- Phenyltrichlorogermane synthesis by the reaction of chlorobenzene and the dichlorogermylene intermediate formed from elemental germanium and tetrachlorogermane
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Phenyltrichlorogermane was synthesized with high selectivity, 96%, from elemental germanium, tetrachlorogermane, and chlorobenzene using no catalyst, almost all germanium and tetrachlorogermane being converted. Dichlorogermylene was formed as a reaction intermediate by the reaction of germanium with tetrachlorogermane and inserted into the C-Cl bond of chlorobenzene to yield phenyltrichlorogermane.
- Okamoto, Masaki,Asano, Takuya,Suzuki, Eiichi
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- Reaction of germanium tetrachloride with chloro(phenyl)silanes in the presence of aluminum chloride
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The effect of the quantity of aluminum chloride on the direction and depth of reaction of germanium tetrachloride with chloro(phenyl)silanes of the general formula PhnSiCl4-n (n = 1 - 3) was studied to show that radical exchange between germanium and silicon is initiated only if the mixture contains no less than 2.5-5 wt % of aluminum chloride. With trichloro(phenyl)silane, the radical exchange is initiated at 5 wt % of aluminum chloride and results in exclusive formation of trichloro(phenyl)germane. The reactions of GeCl4 with dichlorodiphenylsilane and chlorotriphenylsilane in the presence of 2.5-7.5 wt % of aluminum chloride give dichlorodiphenylgermane as the major product, and at AlCl3 concentrations of above 10 wt % the major product becomes to be trichloro(phenyl)germane.
- Zhun',Sbitneva,Chernyshev
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- Selective synthesis of chlorohydrogermanes from mono-, di-, and trihydrogermanes
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Treatment of hydrogermanes, R4-nGeHn (R = Hex, Et, Ph, n = 1-3), with 2 equiv of CuCl2 in ether at room temperature or in toluene under reflux led to selective replacement of an H-Ge bond with a Cl-Ge bond, giving the corresponding chlorohydrogermanes, R4-nGeHn-1Cl, selectively.
- Ohshita, Joji,Toyoshima, Yutaka,Iwata, Arihiro,Tang, Heqing,Kunai, Atsutaka
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- Reaction of tetrachlorogermane with thienyl- and phenylchlorosilanes in presence of aluminum chloride. Synthesis of thienylchlorogermanes
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Reaction of tetrachlorogermane with 2-thienylchlorosilane and methyl(2-thienyl)dichlorosilane in presence of AlCl3 is studied. It was shown that in the reaction with 2-thienyltrichlorosilane 2-thienyltrichlorogermane mainly formed, while in the reactions with methyl(2-thienyl)dichlorosiulane aromatic germaniumcontaining compounds like 2-thienyltrichlorogermane and di(2-thienyl)dichlorogermane were obtained. Quantum-chemical calculations showed that the reaction of chlorine atoms exchange in GeCl4 with aromatic moiety formed from arylchlorosilanes in the presence of AlCl3 proceeds through a four-membered activated complex.
- Lakhtin,Vorob'Eva,Gordeev,Ushakov,Kirillin,Bykovchenko,Golub,Chernyshev
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p. 280 - 284
(2014/04/17)
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- Gas phase reaction of nucleogenic dimethylgermylium cations with benzene
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Reaction of nucleogenic dimethylgermylium cations with benzene in the gas phase was studied by the radiochemical method. The formation of the products of germylation of benzene, dimethylphenylgermane, and phenylgermane is indicative of the formation of dimethylgermylium cations by the β-decay of tritium in the molecule of dimethylditritium germane. Dimethylgermylium cations are shown to undergo a rearrangement in the course of the reaction with benzene, which is consistent with the earlier results of quantum-chemical calculations.
- Myalochkin,Kochina,Avrorin,Vrazhnov,Sinotova
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p. 1762 - 1766
(2011/02/24)
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- Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride
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The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes. Nauka/Interperiodica 2006.
- Zhun,Sbitneva,Polivanov,Chernyshev
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p. 1564 - 1570
(2008/02/09)
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- Convenient syntheses of aryl and perfluoroaryl trichlorogermanes and germatranes via an organotin route
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Aryl- and (perfluoroaryl)trichlorogermanes ArGeCl3(Ar = C 6H5, 2-FC6H4, 3,5-(CF 3)2C6H3, C6F5, 2,3,5,6-F4C5N) are easily obtained in 60-80% yields from the corresponding tributyl-stannanes and GeCl4 (1:1) at 150 °C in the absence of a solvent. Although the tin-to-germanium transmetalation of C6F5 group is sluggish, it is facilitated by addition of 1-2 mol % AIBN (2,2′-azobis(isobutyronitrile)).
- Kultyshev, Roman G.,Prakash, G.K. Surya,Olah, George A.,Faller, Jack W.,Parr, Jonathan
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p. 3184 - 3188
(2008/10/09)
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- Hexachlorodisilane-Initiated Gas-Phase Reaction of Germanium Tetrachloride with 1-Chloroadamantane or Adamantane
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Gas-phase reactions of 1-chloroadamantane and adamantane with germanium tetrachloride in the presence of hexachlorodisilane as initiator were studied. It was found that trichlorogermyladamantane is formed only in the reaction with 1-chloroadamantane, together with ethyl-, propyl-, and butyltrichlorogermanes as by-products.
- Chernyshev, E. A.,Shcherbinin, V. V.,Krivolapova, O. V.,Bykovchenko, V. G.,Komalenkova, N. G.,Bochkarev, V. N.
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p. 1721 - 1723
(2007/10/03)
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- Synthesis and molecular structure of phenyl and tolylgermatranes
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The crystals of arylgermatranes (R=H (I), 4-CH3 (II), 3-CH3 (III), 2-CH3 (IV)), have been obtained to study the influence of a substituent position on coordination of the germanium atom. Compounds I-IV were prepared by the insertion of GeBr2 into the carbon-bromine bond of the corresponding arylbromide, conversion of aryltribromogermanes to triethoxy derivatives by alcoholysis and their transalkoxylation with triethanolamine to germatranes; or by the condensation of halobenzene with GeCl4 in the presence of copper powder followed by alcoholysis and cyclization. The crystal structure of compounds I-IV was studied via the X-ray diffraction method. The intramolecular donor-acceptor bond Ge←N in arylgermatranes (2.212-2.230 A) is longer than that in the corresponding furyl- and thienylgermatranes. Introduction of a substituent into o-position of the benzene ring decreases the N-Ge-C angle value from 177.5 to 144.2°. The quantum chemical calculations were performed to investigate structures I-IV in isolated molecules.
- Lukevics, Edmunds,Ignatovich, Luba,Belyakov, Sergey
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p. 222 - 230
(2007/10/03)
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- Gas-Phase Reaction of Tetrachlorogermane with 1,1-Dichloro-1-silacyclopent-3-ene. Generation of Dichlorogermylene
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The reaction of GeCl4 with 1,1-dichloro-1-silacyclopent-3-ene in the gas phase at 550°C was studied. This reaction yields dichlorogermylenes, which react with chlorobenzene or 1,3-butadiene to form phenyltrichlorogermane or 1,1-dichloro-1-germacyclopent-3-ene.
- Chernyshev,Komalenkova,Yakovleva,Bykovchenko,Khomykh,Bochkarev,Shcherbinin
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p. 1722 - 1724
(2007/10/03)
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- Gas-Phase Synthesis of Phenyltrichlorogermane by Reaction of Germanium Tterachloride with Chlorobenzene in the Presence of Initiators
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The effect of hexachlorodisilane and trichlorosilane as initiators for synthesis of phenyltrichlorogermane were investigated. The mechanism if the influence of these compounds on the reaction of germanium tetrachloride with chlorobenzene is proposed.
- Chernyshev, E. A.,Komalenkova, N. G.,Yakovleva, G. N.,Bykovchenko, V. G.
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p. 1717 - 1720
(2008/10/08)
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- Microwave-assisted Lewis acid catalysis: Application to the synthesis of alkyl- or arylhalogermanes
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Under microwave irradiation, alkyl- or arylhalogermanes RnGeX4-n (R = Et, Bu, Ph; X = Cl, Br) are obtained by redistribution reactions of R4Ge with GeX4. These experimental conditions permit the synthesis of such compounds in good yield in a few minutes at atmospheric pressure. The direct Friedel-Crafts germylation of benzene and toluene by germanium tetrachloride also has been performed, but yields were low.
- Laurent, Régis,Laporterie, André,Dubac, Jacques,Berlan, Jacques
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p. 2493 - 2495
(2008/10/08)
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- ETUDE DE REACTIONS PAR TRANSFERT MONOELECTRONIQUE ENTRE DIVERS HYDROGERMANES A CARACTERE ACIDE ET DES SYSTEMES QUINONIQUES DIA- ET PARA-MAGNETIQUES
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The chlorogermanes PhnCl3-nGe-H (n = 0, 1, 2) were treated with diamagnetic (3,5-di-t-butylorthoquinone) 1 and the paramagnetic galvinoxyl 2.These reactions occur mainly by monoelectron transfer giving the corresponding adducts.In the case of 3,5-di-t-butylorthoquinone, the resulting 1-4 adducts decompose by two simultaneous processes (HCl elimination and redistribution) yielding germadioxolanes.The chlorogermadioxolanes prepared in this way easily cause halogenic redistribution leading to chlorogermanes and germylcatecholates having branched or spiranestructure.In the case of the galvinoxyl radical, the same chlorogermanes lead by monoelectron transfer to the corresponding quinophenol and an intermediate germanium-centered radical.The latter by recombination outside the solvent cage, gives digermane.However, its primary reaction, which occurs within the solvent cage, is with quinophenol to form two isomeric O- and C-germylated catechols.The C-isomer is by far predominant as it also formed in the secondary hydrogermylation of quinophenol produced in the initial stage of the reaction.We have been able to confirm these mechanisms by a comparative study of the reaction of germanium hydrides R3Ge?+-H?-, acidic germanes X3Ge?--H?+, and germanates X3Ge(-)N-H(+) with galvinoxyl and the corresponding quinophenol.Key words: SET reactions; germylations; quinones; chlorohydrogermanes; chlorogermanes; chlorogermanates.
- Riviere, P.,Castel, A.,Abdennadher, C.
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p. 181 - 194
(2007/10/02)
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- Cycloaddition of Germylenes to 3,5-Di-t-butylorthoquinone
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The germylenes X2Ge, RGeX and R2Ge (X= halogen, OR; R= alkyl or aryl) react at room temperature with 3,5-di-t-butyl orthoquinone by regioselective cycloaddition.The corresponding substituted 2-germa-1,3-dioxolans are formed similarly in good yields, but t
- Riviere, Pierre,Castel, Annie,Satge, Jacques,Guyot, Daniel
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p. 157 - 164
(2007/10/02)
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- POLYGERMANES PRECURSEURS D'ESPECES DU GERMANIUM A COORDINNANCE NON USUELLE
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Several thermal or photochemical α-elimination reactions of functional polygermanes lead to germylenes, R2Ge.Photolysis of polygermanes, cyclopolygermanes and polygermylmercury compounds and also hydrogen abstraction from various organohydropolygermanes using t-BuO., lead to the formation of polymetallated chains containing one or two germanium-centered radicals.These polygermyl radicals give germylenes, R2Ge, germanium centered radicals Ge., α-digermyl diradicals (or digermenes) Ge.-Ge. or Ge=Ge> and β- or γ-polygermyl diradicals via ahomolytic monoelectronic α-elimination process.In some cases the formation of α-digermyl diradicals or digermenes can also be seen as occuring through dimerization of germylenes but with lower yields.All these intermediates have been characterized by several trapping reactions with dimethyl disulfide, 2,3-dimethylbutadiene or biacetyl.
- Riviere, P.,Castel, A.,Satge, J.,Guyot, D.
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p. 193 - 206
(2007/10/02)
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- SYNTHESE DE COMPOSES A LIAISON MIVB-MERCURE. PRECURSEURS D'ESPECES MONOVALENTES (GERMYNES), ET BIVALENTES (GERMYLENES), DE RADICAUX CENTROMETALLES ET D'INTERMEDIAIRES
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Polynuclear germyl-mercury compounds are obtained from the reaction of organohydrogermanes PhnGeH4-n or digermanes Ph2nGe2H4-n (n = 1, 2) with dialkylmercury R2Hg.Di- or tri-mercurated geminal polygermates thus synthesized generally present a low stability and undergo thermal- or photodecompositions leading to the corresponding monovalent (germynes), divalent (germylenes) or, trivalent (germanium centered radicals) species and also to intermediate biradicals which could be considered as limit forms of germanium doubly-bonded compounds .Such intermediates have been chemically and spectroscopically characterized.Extension of these reactions to the silicon analogs met with difficulties, and thus previously observed differences between silicon and germanium chemistry were confirmed.
- Riviere, P.,Castel, A.,Satge, J.
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p. 351 - 367
(2007/10/02)
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