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United States Patent 19 [11] 3,940,402 Middleton (45) Feb

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United States Patent 19 [11] 3,940,402 Middleton (45) Feb United States Patent 19 [11] 3,940,402 Middleton (45) Feb. 24, 1976 54 TRIS(SUBSTITUTED AMINO) SULFONIUM OTHER PUBLICATIONS SALTS (75) Inventor: William Joseph Middleton, Chadds J.A.C.S. 84:3374-3387, (1962), Melby et al. Ford, Pa. 73 Assignee: E. I. DuPont de Nemours and Primary Examiner-Sherman D. Winters Company, Wilmington, Del. Attorney, Agent, or Firm-Anthony P. Mentis 22) Filed: Sept. 19, 1974 21) Appl. No.: 507,426 57 ABSTRACT Trisaminosulfonium salts of the formula 52 U.S. C. ...... 260/293.63; 260/80 C; 260/239 B; (RRN)(R'R''N)(R5RN)St X wherein the R groups 260/293.51; 260/293.85; 260/326.61; are alkyl of 1-20 carbons and each alkyl has at least 2 260/326.62; 260/326.82; 260/583 R; alpha hydrogens and X is selected from the group 260/583 EE (CH)SiF, Cl, Br, I, CN, NCO, NCS NO, and N, are 5 Int. Cl.'........................................ C07D 295/22 soluble in organic liquids. They are useful as polymeri 58) Field of Search..... 260/293.63, 326.61, 326.62, zation catalysts and as reagents to replace other atoms 260/326.82, 583 EE, 293.85 or groups in organic compounds with F, Cl, Br, I, CN, NCO, NCS, NO, O N. 56 References Cited UNITED STATES PATENTS 28 Claims, No Drawings 3,162,641 12/1964 Acker et al......................... 260/286 3,940,402 1. 2 The triaminosulfonium difluorotrimethylsilicates of TRES(SUBSTITUTED AMINO) SULFONIUM SALTS the invention are prepared by treating a solution of sulfur tetrafluoride in an anhydrous inert solvent with BACKGROUND OF THE INVENTION at least three equivalents of a (secondary amino)trime 1. Field of the Invention thylsilane. The reaction appears to proceed in three This invention relates to new tris(secondary amino) steps: sulfonium salts that are useful, for example, as fluori 1. In the first step, one equivalent of (secamino)- nating agents and as polymerization catalysts. trimethylsilane reacts with sulfur tetrafluoride to give 2. Prior Art an aminosulfur trifluoride. This step can be conducted No references to difluorotrimethylsilicic acid or any 10 at a temperature range of from -100 to 0. of its salts are known. One reference to a tris(dime 2. In the second step, the produced aminosulfur tri thylamino)sulfonium salt is D. S. Acker & D. C. Blom fluoride reacts with a second equivalent of (sec stron, U.S. Pat. No. 3,162,641 (1964) to Du Pont. The amino) trimethylsilane to give a bis(amino)sulfur diflu preparation of tris-(dimethylamino)sulfonium tet oride. This second step proceeds slowly at -80 but racyano-quinodimethan (TCNQ) salt (TCNQide) by 5 proceeds faster at a temperature of -30 to 0. the reaction of lithium TCNQide with tris(dime 3. In the third step, the bis(amino)sulfur difluoride thylamino)sulfonium fluoride is disclosed. The method reacts with a third equivalent of (sec-amino) trimethyl of preparation or the properties of the fluoride are not silane to give the final product, a tris(amino)sulfonium disclosed. difluorotrimethylsilicate. This step proceeds at a tem 20 perature range of from 0 to 50. DESCRIPTION OF THE INVENTION Each step can be conducted independently and each Statement of Invention of the intermediates isolated or all three steps can be This invention comprises a new class of organic solu conducted in the same reaction vessel without isolation ble salts, their use as polymerization catalysts and as of the intermediates. Method “A” starts with step 1 and reagents for replacing atoms or groups in organic com 25 proceeds to the final product without isolation of the pounds with other atoms or groups, e.g. replacing other intermediate product whereas method “B” starts with halogen atoms in organic compounds with fluorine step 2. The following equations illustrate the reaction. atoms. These salts are trisaminosulfonium salts having Step 1 R -100 to O' R1 SF, + R21)N-si(CH.), R21 N-sf,+ F-sich), Step 2 F R'N RN -80 to OR'S 1R -N-SF. -- cN-SiCH.) -Nin -- F-Si(CH) F Step 3 R2 R3 F O to 50° R N-S-N -* -- R N-such -ma-Ho R-R S -- / N 3 Y . le (CH4).SiFe R2 R4 R6 N F 1N R6 Rs the general formula Salts where X is chloride are prepared by reacting a 50 tris(secondary amino)sulfonium difluorotrimethylsili R R cate with a compound containing removable chlorine, - as for example, o-chlorotoluene to obtain the sulfo 69 xe nium chloride salt as in Example 11 below. Reaction of R6 / N - R' the sulfonium chloride with appropriate reagents such N N NN1 55 as sodium cyanide, etc. will produce the sulfonium R R4 cyanide salt, etc. as illustrated below. Solvents suitable for use in these reactions include wherein ethers, such as diethyl ether, tetrahydrofuran and dime the R groups individually are alkyl of up to 20 carbon thylethylene glycol, and hydrocarbons such as pentane, atoms each alkyl having at least two alpha-hydro 60 hexane, toluene, and xylene. Halogenated hydrocar gen atoms, bons such as methylene chloride and chlorotrifluoro with the proviso that any or all of the pairs R and methane can be used in the first two steps but not in the R, R and Rand R5 and R taken together form third step. When all three steps are done in the same part of a 5- or 6-membered ring containing one reaction vessel without isolation of intermediates, di nitrogen atom, any substituents being alkyl of up 65 ethyl ether is the preferred solvent. Solvents containing to 8 carbon atoms, and active hydrogens must be avoided in all cases. Since is selected from the group consisting of water contains active hydrogen it is obvious the reac (CH3)SiF, Cl, Br, I, CN, NCO, NCS, NO, and Na. tions must be carried out under anhydrous conditions. 3,940,402 3 4. Pressure is not critical. Ambient and/or autogenous A 47.3-g (0.33 mole) sample of pyrrolidinotrimethyl pressure is the most convenient and therefore pre silane was added dropwise to a solution of 5.5 ml (ca. ferred. 0.1 mole) of SF in 100 ml of ether cooled to -78. The The products and intermediates can be isolated and reaction mixture was slowly warmed to room tempera purified by conventional techniques such as distillation 5 ture and then stirred overnight for 16 hours. The solid and recrystallization. that precipitated was collected on a filter under nitro gen and dried in a vacuum desiccator over POs to give SPECIFIC EMBODIMENTS OF THE INVENTION 29.25 g of tris(pyrrolidino)sulfonium difluorotrime The following are illustrative examples in which all thylsilicate; mp 54°-57; H nmr (CDCN) 8 -0.20 parts are by weight and all temperatures are in degrees 10 ppm (s, 9H), 1.84 ppm (m, 12H), and 3.38 ppm (m, Centigrade unless otherwise stated. 12H); 19F nmr (CDCN) 8-60.2 ppm (s). Anal. Calcd for CHFNSSi: C, 50.95; H, 9.41; F, 10,75; N, 11.88; S, 8.07; Si, 7.94. Found: C, 50.71; H, 9.58; F, 10.57; N, 12.01; S, 8.87; Si, 8.01. EXAMPLE 1 15 Tris(dimethylamino )sulfonium Difluorotrimethylsilicate Method A 3(CH),N-Si(CH) -- SF-> EXAMPLE 4 ((CH4),N),S*(CH4),SiF.-- 2(CH)SiF 20 Bis(dimethylamino)pyrrolidinosulfonium A 152-g ( 1.3 mole) sample of dimethylaminotrime Difluorotrimethylsilicate thylsilane was added dropwise to a solution of 22 ml (0.4 mole) of sulfur tetrafluoride in 400 ml of ether SN-SFs + 2 (CHs)2NSi (CH3)a -- cooled to -78. The reaction mixture was slowly 25 warmed to room temperature and stirred for 3 days. The crystalline solid that precipitated was collected on (CH3)2 a filter under dry nitrogen to give 109.0 g (99%) of tris(dimethylamino)sulfonium, difluorotrimethylsilicate D-g (CH3)ssif. as colorless needles; mp 61-67 (dec); 19F nmr 30 N(CH3)2 (CDCN) 8-60.3 ppm (s); H nmr (CDCN) 8 -0.18 ppm (s, 9H) and +2.89 ppm (s, 18H). A 25.8-g (0.22 mole) sample of dimethylaminotrime Anal. Calcd for CHFNSSi: C, 39.23; H, 9.88; F, thylsilane was added dropwise to a solution of 15.9 g 13.79; N, 15.25; S, 11.64; Si, 10.19. Found: C, 38.93; (0.1 mole) of pyrrolidinosulfur trifluoride in 100 ml of H, 10.17; F, 13.91; N, 15.31; S, 11.51; Si, 9.87. 35 ether cooled to -60. The reaction mixture was warmed to room temperature and stirred for 3 days. Two liquid layers separated. The lower layer was sepa rated, washed with ether, and the remaining materials EXAMPLE 2 were distilled off at reduced pressure (0.1 mm at 25). Tris(dimethylamino)sulfonium 40 The residue solidified to give 23.33 g of bis(dime Difluorotrimethylsilicate thylamino)pyrrolidinosulfonium difluorotrimethylsili Method B cate as a light yellow solid; mp 40-45; H nmr (CH3)NSF +2(CH3)NSi(CHa) - ((CH3)N)S (CDCN) 8-0.18 ppm (s, 9H), 1.98 (m, 4H), 2.97 (s, (CH)SiF + (CH)SiF 12H) and 3.20 (m, 4H); 9F nmr (CDCN) 8-59.7 A solution of 20.4 g (0.174 mole) of (dime 45 ppm (s). thylamino) trimethylsilane in 25 ml of ether was added Anal. Calcd for CHFNSSi: C, 43.82; H, 9.69; F, dropwise to a solution of 10.65 g (0.08 mole) of (dime 12.60; N, 13.94. Found: C, 43.52; H, 9.50; F, 12.50; N, thylamino)sulfur trifluoride in 100 ml of ether cooled 14.11.
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