Über Silanolester anorganischer Säuren, II. Reaktionen von Phosphorsäurechloriden mit Alkylsiloxanen und Alkylalkoxysilanen

Abstract

872 SCHMIDT, SCHMIDBAUR und BINGER Jahrg. 93 Butyl-[2-cyan-athylJ/-cyanessigester: Farbloses 61, Sdp.o.02 114 -116", n% 1.4488; Ausb. 70% d. Th. C12HlsN202 (222.3) Ber. C 64.85 H 8.16 N 12.61 Gef. C 64.57 H 8.00 N 12.77 a-Buryl-a-[2-cyan-athyl]-acetessigester: Farbloses 01, Sdp.o.2 138-140", nLo 1.4530; Ausb. 62% d. Th. C13H21NO3 (239.3) n'," 1.4760; Ausb. 84% d. Th. Ber. C 65.24 H 8.85 N 5.86 Gef. C 65.36 H 8.64 N 5.87 Bufyl-[2-cyan-athyll-monothiolmalonsaure-dia~hylesfer: Farbloses 01, Sdp.o.02 125 -128", C~~H~~N O J S (285.4) Ber. C 58.92 H 8.12 N 4.91 S 11.23 Gef. C 59.16 H 8.00 N 4.98 S 11.20 Butyl-[2-cyan-athyl]-dithiolmalonsaure-diathylester: Schwach gelbes 01, Sdp.o.1 166 -168". nL7.' 1.5159; Ausb. 60% d. Th. C14H23N02S2 (301.5) Ber. C 55.77 H 7.69 N 4.65 S 21.28 Gef. C 55.57 H 7.73 N4.68 S 21.20 Buryl-[2-cyan-athyl]-malonsauredinitril: Die Butanol/Dioxan-Reaktionslasung wird in wenig eiskalte verd. Salzsaure gegossen, wobei das Produkt sofort auskristallisiert. Schmp. 55.5" (aus dithanol); Ausb. 65 % d. Th.

Synthesis and Characterization of Silylated Phosphonium [P(OSiMe3)4]+ and Phosphate [O2P(OSiMe3)2]− Salts

“…OP­(OSiMe 3 ) 3 , generated from hexamethyldisiloxane and phosphoric anhydride, was first mentioned in 1944 . Ever since different synthetic approaches have been published. − An easy high-yielding synthetic process was published in 2014 by Wessjohann et al, who treated KH 2 [PO 4 ] with an excess of Me 3 SiCl in formamide affording pure 1 in high yields . We have applied a slightly modified process by using n -hexane as solvent (yield 96%) as illustrated in Scheme (eq 1).…”

Darstellung und spektroskopische Untersuchungen von Me3SiOP(S)Cl2, Me3SiOP(S)Br2 sowie Me3SiOP(O)Br2 / Preparation and Spectroscopic Properties of Me3SiOP(S)Cl2, Me3SiOP(S)Br2 and Me3SiOP(O)Br2

“…Während P0C13 die Si-O-Bindung des Hexamethyldisiloxans unter Bildung des Trimethylsilyldichlorphosphats spaltet [10], verhält sich POBr3 gegenüber Me3SiOSiMe3 indifferent. Nach zweitägi-gem Erhitzen der Komponenten auf 100 °C ist keine, Reaktion feststellbar.…”

Synthesis and characterisation of trimethylsilyl phosphorohalidates: Me3SiOP(O)FX (X = Cl, Br) and (Me3SiO)2P2O3F2

“…Except for Me 3 SiOP(O)Br 2 [3], trimethylsilyl phosphorodihalidates with two identical halogens are generally accessible by the treatment of the phosphoryl fluoride [4,5] or phosphoryl chloride [6] with hexamethyldisiloxane. Both Me 3 SiOP(O)F 2 and Me 3 SiOP(O)Cl 2 have also been prepared from (Me 3 Si) 2 O and P 2 O 3 F 4 [7] and P 2 O 3 Cl 4 [6], respectively, while the silylation of the free acid [4] or its salts [8] with chlorotrimethylsilane remains limited to the synthesis of the former, and the silylation of MeOP(O)Cl 2 with bromotrimethylsilane [9] to the preparation of the latter ester.…”

“…Both Me 3 SiOP(O)F 2 and Me 3 SiOP(O)Cl 2 have also been prepared from (Me 3 Si) 2 O and P 2 O 3 F 4 [7] and P 2 O 3 Cl 4 [6], respectively, while the silylation of the free acid [4] or its salts [8] with chlorotrimethylsilane remains limited to the synthesis of the former, and the silylation of MeOP(O)Cl 2 with bromotrimethylsilane [9] to the preparation of the latter ester.…”