Über Silikone, CIV. Methoxylierung, Methylierung und Reduktion von trichlorsilyl‐substituierten Methanen und Chlormethanen

Müller, Richard; Reichel, Sigrid

doi:10.1002/cber.19660990311

Cited by 15 publications

(3 citation statements)

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“…Corriu et al synthesized preparatively useful amounts of H A by treatment of CHCl 3 with excess Benkeser reagent. The chlorosilane H A was not isolated, but routinely transformed to HC(Si(OEt) 3 ) 3 via ethanolysis (30%; Scheme , top). , Some tetrasilylethane H 2 B forms upon reaction of Cl(H)C(SiCl 3 ) 2 with Si(Cu) at 300–320 °C in a fixed bed reactor; the synthesis of the precursor molecule, Cl(H)C(SiCl 3 ) 2 , requires gas-phase photochlorination of H 2 C(SiCl 3 ) 2 (Scheme ). The corresponding alkene, (Cl 3 Si) 2 CC(SiCl 3 ) 2 ( B ), and alkyne, Cl 3 SiCCSiCl 3 ( C ), are accessible through dechlorinative coupling of Cl 2 C(SiCl 3 ) 2 with Cu metal in a stirred bed reactor as parts of a multicomponent mixture (Scheme , bottom). , Alternatively, CCl 4 gives some C (18%) in the Müller–Rochow Direct Process. , Catalytic hydrosilylation of C has been employed to prepare the 1,1,2-trisilylethene D (88%)…”

Section: Resultsmentioning

confidence: 99%

“…As first reactivity tests, we treated [ n Bu 4 N][ A ] and [ n Bu 4 N] 2 [ B ] with anhydrous MeOH/NMe 2 Et and obtained H A OMe and H 2 B OMe in yields of 59% and 88%, respectively. By the same token, protonation with CF 3 SO 3 H selectively furnished H A and H 2 B , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…The chlorosilane HA was not isolated, but routinely transformed to HC(Si(OEt) 3 ) 3 via ethanolysis (30%; Scheme 3, top). 27,64 Some tetrasilylethane H 2 B forms upon reaction of Cl(H)C-(SiCl 3 ) 2 with Si(Cu) at 300−320 °C in a fixed bed reactor; the synthesis of the precursor molecule, Cl(H)C(SiCl 3 ) 2 , requires gas-phase photochlorination of H 2 C(SiCl 3 ) 2 (Scheme 3). 65 The corresponding alkene, (Cl 3 Si) 2 CC(SiCl 3 ) 2 (B), and alkyne, Cl 3 SiCCSiCl 3 (C), are accessible through dechlorinative coupling of Cl 2 C(SiCl 3 ) 2 with Cu metal in a stirred bed reactor as parts of a multicomponent mixture (Scheme 3, bottom).…”

Section: ■ Introductionmentioning

confidence: 99%

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Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Georg¹,

Teichmann²,

Bursch

et al. 2018

J. Am. Chem. Soc.

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The Cl-induced heterolysis of the Si-Si bond in SiCl generates an [SiCl] ion as reactive intermediate. When carried out in the presence of CCl or ClC═CCl (CHCl solutions, room temperature or below), the reaction furnishes the monocarbanion [C(SiCl)] ([A]; 92%) or the vicinal dianion [(ClSi)C-C(SiCl)] ([B]; 85%) in excellent yields. Starting from [B], the tetrasilylethane (ClSi)(H)C-C(H)(SiCl) (HB) and the tetrasilylethene (ClSi)C═C(SiCl) (B; 96%) are readily available through protonation (CFSOH) or oxidation (CuCl), respectively. Equimolar mixtures of HB/[B] or B/[B] quantitatively produce 2 equiv of the monoanion [HB] or the blue radical anion [B], respectively. Treatment of B with Cl ions in the presence of CuCl furnishes the disilylethyne ClSiC≡CSiCl (C; 80%); in the presence of [HMeN]Cl, the trisilylethene (ClSi)C═C(H)SiCl (D; 72%) is obtained. Alkyne C undergoes a [4+2]-cycloaddition reaction with 2,3-dimethyl-1,3-butadiene (CHCl, 50 °C, 3d) and thus provides access to 1,2-bis(trichlorosilyl)-4,5-dimethylbenzene (E1; 80%) after oxidation with DDQ. The corresponding 1,2-bis(trichlorosilyl)-3,4,5,6-tetraphenylbenzene (E2; 83%) was prepared from C and 2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-one under CO extrusion at elevated temperatures (CHCl, 180 °C, 4 d). All closed-shell products were characterized by H,C{H}, and Si NMR spectroscopy; an EPR spectrum of [ nBuN][B] was recorded. The molecular structures of [ nBuN][A], [ nBuN][B], B, E1, and E2 were further confirmed by single-crystal X-ray diffraction. On the basis of detailed experimental investigations, augmented by quantum-chemical calculations, plausible reaction mechanisms for the formation of [A], [B], C, and D are postulated.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Georg¹,

Teichmann²,

Bursch

et al. 2018

J. Am. Chem. Soc.

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Einfache Synthesen von symmetrischen Bis(trimethylsilyl)‐ethenen

Birkofer

Kühn

1978

Chem. Ber.

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Eingegangen am 22. Dezember 1977trans-l-(Chlordimethylsilyl)-2-(trimethylsilyl)ethen (3) konnte durch direkte Addition von Chlordimethylsilan (2) an Mono(trimethylsily1)ethin (1) in Anwesenheit von H,PtC16 gewonnen und mit CH,MgI in trans-l,2-Bis(trimethylsilyl)ethen (4) ubergefuhrt werden. Die ZnC1,-katalysierte Umsetzung von Chlor bzw. Brom mit 1,2-Bis(trimethylsilyl)ethin (5) ergab trans-1,2-Dichlor-(6) bzw. trans-1,2-Dibrom-1,2-bis(trimethylsilyl)ethen (7). Weitere Einwirkung von Chlor bzw. Brom auf 6 und 7 lieferte 1,1,2,2-Tetrachlor-(8), 1,2-Dibrom-1,2-dichlor-(10) und 1,1,2,2-Tetrabrom-l,2-bis(trimethylsilyl)ethan (9). Durch Chlortrimethylsilan-Eliminierung entstand aus 8 1,1,2-Trichlor-2-(trimethylsilyl)ethen (11). ') trans-l-(Chlorodimethylsilyl)-2-(trimethylsilyl)ethene (3) is obtained by direct addition of chlorodimethylsilane (2) to mono(trimethylsily1)ethyne (I) in the presence of H,PtC16 and transformed into trans-1,2-bis(trimethylsilyl)ethene (4) by reaction with CH,MgI. The zinc chloridecatalyzed reaction of chlorine or bromine with 1,2-bis(trimethylsilyl)ethyne (5) leads to trans-1,2-dichloro-(6) or trans-1,2-dibromo-l,2-bis(trimethylsilyl)ethene (7). Further interaction of chlorine or bromine with 6 or 7 gave 1,1,2,2-tetrachloro-(S), 1,2-dibromo-1,2-dichloro-(lo), and 1,1,2,2-tetrabromo-l,2-bis(trimethylsilyl)ethene (9). Elimination of chlorotrimethylsilane from 8 produced 1,1,2-trichloro-2-(trimethylsilyl)ethene (11). Simple Syntheses of Symmetrical Bis(trimethy1silyl)ethenesDie Synthese von trans-1,2-Bis(trimethylsilyl)ethen erfolgte bisher durch radikalische Halogenierung des (Trichlorsily1)ethans zu 1,2-Dihalogen-2-(trichlorsilyl)ethan, das durch anschlierjende Halogenwasserstoff-Eliminierung in 1 -Halogen-2-(trichlorsilyl)ethen u bergeht. Mittels Methylmagnesiumbromid werden die Siliciumchloratome unter Bildung von l-Halogen-2-(trimethylsilyl)ethen ausgetauscht. Nach Grignardierung oder Zugabe von metallischem Natrium 1aBt man Chlortrimethylsilan einwirken und erhalt truns-1,2-Bis(trimethylsilyl)ethen (4) ' . 3 3 4).

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Sila‐Pharmaka, 36. Sila‐Procyclidin: Eine neue Synthese sowie Untersuchungen zur peripheren und zentralen anticholinergen Wirkung

et al. 1987

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Sila-Procyclidin (1 b) sowie dessen Derivate 2 b (Sila-Trihexyphenidyl), 3 b und 4 b (Sila-Cycrimin) wurdenausgehend von C13SiCH2CIdurch eine neue, sechsstufige Synthese mit einer Gcsamtausbeute von 16 (lb). 19 (Zb), 8 (3b) bzw. 7% (4b) dargcstellt. -Verglcichende in-vivo-Untenuchungen (Maus, per-os-Applikation) hinsichtlich der peripheren und zentralen anticholinergen Wirkung haben gezcigt. daO die Silicium-Verbindung 1 b dem Kohlenstofl-Analogon 1 a (Procyclidin) iiberlegen ist.

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Über Silikone, CIV. Methoxylierung, Methylierung und Reduktion von trichlorsilyl‐substituierten Methanen und Chlormethanen

Cited by 15 publications

References 16 publications

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Einfache Synthesen von symmetrischen Bis(trimethylsilyl)‐ethenen

Sila‐Pharmaka, 36. Sila‐Procyclidin: Eine neue Synthese sowie Untersuchungen zur peripheren und zentralen anticholinergen Wirkung

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Über Silikone, CIV. Methoxylierung, Methylierung und Reduktion von trichlorsilyl‐substituierten Methanen und Chlormethanen

Cited by 15 publications

References 16 publications

Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller–Rochow Direct Process

Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller–Rochow Direct Process

Einfache Synthesen von symmetrischen Bis(trimethylsilyl)‐ethenen

Sila‐Pharmaka, 36. Sila‐Procyclidin: Eine neue Synthese sowie Untersuchungen zur peripheren und zentralen anticholinergen Wirkung

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Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process