Synthesis of Chlorosilanes from (Fluoroalkyl)silanes, Bis(silyl)benzenes, and .alpha.,.omega.-Dihydropolysiloxanes

• Published in: Organometallics Vol. 13; no. 3; pp. 808 - 812
• Main Authors: Ishikawa, Mitsuo, Toyoda, Eiji, Ishii, Michie, Kunai, Atsutaka, Yamamoto, Yasushi, Yamamoto, Masao
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.03.1994; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Exact sciences and technology; Organic chemistry; Organometalloidal and organometallic compounds; Physical Sciences; Preparations and properties; Science & Technology; Si derivatives; Palladium II Chlorides; Silicon Organic compounds; Carbon tetrachloride; Copper II Chlorides; Copper I Iodides; Fluorine Organic compounds; Organosilicon hydride
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om00015a014

The reaction of (fluoroalkyl)silanes CF3CH2CH2SiMeH2, C4F9CH2CH2SiMeH2 (2a), C8F17CH2CH2SiMe2H, C8Fl7CH2CH2SiMeH2 (3a), and C8F17CH2CH2SiH3 with 2 equiv Of CuCl2 in the presence of a catalytic amount of Cul in ether gave the respective monochloro(fluoroalkyl)silanes selectively. The reaction of 2a and 3a with 4 equiv Of CuCl2 (CuI) yielded no dichloro derivatives, while treatment of these compounds with CCl4 in the presence of a PdCl2 catalyst gave the respective dichloro compounds. Similar reaction of 1,3- and 1,4-bis(silyl)benzene with 4 equiv Of CuCl2 (CuI) afforded 1,3- and 1,4-bis(chlorosilyl)benzene in high yields. The reaction of HMe2Si(OSiMe2)nOSiMe2H (n = 0, 2, and 3) (8a-10a) with 4 equiv Of CuCl2 (CuI) underwent redistribution to give a series of alpha,omega-dichloropolysiloxanes, CIMe2Si(OSiMe2)nOSiMe2Cl. Treatment of alpha,omega-dihydropolysiloxanes 8a-10a with a catalytic amount of PdCl2 in refluxing carbon tetrachloride produced the respective alpha,omega-dichloropolysiloxanes in high yields.