Process for fluorination of sulphonyl halide compounds

Abstract

The preparation is described of a compound of formula (I) comprising an —SO.sub.2F function by reacting a compound of formula (II) with a fluorinating agent selected from hydrofluoric acid and an ionic fluoride of a monovalent or divalent cation:
R—SO.sub.2F  (I)
R′—SO.sub.2X  (II)
where R is selected from the groups R1, R2 and R3: R1=—C.sub.nH.sub.aF.sub.b with n=1-10, a+b=2n+1, b≧1; R2=—C.sub.xH.sub.yF.sub.z—SO.sub.2F with x=1-10, y+z=2x and z≧1; R3=φ-C.sub.cH.sub.hF.sub.f with c=1-10; h+f=2c and f≧1;
where R′ is selected from the following groups R′1, R′2 and R′3: R′1=—C.sub.nH.sub.aX.sub.b with n=1-10, a+b=2n+1, b≧1; R′2=—C.sub.xH.sub.yX.sub.z—SO.sub.2X with x=1-10, y+z=2x and z≧1; R′3=φ-C.sub.cH.sub.hX.sub.f with c=1-10; h+f=2c and f≧1; φ denoting a phenyl group; X═Cl, Br.

Claims

1. A non-electrochemical process for preparing a fluorinated compound of formula (I) comprising at least one —SO.sub.2F function, wherein the compound of formula (I) is prepared by reacting a compound of formula (II) with at least one fluorinating agent, wherein the process is carried out in the gas phase and wherein the fluorinating agent is hydrofluoric acid:
R—SO.sub.2F  (I) wherein R is selected from the group consisting of R1, R2 and R3: R1=-C.sub.nH.sub.aF.sub.b with n=1-10, a+b=2n+1, b≧1; R2=-C.sub.xH.sub.yF.sub.z—SO.sub.2F with x=1-10, y+z=2x and z≧1; R3=Φ-C.sub.cH.sub.hF.sub.f with c=1-10; h+f=2c and f≧1; Φ denoting a phenyl group;
R′—SO.sub.2X  (II) wherein R′ is selected from the group consisting of R′1, R′2 and R′3: R′1=-C.sub.nH.sub.aX.sub.b with n=1-10, a+b=2n+1, b≧1; R′2=-C.sub.xH.sub.yX.sub.z—SO.sub.2X with x=1-10, y+z=2x and z≧1; R′3=Φ-C.sub.cH.sub.hX.sub.f with c=1-10; h+f=2c and f≧1; Φ denoting a phenyl group; and X is a halogen atom selected from the group consisting of chlorine and bromine.

2. The preparation process as claimed in claim 1, wherein the radicals R1 and R′1 are perhalogenated so that b=3 and a=0.

3. The preparation process as claimed in claim 1, wherein the radical R of the compound (I) is the radical R1 wherein n=1, a=0 and b=3, or n=1, a=1, b=2 or else n=1, a=2 and b=1.

4. The preparation process as claimed in claim 1, wherein the process uses at least one fluorination catalyst comprising chromium, zinc, nickel, a mixture of chromium and zinc, or a mixture of chromium and nickel.

5. The preparation process as claimed in claim 1, wherein the ratio of the number of moles of hydrofluoric acid to the number of moles of halogenated compound of formula (II) varies between 1 and 30.

6. The preparation process as claimed in claim 1, wherein the compound of formula (II) is obtained by radical halogenation of a compound of formula R′.sub.H—SO.sub.2X (formula III), wherein R′.sub.H is selected from the group consisting of R′.sub.H1, R′.sub.H2 and R′.sub.H3: R′.sub.H1=-C.sub.nH.sub.2n+1 with n=1-10; R′.sub.H2=-C.sub.xH.sub.2x—SO.sub.2X with x=1-10; R′.sub.H3=Φ-C.sub.cH.sub.2c with c=1-10; and X is a halogen atom selected from the group consisting of chlorine and bromine.

7. A process for preparing a compound selected from the group consisting of a sulfonimide compound (R—SO.sub.2).sub.2NH and salts thereof, (R—SO.sub.2).sub.2NMe, and a fluorinated compound having a sulfonic acid function —SO.sub.2OH and having a formula R—SO.sub.2OH, said process comprising: a step of preparing a compound R—SO.sub.2F of formula (I) as claimed in claim 1, a step wherein said fluorinated compound of formula (I) is used as a reactive compound for the synthesis of a sulfonimide compound (R—SO.sub.2).sub.2NH and salts thereof, (R—SO.sub.2).sub.2NMe, or of a fluorinated compound having a sulfonic acid function —SO.sub.2OH and having a formula R—SO.sub.2OH, wherein R is selected from the group consisting of R1, R2 and R3: R1=-C.sub.nH.sub.aF.sub.b with n=1-10, a+b=2n+1, b≧1; R2=-C.sub.xH.sub.yF.sub.z—SO.sub.2F with x=1-10, y+z=2x and z≧1; and R3=Φ-C.sub.cH.sub.hF.sub.f with c=1-10; h+f=2c and f≧1; 1 denoting a phenyl group.

8. The process as claimed in claim 7, wherein the compound synthesized is selected from the group consisting of bis(trifluoromethanesulfonyl)imide of formula (CF.sub.3SO.sub.2).sub.2NH and lithium bis(trifluoromethanesulfonyl)imide of formula (CF.sub.3SO.sub.2).sub.2NLi (LiTFSI).

9. The process as claimed in claim 7, wherein the compound synthesized is trifluoromethanesulfonic acid of formula CF.sub.3SO.sub.2OH.

Description

EXAMPLES 1 TO 7: PREPARATION OF TFSF VIA A FLUORINATION REACTION WITH HF IN THE GAS PHASE

(1) Introduced into a Hastelloy C276 reactor consisting of a tube with a length of 60 cm and an external diameter of 2.5 cm, filled with a catalyst based on chromium oxide (˜150 g) previously dried to constant weight and fluorinated, are trichloromethanesulfonyl chloride (TCSC), pure or dissolved in a solvent, at a flow rate of 0.05 mol/h of TCSC and anhydrous HF at a flow rate of 10 g/h. The solvent is trifluoromethylbenzene (TFMB), trifluoromethoxybenzene (TFMxB) or toluene.

(2) The temperature is, depending on the test, set from 200° C. to 300° C. as an isotherm. Under these conditions, the residence time t.sub.r varies between 10 and 25 s.

(3) After the reaction, the outgoing stream composed of trifluoromethanesulfonyl fluoride, HF and HCl is hydrolysed in potassium hydroxide bubblers mounted in series, and the various acids are assayed in the form of potassium salts by ion chromatography. The TFSF (CF.sub.3SO.sub.2F) is assayed in the form of potassium triflate (CF.sub.3SO.sub.2K).

(4) The results obtained are shown in table (I).

(5) The degree of conversion DC corresponds to the ratio between the number of moles of TCSC substrate converted and the number of moles of TCSC substrate employed.

(6) The yield RY corresponds to the ratio between the number of moles of trifluoromethanesulfonyl fluoride TFSF product formed and the number of moles of TCSC substrate employed.

(7) The yield CY corresponds to the ratio between the number of moles of TFSF product formed and the number of moles of TCSC substrate converted.

(8) TABLE-US-00001 TABLE (I) t.sub.r HF/TCSC Ref. ex Solvent T° C. (s) (mol) DC % RY % CY % 1 — 250 22 10.8 82 75 91 2 — 250 11.5 21 50 47 94 3 TFMB 250 18 11 74 70 95 4 TFMxB 250 12.6 10.7 45 42 93 5 toluene 250 12.3 10.9 46 41 89 6 — 200 25 10.2 42 41 97 7 — 300 20.3 10.6 98 80 82

EXAMPLE 8: PREPARATION OF TFSF VIA A FLUORINATION REACTION WITH HF IN THE LIQUID PHASE

(9) Charged to a 280 ml capacity Hastelloy C276 autoclave are: TCSC: 110 g (0.5 mol) HF: 40 g (2 mol, i.e. ˜4 eq.) SbCl.sub.5: 5 g (0.02 mol, i.e. ˜1 mol % with respect to HF)

(10) The autoclave is brought to 120° C. for 3 h under autogenous pressure, then cooled to 20° C. and degassed in potassium hydroxide bubblers mounted in series; the residual reaction medium is drawn off and scrubbed in aqueous potassium hydroxide.

(11) The potassium hydroxide aqueous phases are combined and analysed by .sup.19F NMR; trifluoromethanesulfonyl fluoride (TFSF), assayed in the form of potassium triflate (TAK of formula CF.sub.3SO.sub.3K), is obtained with a yield of 23%.

EXAMPLE 9: PREPARATION OF TFSF VIA A FLUORINATION REACTION WITH KF

Example 9.1: In a Polar Aprotic Solvent

(12) Introduced into an autoclave made of stainless steel of grade 316L and having a capacity of 150 ml are: KF: 29 g TCSC: 22 g Adiponitrile: 60 ml

(13) The autoclave is sealed and brought to 230° C. under autogenous pressure for 4 h, then cooled to 20° C. and degassed in potassium hydroxide bubblers mounted in series; the residual reaction medium is drawn off and scrubbed in aqueous potassium hydroxide. The potassium hydroxide aqueous phases are combined and analysed by .sup.19F NMR; trifluoromethanesulfonyl fluoride, assayed in the form of potassium triflate (TAK), is obtained with a yield of 47%.

Example 9.2: In Water

(14) Introduced into a perfectly stirred glass reactor having a capacity of 100 ml are: KF: 32.6 g TCSC: 12 g water: 20 ml

(15) The medium is brought to boiling, with stirring, for 1 h, then cooled and brought to neutral pH by addition of aqueous potassium hydroxide.

(16) Analysis of the medium by .sup.19F NMR shows that the potassium triflate (TAK) was formed with a yield of 63%.

EXAMPLE 10: PREPARATION OF DFSF (CHF2SO2F) VIA A FLUORINATION REACTION WITH HF IN THE GAS PHASE

(17) The reaction is carried out under the same conditions as example 1, with the following charges and conditions: DCSC (CHCl.sub.2SO.sub.2Cl): 0.05 mol/h HF: 10 g/h (HF/DCSC ratio: 10)

(18) The temperature is set at 250° C. as an isotherm and the residence time t.sub.r is 22 s.

(19) The degree of conversion DC of the DCSC is 65% and the yield RY of DFSF is 42%.

EXAMPLE 11: PREPARATION OF DIFLUOROMETHANEDISULFONYL DIFLUORIDE (DF2DS: (CF2DS: (CF2(SO2F)2) VIA A FLUORINATION REACTION WITH HF IN THE LIQUID PHASE

(20) The reaction is carried out under the same conditions as example 8, with the following charges and conditions: (CCl.sub.2(SO.sub.2Cl).sub.2): 100 g (0.35 mol) HF: 40 g (2 mol, i.e. ˜6 eq.)

(21) After reacting for 3 h at 120° C., the reaction medium is treated according to example 8.

(22) DF.sub.2DS is obtained with a yield of 28%.

EXAMPLE 12: PREPARATION OF α,α-DIFLUOROBENZYLSULFONYL FLUORIDE (DFBSF: C6H5CF2SO2F) VIA A FLUORINATION REACTION WITH HF IN THE LIQUID PHASE

(23) The reaction is carried out under the same conditions as example 8, with the following charges and conditions: C.sub.6H.sub.5CCl.sub.2SO.sub.2Cl: 100 g (0.4 mol) HF: 40 g (2 mol, i.e. ˜5 eq.)

(24) After reacting for 4 h at 150° C., the reaction medium is treated according to example 8.

(25) DFBSF is obtained with a yield of 19%.