JP2004196724A - Method for producing difluorohaloacetyl fluoride - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel method for producing a difluorohaloacetyl fluoride in high yields from easily available raw materials without using any special apparatus. <P>SOLUTION: The method for producing the difluorohaloacetyl fluoride represented by the formula: XCF<SB>2</SB>COF (wherein X is as defined below) comprises reacting halogenated fluoroethylene represented by the formula: CF<SB>2</SB>=CFY (wherein Y is a halogen atom) with an N-halogenated nitrogen-containing compound and a fluorosulfonic acid compound represented by the formula: ZSO<SB>3</SB>H [wherein Z is a perfluoro group represented by the formula: F(CF<SB>2</SB>)<SB>n</SB>-; and n is an integer of 0 to 20] to form a halosulfonic ester represented the formula: XCF<SB>2</SB>CFYOSO<SB>2</SB>Z (wherein X is Cl, Br, or I; and Y and Z are as defined above) and subjecting the halosulfonic ester to ester decomposition. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing difluorohaloacetyl fluoride.
[0002]
[Prior art]
Difluorohaloacetyl fluoride represented by the general formula: XCF ₂ COF (where X is I, Br or Cl) is useful as an intermediate of various fluorine-containing compounds, and is itself unique. It is a compound that is also useful as having high performance.
[0003]
For example, difluorohaloacetyl fluoride is reacted with hexafluoropropene oxide, and then thermally decomposed, whereby ω-haloperfluorovinyl ether useful as a raw material for a thermosetting resin, an electrolytic membrane, a proton conductive fluororesin, etc. Can be converted to Also, difluorohaloacetyl fluoride can be converted to perfluorosuccinyl fluoride by dehalogen coupling, and the resulting compound is reacted with a nucleophile to have excellent heat resistance and chemical stability. A perfluorodicarboxylic acid derivative useful as a raw material for a fluorinated condensed polymer such as polyamide and polyester can be obtained. Further, difluorohaloacetyl fluoride can also be used as a raw material such as perfluoro (3-oxa-4-pentenoyl fluoride) or oxalyl fluoride which is useful as an intermediate of various fluorine-containing compounds.
[0004]
Among the difluorohaloacetyl fluorides represented by the above general formula, as a method for producing difluoroiodoacetyl fluoride, (1) a method of reacting anhydrous lithium iodide with tetrafluoroethylene oxide in acetic anhydride (see the following patent) (See Document 1), (2) A method of reacting ICF ₂ CF ₂ I with SO ₃ to synthesize an intermediate ICF ₂ CF ₂ OSO _2- and reacting it with KF (see Patent Document 2 below), (3) ) A method of reacting a reagent obtained by mixing iodine and SO ₃ with tetrafluoroethylene to synthesize an intermediate ICF ₂ CF ₂ OSO _2- and reacting it with KF (see Patent Document 3 below), (4) A method of reacting iodofluorosulfuric acid by reacting chlorofluorosulfuric acid with iodine, reacting it with tetrafluoroethylene to obtain an intermediate ICF ₂ CF ₂ OSO ₂ F, and then reacting this intermediate with CsF (See Non-Patent Document 1 below).
[0005]
However, among these methods, in the method (1), it is necessary to use explosive tetrafluoroethylene oxide, and the yield of the target difluoroiodoacetyl fluoride is less than 40% based on tetraethylene oxide. However, it is not satisfactory as an industrial production method. The method (2) has a problem that SO _{3 as} a raw material has a high melting point of 16.8 ° C., solidifies when water enters, and has a stable structure, so that it is difficult to control SO _3. Although described as 80%, it is difficult to achieve such a yield. (3) The method is to use the SO _3, above (2) and has a similar problem, not satisfactory with about 50% yield. According to the method (4), the temperature for synthesizing the intermediate is as low as -196 ° C., and the raw material ClSO ₃ F is obtained by the reaction between highly reactive ClF and SO ₃ , so that it is difficult to handle and industrial production. Processing is difficult.
[0006]
On the other hand, regarding the method for producing difluorobromoacetyl fluoride, (1) 1,2-dibromochlorotrifluoroethane is heated together with 40% fuming sulfuric acid in the presence of mercury oxide, and the gas generated at that time is reacted with alcohol. (See Non-patent Document 2 below), (2) a method of reacting 1,2-dibromochlorotrifluoroethane with 60% fuming sulfuric acid (see Patent Document 4 below), (3) A method of reacting 1-bromo-2-iodotetrafluoroethane 1,2-dibromotetrafluoroethane, 1,2-dibromochlorotrifluoroethane or the like with an oxidizing acid (see Patent Document 5 below), (4) 1, A method of ozone oxidation of 4-dibromohexafluoro-2-butene, (5) a method of reacting difluoroacetic acid fluoride with bromine under light irradiation (see Patent Document 6 below), and the like are known.
[0007]
However, among the above-mentioned methods for producing difluorobromoacetyl fluoride, the method (1) requires a complicated purification step because difluorobromoacetyl chloride which is difficult to separate occurs during the synthesis of difluorobromoacetyl fluoride. . Further, since highly toxic mercury oxide is used, a complicated process is required, which is not suitable as an industrial production process. In the methods (2) and (3), it is difficult to control fuming sulfuric acid, SO _{3, and the} like, and since Br ₂ , Cl _{2, and the} like are generated as by-products, purification is complicated. In addition, purification is difficult because the by-produced SO ₂ azeotropes with the target substance. In the method (4), it is difficult to obtain a raw material. In the method (5), the synthesis of the starting material, difluoroacetic acid fluoride, requires a lot of man-hours. Furthermore, the photoreaction requires a special device, and the PFA tube becomes cloudy as the reaction is repeated, and the quantum efficiency decreases. There are many problems.
[0008]
[Patent Document 1]
US Patent No. 3351619 [0009]
[Patent Document 2]
JP-A-55-164644 [0010]
[Patent Document 3]
JP 57-40435 A
[Patent Document 4]
Japanese Patent Publication No. 57-40433
[Patent Document 5]
Japanese Patent Application Laid-Open No. 57-40434
[Patent Document 6]
JP-A-8-27058
[Non-patent document 1]
Carl. J. Sack et.al., J. Fluorine. Chem., 283-290 (1982)
[0015]
[Non-patent document 2]
Tetrahedron, 33, 1445 (1977)
[0016]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned prior art, and its main object is to use difluorohaloacetyl fluoride in high yield using easily available raw materials and without using a special reactor. To provide a novel production method capable of obtaining the following.
[0017]
[Means for Solving the Problems]
The present inventor has made intensive studies to achieve the above-mentioned object. As a result, a halogenated fluoroethylene represented by the general formula: CF ₂ = CFY (wherein, Y is a halogen atom) is used as a raw material, and is used as an N-halogenated nitrogen-containing compound and a specific fluorosulfonic acid. By reacting with a compound, a halosulfonic acid ester can be obtained in a high yield, and by subjecting the obtained halosulfonic acid ester to ester decomposition, it has been found that a desired difluorohalofluoride can be obtained in a high yield, Here, the present invention has been completed.
[0018]
That is, the present invention provides the following method for producing difluorohaloacetyl fluoride.
1. A halogenated fluoroethylene represented by the general formula: CF ₂ = CFY (wherein Y is a halogen atom) is converted to an N-halogenated nitrogen-containing compound and a general formula: ZSO ₃ H (where Z is F (CF ₂ ) _n — is a perfluoro group represented by _n −, where n is an integer of 0 to 20), and reacted with a fluorosulfonic acid compound represented by the general formula: XCF ₂ CFYOSO ₂ Z (wherein , X is Cl, Br or I. Y and Z are the same as defined above),
A process for producing difluorohaloacetyl fluoride represented by the general formula: XCF ₂ COF (where X is the same as above), characterized in that the halosulfonic acid ester is esterified.
2. Item 2. The method according to Item 1, wherein the N-halogenated nitrogen-containing compound is a linear or cyclic compound having 1 to 3 nitrogen atoms containing Cl, Br or I as a halogen atom bonded to a nitrogen atom.
3. The N-halogenated nitrogen-containing compound is at least one compound selected from the group consisting of N-bromoacetamide, N- (bromo, chloro or iodo) succinimide, N- (bromo, chloro or iodo) phthalimide and trichloroisocyanuric acid Item 3. The method according to Item 2, wherein
4. Any of the above items 1 to 3, wherein the method of esterifying the halosulfonic acid ester is a method of heating to 150 to 450 ° C in the absence of a catalyst, or a method of reacting at 0 to 200 ° C in the presence of a catalyst. The method described in.
5. A halogenated fluoroethylene represented by the general formula: CF ₂ = CFY (wherein Y is a halogen atom) is converted to an N-halogenated nitrogen-containing compound and a general formula: ZSO ₃ H (where Z is F (CF ₂ ) _n — is a perfluoro group represented by _n −, where n is an integer of 0 to 20), and reacted with a fluorosulfonic acid compound represented by the general formula: XCF ₂ CFYOSO ₂ Z (wherein , X is Cl, Br or I. Y and Z are the same as those described above), and from the resulting reaction mixture, N-halogenated nitrogen-containing compound N 5. The method according to any one of the above items 1 to 4, comprising a step of recovering a hydride, converting the hydride to a nitrogen-containing nitrogen-containing compound, and then reusing it as a raw material.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
In the method of the present invention, first, as a first step, a halogenated fluoroethylene represented by a general formula: CF ₂ = CFY (wherein, Y is a halogen atom) is converted into an N-halogenated nitrogen-containing compound and Reacting with a fluorosulfonic acid compound represented by the general formula: ZSO ₃ H (where Z is a perfluoro group represented by F (CF ₂ ) n, and n is an integer of 0 to 20) A halosulfonic acid ester represented by the general formula: XCF ₂ CFYOSO ₂ Z (where X is Cl, Br or I. Y and Z are the same as above) is produced.
[0020]
According to this step, it is possible to obtain the above-mentioned halofluonyl ester in high yield, and the obtained halofuronyl ester can be easily converted into a target difluorohaloacetyl fluoride by an ester decomposition reaction. it can. This makes it possible to obtain the desired difluorohaloacetyl fluoride in high yield.
[0021]
Examples of the halogenated fluoroethylene represented by the general formula CF ₂ = CFY used as a raw material include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CFBr, CF ₂ = CFI and the like. One type may be used alone, or two or more types may be used in combination. Among these compounds, tetrafluoroethylene, chlorotrifluoroethylene and the like are preferable from the viewpoint of easy availability, and particularly, tetrafluoroethylene having a target structure is preferable from the viewpoint of reaction selectivity.
[0022]
As the N-halogenated nitrogen-containing compound, it is preferable to use a linear or cyclic compound having 1 to 3 nitrogen atoms containing Cl, Br or I as a halogen atom bonded to a nitrogen atom. Specific examples of such a compound include N-bromoacetamide as a linear compound, and N- (bromo, chloro or iodo) succinimide, N- (bromo, chloro or iodo) as a cyclic compound Examples include phthalimide and trichloroisocyanuric acid. These compounds can be used alone or in combination of two or more.
[0023]
In the present invention, particularly, as the N-halogenated nitrogen-containing compound, N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide and the like are preferable in terms of easy availability.
[0024]
In the fluorosulfonic acid compound represented by the general formula: ZSO ₃ H, Z is a perfluoro group represented by F (CF ₂ ) n-, where n is an integer of 0 to 20, and It is an integer of 0-7.
[0025]
The reaction between the halogenated fluoroethylene, the N-halogenated nitrogen-containing compound and the fluorosulfonic acid compound can be carried out without a solvent or in an organic solvent. As the organic solvent, any solvent that does not participate in the reaction can be used without any particular limitation. Specific examples of such a solvent include acetonitrile, glyme-based solvents, chloroform, methylene chloride, perfluorohexane, 1-chloro-6-hydroperfluorohexane, and the like.
[0026]
All the above-mentioned raw material components may be mixed at the same time. However, when a solid compound is used as the N-halogenated nitrogen-containing compound, the N-halogenated nitrogen-containing compound and the fluorosulfonic acid compound are mixed in advance. By using it, the handling of the raw material becomes easy. In this case, a mixture immediately after mixing may be used, or a mixture in which a portion of the N-halogenated nitrogen-containing compound has reacted with the fluorosulfonic acid compound after a lapse of time after the mixing may be used.
[0027]
The amount of the N-halogenated nitrogen-containing compound to be used is preferably about 0.2 to 10 mol, more preferably about 0.5 to 2 mol, per 1 mol of the halogenated fluoroethylene. The amount of the fluorosulfonic acid compound to be used is preferably about 0.5 to 10 mol, more preferably about 1 to 5 mol, per 1 mol of the N-halogenated nitrogen-containing compound.
[0028]
In the above reaction, if the reaction temperature is too low, solidification may occur or the reaction rate may decrease. If the reaction temperature is too high, an undesired side reaction such as a decomposition reaction may proceed. From such a point, the reaction temperature is preferably about -50 ° C to 300 ° C, and more preferably about -20 ° C to 150 ° C. The reaction pressure at this time is not particularly limited. For example, the reaction can be performed under a wide range of pressure from a reduced pressure to a pressurized state of about 5 MPa.
[0029]
The reaction time cannot be specified unconditionally because it varies depending on the reaction conditions. However, the reaction time may usually be in the range of about 2 hours to 5 hours.
[0030]
The halosulfonic acid ester represented by the general formula: XCF ₂ CFYOSO ₂ Z obtained by the above reaction may be recovered from the reactor by distillation or may be extracted and recovered by liquid separation.
[0031]
After the completion of the reaction, the resulting halosulfonic acid ester, the raw material component fluorosulfonic acid compound and the like are separated, and the obtained N-halogenated nitrogen-containing compound N-hydride is, for example, New Experimental Chemistry Lecture 15 Oxidation and Reduction [1-I] N-halogenated nitrogen-containing compounds can be returned according to a known method described in p419 and the like. For example, by reacting an N-hydride with an alkali in an aqueous solution containing an alkali such as an alkali metal hydroxide or an alkaline earth metal hydroxide, the N-alkali metal or N-alkaline earth metal The aqueous solution containing the N-alkali metal or N-alkaline earth metal is cooled in an ice bath, and then halogens such as chlorine, bromine and iodine are introduced to thereby convert the N A halogenated nitrogen-containing compound. The N-halogenated nitrogen-containing compound thus obtained can be effectively reused as a raw material by circulating in the first step.
[0032]
Then, the halosulfonic acid ester obtained in the first step is esterified to give a difluorohaloacetylfluoride represented by the desired general formula: XCF ₂ COF (where X is Cl, Br or I). You can get
[0033]
The ester decomposition reaction can be performed in the presence or absence of a catalyst.
[0034]
When the ester decomposition reaction is performed in the absence of a catalyst, for example, the halosulfonic acid ester may be heated to about 150 to 450 ° C.
[0035]
When the ester decomposition reaction is performed in the presence of a catalyst, the reaction can be performed at a lower temperature. For example, the ester decomposition reaction can proceed at about 0 to 200 ° C., and the yield is improved. Examples of the catalyst include alkali metal halides, ammonium halides, quaternary ammonium halides, silver fluoride, sulfuric acid, fuming sulfuric acid and the like. Of these, alkali metal halides such as potassium fluoride, cesium fluoride, and sodium fluoride are preferred because they have good activity and are easily available.
[0036]
The amount of the catalyst to be used may be about 0.01 to 10 mol per mol of the halosulfonic acid ester, and especially about 0.1 to 2 mol in consideration of cost, reaction efficiency and the like. preferable.
[0037]
When a solid-state catalyst is used as the catalyst, the catalytic activity is improved by performing ester decomposition in an aprotic polar solvent, and accordingly, the yield of difluorohaloacetyl fluoride can be improved. . Examples of such a solvent include monoglyme, diglyme, triglyme, tetraglyme, dioxane, sulfolane, tetrahydrofuran, acetonitrile and the like. The amount of the solvent used may usually be in the range of about 1 to 20 times the weight of the above halosulfonic acid ester.
[0038]
The reaction time may be set according to the conditions actually used until the ester decomposition reaction sufficiently proceeds, and usually the reaction time may be about 2 to 5 hours.
[0039]
In addition, difluorohaloacetyl fluoride, which is the target substance, is easily hydrolyzed to difluorohaloacetic acid (XCF ₂ CO ₂ H) in the presence of moisture, and depending on the conditions, hydrolyzed to oxalic acid (HOOC-COOH). May be done. For this reason, in order to obtain difluorohaloacetyl fluoride in high yield, it is desirable to carry out the reaction under substantially anhydrous conditions. For example, it is preferable to use a dry catalyst or solvent.
[0040]
The obtained crude compound may be purified by a known method such as extraction and distillation.
[0041]
【The invention's effect】
According to the production method of the present invention, difluorohaloacetyl fluoride, which is a compound useful as an intermediate of various fluorine-containing compounds, can be obtained without using a special reaction apparatus or complicated purification steps, And can be obtained in high yield.
[0042]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0043]
Example 1
A 100 ml stainless steel autoclave was charged with 17.8 g (0.1 mmol) of N-bromosuccinimide and 50 g (0.5 mol) of fluorosulfuric acid. After charging, the mixture was cooled in an ice bath and reacted with stirring for 1 hour. After the stirring, the inside of the autoclave was replaced with vacuum nitrogen, and ethylene tetrafluoride was charged at a gauge pressure of 0.57 MPa to 10 g (0.1 mol) at 0.1 g / min. After completion of the charging, the reaction was stirred for about 1 hour, and after confirming that the pressure was reduced, the autoclave was opened to recover the liquid. The recovered liquid was separated into two layers, and it was found by NMR measurement, gas chromatography and GC / MS measurement that the upper layer was fluorosulfuric acid and the lower layer was halosulfonic acid ester BrCF ₂ CF ₂ OSO ₂ F. BrCF ₂ CF ₂ OSO ₂ F was obtained with a purity of 99.3% and a yield of 85.6%.
[0044]
Next, a thermometer and a dry ice / acetone condenser were attached to a 50 ml four-necked glass flask, and tetraglyme: 10 ml and KF: 1.1 g (18.4 mmol) were charged therein. 3.6 g (12.8 mmol) of the halosulfonic acid ester obtained in the above reaction was charged into a dropping funnel, and the reaction was carried out by dropping into a reactor at room temperature. Bubbling started at the same time as the dropwise addition, and the gas layer was analyzed by gas chromatography and GC / MS. As a result, formation of SO ₂ F ₂ and BrCF ₂ COF was confirmed. After dropping and foaming were completed, the mixture was stirred for one hour to react.
[0045]
After completion of the reaction, methanol was added to confirm the yield of BrCF ₂ COF to convert to methyl ester and analyzed by NMR.As a result, BrCF ₂ CO ₂ Me was obtained with a selectivity of> 99% and a yield of 68.6%. Had been.
Example 2
A 100 ml SUS autoclave was charged with 10.8 g (48 mmol) of N-iodosuccinimide and 16.6 g (110.7 mmol) of trifluoromethanesulfonic acid. After purging with vacuum nitrogen, chlorotrifluoroethylene (CTFE) was charged to 5.8 g (50 mmol) at a slight pressure under ice temperature. After charging a predetermined amount, the mixture was stirred and reacted for 1 hour. After the completion of the reaction, the internal solution was poured into an ice bath and washed with Na ₂ SO ₃ . Separation was performed with a separating funnel, and the lower organic layer was recovered. The aqueous layer was extracted with CH ₂ Cl _2, it was mixed with the organic layer of the initial recovery. Thereafter, evaporation, drying with MgSO ₃ and filtration were performed to obtain a mixture composed of 14.3 mmol of ICF ₂ CFClOSO ₂ CF _{3 and} 16.9 mmol of ICFCClCF ₂ OSO ₂ CF ₃ . The selectivities were 45.7% and 54.3%, respectively. The total yield of both substances was 31.2 mmol, yield: 65% based on N-iodosuccinimide.
[0046]
A 50 ml glass flask was charged with 5 ml of diglyme and 0.4 g (7.6 mmol) of KF. The flask was cooled in an ice bath, and a mixture of ICF ₂ CFClOSO ₂ CF ₃ (45.7%) / ICFCClCF ₂ OSO ₂ CF ₃ (54.3%) was dropped and reacted with a dropping funnel. Bubbling started at the same time as the dropping, generating heat. When the foaming was completed and the temperature returned to room temperature, methanol quenching and water washing were performed. As a result, the liquid was separated into two layers, and the organic layer (lower layer) was analyzed by gas chromatography. The products were ICF ₂ CO ₂ Me and ICFCClCO ₂ Me, and the raw material conversion was 100%. The selectivities of ICF ₂ CO ₂ Me and ICFCClCO ₂ Me were 41.4% and 58.6%, respectively, which was the same as the ratio of the charged raw materials.
[0047]
Reference Example 1
3.1 g of a solid obtained by evaporating all the compounds obtained in Example 1 was dissolved in 15 ml of a 10 mass% NaOH aqueous solution, and when the solution became homogeneous, Br ₂ : 2 ml was charged and reacted. As the reaction proceeded, a solid was deposited. The solid was separated by filtration and washed with water until bromine disappeared. Drying this solid gave a single yellow solid having a melting point: 173.5 ° C. By NMR measurement, N-bromosuccinimide was obtained in 4.4 g (78% yield).

Claims (5)

A halogenated fluoroethylene represented by the general formula: CF ₂ = CFY (wherein Y is a halogen atom) is converted to an N-halogenated nitrogen-containing compound and a general formula: ZSO ₃ H (where Z is F (CF ₂ ) _n — is a perfluoro group represented by _n −, where n is an integer of 0 to 20), and reacted with a fluorosulfonic acid compound represented by the general formula: XCF ₂ CFYOSO ₂ Z (wherein , X is Cl, Br or I. Y and Z are the same as defined above).
A process for producing difluorohaloacetyl fluoride represented by the general formula: XCF ₂ COF (where X is the same as above), characterized in that the halosulfonic acid ester is esterified. The method according to claim 1, wherein the N-halogenated nitrogen-containing compound is a linear or cyclic compound having 1 to 3 nitrogen atoms containing Cl, Br or I as a halogen atom bonded to a nitrogen atom. The N-halogenated nitrogen-containing compound is at least one compound selected from the group consisting of N-bromoacetamide, N- (bromo, chloro or iodo) succinimide, N- (bromo, chloro or iodo) phthalimide and trichloroisocyanuric acid 3. The method according to claim 2, wherein The method for esterifying the halosulfonic acid ester is a method of heating to 150 to 450 ° C in the absence of a catalyst, or a method of reacting at 0 to 200 ° C in the presence of a catalyst. Crab method. A halogenated fluoroethylene represented by the general formula: CF ₂ = CFY (wherein Y is a halogen atom) is converted to an N-halogenated nitrogen-containing compound and a general formula: ZSO ₃ H (where Z is F (CF ₂ ) _n — is a perfluoro group represented by _n −, where n is an integer of 0 to 20), and reacted with a fluorosulfonic acid compound represented by the general formula: XCF ₂ CFYOSO ₂ Z (wherein , X is Cl, Br or I. Y and Z are the same as those described above), and from the resulting reaction mixture, N-halogenated nitrogen-containing compound N The method according to any one of claims 1 to 4, further comprising a step of collecting the hydride, converting the hydride to an N-halogenated nitrogen-containing compound, and then reusing the hydride as a raw material.