TW584628B - Process for preparation of fluorine-containing carbonyl compounds - Google Patents

Abstract

A process by which fluorine-containing carbonyl compounds having various structures and derivatives thereof can be prepared from alcohols, particularly low-molecular alcohols. The process comprises esterifying R1CHR2OH (1) with Qf(COF)n (2) to thereby obtain an esterification product containing at least one compound represented by the general formula: Qf(COOCHR1R2)m(COF)n-m (3), perfluorinating the esterification product to thereby obtain a fluorination product containing at least one compound represented by the general formula: Qf(COOCFR1fR2f)m(COF)n-m, subjecting the fluorination product to ester linkage cleavage, and then recovering compound (2) and fluorine-containing carbonyl compounds such as R1fCOR2 (5) from the resulting reaction mixture, R1 being hydrogen or the like; R2 being alkyl or the like; R1f being fluoro or the like; R2f being perfluoroalkyl or the like; Qf being perfluorinated alkylene or the like; n being an integer of 2 or above; and m being an integer of 2 or above but not larger than n.

Description

584628 A7 ___B7_ V. Description of the Invention (1) Technical Field of the Invention (Please read the notes on the back before filling out this page) The present invention relates to a method for efficiently producing fluorine-containing carbonyl compounds with various structures. Technical background of the invention It is known that after reacting polyethylene glycol having a molecular weight of 1,000 or more with trifluoroacetic acid, the reaction of fluorination in the liquid phase to obtain a polyethylene glycol having a trifluoromethyl terminal at the end (see Table No. 4-500520) ). In addition, a polyethylene glycol having a trifluoromethyl group manufactured by the method of Table 4-500520 is fluorinated in a liquid phase to decompose the two ester bonds of the perfluorinated polyethylene glycol dimethyl ester. A method for obtaining a perfluorinated difluorenyl fluoride is known (US 5466877). In addition, the present inventors have proposed that, as a method for obtaining a fluorinated carbonyl compound from a non-fluorinated alcohol, a partially fluorinated ester obtained by reacting a fluorine-containing monofluorenyl fluoride in a non-fluorinated alcohol and reacted with fluorine After the perfluorinated ester is obtained, a method for decomposing the ester (WOOO / 56694) is applied. In the decomposition reaction of the ester bond described in US5466877 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, although CFsCOF is formed, it is difficult to recover CF3COF because of its low boiling point (-59 ° C) without actual recycling Of the record. In this method, a fluorinated carbonyl acid (for example, trifluoroacetic acid) corresponding to a fluorinated fluorinated fluoride-containing compound must be prepared, but in general, the fluorinated carbonyl compound is a high-priced product, and the structure that can be purchased is limited. The method of WOOO / 56694 is a method in which a non-fluorine alcohol is reacted with 1 times mole of a fluorine-containing monofluorenyl fluoride. However, the fluorine-containing monofluorinated fluoride is generally a high-value compound, so it has a high cost. problem. The more economical method is a method using a low molecular weight fluorine-containing monofluorinated fluoride, but the paper size of the low molecular weight is applicable. National National Standard (CNS) A4 specification (210X297 male thin) 584628 A7 ___B7_ 5. Description of the invention (2) Because of its low boiling point, the fluorine-containing monofluorenyl fluoride is difficult to recover after the ester decomposition reaction, and it has the problem of no economic value due to recovery and reuse. (Please read the precautions on the back before filling in this page.) Moreover, when using low molecular weight fluorine-containing monofluorenyl fluoride, the vapor pressure of some fluorinated esters will increase. Instead, a gas phase reaction is caused. The reaction in the gas phase has the problems that the reaction is difficult to control and the recovery rate is low. On the other hand, in order to reduce the vapor pressure of partially fluorinated esters, the method of partially fluorinated esters of high molecular weight used has problems such as relatively few types of partially fluorinated esters, high price, and low economic value. Disclosure of the Invention The present invention provides the following manufacturing method that solves the above-mentioned problems. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. A method for producing a fluorocarbonyl compound, characterized in that the compound represented by Formula 1 and the compound represented by Formula 2 are esterified to obtain one or more compounds such as Formula 3 An esterification reaction product of the indicated compound. After the esterification reaction product is converted to perfluorination by a fluorination reaction, one or more fluorination reaction products represented by Formula 4 are obtained, and the fluorination reaction is performed. Decomposition reaction of the ester bond of the product to obtain a decomposition reaction product containing the compound represented by Formula 5 and the compound represented by Formula 2, and from the decomposition reaction product to obtain a fluorine-containing carbonyl compound represented by Formula 5, R ^ HR'OH ... Formula 1 Qf (COF) n ... Formula 2 Qf (COOCHR1R2) m (COF) nm ... Formula 3 Qf (COOCFRlfR2f) m (COF) nm ... Formula 4 RlfC〇R2f ... .. Formula 5 However, the symbols in the formula are as shown below. This paper size is applicable. National Standard (CNS) A4 (210X297 mm) 77 ^ '584628 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of the invention (3) R1, R2: R1 represents hydrogen Or fluorinated monovalent organic group, R2 represents a fluorinated monovalent organic group, R1 and R2 can be fluorinated to form a divalent organic group at the same time, RH'R ^ R1 represents a hydrogen atom when Rlf is fluorine Atom, R1 represents a monovalent organic group. "R1 is a monovalent organic group with R1 perfluorinated, and" R "is a monovalent organic group with R2 perfluorinated. However, R1 and R2 are formed by fluorination at the same time. In the case of a divalent organic group, the ^^ and 11〃 simultaneously form a divalent organic group that is perfluorinated, Qf: a perfluorinated η-valent organic group, η: an integer of 2 or more, and m: 2 or more and η or less 2. The manufacturing method according to item 1 of the scope of patent application, wherein the compound represented by formula 2 which reacts with the compound represented by formula 1 is represented by formula 2 obtained from the decomposition reaction product of an ester bond. 3. The manufacturing method according to item 1 or 2 of the scope of patent application, wherein the molecular weight of the compound represented by Formula 1 is 32 to 200, and the average fluorine content of the esterification reaction product is 20 to 60% by mass. And the molecular weight of the esterification reaction product is 200 ~ 1100. 4. If the manufacturing method of the scope of patent application No. 1, 2 or 3, The intermediate fluorination reaction is a liquid phase fluorination reaction. 5. The manufacturing method according to any one of claims 1 to 4 in the scope of application for a patent, wherein the compound represented by formula 2 is represented by formula (2-1) The compound and the esterification reaction product must have a compound represented by the formula (3-1). The fluorination reaction product is based on the compound represented by the formula (4-1). The decomposition reaction product is based on the formula (5). -1) The compound represented by the formula and formula (2-1) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Tfil '~ (Please read the precautions on the back before filling this page) · Order. Add 584628 A7 ____B7 V. Description of the invention (4) The compound that is not necessary is a fluorinated carbonyl compound is the compound represented by formula (5 -1), (Please read the precautions on the back before filling this page) FC〇Qf2C〇F ..... Formula (2-1) R ^ HR'OCOQ ^ COOCHR ^ 2 ..... Formula (3-1) RlfCFR2f〇C〇Qf2C〇CFRlfR2f ... . · Formula (4-1)

RlfCOR2f ... Formula (5-1) However, the symbols in the formula are as follows, R1, R2, Rlf, R2f: the same meaning as above,

Qf2: Divalent organic group perfluorinated. 6. The manufacturing method according to item 5 of the scope of patent application, wherein the esterification reaction product is a compound represented by formula (3-1H) and a compound represented by formula (3-1H), and a fluorination reaction product To contain the compound represented by formula (4-1H) together with the compound represented by formula (4-1),

RlCHR2OCOQf2COF .. ^ (3-1H)

RlfCFR2fOCOQf2COF .. ^ i (4-1H) However, in the formula, R1, R2, Rlf, R2f, and Qf2 represent the same meanings as above. Ο Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The production method according to item 6, wherein the esterification reaction product contains a compound represented by the following formula (3-2Η) and a fluorination reaction is performed, R ^ HR ^ COQ ^ COOCHR ^ 2 ... ^ (3- 2H), except that R1 and R2 have the same meaning as above, QH2: must have a divalent organic group of hydrogen atom, and be formed into Qf2 by perfluorination. The paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Centi) -7-584628 Α7 Β7 5. The base of invention description (5). (Please read the precautions on the back before filling out this page) 8. The manufacturing method as described in item 7 of the scope of patent application, wherein the compound represented by formula (3-1) is more than 0 mass% and less than mass%. (3-2H) A fluorination reaction is performed in the presence of the compound represented by (3-2H). 9. If the manufacturing method of the 7th or 8th in the scope of patent application, where R1 and R2 are -CH3, Rlf and R2f are <? 3, Qf2 is-(CF2) k_ (However, k represents 2 ~ 8 Integer), and QH2 is-(CH2), or R1 is -Η, R2 is -CH (CH〇2, ruler "is punch, (CF〇2, and QH2 is-(CH2) k-0 10. The manufacturing method according to any one of claims 5 to 9, wherein the liquid phase in the liquid phase fluorination is the compound represented by the formula (4-1) and / or the compound represented by the formula (5-1) The compound represented is necessary. 11. The manufacturing method according to any one of claims 1 to 10 in the scope of the patent application, wherein the compound represented by formula 1 and the compound represented by formula 2 are subjected to an esterification reaction, (1) The amount of the compound represented is 0.5 to 1 mole of the compound represented by Formula 2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12. If any of the items 1 to 11 of the scope of patent application In a manufacturing method, in the fluorination reaction of the compound represented by Formula 3, in the presence of a compound having the same carbon skeleton as the corresponding compound (3) and containing less fluorine than the compound (3), A fluorination reactor. 13. A compound, which is any compound represented by the following formula: (CH3) 2CH0CO (CF04CO0CH (CH3) 2, (CF3) 2CF0CO (CF2) ) 4C〇〇CF (CF3) 2, (CH3) 2CHCH2〇C〇 (CF〇2C〇CH2CH (CH3) 2, this paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm):> 7 '' 584628 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (6) (CF3) 2CFCF2〇C〇 (CF2) 2C〇〇CF2CF (CF3) 2, (CH3) 2CHCH2〇C〇 (CF2 ) 3C0CH2CH (CH3) 2, (CF3) 2CFCF2OC0 (CF03C0CF2CF (CF3) 2. Best Mode for Carrying Out the Invention) The organic group in the present invention is a group which must have a carbon atom. Examples of the fluorinated organic group include an organic group having a CH portion or an organic group having a carbon-carbon unsaturated bond. An organic group having a CH portion is preferred, and particularly, carbon and carbon in the group The bond is preferably only a saturated organic group formed by a single bond. As the organic group having a CH moiety, a saturated hydrocarbon group, a saturated hydrocarbon group containing an etheric oxygen atom, a partially halogenated saturated hydrocarbon group, or a partially A halogenated (saturated hydrocarbon group containing etheric oxygen atom) group is preferred. The partial halogenation means halogenation at the remaining ratio of hydrogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Preferably, a fluorine atom or a chlorine atom is used. Particularly, a halogen atom as a partially halogenated group is preferably a chlorine atom. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, and a monovalent saturated hydrocarbon group having a ring portion (for example, a cycloalkyl group, a cycloalkylalkyl group, or a group having these groups as a partial structure). Base is better. Examples of the divalent hydrocarbon group include a divalent alkyl group, a cycloalkylene group, or a divalent saturated hydrocarbon group having a cyclic portion (for example, a cycloalkyl group, a bicycloalkyl group, or a divalent saturated aliphatic group having a cycloalkyl group as a partial structure). Hydrocarbyl.), Etc., preferably Shenyuanji. As a monovalent group in a saturated hydrocarbon group containing etheric oxygen atoms, the Chinese paper standard (CNS) A4 (210X297 mm) can be applied to this paper size -9-I -------- | ^ batch Clothing ---- „-1T ------ 0 (Please read the precautions on the back before filling this page) 584628 A7 B7 V. Invention Description (7) (Please read the precautions on the back before filling (In this page) an alkyl group having an etheric oxygen atom inserted between carbon-carbon bonds, or a cycloalkyl group having an etheric oxygen atom inserted between carbon-carbon bonds. Also, as a saturated hydrocarbon group containing etheric oxygen atoms, Examples of the divalent group include an alkylene group having an etheric oxygen atom inserted between carbon-carbon bonds or at the terminal end of the group, or a cycloalkylene group having an ethereal oxygen atom inserted between carbon-carbon bonds. Particularly, an oxyalkylene group or a group having a polyoxyalkylene portion is preferred. Among the groups containing etheric oxygen atoms, the number of etheric oxygen atoms may be one or two or more. The so-called perfluorination is a The portion to be fluorinated in the group to be fluorinated is actually all fluorinated. For example, when the organic group having a CH portion is perfluorinated, the CH portion actually becomes C -F, organic radicals with carbon-carbon unsaturated bonds are perfluorinated groups, which means that virtually all unsaturated bonds have fluorine atoms attached to them. It is printed as: Examples of the perfluorinated monovalent organic group include a perfluorinated alkyl group, and specifically, -CF2CF3, -CF2CF2CF3, -CFaCFaCFiCF ;, -CF2CC1F2-, CF2CBrF2, or -CF2 CFC1 CF2C, -CF ( CF3) 2, -CF2CF (CF3) 2, -CF (CF3) CF2 CF3, -C (CFO 3, etc.) Examples of the perfluorinated divalent organic group include perfluorinated alkylene groups. Specifically, Examples include -CF2CF2CF2CF2-, -CF (CF3) CF2CF2CF2-, -CFaCF (CF3) CF2CF2-, etc. Examples of the perfluorinated ether-containing oxygen-containing group include carbon-carbon atoms of these groups An etheric oxygen atom is inserted between the groups. The idea of the manufacturing method of the present invention is shown in the following formula. The paper size is applicable. National Standard (CNS) A4 (21 × 297 mm) 584628 A7 B7 V. Invention Instructions (8)

(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The manufacturing method of the present invention is to perform esterification reaction, fluorination reaction, and decomposition reaction of ester bonds. For the starting compound (1), the method of the present invention is a method which is advantageous when the molecular weight of the compound (1) is small. Therefore, the carbon number of the RtHR2- part is preferably 3 to 10, particularly preferably 3 to 5. . The molecular weight of the compound (1) is preferably 32 to 200, particularly preferably 60 to 150, and most preferably 60 to 120. In the compound (1), when R1 and R2 are fluorinated monovalent organic groups, an alkyl group, an epoxy group, and an alkoxy group are preferred. When R1 and R2 are simultaneously fluorinated to form a divalent organic group, as the divalent organic group, a group having one or more ethereal oxygen atoms interposed between the alkylene group or the carbon-carbon bond of the alkylene group. Better. In addition, as the compound (1), alcohol compounds having various structures can be purchased at low cost, so those having no winning atoms (that is, compounds having a fluorine content of 0% by mass) are preferred. As the compound (1), a compound having a structure corresponding to the intended fluorine-containing ore-based compound (5) is selected and used. Compound R1 in compound (1) or this paper is applicable in g | National Standard (CNS) A4 specification (2 丨 〇 > < 297 mm) -11-584628 A7 _____B7_ V. Description of the invention (9) (please first Read the notes on the back and fill in this page again.) The arrangement of the R2 carbon skeleton is maintained by the Rlf & rule of the fluorine-containing carbonyl compound (5). When the fluorine-containing carbonyl compound (5) is used as the raw material of the fluorine-containing primary alcohol The compound (1) using R2 as a hydrogen atom is preferred. When the fluorine-containing carbonyl compound (5) is used as a raw material of the fluorine-containing secondary alcohol, the compound (1) using R2 as a fluorinated monovalent organic group is In the present invention, the compound (1) is subjected to an esterification reaction with the compound (2). The compound (2) means that at the bond point of the perfluorinated η-valent organic group (Qf), η- A compound of a group represented by COF. Η represents an integer of 2 or more. Qf represents a perfluorinated η-valent saturated hydrocarbon group or a perfluorinated group (an η-valent saturated hydrocarbon group containing an etheric oxygen atom) is preferred. This group (Qf When) is a divalent group (Qf2), a perfluoroalkylene group or a perfluoro (alkylene group containing an etheric oxygen atom) group is particularly preferred. As the compound (2), it is better because FC0 (CF2) kC〇F (k represents an integer of 2 to 8) is easier to obtain, and the reaction yield is high. The present invention is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs For the production method, the compound (2) can be subjected to a stoichiometric method to obtain n-fold mole fluorocarbonyl compound (5). The compound (2) can be recovered, and the recovered compound (2) can be recovered. Can be used multiple times. The method used to recover compound (2) is described later. Specific examples of compound (2) include compound (2-1) when η is 2 described later. Compound (1) and compound (2) The reaction of) can be carried out under well-known esterification reaction conditions. The esterification reaction can be carried out in the presence of an esterification reaction solvent, but it is better from the viewpoint of volumetric efficiency when carried out in the absence of an esterification reaction solvent. When using an esterification reaction solvent, dichloromethane, chloroform, triethylamine, and this paper are applicable. National National Standard (CNS) A4 Specification (210X297 mm) -12-584628 A7 _ B7_ V. Description of the Invention ( 10) (Please read the notes on the back first (Write this page) or a mixed solvent of triethylamine and tetrahydrofuran. The amount of the esterification reaction solvent is preferably 50 to 5000% by mass based on the total amount of the compound (1) and the compound (2). In the reaction between the compound (1) and the compound (2), fluoric acid (HF) is generated, and alkali metal fluorides (preferably NaF and KF) or trialkylamines can exist in the reaction system as HF trapping agents. HF scavenger is preferably used when the reaction-related compound is an acid-labile compound. When HF scavenger is not used, the reaction is carried out at a reaction temperature at which gaseable HF can be generated, and HF and nitrogen are simultaneously discharged from the reaction system. Outside is better. The amount of the HF trapping agent is preferably about 1 to 10 times the molar amount for the theoretical generation of HF. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This esterification reaction is an esterification reaction of a bifunctional acid fluoride or more and a monofunctional alcohol. In this esterification reaction, when the reaction between a highly polar difunctional alcohol or more and a monofunctional acid fluoride is compared, the reaction speed and the reaction result are also high. Further, the alcohol remaining in the product after the esterification reaction is not preferable as described below. From the above, it is understood that the amount of the compound (1) used in the esterification reaction is preferably equal to or less than η Mor (η is the number of bases (η) represented by -COF in the corresponding compound (2)) for the compound (2). It is not economical to use the compound (1) exceeding η, and unreacted compound (1) remains in the reaction product of the esterification reaction. When the unreacted compound (1) remains in the esterification reaction product, a reaction that is not good for the fluorination reaction is caused. Therefore, the amount of the compound (1) used in the esterification reaction is preferably an amount that does not remain in the esterification reaction product, and purification of the esterification reaction product may be omitted. In particular, the amount of the compound (1) is particularly preferably from 0.5η times to η times mole, and most preferably 0.9η times to η times mole. This paper size is applicable. National National Standard (CNS) A4 specification (210 × 297 mm) 771 ~ 584628 A7 B7 V. Description of the invention (11) The advantages of the invention using compound (2), especially the compound (1) Play when molecular weight is relatively low. Since the compound (2) has a fluorenyl fluoride group on the structure (please read the notes on the back before filling this page), more than two compounds (1) in the compound (2) will react. As a result, compared with the case where the compound (1) is reacted in a compound having one fluorenyl fluoride group, since the molecular weight of the compound (3) is larger and the vapor pressure is smaller, it is easier to control the liquid phase fluorination. The reaction proceeds in a reaction with a high yield and is also advantageous for volume efficiency. The lower limit of the reaction temperature of the esterification reaction is generally -50 ° C, the upper limit is + 100 ° C, and the boiling point of the esterification solvent is preferably lower. In addition, the reaction reaction time is appropriately changed in accordance with the feed rate of the raw materials and the amount of the compound actually reacted. The reaction pressure is preferably normal pressure to 2 MPa (gauge pressure, and the following pressure indicates the gauge pressure). The product of the esterification reaction printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs must contain more than one compound (3). R ^ RlQf and η in the compound (3) have the same meanings as described above. m represents the number of radicals (-COOCHW) formed by the esterification reaction, and is an integer of 2 or more and η or less. (N-m) represents the number of -COF groups left without being esterified. When (n-m) is 0, it means that the -COF group of the compound (2) does not exist. Examples of the compound (3) include compounds in which (nm) is 0, compounds in which n > m (that is, compounds in which at least two -COF groups of compound (2) are esterified, but not all esterified compounds ), These ratios are not particularly limited. The esterification reaction product of the present invention, that is, all products produced by the esterification reaction, also contains compounds other than the compound (3). For example, the esterification reaction product also includes the compound (2). Of the two or more -COF groups, only one of the following compounds (3-10) is esterified. The size of the composite paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 14. 584628 Printed by A7 ____B7 _ in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (12) in the product (3-1〇) R1, R2, Qf & n are synonymous with the above. Qf (-COF) ^ (-COOCHRiR2) ···· Formula (3-10) The increase in the amount of production of this compound (3-10) indicates this inefficient production method, so it is a compound for the entire amount of the esterification reaction product (3) An amount exceeding 50 mol% is preferred, and an amount exceeding 60 mol% is particularly preferred. The product of the esterification reaction may be purified depending on its purpose, or the following reactions may be used. From the viewpoint of smoothing the fluorination reaction in the next step, it is preferable to purify the product. In particular, when the esterification reaction product contains the compound (1), the compound (1) is preferably removed by purification. Examples of the purification method include a method in which the product is treated with water and then fractionated, a method in which extraction is performed with an appropriate organic solvent and then distilled, and silica gel column chromatography. In the present invention, the esterification reaction product is esterified. The fluorination reaction is preferably carried out as a liquid phase fluorination reaction as described later. For a smooth liquid phase fluorination reaction, the average fluorine content of the esterification reaction product (especially the compound (3)) is preferably 20 to 60% by mass, particularly 25 to 55% by mass, and 30 to 55% by mass. % Is best. For the esterification reaction product, it is preferable to adjust the Qf structure and carbon number of the compound (2) so that the average fluorine content is within this range. The molecular weight of the esterification reaction product is preferably in the range of 200 to 1100, and particularly preferably in the range of 300 to 800. The average fluorine content for the esterification reaction products in a specific range will greatly improve the solubility in the liquid phase during the fluorination reaction, and has the advantages of improving the operability and reaction yield of the liquid phase fluorination reaction. If the content is in a specific range, it also has the advantage of better economy. If the molecular weight of the esterification reaction product is above a certain molecular weight, there is a circumvention of the Chinese national standard (CNS) A4 specification (210 X297 mm) for this paper size. _ _ (Please read the precautions on the back before filling this page) 584628 A7 _B7_ V. Description of the invention (13) The gas phase fluorination reaction has the advantage of decomposition reaction. When the molecular weight is below a certain amount, it has the advantage that the compound is easier to handle or the product is easier to purify. The fluorination reaction can be carried out using a fluorination method of cobalt fluoride, an electrochemical fluorination method, or a method of reacting with elemental fluorine. Among them, the liquid phase fluorination method which reacts with fluorine in the liquid phase is preferable because the reaction can be carried out efficiently regardless of the structure of the substrate, and the yield of the fluorination reaction is particularly high. An example of a liquid phase fluorination method is given below to illustrate the fluorination reaction. The liquid phase of the liquid phase fluorination method may be a reaction substrate itself, but a fluorination reaction solvent that is not related to a product or a reaction is generally preferred. Fluorine can be used directly, or fluorine gas diluted with an inert gas is preferred. As the inert gas, nitrogen and ammonia are preferable, and for economic reasons, nitrogen is particularly preferable. The amount of fluorine in the nitrogen gas is not particularly limited, and it is preferably at 10 vol% or more because of its high efficiency, and particularly preferably at 20 vol% or more. As the fluorination reaction solvent, an inert solvent is preferred in the fluorination reaction, and a solvent having a higher solubility using an esterification reaction product is particularly preferred. Particularly, it is a solvent capable of dissolving 1% by mass or more of the esterification reaction product, and particularly preferably a solvent capable of dissolving 5% by mass or more of the solvent. Examples of the fluorination reaction solvent include compound (2), compound (4) described later, fluorine-containing carbonyl compound (5), perfluoroalkanes (trade name: FC-72, etc.), and perfluoroethers (trade name: FC-7 5, FC-77, etc.), perfluoropolyesters (brand names: clitox, fanbulin, galden, demnam, etc.), chlorofluorocarbons (brand name: fronrub), chlorofluoropolyethers, perfluoroalkanes Amines (for example, perfluorotrialkylamines, etc.), inert fluids (trade name: flornate), and the like. Among them, compound (2) or fluorine-containing carbonyl compound (5) is fluorinated. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) _ 16 _ (Please read the precautions on the back before filling this page)- Pack-order

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs W 584628 A7 B7 V. Description of the invention (14) (Please read the precautions on the back before filling this page) When using the reaction solvent, it is better because it has the advantage of easier post-processing. The amount of the fluorination reaction solvent is preferably 5 times the mass or more, and more preferably 10 to IX 105 times the mass of the total mass of the esterification reaction product. The reaction form of the fluorination reaction may be a batch method or a continuous method. For example, a method in which a fluorination reaction solvent and an esterification reaction product are charged into a reactor, and a fluorine gas is continuously supplied to the fluorination reaction solvent to perform reaction while stirring. Another example is a method in which a fluorination reaction solvent is charged into the reactor and stirred, and then a fluorine gas and an esterification reaction product are continuously supplied to the fluorination reaction solvent at a predetermined molar ratio. Among them, the fluorination reaction is preferably carried out from the viewpoint of reaction yield and selectivity. In this method, the fluorine gas is preferably used after being diluted with an inert gas such as nitrogen. For the fluorine used in the fluorination reaction, the amount of fluorine contained in the hydrogenation product in the esterification reaction product is preferably maintained in an excess equivalent state from the beginning to the end of the reaction. In particular, the amount of fluorine to the hydrogen atom is 1.05 times the equivalent or more ( And 1.05 mol or more) from the viewpoint of selectivity. In addition, if the amount of fluorine is to be in an excess state from the start of the reaction, it is preferable to dissolve a sufficient amount of fluorine in advance in the fluorination reaction solvent used at the beginning of the reaction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, because the fluorination reaction must be carried out under the ester bond in the compound (3) that is not cut off, so the lower limit of the reaction temperature is preferably the lowest temperature of the boiling point of the esterification reaction product. . In general, from the viewpoint of reaction yield, selectivity, and industrial ease of implementation, the reaction temperature is particularly preferably -50 ° C to + 100 ° C, and -20 ° C to + 50 ° C is optimal. Although the reaction pressure of the fluorination reaction is not particularly limited, it is particularly preferable from the standpoint of reaction yield, selectivity, and industrial ease of implementation at normal pressure to 2 MPa. -17- Qiao 3 paper sizes are applicable. National standard (€ milk) 8 4 specifications (210 father 297 mm) 584628 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page In order to efficiently perform the fluorination reaction, it is preferable to add a CH-containing compound to the reaction system, and leave the esterification reaction product in the reaction system for a long time, or perform operations such as ultraviolet light irradiation. These operations are preferably performed at a later stage of the fluorination reaction. When R2 of the compound (3) represents a group other than a hydrogen atom, the hydrogen atom bonded to the carbon atom bonded to R2 and R1 can be easily fluorinated, so this operation is preferably performed. These operations can efficiently fluorinate the esterification reaction product existing in the reaction system, and the reaction rate can be greatly improved. The compound containing a C-H bond is preferably an aromatic hydrocarbon, that is, benzene, toluene, or the like. The addition amount of the C-H bond-containing compound is preferably 0.1 to 10 mole%, and particularly preferably 0.1 to 5 mole%, based on the total amount of hydrogen atoms in the esterification reaction product. The compound containing a C-H bond is preferably added to a reaction system in which fluorine is present. When a compound containing a C-H bond is added, a pressurized reaction system is preferred. When pressurizing, it is preferably from 0.00 to 5 MPa. In addition, it is preferable to irradiate ultraviolet rays for 0.1 to 3 hours. In the fluorination reaction, the esterification reaction product is perfluorinated to produce a fluorination reaction product containing one or more compounds (4). Compound (4) is a compound of compound (3) which has been perfluorinated. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The fluorination reaction product of the present invention contains all products fluorinated from the esterification reaction product, but must have a compound (4). The composition of the fluorination reaction product varies depending on the composition of the esterification reaction product. When two or more compounds of the esterification reaction product are contained, the number of the fluorination reaction products is two or more. In compound (4), Qf, η, and m are corresponding compounds (3). When Rlf of compound (4) is a monovalent organic group after perfluorination, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied to the perfluoroalkyl sheet standard. 584628 A7 B7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumption cooperatives printed 5. Invention Description (16), perfluorinated bases, all-win fluorenyl radicals, etc., of which perfluorinated bases are the best. When it is a monovalent organic group after perfluorination, a perfluoroalkyl group is the best. Also, as the perfluorinated group when Y2 and R2f together form the divalent perfluorinated group, a perfluorinated divalent saturated hydrocarbon group or a perfluoro (divalent saturated hydrocarbon containing etheric oxygen atom) group Preferably, a perfluoroalkylene group, or a carbon-carbon bond of an alkylene group, in which a group having an etheric oxygen atom of 1 or more inserted through a perfluorinated group is particularly preferred. When the esterification reaction product contains the compound (3-10), the compound is also contained in the following compound (4-10) or the fluorination reaction product after perfluorination. Η, Qf, R2f, and Rlf of compound (4-10) are corresponding compounds (3-10) ° QfGCOFh-K-COOCFRURH) .. Formula (4-10) In addition, the esterification reaction in the fluorination reaction product produces The compound contains one or more partially fluorinated compounds (hereinafter these partially fluorinated compounds are also referred to as hydrogen residual compounds). Fluorine in the liquid phase will by-produce HF with hydrogen atoms replaced by fluorine atoms. To remove HF, it is better to co-exist HF trapping agent in the reaction system, contact the HF trapping agent with the outlet gas at the reactor gas outlet, or cool the outlet gas to agglomerate and recover HF. As the HF trapping agent, the same ones as described above can be used, and NaF is preferred. In addition, the sentimental gas such as nitrogen is taken out of the reaction system with HF at the same time, and alkali treatment is preferred. The amount of the HF scavenger coexisting in the reaction system is preferably 1 to 20 times the mole and particularly preferably 1 to 5 times the mole of the total hydrogen atoms present in the esterification reaction product. When placing HF trapping agent at the reactor outlet, (a) cooler (10 ° C ~ room temperature, especially to maintain about 2 (TC is preferred)) (b) NaF pellet (please read the precautions on the back before filling this page) ) This paper size is applicable. National National Standard (CNS) A4 specification (210X297 mm) -19- 584628 A7 B7 V. Description of invention (17) (Please read the precautions on the back before filling this page) 塡And (C) cooler (-7 8 ° c ~ + lot :, especially to maintain -3 0 ° C ~ 0 ° C) is best set in the order of (a)-(b)-(c) In addition, the liquid to be condensed from the cooler of (c) can be returned to the reactor, and a liquid return route can be set. The fluorination reaction product can be used directly in the next step, and can be purified to become high purity. As a purification method Examples include a method of directly distilling the crude product under normal pressure or reduced pressure. In the present invention, an ester bond decomposition reaction is further performed on the fluorination reaction product. The ester bond decomposition reaction is cleavable. The ester bond present in the compound forms the reaction between compound (2) and fluorine-containing carbonyl compound (5), which is a well-known reaction The ester bond decomposition reaction is preferably performed in the presence of a thermal decomposition reaction or a nucleophile or an electrophile. The thermal decomposition reaction can be carried out by heating the fluorinated reaction product. As a reaction form of the thermal decomposition reaction It is better to choose based on the boiling point of the fluorinated reaction product and its stability. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, for the thermal decomposition reaction of a fluorinated reaction product with a lower boiling point, gas phase heat is used. The decomposition method is preferred. The gas phase thermal decomposition method continuously performs the decomposition reaction in the gas phase, and the generated fluorine-containing carbonyl compound (5) and the compound (2) are condensed by an outlet gas, and the recovery method is performed as follows. The reaction temperature of the gas phase thermal decomposition method is preferably 50 to 350 ° C, 50 to 300 ° C is particularly preferable, and 150 to 250 ° C is the best. Gas phase In the thermal decomposition method, a metal salt catalyst may be used, or an inert gas coexisting in the reaction system that is not directly related to the reaction may be used. Examples of the inert gas include nitrogen gas and carbon dioxide gas. This paper is applicable to this paper. National Standard (CNS ) A4 Regulation (210X: 297 mm): 20-584628 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5. Invention Description (18), etc. The amount of inert gas added is relative to the total amount of fluorinated reaction products It is preferably about 0.01 to 50 vol%. If the amount of the inert gas added is too large, the recovery amount of the product will be reduced. On the other hand, when the boiling point of the fluorination reaction product is high, the liquid in the reactor can be used directly. The liquid-phase thermal decomposition method with a state heating is preferable. The reaction pressure of the liquid-phase thermal decomposition method is not limited. The product of the decomposition reaction may be taken out from the reactor at one time. In addition, compared with the fluorinated reaction product, the decomposition reaction product with an ester bond generally has a lower boiling point. The fluorination reaction is performed using a reaction device with a distillation column, and the product is reacted while being taken out from the distillation. Yes. The reaction temperature of the liquid thermal decomposition method is preferably 50 to 300 ° C. Particularly preferred is 100 to 2501. The liquid-phase thermal decomposition method may be carried out in the absence of a solvent or the decomposition reaction may be carried out in the presence of a solvent, but is preferably carried out in the absence of a solvent. When a decomposition reaction solvent is used, it is preferable to use a solvent that is inert during the reaction and is compatible with the fluorinated reaction product. The decomposition reaction solvent may be one which can be easily separated from the product. As specific examples of the decomposition reaction solvent, an inert solvent such as perfluorinated trialkylamine and perfluorinated naphthalene, and a high-boiling point chlorofluorocarbon chlorotrifluoroethane storage oligomer (for example, trade name: Fulong Lupu) are good. Moreover, the amount of the decomposition reaction solvent is preferably 0.1 to 10 times by mass for the fluorination reaction product. When the ester bond is decomposed by reacting with a nucleophile or an electrophile in the liquid phase, it may be carried out in the absence of a solvent or in the presence of a decomposition reaction solvent, but it is preferably carried out without a solvent. The so-called reaction without solvent, the fluorinated reaction product itself can also function as a solvent, because the reaction product can be omitted. The paper size is applicable. National National Standards (CNS> A4 specifications (210X297 mm) ^ 91. (Please First read the notes on the back before filling in this ear) 584628 A7 ___ B7_ V. The step of separating the solvent in the description of invention (19) is particularly good. The method using nucleophile or electrophile can also be used by the reaction device with distillation tower It is better to perform the distillation below. (Please read the precautions on the back before filling out this page.) F · is preferred as the nucleophile, especially F · from the fluoride of alkali metals. It is the fluoride of alkali metals. NaF, NaHF2, KF, CsF is preferred, NaF is particularly preferred from an economic standpoint, and KF is particularly preferred from a reactive standpoint. In addition, the initial nucleophilic dose of the reaction may be the amount of catalyst, or It may be an excess amount. The amount of nucleophile such as F · is preferably 1 to 500 mole%, particularly preferably 1 to 100 mole%, and 5 to 50% is most preferable for the fluorination reaction product. The lower limit of the reaction temperature is preferably -30 ° C, and the upper limit is -20 ° C ~ 250 ° C. The product of the decomposition reaction of the present invention contains all the products produced by the ester bond decomposition reaction, and must contain the compound (2) and the fluorine-containing carbonyl compound (5). Because of the ester bond decomposition reaction of the compound (4-10) The resulting compound is also a compound (2) and a fluorine-containing carbonyl compound (5), so that the compound (4-1 〇) and the compound (4) are simultaneously subjected to an ester bond decomposition reaction. As the compound (2) and fluorine-containing compound Examples of the decomposition reaction products other than the carbonyl compound (5) include compounds in which the ester bond of the remaining hydrogen compound is decomposed as described later. The fluorocarbonyl compound (5) produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is produced by the present invention. Is R2f-COF or Rlf-CO-R2f. In the present invention, it is preferable to separate the compound (2) and the fluorine-containing carbonyl compound (5) from the decomposition reaction product to obtain the fluorine-containing carbonyl compound (5). As a separation method, Distillation is preferred. The fluorine-containing carbonyl compound (5) obtained by the method of the present invention can be used directly or indirectly as other compounds and useful compounds for various applications. Examples of conversion to other compounds It is not introduced at the end after thermal decomposition reaction -22- This paper size is applicable. National National Standard (CNS) A4 size (210 X 297 mm) 584628 A7 _B7_ V. Description of the invention (2) Saturation bonding is used in An example of a fluororesin monomer or an example of a fluoroalcohol produced by reducing the terminal to a hydroxyl group through a reduction reaction. (Please read the precautions on the back before filling out this page.) Also, the compound (2) contained in the decomposition reaction product A part or all of the compounds (2) which can be reacted with the compound (1) are advantageous and can be manufactured with good recyclability. The method for recovering and reusing the compound (2) from the decomposition reaction product is a method of continuously adding the compound (1) to the reaction system to produce a fluorocarbonyl compound (5). This continuous manufacturing method is performed once per cycle. 'Stoichiometrically, from 1 mole of compound (2), η mole of fluorine-containing curtain compound (5) and 1 mole of compound (2) can be produced. Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau and the manufacturing method of the present invention, the compound with η of 2 is better because it is easier to control the reaction during the implementation or the adjustment of compound (2), especially for the implementation of ^ 2 and Qf is The compound (2-1) having a perfluorinated divalent organic group (Qf2) is preferred. That is, the esterification reaction of the compound (1) and the compound (2-1) yields an esterification reaction product containing one or more compounds (3-1), and the esterification reaction product is perfluorinated by a fluorination reaction. Then, one or more compounds (Heart 1) are obtained, and the decomposition reaction of the ester bond in the fluorination reaction product can be obtained by the decomposition reaction of the compound (4-1) and the compound (2-1). It is preferable to produce a fluorine-containing carbonyl compound (5) as a characteristic from the decomposition reaction product. However, R1, R2, 1 ^ ", 1 ^, and Qf2 in the following formulas have the same meaning as above. FCOQf2COF .............. Formula (2-1) I ^ CHI ^ OCOQUCOOCHR1! ^ ...... Formula (3-1)

RlfCFR2f〇C〇Qf2C〇CFRlfR2f ... Formula (4-1) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 23 _ 584628 A7 B7 V. Description of the invention (21) As the compound of the present invention Specific examples of (1) include the following compounds. (CH3) 2CHOH,

CyCH2OH (Cy represents a cycloalkyl group. The same applies hereinafter).

CyOH, CH2C1CHC1CH2CH20H, (CH3) 2CHCH2OH, CH3CH2CH2OH. Specific examples of the compound (2) include the following compounds. FCOCF2CF2COF, FCOCF2CF2CF2CF2COF 'FCOCF (CF3) OCF2CF2CF2COF, FCOCF (CF3) OCF2CF2CF2CF2COF, FCOCF2CF (CF3) OCF2CF2CF2CF2COF, FCOCF2CF (CF3) OCF2CF2CF2CF2CF2CF2CF2CFF. Specific examples of the compound (3) include the following compounds. (CH3) 2CHOCOCF2CF2CF2CF2COOCH (CH3) 2, CyCH2OCOCF2CF2CF2CF2COOCH2Cy, CyOCOCF2CF2CF2CF2CF2COOCy, CH2CICHCICH2CH2OCOCF2CF2CF2CF2CF2CO2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2O2 Specific examples of the compound (3-10) include the following compounds. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page). A7 _B7__ 5. Description of the invention (22) (Please read the precautions on the back before filling in this page) (CH3) 2CHOCOCF2CF2CF2CF2COF, CyCH2OCOCF2CF2CF2CF2COF, CyOCOCF2CF2CF2CF2CF2CF2CF2CF2CO2CO2CO2CO2CICH2CH2OCOCF2CF2CF2CF2CF2CF2CO2CO2COF2 Specific examples of the compound (4) include the following compounds. (CF3) 2CFOCO (CF2) 4COOCF (CF3) 2

CyfCF2OCO (CF2) 4COOCF2Cyf (However, Cy represents a perfluorinated cycloalkyl group. The same applies below.),

CyfOCOCF2CF2CF2CF2CF2COOCyf, CF2CICFCICF2CF2OCOCF2CF2CF2CF2COOCF2CF2CFCIC F2CI '(CF3) 2CFCF2OCOCF2CF2CF2CF2COOCF2CF (CF3) 2, CF3CF2CF2OCOCF2CF2CF2CF2CF2CF2CF2CFOCF. (CF3) 2CFOCO (CF2) 4COF Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

CyfCF2OCO (CF2) 4COF,

CyfOCOCF2CF2CF2CF2COF, CF2C1CFC1CF2CF20C0CF2CF2CF2CF2C0F, (CF3) 2CFCF2OCOCF2CF2CF2CF2CF2COF, CF3CF2CF2OCOCF2CF2CF2CF2COF o As specific examples of the fluorine-containing carbonyl compound (5) and the cyclic oxides, the following can be mentioned. However, CYf stands for perfluorinated cyclohexyl. -25- This paper size applies to Chinese national standards (CNS> A4 size (210 X 297 mm) 584628 A7 ___B7 V. Description of the invention (23) (CF3) 2CO (5-2), CYfCOF, CF2C1CFC1CF2C0F, (Please read first Note on the back page, please fill in this page again) (CF3) 2CFCOF (5-3), CF3CF2COF, CF3CF2CF2OCF (CF3) COF, CF3CF2CF2OCF (CF3) CF2〇CF (CF3) COF, CF3CF2CF2OCF2CF2COF. And 'as the manufacturing method of this invention, From the point of view of the usefulness of the product and its superior manufacturing method, the method for producing compound (5-2) when η is 2, R1 and R2 are -CH3, and Rlf and R2f are -CF3, The compound (5-3) is better when R1 is -H, R2 is -CH (CH3) 2, Rlf is, and R2f is _CF (CF3) 2. It is printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs and 'As a preferable form of the production method of the compound (5-2), the following production methods are mentioned. Among them, k represents an integer of 2 to 8 and k is an integer of 4 to 6 because it is easier to obtain. That is, the compound (I-2) is subjected to an esterification reaction with the compound (2-2) to obtain an esterification reaction containing the compound (3-2). 'The esterification reaction product containing the compound (3-2) is subjected to a fluorination reaction to obtain a perfluorinated fluorination reaction product containing the compound (4-2). In this fluorination reaction, an ester bond is decomposed. The reaction is to obtain a decomposition reaction product containing the compound (5-2) and the compound (.2-2), and a method for obtaining the compound (2-2) from the decomposition reaction product is preferable. Compound (2-2), which is used as the compound (2-2) that reacts with compound (1-2), and the compound (5-2-26-26) can be continuously produced by performing the same reaction. (CNS) A4 specification (210X297 mm) 584628 A7 B7 5. Invention description (24)) is better. (CH3) 2CHOH (1-2), (Please read the precautions on the back before filling this page) FCO (CF2 ) kCOF (2-2), (CH3) 2CHOCO (CF2) kCOOCH (CH3) 2 (3-2), (CF3) 2CF OCO (CF2) kCOOCF (CF3h (4-2), CF3COCF3 (5-2). Compound (5-2) (that is, hexafluoroacetone. Hereinafter referred to as HFA) and compound (5-3) are known compounds useful as various intermediate systems in themselves, but It can be produced (CF3) 2CHOH (1,1,1,3,3,3- hexafluoro-2-propanol, hereinafter referred to as HFIP) when reduced to this known method, and (CF3) 2CFCHOH. HFIP is also a well-known compound useful as a solvent and various intermediates. The idea of this manufacturing method is shown below.

(CH3 > 2CH〇CO (CF2) 4COOCH (CH3) 2 fco (cfz) 4cof I ^ 1 (cf3) 2CF〇CO (CF2) 4COOCF (CF3) 2 Printed by cf3c〇cf3 in the Intellectual Property Bureau of the Ministry of Economy's Consumer Cooperatives) The manufacturing method of the present invention is a more efficient manufacturing method through a method such as recycling a product. The efficient manufacturing method is exemplified below. In addition, if there is no specific definition below, it means the same as above. (I) Recovered compound (2) The method is to recover the compound (2) produced from the decomposition reaction product of the ester bond, and use this as the standard of the compound on this paper. National Standard (CNS) A4 Specification (210X297 Gt) ^ 97-584628 A7 _B7_ V. Description of the invention (25) (Please read the precautions on the back before filling out this page) (1) Method for compound (2) for esterification. This method is a compound that can be used multiple times ( 2) An economical and efficient method. As a specific example, in the HFA production method described above, FC0 (CF2) 4C0F produced by the decomposition reaction of the ester bond is recovered, and esters are formed with (CH3) 2CH0H. Method of chemical reaction (II) Fluorination reaction When a part of the fluoride is contained, the method of recovering the part of the fluoride in the fluorination reaction system; the product of the fluorination reaction of the compound (3) may contain the part of the fluoride of the compound (3). Examples of the partial fluoride include a hydrogen residual compound (that is, a compound fluorinated at a ratio of at least one hydrogen atom remaining in the compound (3). Part of the fluoride can be returned to the fluorination reaction. In the reaction system, the fluorination reaction is performed again to become the compound (4). For example, when the compound (1) is (CH3) aCHOH and the compound (2) is FCO (CF2) kCOF, it is (CH3) 2CHOCO (CF2) The following compounds of partial fluorides of kCOOCH (CH3) 2 are contained in the fluorination reaction product: (CF3) 2CH〇C〇 (CF〇kC〇〇CH (CF3) 2, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs) (CF3) 2CH0C0 (CF2) kC0CF (CF3) 2, (CF2H) 2CH0C0 (CF2) kC0CH (CHF2) 2. In addition, the fluorination reaction product was used as (CH3) 2 CH0C0 (CF2) kC0F, the following compounds of fluoride, it is also included in the fluorination reaction. (CF〇2CH〇C〇 (CF〇kCOF, (CF2H) 2CH〇C〇 (CF2) kCOF). The P-scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Ministry of Economy Printed by the Intellectual Property Bureau Employee Cooperatives 584628 A7

5. Description of the invention (26) These partial fluorides can be recovered 'in the system of the fluorination reaction and converted into complete fluorides. The idea of this method is as follows.

(III) a method of directly carrying out the decomposition reaction of the vinegar bond in the case of containing a part of fluoride, separating the fluorine-containing carbonyl compound (5) from the reaction product, and recovering it into the reaction system of the esterification reaction; Although a compound having a -CF0C0- moiety can decompose the moiety through an ester bond decomposition reaction, it does not decompose the portion of a compound having a -CH0C0- moiety. Regardless of whether or not the ester bond is separated, 'a part of the fluoride exists in the decomposition reaction system of the ester bond', and after the fluorocarbonyl compound (5) is separated from the product, it is recovered to the reaction system of the esterification reaction. It becomes compound (4). As a specific example of this method, (CF3) 2CHOCO (CF2) kCOOCF (CF3) 2 is generated as a partial oxide, and (CF3) 2CH0C0 (CF2) kC0F is obtained by decomposition reaction of an ester bond. (CF3) 2C = 0, (CF3) 2C = 0, and (CF3) 2CH0C0 (CF2) kC0F and FC0 (CF2) kC0F are simultaneously (<: 3) 2 (: ίΙ〇Η [Method of reaction. The idea of the reaction is shown below. (Please read the precautions on the back before filling this page)

The size of this paper is applicable. National National Standard (CNS) A4 specification (210X297 mm) -29- 584628 A7 B7 V. Description of invention (27)

(Please read the notes on the back before filling this page) (CH3) 2CHOCO (CF2) 4COOCH (CH3) 2 (C F3) 2 CHOC O (C F2hc Ο 0 CH (CHzh

FCO (CF2) 4C〇F and -f [(CF3) 2CHOCO (CF2) 4COF j — (CF3) 2CFOCO (CF2> 4COOCF (CF3) 2 f ten [(CF3) 2CHOCO (CF2> 4COOCF (CF3) 2 CF3COCF3 and When a non-decomposed (CF;) 2CHOCO (CF2) kCOF compound is generated as a partial fluoride, it can be separated and recovered in the fluorination reaction system according to the method described in (2). In the ester bond decomposition reaction system, after the next ester bond decomposition reaction, it will be recovered with FC〇 (CF2) kC〇F-(CF3) 2CH0C0 (CF2) kCOF 'can be used for the ester with (CH3) 2CH0H The chemical reaction is also available. When the compound (3) printed by (IV) Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has a fluorination reaction, it has a carbon skeleton corresponding to the compound (3), and the fluorine content is less than the compound (3) A method for performing fluorination in the presence of a compound; 'This method is a particularly advantageous method when the yields of the fluorination reaction and the ester decomposition reaction are low. The reason is that the compound (2) is used for recovery with the compound (1) ) When performing step (1) of the reaction, 'it is generally difficult to make the recovery of compound (2) reach 100%. Repeated and continuous manufacturing 'There will be a problem of reducing the amount of compound (2) which reacts with compound (1) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -30-584628 A7 B7 V. Description of the invention ( 28) (Please read the precautions on the back before filling this page) To solve this problem, in the fluorination step, a compound with a lower fluorine content than the compound (3) is present at the same time as the compound (3) (the following compounds ( 3H) is preferred) The fluorination reaction is preferably performed. However, the symbol in the formula has the same meaning as above, QH represents a group of a η-valent organic group which requires a hydrogen atom and is fully fluorinated.

QH (COOCHR1R2) m (COF) nm ······························································································································· The coexistence of the structured compound (3) has the advantage of improving solubility in the liquid phase. In particular, when QH is a group having an ester bond, there is an advantage that the solubility of the compound (3) or the compound (3H) is further improved. From the viewpoint of economy, the compound (3H) is preferably a compound containing no fluorine. When the compound (3) is the compound (3-1), specific examples of the compound (3H) include the following compound (3H-1). However, QH2 represents a divalent organic group which requires a hydrogen atom and is a perfluorinated Qf2 group. R ^ HR ^ COQ ^ COOCHR ^ 2 ···· .. Formula (3H-1) QH2 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a non-fluorine-containing bivalent organic group with a carbon skeleton corresponding to Qf2. In particular, it is preferable to insert an etheric oxygen atom between the carbon-carbon bonds of the alkylene group and the alkylene group. Specific examples of the compound (3H-1) include (CH3) 2CHOC (CH2) kCO (CH3) 2. The idea of carrying out the continuous reaction method in the presence of the compound (3-1) is shown below. -31-This paper is applicable in China National Standard (CNS) A4 specification (210X297mm) 584628 A7 B7 V. Description of invention (29)

(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

The amount of the compound (3H) of the compound (3) is not particularly limited as long as it is not an unsuitable amount for the fluorination reaction. When the fluorination reaction is carried out in the liquid phase fluorination reaction, the range in which both the compound (3) and the compound (3H) can be sufficiently dissolved in the liquid phase is not particularly limited. For the compound (3), the compound (3H) The amount is preferably 0.001 times mole to 0.2 times mole. The total amount of the compound (3H) and the compound (3) is preferably 5% by weight or less, and more preferably 0.5% by weight or less in a fluorinated solvent. The compound (3H) may be esterified in a commercially available product or other synthesizers before the fluorination step, or the compound (2H) may be esterified in the presence of the compound (2). However, the symbols in the formula are the same as above. QH (CoF) n ... S2H The esterification reaction of the compound (2H) and the compound (1) generally proceeds simultaneously with the esterification reaction of the compound (2) and the compound (1). Compound (2H) This paper size is applicable to China National Standard (CNS) VIII (210X 297mm) -32- 584628 Printed by A7 ___ B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The specific description of the invention (30) Examples include the following compound (2H-1). However, X represents a halogen atom or a hydroxyl group. XC〇 (CH2) kCOF ... Formula (2H-1) A specific example of a reaction in the presence of a compound (2H) is shown below. ! H0OC (CH2) 4C00H (CH3) 2CHOCO (CH2) 4COOCH (CH3) 2+ + (CH3) 2CHOH / (CH3) 2CHOCO (CF2> 4COOCH (CH3) 3 FCO < CF2) 4COF V --- (CF3) 2CFOCO (CF2) 4COOCF (CF3) 2 CF3COCF3 The use of the fluorine-containing carbonyl compound (5) obtained by the production method of the present invention is not particularly limited. The compound can be used directly or used in a variety of other applications. For example, reduction of the fluorine-containing carbonyl compound (5) can produce various useful fluorine-containing alcohols. Examples The present invention is described in detail below, but the present invention is not limited by these. In addition, as described below, 1,1,2-trichloro-1,2,2-trifluoroethane is represented by R-113, and the pressure is a gauge pressure. In addition, gas chromatography is shown by GC, and the peak area ratio of GC analysis is shown by GC analysis. The gas chromatography mass analysis is shown by GC-MS. The peak area of NMR is expressed as a ratio. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -33-

(Please read the precautions on the back before filling in this page) 584628 A7 B7 V. Description of the invention (31) [Example 1] (CF3) Manufacturing example of 2C0 [Example 1-1] (CH3) 2CHOH and FC. (CF2) 4C0F's purpose (Please read the precautions on the back before filling out this page) Put 2CHH (600g) in a 2L autoclave made of heat-resistant and corrosion-resistant nickel-based alloy C. Cool the reactor and keep the internal temperature below 30 ° C under normal pressure. Slowly introduce FCO (CFO 4COF (1540g). While fully stirring while bubbling nitrogen, the HF produced by the reaction is released systematically. Full amount of FC is introduced. After (CFa) 4C0F, a reaction was performed at 50 ° C for 5 hours to obtain a product. GC analysis of the product yielded 98.9% of (CH3) 2CHOC (CF2) 4 (C〇CH (CH3) ) 2, 1.1% of ((^ 3) 2 (: 11〇 (: 〇 (?? 2) 4.〇 ?, no unreacted isopropyl alcohol was detected, and the product did not require purification, and was used in the following reaction (CH3) 2CH0C0 (CF2) 4CO0CH (CH3) 2 spectral data; j-NMRUOOJMHz, solvent: CDCh, reference: TMS) 5 (ppm): 1.40 (d, 6H), 5.21 (m, lH). 19F-NMR (282.7MHz, solvent: CDCh, reference: CFCh) 5 (ppm): 119.5, 123.1, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 1-2]

(CF3) 2CF0C0 (CFi) 4 Co. CF (CF3) 2 Manufacture In a 500 mL nickel autoclave, R-113 (200g) was placed, and then kept at 25 ° C while stirring. The autoclave gas outlet is provided with a cooler maintained at 20 ° C, a NaF raw material charging tower, and a cooler maintained at -10 ° C. In addition, the setting is to return the liquid condensed by the cooler kept at -10 ° C to the liquid return of the autoclave. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 34-584628 A7 B7 V. Invention Explanation (32) course. After blowing nitrogen at room temperature for 1 hour, the fluorine gas diluted with nitrogen to 20% (hereinafter referred to as 20% diluted fluorine gas) is blown at room temperature at a flow rate of 9.76 L / h for 1 hour. Then, while blowing 20% diluted fluorine gas at the same flow rate, the solution obtained by dissolving the product (7g) obtained in Example 1- 丨 in R-113 (140g) was injected for 6.1 hours. Continue, blowing at the same flow rate Add 20% diluted fluorine gas, while increasing the internal pressure of the autoclave to 0.15 MPa, R-113 solution with a benzene concentration of 0.01 g / mL, while injecting 9 mL from 25 ° C to 40 ° C, closed the autoclave benzene solution injection At the inlet, stirring was continued for 0.3 hours. The internal pressure of the reactor was maintained at 0.15 MPa, and the temperature in the reactor was maintained at 40 ° C, and 6 ml of the benzene solution was injected. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The operation was repeated 3 times. The total injection amount of benzene was 0.34g, and the total injection amount of R-113 33mL. In addition, while blowing 20% diluted fluorine gas at the same flow rate, continue to stir for 1.1 hours. Continue to use the internal pressure of the reactor as normal pressure and nitrogen for 2 hours to remove R-113 from the obtained mixture to obtain a product ( 14. lg). As a result of 19F-NMR analysis of the product, it was confirmed that the yield of the labeled compound was 23.5%. In the product, one or more kinds of partial fluorides of the product obtained in Example 1-1 (total yield) 67.7%). The fluorinated reaction product can be directly used in the following reactions. 19F-NMR (282.7MHz, solvent: CDCh, reference: CFCh) 5 (ppm): -79.3 (12F), -118.7 (4F) , -122.5 (4F), 142.8 (2F). [Example 1-3] Decomposition reaction of ester bond: 4 paper sizes are applicable to China National Standard (CNS) A4 specification (210X297 mm) I ------ --9-Handling— (Please read the notes on the back before filling this page) Order printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-35- 584628 A7 B7 V. Invention Description (33) Equipped with distillation tower and can Cold water-cooled Liebich condenser distilling route, receiver, and dry ice condensate valve 20ml reaction prepared in the upper part of the reaction vessel Put KF (0.7g) in the container and heat it at 150 ° C. The fluorination reaction product obtained in Example 1-2 was slowly added to the reaction container. One hour after the end of the addition, the reaction was completed when no gas was generated. Acceptor The product was recovered in an amount of 5.82 g. The product was FC0 (CF2) 4COF (GC yield 29%), and FC0 (CF2) 4 COCH (CF3) 2 (GC yield 60%) was obtained. In addition, a liquid (4.10 g) containing (CF3) 2CHOC (CF2) 4COOCH (CF3) 2 as a main component was produced in the reaction vessel. The GC purity of the gas trap was 95% (CF3) 2CO (3.74 (g)). [Example 1-4] (CF) 2CFOCO (CF2) 4COOCF (CF3) 2 3L made of nickel after fluorination In a pressure cooker, CFs (CF2) 2〇CF (CF3) CF2OCF (CF3) COF (2534g) was added as a fluorination reaction solvent, and the temperature was maintained at 25 ° C. The autoclave gas outlet was set to a cooler maintained at -10 ° C. Nitrogen blowing After 3.5 hours, the nitrogen gas is diluted to 50% fluorine gas (hereinafter referred to as 50% diluted fluorine gas) and blown in at a flow rate of 94.89 L / h for 2 hours. Then, while 50% diluted fluorine gas is blown in at the same flow rate, The product containing the product (CHs) 2CHOCO (CF2) 4COOCH (CH3) 2 (7g) (943g) obtained in Example 1-1 was injected over 20.0 hours. 1523 g of the reaction crude liquid was taken out. Continue, blowing at the same flow rate 50% dilution of fluorine gas, and (CH3) 2CHOCO (CF!) 4COOCH (CEh) 2 (953) g obtained from Example 1 and (CH3) 2CHOCO ( CH2) 4C〇CH (CH3) 2 (This paper size applies Chinese National Standard (CNS) A4 specification (210 X297 mm) _ 36-(Please read the precautions on the back before filling this page) • Binding and ordering Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, 8th Industrial Cooperative, 584628 A 7 B7 V. Description of the invention (34) 3〇2) After 21.8 hours injection, take out the reaction crude solution (1612 £). (Please read the notes on the back before filling (This page) Also, while blowing 50% of the diluted fluorine gas at the same flow rate, it was mixed with the (CH3) 2CHOCO (CF2) 4COOCH (CHs) 2 (946g) product and (CHs) aCHOCO (CHa) ) 4COOCH (CH3) a (58g) was injected over 23.2 hours. Continue to adjust to 3 hours while blowing 50% diluted fluorine gas at the same flow rate. Then nitrogen was blown for 3 hours to recover the crude reaction liquid (4212g). As a result of GC-MS analysis of each reaction crude liquid, a product containing CF3CF2CF2OCF (CF3) CF2OCF (CFs) COF containing the labeled compound as the main product and the labeled compound was obtained. [Example 1-5] The decomposition reaction through an ester bond (CF3) 2CO manufacturing example has a distillation tower and a cold water-cooled Liebich condenser distillation line, receiver, and dry ice condensate valve are placed in a 300ml reaction container at the top of the reaction container, and put into KF (29g), Heat at 150 ° C. The reaction container containing the product printed in Example 1-2 at 313 g / hour for 10 hours was printed with (CF3) 2CFOC (CF2) 4COCF (CF3) 2 produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. One hour after the end of Tim D, the reaction was completed when no gas was generated in the reaction vessel. The receiver recovered FCO (CF2) 4COF with a purity of 98% CF. The condensate valve recovered (CF3) 2CO (1505g) with a purity of 95% CF. [Reference Example 1] Production Example of (CF3) 2CHOH After Reduction of (CF3) 2CO The (CF3) 2CO with 95% GC purity obtained in Example 1-3 was treated with 3 sheets of Trap-T0- -37- The scale is applicable to the National Standard (0 milk) and 8 specifications (210 \ 297 mm) 584628 A7 ___B7_ V. Description of the invention (35) (Please read the precautions on the back before filling this page)

Purification by Trap method gave (CF3) 2CO with a GC purity of 99.5%. 10 g of carbon-supported 3% palladium catalyst was filled into a heat-resistant glass tube with an inner diameter of 10 mm, and (CF3) 2C0 with a GC concentration of 99.5% was supplied at 10 g / hour, and (CF3) 2C was supplied. In terms of 2 moles of hydrogen. The contact time was 10 seconds and the reaction temperature was 150 ° C. (CF3) 2CHOH was obtained by reduction. The reaction conversion was 99.8% and the selectivity was 99%. [Example 2] (Example of manufacturing of CF3) 2CFC〇F [Example 2-1] (CH3) 2CHCH20H and FCO (CF2) 3COF The reaction to the degeneration of the Ministry of Economic Affairs Intellectual Property Bureau Employee Consumer Cooperative printed a heat-resistant and corrosion-resistant nickel-based C alloy 2L autoclave (CHO 2CHOH (700g). Cool the reactor and seal with nitrogen and keep the internal temperature below 30 ° C. FCO (CF2) 3COF (1190g) is slowly introduced. Put After the full amount of FCO (CF2) 3COF, the reaction was performed at 50 ° C for 5 hours to obtain the product, and the by-product HF was discharged out of the system through nitrogen gas. The product was obtained by GC analysis, and 98.7% of the product was produced. (CH3) 2CHCH2OCO (CF2) 3COOCH2CH (CH3) 2, 1.3% (CH3) 2 CHCHaOCO (CF2) 3COF) No unreacted isobutyl alcohol was detected. This product was obtained without purification The following reactions were used: 3H-NMR (300.4 MHz, solvent: CDCh, reference: TMS) δ (ppm): 0.98 (d, 6H), 2.06 (m, 1H), 4.15 (d, 2H). 19F-NMR ( 282.7MHz, solvent: CDC13, benchmark: CFC13) 5 (ppm): -118.9, -124.3. This paper size is applicable. National National Standard (CNS) A4 specification (210X297 mm) 584628 A7 B7 Explanation of the invention (36) [Example 2-2] Production example of (CF3) 2CFCF2〇C〇 (CF2) 3CO〇CF2CF (CF3) 2 after fluorination (please read the precautions on the back before filling this page) A nickel pressure cooker with the same reaction device as in Example 1-2 was prepared. After putting R-113 (312g), a 20% diluted fluorine gas was blown in at a flow rate of 10.60 L / h. The other conditions were the same as in Example 1-2. A solution of the product (5 g) obtained in Example 2-1 and dissolved in R_113 (95 g) was injected into the autoclave over 5.5 hours. Continue, while blowing 20% diluted fluorine gas at the same flow rate, while increasing the inner pressure of the autoclave to 0.15 MPa The R-113 solution with a benzene concentration of 0.01 g / mL was injected from 9 ° C to 25 ° C to 40 ° C. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. Then, the internal pressure of the reactor was maintained at 0.1 5 MPa. The temperature in the reactor was maintained at 40 ° C and 6 ml of the above benzene solution was injected. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The same operation was repeated 3 times. The total amount of benzene injection was 0.22 g. The total injection volume was 22 mL, and stirring was continued for 1.0 hour while blowing 20% diluted fluorine gas at the same flow rate. The pressure in the reactor was continued as normal pressure, and nitrogen was blown in for 1.0 hour. 19F-NMR analysis of the product confirmed that the yield of the labeled compound was 87. 19F-NMR (282.7MHz, solvent: CDC13, standard: CFC13) printed by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs 5 (ppm): -73.8 ( 12F), -80.5 (4F), -118.6 (4F), -123.6 (2F), -187.9 (2F) o [Example 2-3] Manufacturing example of (CF3) 2CFCOF via decomposition reaction of ester bond This paper size In use. National Standard (CNS) A4 (210 > < 297 mm) 〇9- 584628 A7 __B7 V. Description of the invention (37) (Please read the precautions on the back before filling this page) Equipped with a distillation column The distilling route, receiver, and dry ice condensate valve of the Liebich condenser that can be cooled by cold water are prepared in a 20ml reaction container at the top of the reaction container, put into KF (0.7g), and heated at 150 ° C. In the reaction vessel, 9 g of a liquid from which the fluorination reaction product r_i π obtained in Example 7 was removed was gradually added. One hour after the end of the addition, the reaction was completed when no gas was generated. 5.72g of product was recovered in the receiver. The products were FCO (CF0COF (GC area 55%), FC0 (CF2) 3CO0CF2CH (CF3) 2 (GC area 15%), and (CF0CFC0F (GC area 30%)). In the condensate valve, the GC purity was 97% (CF3) 2CFC0F (3.12%) was recovered. [Example 2-4] (CH3) 2CHCH2OH esterification reaction of FC0 (CF2) 2C0F Example 2- Except for changing C0 (CF2) 3C0F and performing FC0 (CF2) 2C0F (950g) in 1, the reaction was performed in the same manner as in 2-1. As a result of GC analysis of the product, 98.8% of (CH3) 2CHCH2 was generated. C〇 (CF2) 2C〇CH2CH (CH3) 2, 1.2% of (CH ^ CHdOCCKCF + COF) did not detect unreacted isobutyl alcohol. This product does not need to be purified and used in the following reactions. Employees, Bureau of Intellectual Property, Ministry of Economic Affairs W-NMRUoodMHz printed by Consumer Cooperative, solvent: CDCh, reference: TMS) 5 (ppm): 0.98 (d, 6H), 2.05 (m, 1H), 4.13 (d, 2H, 19F-NMR (282.7MHz, solvent : CDCh, benchmark: CFCh) 5 (ppm): -120.2 〇 [Example 2-5] (CF3) 2CFCF2 OC (CF2) 2 C 〇CF2CF (CF〇2) produced by the fluorination reaction! 1 The paper size is applicable to Chinese National Standard (CNS) M specifications (210X297 mm) -40-584628 A7 B7 V. Description of the invention (38) A nickel pressure cooker with the same reaction device as in Example 1-2 was prepared. After putting R-113 (312g), 20% diluted fluorine gas was blown in at a flow rate of 12.16L / h. -2 under the same conditions. Into the autoclave, the product (5g) obtained in Example 2-4 was dissolved in R-113 (100g) over 5.7 hours. Continue, while blowing 20% diluted fluorine gas at the same flow rate, increase The internal pressure of the autoclave was 0.15 MPa, and the R-113 solution with a benzene concentration of 0.01 g / mL was injected from 9 ° C to 25 ° C to 40 ° C. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The internal pressure of the reactor was maintained at 0.15 MPa, and the temperature of the reactor was maintained at 40 ° C. 6 ml of the benzene solution was injected. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The same operation was repeated 3 times. The injection of benzene The total amount was 0 · 2 2 g, and the total injection amount of R -11 3 was 21 m L. Furthermore, while the 20% diluted fluorine gas was blown in at the same flow rate, the stirring was continued for 1.0 hours. The pressure in the reactor was kept constant. Pressure, and nitrogen was blown in for 1.0 hour. 19F-NMR analysis of the product confirmed that the yield of the labeled compound was 90%. 19F-NMR (282.7MHz, solvent: CDCh, reference: CFCl3) 5 (ppm): - 73.8 (12F), - 80,4 (4F), - 119.2 (4F), - 187.8 (2F). [Example 2-6] Production Example of (CF3) 2CFCOF via Decomposition Reaction of Ester Bond The fluorination reaction product of Example 2-3 was changed to the fluorination reaction product obtained in Example 2-5, and slowly added. The same reaction was performed except for the liquid 8.11 lg of R11 3 which was the fluorination reaction product. 1.02g of product recovered in the receiver. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) —-------- installation— (Please read the precautions on the back before filling This page), 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -41-584628 A7 B7 V. Invention Description (39) (Please read the precautions on the back before filling this page). The product is FC0 (CF2) 2C0F (GC area 35%), FC0 (CF2) 2C0 CF2CH (CF3) 2 (GC area 60%), (CF3) 2CFC0F (GC area 5%) ). 6.94g was recovered from the gas trap. The product was composed of FC0 (CF2) 2COF (GC area 30%) and (CF3) 2CFCOF (GC area 70%). Industrial Applicability The compound (1) as a raw material of the production method of the present invention is a commercially available product of various compounds having a carbon skeleton, and it can be obtained at low cost. Therefore, the production method of the present invention can freely produce a fluorine-containing compound having a variety of skeletons in a short step and at a high yield from this raw material compound. In addition, by using the method of the present invention, it is possible to easily synthesize a low-molecular fluorinated compound or a fluorinated compound with a complicated structure that was difficult to obtain by conventional methods. In addition, the production method of the present invention is not limited to the compounds described in the above specific examples, but can be applied to a wide variety of other compounds with excellent versatility. In addition, the method of the present invention can be a more industrially applicable and efficient manufacturing method by using a method such as recovery of a compound. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -42- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

584628 A8 B8 C8 D8 VI. Application for Patent Scope No. 9 1 1 1 4439 Chinese Application for Patent Scope Amendment The Republic of China August 15, 1992 Amendment 1. A method for manufacturing a fluorine-containing carbonyl compound, characterized by formula 1 The reaction temperature between the compound represented by the formula and the compound represented by the formula 2 was 0.50. 〇 ~ + 100 ° C, and the reaction pressure is from normal pressure to 2 MPa (gauge pressure), an esterification reaction product containing one or more compounds represented by Formula 3 is obtained, and the esterification reaction product undergoes -50 ° C ~ + 100 ° C which reacts with fluorine in the liquid phase. After the liquid phase fluorination reaction becomes perfluorination, one or more kinds of fluorination reaction products represented by Formula 4 are obtained. The reaction product undergoes thermal decomposition reaction (50 ~ 350 ° C in the gas phase and 50 ~ 300 ° C in the liquid phase). Decomposition reaction of ester bond, or ester bond in the presence of nucleophile or electrophile- 30 ° C to + 25 0 ° C Decomposition reaction 'to obtain a decomposition reaction product containing the compound represented by Formula 5 and the compound represented by Formula 2. From this decomposition reaction product, a fluorine-containing carbonyl group represented by Formula 5 is obtained For compounds, R] CHR2OH ... Formula 1 Qf (COF) n ... Formula 2 Qf (COOCHR1R2) m (COF) nm ... Formula 3 Qf (COOCFRlfR2f) m (COF) nm ... Formula 4 RlfCOR2f ·····. Formula 5 However, the symbols in the formula are as follows, R1, R2: R] represents a hydrogen atom or a fluorinated monovalent organic group, and R2 represents a fluorinated monovalent organic group. R1 and R2 can be fluorinated together to form a bivalence. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page), IT. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 584628 A8 B8 C8 D8 々 Organic patent application scope, RH'R ^ R1 represents a hydrogen atom when RIf is a fluorine atom, R1 represents a monovalent organic group when RIf is R1 Perfluorinated monovalent organic group, R2f is a monovalent organic group of R2 after perfluorination, but when 'R1 and R2 are fluorinated at the same time to form a divalent organic group, RIf and R2i together form the divalent organic group. Perfluorinated group Qf: Perfluorinated η-valent organic group, η: An integer of 2 or more, m: An integer of 2 or more and η, but R1 and R2 are monovalent organic groups, and RIf and R "are When perfluorinated monovalent organic group, carbon number is 2-9; R1, R2 are divalent organic group, Rlf, R2f are perfluorinated divalent organic group, carbon number is 2-9; Qf The carbon number of the perfluorinated η-valent organic group is 2 to 8. 2. The manufacturing method according to item 1 of the scope of patent application, wherein the compound represented by formula 2 is reacted with a compound represented by formula 1, It is a compound represented by Formula 2 obtained from the decomposition reaction product of an ester bond. 3. The manufacturing method according to item 1 or item 2 of the scope of patent application, wherein The molecular weight of the compound represented by 1 is 32 to 200, the average fluorine content of the esterification reaction product is 20 to 60% by mass, and the molecular weight of the esterification reaction product is 200 to 1 100. 4. If the scope of the patent application is the first The production method according to item 1, wherein the compound represented by Formula 2 is a compound represented by Formula (2-1), and the esterification reaction product is a compound represented by Formula (3-1) as necessary, and the fluorination reaction The paper size of the paper applies to the Chinese National Standard (CNS) Α4 specification (21G X 297 mm) · 2-(Please read the precautions on the back before filling this page) Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 584628 A8 B8 C8 D8 VI. The scope of the patent application is necessary if the compound represented by formula (4 -1) is required, and the decomposition reaction product is represented by formula (5 -1) The compound represented by the formula and the compound represented by the formula (2-1) are indispensable. The fluorine-containing forging-based compound is a compound represented by the formula (5-1), and FC〇Qf2C0F ... Formula (2-1) R ] CHR2〇C〇Qf2C〇CHR] R2 ... Formula (3-1) RlfCFR2fOCOQf2COOCFRlfR2f ... Formula (4-1) RlfC〇R2f ... Formula (5-1) However, the symbols in the formula are as shown below R1, R2, RIf, R2 have the same meanings as above, Qi2: a divalent organic group which is perfluorinated. 5 ^ • The manufacturing method according to item 4 of the scope of patent application, wherein the esterification reaction product is a compound represented by formula (3d η) and the compound represented by formula (3-1d), and the fluorination reaction product In addition, the compound represented by the formula (4.1) contains the compound represented by the formula (4 -1 Η), R ^ HR'OCOQ ^ COF .. ^ (3-1H) RlfCFR2f〇CQQ2C. F. Formula (4-1H) However, in the formula, R1, R2, RH, 11 ", and Qi2 have the same meanings as described above. 6. For the manufacturing method of the 4th or 5th in the scope of patent application, in which esterification is performed The reaction product contains a compound represented by the following formula (3-2H), and the person performing the fluorination reaction, R ^ HR'OCOQ ^ COOCHR ^ 2 ... ^ (3-2H), however, the paper size is applicable to China National Standard (CNS) A4 Specification (210X297 mm) -3-(Please read the precautions on the back before filling this page), printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economy and Economy 584628 A8 B8 C8 D8 范围, patent application scope R1, R2: Same meaning as above, (Please read the notes on the back before filling this page) The base is a base of Qf2 after perfluorination. 7. The manufacturing method according to item 6 of the scope of patent application, wherein the content is more than 0% by mass and 10% by mass relative to the compound represented by formula (3-1). Those who carry out the fluorination reaction in the presence of the compound represented by the following formula (3-2。). 8. The manufacturing method as described in item 7 of the scope of patent application, wherein y and r2 are _ CH3, RIf and R2 "is -CF3 , Qf2 is-(CFO k_ (however, k represents an integer from 2 to 8), and QH2 is-(CH2))-, or R1 is -H, R2 is -CH (CH3) 2, RIf is -F, R2f Is -CF (CF〇2, and qw is _ (CH2). 9. The manufacturing method according to item 4 of the patent application scope, wherein the liquid phase in the liquid phase m is represented by the formula (4 -1) And / or the compound represented by the formula (5 -1) are indispensable. 10. The manufacturing method according to item 4 of the scope of patent application, wherein the compound represented by the formula 1 and the compound represented by the formula 2 are esterified. In the reaction, the amount of the compound represented by the formula (1) is 0.5 to 1 mole of the compound represented by the formula 2. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 1 · If applied The manufacturing method of the fourth item, wherein in the fluorination reaction of the compound represented by Formula 3, in the presence of a compound having the same carbon skeleton of the corresponding compound (3) and containing less fluorine than the compound (3), Those who carry out the fluorination reaction. This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X297 mm)