Silicon-carbon unsaturated compounds. 33. Regiochemistry in the photochemical formation of silenes from 1,2,2,2-tetramethyl-, 1,1,2,2-tetramethyl-, and 2-ethyl-1,2,2-trimethylphenylvinyldisilane

Ishikawa, Mitsuo; Nishimura, Yukihiro; Sakamoto, H.

doi:10.1021/om00054a035

Cited by 21 publications

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“…The formation of a photoproduct 3 can best be explained in terms of the nucleophilic attack at α silicon atom of pentamethyldisilanyloxymethyl group in the photoexcited state of 1 by methanol (path d). Indeed, it is well known that the photolysis of substituted phenylpentamethyldisilanes has four reaction pathways: 33 (path a) formation of a silene compound and a trimethylsilane, 34 (path b) formation of a silatriene compound arising from 1,3-shift of trimethylsilyl radical, which is formed via homolytic cleavage of siliconsilicon bond to the C6 position of benzene ring, [35][36][37][38][39][40][41][42][43][44][45][46] (path c) formation of a trimethylsilyl compound via elimination of a silylene, 47 (path d) formation of a direct solvolysis compound accompanied by the formation of trimethylalkoxysilane and trimethylsilane. 48,49 In relation to the photoreactions of the compounds with bis(disilanyl) group similar to the compound † This paper is dedicated to Professor Sunggak Kim on the occasion of his honorable retirement.…”

Section: Methodsmentioning

confidence: 99%

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Park¹,

Gong²

2010

Bulletin of the Korean Chemical Society

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Section: Methodsmentioning

confidence: 99%

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Park¹,

Gong²

2010

Bulletin of the Korean Chemical Society

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“…14,15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O…”

Section: 13mentioning

confidence: 99%

“…14, 15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O [23][24][25][26] , and C=C 27-31 bonds resulted in the formation of the addition products.…”

Section: 13mentioning

confidence: 99%

Photoreactions of (2-Acetoxyphenyl)pentamethyldisilane

Park¹,

Kim²

2011

Bulletin of the Korean Chemical Society

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It is well known that the photoreactions of aryldisilanes show four reaction patterns 1 since the first report on the photolysis of phenylpentamethyldisilane and (p-tolyl)pentamethyldisilane by Ishikawa et al.2 in 1975 : (path a) formation of a silene compound via elimination of a trimethylsilane 3 , (path b) formation of a silene compound arising from 1,3-shift of trimethylsilyl radical, which is formed via homolytic cleavage of silicon-silicon bond [4][5][6][7][8][9] , (path c) formation of a trimethylsilyl compound via elimination of a silylene 10,11 , (path d) formation of a direct solvolysis compound via elimination of a trimethylalkoxysilane or pentamethylalkoxydisilane. 12,13Silenes having the C=Si moiety are regarded as highly interesting intermediates. Consequently the synthesis and reactions of silenes as useful intermediates have been extensively investigated.14,15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O 23-26, and C=C 27-31 bonds resulted in the formation of the addition products.In connections with the photolysis of aryldisilanes, we recently disclosed the intramolecular reactions between the silene intermediates resulted from the photoreactions of ortho-substituted aryldisilanes and ortho-substituents to give the novel silicon-containing heterocyclic compounds such as the photoinduced intramolecular reactions of (2-substitutedphenyl)pentamethyldisilanes 32 , (2-alkoxymethylphenyl)pentamethyldisilanes 33 , 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 34 and (2-hydroxyethoxyphenyl)pentamethyldisilane. 35 We have also investigated the synthesis of siliconcontaining heterocyclic compounds through the intramolecular reactions of silacyclopropene or 1-silaallene moiety with ortho-substituents in ortho-substituted-phenylethynylpentamethyldisilanes 36. As a part of our continuous studies utilizing the silenes as reaction intermediates for the synthesis of silicon-containing heterocyclic compounds, we investigated the photoreactions of (2-acetoxyphenyl)pentamethyldisilane which has the acetoxy group as ortho substituent to phenylpentamethyldisilane because it was expected that the novel photoproducts could be formed from the intramolecular reaction of ortho-substituted acetoxy group with the silene intermediate. In this note, we would like to report the detailed photochemical study of (2-acetoxyphenyl)pentamethyldisilane.The starting (2-acetoxyphenyl)pentamethyldisilane 2 was prepared from the reaction of (2-hydroxyphenyl)pentamethyldisilane 1 35 with acetyl chloride using triethylamine as base in tetrahydrofuran at room temperature (Scheme 1).In order to investigate a possibility that the C=O bond as ortho substituent in 2 reacts intramolecularly with a silene, the photolysis of 2 was performed.Irradiation of 2 in deaerated benzene with 254nm UV light afforded two photo-Fries rearrangement products 4 (18% yield) and 5 (10% yield) along with some decomposition products of unknown structu...

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“…[2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] However, relatively little is known about the photoreactions of ortho-substituted phenylpentamethyldisilanes.…”

Section: Introductionmentioning

confidence: 99%

A Novel Photoreaction of (2-Hydroxyethoxyphenyl)pentamethyldisilane

2009

Bulletin of the Korean Chemical Society

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Photolysis of (2-hydroxyethoxyphenyl)pentamethyldisilane 2 in benzene provides a novel intramolecular cyclization photoproduct 9 which was probably formed from the intramolecular reaction to form a seven-membered ring in silatriene intermediate 7 and then the photochemical disrotatory ring closure of 1,3-butadiene moiety to cyclobutene. Irradiation of 2 in methanol afforded photoproducts 5 and 6 which were formed by the nucleophilic attack of methanol to β or α silicon atom in pentamethyldisilanyl group of the photoexcited state of 2. Compounds 10 and 11 were also formed by the same way as in the formation of the photoproducts 5 and 6 in the photolysis of (2-allyloxyethoxyphenyl)pentamethyldisilane 3 in methanol solvent. Photoreaction of (2-acetoxyethoxyphenyl) pentamethyldisilane 4 in methanol gave a photoproduct 12 which was formed via the elimination of dimethylsilylene species in the photoexcited state of 4.

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Silicon-carbon unsaturated compounds. 33. Regiochemistry in the photochemical formation of silenes from 1,2,2,2-tetramethyl-, 1,1,2,2-tetramethyl-, and 2-ethyl-1,2,2-trimethylphenylvinyldisilane

Cited by 21 publications

References 0 publications

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Photoreactions of (2-Acetoxyphenyl)pentamethyldisilane

A Novel Photoreaction of (2-Hydroxyethoxyphenyl)pentamethyldisilane

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