- Nickel(0) catalyzed oxidation of organosilanes to disiloxanes by air as an oxidant
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We report here an efficient non-aqueous route to symmetrical disiloxanes from their corresponding organosilanes using Ni(COD)2 with 3,4,7,8-tetramethyl-1,10-phenanthroline in air. Our methodology is very simple and high yielding. The reaction mechanism is also proposed.
- Lv, Haiping,Laishram, Ronibala Devi,Li, Jiayan,Shi, Guangrui,Sun, Weiqing,Xu, Jianbin,Yang, Yong,Luo, Yang,Fan, Baomin
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supporting information
p. 971 - 974
(2019/03/07)
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- Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction
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We report the first example of a silyl-Negishi reaction between secondary zinc organometallics and silicon electrophiles. This palladium-catalyzed process provides direct access to alkyl silanes. The delicate balance of steric and electronic parameters of the employed DrewPhos ligand is paramount to suppressing isomerization and promoting efficient and selective cross-coupling.
- Cinderella, Andrew P.,Vulovic, Bojan,Watson, Donald A.
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supporting information
p. 7741 - 7744
(2017/06/21)
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- Preparation method of 1,3-diphenyl-1,1,3,3-tetramethyl disiloxane
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The invention discloses a preparation method of 1,3-diphenyl-1,1,3,3-tetramethyl disiloxane. The preparation method is characterized in that the Wurtz method or Grignard method is adopted, and 1,3-diphenyl-1,1,3,3-tetramethyl disiloxane is synthesized through disiloxane rectified from an organosilicon high-boiling component and a halogenated compound. According to the preparation method, market application and high-value utilization of the organosilicon high-boiling component are expanded, and a raw material basis can be further provided for preparation of organosilicon materials with special functions.
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Paragraph 0022
(2017/05/25)
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- Supported gold nanoparticle catalyst for the selective oxidation of silanes to silanols in water
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Hydroxyapatite-supported gold nanoparticles (AuHAP) can act as highly efficient and reusable catalysts for the oxidation of diverse silanes into silanols in water; this is the first catalytic methodology for the selective synthesis of aliphatic silanols using water under organic-solvent-free conditions.
- Mitsudome, Takato,Noujima, Akifumi,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information; experimental part
p. 5302 - 5304
(2010/01/31)
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- Zur Synthese von Siloxanen XIV. Die Umsetzung von Chlorsilanen mit Silanolen im sauren Medium
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The reactions of aryldimethylchlorosilanes with benzyldimethylsilanol in C6D6/dioxane (2.8/1) have been investigated by 1H NMR spectroscopy.Fast substituent exchange reactions were observed in the presence of H2O or HCl.In this process both substances establish chlorosilane/silanol equilibria which are related to the concetration of H2O and HCl formed.A ρ-value of 1.3 was found for the reaction of substituted aryldimethylchlorosilanes with benzyldimethylsilanol in the presence of H2O.In time the equilibria are disturbed by condensation processes.
- Ruehlmann, K.,Grosse-Ruyken, H.,Scheller, D.,Scheim, U.
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- Base Cleavage of R-Si Bonds of Silanols RSiMe2OH. A Proposed New Mechanism of Substitution at Silicon
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Cleavage of R-Si bonds has been found to occur unexpectedly rapidly in solutions of RSiMe2OMe (R = m-ClC6H4CH2 or PhCC) in 5 vol-percent H2O-MeOH containing relatively small concentrations of NaOMe, but with a levelling off of the rate at high concentrations of the base.The behaviour is attributed to the formation of RSiMe2OH and hence RSiMe2O-, and it is suggested that unimolecular dissociation of the silanolate anion RSiMe2O- to give R- and the silianone Me2Si=O (both of which react rapidly with the solvent) plays a significant role.The silanols RSiMe2OH are roughly estimated to have pKa values of 11 (R = m-ClC6H4CH2) and 9.8 (R = PhCC) in water.
- Eaborn, Colin,Stanczyk, Wlodzimierz
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p. 2099 - 2104
(2007/10/02)
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- Some Methoxysilanes, Disiloxanes and Digermoxanes with Effectiveness of Odour. Sila-Substituted Perfumes, III.
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The odour of the formerly unknown compounds benzyldimethylmethoxysilane 2a (flower-honey like with a minty component; intensity middle), bis(benzyl)tetramethyldisiloxane 4a (flowerlike; very weak) and bis(benzyl)tetramethyldigermoxane 9 (almond-soapy like; relatively strong) was registered and compared with related compounds (for example benzyldimethylmethoxymethane 5a, camphor-radish like).Information is given on preparation and analytical and structural investigation of several methoxysilanes and disioxanes with benzyl and phenethyl groups (compare equations and experimental part). - Keywords: Digermoxanes; Disiloxanes; Methoxysilanes; Odour; Sila-perfumes
- Wrobel, Dieter,Wannagat, Ulrich,Harder, Ulrich
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p. 381 - 388
(2007/10/02)
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- Sila Perfumes, I. Sila Analogues of Tertiary Carbinols as Perfumes
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Silanols RR'R''SiOH 7 which are analog to carbinols 1 with strong odour in the region of flowery notes (lily of the valley-hyacinth-rose) were prepared via reaction steps (3) and partially unknown intermediates 6.Sila perfumes 7 are similar in intensity and spectrum of odour to 1 but a shift from lily of the valley towards hyacinth notes is generally observed.
- Wrobel, Dieter,Tacke, Reinhold,Wannagat, Ulrich,Harder, Ulrich
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p. 1694 - 1704
(2007/10/02)
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