Metallorganische Peroxyde, IV. Organo‐peroxy‐Verbindungen des Germaniums, Zinns und Bleis

Rieche, Alfred; Dahlmann, J.

doi:10.1002/jlac.19646750104

Cited by 27 publications

(31 citation statements)

References 9 publications

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“…Ph 3 GeOOH was synthesized by an analogous procedure from Ph 3 GeBr, mp 136oC [41]. Et 3 GeOOBu-t was obtained by reaction of Et 3 GeCl with t-BuOOH, bp 79oC (14 mm Hg), n D 20 1.3458 [42]. The activity of the peroxides was no less than 98%.…”

Section: Methodsmentioning

confidence: 99%

Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

et al. 2005

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Trialkyl(aryl)silanes and -germanes effectively react with metal (Al, Ti) tert-butylate3tert-butylhydroperoxide under mild conditions (room temperature, benzene or tetrachloromethane) mainly by the element3hydrogen bond. The character of the products depends on the nature of the element, the structure of the radical bound to it, and the solvent. The process is radical in nature. It includes the stages of formation of element-centered radicals and their reaction with the oxygen generated by the system. The intermediate organometallic peroxides can also acts as oxidants for the element (Si, Ge)3hydrogen bonds.The oxidative activity of organosilicon and organogermanium hydrides depends on the structure of the radicals bound with the heteroatom and the nature of the oxidant. Potassium permanganate [1], hydrogen peroxide on a Zeolite catalyst [2], and perbenzoic acid [3] convert trialkyl(aryl)silanes to corresponding hydroxy derivatives. Triethylsilane and triethylgermane react with mineral acids (H 2 SO 4 , HNO 3 ), as well as with Ag 2 O at the boiling points of the hydrides to form siloxane and germanoxane [4].Over the past years dimethyldioxirane [5, 6] has been offered as a mild oxidant that converts trialkylsilanes of various structure to hydroxysilanes. The reaction involves the Si3H bond and occurs at temperatures ranging from 370oC to 20oC with a high conversion and selectivity by the molecular and radical mechanisms, the first prevailing.The reaction of organosilicon hydrides with ozone at 370oC to 380oC involves formation of hydrotrioxides R 3 SiOOOH [639]. At elevated temperatures, the latter decompose with liberation of singlet oxygen, hydroxysilane, and, to a smaller degree, siloxane [6,8]. The mechanism of the decomposition of silicon hydrotrioxides is mostly molecular.Silicon and germanium monohydrides are sufficiently stable toward free oxygen. Triphenylsilane undergoes oxidation to Ph 3 SiOH, initiated by benzoyl peroxide (C 6 H 6 , 95oC) [10]. However, the ability of R 3 GeH to oxidation is much dependent on the structure of the radical. Triphenylgermane is extremely slowly oxidized by atmospheric oxygen [11,12], but tricyclohexylgermane is fast oxidized on exposure to air to form tricyclohexylgermanol.Hence, E3H can bonds can be oxidized with a fairly broad range of reagents, and the reactions are accelerated by radical initiators. There is no information in the literature concerning reactions of silicon and germanium hydrides with oxidative systems comprising organoelement compounds or element alcoholates and hydroperoxides, that are known as effective and selective oxidants for C3H bonds in various substrates [13].It was previously shown that aluminum and titanium tert-butylates (I and II) react with tert-butylhydroperoxide (III) at a 1 : 2 ratio under mild conditions (C 6 H 6 , CCl 4 , 20oC) via formation of metalcontaining trioxides [14,15]. The latter decompose with evolution of oxygen, including singlet oxygen, as well as homolytically by the peroxide bonds with generation of alkoxyl and pero...

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Section: Methodsmentioning

confidence: 99%

Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

et al. 2005

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“…By NMR, no trimethylene oxide was formed. Preparative VPC at 35 °C gave pure 1,2-dioxolane: 1H NMR (CC14) 2.53 (2 H, quintet, 7 = 7 Hz), 3.92 (4 H, t, 7 = 7 Hz); IR (cm-1) 1150 (s), 1110 (s), 987 (m), 925 (m), 780 (w); mass spectrum (70 eV) m/e (rel intensity) 26 (28), 27 (48), 28 (64), 29 (100), 30 (25), 31 (39), 42 (41), 43 (47), 44 (26), 46 (20), 74 (44).…”

Section: Methodsmentioning

confidence: 99%

“…Selective reduction with diimide of the adduct of singlet oxygen with cyclopentadiene is presently the method of choice for preparation of the nucleus 7 of prostaglandin endoperoxides. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Several grams are readily prepared in 1 day in about 50% yield. However, this synthetic approach cannot be extended to synthesis of trans-5,6-disubstituted derivatives such as 37 since addition of hydrogen occurs stereospecifically cis.…”

Section: Otfmentioning

confidence: 99%

The peroxide transfer reaction

Salomon¹,

Salomon²

1979

J. Am. Chem. Soc.

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A new method for synthesis of dialkyl peroxides is described which is based on the novel peroxide transfer reaction between germanium or tin peroxides and alkyl trifluoromethanesulfonates (triflates). Yields are generally superior to those obtainable by alkylation of hydrogen peroxide with alkyl methanesulfonates (mesylates) in the presence of base, especially for secondary alkyl peroxides. Mixed dialkyl peroxides are obtained from the reaction of tri-M-butyltin peralkoxide with alkyl triflates. Bis(tri-n-butyltin) peroxide reacts with alkyl triflates to afford symmetrical dialkyl peroxides, and with alkyl bistriflates to afford fiveto eight-membered cyclic peroxides. The strained bicyclic peroxide nucleus of prostaglandin endoperoxides, 2,3-dioxabicyclo[2.2.1]heptane, is obtained in 22% yield from the bistriflate of m-l,3-cyclopentanediol.

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“…For instance, Bu 3 SnOO-t-Bu has been obtained by both methods 73,74 . For instance, Bu 3 SnOO-t-Bu has been obtained by both methods 73,74 .…”

Section: Peroxidesmentioning

confidence: 99%

Preparation of organotin reagents

Pereyre

Quintard

Rahm

1987

Tin in Organic Synthesis

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Metallorganische Peroxyde, IV. Organo‐peroxy‐Verbindungen des Germaniums, Zinns und Bleis

Cited by 27 publications

References 9 publications

Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

Reaction of Organoelement Hydrides R3EH (E = Si, Ge) with Metal tert-Butylate (M = Al, Ti)-tert-Butyl Hydroperoxide Oxidative Systems

The peroxide transfer reaction

Preparation of organotin reagents

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