WO1992008710A1

WO1992008710A1 - Process for the preparation of difluoromaleic anhydride and intermediate compounds produced thereby

Info

Publication number: WO1992008710A1
Application number: PCT/US1990/006693
Authority: WO
Inventors: Carl George Krespan
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1990-11-15
Filing date: 1990-11-15
Publication date: 1992-05-29

Abstract

A process for producing difluoromaleic anhydride by reacting sulfur trioxide with a fluorinated precursor selected from the group consisting of hexafluoro-2,5-dihydrofuran, hexafluoro-2,5-dihydrothiophene, difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one. Also disclosed are the compounds difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one.

Description

TITLE PROCESS FOR THE PREPARATION OF DIFLUOROMALEIC ANHYDRIDE AND INTERMEDIATE COMPOUNDS PRODUCED THEREBY

FIELD OF INVENTION The present invention relates to a process for the preparation of difluoromaleic anhydride. More particularly, this invention relates to reacting sulfur trioxide with certain fluorinated precursors to produce difluoromaleic anhydride or intermediates thereof. . BACKGROUND OF THE INVENTION U. S. Patent 2,891,968 describes the preparation of difluoromaleic anhydride by the dehydration of difluoromaleic acid, which in turn is obtained by the dehydrofluorination of trifluorosuccinic acid. The present invention represents an improvement over this preparation with respect to ease of synthesis of the difluoromaleic anhydride. L. S. Kobrina, et. al., Zh. Org. Khim., vol. 8, pp. 2165-2167 (1972) obtained difluoromaleic acid (which can be converted to the anhydride, see U. S. Patent 2,891,968, supra) in 54% yield by treatment of pentafluorophenol with peroxyacetic acid. Difluoromaleic acid was also obtained by analogous reactions of tetrafluoro-p- or tetrafluoro-o- benzoquinone, tetrafluoropyrocatechol and tetrafluoro- muconic acid. However, the preparation of this reference requires the oxidation of a fluorophenol, which is not necessary to the present procedure.

C. G. Krespan and and D. A. Dixon, J. Org. Chem., vol. 51, pp. 4460-4466 (1986) describe the reaction of SO₃ with perfluoro-2-butene. In this reaction only one of the terminal carbons reacted to form a carbonyl group, yielding the compound CF₃CF=CFCθ₂Sθ₂F in relatively low yields even though high reaction temperatures and long reaction times were used. A small amount (0.05%) of trimethyl borate was present as a stabilizer in the SO₃ used. The use of boron compounds as catalysts is discussed in this paper. However, neither difluoromaleic anhydride nor difluoromaleic acid are produced in the reviewed reactions.

Difluoromaleic anhydride is useful for the capping of polyimide prepolymers and polymers (U.S. Patent 4,173,700), as a "cure site" monomer in fluoropolymers (D. S. Patents 3,792,022 and 3,761,453) and as a comonomer with phenyl vinyl ether to form an alternating copolyraer (G. Canessa C, Bol. Soc. Chil. Quim., vol. 26, pp. 25-37). In German Patent 2,649,743 it is used as a component of an antifouling coating. It is used as a chemical intermediate in the preparation of biologically active compounds in ϋ. S. Patents 3,485,829 and 3,485,827.

It is an object of the present invention to provide a one step process for the production of difluoromaleic anhydride from commonly available starting materials. A feature of the present invention is the production of usef l intermediate compounds. It is an advantage of the present invention to provide catalysts for the reaction to facilitate commercial scale production of difluoromaleic anhydride. These and other objects, features and advantages of the present invention will become apparent upon having reference to the following description of the invention. SUMMARY OF THE INVENTION

A process for the production of difluoromaleic anhydride is provided, comprising reacting sulfur trioxide with a fluorinated precursor, selected from the group consisting of hexafluoro-2,5-dihydrofuran, hexafluoro-2,5-dihydrothiophene, difluoro-2,5- dihydrothiophene-2,5-dione and tetrafluoro-2,5- dihydrothiophene-2-one. Usually at least about 3 moles of sulfur trioxide is used for each mole of fluorinated precursor used. The reaction may optionally be catalyzed by trivalent boron compounds. Also provided are the compounds difluoro-2,5-dihydrothiophene-2, 5- dione and tetrafluoro-2,5-dihydrothiophene-2-one which are useful as intermediates in the production of difluoromaleic anhydride. DETAILS OF THE INVENTION

Difluoromaleic anhydride is prepared by the reaction of sulfur trioxide (SO₃) with a fluorinated precursor selected from the group consisting of hexafluoro-2,5-dihydrofuran, hexafluoro-2,5- dihydrothiophene, difluoro-2,5-dihydrothiophene-2,5- dione and tetrafluoro-2,5-dihydrothiophene-2-one. The sulfur trioxide is preferably present as SO₃ alone, or it may be present in solution in sulfuric acid, commonly known as oleum. Usually at least about 3 moles of SO₃ are present for each mole of fluorinated precursor. Although no upper limit on the molar ratio of SO₃ to fluorinated precursor is known, molar ratios of SO₃ to fluorinated precursor of about 3 to about 10 are preferred. Hexafluoro-2,5-dihydrofuran can be prepared by the method of W. J. Feast, et. al., J. Chem. Soc. C, vol. 1971, pp. 769-772. U. S. Patent 3,069,431 reports a method for the synthesis of hexafluoro-2,5- dihydrothiophene. The precursor for the thiophene, hexafluorocyclobutene, is commercially available.

Both difluoro-2,5-dihydrothiophene-2,5-dione and tetrafluoro-2,5-dihydrothiophene-2-one are made by the reaction of SO₃ with hexafluoro-2,5-dihyrothiophene (Example 3, infra) . Thus reaction of the hexafluoro- 2,5-dihydrothiophene with SO₃ under reaction conditions less vigorous than those reported herein that produce difluoromaleic anhydride will produce difluoro-2,5- dihydrothiophene-2,5-dione and/or tetrafluoro-2,5- dihydrothiophene-2-one. Less vigorous conditions 5 include one or more of lower reaction temperatures, shorter reaction times, lesser amounts of SO₃ and the absence of catalysts. Since difluoro-2,5- dihydrothiophene-2,5-dione and tetrafluoro-2,5- dihydrothiophene-2-one are both intermediates in the

10 reaction of hexafluoro-2,5-dihydrothiophene with SO₃ to produce difluoromaleic anhydride, reaction of either difluoro-2,5-dihydrothiophene-2,5-dione or tetrafluoro- 2,5-dihydrothiophene-2-one with SO₃ under conditions described herein will yield difluoromaleic anhydride.

15 Compounds containing trivalent boron may optionally be added as catalysts to accelerate the formation of difluoromaleic anhydride. They are especially useful at relatively low reaction temperatures. Active catalysts include, but are not limited to trimethyl borate, boron

20 trifluoride, boric oxide and boron trichloride. The amount of boron catalyst used is preferably about 0.5 to about 5 weight percent of the SO₃ present.

The reaction to produce difluoromaleic anhydride is run at 25-200°C, preferably 50-100°C. Reaction times

25 typically vary from about 0.5-24 hr., the longer times being needed at lower temperatures. Reactions may be run at atmospheric pressure, but to achieve higher reaction temperatures, the reaction can be run under pressure,' typically up to about 20 atm. A solvent inert

30 to the starting materials and products may be present, but it is preferred to conduct the reaction in the absence of solvent. Water should be excluded to a reasonable extent, thus starting materials should be dry and moist air should be excluded from the reaction. Reaction vessels should be inert to the starting materials and products. Glass and alloys such as stainless steel and Hastelloy®, a trademark of Stoody

Deloro Stellite, Inc., are suitable for reaction vessels.

Products may be isolated by standard methods known to those skilled in the art such as distillation and crystallization. Such methods are illustrated in the Examples. EXAMPLE 1

Preparation of Difluoromaleic Anhydride from Hexafluoro-2.5-dihvdrofuran Sulfur trioxide (336 g, 4.2 mol) was stirred at 25°C while 83 g (0.47 mol) of hexafluoro-2,5- dihydrofuran was distilled in. No interaction was apparent while the temperature dropped to 15°C and the SO₃ solidified. Addition of 1 g of trimethyl borate initiate. reaction, which was allowed to progress overnight. Then another 42 g (0.24 mol) of hexafluoro- 2,5-dihydrofuran was added, and the mixture was refluxed for 12 hr. while the temperature rose to 92°C. Distillation afforded, after a large foreshot, 69.0 g (74%) of crude difluoromaleic anhydride, bp 100-125°C. Redistillation gave 50.0 g (53%) of difluoromaleic anhydride, bp 125-126°C. IR (1% in CHCI₃) : 1880 (w) , 1815 (s) and 1760 (m) (OO, OC) , 1290 and 1185 cm"¹ (C-F) NMR (acetone-dβ) : ¹⁹F0 -141.2 (s, =CF) . UV: ε isooctane/235 nm 3,176.

Confirmation of the structure was obtained when the anilide was prepared by adding 2.9 g (0.022 mol) of difluoromaleic anhydride to a solution of 1.9 g (0.020 mol) of aniline in 100 ml of ether. The mixture was stirred for 15 min., filtered, and the filter cake dried to give 4.0 g (88%) of anilide, mp 192-193°C (literature mp 193-195°C) . NMR (acetone-dβ) : ¹⁹F0 - 124.9 ( , IF, =CF) , -132.8 (d, J_FF4.7 Hz, IF, (=CF) .

EXAMPLE 2 Preparation of Difluoromaleic Anhydride 5 f om Hexafluoro-2,5-dihvdrothiophβne

Commercial sulfur trioxide (176 g, 2.20 mol) was treated cautiously with 2.0 g of trimethyl borate, and the mixture was stirred while 72.9 g (0.38 mol) of hexafluoro-2,5-dihydrothiophene was added over 30 min. 10 A mildly exothermic reaction caused reflux. The mixture was stirred 1 hr. while the temperature came down and then was heated to 60°C where a second exotherm was accompanied with pronounced gassing. A sample of the off-gases was shown by IR to be SO₂ with a minor amount 15 of FSO₂OSO₂F present. Reaction was continued at 60-65°C until gas evolution subsided, then at reflux for 2 hr. while the pot temperature fell from 90°C to 80°C. Distillation gave a large foreshot, bp 40-100°C followed by 37.0 g (73%) of crude difluoromaleic anhydride, bp 20 100-125°C, nearly pure by GC. The IR spectrum was substantially the same as that of a known sample.

EXAMPLE 3 Preparation of Tetra luoro-2.5-dihvdro- thiophene-2-one and Difluoro-2.5- 25 tiihytirPthiPPhene-2 ,5-d pne

Sulfur trioxide (128.0 g, 1.60 mol) was added rapidly to 77.6 g (0.40 mol) of hexafluoro-2,5- dihydrothiophene. After an initial exotherm, the mixture was refluxed for 30 min. and fractionated to 30 give 121.9 g, bp 42-55°C, shown to be mainly pyrosulfuryl fluoride by ¹⁹F NMR, and 29.5 g of crude tetrafluoro-2,5-dihydrothiophene, bp 77-85°C. Redistillation of this product afforded 16.9 g (25%) of tetrafluoro-2,5-dihydrothiophene-2-one, bp 83°C. IR 35 (CCI₄) : 1755 (OO) and 1740 cm"¹(OC) . NMR (CCI₄) : ¹⁹F0 -92.0 (d of d, J_FF14.7, 5.5 Hz, 2F, CF₂) , -133.5 (q, J_FF14.3 Hz, IF, CF), -144.3 (d of t, J_FF13.9, 5.5 Hz, IF, CF) . MS: m/e 171.9615 (M⁺; calcd for C₄F₄OS, 171.9606), 143.9664 (M+ -CO; cald, 143,9657), 121.9641 (M+ -CF₂; calcd, 121.9638) . Anal. Calcd for C₄F₄OS: C, 27.91; S, 18.63 Found: C, 28.27; S, 19.16.

Further distillation of the reaction mixture afforded 32.6 g of crude difluoro-2,5-dihydrothiophene- 2,5-dione bp 80-86°C (100 mm), which solidified on standing. Recrystallization from hexane/ether followed by sublimation at 45-50°C (10 mm) gave 12.7 g of nearly colorless difluoro-2,5-dihydrothiophene-2,5-dione, mp 57-58°C. Evaporation of the filtrate and sublimation at 40°C (10 mm) gave an additional 4.7 g of difluoro-2,5- dihydrothiophene-2,5-dione, mp 52-56°C, for a total yield of 17.4 g (29%). An analytical sample, mp 58-59°C, was prepared by sublimation at 30°C (10 mm) . IR (CCI₄) : 1760 (w) and 1715 (s) cm'¹ (OO and OC) . NMR (CCI₄) : ¹⁹F0 -132.2 (s, CF) . Anal. Calcd for C₄F₂0₂S: C, 32.00; S, 21.36. Found: C, 32.81; S, 21.64.

Although preferred embodiments of the invention have been described hereinabove, it is to be understood that there is no attempt to limit the invention to the precise constructions herein disclosed, and it is to be further understood that the right is reserved to all changes coming within the scope of the invention as defined by the appended claims.

Claims

CLAIMS What is claimed is:

1. A process for the production of difluoromaleic anhydride, comprising, reacting sulfur trioxide with a fluorinated precursor selected from the group consisting of hexafluoro-2,5-dihydrofuran, hexafluoro-2,5- dihydrothiophene, difluor o-2,5-dihydrothiophene-2,5- dione and tetrafluor o-2,5-dihydrothiophene-2-one.

2. The process of Claim 1 wherein the molar ratio of said sulfur trioxide to said fluorinated precursor is at least about 3.

3. The process of Claim 2 wherein said molar ratio is about 3 to about 10.

4. The process of Claim 1 wherein the temperature is about 25°C to about 200°C.

5. The process of Claim 4 wherein the temperature is about 50°C to about 100°C.

6. The process of Claim 3 wherein the temperature is about 25°C to about 200°C.

7. The process of Claim 6 wherein the temperature is about 50°C to about 100°C.

8. The process of Claim 1 wherein a compound containing trivalent boron is present as a catalyst.

9. The process of Claim 8 wherein the amount of said catalyst present is about 0.5% to 5% by weight of said sulfur trioxide.

10. The process of Claim 8 wherein said catalyst is selected from the group consisting of trimethyl borate, boron trifluoride, boric oxide and boron trichloride.

11. The process of Claim 3 wherein a compound containing trivalent boron is present as a catalyst.

12. The process of Claim 11 wherein the amount of said catalyst present is about 0.5% to 5% by weight of said sulfur trioxide. *

13. The process of Claim 11 wherein said catalyst

5 is selected from the group consisting of trimethyl " borate, boron trifluoride, boric oxide and boron trichloride.

14. The process of Claim 8 wherein the temperature is about 25°C to about 200°C. 10

15. The process of Claim 14 wherein the temperature is about 50°C to about 100°C.

16. The process of Claim 11 wherein the temperature is about 25°C to about 200°C.

17. The process of Claim 16 wherein the 15 temperature is about 50°C to about 100°C.

18 . The process of Claim 12 wherein the temperature is about 25°C to about 200°C.

19. The process of Claim 18 wherein the temperature is about 50°C to about 100°C.

20 20. The process of Claim 1 wherein said sulfur trioxide is added as oleum.

21. The process of Claim 3 wherein said sulfur trioxide is added as oleum.

22. The process of Claim 1 wherein the pressure is 25 about 1 to about 20 atmospheres.

23. The compound difluoro-2,5-dihydrothiophene- 2,5-dione.

24. The compound tetrafluoro-2,5-dihydrothiophene- 2-one.

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