Reactions of fluoride ion sources with haloalkyl derivatives of phenazasilines and phenoxasilins

Corey, Joyce Y.; Corey, E. Raymond; Chang, Vincent H. T.; Hauser, Michael A.; Leiber, Mark A.; REINSEL, T. E.; RIVA, M. E.

doi:10.1021/om00085a015

Cited by 27 publications

(3 citation statements)

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“…On the other hand, nucleophilic displacement at silicon of chloromethyl substituted silanes is known to undergo rearrangement reactions of organic groups from silicon to carbon. The rearrangement is induced by various nucleophiles and the pathway of the reaction is markedly affected by the reaction medium (39)(40)(41)(42)(43)(44). Pentacordinate transition states are often invoked to account for the products formation.…”

Section: Scheme 5 Tran-silylation Of Bis (Trimethylsilyl) Acetamidementioning

confidence: 99%

UV Curable Silicones from Acryloxymethyldimethylacryloxysilane

Chu¹

2000

ACS Symposium Series

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A facile preparation of acrylate terminated silicones by the condensation reaction between the readily available silanol terminated silicone fluids and acryloxymethyldimethylacryloxysilane is described. The simplicity of the reaction provides a practical route for the preparation of UV curable silicones. The surprising ease of the reaction between the silane and silanol is attributed to the possible hypervalent silicon transition state even though 29 Si-NMR evidence suggests the silane is tetracovalent.The constant quest for faster curing silicones for various industrial applications has led to many important developments for radiation curable silicones in recent years (1,2). Notable examples among these developments include cationic curing silicones (5-7), free-radical curing thiol-ene (8-10% acrylate or acrylamide (11-14) functional silicones, and photohydrosilylation curing silicones (15)(16)(17). Each of these developments offers certain advantages but at the same time imposes limitations in their applications. Cationic curing silicones using iodonium or sulfonium salts as the photoinitiators for the curing of epoxy and vinyl ether functional silicones allows fast cure without the tacky surface that is often associated with the oxygen inhibition of the acrylate cure. However, the high cost of the photoinitiators and the compatibility of the photoinitiator with silicones are problems. Also, acid generated from the decomposition of the onium salt during UV irradiation is responsible for the cationic cure. However, the acid thus generated remains in the cured silicone network. The presence of the strong acid in a siloxane network clearly begs the question of whether the cured silicone will be durable enough for the intended applications. Thiol-ene crosslingking of mercaptosiloxanes and vinylsiloxanes in the presence of free radical initiator is also well known. The curing is fast and also free of oxygen inhibition. However, the shelf stability of the uncured silicones and the thermal stability of the 170

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Section: Scheme 5 Tran-silylation Of Bis (Trimethylsilyl) Acetamidementioning

confidence: 99%

UV Curable Silicones from Acryloxymethyldimethylacryloxysilane

Chu¹

2000

ACS Symposium Series

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“…Six-membered silacyclic compounds, such as phenoxasilin and phenothiasilin derivatives, are attractive compounds for applications as organic electronic materials [1][2][3][4], ligands [5][6][7][8][9][10], and reagents [11][12][13][14]. Therefore, the development of new methods to construct silacyclic skeletons is highly desirable.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel–Crafts reaction

Dong

Sakai

Fuji

et al. 2020

Beilstein J. Org. Chem.

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We have developed a catalytic synthetic method to prepare phenoxasilins. A borane-catalyzed double sila-Friedel–Crafts reaction between amino group-containing diaryl ethers and dihydrosilanes can be used to prepare a variety of phenoxasilin derivatives in good to excellent yields. The optimized reaction conditions were also applicable for diaryl thioethers to afford their corresponding six-membered silacyclic products. The gram-scale synthesis of a representative bis(dimethylamino)phenoxasilin and the transformation of its amino groups have also been demonstrated.

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“…The seven-membered heterocycle of 2,8-dibromo-5,10-dimethyl-10-fluoro-10,11-dihydro-5H-dibenzo[ö,/]azasilepine 177 [301] containing a nitrogen heteroatom in addition to the silicon atom has a more bent framework than compounds 173 and 174. Molecules of the compound 177 assume a folded boat conformation with a dihedral angle between benzo group planes of 112° and a distance between their centres of 4.79 A.…”

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confidence: 99%

Molecular Structure of Sila-Heterocycles

Lukevics¹,

Pudova²

1998

Main Group Metal Chemistry

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The present review provides a comprehensive survey on the molecular structure of silaheterocyclic compounds (silacyclopropanes, silacyclobutanes, silacyclopentanes, silacyclohexanes and derivatives with larger rings, as well as compounds with fused and unsaturated heterocycles). In a lot of cases the heterocycles include also heteroatoms other than silicon, however, all silaheterocycles under consideration contain only Si-C bonds. INTRODUCTIONThe results of the structural investigations of the organosilicon heterocycles were reviewed in 1989 [1], However, sila-heterocycles have been the subject of extensive studies over the last 10 years. Much attention has been focused on the synthesis and structural characterization both derivatives with small rings and the macrocyclic compounds. There has been also a considerable interest in the cyclic π-electronic systems containing the silicon atom. Much of this interest concerns the possibility of aromatic character for the silole anions and dianions. Recently the first neutral silaaromatic compound -2-silanaphthalene was successfully isolated and structurally characterized. Our review is an attempt to summarize and systematize the numerous papers scattered in literature on this subject.

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Reactions of fluoride ion sources with haloalkyl derivatives of phenazasilines and phenoxasilins

Cited by 27 publications

References 0 publications

UV Curable Silicones from Acryloxymethyldimethylacryloxysilane

UV Curable Silicones from Acryloxymethyldimethylacryloxysilane

Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel–Crafts reaction

Molecular Structure of Sila-Heterocycles

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