- Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides
-
Phosphoranides are interesting hypervalent species which serve as model compounds for intermediates or transition states in nucleophilic substitution reactions at trivalent phosphorus substrates. Herein, the syntheses and properties of stable trifluoromet
- Shyshkov, Oleg O.,Kolomeitsev, Alexander A.,Hoge, Berthold,Lork, Enno,Haupt, Axel,Ke?ler, Mira,R?schenthaler, Gerd-Volker
-
supporting information
(2022/02/19)
-
- Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF3
-
Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.
- Zheng, Changge,Jiang, Chao,Huang, Shuai,Zhao, Kui,Fu, Yingying,Ma, Mingyu,Hong, Jianquan
-
supporting information
p. 6982 - 6986
(2021/09/08)
-
- Practical and efficient synthesis of aryl trifluoromethyl sulfones from arylsulfonyl chlorides with Umemoto's reagent II
-
A practical and efficient method for the synthesis of aryl trifluoromethyl sulfones has been developed by a tandem reaction of arylsulfonyl chlorides with Umemoto's reagent II. The advantageous features of this method are simple operation, mild reaction conditions, wide scope of substrates, high yield of products, and easy scalability.
- Zhou, Xiaocong,Hu, Dufen,He, Xinyi,Li, Yuanqiang,Chu, Youqun,She, Yuanbin
-
supporting information
(2019/12/24)
-
- Synthesis of Aryl Triflones through the Trifluoromethanesulfonylation of Benzynes
-
The direct synthesis of aryl triflones, that is, trifluoromethanesulfonyl arenes, was achieved through the trifluoromethanesulfonylation of benzynes. The trifluoromethanesulfonyl group, one of the fluorinated functional groups, is a highly electron-negative and mild lipophilic substituent. Aryl triflones have high potential in the synthesis of bioactive compounds and specialty materials. The treatment of 2-(trimethylsilyl)aryl trifluoromethanesulfonates with cesium fluoride in the presence of 15-crown-5 generated benzynes, which reacted with sodium trifluoromethanesulfinate followed by protonation with tBuOH under heating conditions, provided aryl triflones in moderated to good yields. Both symmetrical and unsymmetrical triflones were nicely accessed under the same reaction conditions. Interestingly, the trifluoromethanesulfonylation of unsymmetrical benzyne precursors proceeded smoothly to furnish corresponding aryl triflones in good yields with good to high regioselectivities. The balance of polarization of electric charge as well as steric hindrance of the benzyne intermediates are central factors to control the outcome of regioselectivity.
- Sumii, Yuji,Sugita, Yutaka,Tokunaga, Etsuko,Shibata, Norio
-
p. 204 - 211
(2018/03/02)
-
- A method of manufacturing a benzene derivative (trifluoromethylsulfonyl)
-
PROBLEM TO BE SOLVED: To provide a method for producing a (trifluoromethylsulfonyl)benzene derivative which is useful as a medicine, an agricultural chemical, a functional material and a production intermediate thereof. SOLUTION: In this method, a (trifluoromethylsulfonyl)benzene derivative is produced by reacting diaryliodonium salt represented by general formula (1) with trifluoromethanesulfinic acid salt in the presence of a copper (I) salt. (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9and R10each independently represents a hydrogen atom, a 1-6C alkyl group, a 1-6C haloalkyl group, a 1-6C alkoxy group, a 2-6C acyl group, (1-5C alkoxy)carbonyl group, a nitro group, a cyano group, a chlorine atom or a bromine atom). COPYRIGHT: (C)2013,JPOandINPIT
- -
-
Paragraph 0057; 0058
(2016/10/08)
-
- METHOD FOR PRODUCING TRIFLUOROMETHYLSULFONYL COMPOUND DERIVATIVE
-
PROBLEM TO BE SOLVED: To provide a method for producing a trifluoromethylsulfonyl compound derivative useful as synthetic intermediates for medicines and agrochemicals. SOLUTION: The method for producing a trifluoromethylsulfonyl compound derivative repre
- -
-
Paragraph 0019-0020;0021-0023
(2017/05/12)
-
- Organocatalyzed Trifluoromethylation of Ketones and Sulfonyl Fluorides by Fluoroform under a Superbase System
-
Fluoroform (HCF3, HFC-23) is a side product in the manufacture of polytetrafluoroethylene (Teflon). Despite its attractive properties, taming HCF3 for trifluoromethylation is quite problematic owing to its low acidity and the labilit
- Okusu, Satoshi,Hirano, Kazuki,Tokunaga, Etsuko,Shibata, Norio
-
p. 581 - 585
(2015/10/20)
-
- A new method for the synthesis of trifluoromethylating agents-Diaryltrifluoromethylsulfonium salts
-
A new synthetic method has been developed to prepare diaryltrifluoromethylsulfonium salts from diaryldifluorosulfuranes by the action of Me3SiCF3/F-. This reaction is the transformation of nucleophilic trifluoro-methylating reagent into electrophilic one.
- Yagupolskii, Lev M.,Matsnev, Andrej V.,Orlova, Raisa K.,Deryabkin, Boris G.,Yagupolskii, Yurii L.
-
p. 131 - 136
(2008/09/21)
-
- PREPARATION AND FLUORINATION OF ARYLTRIFLUOROMETHYLSULPHONES
-
A series of chloro- and nitrophenyl trifluoromethyl sulphides and sulphones have been synthesised from the corresponding aryl halides .The fluorination of these compounds by tetra-n-butyl ammonium fluoride and potassium fluoride has been investigated.Our results show that generally they are more susceptible to fluorodenitration than fluorodechlorination.
- Beaumont, Andrew J.,Clark, James H.
-
p. 295 - 300
(2007/10/02)
-
- A convenient route to aryl trifluoromethyl sulfones by fluoride-catalyzed cross-coupling of arenesulfonyl fluorides with (trifluoromethyl)trimethylsilane and (trifluoromethyl)trimethylstannane
-
Trifluoromethylsulfonyl substituted aromatic compounds 3a-d are prepared from the corresponding sulfonyl fluorides 1a-d by reacting with (trifluoromethyl)trimethylsilane (or-stannane) in the presence of a base under mild conditions in high yields.
- Kolomeitsev,Movchun,Kondratenko,Yagupolski
-
p. 1151 - 1152
(2007/10/02)
-
- SYNTHESIS AND REACTIVITY OF TRIFLUOROMETHYLAZOSULFONYLARENES
-
Trifluoromethylazosulfonylarenes were synthesized in high yields by treatment of trifluoronitrosomethane with arenesulfonamides in the presence of a base and their reactivity was examined.It was found that they acted as effective hydrogen-acceptors as well as trifluoromethylating agents.
- Sekiya, Akira,Umemoto, Teruo
-
p. 1519 - 1520
(2007/10/02)
-
- Stereoelectronic and Conformational Effects in Meisenheimer Complexes. Intrinsic Reactivities of Spiro vs. 1,1-Dimethoxy and 1-Methoxy-1-phenoxy Complexes
-
Rate and equilibrium constants of formation of spiro Meisenheimer complexes derived from 1-(2-hydroxyethoxy)-2,6-dinitro-4-X-benzenes in aqueous solution are compared with those for 1,1-dimethoxy Meisenheimer complexes derived from 2,4-dinitro-4-X-anisoles.Hammett ρ values for the equilibrium constants are 8.2 for the dimethoxy and 5.9 for the spiro complexes, while the normalized ρ values for the rate constants of complex formation (cleavage) are 0.44 (-0.56) for the dimethoxy and 0.58 (-0.42) for the spiro complexes.The large difference in the equilibrium ρ values is attributed to a conformation of a dimethoxy complexes in which there is repulsion between the lone pairs on the ketal and the o-nitro group oxygens.A procedure for making the reactions in the two families thermodynamically comparable by correcting the rate and equilibrium constants for the pKa difference in the nucleophile and for intramolecularity of spiro complex formation was applied.The corrected parameters show that the spiro complexes form and decompose much faster than the dimethoxy complexes.This enhanced reactivity, ΔΔG, is attributed to a stereoelectronic effect or p-? overlap between a lone pair orbital of the nonreacting oxygen and the benzene ring, which is only feasible in the transition state of the spiro complex reaction (14) but not in the thransition state of the dimethoxy complex reaction (15).This interpretation is strongly supported by the fact that ΔΔG increases with increasing electron-withdrawing strength of X substituent.The enhanced rate of formation and decomposition of the spiro complex from catehol 2,4,6-trinitrophenyl ether compared to that of the corresponding 1-methoxy-1-phenoxy complex can be explained in a similar way.
- Bernasconi, Claude F.,Howard, Keith A.
-
p. 7248 - 7257
(2007/10/02)
-