Synthesis of the Multifunctional (Chloromethyl)silanes Cl₂Si(CH₂Cl)₂, (MeO)₂Si(CH₂Cl)₂, RSi(CH₂Cl)₃ (R = 2,4,6-Trimethoxyphenyl), ClSi(CH₂Cl)₃, MeOSi(CH₂Cl)₃, Si(CH₂Cl)₄, and ClCH₂CH₂Si(CH₂Cl)₃

Abstract

A series of multifunctional (chloromethyl)silanes have been synthesized: Cl 2 Si(CH 2 Cl) 2 (1), (MeO) 2 Si(CH 2 Cl) 2 (2), tris(chloromethyl)(2,4,6-trimethoxyphenyl)silane (3), ClSi(CH 2 -Cl) 3 (4), MeOSi(CH 2 Cl) 3 (5), Si(CH 2 Cl) 4 ( 6), and ClCH 2 CH 2 Si(CH 2 Cl) 3 ( 7). The synthesis of these compounds is based on coupling reactions between (chloromethyl)lithium, generated in situ from bromochloromethane and n-butyllithium in tetrahydrofuran, and chlorosilanes. Compounds 1-7 were characterized by NMR studies ( 1 H, 13 C, 29 Si) and elemental analyses, and 3 and 6 were additionally studied by single-crystal X-ray diffraction. Silanes with more than one SiCH 2 Cl moiety and compounds of this type with additional Si-functional groups are of great interest for synthetic organosilicon chemistry.

Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

“…All solvents were dried and distilled according to standard methods prior to use. Li[Et 3 BH] (1.0 m in THF), 1,2‐dibromobenzene, and bis(chloromethyl)dichlorosilane are commercially available and were used without further treatment or synthesized to known procedures 62. Infrared spectra were recorded by a Nicolet Nexus Fourier transform and by a Bruker Vertex 70 spectrometer.…”

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

“…Cleavage of PhÀSi bonds is reported during NHSG as a by-product of the reaction (PhSiCl 3 /iPr 2 O/Lewis acid catalysts). [31,32] Homofunctional condensation of chlorosilane (in situ formation of alkoxysilane) According to the result, the PhÀSi bond is cleaved during the reaction.…”

Synthesis of palladium(II) complexes of bidentate phosphano ligands with carbosilane substituents

“…The absence of direct siliconechloro bonds in the (chloromethyl)dimethylsilane avoids problems of contamination with HCl and therefore of undesired cleavage of the siliconearyl bonds. Cleavage is in this case conveniently performed with hydrogen chloride, which directly converts the Si-aryl of Ar:G1:(CH 2 Cl) 3 into a SieCl bond in Cl:G1:(CH 2 Cl) 3 under milder conditions [24].…”

“…Unless otherwise stated, reagents were obtained from commercial sources and used as received. Diallyl(methyl) phenylsilane [26], trichloro (2,4,6-trimethoxyphenyl)silane [24], trichloro(4-methoxyphenyl)silane, triallyl(4-methoxyphenyl)silane [27], 4-bromo-N,N-bis(diphenylphosphanomethyl)aniline (PP:Br), 4-(bis(diphenylphosphanomethyl)amino)phenol (PP:OH) [18], [PdCl 2 (cod)] (cod ¼ 1,5-cyclooctadiene) [28], and [PdCl 2 {(P(Ph) 2 -CH 2 ) 2 NPh}] [22] were prepared according to reported procedures. Solvents were dried prior to use and distilled under argon, as described elsewhere [29].…”