27607-77-8Relevant articles and documents
NEW METHOD FOR THE PREPARATION OF t-BUTYLDIMETHYLSILYL TRIFLATE
Hudrlik, Paul F.,Kulkarni, Ashok K.
, p. 1389 - 1390 (1985)
t-Butyldimethylsilyl triflate is easily prepared from the reaction of triflic acid with isopropenyltrimethylsilane.
ELECTROPHILE-INITIATED SELECTIVE RING TRANSFORMATIONS OF CYCLOPROPYL KETONES
Demuth, Martin,Mikhail, Gamal
, p. 991 - 997 (1983)
Electrophile-mediated cyclopropane cleavage in tricyclo2,8>octan-3-one (1a) is increasingly directed towards the maximum bond overlap site in the following order of reagents: acetyl methanesulfonate, +Br(1-) or I(1-); t-butyl-dimethylsilyl iodide; t-butyldimethylsilyl trifluoroacetate; trimethylsilyl trifluoroacetate.The latter reagent gives rise to one single regioisomer (->6a).Routine yields of isolated products lie between 78 and 87percent.Increasing regioselectivity is governed by increasing electrophilic power and lowered nucleophilic strength of the reagents.Independent of these two factors, a C(4)-exo substituent in 1 directs the opening modes undirectionally (->2b, 6b).Irrespective of the substitution pattern at C(4) (1a-d), the cyclopropane moiety rearranges smoothly to olefinic ketones (8a-d) when the polymer-supported triflate analog Nafion-TMS is used in toluene at 80 deg C.The reaction proceeds via intramolecular proton (deuterion) abstraction by the transient electron-rich enoxy double bond.This is the first fully proved case of such an intramolecular process.Aro-semibullvalenes (18,22) similarly rearrange to aro-semibarrelenes (e.g. 21, 23) in the presence of Nafion-TMS.The latter rearrangement also takes place at room temperature when 18 or 22 are treated with commercial tetramethylsilane (TMS) and a catalytic amount of trifluoroacetic acid.An unknown impurity in the TMS reacts with the acid to form a powerful electrophilic composition.A cheap and convenient in situ preparation of TMS-triflate is described by mixing trifluoromethanesulfonic acid and TMS at room temperature.
REAGENTS AND SYNTHETIC METHODS 55. NEW METHODS FOR THE PREPARATION OF t-BUTYLDIMETHYLSILYL TRIFLATE AND TRIMETHYLSILYL TRIFLATE.
Aizpurua, Jesus M.,Palomo, Claudio
, p. 6113 - 6114 (1985)
An expeditious synthesis of t-butyldimethylsilyl triflate is described from triflic acid and t-butyldimethylsilane.Reaction between trichloromethyltrimethylsilane and triflic acid is also reported.
Further reactions of chlorine(I) and bromine(I) trifluoromethanesulfonate and bromine(I)fluorosulfate
Johri, Kamalesh K.,Katsuhara, Yutaka,DesMarteau, Darryl D.
, p. 227 - 242 (1982)
Substitutive electrophilic dehalogenation reactions of CF3SO2OX (X=Cl,Br) are reported with some covalent inorganic chlorides. These reactions result in the formation of XX′(X,X′Cl,Br) and several new trifluoromethanesulfonate derivatives in excellent yields. Chlorine(I) trifluoromethanesulfonate also oxidatively adds to unsaturated inorganic substrates such as CO, SO2 and SF4 forming new compounds. The reactivity of CF3SO2OCl is rather similar to that of FSO2OBr and some comparisons between the two are given.
Synthesis method of trimethylsilyl trifluoromethanesulfonate
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Paragraph 0018-0023, (2021/04/29)
The invention relates to a synthesis method of trimethylsilyl trifluoromethanesulfonate. The target product trimethylsilyl trifluoromethanesulfonate is synthesized by taking trifluoromethanesulfonic acid and trimethylchlorosilane as main raw materials and n-heptane as a solvent through a one-step method. The method has the advantages of simple and easily available raw materials, simple and convenient operation, mild synthesis conditions, and good social and economic benefits.
Divergent Synthesis of Vinyl-, Benzyl-, and Borylsilanes: Aryl to Alkyl 1,5-Palladium Migration/Coupling Sequences
Han, Jie-Lian,Ju, Cheng-Wei,Qin, Ying,Zhao, Dongbing
supporting information, p. 6555 - 6560 (2020/03/03)
Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through-space metal/hydrogen shifts allow functionalization of C?H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5-palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl-, benzyl-, and borylsilanes, constituting a unique C(sp3)?H transformation based on a 1,5-palladium migration process.
A kind of triflic acid trimethyl Estersil method for the preparation of
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Paragraph 0113-0116, (2017/04/11)
The invention relates to a preparation method of Trimethylsilyl trifluoromethanesulfonate, and belongs to the field of a fine chemical industry. The preparation method comprises the following specific steps: a compound of which the general formula is CF3SO2X reacts with hydroxytrimethylsilane, wherein X is Cl, F or OSO2CF3, and hydroxytrimethylsilane is used as a silicon alkylation reagent of the reaction; the reduced pressure distillation is carried out on a reaction mixture after the reaction is finished to collect Trimethylsilyl trifluoromethanesulfonate of which the mass content is higher than 99.0%, wherein the mole ratio of the CF3SO2X to the hydroxytrimethylsilane in the reaction is (1.00: 0.80) to (1.00: 1.60), the reaction time is 1 to 10 hours, the reduced pressure distillation is carried out on the reaction mixture after the reaction is finished, and the pressure is 0.005 to 0.030MPa.
Redox Reactions of a Stable Dialkylphosphinyl Radical
Hirakawa, Fumiya,Ichikawa, Hitomi,Ishida, Shintaro,Iwamoto, Takeaki
supporting information, p. 2714 - 2716 (2015/06/30)
A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P?), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P? with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]- and [K(crypt-222)]+[RH2P]-. Whereas [K(18-c-6)]+[RH2P]- exists as a contact ion pair, [K(crypt-222)]+[RH2P]- exists as a solvent-separated ion pair in the solid state. Reaction of RH2P? with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).
Versatile reagent Ph3As(OTf)2: One-pot synthesis of [P7(AsPh3)3][OTf]3 from PCl3
Donath, Maximilian,Bodensteiner, Michael,Weigand, Jan J.
supporting information, p. 17306 - 17310 (2015/02/19)
Compound Ph3As(OTf)2 as a pentacoordinated AsV Lewis acid readily forms dicationic Lewis acid/base ad-ducts upon addition of various Lewis bases. It also represents a stronger chloride-abstracting agent than Me3SiOTf and facilitates the reductive coupling of PCl3 in the presence of AsPh3 to the unprecedented cation [P7(AsPh3)3]3+ as triflate salt. This crystallographically characterized nor-tricyclane-type cation represents a P7R3-derivative with the most electron-withdrawing substituents, resulting in a pronounced effect on the structural parameters of the P7 core.
Reaction of Carbodiimides with trifluoromethanesulfonic acid
Tolstikova,Shainyan,Chipanina
, p. 1853 - 1858 (2014/01/06)
Carbodiimides RN=C=NR (R = i-Pr, c-C6H11, Ph) react with trifluoromethanesulfonic acid with successive formation of O-triflyl isoureas RNHC(OTf)=NR, the isomeric N-triflyl ureas RN(Tf)C(O)NHR, and symmetrically substituted ureas RNHC
