183267-04-1Relevant articles and documents
Preparation and reactivity of tris(trifluoromethylselanyl)carbenium |(CF3Se)3C+l and trifluromethylsulfanylacetic acid derivates [CF3S3-nCXn(O)R]
Haas, Alois,Moeller, Guido
, p. 1383 - 1388 (1996)
Reaction pathways for the synthesis of the (CF3E)3C moieties (E = Se, S) are described. [(CF3Se)3C+HAsF6-] was found to be a suitable synthon for the preparation of (CF3Se)3C derivatives. It can be prepared either from (CF3Se)4C or (CF3Se)3CF and AsF5 in liquid SO2. Direct access to (CF3Se)3CF was realized by the reaction of FCBr3 with Hg(SeCF3)2. Treatment of [(CF3Se)3C+][AsF6-] with potassium halides provided (CF3Se)3CX (X = F, Cl, Br). A different course took the reaction with KI, as CF3SeSeCF3 and (CF3Se)2C=C(SeCF3)2 were formed as main products. Minor amounts of (CF3Se)3CC(SeCF3)3 were formed which could be isolated and unambiguously characterized. Only two routes led to a threefold CF3S-substituted acetic acid ester (CF3S)3CC(O)OR [R= CH3, (CH3)3C]: Metatheses between (CF3S)2CBrC(O)OCH3 and Hg(SCF3)2 and metalation of (CF3S)2CHC(O)OR [R = CH3, (CH3)3C] with NaH followed by reaction with CF3SCL. Other precursors such as (CF3S)2CXC(O)OR′ [X = H, Br; R′ = Me3Si, (n-C4H9)3Sn] and (CF3S)2CBrC(O)Y (Y = Cl, Br) were synthesized but could not be converted to the corresponding (CF3S)3C derivatives. Attempts to hydrolyze (CF3S)3CC(O)OR to (CF3S)3CC(O)OH failed. VCH Verlagsgesellschaft mbH, 1996.
Synthetic method of succinimide type trifluoromethyl sulfuration reagent
-
Paragraph 0013-0014, (2021/05/12)
The invention belongs to the technical field of synthesis of organic compounds, and relates to a synthesis method of a succinimide type trifluoromethyl sulfide reagent. The CAS number of the reagent is 183267-04-1, and the structural formula of the reagent is shown in a formula (1) as described in the specification. According to the synthetic method of the succinimide type trifluoromethyl sulfide reagent, a nitrogen halogenated compound containing a succinimide structural framework, trifluoromethanesulfonate, nonafluorobutyl sulfonate, methanesulfonate and p-toluenesulfonate are used as reaction substrates and trifluoromethylthioester is used as a trifluoromethylthio source, for synthesis of the trifluoromethyl sulfuration reagent. According to the method, trifluoromethylthioester is taken as the trifluoromethylthio source, generates trifluoromethylthio negative ions under activation of fluorine negative ions, and conducts nucleophilic substitution on a reaction substrate, so the construction of a nitrogen-sulfur bond is realized, and the trifluoromethyl sulfuration reagent is obtained after separation and purification. According to the synthesis method of the trifluoromethyl sulfuration reagent, the raw materials are easy to prepare, the reaction reagent is low in price, the synthesis cost of the trifluoromethyl sulfuration reagent is remarkably reduced, and industrial production is facilitated; synthesis conditions are mild, and operation is simple and safe; and transition metal elements are not needed, and the method is green and environment-friendly.
Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents
Zhang, Jingjing,Yang, Jin-Dong,Zheng, Hanliang,Xue, Xiao-Song,Mayr, Herbert,Cheng, Jin-Pei
supporting information, p. 12690 - 12695 (2018/09/25)
The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free-energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido-derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X?SCF3 bonds (Tt+DA), the cumol-derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O?S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis.
Preparation of Electrophilic Trifluromethylthio Reagents from Nucleophilic Tetramethylammonium Trifluoromethylthiolate
Kovács, Szabolcs,Bayarmagnai, Bilguun,Goossen, Lukas J.
supporting information, p. 250 - 254 (2017/02/05)
A straightforward synthetic entry to the principal classes of electrophilic trifluoromethylthiolating agents is presented. It draws on inexpensive, shelf-stable tetramethylammonium trifluoromethylthiolate (Me4N–SCF3) as the SCF3source in the place of stoichiometric coinage metal-SCF3complexes. (Figure presented.).
A conjugate Lewis base-Br?nsted acid catalyst for the sulfenylation of nitrogen containing heterocycles under mild conditions
Nalbandian, Christopher J.,Miller, Eric M.,Toenjes, Sean T.,Gustafson, Jeffery L.
supporting information, p. 1494 - 1497 (2017/02/05)
Catalysts that contain a thiourea tethered to a carboxylic acid were found to affect the sulfenylation of indoles and other N-heterocycles on the hour time scale at room temperature. The mild nature of these conditions allowed for the incorporation of diverse functionalities into more complex heterocycles.
Oxidative trifluoromethylthiolation of terminal alkynes with AgSCF 3: A convenient approach to alkynyl trifluoromethyl sulfides
Zhu, Sheng-Qing,Xu, Xiu-Hua,Qing, Feng-Ling
supporting information, p. 4453 - 4456 (2014/08/05)
A new method for the efficient synthesis of alkynyl trifluoromethyl sulfides was developed. By combining AgSCF3 and NCS in N,N-dimethylacetamide, an electrophilic active intermediate was produced, which was then treated with a variety of terminal alkynes to afford the corresponding trifluoromethanesulfenylated products in moderate to excellent yields. A new oxidative trifluoromethylthiolation system, AgSCF3/NCS, is developed and applied in the efficient synthesis of alkynyl trifluoromethyl sulfides. Various desired compounds are obtained under mild conditions in moderate to excellent yields. Copyright
Palladium-catalyzed trifluoromethylthiolation of aryl C-H bonds
Xu, Chunfa,Shen, Qilong
supporting information, p. 2046 - 2049 (2014/05/06)
A method for monotrifluoromethylthiolation of arenes via palladium-catalyzed directed C-H bond activation was described. The reaction was compatible with a variety of functional groups. Initial mechanistic studies disclosed that the turnover limiting step of the catalytic cycle did not involve C-H activation.
