Reactions of compounds of the type (Me3Si)2C(SiMe2C6H4Y)(SiMe2X) with trifluoroacetic acid

Eaborn, Colin; Jones, Karen L.; Lickiss, Paul D.

doi:10.1016/0022-328x(93)83269-2

Cited by 6 publications

(5 citation statements)

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“…The second model reaction is the acid-catalyzed decomposition of hb -PSPs (Scheme ). It is well-known that strong protonic acids such as CF 3 COOH, HClO 4 and H 2 SO 4 can promote the cleavage of Si−C bond. − When a mixture of hb -PSP(2) and CF 3 COOH is refluxed in DCM for 96 h under nitrogen, the polymer decomposes to give TPBs, as confirmed by the IR, NMR, and MS analyses. The spectroscopic results further confirm that new benzene rings have been formed in the TaBr 5 -catalyzed polymerization of SDY(2).…”

Section: Resultsmentioning

confidence: 83%

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A₂-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

et al. 2007

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A group of hyperbranched poly(silylenephenylenes) (hb-PSPs) were synthesized in high yields (up to 100%) by TaBr 5 -catalyzed polycyclotrimerization of A 2 -type monomers of silylenediynes The hb-PSPs are completely soluble in common organic solvents such as chloroform, toluene, and THF. Spectroscopic and modeling studies confirmed that the polymers had formed via a [2 + 2 + 2] cyclotrimerization mechanism. Analysis of the triple-bond conversion processes led to the establishment of a relationship between the degree of branching and the fraction of dendritic unit. Computational simulation shed light on the real topological structures of the hb-PSPs. The polymers lost little weights when heated up to 480 °C and carbonize in high yields (up to 71%) after pyrolysis at 800 °C. The hb-PSPs possess a unique σ-π conjugated electronic structure and emit strong violet-blue light upon photoexcitation. The triple bonds on the peripheries allowed the thin films of the polymers to be readily photo-cross-linked, generating fluorescent photoimages in high resolutions.

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Section: Resultsmentioning

confidence: 83%

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A₂-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

et al. 2007

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“…The Si−C cleavage of the Si -2,4,6-TMOP moiety has been demonstrated to occur with hydrogen chloride in diethyl ether at 0 °C, without use of any catalyst (such as AlCl 3 ), to yield a chlorosilane. The Si -allyl group and other Si -aryl moieties have also been reported to be removable by Si−C cleavage; however, these cleavage reactions have been accomplished with triflic acid 2k,6 or trifluoroacetic acid . Thus, the easily and selectively removable Si -2,4,6-TMOP group complements the toolbox of protecting groups in organosilicon chemistry that can be removed by acid-induced Si−C cleavage.…”

Section: Discussionmentioning

confidence: 99%

The Si-2,4,6-Trimethoxyphenyl Moiety as a Novel Protecting Group in Organosilicon Chemistry: Alternative Synthesis of rac-Sila-venlafaxine

et al. 2004

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The Si-2,4,6-trimethoxyphenyl (Si-2,4,6-TMOP) moiety is claimed to be an effective protecting group for synthetic organosilicon chemistry. To demonstrate its high synthetic potential, the Si-2,4,6-TMOP protecting group has been used for a novel multistep synthesis of rac-sila-venlafaxine (a sila-analogue of the serotonin/noradrenaline reuptake inhibitor rac-venlafaxine), starting from 1,1-dichloro-1-silacyclohexane. In addition, the Si-2,4,6-TMOP moiety has been used as a protecting group in silacyclobutane chemistry.

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“…A range of simple bis-functionalized tetrasilylmethanes (XMe 2 Si) 2 C(SiMe 3 ) 2 (for example, X = H, − F, − Cl, ,− Br, ,,,, I, ,,,, OH, ,,,, OMe, ,− OAc, ,, O 2 CCF 3 , − ,, OClO 3 , OSO 2 CF 3 , OSO 2 - p -C 6 H 4 Me, and vinyl , ) are known, but apart from the diol (HOMe 2 Si) 2 C(SiMe 3 ) 2 , little structural information is available for them. The structure of the permethyl species, (Me 3 Si) 4 C, has, however, been studied by NMR spectroscopy, − X-ray diffraction, − gas electron diffraction (GED), , computational methods , and vibrational spectroscopy …”

Section: Introductionmentioning

confidence: 99%

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

et al. 2015

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Article:Wann, Derek A. orcid.org/0000-0002-5495-274X, Robinson, Matthew S., Bätz, Karin et al. eprints@whiterose.ac.uk https://eprints.whiterose.ac.uk/ Reuse Unless indicated otherwise, fulltext items are protected by copyright with all rights reserved. The copyright exception in section 29 of the Copyright, Designs and Patents Act 1988 allows the making of a single copy solely for the purpose of non-commercial research or private study within the limits of fair dealing. The publisher or other rights-holder may allow further reproduction and re-use of this version -refer to the White Rose Research Online record for this item. Where records identify the publisher as the copyright holder, users can verify any specific terms of use on the publisher's website. TakedownIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing eprints@whiterose.ac.uk including the URL of the record and the reason for the withdrawal request. The structures of the molecules C(SiXMe 2 ) 4 (X = H, F, Cl, Br) have been determined by gas electron diffraction (GED). Ab initio calculations revealed nine potential minima for each species, with significant ranges of energies. For the H, F, Cl, and Br derivatives nine, seven, two, and two conformers were modelled, respectively, as they were quantum-chemically predicted to be present in measurable quantities. Variable-temperature 1 H and 29 Si solutionphase NMR studies and, where applicable, 13 C NMR, 1 H/ 29 Si NMR shift-correlation, and 1 H NMR saturation-transfer experiments are reported for C(SiXMe 2 ) 4 (X = H, Cl, Br, and also I).At low temperature in solution two conformers (one C 1 -symmetric and one C 2 -symmetric) are observed for each of C(SiXMe 2 ) 4 (X = Cl, Br, I), in agreement with the isolated molecule ab initio calculations carried out as part of this work for X = Cl, Br. C(SiHMe 2 ) 4 is present as a single C 1 -symmetric conformer in solution at the temperatures at which the NMR experiments were performed.

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Reactions of compounds of the type (Me3Si)2C(SiMe2C6H4Y)(SiMe2X) with trifluoroacetic acid

Cited by 6 publications

References 11 publications

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A₂-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A₂-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

The Si-2,4,6-Trimethoxyphenyl Moiety as a Novel Protecting Group in Organosilicon Chemistry: Alternative Synthesis of rac-Sila-venlafaxine

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

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Reactions of compounds of the type (Me3Si)2C(SiMe2C6H4Y)(SiMe2X) with trifluoroacetic acid

Cited by 6 publications

References 11 publications

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A2-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A2-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

The Si-2,4,6-Trimethoxyphenyl Moiety as a Novel Protecting Group in Organosilicon Chemistry: Alternative Synthesis of rac-Sila-venlafaxine

Structures of Tetrasilylmethane Derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

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Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A₂-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

Hyperbranched Poly(silylenephenylenes) from Polycyclotrimerization of A₂-Type Diyne Monomers: Synthesis, Characterization, Structural Modeling, Thermal Stability, and Fluorescent Patterning

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution