[Molecules: 12] [Related articles/posters: 001 018 024 039 052 ]

Reaction of a-trimethylsilylmethyl-substituted aromatic N-heterocycles with methyl perfluoro(2-methylprop-1-enyl) ether

T. Konakahara, Y. Ono and S. Tamura

In order to compare the reactivity of methyl perfluoro(2-methylprop-1-enyl) ether 1 with perfluoro(2-methylpent-2-ene) 2, the reaction of 1 with 2-(trimethylsilylmethyl)pyridines 3 and their analogues was performed. When a mixture of 2-(trimethylsilylmethyl)pyridine 3a and potassium fluoride was treated with 1 in THF, a methylated adduct, 2-[2-methoxy-3,3-bis (trifluoromethyl)but-1-enyl]pyridine 4a, was obtained in 50% yield instead of a cyclized adduct, 2-pentafluoroethyl-3-trifluoromethyl-4H-quinolizin-4-one 5a, which was given from 2.¹ However, 2-(trimethylsilylmethyl)quinoline 6a gave an adduct, 2-(4,4,4-trifluoro-2-methoxy-3-trifluoromethylbut-1-enyl) quinoline 7a in 58% yield, accompanied by 23% of the corresponding methylated adduct. The analogous reaction of 2-(trimethylsilylmethyl)benzothiazole is also discussed.

1. T. Konakahara, T. Murayama, K. Sano and S. Kubota, J. Chem. Res. (M), 1996, 844.

Introduction

Results and discussion

Reaction of 2-(trimethylsilylmethyl)prydine (3) with methyl perfluoro(2-methylprop-1-enyl) ether (1)

Reaction of 2-(trimethylsilylmethyl)quinolines (6) with the ether (1)

Reaction of 2-(trimethylsilylmethyl)benzothiazole (10) with the ether (1)

Attempts to cyclize the adduct (11)

Reaction of the adduct 11 with sodium alkoxides

Reaction mechanism