116429-87-9Relevant academic research and scientific papers
Silaheterocyclen. XI. Erzeugung und Cycloadditionsverhalten des Diphenylneopentylsilaethens, Ph2Si=CHCH2tBu
Auner, N.,Ziche, W.,Herdtweck, E.
, p. 1 - 22 (2007/10/02)
Diphenylneopentylsilene, Ph2Si=CHCH2tBu (3), is prepared as a reactive intermediate by the reaction of diphenylvinylchlorosilane (1) with LitBu in nonpolar solvents via the α-lithioadduct Ph2Si(Cl)CH(Li)CH2tBu (2).This lithiated species can be trapped by trimethylsilyltriflate and yields silene 3 by 1,2-LiCl-elimination.Without suitable Si=C-trapping agents, the E/Z-isomeric tetraphenyl-2,4-dineopentyl-1,3-disilacyclobutane (6) is formed by cyclodimerization.In the presence of dienes like 2,3-dimethyl (DMB)-and 2-methyl-1,3-butadiene (MBD) the Diels-Alder and ene-products are formed in competition, while the cycloaddition of 3 with norbornadiene, cyclohexa-1,3-diene, cyclopentadiene and anthracene yields the - or the products exclusively.Exo/endo-(2,2-diphenyl-3-(2',2'-dimethylpropyl)-2-silabicyclooct-5-ene) (19) is a crystalline solid as well as compound E-6, whose structures are presented in this paper.
Silaheterocyclen IX. Darstellung und Charakterisierung von 2,4-Dineopentyl-1,3-disilacyclobutanen
Auner, N.,Gleixner, R.
, p. 33 - 56 (2007/10/02)
The E/Z-isomers of 2,4-dineopentyl-1,3-disilacyclobutanes (R1R2SiCHCH2tBu)2 are obtained in good yields from the reaction of diorganovinylchlorosilanes R1R2Si(Cl)CH=CH2 with LitBu in non-polar solvents.This synthetic route becomes less attractive as the number of chlorosubstituents at the vinylsilane increases: Thus, tetrachloro-2,4-dineopentyl-1,3-disilacyclobutane (2) cannot be prepared from Cl3SiCH=CH2 (1) and LitBu in a preparative scale.Addition of a twice-molar amount of NEt3 to the mixture of 1/LitBu results in the formation of this basic disilacyclobutane as the sole reaction product in nearly quantitative yield.Evidently the bis-donor stabilized neopentylsilene (Et3N)2Cl2Si=CHCH2tBu (δ), whose reactivity is comparable for this clean reaction.These experimental findings are in good agreement with the cycloaddition behaviour of δ.Careful refunctionalization of the tetrakissubstituted disilacyclobutane 6 with gaseous HCl at low temperature is an alternative route to 2, which can be transformed into the H-, F- and organo-substituted derivatives by substitution reactions.However, the preparation of disilacyclobutanes of the type by selective replacement of the chloroatoms failed.These compounds can be obtained from the reaction of the corresponding vinylchlorosilanes with LitBu in the presence of NEt3 as the Lewis base in good yields.
