Synthetic routes to S-(trifluoromethyl)phenyl-4-fluorophenylsulfonium triflate (8), S-(trifluoromethyl)phenyl-2,4-difluorophenylsulfonium triflate (9), S-(trifluoromethyl)phenyl-3-nitrophenylsulfonium triflate (10), and S-(trifluoromethyl)-4-fluorophenyl-3-nitrophenylsulfonium triflate (11) are described. They are stable molecules and conveniently prepared by treating phenyl trifluoromethyl sulfoxide with benzene and its derivatives. These novel electrophilic trifluoromethylating agents react under mild conditions with a variety of aromatic rings (p-hydroquinone, pyrrole, and aniline) to give trifluoromethylated compounds (2-trifluoromethyl-p-hydroquinone, 2-trifluoromethylpyrrole, 2-trifluoromethylaniline, and 4-trifluoromethylaniline) in moderate to high yields. The electrophilic trifluoromethylating potential can be altered by placing electron-withdrawing substituents on the benzene rings.

The low reactivity of carboxylic esters toward (trifluoromethyl)trimethylsilane (TMS−CF3) was investigated. A universal cesium fluoride catalyzed procedure for nucleophilic trifluoromethylation was developed. At room temperature (25 °C), with catalytic amounts of cesium fluoride, carboxylic esters were found to react to give the silyl ether intermediates, which afforded the trifluoromethyl ketones after hydrolysis. Sulfonic, sulfinic, and selenic esters also show good reactivity, giving novel trifluoromethylated compounds. The trifluoromethylation method was also applied to aldehydes and ketones, which were transformed to trifluoromethyl silyl ether intermediates and afforded trifluoromethylated alcohols in excellent yields after acid hydrolysis. Ethylene glycol dimethyl ether was used as solvent for solid or high boiling substrates, and benzonitrile was used for the low boiling substrates.

Lithium bis((trifluoromethyl)sulfonyl)amide (1) reacts with S2O6F2 to form FS020N(S02CF3)2 (2). Reaction of 2 with KF results in the cleavage of the S-N bond with the concomitant formation of CF3S02F. The ease of electrophilic addition reactions of HN(S02CF3)2 (3) with CH2=CHF, CH2=CF2, and CHF=CF2 depends upon the hydrogen content of the olefin. Addition occurs in a unidirectional fashion according to Markovnikov's rule to form CH3CHFN(S02CF3)2 (4), CH3CF2N(S02CF3)2 (5), and CH2FCF2N(S02CF3)2 (6), respectively. Cleavage of the CF3-N bond in 5 by reaction with CsF leads to the formation of CH3CF3 in about 12% yield. The major product formed is CF3S02F. The reactivity of fluorine atoms of the difluoromethylene group of 5 is shown by its reaction with (CH3)3SiN(CH3)2 in the presence of CsF under mild conditions where CF3S02F, (CH3)3SiF, and CH3C [N(CH3)2]=NS02CF3 (7) are formed. AgN(S02CF3)2 is formed by the reaction of Ag2C03 with an aqueous solution of 3 and undergoes metathetical reactions readily with compounds containing active halogen atoms to introduce the N(SC>2CF3)2 group. Strong Lewis acids such as ZN(S02CF3)2 [Z = R3Sn, R = CH3 (8), H-C4H9 (9), and CeHs (10); Z = (CH3)3Si ( 11)] can thus be conveniently prepared. The vinyltin(IV) compound (CH3)3-SnCF=CF2 ( 12) is synthesized by the reaction between (CH3)3SnCl and CF2=CFBr in hexaethylphosphorus triamide and benzonitrile. Multinuclear NMR studies of the trialkylstannyl/silyl derivatives suggest a quasitetrahedral structure around the central silicon or tin atom as reflected by their very low 29Si (55.9 ppm) and u9Sn (~250 ppm) NMR chemical shifts and V(119Sn-13C) and 2/(119Sn-'H) coupling constants. Compounds 8,9, and 11 can also be isolated by reaction of C1N(S02CF3)2 ( 13) with the respective alkylmetal chlorides in a noncoordinating solvent. However, 13 fails to add across the perfluorovinyl group in CF2=CFSn(CH3)3 ( 12) and forms CF2=CFC1 1and 8 instead. Reactions of 13 with a variety of per/polyfluoroolefins, such as CF2=CFX

Bifunctional trimethylsilyl ethers/thioethers/dithioethers react readily with N3P3F6 in the presence of a catalytic amount of CsF in THF to yield spirofluorophosphazenes or dangling or bridged fluorophosphazenes with concomitant elimination of Me3SiF. With sulfur-containing aliphatic bifunctional reagents of the type Me3SiX(CH2) n SSiMe3, five- and six-membered monospirofluorophosphazenes, N3P3F4[X(CH2) n S] [X = O or S; n = 2 or 3] (1−4), are formed in good yield. Crystals of N3P3F4[OCH2CH2S] (1) are monoclinic, P21/c; fw = 287.05, a = 8.727(10) Å, b = 11.246(2) Å, c = 9.787(2) Å, β = 100.91(10)°, V = 943.2(3) Å3, and Z = 4. N3P3P4[OCH2CH2CH2S] (2) is orthorhombic, Pbca; fw = 301.08, a = 12.399(4) Å, b = 10.105(2) Å, c = 16.787(2) Å, V = 2103.3(9) Å3, Z = 8. N3P3F4[SCH2CH2S] (3) is triclinic, P1̄; fw = 303.11, a = 9.501(2) Å, b = 9.764(3) Å, c = 11.092(5) Å, α = 74.97°, β = 88.03°, γ = 85.85°, V = 991.0(6) Å3, and Z = 2. N3P3F4[SCH2CH2CH2S] (4) is orthorhombic, Fdd2; fw = 317.14, a = 18.238(4) Å, b = 41.390(8) Å, c = 5.965(12) Å, V = 4503(2) Å3, and Z = 16. The 31P NMR spectra of these derivatives show a large dependence on the ring size and an attempt is made to explain this observation on the basis of structural parameters. Reactions of N3P3F6 with disiloxanes such as (Me3SiOCH2CH2)2O at temperatures below 80 °C yield only the dangling product 5a. When the reaction temperature is elevated to ∼110 °C, an oily liquid that is identified as the bridged fluorophosphazene (N3P3F5OCH2CH2)2O (5b) is isolated. When [Me3SiOC(CF3)2]2C6F4 acts as a bifunctional reagent, a totally fluorinated bridged phosphazene, [N3P3F5OC(CF3)2]2C6F4 (6), forms at ∼65 °C. Aromatic disiloxanes are very facile reagents for the formation of spirocyclic products when N3P3F6 is reacted under mild conditions with the bis(trimethylsilyl) ethers of 1,2-catechol, 3-fluoro-1,2-catechol, 2,3-naphthalenediol, and 2,2‘-biphenol. No ring degradation is observed with 3-F-1,2-C6H3(OSiMe3)2 and 1,2-C6H4(OSiMe3)2, which give the monospiro derivatives N3P3F4[3-F-1,2-C6H4O2] (7) and N3P3F4[1,2-C6H4O2] (8a) in good yields as well as the dispirophosphazene derivative N3P3F2[1,2-C6H4O2]2 (8b). Crystals of 8a are orthorhombic Imma; fw = 319.03, a = 7.4642(5) Å, b = 9.5108(7) Å, c = 16.2807(12) Å, V = 1155.78(14) Å3, and Z = 4; 8b is monoclinic, P21/n; fw = 389.12, a = 10.015(10) Å, b = 5.612(10) Å; c = 27.818(4) Å, β = 96.70°, V = 1552.8(4) Å3, Z = 4. N3P3F4[2,3-C10H6O2] (9a) is monoclinic, P21/c; fw = 369.09, a = 11.291(2) Å, b = 17.139(3) Å, c = 7.183(10) Å, β = 101.68°, V = 1361.2(4) Å3, Z = 4; N3P3F4[2,2‘-C12H8O2] (10) is monoclinic C2/c; fw = 395.12, a = 24.932(5) Å, b = 7.930(10) Å; c = 18.875(4) Å, β = 124.55°, V = 3073.6(10) Å3, Z = 8. The residual fluorine atoms on the phosphazene rings in 7, 8a, 9a, and 10 can be substituted by fluorophenoxy groups on reaction with the corresponding o-, m-, or p-(trimethylsilyl)phenoxy ether to give fully substituted phosphazenes of the type N3P3X(OC6H4F)4 [X = 3-F-1,2-C6H3O2 (11), 1,2-C6H4O2 (12), 2,3-C10H6O2 (13−15)...