- Ag-Mediated Trifluoromethylthiolation of Inert Csp3-H Bond
-
Ag-mediated trifluoromethylthiolation of inert Csp3-H bond with CF3SOCl is described. Widely available reagents and operational simplicity make this protocol attractive.
- Zhao, Yue,Lin, Jin-Hong,Hang, Xiao-Chun,Xiao, Ji-Chang
-
-
Read Online
- Boron Trifluoride-Mediated Trifluoromethylthiolation of N-Acyliminiums
-
Herein, we describe a hitherto unprecedented trifluoromethylthiolation of N-acyliminiums promoted by boron trifluoride etherate to enable a convenient access to various α-amino trifluoromethylthiolate derivatives in good yields. The reaction proceeds under mild conditions, relying on copper(I) trifluoromethylthiolate as a nucleophilic partner. (Figure presented.).
- Maury, Julien,Force, Guillaume,Darses, Benjamin,Leb?uf, David
-
-
Read Online
- Copper-Catalyzed Domino Cyclization/Trifluoromethylthiolation of Unactivated Alkenes: Access to SCF3-Containing Pyrrolines
-
A novel and efficient copper-catalyzed cascade cyclization/trifluoromethylthiolation of unactivated olefins has been achieved with the stable and readily available AgSCF3 as the SCF3 source. A range of SCF3-substituted pyr
- Guo, Kang,Zhang, Honglin,Cao, Shujun,Gu, Chen,Zhou, Huating,Li, Jie,Zhu, Yingguang
-
-
Read Online
- -
-
2-Chloro-1,1,2,3,3,4,4,-heptafluoro-1,3-dithietane (7b), 2,4-dichloro-1,1,2,3,3,4-hexafluoro-1,3-dithietane (7c), 2-chloro-1,1,2,4,4-pentafluoro-3,3-dioxo-1,3-dithietane (9b), 2,4-dichloro-1,1,2,4-tetrafluoro-3,3-dioxo-1,3-dithietane (9c), and 1,1,2,2,4,4
- Henn,Sundermeyer,Witz,Pritzkow
-
-
Read Online
- A plasma synthesis for the perfluoroalkyl di-, tri-, and tetrasulfides: Reaction of trifluoromethyl radicals with sulfur vapor
-
A new synthesis for a number of perfluoroalkyl di-, tri-, and tetrasulfides (CF3SnCF3, C2F5SnCF3, C2F5SnC2F5, n = 2-4) has been developed using a low-temperature glow discharge to dissociate sulfur vapor and generate trifluoromethyl radicals from hexafluoroethane. These compounds were characterized by mass spectra, infrared spectra, and NMR spectra.
- Yasumura, Takashi,Lagow, Richard J.
-
-
Read Online
- Catalyst-Free Decarbonylative Trifluoromethylthiolation Enabled by Electron Donor-Acceptor Complex Photoactivation
-
A catalyst- and additive-free decarbonylative trifluoromethylthiolation of aldehyde feedstocks has been developed. This operationally simple, scalable, and open-to-air transformation is driven by the selective photoexcitation of electron donor-acceptor (EDA) complexes, stemming from the association of 1,4-dihydropyridines (donor) with N-(trifluoromethylthio)phthalimide (acceptor), to trigger intermolecular single-electron transfer events under ambient- and visible light-promoted conditions. Extension to other electron acceptors enables the synthesis of thiocyanates and thioesters, as well as the difunctionalization of [1.1.1]propellane. The mechanistic intricacies of this photochemical paradigm are elucidated through a combination of experimental efforts and high-level quantum mechanical calculations [dispersion-corrected (U)DFT, DLPNO-CCSD(T), and TD-DFT]. This comprehensive study highlights the necessity for EDA complexation for efficient alkyl radical generation. Computation of subsequent ground state pathways reveals that SH2 addition of the alkyl radical to the intermediate radical EDA complex is extremely exergonic and results in a charge transfer event from the dihydropyridine donor to the N-(trifluoromethylthio)phthalimide acceptor of the EDA complex. Experimental and computational results further suggest that product formation also occurs via SH2 reaction of alkyl radicals with 1,2-bis(trifluoromethyl)disulfane, generated in-situ through combination of thiyl radicals. (Figure presented.).
- Lipp, Alexander,Badir, Shorouk O.,Dykstra, Ryan,Gutierrez, Osvaldo,Molander, Gary A.
-
supporting information
p. 3507 - 3520
(2021/06/11)
-
- Facile syntheses of 3-trifluoromethylthio substituted thioflavones and benzothiophenes via the radical cyclization
-
3-CF3S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles, respectively, promoted by persulfate. This protocol possesses good functional group tolerance and high yields. Mechanistic studies suggested that a classic two-step radical process was involved, which includes addition of CF3S radical to triple bond and cyclization with SMe moiety.
- Wang, Lu,Wang, Huaiyu,Meng, Weidong,Xu, Xiu-Hua,Huang, Yangen
-
p. 389 - 392
(2020/03/04)
-
- Trifluoromethylthiolation and trifluoromethanesulfonylation of β,γ-unsaturated hydrazones
-
The trifluoromethylthiolation and trifluoromethanesulfonylation of β,γ-unsaturated hydrazones was accomplished with silver(I) trifluoromethanethiolate (AgSCF3) as a CF3S source and sodium trifluoromethylsulfinate (CF3SO2Na) as a CF3SO2 source, respectively. These general methods for the preparation of dihydropyrazoles containing CF3S or CF3SO2 groups were characterized by mild reaction conditions and good functional group tolerance.
- Xiao, Hongqing,Meng, Weidong,Xu, Xiu-Hua,Huang, Yangen
-
-
- Hydrotrifluoromethylthiolation of Unactivated Alkenes and Alkynes with Trifluoromethanesulfonic Anhydride through Deoxygenative Reduction and Photoredox Radical Processes
-
An ongoing challenge in trifluoromethylthiolation reactions is the use of less expensive and easily available trifluoromethylthio sources. Herein, we disclose an unprecedented usage of trifluoromethanesulfonic anhydride (Tf2O) as a radical trifluoromethylthiolating reagent. Hydrotrifluoromethylthiolation of unactivated alkenes and alkynes with Tf2O in the presence of PMePh2 and H2O under visible-light photoredox catalysis gave the addition products. The trifluoromethylthio radical (.SCF3) was first formed from Tf2O through a photoredox radical processes and deoxygenative reduction of PMePh2, and H2O serves as the H-atom donor for the hydrotrifluoromethylthiolation reaction. This reaction provides a new strategy for radical trifluoromethylthiolation.
- Ouyang, Yao,Xu, Xiu-Hua,Qing, Feng-Ling
-
supporting information
p. 18508 - 18512
(2019/11/14)
-
- TfNHNHBoc as a SCF3 source for the sulfenylation of indoles
-
An unprecedented use of trifluoromethanesulfonyl hydrazides as effective SCF3 sources has been established in the sulfenylation of indoles. A range of substituted indoles participated in CuCl-catalyzed oxidative sulfenylation reaction with TfNHNHBoc in the presence of dimethyl sulfoxide to furnish structurally diverse 3-indolyl trifluoromethyl thioethers in moderate to good yields with very high regioselectivity.
- Guo, Jing-Yu,Dai, Rui-Han,Xu, Wen-Cong,Wu, Ruo-Xin,Tian, Shi-Kai
-
supporting information
p. 8980 - 8982
(2018/08/21)
-
- Silver-mediated radical aryltrifluoromethylthiolation of activated alkenes by S-trifluoromethyl 4-methylbenzenesulfonothioate
-
Herein, we describe the preparation of trifluoromethylthiol-substituted oxindoles by silver-mediated aryltrifluoromethylthiolation of activated alkenes, using S-trifluoromethyl 4-methylbenzenesulfonothioate as a F3CS radical source and showing that the reagent availability, mild conditions, and broad functional group compatibility of this transformation make it a viable alternative strategy of constructing Csp3–SCF3 bonds.
- Zhao, Xia,Yang, Bo,Wei, Aoqi,Sheng, Jianqiao,Tian, Miaomiao,Li, Quan,Lu, Kui
-
p. 1719 - 1722
(2018/04/02)
-
- Radical Aromatic Trifluoromethylthiolation: Photoredox Catalysis vs. Base Mediation
-
Trifluoromethyl aryl sulfides (Ar-SCF3) constitute highly attractive building blocks due to their exceptional lipophilicity and chemical properties. Related protocols of radical aromatic trifluoro-methylthiolation of arenediazonium salts were developed that are based on the facile generation of intermediate aryl radicals. Their reactions with commercial F3CS-SCF3 under very mild conditions afforded a diverse set of Ar-SCF3 (3]Cl2} with the weak base-mediated dark reaction documented higher synthetic efficiency of the former but higher operational simplicity of the latter strategy.
- Koziakov, Denis,Majek, Michal,Jacobi von Wangelin, Axel
-
supporting information
p. 6722 - 6725
(2017/12/07)
-
- Silver-Mediated Oxidative Decarboxylative Trifluoromethylthiolation of Coumarin-3-carboxylic Acids
-
The introduction of trifluoromethylthio groups into organic compounds, in particular heterocycles, is important because of the prevalence of these structures in medicinally and agriculturally relevant molecules. Herein, the silver-mediated oxidative decarboxylative trifluoromethylthiolation of coumarin-3-carboxylic acids is reported. This methodology utilizes existing carboxylic acid functionalities for the direct conversion to CF3S groups and results in a broad scope of 3-trifluoromethylthiolated coumarins, including analogues of natural products, in moderate to excellent yields.
- Li, Minghao,Petersen, Jeffrey L.,Hoover, Jessica M.
-
supporting information
p. 638 - 641
(2017/02/10)
-
- (Pentamethylcyclopentadienyl)cobalt(III)-Catalyzed Direct Trifluoromethylthiolation of Arenes via C?H Activation
-
The direct trifluoromethylthiolation of arenes was realized via (pentamethylcyclopentadienyl)cobalt(III)-catalyzed C(sp2)-H activation and coupling with AgSCF3 under the assistance of a directing group. The reaction features redox-neutrality, mild conditions, broad substrate scope, and good functional group tolerance. Preliminary mechanistic studies have been conducted. (Figure presented.).
- Liu, Xu-Ge,Li, Qingjiang,Wang, Honggen
-
supporting information
p. 1942 - 1946
(2017/06/09)
-
- Novel Use of CF3SO2Cl for the Metal-Free Electrophilic Trifluoromethylthiolation
-
The regioselective trifluoromethylthiolation of indole derivatives was achieved under reductive conditions with trifluoromethanesulfonyl chloride as the readily available source of electrophilic SCF3 and a phosphine as the reducing agent. It is a straightforward process free from any metal and also applicable for the trifluoromethylthiolation of other azaarenes, enamines, and enoxysilanes.
- Chachignon, Hélène,Maeno, Mayaka,Kondo, Hiroya,Shibata, Norio,Cahard, Dominique
-
supporting information
p. 2467 - 2470
(2016/06/09)
-
- Copper-Catalyzed Perfluoroalkylthiolation of Alkynes with Perfluoroalkanesulfenamides
-
Copper-catalyzed direct perfluoroalkylthiolation of alkynes by using the corresponding perfluoroalkanesulfenamide reagent is reported. The selective mono- and bis-perfluoroalkylthiolation of alkynes can be conducted under very mild conditions (no base, room temperature) in very good to excellent yields. This approach, which uses a low toxicity, inexpensive copper catalyst that incorporates a commercially available ligand, is applied in the absence of any additional base. Preliminary mechanistic investigations shed some light on the nature of the unprecedented reactivity observed.
- Tlili, Anis,Alazet, Sébastien,Glenadel, Quentin,Billard, Thierry
-
supporting information
p. 10230 - 10234
(2016/07/19)
-
- Triphenylphosphine-Mediated Deoxygenative Reduction of CF3SO2Na and Its Application for Trifluoromethylthiolation of Aryl Iodides
-
We report herein a practical method for taming Langlois' reagent CF3SO2Na to generate CuSCF3 by a triphenylphospine-mediated deoxygenative reduction process. This chemistry highlights a novel utilization of the inherent CF3S skeleton of Langlois' reagent as a CF3S feedstock under mild conditions. The CuSCF3 intermediate generated by this protocol can react with a wide array of supporting ligands to furnish several air-stable [LCu(SCF3)] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF3 intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency. Efficient synthesis! A low cost method for the generation of CuSCF3 by a triphenylphospine-mediated deoxygenative reduction of Langlois' reagent (CF3SO2Na) has been developed (see scheme). This method can be applied for the convenient synthesis of a wide array of ligated and air-stable CuSCF3 complexes. Additionally, the CuSCF3 complexes generated in situ by this protocol were found to trifluoromethylthiolate (hetero)aryl iodides with high efficiency.
- Yang, Yi,Xu, Long,Yu, Siqi,Liu, Xiaoqiang,Zhang, Yu,Vicic, David A.
-
supporting information
p. 858 - 863
(2016/01/16)
-
- Direct electrophilic trifluoromethylthiolation of N-benzyl indoles using AgSCF3
-
A novel electrophilic trifluoromethylthiolation reaction system has been developed with AgSCF3used directly as the SCF3source, in the presence of KI/K2S2O8/I2. Various N-benzylindoles have been trifluoromethylthiolated successfully with this system, and the mechanism of investigation showed an electrophilic reagent was generated in situ.
- Ma, Lan,Cheng, Xiu-Fen,Li, Yan,Wang, Xi-Sheng
-
supporting information
p. 2972 - 2975
(2016/07/06)
-
- Copper(I)-mediated direct trifluoromethylthiolation of allylic halides with elemental sulfur and (trifluoromethyl)trimethylsilane
-
Abstract A new method has been developed for the copper-mediated trifluoromethylthiolation of allylic halides by using potassium fluoride, elemental sulfur, and (trifluoromethyl)trimethylsilane in anhydrous N,N-dimethylformamide. This protocol provides facile access to a variety of allylic trifluoromethyl thioethers in moderate to good yields under mild, ligand-free reaction conditions.
- Li, Jue,Wang, Peiqiang,Xie, Fei-Fei,Yang, Xi-Gang,Song, Xiao-Nan,Chen, Wei-Dong,Ren, Jiangmeng,Zeng, Bu-Bing
-
supporting information
p. 3568 - 3571
(2015/06/08)
-
- Silver-mediated oxidative aliphatic C-H trifluoromethylthiolation
-
The first example of a practical and direct trifluoromethylthiolation reaction of unactivated aliphatic C-H bonds employs a silver-based reagent. The reaction is operationally simple, scalable, and proceeds under aqueous conditions in air. Furthermore, its broad scope and good functional-group compatibility were demonstrated by applying this method to the selective trifluoromethylthiolation of natural products and natural-product derivatives.
- Guo, Shuo,Zhang, Xiaofei,Tang, Pingping
-
supporting information
p. 4065 - 4069
(2015/03/30)
-
- Copper-catalyzed regioselective trifluoromethylthiolation of pyrroles by trifluoromethanesulfonyl hypervalent iodonium ylide
-
The copper-catalyzed trifluoromethylthiolation of pyrroles with a trifluoromethanesulfonyl hypervalent iodonium ylide under mild conditions has been achieved. A broad set of pyrroles could be transformed to the corresponding products in moderate to excellent yields. The reaction mechanism is hypothesized.
- Huang, Zhongyan,Yang, Yu-Dong,Tokunaga, Etsuko,Shibata, Norio
-
supporting information
p. 1094 - 1097
(2015/03/14)
-
- Copper-catalyzed intramolecular oxytrifluoromethylthiolation of unactivated alkenes
-
A mild, versatile, and convenient method for efficient intramolecular oxytrifluoromethylthiolation of unactivated alkenes catalyzed by Cu(OAc)2 has been developed. The reactions were carried out under aerobic conditions and formed a variety of isoxazolines bearing a -SCF3 substituent. (Chemical Equation Presented).
- Zhu, Liping,Wang, Guoqiang,Guo, Quanping,Xu, Zhaoqing,Zhang, Di,Wang, Rui
-
supporting information
p. 5390 - 5393
(2015/01/09)
-
- Reaction of trifluoromethylsulfenyl chloride with 3-chloro- and 3-hydroxypropynes
-
Vinylsulfides are often obtained via the reaction of substituted acetylenes with sulfur-containing reagents. The presence of other functional groups such as the halide or the hydroxyl moieties enhances the usefulness of the vinylsulfide intermediates. To this end, propargyl alcohol and halides have found wide application. With a view to enhance the biological properties of the end products synthesized from the vinylsulfide intermediates, the trifluoromethylthio function has now been incorporated as a part of the vinylic system. This communication presents the free-radical addition of trifluoromethyl-sulfenyl chloride to 3-chloro- and 3-hydroxypropynes, and the mechanism of the formation of the various products and their spectral characterization.
- Munavalli,Rohrbaugh,Rossman,Berg,Durst
-
p. 1645 - 1655
(2007/10/03)
-
- A new synthesis of trifluoromethanethiolates - Characterization and properties of tetramethylammonium, cesium and di(benzo-15-crown-5)cesium trifluoromethanethiolates
-
[NMe4]SCF3, CsSCF3 and [(B-15-C-5)2Cs]SCF3 (B-15-C-5: benzo-15-crown-5) are formed from reactions of the corresponding fluorides, trimethyl(trifluoromethyl)silane, Me3SiCF3, and elemental sulfur in glyme or THF. All compounds are colorless to pale ochre solids decomposing significantly above ambient temperature. Excellent agreement between experimental and theoretical vibrational frequencies, calculated at the B3PW91 level of theory, impressively confirms the salt-like nature of [NMe4]SCF3. The properties of the title compounds as nucleophilic SCF3 transfer reagents were checked with a variety of organic, organometallic and inorganic compounds.
- Tyrra, Wieland,Naumann, Dieter,Hoge, Berthold,Yagupolskii, Yurii L.
-
p. 101 - 107
(2007/10/03)
-
- Reactions of trifluoromethylthiocopper with halomethanes
-
The reaction of trifluoromethylthiocopper with halomethanes, namely di-and triiodo-, dibromodichloro-, dibromochlorofluoro-, dibromo-difluoro-, bromochlorofluoro-, phenyltrichloro-, bromocyano-and dibromofluoro-methanes, has been investigated in detail. In addition to the expected compounds, the formation of unusual products such as bis (trifluoromethyl) trithiocarbonate, dimethyl (trifluoromethylthio) benzene, bis (trifluoromethylthio) fluoromethane, (trifluoromethylthio) carbonyl fluoride, carbon disulfide, carbon tetrachloride, trifluoromethylthio-benzoate, etc. was observed. In some cases, bis (trifluoromethylthio) mercury has been used instead of trifluoromethylthiocopper. The mechanism of formation of the various products and their mass spectral fragmentation behavior are described.
- Munavalli,Rossman,Rohrbaugh,Ferguson,Durst
-
-
- Synthesis, Structures and Properties of CF3S-Substituted Tellurium Compounds
-
New preparations for the following compounds are described: Te(SCF3)2, Te(NSO)2, and Cl2Te(NSO)2.The catalytic or thermal SO2 elimination from Cl2Te(NSO)2 affords a coordinated or non-coordinated thiachalcogenadiazole.Conversions of these compounds are reported.Evidence for the proposed mechanism for the reaction between Te(NSO)2 and SbCl5 is provided.Cl4Te2N2(SCF3)2, prepared from TeCl4 and CF3SN(SiMe3)2, reacts with LiN(SiMe3)2 to form 4Te2N2(SCF3)2.An X-ray structural analysis of Cl4Te2N2(SCF3)2 is presented. - Key Words: Tellurium, bis(sulfinylamido)-, bis(trifluoromethylthio)- / Thiachalcogenadiazole / Ditelluradiazetidine
- Boese, Roland,Dworak, Juergen,Haas, Alois,Pryka, Michael
-
p. 477 - 480
(2007/10/02)
-
- Synthesis of bis(trifluoromethyl)trisulfide and bis(trifluoromethylthio)selenide
-
The use of 4-dimethylaminopyridine as a catalyst in the reaction of trifluoromethylsulfenyl chloride with hydrogen sulfide at -78 deg C cuts down the time of reaction from 30 d to 1 d and gives up to 70percent yield of bis(trifluoromethyl)trisulfide (1).Similarly, bis(trifluoromethylthio)selenide (2) can be prepared from hydrogen selenide and trifluoromethylsulfenyl chloride.The influence of other catalysts on the course of the reaction, the formation of unusual by-products, the NMR and mass spectral data of 1 and 2 are presented in this paper.
- Munavalli, S.,Muller, A. J.,Rossman, D. I.,Rohrbaugh, D. K.,Ferguson C. P.
-
-
- Synthesis and Properties of S-(Trifluoromethyl)polysulfanemonosulfonates CF3SxSO2M
-
Hydrolysis of CF3SNSO with 2 equiv. of H2O provides (1), which on treatment with chlorine gives CF3SCl and .Trifluoromethyl thiosulfates are synthesized from Hg(SCF3)2 and ClSO2M .Insertion of SO3 into Hg(SCF3)2 provides Hg2 (6).Similarly, S-(trifluoromethyl)thiosulfuric acid (5) is obtained from CF3SH and SO3.New preparations for CF3SxNSO (x=1, 2) are described.These compounds are formed either from Hg(NSO)2 or (CH3)3SiNSO and CF3SxCl in good yields.CF3SSNSO (8) reacts with water to give (9).A 1:1 adduct (10) is obtained from CF3SNSO and AsF5.A preliminary X-ray structure investigation proved that AsF5 is coordinated to the oxygen atom.Some reactions of and CF3SSO2OSi(CH3)3 are mentioned. - Key Words: (Trifluoromethyl)sulfane- and -disulfanesulfonic acids / Mercury compounds / (Trifluoromethyl)sulfanyl-, -disulfanyl-, and -sulfinylimine / Arsenic compounds
- Brosius, Axel,Haas, Alois,Pryka, Michael
-
p. 457 - 464
(2007/10/02)
-
- Syntheses and Reactions of Fluoroorganic Acyclic Thiocarbenium Ions
-
Arsenic pentafluoride oxidizes (F3CS)4C (1) but not (F3CS)2C=C(SCF3)2 (2) to yield the stable salt (F3CS)3C(+)AsF6(-) (3).It reacts with halide ions to form (F3CS)3CX (3a-c, X = F, Cl, Br).Iodide is oxidized to iodine with formation of (F3CS)3CC(SCF3)3 (4) which reacts with nitrogen dioxide to give (F3CS)3CNO2 (3e). - (F3CS)3C(+)AsF6(-) (3) removes from (5a) a ring-bound fluorine atom to afford (F3CS)3CF and (5).When (F3CS)3CCl (3b) is treated with AsF5, 3 and (+)AsF6(-) (6) are formed in a 2:1 molar ratio.The latter reacts with F(-) or Cl(-) to give (F3CS)2CClX (6a,b; X = F, Cl).AsF5 is capable of abstracting a fluoride ion from (F3CS)3-nClnCF only if n = 0 or 1.For n = 2 no similar reaction takes place, but with AlCl3 in BCl3 halogen exchange to F3CSCCl3 (7b) is observed. - Alkylation of (F3CS)2C=S (8) with H3CF/AsF5 yields (+)AsF6(-) (9), which adds a fluoride ion to give (F3CS)2(H3CS)CF (9a).The molecular structures of (F3CS)2C=C(SCF3)2 (2) and (F3CS)3CC(SCF3)3 (4) have been determined by X-ray diffraction methods. - Key Words: (Trifluoromethylthio)carbon / Carbenium ions / One-electron oxidation / Superacidic systems
- Boese, Roland,Haas, Alois,Krueger, Carl,Moeller, Guido,Waterfeld, Alfred
-
p. 597 - 604
(2007/10/02)
-
- Tris(perfluoroorganochalkogenyl)methyl Compounds: Synthesis, Structures, and Properties
-
Reaction of (CF3S)2CHC(OC2H5)3 with CF3SCl or CF3SeCl in the presence of NaH in ether provides X(CF3S)2CC(O)OC2H5 (1a, b: X = CF3S, CF3Se).These compounds react with NH3 to form (CF3S)2CHC(O)NH2 (2b) which is also obtained from (CF3S)2CHC(O)OC2H5 and NH3.Dehydration of the amide 2b yields (CF3S)2CHCN (3b), which reacts with NaH and then with CF3SX (X = Cl, SCF3) or with RfCl (Rf = CF3Se, C6F5S) to give R'f(CF3S)2CCN f = CF3S (3c), CF3Se (3d), C6F5S (3e)>. 3c is also obtained from (CF3S)3CBr and AgCN.Hydrolysis of 3c with conc.H2SO4 leads almost quantitatively to (CF3S)3CC(O)NH2 (2c), which on treatment with COCl2 gives only 3c and not the corresponding isocyanate.If phosgene is replaced by oxalyl chloride and treated with 2c in a 1:1 molar ratio, (CF3S)3CC(O)NCO (4a) is formed.The urea derivative (CF3S)3CC(O)NHC(O)NHC(O)C(SCF3)3 (4b) is obtained either by using a 2:1 molar ratio of 2c and 2 or from 2c and 4a.Attempts to substitute (CF3S)2CHCO2H - after treatment with NaH in ether - with CF3SCl provides low yields of 2,4-bis-1,3-dithietane (5).X-ray structure analyses are performed for (CF3S)3CCN (3c) and the 1,3-dithietane 5. - Key Words: Trifluoromethylsulfanyl compounds / Pentafluorophenylsulfanyl compounds / Trifluoromethylselenanyl compounds
- Boese, Roland,Haas, Alois,Lieb, Max,Roeske, Ulrich
-
p. 449 - 456
(2007/10/02)
-
- Synthesis and biological screening of trifluoromethylthioarsenicals
-
The title compounds have been prepared from the reaction of trifluoromethylthiocopper and alkyl mono- and di-haloarsines.This communication describes their synthesis, biological screening and mass spectral fragmentation behavior.
- Munavalli, S.,Rossman, D. I.,Rohrbaugh, D. K.,Ferguson, C. P.,Buettner, L.
-
-
- Reactions of CF3SF: Addition to C=S Double Bonds
-
Trifluoromethanesulfenylfluoride, CF3SF, adds to the carbon-sulfur double bond to form fluorinated compounds containing a trifluoromethyldisulfanyl group.Reactions of CF3SF with CS2, CF2S, CCl2S and (CF3S)2CS are described. Keywords: Trifluoromethanesulfenylfluoride, Carbon Disulfide, NMR Spectra, Difluorobis(trifluoromethyldisulfanyl)methane, Fluorobis(trifluoromethylsulfanyl)(trifluoromethyldisulfanyl)methane
- Gombler, Willy,Bollmann, Gerd
-
p. 369 - 372
(2007/10/02)
-
- Simultaneous scission of C-S and S-S bonds of bis(trifluoromethyl)trisulfide by Grignard reagents
-
Trifluoromethyl mono-, di- and tri-sulfides, and alkyl sulfides and disulfides, as well as dimerized products, are formed as a result of the simultaneous cleavage of the C-S and S-S bonds of bis(trifluoromethyl)trisulfide by Grignard reagents at -78 deg C.The formation of various products has been rationalized on the basis of the involvement of free radicals.
- Munavalli, Shekar,Rossman, David I.,Rohrbaugh, Dennis K.,Ferguson, C. Parker,Szafraniec, Leonard J.
-
-
- REACTION OF ORGANIC COMPOUNDS WITH THE SF4-HF-HALOGENATING SYSTEM IX. REACTIONS OF PERFLUOROOLEFINS WITH THE SF4-HF-S2Cl2 SYSTEM
-
The reaction of perfluoroolefins with the SF4-HF-S2Cl2 system leads to perfluoroalkanesulfenyl chlorides, thiosulfenyl chlorides, and polysulfides.Preparative methods were developed for the production of trifluoromethanesulfenyl, perfluoroethanesulfenyl, perfluoro(1-methylethane)sulfenyl, and perfluoro(1-methylheptane)sulfenyl chlorides and the corresponding sulfonyl chlorides.
- Kunshenko, B. V.,Omarov, V. O.,Muratov, N. N.,Yagupol'skii, L. M.
-
p. 684 - 690
(2007/10/02)
-
- TRANSFORMATION OF ORGANOPHOSPHORUS S-TRIFLUOROMETHYLTHIOATES RR'P(O)SCF3 INTO FLUORIDES RR'P(O)F. STEREOCHEMICAL ASPECTS OF THIOCARBONYL FLUORIDE EXTRUSION
-
The stereochemical course of the thermal or by nucleophiles catalyzed extrusion reaction of thiocarbonyl fluoride from two diastereomeric (6) and optically active (10) organophosphorus S-trifluoromethylthioates has been investigated.To explain the observed retention of configuration at phosphorus in fluoridates 7 formed in the thermal reactions, a four center transition state for such reactions has been proposed.The lack of the stereoselectivity in the catalyzed reactions of 6, and the observed racemization of the final product 11 are briefly discussed.
- Lopusinski, Andrezej
-
p. 383 - 390
(2007/10/02)
-
- The preparation of thiazyltrifluoromethane, CF3SN, the hexachloro-3-cyclopentenylidenaminosulfides C5Cl6NSX (X = CF3, Cl, NSO, SCF3, C5Cl6N) and the crystal structures of C5Cl6NSX (X = CF3, Cl)
-
CF3S(Cl)=NSi(CH3)3 is found to undergo intermolecular decomposition to give oligomeric, possibly cyclic (CF3SN)x rather than monomeric CF3SN, formed by intramolecular decomposition.Monomeric thiazyltrifluoromethane, CF3SN, is formed in the thermal decomposition of CF3SN3 and may be trapped before polymerizing by formation of a 1 : 1 adduct with hexachlorocyclopentadiene.The structure of this adduct is determined by single crystal X-ray diffraction.From the molecular structure it is evident that a (4 + 2) cycloaddition has not occurred but rather the formation of a thioketimine (I).The same material is formed when a suspension of CF3SNH2 and lead(IV) acetate in CH2Cl2 is refluxed and the intermediate CF3SN is again trapped by C5Cl6.By comparison ClSN and C5Cl6 interact in an analogous manner to give C5Cl6NSCl (II), whose structure was determined by single crystal X-ray diffraction.FSN, on the other hand, when reacted with C5Cl6 yields the corresponding fluoro derivative only as an intermediate.At 20 deg C using SO2 as solvent C5Cl6NSCl (II) is formed.A 75 deg C in SO2 the new compound C5Cl6N-S-NSO forms.The latter compound may also be formed from (II) and Hg(NSO)2.In the reaction of FSN with C5F6 only decomposition products were observed.Some of the reactions of C5Cl6NSCl (II) were investigated.With Hg(SCF)2 C5Cl6N-SSCF3 is obtained; with SbCl5 in SO2C5Cl6N-S-NC5Cl6 forms as the main product.Key words: synthesis of CF3SN, preparation of C5Cl6NSX (X = CF3, Cl, NSO, SCF3, C5Cl6N), crystal structures of C5Cl6NSX (X = CF3, Cl), chemical properties of C5Cl6NSCl, nmr-, ir-, ms-data.
- Haas, Alois,Mischo, Thomas
-
p. 1902 - 1908
(2007/10/02)
-
- ON SOME NEW TRIFLUOROMETHYL IODINE(III) COMPOUNDS: REACTIONS OF CF3IF2 WITH BORON AND SILICON COMPOUNDS AND CF3ICl2 WITH SILVER SALTS
-
CF3IF2 undergoes fluorine exchange reactions with BX3 (X = Cl, Br, I, OCOCF3) to form the compounds CF3IX2.The reactions of CF3IF2 with (CF3)2BN(CH3)2, (CH3)3SiNCO and (CH3)3SiN(CH3)COCF3 yield the corresponding new trifluoromethyl iodine (III) nitrogen compounds.A preparative method for the synthesis of CF3ICl2 is found by reacting CF3IF2 with (CH3)3SiCl.CF3ICl2 reacts with AgX (X = OCOCF3, SCF3) to yield the corresponding CF3IX2 compounds and with (C6H5)4AsCl the novel ion (-) is detected.Products were identified by n.m.r. spectroscopy.
- Tyrra, Wieland,Naumann, Dieter
-
p. 401 - 416
(2007/10/02)
-
- Preparation and Chemical Properties of S-(Trifluoromethyl)-S,N-dihalosulfimides, (Trifluoromethylthio)(thiosulfinyl)amine, and Bis(trifluoromethyldithio)sulfur Diimide
-
Oxidative halogenation of CF3SN(SiMe3)2 with F2 or Cl2 leads to CF3S(X)=NX (X=F, Cl) (2a, b).During the chlorination process CF3S(Cl)=NSiMe3 (3a) was isolated and characterized as an intermediate.It reacts with CF3SCl to give CF3S(Cl)=NSCF3 (3b) which was also obtained from (CF3S)2NH and Cl2 at -60 deg C.Similarly, CF3S(F)=NSCF3 (3c) was synthesized from (CF3S)2NH and F2 or from CF3SF3 and CF3SNH2. 3a-c decompose already at temperatures 5a, b).Analoguosly, CF3SN=S=NSCF3 (4b) reacts with cyclopentadiene to give 5c.Ringopening takes place during the reaction of + Cl- (6) with Hg(SCF3)2 with formation of CF3SSN=S=NSSCF3 (7) which was also obtained from (CF3SS)2NH and (ClSN)3 in the presence of pyridine.Physical and spectroscopic data of the compounds are reported.
- Haas, Alois,Walz, Ruediger
-
p. 3248 - 3257
(2007/10/02)
-
- DARSTELLUNG UND THERMOLYSE VON HEXAKIS(PERFLUORORGANYLTHIO/SELENO)ETHANEN
-
Thiocarbonylcompounds such as 1a, 1b, 1c, 1d, 1e and 1f were prepared and irradiated with UV-light in hexane solution.The products obtained in this photolyses are 3a, 3b and 3c.Only 3c dissociates in the temperature range 140-190 deg C reversible to 2c.The others, 3a and 3b, decompose yielding bis(trifluoromethyl)diselenide, 6b and 6d, without forming the corresponding methyl radical 2a and 2b.This was proved by spin-trapping experiments utilizing phenyl-t-butylnitrone.Attempts to prepare 3e were unsuccessful but led to the new compounds 7a, 7b, 7c, 1,1,1-tris(trifluoromethylseleno)ethan (7d) and, surprisingly, 9.Physical and spectroscopic data of the newly prepared substances are provided.
- Haas, Alois,Kempf, Karl W.
-
p. 4963 - 4972
(2007/10/02)
-
- (Perhalomethylthio)heterocycles, XIV. Preparation and Properties of N-Substituted Tetrakis(trifluoromethylthio)pyrroles
-
2,3,4,5-Tetrakis(trifluoromethylthio)pyrrole (1) reacts with bases and Lewis bases to give salts and 1:1 adducts, respectively.The potassium (2b) and sodium salt (2c) as well as the adducts of pyridine (2d), NH3 (2e), and trimethylamine (2f) were prepared.Reactions of the silver or potassium salts with sulfenyl chlorides or SxCl2 (x = 1,2) give N-sulfenylated pyrroles 6a-f as well as dipyrrolylsulfane 5a and -disulfane 5b.Pentakis(trifluoromethylthio)pyrrole (6a) is a good mild sulfenylating agent, exchanging the CF3S group for acidic hydrogen atoms in alcohols, thioalcohols and amines.The silver salt 2a reacts with CF3SeCl to form 1-(trifuoromethylselenyl)-2,3,4,5-tetrakis(trifluoromethylthio)pyrrole (6g).Except 2a,d,f all other substances are sensitive against hydrolysis.
- Ceacareanu, Dumitru M.,Gerstenberger, Michael R. C.,Haas, Alois
-
p. 3325 - 3331
(2007/10/02)
-
- Reversible N-N Bond Homolysis in (CF3S)2N-N(SCF3)2 at Room Temperature. Electron Spin Resonance, Thermodynamic, and Kinetic Results
-
In perhaloalkane solvents at 250-315 K (CF3S)2N-N(SCF3)2 undergoes reversible homolytic cleavage reaction to yield (CF3S)2N* radicals which were identified by ESR.From the dependence of the stationary concentration of (CF3S)2N* on temperature the N-N bond dissociation energy is determined to be 32 +/- 2 kJ/mol (7.7 kcal/mol).At 298 K the equilibrium constant for N-N homolysis is (4 +/- 2) * 10-6 M.The change in entropy occuring on N-N homolysis corresponds to 3 J/K mol (0.7 eu).The activation enthalpy and entropy for N-N bond cleavage are 77 kJ/mol (18.4 kcal/mol) and 5 J/K mol (1 eu), respectively.The experimental results concerning the facile N-N homolysis are interpreted in terms of sterically and electronically induced destabilisation of the N-N bond in (CF3S)2N-N(SCF3)2.
- Schlosser, K.,Steenken, S.
-
p. 1504 - 1506
(2007/10/02)
-
- Preparation and Properties of Tetrakis(trifluoromethylthiazyl), (CF3SN)4
-
Tetrakis(trifluoromethylthiazyl) was prepared from CF3SCl and (CH3)3SiN3.At -30 deg C it is stable for a few days.On standing it oligomerizes and after 7 days at 20 deg C the melting point is above 180 deg C.By addition of F2 to CF3SNCO at -78 deg C CF3S(F)N=C(O)F is formed in good yield.In the presence of HgF2 it decomposes at 25 deg C to (CF3SN)x. - 19F NMR, IR, UV, and mass spectra are given.
- Bielefeldt, Dietmar,Haas, Alois
-
p. 1257 - 1260
(2007/10/02)
-
- (PERHALOGENMETHYLTHIO)-HETEROCYCLEN, XV. Saeure- und basekatalysierte Umsetzungen von Furan, Selenophen und Pyridin
-
In the presence of Lewis acids furan reacts with CF3SCl to form 2-trifluoromethylmercaptofuran 1 in yields of less than 1 percent.The yield is increased to 35 percent, if the reaction is carried out in the presence of pyridine. 2-Methyl-5-chlorofluoromethylmercaptofuran 4b-d were prepared similarly.Oxidation of 1 with m-chloroperbenzoic acid leads to the formation of 2-trifluoromethylsulfinyl- 5 and 2-trifluoromethylsulfonylfuran 6 in low yield.Cyclisation of 2,5-hexanedione in the presence of CFnCl3-nSCl gives 2,5-dimethyl-3-CFnCl3-nS-furan (for n = 3, 7a; n = 2, 7b) and 1-chlorodifluoromethylmercapto-2,5-hexanedione 8 for n = 2.Selenophene reacts with CF3SCl in the presence of SnCl4 to give 2-trifluoromethylmercaptoselenophene 9, which, with the aid of CF3SO3H, can be disubstituted to 2,5-bis(trifluoromethylmercapto)selenophene 10. 3,5-Bis(trifluoromethylmercapto)pyridine 12 can be isolated in small amounts as a byproduct obtained during the syntheses of 3-trifluoromethylmercaptopyridine 11.
- Gerstenberger, M. R. C.,Haas, A.
-
p. 525 - 540
(2007/10/02)
-
- Preparation of Perfluorinated Hexakis(alkylthio- and -seleno)ethanes
-
The perfluorinated perhetero-substituted ethanes 2a - c are prepared by irradiation of the thiocarbonates 1a - c.Upon UV-irradiation (λmax = 300 nm) bis(trifluoromethyl) trithiocarbonate (1a) decomposes by a cage process to give carbon disulfide, trifluoromethyl- and trifluoromethylthiyl radicals.In the solvent cage these radicals partly dimerize producing 3.The formation of 2a is interpreted in terms of a competition between this combination process and trapping of trifluoromethyl radicals by 1a, forming 4a, which then dimerizes.A similar mechanistic pathway is pro posed for the formation of 2b and 2c.
- Schlosser, Karl
-
p. 1083 - 1088
(2007/10/02)
-
- Photochemical Behaviour of Bis(trifluoromethylthiyl)trithiocarbonate in Solution
-
Bis(trifluoromethylthiyl))trithiocarbonate showes electronic transitions at 496 nm (n?*), 299 nm (??*) and 259 (n?*).Photolysis with 254 and 300 nm light at 200 and 309 K in pentane, and at 371 K in heptane yields a mixture of CS2 and perfluorinated compounds such as F3CSCF3, F3CSSCF3, (F3CS)3C-C(SCF3)3, (F3CS)2C=C(SCF3)2, (F3CS)3CH and F3CS-substituted solvent.The concentration of these newly formed products versus time of irradiation has been monitored.The primary photochemical process is the intramolecular decomposition into CS2 and F3CS and F3C radicals which dimerize in a solvent cage.The formation of (F3CS)3C-C(SCF3)3 is interpreted in terms of a competition between this combination process and trapping of trifluoromethyl radicals by (F3CS)2CS, forming (F3CS)3C, which subsequently dimerizes.On irradiation at 496 nm (n?*) no photochemical process has been observed. - Key words: Bis(trifluoromethylthiyl)trithiocarbonate, Electronic Spectra, Photochemical Behaviour, Tris(trifluoromethylthiyl)methyl Radical
- Schlosser, Karl
-
p. 172 - 178
(2007/10/02)
-
- Chemistry of Trifluoromethyl-Sulfur-Nitrogen Compounds, XI. Reactions of (CFnCl3-nS)xNH3-x with Selected Aldehydes
-
CF3SNH2 and CF2ClSNH2 react with formaldehyde to yield (RNCH2)n (n = 3, 4, 5, R = SCF3 2c, d, e; n = 3, 4, R = SCF2Cl 2a, b), (2f), (2g), (2h), and CF2ClSN(CH3)CH2N(CH3)SCF2Cl (3), respectively, and with benzaldehyde to give C6H5CH=NR (R = SCF3 1b, SCF2Cl 1a). (CF3S)2NH reacts with formaldehyde under various conditions to yield (CF3S)2NCH2OH (4), (CF3S)2NxCH2N(SCF3)2 (x = 0 - 5, 5a - f), (CF3S)2NmCH2N(SCF3)2 (m = 1, 2, 6a, b), and (CF3SNH2)3 (2c).In the reaction of the less reactive (CF2ClS)2NH with formaldehyde (CF3ClS)2NnCH2N(SCF2Cl)2 (n = 1, 2, 8a, b) are obtained.The base adduct (CF3S)2NH.N(CH3)3 decomposes thermally to yield (CF3S)2NCH2N(H)SCF3 (7) and 5a.A reaction path is proposed.IR-, 1H-, 13C-, 19F NMR data well as mass spectra are presented.
- Borowski, Herbert E.,Haas, Alois
-
p. 523 - 532
(2007/10/02)
-
- Free-Radical Reactions of Fluoroalkanesulfenyl Halides. 4. Reactions of Perfluoroalkane- and Pentafluorobenzenesulfenyl Chlorides with Hydrocarbons in the Presence of Fluorinated Disulfides
-
Free-radical reactions of perfluoroalkanesulfenyl chlorides and pentafluorobenzenesulfenyl chloride with cyclohexane and toluene were carried out in the presence of bis(perfluoroalkyl) disulfides and bis(pentaflurophenyl)disulfide to assess the competition between the disulfide and the sulfenyl chloride for reaction with hydrocarbon radicals.With added bis(perfluoroalkyl) disulfides, radical attack occurs only on the sulfenyl chloride, but with added bis(pentafluorophenyl) disulfide, attack occurs on both sulfenyl chloride and disulfide.
- Harris, J. F.
-
p. 268 - 271
(2007/10/02)
-
- Tetrakis(trifluoromethylthiyl)hydrazine - an Unusually Thermolabile Hydrazine Derivative
-
2 (1) prepared by irradiation of (CF3S)3N underwent homolytic N-N-bond dissociation below room temperature to give (CF3S)2N-radicals, which were identified by ESR.The easy N-N-bond cleavage is ascribed to steric strain in 1 and electronic stabilization of 2. - Keywords: Tetrakis(trifluoromethylthiyl)hydrazine, Bis(trifluoromethylthiyl)aminyl Radical, Homolytic N-N-Bond Cleavage, ESR Spectra
- Schlosser, Karl
-
p. 1544 - 1546
(2007/10/02)
-
- High-pressure interaction of sulfur hexafluoride with carbon disulfide and carbonyl sulfide
-
Sulfur hexafluoride has been found to react with carbon disulfide and carbonyl sulfide. At a minimum of 485° (1360 atm) with carbon disulfide the products are (CF3)2S, (CF3)2S2, carbon, and sulfur. Carbonyl sulfide reacts at 500° (270 atm) forming CF4, SOF2, and sulfur. No reaction takes place with carbon monoxide or carbon dioxide at conditions up to 500° (4000 atm). Graphite reacts at 500° (135 atm) forming CF4 and SF4 in a reaction which becomes nearly quantitative at 500° (4000 atm). When (CF3)2S2 is combined with carbon disulfide at 540° (4000 atm) the products include carbon, sulfur, and fluoroalkanes. The observed interaction of CO2, COS, and CS2 with SF6 can be best explained by an initial reaction which results in the formation of SF4, COF2 or CSF2, and sulfur.
- Hagen, Arnulf P.,Callaway, Bill W.
-
p. 2825 - 2827
(2007/12/03)
-