JPH0521908B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to β-substituted polyfluoropropionate salts and derivatives thereof, including copolymers. It is known that a variety of polyfluorinated propionates can be prepared from polyfluorinated olefins.
CF ₂ =CXY can be reacted with water and an alkali metal cyanide to give polyfluoramides and polyfluoropropionates having the formula HCXYCF ₂ CO ₂ M, as disclosed, for example, in U.S. Pat. No. 2,802,028. . In both formulas above, X is -
F or -Cl, Y is -H, -F, -Cl, alkyl, cycloalkyl or alkyl substituted with F or Cl, and M is an alkali metal.
In this patent, perfluoronitrile HCXYCF ₂ CN, where X and Y are as described above, is identified as a possible intermediate. US Pat. No. 3,311,657 discloses a process for producing CF ₃ CX'Y'CO ₂ M by reaction of fluoroolefins such as tetrafluoroethylene or chlorotrifluoroethylene with CO ₂ and an alkali metal fluoride. In the formula, X' is -F,
Y' can be -Cl, -F or trifluoromethyl. Kolb et al., Adv.Chem.Series Amer.Chem.
Soc. 129 , 13 (1973), by reaction of tetrafluoroethylene with CO ₂ and potassium pentafluorophenoxide (C ₆ F ₅ )
Discloses a method for producing OCF ₂ CF ₂ CO ₂ K. JP-A-46-10532 discloses the preparation of various non-fluorinated quaternary esters by reacting carboxylic acid esters with tertiary amines in the presence of phenol.
A method for producing grade ammonium salts is disclosed. U.S. Patent No. 3,535,351 discloses that R has 1 to 1 carbon atom.
Compounds of the formula NC( _CF2 ) _aCO2R are disclosed, where 25 alkyl or aralkyl and a is _1-12 . NC( _CF2 ) _a of ω-cyanoperfluorinated alkanoate in which ^R1 is polyhaloalkyl
Conversion to CO ₂ R ¹ is disclosed in US Pat. No. 3,532,725. Known polyfluoropropionate derivatives include CN( _CF2 ) _a COX'', where X'' is -Cl, -F, -Br or -I and a is 1-12, and It can be made from the above polyhaloalkyl cyanoperfluorinated alkanoates as disclosed in Patent No. 3,557,165.
Bans is “Fluorocarbons and Their
"Derivatives", Elsevier, p. 23 (1970) describes a method for the preparation of 1:1 adducts of tetrafluoroethylene by reaction with alcohols, phenols, thiols, thiophenols and ketoximes in the presence of their sodium salts. GB2051831A discloses _{a compound} having the formula

【formula】

[Formula] or

[Formula] can be. Substituted fluorocarbons having the following are disclosed. U.S. Pat. No. 4,275,226 describes the formula XR _F CF ₂ OCF=CF ₂ where X is -H, -Cl, -Br, -F, -CONRR',
-COF, _-CO2R , _-SO2F or -PO(OR) ₂ ; R is _C1-10 alkyl; R' is -H or _C1-10 alkyl; and R _F is Fluorocarbons are described that have C _1-20 difunctional perfluoro-containing groups which may have one or more ether linkages. This compound is iodide, i.e. XR _F
It is mentioned that CF ₂ OCF ₂ CF ₂ I can be produced by heating in the presence of certain metals or organometallic compounds. It is said that this iodide can be produced from the acid fluoride XR _F COF by reaction with tetrafluoroethylene, iodine and metal halides. However, this patent
It does not teach or suggest methods for making various starting acid fluorides, including those in which X is PO(OR) ₂ . As a result, this patent also does not disclose a method for making the corresponding vinyl ether. Warmell U.S. Pat. No. 3,311,658 states that n is 0.
~5, I(CF ₂ ) _o COF and its hexafluoropropene adduct, I(CF ₂ ) _o (-
CF ₂ OCF (CF ₃ ))-- _CRF is disclosed and it is shown that this adduct can be converted to vinyl ether-containing iodo compounds. Kato et al., J.Chem.Soc.Chem.Conanun.
1173 (1981), the reaction RFI→RFP(O)(OC ₂ H ₅ ) where R _F is C _1-6 perfluoroalkyl. is disclosed. JP-A-56-51495 published by Asahi Glass Co., Ltd. discloses the reaction of _F2ClCFClO ( _CF2 ) _3I → _F2ClCFClO ( _CF2 ) _3P (O)( _OC2H5 ) _{2 .} ing. Kato was born in Florida Daytoua in February 1981.
Fifth Winter Fluorine Conference at Beach
Fluorine Conference), Unexamined Japanese Patent Publication 1986-
The reaction disclosed in Publication No. 51495 and its product,
Vinyl ether-containing phosphonate, CF ₂ = CFO
(CF ₂ ) ₃ P(O)(OC ₂ H ₅ ) ₂ and this phosphonate has the formula CF ₂ =CFO, respectively.
(CF ₂ ) ₃ P(O)Cl ₂ and CF ₂ = CFO(CF ₂ ) ₃ P(O)
It was announced that (OCH ₃ ) ₂ can be converted into phosphonyl chloride or methylphosphonate ester. Ezzell et al., in European Patent Application No. 41736,
Formula Y' (CF ₂ ) - _a (CFR) - _b C(O)R' FIn _{the formula} , Y' is -SO ₂ Z', -C(O)Z', or -P(O)Z' ₂
Z' is -OH, -OM, -OR, -F, -Br, -Cl or -I; R is alkyl; M is an alkali metal or quaternary ammonium; a and b is 0 or an integer; and R _F and R' _F are -F, -Cl, _-CF2 or _-CF2Cl . This reference does not teach or suggest a method for preparing compounds in which Y' is -PO(OR) ₂ , -P(O) _Cl2 or -P(O) _F2 . European Patent Application No. 41736 also describes the formula Derivatives are disclosed having the formula: where X'' is -F, -Cl or -Br; X is -Cl or -Br; and n is at least 1. The European patent to Ezzell et al. Application No. 41738 is similar to the above derivative and has the formula where R _F and R′′′′ _F are -F, -Cl, perfluoroalkyl or fluorochloroalkyl; X is -Cl, -I or -Br; and a and b are 0 to 3 Discloses compounds having the following, with the proviso that a+b=2 or 3. European Patent Application No. 41737 and Ezzell et al.
No. 41735 is a formula derived from the derivative of No. 41736. and copolymers derived therefrom are disclosed. However, as in other references by Ezzell et al., Y′ is −PO(OR) ₂ , −P
No method is taught or suggested for making compounds that are (O) _Cl2 or -P(O) _F2 . US Pat. No. 3,853,720 to Korach et al. discloses fluoropolymers that contain pendant acid groups, have ion exchange properties, and are useful as membranes in electrolytic cells. An object of the present invention is to provide a new polyfluoropropionate and a method for producing the same. A further object is to provide new derivatives of polyfluoropropionates as well as copolymerizable monomers prepared from these derivatives. For a further understanding of the invention and its objects and advantages, reference may be made to the following description and claims which particularly point out various novel features of the invention. The present invention _{provides a β-} A method for producing a substituted polyfluorinated propionate salt, _where X is -CN, _-N2 , -SR or -PO(OR') ₂ ; is aryl or alkaryl _; R' is _-CH3 , _-C2H5 , _-CH2CF3 or _-CH2CF2CF2H ; Y is -Cl _{, -F} , _-Br or -OR _F , provided that when X is -CN, Y is -Cl, -F or -Br; R _F is a branched or linear perfluoroalkyl or ether oxygen having 1 to 10 carbon atoms. such perfluoroalkyl having one or more intervening carbon-carbon bonds; M is an alkali metal, alkaline earth metal or -
NR ¹ R ² R ³ R ⁴ where R ¹ to ^{R 4} are C _1-6 linear alkyl, allyl or benzyl; preferably R ¹ to ^{R 4} are methyl; and n is The valence of M is 1 or 2. Furthermore, the present invention provides β-substituted polyfluoropropionate salts produced by the above method and certain derivatives thereof; methods for producing the derivatives; copolymers produced from the derivatives; cyano-substituted fluorinated copolymers. and a molded article, such as a film, of such a copolymer. The β-substituted polyfluoropropionate salt has the formula (XCF ₂ CFYCO ₂ ) _o Y, where X is -CN, -N ₃ , -PO(OR') ₂ , -SR or -SO ₂ R; and Y, M and n are as above. Sulfones are described, for example, in Ward, J.Org.
Derived from the thioether by oxidation with hydrogen peroxide in the presence of acetic acid as described in Chem. 30 , 3009 (1965) and Example 23. Derivatives of β-substituted polyfluoropropionate salts have the formula X′CF ₂ CFYZ where X′ is −N ₃ , −SR, −SO ₂ R, −PO(OR′) ₂ ,
-P(O) _Cl2 or -P(O) _F2 ; R, R' and Y are as above; Z is -COCl, _-CO2R '', _-CO2H ,

【formula】

【formula】

[Formula] or

[Formula] OCF= _CF2 ; R″ is C _1-6 linear alkyl, allyl or benzyl; m is 0-6; p is 1-6; and q is 1-5 , with the proviso that when Z is a CO ₂ M-containing group, X' is -N ₃ , -SR or -P(O)(OR') ₂ . The union is the formula

[Formula] In the formula, Q is or

[Formula]; Y' is -F or -H; Y'' is -F, -H, -Cl, -R' _F or -OR'_F; R _F ' is perfluoroalkyl, Number of carbon atoms: 1
s is about 2 to about 1000, preferably about 10 to about 200; and Y, X', q and m are as defined above; q and m are preferably 0 or 1, and contains a repeating unit having the following. Copolymer molded articles include films. X′ is −
PO(OR') ₂ , -P(O)Cl ₂ , -P(O)F ₂ , -SR or -
When SO ₂ R, the film is chemically converted into an ion exchange membrane. In the salt production method of the present invention, the reactants can be mixed in any order. Preferably, the reactants are mixed in a solvent at a low temperature, such as below about -20°C, and the mixture is then heated at a temperature of about -20°C to about 150°C,
Preferably, the temperature is from about 0 to about 100°C. To further illustrate, _CO2 can be added to a mixture of MXn and a solvent and then a fluoroolefin can be introduced at the reaction temperature, or a mixture of MXn and a solvent can be added to a mixture of _CO2 and a polyolefin at a reaction temperature. Good too. The reaction pressure is not critical. Preferably the reaction pressure is about 100 to about 2000 psi (690 to
13,800kpa). Suitable solvents include, for example, dimethyl sulfoxide,
Acetonitrile, glyme such as mono-, di-,
tri- and tetraethylene glycol dimethyl ether, polyethylene oxide ethyl ether,
Tetrahydrofuran, tetramethylene sulfone,
Includes dimethylformamide, hexamethylphosphoramide, tetraalkylurea and mixtures thereof. The relative amounts of reactants are not critical. Typically,
The number of moles of CO ₂ is greater than the number of moles of MXn. The number of moles of fluoroolefin is typically MXn
It is approximately the same as MXn, but it is about 1/2 to MXn.
A molar ratio of about 4/1 can be advantageously used. The β-substituted polyfluorinated propionate salts of the present invention may be collected in crude product form after terminating the reaction by removing the solvent at low pressure. However, for convenience, this salt can be converted into an ester and separated off, for example by distillation or washing with water. Conversion to the ester may be carried out by treating the reaction mixture with an alkylating agent such as methyl acetate, allyl acetate, ethyl iodide, dimethyl sulfate, methyl fluorosulfate or methyl p-toluenesulfonate. can. The quaternary ammonium propionate salts of the present invention, i.e., the salts in which M is -NR ¹ R ² R ³ R ⁴ , may also be used as esters of other propionate salts of the invention, i.e.
is -N ₃ , -SR, -SO ₂ R or -CN, and Y,
Formula XCF ₂ CFYCO ₂ R ⁴ where R and R ⁴ are as above
by reacting it with a suitable tertiary amine of the formula NR ¹ R ² R ³ . The preparation of quaternary ammonium propionate salts from cyano esters as described in Reference Example 9A was unexpected due to the tendency of nucleophiles to attack cyano esters non-selectively. The derivatives of the invention can be produced by various methods. For example, a derivative ester, i.e. Z is −CO ₂ R″
X'CF ₂ CFYZ can be prepared by treating the salt in the reaction mixture or separately from the reaction mixture with an alkylating agent as described above. Z is −COOl or −COF [i.e., when m is 0

Derivatives of the formula are prepared by treating the propionate salt of the invention with a chlorinating agent such as thionyl chloride or phosphorous pentachloride to produce an acyl chloride, which is further treated with a suitable fluoride salt, such as
Acyl fluoride can be produced by reacting with NaF. The acyl fluoride is a propionate salt, preferably a quaternary ammonium propionate salt, perfluoroallyl fluorosulfate, SF ₄ or
It can also be produced by treatment with COF ₂ .
Acyl halides in which X' is -CN and are therefore not included in the present invention can also be prepared by these methods; if a cyano group is to be included, after converting the propionate salt to an ester, the method described in U.S. Pat. No. 3,557,165 method can be used. Acyl fluorides are described, for example, in U.S. Pat.
4131740, by reacting an acyl fluoride with hexafluoropropene oxide in the presence of fluorine ions, Z is

[Formula] and m can be converted into a derivative in which m is 1 to 6. This derivative in which X′ is -N ₃ , -SR or -SO ₂ R, as well as related cyano functional derivatives not of the invention, also include those in which X is -N ₃ , -
The corresponding quaternary ammonium salts of the invention, which are SR, _-SO2R or -CN, can be prepared from the salts by reacting them with carbonyl fluoride followed by hexafluoropropene oxide. Quaternary ammonium salts can be prepared in situ by reacting fluoroesters with tertiary amines as described above. Z is a fluorinated vinyl ether-containing group

A derivative that is [formula] Yes, Z is

and m is at least 1 and preferably at least 2, in a neutral solvent, as an alkali or alkaline earth metal carbonate, phosphate, sulfite or sulfate salt, preferably sodium carbonate or trisodium phosphate. It can be produced by pyrolysis in the presence of. As described in Reference Example 12, derivatives in which Z is the above-mentioned fluorinated vinyl ether-containing group also include

It can be prepared by thermally decomposing a derivative of the formula in the absence of a solvent or added salt. The latter derivatives can be prepared by hydrolysis of the reacting acyl fluoride with the ester. By either method,

[Formula] Group is lost. Here, m must be at least 1, and q is one less than m or p. When pyrolyzing the derivatives of the invention in which X′ is −PO(OR′) ₂ , R′ is preferably −
_{CH2CF3 .} Copolymers made from vinyl ether-containing compounds in which q is at least 1 are suitable for use as ion exchange membranes. Z is an allyl ether-containing group

Derivatives of the formula are those in which Z is

A derivative of the formula can be prepared by reacting with perfluoroallyl fluorosulfate or perfluoroallyl chloride in the presence of fluorine ions. Derivatives in which Z is a fluorinated allyl ether-containing group as described above and m is 0, as well as related cyano-functional fluorinated allyl ethers, i.e. those in which X' is CN ( _not according to the invention), , −SR, −
The quaternary ammonium propionate salts of the present invention which are ^SO2R , -PO(OR') ₂ or -CN were prepared in Examples
13B, or preferably directly by reaction with carbonyl fluoride followed by perfluoroallyl sulfate as described in Examples 5 and 6. can do. Quaternary ammonium salts may be prepared in situ by reacting the fluoroester with a tertiary amine as described above. Derivatives of the invention in which Z is a vinyl fluoride- or allyl ether-containing group as defined above, as well as related cyano-functional vinyl fluoride- or allyl ethers, i.e. compounds in which X' is -CN and which are not of the invention, include fluoroolefins such as tetra Fluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, or these together with hexafluoropropene or perfluoroalkyl vinyl ether, for example, R′ _F is perfluoroalkyl having 1 to 4 carbon atoms.
It can be copolymerized with a mixture of CF ₂ =CFOR' as described in Reference Example 10 and US Pat. The derivatives of the present invention in which X' is -P(O) _Cl2 are MXn
can be prepared by the process of the invention and the resulting salt in which M[PO(OR') ₂ ] _o is treated with phosphorus pentachloride, for example as described in Example 8. _Derivatives in which
It can be prepared from phosphonyl chloride by treatment with NaF. The copolymers of the invention, which can be formed into shaped articles, such as films, have pendant functional groups which give them particular utility. A pendant group, i.e. -
PO(OR') ₂ , -P(O)Cl ₂ , -P(O)F ₂ , -SR or -
Copolymers with SO ₂ R have ion exchange properties after hydrolysis. The latter two groups are
Requires prior conversion to the sulfonate or carboxylate as described by Ward, J.Org.Chem. 30 , 3009 (1965). - of the pendant
The use of fluoropolymers containing PO(OR') ₂ , -P(O)Cl ₂ , sulfonate or carboxylate groups as membrane materials for electrolytic cells is described in U.S. Pat.
No. 4164463 and No. 3853720. The use of fluoropolymers containing pendant sulfonate or carboxylate groups as ion exchange membranes is disclosed in US Pat. No. 4,176,215. Copolymers with pendant azide groups are
By heating the _N2 to a liberating temperature and using this gas as a blowing agent, it can be converted into a chemically stable structural form. Such copolymers may be added to useful cyano _- containing copolymers by reacting the pendant _-CF2N3 groups with a tertiary group such as triphenylphosphinephosphine. Cyano-substituted copolymers, i.e. copolymers in which or

It can be produced from a copolymer of the formula and where X' is _-N3 by reacting it with a tertiary phosphine as shown in Reference Example 9D. The cyano substituent imparts a curing point to such copolymers and
They are converted into fluoroelastomers as described in European Patent Application No. 11853 of the date. Useful perfluoroalkylene triazine polymers are derived from cyano-functional propionate salts after conversion to methyl esters, as described in US Pat. Nos. 3,532,725 and 3,557,165.
The pendant cyano groups are converted into carboxyl and carboxyl bases, respectively, by known methods, i.e. -
It may also be a copolymer that is converted into CO ₂ H and -CO ₂ ^- M ⁺ and thereby has ion exchange properties. Other fluoropolymers can be made indirectly from the propionate salts of this invention. For example, when X is -CN and Y is -F, the salt can be hydrolyzed with an aqueous acid or an aqueous alkali to give tetrafluorosuccinic acid, which can be further converted to carbonyl fluoride under the conditions described in U.S. Pat. No. 3,213,062. It can be made to react with perfluorobutyrolactone. Perfluorobutyrolactone is a U.S. Patent No.
It is a useful intermediate for carboxylated perfluoropolymers such as those described in US Pat. No. 4,127,731. In the following examples illustrating the invention, all parts and percentages are by weight and temperatures are in °C, unless otherwise indicated. Reference Examples 1 to 9 and 11 illustrate methods for producing propionate salts, recovery as esters or conversion to acids, recovery of acids as esters, etc. Examples 1-3, 5 and 6 illustrate the preparation of propionate salts of the invention and, with the exception of Example 6, their conversion into derivatives of the invention. Example 4 illustrates the preparation of propionate salts of the invention and their conversion into useful compounds not of the invention. Reference Examples 10 and 13 illustrate methods for producing copolymers. Examples 7-9 illustrate methods for making derivatives of the invention. Preferred specific examples related to the present invention are Example 1,
8A, 8C, is exemplified by the combination of Example 9, Reference Examples 12 and 13 and the combination of Example 6.5B and Reference Example 10 to produce a vinyl ether copolymer. That is, in the latter case, the tetramethylammonium salt is prepared as described in Example 6 except that the solvent is diglyme, and the salt is then prepared as described in Example 6.
perfluoro-4-oxa as described in 5B.
Convert to 6-heptenyl azide and convert it into Reference Example 10
Allyl ether copolymers can be produced by copolymerization as described in . Reference example 1 A Potassium 3-cyanotetrafluoropropionate and tetrafluorosuccinic acid and ester in dimethylformamide KCN + CF ₂ = CF ₂ + CO ₂ → NCCF ₂ CF ₂ CO ₂ ^- K ⁺ H ⁺ /H ₂ O --- → HO ₂ CCF ₂ CF ₂ CO ₂ H KCN26.0g (0.4 mol), dimethylformamide
150ml, 50g of tetrafluoroethylene (TFE)
(0.50 mol) and 50 g of CO ₂ was kept at 50° C. for 4 hours and then at 100° C. for 4 hours under a maximum pressure of 1100 psi (7.6×10 ³ kpa). The resulting mixture was dark in color and free of insoluble salts. Volatile compounds were removed from the mixture under reduced pressure to yield a viscous residue of potassium 3-cyanotetrafluoropropionate, which was subsequently triturated with ether to substantially solidify to a deliquescent semi-solid. . IR (pure substance): 2288 (weak, covalently bonded CN), 1680 (strong,
CO ₂ ) and 1250 to 1100 cm ^- (C-F, C-O) and
Broad hydrogen bonded OH and 2940 at 3450cm ^-1
CH saturated in cm ^-1 (weak). This residue was stirred with a mixture of 300 ml water and 110 ml concentrated H ₂ SO ₄ at 25° C. for 1 day. Extracted continuously with ether for 30 hours and evaporated the ether extract,
A residue of crude tetrafluorosuccinic acid was obtained which was refluxed for 18 hours with 500 ml of absolute ethanol and 2 ml of concentrated HCl. The water/ethanol mixture was distilled off and the above steps were repeated with 400 ml of absolute ethanol and 5 ml of concentrated HCl and with 500 ml of absolute ethanol and 1 ml of concentrated Cl. As a result of distillation, the boiling point is almost 77° (1 mm
Hg) diethyltetrafluorosuccinate
19.5 g (20% based on KCN) was obtained. IR and
After treatment with ammonia, a tetrafluorosuccinamide with a melting point of 257-260° (sublimation) was obtained in 82% yield, as identified by ¹⁹ F and ¹ H NMR. The melting point did not decrease upon mixing with standard tetrafluorosuccinamide. B Potassium 3-cyanotetrafluoropropionate and tetrafluorosuccinic acid and ester in N,N'-dimethylethylene urea 26.0 g (0.40 mol) KCN, 150 ml N,N'-dimethylethylene urea, ₅₀ g CO2 (1.1 mol) ) and 50 g (0.50 mol) of tetrafluoroethylene in a 400 ml metal tube at 50°C for 4 hours and then at 100°C.
Shake at ℃ for 4 hours. Boiling point 40~43° (0.1mm, 1.3
x10 ² kpa) of solvent was distilled off from the dark reaction mixture and the partially crystallized residue of potassium 3-cyanotetrafluoropropionate was extracted twice with ether. The residue was stirred with 300 ml of H ₂ O and 200 ml of concentrated H ₂ SO ₄ at 60° C. for 3 days. Crude tetrafluorosuccinic acid was obtained by successively extracting the resulting mixture with ether and evaporating the extracts. This was refluxed for 1 day with 600 ml of absolute ethanol and 2 ml of concentrated HCl. distilling off the water/ethanol mixture;
500 ml of ethanol and 1 ml of concentrated HCl were added. By slowly distilling off the solvent and rectifying the high boiling point compounds, ^a
12.9 g (13%) of diethyl tetrafluorosuccinate, identified by IR analysis, was obtained. Reference Example 2 Tetraethylammonium 3-cyanotetrafluoropropionate and tetrafluorosuccinic acid and ester (C ₂ H ₅ ) ₄ NCN + CF ₂ = CF ₂ +CO ₂ →NCCF ₂ CF ₂ CO ₂ ^- N ⁺ (C ₂ H 5 ) in acetonitrile
₅ ) _4- tetraethylammonium cyanide 52.1g
(0.33 mol), acetonitrile 150 ml, CO ₂ 50 g
(1.1 mol) and 50 g of tetrafluoroethylene
(0.50 mol) was stirred at 50°C for 4 hours and then at 100°C for 4 hours. The liquid reaction mixture was evaporated to leave a viscous oil and 96 g of solid tetraethylammonium 3-cyanotetrafluoropropionate. A 48 g sample of the crude product was hydrolyzed down 70° with aqueous H ₂ SO ₄ . Extraction of tetrafluorosuccinate with ether and esterification with ethanol/HCl yields diethyl tetrafluorosuccinate, identified by IR analysis, with a boiling point of 68-70° (5 mm, 6.5 x 10 ^-1 kpa).
16.6g (41%) was obtained. Reference Example 3 Tetraethylammonium 3-cyanotetrafluoropropionate and 3-cyanotetrafluoropropionate in acetonitrile
Methyl cyanotetrafluoropropionate Tetraethylammonium cyanide 62.4g
(0.40 mol), acetonitrile 150 ml, CO ₂ 33 g
(0.75 mol) and tetrafluoroethylene (TFE)
100 400ml metal tubes containing 40g (0.40mol)
Stirred at ℃ for 8 hours. Pressure 300psi through this
(21×10 ³ kpa). Evaporation of the volatiles gave 110 g of a dark solid containing tetraethylammonium 3-cyanotetrafluoropropionate. This solid was treated with 300 ml of diethyl ether and 45.6 g (0.40 mol) of methylfluorosalophate. After 3 days, the mixture was filtered and most of the ether was distilled off. The product was transferred to a cold top under 5 mm (6.5 x 10 ^-1 kpa) and then rectified to reduce the boiling point from 95 to
34.4 g (46%) of 98° methyl 3-cyanotetrafluoropropionate was obtained. This is standard material 3-
IR of methyl cyanotetrafluoropropionate
Identification was made by comparison with the spectrum. Reference Example 4 A Sodium 3-cyanotetrafluoropropionate and methyl 3-cyanotetrafluoropropionate in dimethyl sulfoxide 19.6 g (0.40 mol) NaCN, 33 g (0.75 mol) CO ₂ and 50 g (0.50 mol) TFE in dimethyl Mixture in 150 ml of sulfoxide (DMSO), approx.
A dark liquid mixture containing sodium 3-cyanotetrafluoropropionate was obtained by maintaining at 100° C. for 1 hour under 700 psi (4.8×10 ³ kpa). The resulting mixture was treated with 63 g (0.50 mol) of dimethyl sulfate until the end of the initial mild exothermic reaction.
and then heated to 60° C. for 1 hour. Volatile compounds in the mixture were removed by warming the mixture to 64° (5 mm, 6.5×10 ⁻¹ kpa). The volatiles were rectified to yield 43.1 g (58% based on NaCN) of methyl 3-cyanotetrafluoropropionate identified by IR, boiling point 90-96°C. B Sodium 3-cyanotetrafluoropropionate and methyl 3-cyanotetrafluoropropionate in DMSO at 25°C 24.5 g (0.50 mol) NaCN, 33 g (0.75 mol) CO ₂ and 50 g (0.50 mol) TFE in DMSO 150
ml mixture was maintained at 17-25° for about 19 hours or more. During this time the pressure increases from 600 to 250 psi (4.1 x ¹⁰³
1.7×10 ³ kpa). After maintaining the temperature at approximately 25°C for an additional 2 days, the reaction mixture containing sodium 3-cyanotetrafluoropropionate was treated with 69.3 g (0.55 g) of dimethyl sulfate.
mol), stirred and left overnight. By rectification of the volatile product, 53.3 g of methyl 3-cyanotetrafluoropropionate (58
%) was obtained. C Sodium 3-cyanotetrafluoropropionate and methyl 3-cyanotetrafluoropropionate in tetraglyme Tetragrams of 24.5 g (0.50 mol) NaCN, 33 g (0.75 mol) CO ₂ and 50 g (0.50 mol) TFE
The mixture in 150ml is approximately 1330~1100psi (9.2× ¹⁰³ ~7.6
×10 ³ kpa) and maintained at 100° for 8 hours to obtain sodium 3-cyanotetrafluoropropionate. 63.0g of dimethyl sulfate was added to this product.
(0.50 mol), boiling point 90-96°, IR
35.8 g (39%) of methyl 3-cyanotetrafluoropropionate, identified by , was obtained. Reference Example 5 Sodium 3-cyanotetrafluoropropionate and allyl 3-cyanotetrafluoropropionate The reaction of Example 4A was repeated to obtain sodium 3-cyanotetrafluoropropionate, and the reaction mixture was mixed with 48.4 g (0.40 mol) of allyl bromide. )
and stirred for 2 hours. Volatile products at 50° (5
mm, 6.7×10 ⁻¹ kpa) and rectified to yield 29.9 g (35%) of allyl 3-cyanotetrafluoropropionate with a boiling point of 55° (50 mm, 6.7 kpa). IR (CCl ₄ ): 3090 (saturated CH), 2960 and 2860 (saturated CH), 2260 (CN), 1785 (C=O), 1650 (C=
C), and 1200-1100 cm ^-1 (CF, C-O). NMR
(CCl ₄ ): ¹ H5.6 ( ^2nd orderm, 3H=CH) and
4.92ppm (d, _JHH 5.4Hz, 2H, _CH2 ); ¹⁹ F−107.5
(t, J _FF 5.8Hz, 2F, CF ₂ CN) and -119.5ppm
(t, J _FF 5.8Hz, 2F, CF ₂ C=O). Analysis C ₇ H ₅ F ₄ NO ₂ : Calculated value: C, 39.82; H,
2.39; N, 6.64. Experimental value: C, 39.92; H, 2.49;
N, 6.75. Reference example 6 Calcium 3-cyanotetrafluoropropionate and methyl 3-cyanotetrafluoropropionate Ca(CN) ₂ 23.0g (0.25mol), DMSO150ml,
33g (0.75mol) of _CO2 and 50g (0.50mol) of TFE
Calcium 3-cyanofluoropropionate was obtained by shaking a 400 ml metal tube at 50° for 6 hours and at 100° for 4 hours. The reaction mixture was then stirred with 69.3 g (0.55 mol) of dimethyl sulfate until the initial exothermic reaction ceased. By removing the volatiles under reduced pressure and distilling it, 14.6 g (16%) of methyl 3-cyanotetrafluoropropionate with a boiling point of 90-97° were obtained.
I got it. Reference Example 7 Sodium 2-chloro-3-cyanotrifluoropropionate and methyl 2-chloro-3-cyanotrifluoropropionate A reaction mixture of 24.5 g (0.50 mol) NaCN, 33 g (0.75 mol) CO ₂ , 58 g (0.50 mol) chlorotrifluoroethylene, and 150 ml DMSO was reacted in a 400 ml metal tube while warming from below 0°C.
Pressure is 290 psi (2.0 x 10 ³ kpa) at 4° for 20 hours
to 220 psi (1.5×10 ³ kpa) at 24°.
As a result, a mixture containing sodium 2-chloro-3-cyanotrifluoropropionate was obtained. Dimethyl sulfate (69.3 g, 0.55 mol) was added dropwise and the resulting mixture was stirred for 3 hours while maintaining the temperature in a cooling bath below 30°.
Volatility is removed under reduced pressure and rectified to a boiling point of 57~58° (50
64.9 g (64%) of 2-chloro-3-cyanotrifluoropropionic acid (mm, 6.7 kpa) were obtained. IR ( _CCl4 ): 3020, 2960, and 2950 (saturated CH),
2250 (CN), 1770 (C=O), and 1100−1250 cm ^-1
(CF, CO). NMR (CCl ₄ ): ¹ H3.95ppm (s,
OCH ₃ ); ¹⁹ F−132.9ppm (t, J _FF 13.6Hz, 1F ⁴ ,,
CF) and AB type for CF ₂ , −9283, −9570, −
9633, and -9921Hz (d, J _FF 13.6Hz2F). Analysis C ₅ H ₃ ClF ₃ NO ₂ ; Calculated value: C, 29.80; H,
1.50; N, 6.95. Experimental value; C, 30.04; H, 1.84;
N, 6.96. Example 1 Sodium 3-azidotetrafluoropropionate and methyl 3-azidotetrafluoropropionate A 400 ml metal tube containing 26.0 g (0.40 mol) of NaN ₃ , 33 g (0.75 mol) of CO ₂ , 50 g (0.50 mol) of TFE, and 150 ml of DMSO was heated to 730 psi (5.0
10 ³ kpa) to 520 psi (3.6 x 10 ³ kpa) for 4 hours and then about 765-800 psi (5.3
×10 ³ to 5.5 × 10 ³ kpa) and heated to 100° C. for 2 hours to obtain sodium 3-azidotetrafluoropropionate. The reaction mixture was then stirred with 56.7 g (0.45 mol) of dimethyl sulfate until the initial exothermic reaction ceased. The volatiles were removed under reduced pressure and rectified to yield 73.2 g (91%) of methyl 3-azidotetrafluoropropionate, boiling point 54° (50 mm, 6.7 kpa). IR (CCl ₄ ); 3010, 2960, and 2855 (saturated CH);
2160 (N ₃ ), 1785 (C=O) and 1100-1300 cm ^-1
(CF, C-O). NMR (CCl ₄ ): ¹ H3.99ppm (s,
OCH ₃ ); ¹⁹ F−91.7 (t, J _FF 4.7Hz, 2F, CF ₂ N ₃ )
and −120.5 ppm (t, J _FF 4.7 Hz, 2F, CF ₂ C=O). Analysis C ₄ H ₃ F ₄ N ₃ O ₂ : Calculated value: C, 23.89; H,
1.50; N, 20.90. Experimental value: C, 24.27; H,
1.71; N, 21.31. Example 2 Sodium 3-azido-2-trifluoromethoxytrifluoropropionate and methyl 3-azido-2-trifluoromethoxytrifluoropropionate 32.5 g (0.50 mol) NaN _{3 ,} 33 g (0.75 mol) CO ₂ , 83 g (0.50 mol) trifluoromethylfluorovinyl ether, and dimethyl sulfoxide
150ml of the mixture at 25-27° and 380-280psi (2.6
10 ³ to 1.9×10 ³ kpa) for 10 hours. The resulting solution containing sodium 3-azido-2-trifluoromethoxytrifluoropropionate was stirred for 3 hours with 69.3 g (0.55 mol) of dimethyl sulfate until the initial exothermic reaction had ceased. Volatility was removed at 50° (2 mm, 2,6 x 10 ^-1 kPa) and the resulting crude ester was rectified to a boiling point of 38~
Methyl 3-azido-2-trifluoromethoxytrifluoropropionate at 41° (24 mm, 21 kPa)
111.8g (84%) was obtained. IR ( _CCl4 ): 3010, 2960,
and 2850 (saturated CH); 2150 (N ₃ ), 1780 (C=O),
and 1100−1250 cm ⁻¹ (C−F). NMR (CCl ₄ );
¹ H3.89ppm (s, OCH ₃ ); ¹⁹ F−56.0 (d, J _FF 8.6
Hz, 3F, OCF ₃ ), and −131.6ppm (qoft, J _FF 8.6,
5Hz, 1F, CF) and type AB for CF ₂ N ₃ , -
8333 and -8521Hz (d, J _FF 5.0Hz, 1F) and -
8548 and -8763Hz (d, J _FF 5.6Hz, 1F). Analysis C ₅ H ₃ F ₆ N ₃ O ₃ : Calculated value: C, 22.49; H,
1.13; N, 15.73. Experimental value: C, 22.81; H,
1.48; N, 16.00. Example 3 Sodium 3-azido-2-heptafluoro-n-propoxytrifluoropropionate and sodium 3-azido-2-heptafluoro-n-propoxytrifluoropropionate 26.0 g (0.40 mol) of NaN ₃ , 33 g (0.75 mol) of CO ₂ , 106 g (0.40 mol) of heptafluoro-n-propyl trifluorovinyl ether, and
A mixture of 150 ml of DMSO in a 400 ml tube.
It was shaken at 25° for 16 hours. The obtained 3-azido-2-heptafluoro-n
- A mixture containing sodium propoxytrifluoropropionate was added to 56.7 g of CH ₃ OSO ₂ OCH ₂
(0.54 mol), stirred overnight and then poured into cold water 1.5 mol. Wash the organic phase with 500 ml of water,
Dry with CaSO ₄ and distill to a boiling point of 44-45° (10 mm.
3-azido-2-heptafluoro-
115.8 g (79%) of methyl n-propoxy-trifluoropropionate was obtained. IR (CCl ₄ ); 3010, 2970, and 2850 (saturated CH),
2150 (N ₃ ), 1780 (C=O), and 1100−1250 cm ⁻¹
(CF, C-O). NMR (CCl ₄ ); ¹ H3.92ppm (s,
OCH ₃ ); ¹⁹ F−82.1(t, J _FF 7.3Hz, 3F, CF ₃ ), −
130.3 (t d d, J _FF 19.6, 6, 6Hz, 1F,
CF), and -130.4ppm (s, 2F, CF ₂ ), and
Type AB multiplet for OCF ₂ , −7443 and −7592Hz
(d of q, J _FF 19.6, 7.3Hz, 1F) and -8189 and -
8340Hz (d q, J _FF 7.3, 6Hz, 1F) and CF ₂ H ₃
AB types -8359, -8547, -8567 and -8757 for
Hz (dJ _FF 6Hz, 2F). Analysis C ₇ H ₃ F ₁₀ N ₃ O ₃ : Calculated value C, 22.90; H,
0.82; N, 11.45. Experimental value: C, 22.45; H,
1.09; N, 11.70. Reference Example 8 Sodium 3-t-butylthiotetrafluoropropionate and methyl 3-t-butylthiotetrafluoropropionate 50% HaH/mineral oil 24g (0.50mol),
The suspension in 140 ml of DMSO was stirred and 45 g (0.50 mol) of t-butyl mercaptan was added dropwise.
It was maintained at 45°. The viscous mixture is then stirred and
Heat to 45° for approximately 4.5 hours until very little hydrogen evolution occurs. The resulting slurry was washed into a 400ml metal tube with 10ml of DMSO, and 33g of CO ₂ was added.
(0.75 mol) and TFE50g (0.50 mol) were added,
The mixture was stirred at 100° for 8 hours. The resulting dark colored solution containing sodium 3-t-butylthiotetrafluoropropionate was
dimethyl sulfate while maintaining the temperature at 30°.
69.3g (0.55 mol) was stirred. After the initial exothermic reaction had finished, the mixture was stirred overnight and then distilled to give a crude product with a boiling point of about 45° (2 mm, 2.6×10 ^-1 kPa). This distillate was washed with 1 part of water and dry rectified to give 3 ^- t
-Methyl butylthiotetrafluoropropionate
52.1g (42%) was obtained. IR (pure substance): 2970 (saturated
CH), 1775 (C=O), 1100−1250 cm ^-1 (CF).
NMR (CCl ₄ ): ¹ H3.87 (s, 3H, COH ₃ ) and
1.52ppm(s, 9H, C( _CH3 ) ₃ ; _19F -86.3(t, _JFF
7.1Hz, 2F, CF ₂ S) and -117.6ppm (t, J _FF 7.1
Hz, 2F, _CF2C =O). Analysis C ₈ H ₁₂ F ₄ O ₂ S: Calculated value C, 38.71; H,
4.87. Experimental values: C, 38.99; H, 5.05. Example 4 Sodium 3-dimethylphosphonotetrafluoropropionate and related salts thereof 50% NaH/mineral oil 24.0g (0.50mol)
55 g (0.50 mol) of dimethyl phosphite were added to the suspension in 150 ml of DMSO while stirring the mixture. Since it foamed considerably, it was necessary to add it slowly and dropwise, and the reaction was allowed to continue for a long time after the addition of the phosphite was completed. The resulting mixture was mixed with 33 g (0.75 mol) of CO ₂ and 50 g of TFE.
(0.50 mol) in a 400 ml tube, first at 50°C for 4 hours and then at 100°C for 1 hour.
Remove the solvent from the resulting solution at 75° (0.4 mm, 5.3
10 ^-2 kPa) to obtain a residue. This solidified on standing to give 106 g of material. IR (pure substance);
2950, 2920, and 2850 (saturated CH), 1770 (ester C=O), 1690 and 1440 (CO ₂ ), 1260 (P=O),
and 1000-1200 cm ^-1 (CF, P-O-C). NMR
(DMSO): ¹⁹ F indicates a 55:45 mixture; main components -118.9 (t, J _FF 4.6Hz, 2F, CF ₂ C=O) and -
122.3ppm (d of t, J _FF 71Hz, J _FF 4.6Hz, 24,
CF ₂ P) and subcomponents −118.4 (Prode s, 2F,
CF ₂ C=O) and −122.3 ppm (Broad d, J _FP 72
Hz, 2F, _CF2P ). _The spectrum showed _{a mixture of} ( _CH3O ) _2P (O) _CF2CF2CO2 ^- Na ⁺ and _{CH3OP (} O) _CF2CF2CO2CH3 . Reference example 9 A 3-cyanotetrafluoropropionate methyltriethylammonium 9.3 g (0.05 mol) of methyl 3-cyanotetrafluoropropionate prepared as in Reference Example 3
A homogeneous solution of 5.1 g (0.05 mol) and triethylamine in 25 ml of ether was stirred at 25°. 4
After a day, a second layer slowly formed; no increase was observed for another 2 days. The volatiles were removed under 25° full pump pressure to yield a deliquescent yellow solid, methyltriethylammonium 3-cyanotetrafluoropropionate, mp 52-55°C. IR
( _CDCl3 ): 2965 (saturated CH), 2255 (CN), 1690
(CO ₂ ), and 1250−1100 cm ⁻¹ (CF). NMR
(CDCl ₃ ): ¹ H3.47 (q, J _FF 7.1Hz, 6H, CH ₂ -N,
3.08 (s, 3H, CH3 _- N), and 1.37ppm (t, J _FF
7.1Hz, ofm, 9H, CH ₃ ); ¹⁹ F−108.5 (t, J _FF 8.4
Hz, 2F, CF ₂ CN) and -119.3ppm (t, J _FF 8.4
Hz, 2F, CF ₂ C=O). Only 3% impurities were present. Further confirmation of the structure was obtained from the reaction of this material as described below. Subsequent preparations on a 0.2-0.34 molar scale gave methyltriethylammonium 3-cyanotetrafluoropropionate in 92-95% yield. The material varied in purity from a slightly damp solid to a semi-liquid substance at 25°. B Cyanotetrafluoropropionyl fluoride and perfluoro-5-oxa-7-octenenitrile 53.9 g of methyltriethylammonium 3-cyanotetrafluoropropionate produced in A
(0.2 mol) in 300 ml of diglyme was added to 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate.
mol) was added rapidly while stirring at -10 to -5°. The mixture was then stirred for 1 hour at -10 to -5°, followed by 4 hours at -5 to 0°. The volatiles were removed through a liquid _N2 trap at 35° (5 mm, 6.7 x 10 ^-1 kPa) and rectified to yield 10.0 g (29%) of 3-cyanotetrafluoropropionyl fluoride with a boiling point of 19-20°. . IR (gas phase): 2265 (CN), 1888 (COF), and
1300−1100 cm ^-1 (CF), and traces of CO ₂ , SO ₂ F ₂
and SiF ₄ present. NMR (CCl ₄ ; 0°); ¹⁹ F25.8 (t
t of t, J _FF 10.1, 5.0Hz, 1F, COF), −106.7 (d of t, J _FF 5.0, 4.6Hz2F, CF ₂ , CF ₂ CN), and −
118.5ppm (t d, J _FF 10.1, 4.6Hz, 2F, CF ₂ C=
O). By further rectification, the recovered perfluoroallyl fluorosulfate with a boiling point of 62-63°
3.9 g and 8.0 g (12%) of perfluoro-5-oxa-7-octenenitrile with a boiling point of 81-83° were obtained.
IR (CCl ₄ ): 2265 (CN), 1790 (C=C), and 1300
-1100cm ^-1 (CF, C=O). NMR (CCl ₄ ): −71.9
(d t d d, J _FF 25.2, 13.9, 11.6, 7.3Hz,
2F, OCF ₂ C=), -83.7 (t of m, J _FF 11.6,
9, 2F, OCF ₂ ), -91.0 (d of t, J _FF 50.8,
39.5, 7.3, Hz, 1F, cis-CF ₂ CF=CFF);-
104.7 (t d d, J _FF 118.0, 50.8, 25.2Hz, 1F,
trans-CF ₂ CF = CFF), -106.4 (d t, J _FF 8.8, 4.4, 1.6Hz, 2F, CF ₂ CN), -127.5
(t of t, J _FF 4.4, 2.3Hz, 2F, CF ₂ ), and −
190.8ppm (t of t of d of d, J _FF 118.0, 39.5,
13.9, 16.Hz, 1F, CF ₂ CF=). Analysis _{C7F11 NO} : Calculated: C, 26.02; N, 4.34.
Experimental values: C, 26.36; N, 4.41. C Perfluoro-5-oxa-7-octenenitrile with excess fluorosulfate 54.5 g of methyltriethylammonium 3-cyanotetrafluoropropionate prepared in A
(0.2 mol), flame dried KF11.6g (0.20 mol)
Perfluoroallyl fluorosulfate (92.0 g, 0.40 mol) was slowly added to a stirred mixture of 300 ml of diglyme and diglyme at -10 to -5°C. The mixture was then stirred at -10 to -5° for 3 hours and poured with ice water at 1.5°C.
I poured it inside. Wash the lower layer with 500ml of cold water,
Dry with CaSO ₄ and rectify to obtain perfluoro-5-oxa-7-octenenitrile with a boiling point of 80-84°21.9
g ( ₃₄ % _{from NCCF2CF2CO2CH3} ) _. It was found to be essentially pure by gas chromatography (GC). The reference example shows that when an excess of fluorosulfate is used, alriether is obtained in high yields. D Perfluoro-5-oxa-7-octenenitrile and copolymer 54.2 g of 3-cyanotetrafluoropropionate methyltrimethylammonium produced in A
(0.2 mol) in 300 ml of diglyme was stirred at -15 to -10° while slowly adding 14 g (0.21 mol) of carbonyl fluoride. This mixture was heated at -15 to -10° for 30 minutes, then at -10 to -5°.
Stirring was continued for 30 minutes, followed by the addition of 50.6 g (0.22 mol) of perfluoroallyl fluorosulfate.
The mixture was stirred for a further 1 hour at -5 to 0°C and then poured into 1.5 liters of cold water. The lower layer was washed with 500 ml of water, dried with _CaSO4 , and distilled to give a solution with a boiling point of 80-85°.
30.2 g perfluoro-5-oxer-7-octenenitrile identified by IR and GC
(NCCF ₂ CF ₂ CO ₂ CH ₃ ) was obtained. NCCF ₂ CF ₂ CF ₂ OCF ₂ CF=
15.8 g (0.049 mol) of CF ₂ and F-113 (1,1,
2-trifluoro-1,2,2-trichloroethane) (20 ml) were mixed and cooled to 0°C. 5% perfluoropropionyl peroxide 2 in F-113
ml and place the mixture into a 100ml tube and add TFE.
The pressure was increased to 50 psi (345 kPa) at a 20° angle. temperature
Increase the temperature to 40°C and then increase the pressure to 100Ppsi by adding more TFE until the reaction is complete after about 6 hours.
(689kPa) and maintained at this pressure. A total of 11.1 g (0.11 mol) of TFE was added. 37.5 g of a damp white solid were recovered; after drying under vacuum to constant weight, 4.5 g of white polymer was obtained.
The presence of pendant cyano groups in the polymer
Confirmed with IR. 7.3 g (46%) of the volatile starting cyanoolefin was recovered. Example 5 A 3-azidotetrafluoropropionate methyltriethylammonium A mixture of 37.0 g (0.18 mol) of methyl 3-azidotetrafluoropropionate prepared in Example 2, 20.2 (0.20 mol) of triethylamine and 50 ml of ether was stirred at 25°. A second layer slowly formed. The reaction was stopped after 24 hours. At this point the second layer did not increase its volume. The volatiles were distilled off under full pump vacuum pressure to give 54.9 g (99% of theory) of methyltriethylammonium 3-azidotetrafluoropropionate as a wet solid. IR ( _CHCl3 ): 3020 (saturated CH), 2170 ( _N3 ),
1690 (CO ₂ ), and 1250−1100 cm ⁻¹ (CF). NMR
(DMSO−d ₆ ); ¹ H3.31 (q, J _HH 7Hz, 6H,
_CH2 ), 2.93(s,3H, _NCH3 ), and 1.22ppm
(t, J _HH 7Hz, 9H, CH ₃ ); ¹⁹ F−90.8 (t, J _FF 6.3
Hz, 2F, CF ₂ N ₃ ) and −115.6ppm (t, J _FF 6.3Hz,
2F, CF ₂ C=O). B Perfluor-4-oxa-6-heptenyl azide An impure sample of methyltriethylammonium 3-azido-tetrafluoropropionate prepared as described above (54.9 g, approximately 0.18 mol) is dissolved in 300 ml of diglyme and 13.5 g (0.20 mol) of COF ₂ is completely absorbed. The mixture was stirred at -20 to -15° while passing slowly enough to allow the temperature to rise. The mixture was stirred at 0° C. for 1 hour, and then 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate was added to −5
Added quickly at ~0°. Break the resulting solid,
The mixture was stirred at -5 to 0° for 1.5 hours and at 0 to 5° for 1 hour, then poured into cold water for 1.5 hours. Cool organic layer with cold water
Wash with 200 ml, dry with CaSO ₄ and distill to boiling point
59-60° (110mm, 14.6kPa) perfluoro-4-
Oxa-6-heptenyl azide 21.3g
( ₃₅ % _{from N3CF2CF2CO2CH3 ) .} IR
( _CCl4 ): 2160 ( _N3 ), 1790 (C=C), 1250-1100
cm ^-1 (CF, CO). NMR (CCl ₄ ): ¹⁹ F−72.0 (d
t d d, J _FF 25.0, 14.0, 12.3, 7.3Hz, 2F,
OCF ₂ =), -84.3 (t of m, J _FF 12.3, 9Hz,
2F, OCF ₂ CF ₂ ), -89.6 (mt, J _FF 9Hz, 2F,
CF ₂ N ₃ , -92.0 (d of t, J _FF 52.3, 39.1, 7.3
Hz, 1F, cis−CF ₂ CF=CFF), −105.3 (d of t, J _FF 117.7, 52.3, 25.0Hz, 1Ftrans−CF ₂ CF=
CFF), −128.3 (broad s, 2F, CF ₂ ), and −
190.5ppm (t of t of d of d, J _FF 117.7, 39.1,
14.0, 1.6Hz, 1F, CF ₂ CF=). Analysis C ₆ F ₁₁ N ₃ O: Calculated value: C, 21.25; N,
12.39. Experimental values: C, 21.85; N, 12.86. Reference Example 10 Copolymerization of TFE and perfluoro-4-oxa-6-heptenyl azide N ₃ (CF ₂ ) ₃ OCF ₂ CF= produced in Example 5B
16.3 g (0.048 mol) of CF ₂ and F-113 (1,1,2
-trifluoro-1,2,2-trichloroethane) were mixed and cooled to 0°. 5% perfluoropropionyl peroxide 2 in F-113
ml and charge the mixture into a 100ml tube and add TFE.
Pressure was applied to 100 psi (689 kPa) at a angle of 22 degrees below (approximately 30 g
addition). The temperature was increased to 40° (pressure 160 psi, 1103 kPa). After 6 minutes, the pressure had dropped to 110 psi (758 kPa). The mixture was then heated to 72°. Ten
After minutes, the temperature and pressure are 42° and 80psi (551kPa)
It dropped to . The flask was then heated to 210psi with TFE.
(1447kPa). The total amount of TFE added was 40g. The flask was held at 40° for 2.5 hours. The pressure dropped to 70 psi (482 kPa) within 1 hour and then stabilized. 52.4 g of a damp white solid was recovered. Volatiles were removed under vacuum to constant weight (1.5 hours). 17.9 g of a white copolymer of TFE and perfluoro-4-oxa-6-heptenyl azide was obtained. The presence of pendant azide groups in the polymer was confirmed by IR. N ₃ (CF ₂ ) ₃ OCF ₂ CF=CF ₂ 11.2g (69%)
was recovered from volatiles. Example 6 3-azidotetrafluoropropionate tetramethylammonium N ₃ CF ₂ CF 2 CO ₂ CH ₃ +N(CH ₃ ) ₃ →→N ₃ CF ₂ CF ₂ CO ₂ ^{- N +} ₍ CH ₃
) ₄ To a solution of 37.0 g (0.184 mol) of methyl 3-azidotetrafluoropropionate prepared in Example 2 in 100 ml of ether was added trimethylamine (10.6 g,
0.18 mol) was introduced by distillation. The product precipitated with a slight exotherm. According to gas chromatography, the reaction was found to be almost complete after 4 hours. The mixture was stirred overnight and then evaporated to dryness under vacuum. This residue has a melting point
31.8 g (68%) of 3-azidotetrafluoropropionate with a decomposition angle of 144-145°. IR (Nujiyor): 2170 (N ₃ ), 1680 (Broad, CO ₂ ^- ),
and 1250−1100 cm ⁻¹ (CF), NMR (DMSO−d ₆ ):
¹ H3.25ppm (s, CH ₃ ); ¹⁹ F−90.8 (t, J _FF 6.2Hz,
2F, CF ₂ N ₃ ) and −115.8ppm (t, J _FF 6.2Hz,
2F, CF ₂ C=O). Analysis C ₇ H ₁₂ F ₄ N ₄ O ₂ : Calculated value: C, 32.31; H,
4.65; N, 21.53. Experimental value: C, 32.23; H,
4.56; N, 21.30. Propionate salts can be used, for example, in Example 5B above.
and Reference Example 10, it can be converted into the derivative or copolymer of the present invention. Reference example 11 Sodium 3-methylthio-2,2,3,3-tetrafluoropropionate and methyl ester A slurry of 24 g (0.50 mol) of 50% NaH/mineral oil in 140 ml of anhydrous dimethyl sulfoxide was stirred while 24 g (0.50 mol) of methyl mercaptan was added by distillation over 2 hours. The mixture was then stirred until very slow evolution of gas and then left overnight. The resulting mixture was a viscous paste. Dilute this with 50 ml of dimethyl sulfoxide and make 33 g (0.75 mol) of carbon dioxide.
and 50 g (0.50 mol) of tetrafluoroethylene into a 400 ml metal tube. this tube
It was shaken at 100° for 4 hours. The resulting solution was treated with 69.3 g (0.55 mol) of dimethyl sulfate.
After an initial exotherm (maximum temperature 50°), the mixture was stirred for 3 hours. The product is then removed under vacuum and rectified to give 3-methylthio-2,2,3,3-tetrafluoropropionic acid with a boiling point of 53° (10 mm, 1.3 kPa).
63.9g (62%) was obtained. IR (pure substance): 3020, 2970
and 2860 (saturated CH), 1780 (C=O), and 1250~
1100cm ^-1 (C-F). ¹ H and ¹⁹ FNMR were consistent with the identified structure. analysis. C ₅ H ₆ F ₄ O ₂ S: Calculated value: C, 29.13; H,
2.93; F, 36.86. Experimental value: C, 29.42; H,
3.07; F, 36.74. Example 7 Methyl 3-dimethoxyphosphonyltetrafluoropropionate To 106 g of a crude preparation of sodium 3-dimethylphosphonyltetrafluoropropionic acid prepared as in Example 4, an excess of 329 g of POCl ₃ was added.
(1.5 mol) was added. The mixture was warmed to 60°. At this time an exothermic reaction occurred. After the reaction was completed, the solids were removed by filtration and rinsed with CCl ₄ .
The liquid and cleaning solution are distilled to remove volatiles and remove heavy oils.
56.7g was obtained. This oil was stirred overnight with 50 ml of methanol, the methanol layer was separated and distilled to give 5.5 g of a liquid with a boiling point of 60-66° (0.4 mm, 5.3 x 10 ^-2 kPa).
I got it. NMR (CD ₃ CN): ¹ H3.98 (s, 3H, C
(=O) OCH ₃ ) and 3.90ppm (d, J _HP 7Hz, 6H,
Absorption for P-OCH ₃ ) and (CH ₃ O) ₃ P=O also exists; ¹⁹ F-118.7 (t, J _FF 2.9Hz, 2F, CF ₂ C=
O) and -121.5ppm (d, J _FF 88.6Hz, oft, J _FF 2.9
Hz, 2F, CF2 _- P). IR (pure substance) shows no P-OH or C-OH, and ( _CH3O ) _2P (O)
It showed the presence of a mixture of CF ₂ CF ₂ CO ₂ CH ₃ and (CH ₃ O) ₃ P=O. Example 8 3-dichlorophosphonyltetrafluoropropionyl chloride A. A stirred suspension of 24.0 g (0.50 mol) of 50% NaH/mineral oil in 150 ml of dimethyl sulfoxide was treated dropwise with 55 g (0.50 mol) of dimethyl sulfosphite. After the gas evolution has finished, a suspension of dimethylsodium phosphite is charged into a 400 ml metal tube, and then 33 g (0.75 mol) of CO ₂ and 50 g (0.50 mol) of tetrafluoroethylene are added.
It was added at 13°. The reaction was carried out at 25° for 4 hours and then at 50° for 8 hours. The reaction mixture was concentrated.
200 ml of H ₂ SO ₄ were mixed into a solution of 1 in water and the resulting solution was extracted continuously with ether for 30 hours. The extract was stripped of volatiles to yield 51 g of oil, which was added to 416 g (2.0 moles) of phosphorous pentachloride. The mixture was slowly heated to reflux. At this point gas evolution substantially ceased. The residue was heated to 40° (1.6 mm, 2.1 x 10 ^-1 kPa) and the volatiles were transferred to a cold trap. By distillation of volatiles, the boiling point is 90-115° (100mm,
5.7 g of crude 3-dichlorophosphonyltetrafluoropropionyl chloride (CF ₂ =
A yield of 4% from CF ₂ was obtained. IR ( _CCl4 ): 1800
(C=O), 1310 (P=O), and 1250−1100 cm ^-1
(CF). NMR (CCl ₄ ): ¹⁹ F−110.6 (m, 2F,
CF ₂ C=O) and -116.0ppm (d, J _FP 113Hz,
oft, J _FF 2.3Hz, 2F, CF ₂ −P). Mass spectrum: m/e245 (M ⁺ -Cl), 217 (M ⁺ -COCl),
117 (POCl ₂ ⁺ ), 113 (CLCOCF ₂ ⁺ ), 100 (C ₂ F ₄ ⁺ ),
and 63 (COCl ⁺ ). The expected Cl isotope peak was present. The main impurity was found to be CH ₃ SCCl ₃ . B The reaction of A was carried out in tetrahydrofuran for 50
It was carried out at ~100°. Evaporate the solvent and remove the residue.
By treatment with PCl ₅ and rectification, boiling point 47
~49° (10mm, 1.3kPa) 3-dichlorophosphonyltetrafluoropropionyl chloride 4.3
g (3%) was obtained. C Excess sodium diethyl phosphite in dimethyl sulfoxide is reacted with CO ₂ and tetrafluoroethylene at 50-100° and after treatment with PCl ₅ 3-dichlorophosphonyltetra with a boiling point of 59-69° (20 mm, 2.6 kPa) Fluoropropionyl chloride was obtained with a yield of 14%. Example 9 A Adduct of 3-azido-2-heptafluoropropoxytrifluoropropionyl fluoride and hexafluoropropene oxide The reaction of 26.0 g (0.40 mol) of sodium azide, 33 g (0.75 mol) of carbon dioxide, and 106 g (0.40 mol) of perfluoro(propyl vinyl ether) in dimethyl sulfoxide was carried out in a 400 ml metal tube at a 25° angle. . The reaction mixture was poured into a solution of 250 ml of concentrated sulfuric acid in 900 ml of water. Successive extractions with ether and evaporation of the extracts yielded 140 g of crude 3-azido-2-heptafluoropropoxytrifluoropropionic acid hydrate. This acid,
SF ₄ 150 under autogenous pressure in a metal tube of 1
g (1.39 mol) and 84 g of NAF in 80 ml of CFCl ₂ CF ₂ Cl
(2.0 mol) at 80° for 12 hours. Distillation yielded 82.9 g (total yield 58%) of 3-azido-2-heptafluoropropoxytrifluoropropionyl fluoride with a boiling point of 51-53° (100 mm, 13.3 kPa). IR ( _CCl4 ): 2150 ( _N3 ), 1875 (COF), and
1300−1100 cm ⁻¹ (CF, C−O). NMR ( _CCl4 ):
¹⁹ F26.0 (p, J _FF 6Hz, 1F, COF), -82.0 (t, J _FF
7.5Hz, 3F, CF ₃ ), -129.3 (d of p, J _FF 20, 6Hz,
1F, CF), and -130.2ppm (s, 2F, CF ₂ ), and
Type AB for CF ₂ O, −7417 and −7567Hz (d of q, J _FF 20, 7.5Hz, 1F) and −8181 and −8332Hz
(q, J _FF 7.5Hz, 1F), and AB type for CF ₂ N ₃ ,
-8244 and -8430Hz (t, J _FF 5.5Hz, 1F) and -
8465 and -8651Hz (t, J _FF 6.2Hz, 1F). B Acid fluoride (72 g, 0.20 mol) produced in A was dried with a flame to produce 10.0 g (0.17 mol) of KF.
and 9:1 adiponitrile/tetraglyme 100
ml of suspension. The system was degassed to an atmosphere of pure hexafluoropropene. The mixture was stirred and 67 g (0.40 mol) of hexafluoropropene oxide was added as needed over 2 hours at 1 atmosphere (1.0 x 10 ² kPa). The temperature slowly rose from 20° to 42°. 50゜(0.3mm, 4.0×
Volatiles by distillation up to 10 ^-2 kPa) 135.9
g, which was then rectified. 35.0 g (34%) of the 1:1 adduct (n=0) was obtained as an oil with a boiling point of 46-47.5° (9.5 mm, 1.3 kPa). IR (pure substance): 2170
(N ₃ ), 1800 (COF), and 1300−1100 cm ^-1 (CF,
C-O). ^19F NMR spectrum is N ₃ CF ₂ CF
(OCF ₂ CF ₂ CF ₃ ) CF ₂ OCF (CF ₃ ) coincided with COF. analysis. C ₉ F ₁₇ N ₃ O ₃ : Calculated value: C, 20.74; N,
8.06. Experimental values: C, 20.47; N, 8.14. 2:1 adduct (n=1) with boiling point 43-46 (1.2 mm,
5.2 g ( ⁴ %) of the oil was obtained.
IR (pure substance): 2170 (N ₃ ), 1890 (COF), and 1300
−1100 cm ⁻¹ (CF, C−O). ^19F _{NMR spectrum is N3CF2CF} ( _OCF2CF2CF3 ) _CF2OCF ( _CF3 )
Consistent with COF. Analysis, _C12F23N3O4 : Calculated value _{: C} , _20.98 ; N,
6.12: Experimental value: C, 21.26; N, 6.39 Reference example 12 9-azido-8-heptafluoropropoxy-
5-trifluoromethyl-undecafluoro-
3,6-dioxanonene 2:1 adduct prepared in Example 9 (n=1)
(18.0 g, 0.026 mol) was stirred with 50 ml of water while adding aqueous NaOH to the end of phenolphthalene. The volatiles were removed with a stream of air and the product salt was dried at 140° (0.1 mm, 1.3×10 ^-2 kPa). Pyrolysis of the salt was carried out at 220-235° for 5 hours. During this period, the pressure increases from 1.8 mm (2.4 × 10 ^-1 kPa) to 0.1 mm (1.3 ×
10 ^-2 kPa). The crude product was collected in a cold trap, washed with water, dried over calcium sulfate, and rectified to yield 7.7 g (48%) of trifluorovinyl ether with a boiling point of 64-68° (9.5 mm, 1.3 kPa). IR (pure substance): 2150 (N ₃ ), 1835 (C=C), and
1300−1100 cm ^-1 (CF, C=O). Analysis, _C11F21N3O3 : Calculated _value : _C , _21.27 ; N,
6.76: Experimental value: C, 21.10; N, 6.88 Reference example 13 TFE and N ₃ CF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₂ OCF
(CF ₃ ) CF ₂ OCF=Copolymer of CF ₂ 7.3 g (0.012 mol) of trifluorovinyl ether prepared in Reference Example 12, 3 ml of 3% perfluoropropionyl peroxide in CFCl ₂ CF ₂ Cl, and
A solution of 20 ml of CFCl ₂ CF ₂ Cl was placed in a 100 ml metal tube and shaken at 25-30° while adding 25 g (0.25 mol) of tetrafluoroethylene in portions. The reaction was then carried out at 40° for 2 hours. The resulting polymer was suspended twice in CFCl ₂ CF ₂ Cl, filtered and then dried under high vacuum to yield 3.3 g of the title copolymer as a white solid. IR (nujiyor): 2150cm
^-1 , absorption band for _N3 present. Reference example 14 A Sodium 3-methylsulfonyltetrafluoropropionic acid, 3-methylsulfonyltetrafluoropropionic acid and its methyl ester 50% NaH in 170ml dimethyl sulfoxide/mineral oil
NaSCH ₃ was prepared by introducing 24 g (0.50 mol) of methyl mercaptan by distillation into a stirred suspension of 24 g (0.50 mol) over a period of 2 hours. This mixture was charged into a 400 ml tube with 27 g (0.6 mol) of CO ₂ and 50 g (0.50 mol) of tetrafluoroethylene and shaken at 50° for 8 hours. The reaction mixture was poured into a cold solution of 300 ml of concentrated HCl in 1 part of water and the resulting mixture was extracted successively with ether. 3- by removing volatiles from the extract at 5 mm.
94.6 g of methylthiotetrafluoropropionic acid was obtained. Add this acid to 125 ml (approximately 1.2 moles) of 30% H ₂ O ₂
and 75 ml of acetic acid were added dropwise over 2 hours while stirring at 85° to 95°. The mixture was stirred at 90-95° for over 3 hours and then degassed at full pump pressure to remove volatiles. The remaining oil was extracted with pentane to remove mineral oil and then treated with aqueous NaOH to regenerate or esterify the sodium salt. For the methyl ester, mix the acid with 500 ml of methanol and 2 ml of concentrated HCl.
Produced by refluxing for hours. Chloroform (500ml) was added and the mixture was distilled to a temperature of 63°. A further 500 ml of methanol and 1 ml of concentrated HCl were added and esterification was allowed to proceed for 3 days at 25°.
Chloroform (500ml) was added and the mixture was rectified to give 64g (54% from TFE) of methyl 3-methylsulfonyltetrafluoropropionate, boiling point 75° (1.2mm). IR (pure substance): 3020, 2970,
2940 and 2860 (saturated OH) 1780 (C=O) 1355
(SO) and 1250-1100 cm ^-1 (CF, CO, _SO2 ).
NMR ( _CDCl3 ): ¹ H3.99 (s, 3H, _CH3O ) and
3.16ppm (t of t, J _HF 1.8, 0.7Hz, 3H,
CH ₃ SO ₂ ); ¹⁹ F−116.4 (t of t, J _FF 3.8Hz, t,
J _HF 2Hz, 2F, CF ₂ SO ₂ ) and -117.5ppm (t, J _FF
3.8Hz, 2F, _CF2C =O). Analysis _{, C5H6F4O4S} : Calcd: _C , _25.22 ; H, 2.54. Experimental value: C,
25.49; H, 2.98. B Tetramethylammonium 3-methylsulfonyltetrafluoropropionate 47.8 g (0.20 mol) of methyl 3-methylsulfonyltetrafluoropropionate in 100 ml of Utel
Trimethylamine (12.4 g,
0.21 mol) was added by distillation. The mixture was stirred overnight, filtered under nitrogen, and the solids were dried under vacuum. As a result, 52.1 g of 3-methylsulfonyltetrafluoropropionic acid with a melting point of 98° to 100°
(88%) was obtained as deliquescent crystals. NMR
(DMSO−d ₆ ): ¹ H3.40 (t, J _HF 2Hz, 3H,
CH ₃ SO ₂ ) and 3.17 ppm (s, 12H,
(CH ₃ ) ₄ N ⁺ ); ¹⁹ F−112.3 (t, J _FF 3.0Hz, 2F,
CF ₂ C=O) and -114.4ppm (t, J _FF 3.0Hz, m,
2F, _{CF2SO2 )} . Analysis, C ₈ H ₁₅ F ₄ NO ₄ S: Calculated value:
C, 32.32; H, 5.09; N, 4.7. Experimental value: C,
32.20; H, 5.17; N, 4.44. The propionates and derivatives of the present invention contain tetrafluorosuccinic acid, perfluorobutyrolactone, and fluorinated polymers, such as cure points or ion exchange It is useful as an intermediate for fluorinated functional allyl and vinyl ethers that can provide groups. Although the foregoing description has illustrated and described preferred embodiments of the invention, the invention is not limited to the precise embodiments disclosed herein, but is intended to include all claims that fall within the scope of the claims. It should be understood that the right to variations and modifications is reserved.

Claims (1)

[Claims] 1. (i) a fluoroolefin having the formula CF ₂ =CFY, (ii) a salt having the formula MXn, and (iii) CO ₂ in a polar neutral solvent at a temperature of about −20° C. to 150° C. (XCF ₂ CFYCO ₂ ) nM In the above formula, X is -N ₃ or -PO(OR') ₂ ; R' is -CH ₃ or -C ₂ H ₅ ; Y is -Cl, -F, -Br or -OR _F ; R _F is perfluoroalkyl having 1 to 4 carbon atoms; M is an alkali metal, an alkaline earth metal or -
NR ¹ R ² R ³ R ⁴ , where R ¹ to ^{R 4} are independently C _{1 to 6}
A method for producing a β-substituted fluoropropionate salt, which is a straight-chain alkyl; and n is the valence of M and is 1 or 2. 2 Formula (XCF ₂ CFYCO ₂ ) nM In the formula, X is -N ₃ or -PO(OR') ₂ ; R' is -CH ₃ or -C ₂ H ₅ ; Y is -Cl, -F , -Br or -OR _F ; R _F is perfluoroalkyl having 1 to 4 carbon atoms; M is an alkali metal, an alkaline earth metal or -
NR ¹ R ² R ³ R ⁴ , where R ¹ to ^{R 4} are independently C _{1 to 6}
A β-substituted fluoropropionate salt having the following: straight-chain alkyl; and n is the valence of M and is 1 or 2. 3 Fluoropropionate of formula XCF ₂ CFYCO ₂ R ^{4 is} converted to ^the fluoropropionate ^of formula
XCF ₂ CFYCO ₂ NR ¹ R ² R ³ R ⁴ where X is _-N3 ; Y is -Cl, -F, -Br or -OR _F Preparation of a β-substituted fluoropropionate salt having; R _F is perfluoroalkyl having 1 to 4 carbon atoms; and R ¹ to ^{R 4} are independently C _1-6 linear alkyl. Method.