). Moreover, the above reaction conducted in sulpholane solution gave, in addition to (15) and (16), a 2 : 1 adduct (17). The structure of the latter was confirmed by X-ray analysis. Treatment of compound (8) in benzene with methyl propiolate (MP) gave only a 2 : 1 adduct, (20). The reaction of the 2-thianaphthalene (9) with DMAD afforded only a dihydrocyclopropa[a]naphthalene derivative (14), whose structure was determined by X-ray crystallography. Parallel reactions with other electrophiles such as tetracyanoethylene, diphenylcyclopropenone, and diethyl azodicarboxylate gave a number of unexpected products for which reaction mechanisms are proposed.

X-ray crystal structure of a thiabenzene derivative

Abstract The first success of an X-ray analysis of a thiabenzene derivative, 1-benzoyl-2-methyl-2-thianaphthalene is described.

REACTIONS OF CYCLIC SULFOXIDES AND SULFONIUM SALTS WITH ORGANOMETALLIC REAGENTS

9-Phenyl-thioxanthen-10-oxid (I) und 1-Phenyl-2-thiochromen-2-oxid (II) werden mit Organo-Metallverbindungen zu Thiabenzol-Analogen (9,10-Diphenyl-10-thiaanthracen bzw. 1,2-Diphenyl-2-thianaphthalin) umgesetzt.