JP4362710B2 - Method for producing fluorine-containing carbonyl compound - Google Patents

Description

  The present invention relates to a method for efficiently producing fluorine-containing carbonyl compounds having various structures.

  A reaction in which polyethylene glycol having a molecular weight of 1000 or more is reacted with trifluoroacetic acid and then fluorinated in a liquid phase to obtain a polyethylene glycol having a trifluoromethyl group at the terminal (Japanese Patent Publication No. 4-500520) is known. In addition, polyethylene glycol having a trifluoromethyl group produced by the method of JP 4-500520 is fluorinated in the liquid phase to decompose the two ester bonds of the perfluorinated polyethylene glycol dimethyl ester to be perfluorinated. A method for obtaining diacyl fluoride is also known (US Pat. No. 5,466,877).

  In addition, as a method for obtaining a fluorine-containing carbonyl compound from a non-fluorine alcohol, the present applicant reacts a partially fluorinated ester obtained by reacting a fluorine-containing monoacyl fluoride with a non-fluorine alcohol with fluorine. An application has already been filed for a method of decomposing the ester after converting it to a perfluoroester (WO 00/56694).

In the ester bond decomposition reaction described in US Pat. No. 5,466,877, CF ₃ COF is produced, but since CF ₃ COF has a low boiling point (−59 ° C.), recovery is difficult, and there is no description indicating that it was actually recovered. . Further, in this method, it is necessary to prepare a fluorinated carboxylic acid (for example, trifluoroacetic acid) corresponding to the fluorinated acyl fluoride compound, but the fluorinated carboxylic acid is generally expensive and has a limited structure available.

  The method of WO 00/56694 is a method in which a fluorine-containing monoacyl fluoride is reacted with a non-fluorinated alcohol in a 1-fold molar ratio. However, since the fluorine-containing monoacyl fluoride is generally expensive, there is a problem inferior in economy . In order to make it more economical, there is a method using a low molecular weight fluorine-containing monoacyl fluoride. However, since the low molecular weight fluorine-containing monoacyl fluoride has a low boiling point, it is difficult to recover after the ester decomposition reaction. In addition, there is a problem that the economic benefits of reuse cannot be utilized.

  Furthermore, when a fluorine-containing monoacyl fluoride having a low molecular weight is employed, the vapor pressure of the partially fluorinated ester is increased, and the reaction in the gas phase part can occur accompanying the gas in the liquid phase fluorination reaction. The reaction in the gas phase has problems that it is difficult to control the reaction and leads to a decrease in yield. On the other hand, in order to reduce the vapor pressure of the partially fluorinated ester, the method using a high molecular weight partially fluorinated ester has problems such as few types of partially fluorinated ester, high cost, and poor economic efficiency. .

The present invention provides the following production method for solving the above-mentioned problems.
1. The compound represented by the following formula (1) is the compound represented by the following formula (2) (however, the compound represented by the formula (2) is a compound represented by the formula (2) obtained from the decomposition reaction product of the ester bond. And an esterification reaction product containing one or more of the compounds represented by the following formula (3) to obtain an esterification reaction product, A compound fluorinated in such a ratio that at least one hydrogen atom of the compound represented by the formula (3) remains (however, the compound is obtained from the fluorination reaction product of the compound represented by the following formula (3)). And a compound having at least one -COOCH- moiety) by perfluorination by a fluorination reaction, thereby including at least one compound represented by the following formula (4): A reaction product is obtained and the fluorination reaction product By performing an ester bond decomposition reaction, a decomposition reaction product containing a compound represented by the following formula (5) and a compound represented by the following formula (2) is obtained, and the following formula is obtained from the decomposition reaction product. A method for producing a fluorinated carbonyl compound, comprising obtaining the fluorinated carbonyl compound represented by (5).
R ¹ CHR ² OH .. Formula (1)
Q ^f (COF) _n ·· Formula (2)
^{Q f (COOCHR 1 R 2)} m (COF) n-m ·· formula (3)
_{^{Q f (COOCFR 1f R 2f)}} m (COF) n-m ·· formula (4)
R ^1f COR ^2f .. Formula (5)
However, the symbol in a formula shows the following meanings.
R ^{1, R 2:} R ¹ represents a monovalent organic group which can be off Tsu fluorinated, R ² represents a monovalent organic group which can be fluorinated, R ¹ and R ² can be fluorinated jointly A divalent organic group may be formed.
R ^1f , R ^2f : R ^1f is a monovalent organic group in which R ¹ is perfluorinated. R ^2f is a monovalent organic group in which R ² is perfluorinated. However, when R ¹ and R ² jointly form a divalent organic group that can be fluorinated, R ^1f and R ^2f jointly perfluorinate the divalent organic group. Form a group.
Q ^f : a perfluorinated n-valent organic group.
n: An integer of 2 or more.
m: An integer of 2 or more and n or less.
2. The molecular weight of the compound represented by the formula (1) is 32-200, the average fluorine content of the esterification reaction product is 20-60% by mass, and the molecular weight of the esterification reaction product is 200-1100. 2. The manufacturing method according to 1.
3. 3. The production method according to 1 or 2, wherein the fluorination reaction is a liquid phase fluorination reaction.
4). The compound represented by the formula (2) is a compound represented by the formula (2-1), the esterification reaction product essentially comprises the compound represented by the formula (3-1), and a fluorination reaction product. In which the compound represented by formula (4-1) is essential, the decomposition reaction product is essentially the compound represented by formula (5-1) and the compound represented by formula (2-1), and contains fluorine. The manufacturing method in any one of 1-3 whose carbonyl compound is a compound represented by Formula (5-1).
FCOQ ^f2 COF .. Formula (2-1)
R ¹ CHR ² OCOQ ^f2 COOCHR ¹ R ² ..Formula (3-1)
R ^1f CFR ^2f OCOQ ^f2 COOCFR ^1f R ^2f .. Formula (4-1)
R ^1f COR ^2f .. Formula (5-1)
However, the symbols in the formulas have the following meanings.
R ¹ , R ² , R ^1f , R ^2f : same meaning as above.
Q ^f2 : Perfluorinated divalent organic group.
5. The esterification reaction product includes a compound represented by formula (3-1H) together with a compound represented by formula (3-1), and the fluorination reaction product is represented by formula (4-1). 5. The production method according to 4, comprising a compound represented by formula (4-1H) together with the compound.
R ¹ CHR ² OCOQ ^f2 COF .. Formula (3-1H)
R ^1f CFR ^2f OCOQ ^f2 COF .. Formula (4-1H)
However, R ¹ , R ² , R ^1f , R ^2f and Q ^f2 in the formula have the same meaning as described above.
6). 6. The production method according to 4 or 5, wherein the esterification product is subjected to a fluorination reaction by including a compound represented by the following formula (3-2H).
R ¹ CHR ² OCOQ ^H2 COOCHR ¹ R ² Formula (3-2H)
However,
R ¹ , R ² : same meaning as above.
Q ^H2 : a divalent organic group that essentially ^{requires a} hydrogen atom, and a group that is perfluorinated to become Q ^f2 .
7). 7. The production method according to 6, wherein the fluorination reaction is carried out by allowing the compound represented by the formula (3-2H) to be present in an amount of more than 0% by mass and 10% by mass or less with respect to the compound represented by the formula (3-1). .
8). R ¹ and R ² are —CH ₃ , R ^1f and R ^2f are —CF ₃ , Q ^f2 is — (CF ₂ ) _k — (wherein k represents an integer of 2 to 8), and Q ^H2 is - _{(CH 2) k} - in which method according to 6 or 7.
9. The production according to any one of 4 to 8, wherein the liquid phase in the liquid phase fluorination contains the compound represented by the formula (4-1) and / or the compound represented by the formula (5-1) as an essential component. Method.
10. In the esterification reaction of the compound represented by the formula (1) with the compound represented by the formula (2), the amount of the compound represented by the formula (1) is set to 0. 0 of the compound represented by the formula (2). The manufacturing method in any one of 1-9 made into 5 times 1 times mole.
11. In the fluorination reaction of the compound represented by the formula (3), it has the same carbon skeleton corresponding to the compound represented by the formula (3) and contains more fluorine than the compound represented by the formula (3). The manufacturing method in any one of 1-10 which performs a fluorination reaction in presence of a compound with little quantity.

  The organic group in the present specification refers to a group in which a carbon atom is essential. Examples of the organic group that can be fluorinated include an organic group having a C—H moiety and an organic group having a carbon-carbon unsaturated bond, and an organic group having a C—H moiety is preferred. -Saturated organic groups in which the carbon bond consists only of a single bond are preferred.

  Examples of the organic group having a C—H moiety include a saturated hydrocarbon group, a saturated hydrocarbon group containing an etheric oxygen atom, a partially halogenated saturated hydrocarbon group, or a partially halogenated (etheric oxygen atom-containing saturated hydrocarbon) group. preferable. Here, the partial halogenation means that the hydrogen atom is halogenated in a ratio that remains. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom or a chlorine atom is preferable. In particular, the halogen atom in the partially halogenated group is preferably a chlorine atom.

  The monovalent saturated hydrocarbon group is an alkyl group, a cycloalkyl group, or 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. And an alkyl group is preferable.

  As the divalent saturated hydrocarbon group, an alkylene group, a cycloalkylene group, or a divalent saturated hydrocarbon group having a ring portion (for example, a divalent saturated hydrocarbon having a partial structure of a cycloalkyl group, a bicycloalkyl group, or a cycloalkylene group) An aliphatic hydrocarbon group.) And the like, and an alkylene group is preferable.

  The monovalent group in the saturated hydrocarbon group containing an etheric oxygen atom includes an alkyl group having an etheric oxygen atom inserted between carbon-carbon bonds, or an etheric oxygen atom inserted between carbon-carbon bonds. And a cycloalkyl group. The divalent group of the etheric oxygen atom-containing saturated hydrocarbon group includes a carbon-carbon bond, an alkylene group in which an etheric oxygen atom is inserted at the bond terminal of the group, or a carbon-carbon bond. And a cycloalkylene group in which an etheric oxygen atom is inserted, and an oxyalkylene group or a group having a polyoxyalkylene moiety is particularly preferable. In the group containing an etheric oxygen atom, the number of etheric oxygen atoms may be one or two or more.

  Perfluorination means that substantially all of the fluorinated moieties present in a fluorinated group are fluorinated. For example, in a group in which an organic group having a C—H moiety is perfluorinated, substantially all of the C—H moiety is converted to C—F, and the organic group having a carbon-carbon unsaturated bond is perfluorinated. In, fluorine atoms are added to substantially all unsaturated bonds.

Examples of the perfluorinated monovalent organic group include a perfluoroalkyl group, specifically, —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CClF. ₂ , —CF ₂ CBrF ₂ , or —CF ₂ CFClCF ₂ Cl, —CF (CF ₃ ) ₂ , —CF ₂ CF (CF ₃ ) ₂ , —CF (CF ₃ ) CF ₂ CF ₃ , —C (CF ₃ ) ₃ etc. are mentioned. Examples of the perfluorinated divalent organic group include a perfluoroalkylene group, specifically, —CF ₂ CF ₂ CF ₂ CF ₂ —, —CF (CF ₃ ) CF ₂ CF ₂ CF ₂ —, —CF _2. CF (CF ₃ ) CF ₂ CF ₂ — and the like can be mentioned. Examples of perfluorinated etheric oxygen atom-containing groups include groups in which etheric oxygen atoms are inserted between carbon-carbon atoms of these groups.

  The concept of the production method of the present invention can be expressed by the following formula.

  In the production method of the present invention, an esterification reaction, a fluorination reaction, and an ester bond decomposition reaction are performed.

In the starting compound (1), since the method of the present invention is advantageous when the molecular weight of the compound (1) is small, the carbon number of the R ¹ CHR ² -moiety is 3-10. Is preferable, and 3 to 5 is particularly preferable. The molecular weight of the compound (1) is preferably from 32 to 200, particularly preferably from 60 to 150, particularly preferably from 60 to 120.

In the compound (1), when R ¹ and R ² are each a monovalent organic group that can be fluorinated, an alkyl group, a cycloalkyl group, and an alkoxy group are preferable. When R ¹ and R ² jointly form a divalent organic group that can be fluorinated, the divalent organic group is an alkylene group or one or more between the carbon-carbon bonds of the alkylene group. A group in which an etheric oxygen atom is inserted is preferred.

  In addition, as the compound (1), alcohol compounds having various structures are commercially available and can be obtained at low cost. Therefore, a compound containing no fluorine atom (that is, a compound having a fluorine content of 0% by mass) is preferable.

As the compound (1), a compound having a structure corresponding to the structure of the target fluorine-containing carbonyl compound (5) is selected and used. The arrangement of the carbon atom skeleton of R ¹ and R ^{2 in} the compound (1) can be retained at R ^1f and R ^2f in the fluorinated carbonyl compound (5). Further, when the fluorine-containing carbonyl compound (5) as a raw material for a fluorine-containing secondary alcohols, compounds wherein R ² is a monovalent organic group which can be fluorinated (1) is preferably used.

In the present invention, compound (1) is esterified with compound (2). The bond of the compound (2) is perfluorinated n-valent organic group (Q ^f), Ri compound der the group represented by -COF has n pieces binding was obtained from the decomposition reaction product of an ester bond formula It is a compound represented by (2) . n represents an integer of 2 or more. Q ^f is preferably a perfluorinated n-valent saturated hydrocarbon group or a perfluoro (etheric oxygen atom-containing n-valent saturated hydrocarbon) group. When the group (Q ^f ) is a divalent group (Q ^f2 ), a perfluoroalkylene group or a perfluoro (etheric oxygen atom-containing alkylene) group is particularly preferred. Further, the compound (2) is preferably FCO (CF ₂ ) _k COF (k is an integer of 2 to 8) from the viewpoint of easy availability and high reaction yield.

  When the production method of the present invention is carried out once, the fluorine-containing carbonyl compound (5) can be obtained in an n-fold molar amount relative to the compound (2) stoichiometrically. Further, the compound (2) can be recovered, and the recovered compound (2) can be used any number of times. A method for recovering and using the compound (2) will be described later. Specific examples of the compound (2) include the compound (2-1) when n described later is 2.

  The reaction between the compound (1) and the compound (2) can be carried out under known esterification reaction conditions. The esterification reaction may be performed in the presence of an esterification reaction solvent, but is preferably performed in the absence of the esterification reaction solvent from the viewpoint of volume efficiency. When an esterification reaction solvent is used, dichloromethane, chloroform, triethylamine, or a mixed solvent of triethylamine and tetrahydrofuran is preferable. The amount when the esterification reaction solvent is used is preferably 50 to 500% 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), hydrofluoric acid (HF) is generated. Therefore, alkali metal fluoride (NaF, KF is preferable), trialkylamine or the like is used as a HF scavenger in the reaction system. May be present. The HF scavenger should be used when the compound involved in the reaction is an acid labile compound. In addition, when no HF scavenger is used, it is preferable to carry out the reaction at a reaction temperature at which HF can be vaporized, and to discharge HF out of the reaction system accompanied by a nitrogen stream. The amount of the HF scavenger is preferably about 1 to 10 times mol of the theoretical amount of HF generated.

  The esterification reaction is an esterification reaction between a bifunctional or higher acid fluoride and a monofunctional alcohol. The esterification reaction has a high reaction rate and reaction result when compared with a reaction between a bifunctional or higher alcohol having a high polarity and a monofunctional acid fluoride. Moreover, it is not preferable that alcohol remains in the product after the esterification reaction for the reason described later. From the above, the amount of the compound (1) used for the esterification reaction is n-fold moles relative to the compound (2) (n is the number of groups represented by —COF in the compound (2) (n)). The following is preferable. It is not economical to use the compound (1) in a molar amount exceeding n times, and unreacted compound (1) may remain in the reaction product of the esterification reaction. When the unreacted compound (1) remains in the esterification reaction product, an undesirable reaction may be caused in the fluorination reaction. Therefore, the amount of the compound (1) used for the esterification reaction is preferably set to an amount that does not remain in the esterification reaction product, and the labor for purification of the esterification reaction product can be omitted. Particularly, the amount of the compound (1) is particularly preferably 0.5 n-fold to n-fold mole, particularly preferably 0.9 n-fold to n-fold mole.

  The advantage of the present invention using the compound (2) is exhibited particularly when the molecular weight of the compound (1) is low. Since compound (2) has two or more acyl fluoride groups in its structure, two or more molecules of compound (1) react with compound (2). As a result, compared with the case where the compound (1) is reacted with a compound having one acyl fluoride group, the molecular weight of the compound (3) is increased, so that the vapor pressure is reduced and the liquid phase fluorination reaction is performed. This makes it easier to control the reaction, increases the yield, and is advantageous in terms of volumetric efficiency.

  The lower limit of the esterification reaction temperature is usually preferably −50 ° C., and the upper limit is preferably set at a lower temperature of + 100 ° C. and the boiling point of the esterification solvent. The reaction time of the reaction can be appropriately changed according to the feed rate of the raw material and the amount of the compound that actually reacts. The reaction pressure is preferably normal pressure to 2 MPa (gauge pressure, hereinafter, pressure is described as gauge pressure).

It is essential that the product of the esterification reaction contains at least one compound (3). R ¹ , R ² , Q ^f , and n in the compound (3) have the same meaning as described above. m represents the number of groups (—COOCHR ¹ R ² ) formed by the esterification reaction, and represents an integer of 2 or more and n or less. (Nm) indicates the number of —COF groups remaining without being esterified, and (nm) is 0 when all of the —COF groups of the compound (2) are esterified. This means that there is no -COF group in the compound (3). As the compound (3), a compound in which (nm) is 0, a compound in which n> m is satisfied (that is, two or more of the —COF groups of the compound (2) are esterified, but all are esterified. The ratio of these is not particularly limited.

The esterification reaction product in the present invention refers to all products generated by the esterification reaction, and may include compounds other than the compound (3). For example, as the esterification reaction product, the compound (2) The following compound (3-10) in which only one of two or more —COF groups present therein is esterified is also included. R ¹ , R ² , Q ^f , and n in the compound (3-10) have the same meaning as described above.

_{^{Q f (-COF) n-1}} (-COOCHR 1 R 2) ··· formula (3-10)
Since an increase in the amount of compound (3-10) produced is not an efficient production method, the amount of compound (3) relative to the total amount of the esterification reaction product exceeds 50 mol%. Is more preferable, and it is especially preferable that it is more than 60 mol%.

  The product of the esterification reaction may be purified according to the purpose, or may be used as it is for the next reaction or the like, and is preferably purified from the viewpoint of smoothly performing the fluorination reaction in the next step. In particular, when the esterification reaction product contains the compound (1), it is preferable to remove the compound (1) by purification.

  Examples of the purification method include a distillation method, a method of separating the product after treatment with water and the like, a method of distillation after extraction with an appropriate organic solvent, and silica gel column chromatography.

In the present invention, the esterification reaction product is fluorinated. The fluorination reaction is preferably carried out by a liquid phase fluorination reaction described later. In order to facilitate the liquid phase fluorination reaction, the average fluorine content of the esterification reaction product (particularly the compound (3)) is preferably 20 to 60% by mass, particularly 25 to 55% by mass. It is preferable to be 30 to 55% by mass. In the esterification reaction product, it is preferable to adjust the Q ^f structure and the carbon number of the compound (2) so that the average fluorine content falls within this range. The molecular weight of the esterification reaction product is preferably in the range of 200 to 1100, particularly preferably in the range of 300 to 800. In the esterification reaction product having an average fluorine content in a specific range, the solubility in the liquid phase during the fluorination reaction is greatly improved, and the operability and reaction yield of the liquid phase fluorination reaction are improved. There is an advantage, and the fact that the average fluorine content is in a specific range also has an advantage of being economical. Further, when the molecular weight of the esterification reaction product is a specific molecular weight or more, there is an advantage of avoiding the risk of a decomposition reaction due to the gas phase fluorination reaction, and when the molecular weight is below a specific amount, There is an advantage that it is easy to handle the compound and purify the product.

  The fluorination reaction can be performed by a fluorination method using cobalt fluoride, an electrochemical fluorination method, a method of reacting with fluorine (elemental fluorine), or the like. Among these, the liquid phase fluorination method in which the reaction can be carried out efficiently irrespective of the structure of the substrate and the yield of the fluorination reaction is remarkably high, for example, is reacted with fluorine in the liquid phase. Hereinafter, the fluorination reaction will be described by taking the liquid phase fluorination method as an example.

  The liquid phase in the liquid phase fluorination method may be the reaction substrate itself, but is usually preferably a fluorination reaction solvent that does not participate in the product or reaction. As fluorine, it is preferable to use fluorine gas as it is or fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economical reasons. The amount of fluorine gas in the nitrogen gas is not particularly limited, and it is preferably 10 vol% or more from the viewpoint of efficiency, and particularly preferably 20 vol% or more.

  As the fluorination reaction solvent, a solvent inert to the fluorination reaction is preferable, and a solvent having a high solubility of the esterification reaction product is particularly preferable. In particular, 1% by mass or more of the esterification reaction product is dissolved. It is preferable to use a solvent that can dissolve, particularly 5% by mass or more.

Examples of the fluorination reaction solvent include compound (2), compound (4) described later, fluorine-containing carbonyl compound (5), perfluoroalkanes (trade name: FC-72, etc.), perfluoroethers (trade name: FC). -75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, demnam, etc.), chlorofluorocarbons (trade name: CFC), chlorofluoropolyethers, perfluoroalkylamines (for example, , Perfluorotrialkylamine, etc.), inert fluid (trade name: Florinato) and the like. Among these, it is preferable to use the compound (2) or the fluorine-containing carbonyl compound (5) as a fluorination reaction solvent because there is an advantage that post-treatment is facilitated. The amount of the fluorination reaction solvent is preferably 5 times or more, more preferably 10 to 1 × 10 ⁵ times the mass of the total mass of the esterification reaction product.

  The reaction format 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 in a reactor, stirred, and then reacted while continuously supplying fluorine gas into the fluorination reaction solvent. In addition, there is a method in which a fluorination reaction solvent is charged into a reactor and stirred, and then a fluorine gas and an esterification reaction product are continuously fed into the fluorination reaction solvent at a predetermined molar ratio. Of these, the fluorination reaction is preferably carried out by the latter method from the viewpoint of reaction yield and selectivity. Further, the fluorine gas in the method is preferably diluted with an inert gas such as nitrogen gas.

  The fluorine used in the fluorination reaction is preferably kept so that the amount of fluorine relative to the amount of hydrogen atoms contained in the esterification reaction product is always an excess equivalent from the beginning to the end of the reaction. From the viewpoint of selectivity, it is preferable to keep 1.05 times equivalent or more (that is, 1.05 times mole or more), and it is preferable to keep 2 times or more equivalent (that is, 2 times mole or more). More preferable in terms of rate. In order to make the amount of fluorine excessive even at the start of the reaction, it is preferable that a sufficient amount of fluorine is dissolved in advance in the fluorination reaction solvent used at the beginning of the reaction.

  Further, since the fluorination reaction needs to be carried out without breaking the ester bond in the compound (3), the lower limit of the reaction temperature is preferably the lowest temperature among the boiling points of the esterification reaction product. . In usual cases, the reaction temperature is particularly preferably −50 ° C. to + 100 ° C., and particularly preferably −20 ° C. to + 50 ° C. from the viewpoint of reaction yield, selectivity, and ease of industrial implementation. The reaction pressure of the fluorination reaction is not particularly limited, and it is particularly preferably from normal pressure to 2 MPa from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.

Furthermore, in order to advance the fluorination reaction efficiently, a C—H bond-containing compound is added to the reaction system, the esterification reaction product is retained in the reaction system for a long time, or ultraviolet irradiation is performed. It is preferable to perform such operations. These operations are preferably performed at the later stage of the fluorination reaction. Further, when R ² of the compound (3) is a group other than a hydrogen atom, it is preferable to perform this operation because the hydrogen atom bonded to the carbon atom to which R ² and R ¹ are bonded can be well fluorinated. These operations can efficiently fluorinate the esterification reaction product present in the reaction system, and can drastically improve the reaction rate.

  As the C—H bond-containing compound, an aromatic hydrocarbon is preferable, and benzene, toluene and the like are particularly preferable. The addition amount of the CH bond-containing compound is preferably 0.1 to 10 mol%, particularly 0.1 to 5 mol%, based on the total amount of hydrogen atoms in the esterification reaction product. Is preferred. The C—H bond-containing compound is preferably added to the reaction system in which fluorine is present. When a C—H bond-containing compound is added, the reaction system is preferably pressurized. When pressurizing, it is preferably 0.01 to 5 MPa. Moreover, when performing ultraviolet irradiation, it is preferable to irradiate 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 obtained by perfluorinating compound (3).

  The fluorination reaction product in the present invention includes all products in which the esterification reaction product is fluorinated, and the compound (4) is essential. The composition of the fluorination reaction product is changed depending on the composition of the esterification reaction product. When the esterification reaction product contains two or more compounds, the fluorination reaction product can also be two or more.

Q ^f , n, and m in the compound (4) correspond to the compound (3). When R ^1f of the compound (4) is a perfluorinated monovalent organic group, a perfluoroalkyl group, a perfluorocycloalkyl group, a perfluoroalkoxy group or the like is preferable, and a perfluoroalkyl group is particularly preferable. When R ^2f is a perfluorinated monovalent organic group, a perfluoroalkyl group is preferred. In addition, when R ^1f and R ^2f jointly form a perfluorinated group of the divalent organic group, the perfluorinated group includes a perfluorodivalent saturated hydrocarbon group or a perfluoro (ether A group comprising a perfluoroalkylene group or a group having one or more etheric oxygen atoms inserted between carbon-carbon bonds of the alkylene group perfluorinated. .

When the esterification reaction product includes the compound (3-10), the following compound (4-10) obtained by perfluorination of the compound is also included in the fluorination reaction product. N, ^Qf , ^R2f , ^R1f in a compound (4-10) respond ^| corresponds to a compound (3-10).

_{^{Q f (-COF) n-1}} (-COOCFR 1f R 2f) ·· formula (4-10)
Further, the fluorination reaction product may contain one or more compounds obtained by partially fluorinating the esterification reaction product (hereinafter, these partially fluorinated products are also referred to as hydrogen residue compounds).

  In fluorination in the liquid phase, hydrogen atoms are replaced by fluorine atoms, and HF is by-produced. In order to remove HF, the HF scavenger is allowed to coexist in the reaction system, the HF scavenger and the outlet gas are brought into contact with each other at the reactor gas outlet, or the outlet gas is cooled to condense and recover the HF. preferable. As the HF scavenger, the same ones as described above are used, and NaF is preferable. Moreover, it is preferable to carry out an alkali treatment by introducing HF into an inert gas such as nitrogen gas and guiding it to the outside of the reaction system.

  The amount of the HF scavenger in the reaction system is preferably 1 to 20 times mol, particularly preferably 1 to 5 times mol, based on the total amount of hydrogen atoms present in the esterification reaction product. When placing the HF scavenger at the reactor gas outlet, (a) a cooler (preferably maintained at 10 ° C. to room temperature, especially about 20 ° C.) (b) NaF pellet packed bed, and (c ) It is preferable to install a cooler (preferably maintained at −78 ° C. to + 10 ° C., particularly at −30 ° C. to 0 ° C.) in series in the order of (a)-(b)-(c). Moreover, you may install the liquid return line for returning the condensed liquid to the reactor from the cooler of (c).

  The fluorination reaction product may be used in the next step as it is, or may be purified to have a high purity. Examples of the purification method include a method of distilling the crude product as it is under normal pressure or reduced pressure.

  In the present invention, an ester bond decomposition reaction is further performed in the fluorination reaction product. The ester bond decomposition reaction is a reaction in which an ester bond existing in a compound is cleaved to form a compound (2) and a fluorine-containing carbonyl compound (5), and is a known reaction. The ester bond decomposition reaction is preferably performed by a thermal decomposition reaction or a decomposition reaction performed in the presence of a nucleophile or an electrophile.

  The thermal decomposition reaction can be performed by heating the fluorination reaction product. The reaction mode of the thermal decomposition reaction is preferably selected depending on the boiling point of the fluorination reaction product and its stability.

  For example, when the pyrolysis reaction is performed on a fluorination reaction product having a low boiling point, it is preferable to employ a gas phase pyrolysis method. The gas phase thermal decomposition method is preferably performed by a method in which a decomposition reaction is continuously performed in the gas phase, and the resulting fluorinated carbonyl compound (5) and the compound (2) are condensed from the outlet gas and recovered. .

  The reaction temperature of the gas phase pyrolysis method is preferably 50 to 350 ° C, particularly preferably 50 to 300 ° C, and particularly preferably 150 to 250 ° C. In the gas phase pyrolysis method, a metal salt catalyst may be used, and an inert gas that does not directly participate in the reaction may coexist in the reaction system. Examples of the inert gas include nitrogen gas and carbon dioxide gas. The addition amount of the inert gas is preferably about 0.01 to 50 vol% with respect to the total amount of the fluorination reaction product. When there is too much addition amount of an inert gas, the recovery amount of a product may reduce.

  On the other hand, when the boiling point of the fluorination reaction product is high, it is preferable to employ a liquid phase pyrolysis method in which the liquid is heated in the reactor. The reaction pressure in the liquid phase pyrolysis method is not limited. The product of the decomposition reaction may be extracted from the reactor at a time. In addition, taking advantage of the fact that the product of the ester bond decomposition reaction usually has a lower boiling point than the fluorination reaction product, a fluorination reaction is carried out using a reactor equipped with a distillation column, and the product is distilled. The reaction may be carried out while extracting. The reaction temperature of the liquid phase pyrolysis method is preferably 50 to 300 ° C, particularly preferably 100 to 250 ° C.

  The liquid-phase thermal decomposition method may be performed without a solvent or in the presence of a decomposition reaction solvent, and is preferably performed without a solvent. When a decomposition reaction solvent is used, it is preferable to use a solvent that is inert to the reaction and that is compatible with the fluorination reaction product. Moreover, it is preferable to use a decomposition reaction solvent that is easily separated from the product. As specific examples of the decomposition reaction solvent, inert solvents such as perfluorotrialkylamine and perfluoronaphthalene, and chlorotrifluoroethylene oligomers (for example, trade name: CFC) that are high boiling chlorofluorocarbons are preferable. Moreover, it is preferable that the quantity of a decomposition reaction solvent is 0.10 times-10 times mass with respect to a fluorination reaction product.

  When the ester bond is decomposed by reacting with a nucleophile or electrophile in the liquid phase, it may be solvent-free or in the presence of a decomposition reaction solvent. Is preferred. It is particularly preferable to carry out the reaction without a solvent because the fluorination reaction product itself acts as a solvent, and the labor for separating the solvent from the reaction product can be omitted. The method using a nucleophile or electrophile is also preferably carried out while distillation in a reaction apparatus equipped with a distillation column.

As the nucleophile, F ⁻ is preferable, and F ⁻ derived from an alkali metal fluoride is particularly preferable. As the alkali metal fluoride, NaF, NaHF ₂ , KF, and CsF are preferable, and NaF is particularly preferable in terms of economy, and KF is particularly preferable in terms of reaction activity. Further, the initial nucleophile amount in the reaction may be a catalytic amount or an excess amount. The amount of the nucleophilic agent such as F ⁻ is preferably 1 to 500 mol%, particularly preferably 1 to 100 mol%, particularly preferably 5 to 50 mol% based on the fluorination reaction product. The lower limit of the reaction temperature is preferably -30 ° C, and the upper limit is particularly preferably -20 ° C to 250 ° C.

  The decomposition reaction product in the present invention includes all products generated by the decomposition reaction of the ester bond, and the compound (2) and the fluorine-containing carbonyl compound (5) are essential. Since the compound produced by the decomposition reaction of the ester bond of the compound (4-10) is also the compound (2) and the fluorinated carbonyl compound (5), the compound (4-10) is an ester bond together with the compound (4). It is preferable to carry out the decomposition reaction. Examples of the decomposition reaction product other than the compound (2) and the fluorine-containing carbonyl compound (5) include compounds obtained by decomposing an ester bond of a hydrogen residue compound described later.

The fluorine-containing carbonyl compound (5) in the present invention is R ^2f —COF or R ^1f —CO—R ^2f . In the present invention, it is preferable to obtain the fluorinated carbonyl compound (5) by separating the compound (2) and the fluorinated carbonyl compound (5) from the decomposition reaction product. The separation method is preferably a distillation method.

  The fluorine-containing carbonyl compound (5) obtained by the method of the present invention is a useful compound that can be used for various uses as it is or by converting it to another compound. Examples of conversion to other compounds include monomer examples for fluororesins by introducing unsaturated bonds at the ends by thermal decomposition reaction, examples of producing fluorinated alcohols by converting the ends to hydroxyl groups by reduction reaction, etc. Can be mentioned.

  Furthermore, it is advantageous in terms of production and is preferred that a part or all of the compound (2) contained in the decomposition reaction product is reused as the compound (2) to be reacted with the compound (1). The method for recovering the compound (2) from the decomposition reaction product and reusing it is a method for continuously producing the fluorinated carbonyl compound (5) by adding the compound (1) to the reaction system. When this continuous production method is carried out for 1 cycle, stoichiometrically, 1 mol to n mol of the fluorinated carbonyl compound (5) and 1 mol of the compound (2) can be produced.

Furthermore, the production method of the present invention is preferably carried out in a compound in which n is 2, because it is easy to control the reaction and procure the compound (2), and in particular, n is 2 and Q ^f is perfluoro. It is preferable to carry out in the compound (2-1) which is a converted divalent organic group (Q ^f2 ). That is, the compound (1) and the compound (2-1) are esterified to obtain an esterification reaction product containing at least one compound (3-1), and the esterification reaction product is fluorinated. By perfluorination by reaction, a fluorination reaction product containing at least one compound (4-1) is obtained, and by performing ester bond decomposition reaction in the fluorination reaction product, compound (4- A method for producing a fluorinated carbonyl compound, wherein a decomposition reaction product containing 1) and the compound (2-1) is obtained and a fluorinated carbonyl compound (5) is obtained from the decomposition reaction product, is preferred. However, R ¹ , R ² , R ^1f , R ^2f , and Q ^f2 in the following formula have the same meaning as described above.

FCOQ ^f2 COF .. Formula (2-1),
R ¹ CHR ² OCOQ ^f2 COOCHR ¹ R ² .. Formula (3-1),
R ^1f CFR ^2f OCOQ ^f2 COOCFR ^1f R ^2f ... Formula (4-1).
Specific examples of the compound (1) in the present invention include the following compounds.
(CH ₃ ) ₂ CHOH ,
CyOH (Cy represents a cycloalkyl group; the same shall apply hereinafter).

Specific examples of the compound (2) include the following compounds.
FCOCF ₂ CF ₂ COF,
FCOCF ₂ CF ₂ CF ₂ CF ₂ COF,
FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₂ COF,
FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ COF,
FCOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ COF,
FCOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ COF.

Specific examples of the compound (3) include the following compounds.
(CH ₃ ) ₂ CHOCOCF ₂ CF ₂ CF ₂ CF ₂ COOCH (CH ₃ ) ₂ ,
CyOCOCF ₂ CF ₂ CF ₂ CF ₂ COOCy .

Specific examples of the compound (3-10) include the following compounds.
(CH ₃ ) ₂ CHOCOCF ₂ CF ₂ CF ₂ CF ₂ COF ,
CyOCOCF ₂ CF ₂ CF ₂ CF ₂ COF .

Specific examples of the compound (4) include the following compounds.
(CF ₃ ) ₂ CFOCO (CF ₂ ) ₄ COOCF (CF ₃ ) ₂ ,
Cy ^f OCOCF ₂ CF ₂ CF ₂ CF ₂ COOCy ^f (where Cy ^f represents a perfluorocycloalkyl group; the same shall apply hereinafter).

Specific examples of the compound (4-10) include the following compounds.
(CF ₃ ) ₂ CFOCO (CF ₂ ) ₄ COF ,
Cy ^f OCOCF ₂ CF ₂ CF ₂ CF ₂ COF .

Specific examples of the fluorine-containing carbonyl compound (5) include the following compounds and perfluorocyclohexanone .
_{(CF 3) 2 CO (5-2} ).

Furthermore, as a production method of the present invention, n is 2, R ¹ and R ² are —CH ₃ , R ^1f and R ¹ from the viewpoint of the usefulness of the product and superiority to the conventional production method. compound when ^2f and is -CF ₃ production how the (5-2) are preferred.

  Furthermore, as a preferable aspect of the manufacturing method of a compound (5-2), the following manufacturing method is mentioned. Here, k represents an integer of 2 to 8, and k is preferably an integer of 4 to 6 in terms of availability. That is, the compound (1-2) is esterified with the compound (2-2) to obtain an esterification reaction product containing the compound (3-2), and the esterification containing the compound (3-2) is obtained. The reaction product is perfluorinated by a fluorination reaction to obtain a fluorination reaction product containing the compound (4-2), and the ester bond is decomposed in the fluorination reaction, whereby the compound (5-2) and the compound are obtained. It is preferable to obtain a decomposition reaction product containing (2-2) and obtain a compound (5-2) from the decomposition reaction product. Furthermore, compound (2-2) is obtained from the decomposition reaction product, and this is used as compound (2-2) to be reacted with compound (1-2). ) Is preferably produced continuously.

(CH ₃ ) ₂ CHOH (1-2),
FCO (CF ₂ ) _k COF (2-2),
(CH ₃ ) ₂ CHOCO (CF ₂ ) _k COOCH (CH ₃ ) ₂ (3-2),
(CF ₃ ) ₂ CFOCO (CF ₂ ) _k COOCF (CF ₃ ) ₂ (4-2),
CF ₃ COCF ₃ (5-2).

Compound (5-2) (that is, hexafluoroacetone; hereinafter referred to as HFA ) is a known compound useful as various intermediates per se, but is reduced by a known method (CF ₃ ) ₂ CHOH (1,1,1,3,3,3-hexafluoro-2-propanol, hereinafter referred to as HFIP) and (CF ₃ ) ₂ CFCHOH can also be produced. HFIP is also a known compound useful as a solvent and various intermediates. The concept of this manufacturing method can be shown by the following formula.

  The production method of the present invention can be a more efficient production method by a method such as recycling the product. An example of an efficient manufacturing method will be described below with a specific example. In addition, the group which does not write a definition below shows the same meaning as the above.

(I) A method of recycling the compound (2); a method of recovering the compound (2) produced in the ester bond decomposition reaction product and using it as the compound (2) to be esterified with the compound (1), It is. This method is an economical and efficient method in that the compound (2) can be used many times. As a specific example, in the above-mentioned HFA production method, there is an example of a method in which FCO (CF ₂ ) ₄ COF produced by the ester bond decomposition reaction is recovered and esterified with (CH ₃ ) ₂ CHOH.

  (II) When a partially fluorinated product is contained in the fluorination reaction product, a method of recycling the partially fluorinated product into the fluorination reaction system; in the product of the fluorination reaction of compound (3), In some cases, a partially fluorinated compound (3) may be contained. Examples of the partially fluorinated product include a hydrogen remaining compound (that is, a compound in which the compound (3) is fluorinated in a ratio in which at least one hydrogen atom remains). The partially fluorinated product can be converted into the compound (4) by returning it to the reaction system of the fluorination reaction and performing another fluorination reaction.

For example, when the compound (1) is (CH ₃ ) ₂ CHOH and the compound (2) is FCO (CF ₂ ) _k COF, (CH ₃ ) ₂ CHOCO (CF ₂ ) _k COOCH (CH ₃ ) _{The following} compounds as the partially fluorinated product of ₂ can be included in the fluorination reaction product.
(CF ₃ ) ₂ CHOCO (CF ₂ ) _k COOCH (CF ₃ ) ₂ ,
(CF ₃ ) ₂ CHOCO (CF ₂ ) _k COOCF (CF ₃ ) ₂ ,
_{(CF 2 H) 2 CHOCO (} CF 2) k COOCH (CHF 2) 2.

In the fluorination reaction product, the following compound as a partial fluorination product of (CH ₃ ) ₂ CHOCO (CF ₂ ) _k COF may also be included in the fluorination reaction product.
(CF ₃ ) ₂ CHOCO (CF ₂ ) _k COF,
(CF ₂ H) ₂ CHOCO (CF ₂ ) _k COF.

  These partially fluorinated products can be converted into fully fluorinated products by recycling them into the fluorination reaction system. The concept of the method can be shown by the following formula.

  (III) A method in which an ester bond is decomposed while containing a partially fluorinated product, and the fluorinated carbonyl compound (5) is separated from the reaction product and then recycled into the reaction system of the esterification reaction;

  Among the partially fluorinated compounds, a compound having a -CFOCO- moiety is decomposed by an ester bond decomposition reaction, but the moiety of a compound having a -CHOCO- moiety is not decomposed. Whether the ester bond is decomposed or not, the partially fluorinated product is present in the ester bond decomposition reaction system, and the fluorine-containing carbonyl compound (5) is separated from the product and then recycled into the reaction system of the esterification reaction. Thus, the partially fluorinated product can be converted into the compound (4).

As a specific example of the method, when (CF ₃ ) ₂ CHOCO (CF ₂ ) _k COOCF (CF ₃ ) ₂ is generated as a partially fluorinated product, a decomposition reaction of an ester bond is performed to (CF ₃ ) ₂ CHOCO. After obtaining (CF ₂ ) _k COF and (CF ₃ ) ₂ C═O and separating (CF ₃ ) ₂ C═O, (CF ₃ ) ₂ CHOCO (CF ₂ ) _k COF is converted to FCO (CF ₂ ) a method of reacting with _k COF and _{(CH 3)} 2 CHOH, and the like. The concept of the reaction can be shown by the following formula.

In addition, (CF ₃ ) ₂ CHOCO (CF ₂ ) _k COF as a partially fluorinated product
When an undecomposable compound is produced, it may be separated and recycled into the fluorination reaction system according to the method described in (2), or the ester bond decomposition reaction without separation. Next, after the decomposition reaction of the ester bond, (CF ₃ ) ₂ CHOCO (CF ₂ ) _k COF is recovered together with FCO (CF ₂ ) _k COF, and (CH ₃ ) ₂ CHOH and You may use for esterification reaction.

(IV) When fluorinating compound (3), fluorination is carried out in the presence of a compound having a carbon skeleton corresponding to compound (3) and having a lower fluorine content than compound (3). Method;
This method is particularly advantageous when the yield of the fluorination reaction and the ester decomposition reaction is low. This is because when recovering the compound (2) and carrying out the process (1) used for the reaction with the compound (1), in practice, the recovery rate of the compound (2) is usually 100%. It is difficult. That is, there is a problem that the amount of the compound (2) to be reacted with the compound (1) decreases as continuous production is repeated.

In order to solve this problem, in the fluorination step, the compound (3) and a compound having a lower fluorine content than the compound (3) (preferably the following compound (3H)) are present in the fluorination step. Preferably it is done. Provided that the symbols in the formula have the same meanings as described above, Q ^H is an n-valent organic radical essentially containing hydrogen atoms, and a group to be perfluorinated with Q ^{f.
Q H (COOCHR 1 R 2)} m (COF) n-m ·· formula (3H)

When the fluorination reaction is performed by a liquid phase fluorination reaction, the compound (3H) is difficult to dissolve in the liquid phase by itself, but the compound (3) having a similar structure coexists so that the solubility in the liquid phase is increased. Has the advantage of improving. In particular, when Q ^H is a group having an ether bond, the solubility of the compound (3) or compound (3H) has the advantage of further improved. The compound (3H) is preferably a compound containing no fluorine from the viewpoint of economy.

The following compound (3H-1) is mentioned as a specific example of a compound (3H) in case a compound (3) is a compound (3-1). However, ^QH2 is a divalent organic group that essentially requires a hydrogen atom, and is a group that is perfluorinated to become ^Qf2 .
R ¹ CHR ² OCOQ ^H2 COOCHR ¹ R ² Formula (3H-1)
Q ^H2 is preferably a divalent organic group having a carbon skeleton corresponding to Q ^f2 and not containing fluorine, and in particular, an alkylene group and a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of the alkylene group. preferable.

Specific examples of the compound (3H-1) include (CH ₃ ) ₂ CHOCO (CH ₂ ) _k COOCH (CH ₃ ) ₂ . The concept of the method for carrying out the continuous reaction in the presence of the compound (3H-1) can be represented by the following formula.

  The amount of the compound (3H) relative to the compound (3) is not particularly limited as long as it is an amount that is not inconvenient in the fluorination reaction. When the fluorination reaction is carried out by a liquid phase fluorination reaction, it is not particularly limited as long as both the compound (3) and the compound (3H) can be sufficiently dissolved in the liquid phase. The amount of the compound (3H) relative to 3) is preferably 0.001 times to 0.2 times mol. The total amount of the compound (3H) and the compound (3) is preferably 5% by weight or less in the fluorinated solvent, and more preferably 0.5% by weight or less.

Compound (3H) may be a commercially available product or a separately synthesized compound that may be present in the system prior to the fluorination step. Alternatively, the following compound (2H) may be present together with compound (2) for the esterification reaction. Good. However, the symbols in the formula have the same meaning as above.
Q ^H (COF) n _... formula (2H)

In general, the esterification reaction between the compound (2H) and the compound (1) can proceed in the same manner as the esterification reaction between the compound (2) and the compound (1). Specific examples of the compound (2H) include the following compound (2H-1). However, X shows a halogen atom or a hydroxyl group.
XCO (CH ₂ ) _k COF Formula (2H-1)

  A specific example in which the reaction is carried out in the presence of the compound (2H) can be represented by the following formula.

  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 in various applications as it is or by introducing it to other applications. For example, various useful fluorine-containing alcohols can be produced by reducing the fluorine-containing carbonyl compound (5).

  The present invention is described in detail below, but the present invention is not limited thereto. In the following, 1,1,2-trichloro-1,2,2-trifluoroethane is referred to as R-113, and the pressure is referred to as gauge pressure. Moreover, gas chromatography is described as GC, and the peak area ratio in GC analysis is defined as the GC analysis value. Moreover, gas chromatography-mass spectrometry is described as GC-MS. NMR peak area indicates ratio.

[Example 1] Production example of (CF ₃ ) ₂ CO [Example 1-1] Esterification reaction of (CH ₃ ) ₂ CHOH and FCO (CF ₂ ) ₄ COF In a ₂ L autoclave made of Hastelloy C (CH ₃ ) ₂ CHOH (600 g) was added. The reactor was cooled, and FCO (CF ₂ ) ₄ COF (1540 g) was slowly introduced so that the internal temperature was maintained at 30 ° C. or lower at normal pressure. At the same time, while sufficiently stirring, nitrogen gas was bubbled, and HF generated by the reaction was driven out of the system. After adding the total amount of FCO (CF ₂ ) ₄ COF, reaction was further performed at 50 ° C. for 5 hours to obtain a product. As a result of GC analysis of the product, (CH ₃ ) ₂ CHOCO (CF ₂ ) ₄ COOCH (CH ₃ ) ₂ was 98.9%, and (CH ₃ ) ₂ CHOCO (CF ₂ ) ₄ COF was 1.1%. Unreacted isopropyl alcohol was not detected. This product was used in the following reaction without purification.
Spectral data of (CH ₃ ) ₂ CHOCO (CF ₂ ) ₄ COOCH (CH ₃ ) ₂ ;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.40 (d, 6H), 5.21 (m, 1H).
¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 119.5, 123.1.

[Example 1-2] Production example of (CF ₃ ) ₂ CFOCO (CF ₂ ) ₄ COOCF (CF ₃ ) ₂ by fluorination reaction To a 500 mL nickel autoclave, R-113 (200 g) was added and stirred. Maintained at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a packed bed of NaF pellets, and a cooler maintained at −10 ° C. were installed in series. In addition, a liquid return line for returning the agglomerated liquid to the autoclave was installed from the cooler maintained at −10 ° C. After nitrogen gas was blown at room temperature for 1 hour, fluorine gas diluted to 20% with nitrogen gas (hereinafter referred to as 20% diluted fluorine gas) was blown at room temperature at a flow rate of 9.76 L / h for 1 hour. Next, a solution obtained by dissolving the product (7 g) obtained in Example 1-1 in R-113 (140 g) was injected over 6.1 hours while blowing 20% diluted fluorine gas at the same flow rate.
Next, the pressure inside the autoclave is increased to 0.15 MPa while blowing 20% diluted fluorine gas at the same flow rate, and the R-113 solution having a benzene concentration of 0.01 g / mL is heated from 25 ° C. to 40 ° C. While injecting 9 mL, the benzene solution inlet of the autoclave was closed and stirring was continued for 0.3 hours.
Next, while maintaining the reactor pressure at 0.15 MPa and the reactor temperature at 40 ° C., 6 mL of the above benzene solution was injected, the benzene solution inlet of the autoclave was closed, and stirring was continued for 0.3 hours. Furthermore, the same operation was repeated 3 times. The total amount of benzene injected was 0.34 g, and the total amount of R-113 injected was 33 mL.
Further, stirring was continued for 1.1 hours while blowing 20% diluted fluorine gas at the same flow rate. Next, the pressure in the reactor was made normal, nitrogen gas was blown in for 2.0 hours, and R-113 was distilled off from the resulting mixture to obtain a product (14.1 g). The product was analyzed by ¹⁹ F-NMR. As a result, it was confirmed that the title compound was contained in a yield of 23.5%. The product contained one or more partially fluorinated products of the product obtained in Example 1-1 (total yield: 67.7%). The fluorination reaction product was directly used in the following reaction.
¹⁹ F-NMR (282.7 MHz, solvent CDCl 3, standard: CFCl 3) δ (ppm): −79.3 (12 F), −118.7 (4 F), −122.5 (4 F), −142.8 ( 2F).

[Example 1-3] Decomposition reaction of ester bond In a 20 ml reaction vessel equipped with a distillation column, a distillation line equipped with a Liebig condenser capable of cooling with cold water, a receiver, and a dry ice strap at the top of the reaction vessel, KF (0.7 g) was charged and heated to 150 ° C. The fluorination reaction product obtained in Example 1-2 was slowly added into the reaction vessel. One hour after the end of the addition, the reaction was terminated when no more gas was generated. The receiver recovered 5.82 g of product. The product contained FCO (CF ₂ ) ₄ COF (GC yield 29%) and FCO (CF ₂ ) ₄ COOCH (CF ₃ ) ₂ (GC yield 60%). Further, the reaction vessel was produced is _{(CF 3) 2 CHOCO (CF} 2) 4 COOCH (CF 3) 2 as main components liquid (4.10 g). In addition, (CF ₃ ) ₂ CO (3.74 g) having a GC purity of 95% was recovered in the trap.

[Example 1-4] Production example of (CF ₃ ) ₂ CFOCO (CF ₂ ) ₄ COOCF (CF ₃ ) ₂ by fluorination reaction CF ₃ (CF ₂ ) ₂ as a fluorination reaction solvent was added to a ₃ L nickel autoclave. OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF (2534 g) was added and stirred and kept at 25 ° C. A cooler maintained at −10 ° C. was installed at the autoclave gas outlet. After blowing nitrogen gas for 3.5 hours, fluorine gas diluted to 50% with nitrogen gas (hereinafter referred to as 50% diluted fluorine gas) was blown for 2 hours at a flow rate of 94.89 L / h. Next, a product containing (CH ₃ ) ₂ CHOCO (CF ₂ ) ₄ COOCH (CH ₃ ) ₂ (943 g) obtained by the method of Example 1-1 while blowing 50% diluted fluorine gas at the same flow rate was obtained. Infused over a period of 0 hours. 1523 g of reaction crude liquid was extracted.
Next, along with a product containing (CH ₃ ) ₂ CHOCO (CF ₂ ) ₄ COOCH (CH ₃ ) ₂ (953 g) obtained by the method of Example 1-1 while blowing 50% diluted fluorine gas at the same flow rate ( CH ₃ ) ₂ CHOCO (CH ₂ ) ₄ COOCH (CH ₃ ) ₂ (30 g) was injected over 21.8 hours. The reaction crude liquid (1612 g) was extracted.
Furthermore, while blowing 50% diluted fluorine gas at the same flow rate, together with a product containing (CH ₃ ) ₂ CHOCO (CF ₂ ) ₄ COOCH (CH ₃ ) ₂ (946 g) obtained by the method of Example 1-1 ( CH ₃ ) ₂ CHOCO (CH ₂ ) ₄ COOCH (CH ₃ ) ₂ (58 g) was injected over 23.2 hours.
Next, it was adjusted for 3 hours while blowing 50% diluted fluorine gas at the same flow rate. Next, nitrogen gas was blown in for 3.0 hours to recover a reaction crude liquid (4212 g).
As a result of analyzing each reaction crude liquid by GC-MS, a product containing the title compound as a main product and containing CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF and the title compound is obtained. It was.

[Example 1-5] (CF ₃ ) ₂ CO Production Example by Decomposition Reaction of Ester Bond A distillation line equipped with a distillation tower and a Liebig condenser capable of cooling with cold water, a receiver, and a dry ice trap were placed in a reaction vessel. A 300 ml reactor at the top was charged with KF (29 g) and heated to 150 ° C. Thereto was added a product containing (CF ₃ ) ₂ CFOCO (CF ₂ ) ₄ COCF (CF ₃ ) ₂ obtained by the method of Example 1-2 at 313 g / hour for 10 hours. One hour after the end of the addition, the reaction was terminated when no more gas was observed in the reaction vessel. In the receiver, FCO (CF ₂ ) ₄ COF having a GC purity of 98% was recovered. In addition, (CF ₃ ) ₂ CO (1505 g) having a GC purity of 95% was recovered in the trap.

[Reference Example _{1] (CF 3) 2 (} CF 3) due to reduction CO 2 CHOH GC purity of 95% obtained in Production Example Example 1-3 _{(CF 3)} 2 CO trap to-trap method (TRAP- (CF ₃ ) ₂ CO having a GC purity of 99.5% was obtained by purification by To-Trap method. A heat-resistant glass tube having an inner diameter of 10 mm is filled with 10 g of a carbon-supporting 3% palladium catalyst, (CF ₃ ) ₂ CO having a GC purity of 99.5% is supplied at 10 g / hour, and hydrogen is supplied to (CF ₃ ) ₂ CO. 2 times mole was fed. The contact time was 10 seconds and the reaction temperature was 150 ° C. (CF ₃ ) ₂ CHOH was obtained by a reduction reaction. The reaction conversion rate was 99.8%, and the selectivity was 99%.

Reference Example 2 Production Example of (CF ₃ ) ₂ CCFOF [Example 2-1] Esterification Reaction of (CH ₃ ) ₂ CHCH ₂ OH and FCO (CF ₂ ) ₃ COF In a ₂ L autoclave made by Hastelloy C (CH ₃ ) ₂ CHCH ₂ OH (700 g) was added and stirred, and FCO (CF ₂ ) ₃ COF (1190 g) was slowly introduced so that the internal temperature was kept at 30 ° C. or lower under a nitrogen seal. After the entire amount of FCO (CF ₂ ) ₃ COF was added, the reaction was further performed at 50 ° C. for 5 hours, and then HF produced as a by-product by nitrogen bubbling was driven out of the system to obtain a product. As a result of GC analysis of the product, (CH ₃ ) ₂ CHCH ₂ OCO (CF ₂ ) ₃ COOCH ₂ CH (CH ₃ ) ₂ was 98.7%, (CH ₃ ) ₂ CHCH ₂ OCO (CF ₂ ) ₃ COF was 1.3% was formed, and unreacted isobutyl alcohol was not detected. This product was used in the following reaction without purification.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.98 (d, 6H), 2.06 (m, 1H), 4.15 (d, 2H).
¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −118.9, −124.3.

[Example 2-2] Production example of (CF ₃ ) ₂ CFCF ₂ OCO (CF ₂ ) ₃ COOCF ₂ CF (CF ₃ ) ₂ by fluorination reaction Prepare the same nickel autoclave as the reactor used in Example 1-2 Then, the conditions were the same as in Example 1-2 except that R-113 (312 g) was added and the flow rate of the 20% diluted fluorine gas was 10.60 L / h. A solution prepared by dissolving the product (5 g) obtained in Example 2-1 in R-113 (95 g) was poured into the autoclave over 5.5 hours.
Next, the pressure inside the autoclave is increased to 0.15 MPa while blowing 20% diluted fluorine gas at the same flow rate, and the R-113 solution having a benzene concentration of 0.01 g / mL is heated from 25 ° C. to 40 ° C. While injecting 9 mL, the benzene solution inlet of the autoclave was closed and stirring was continued for 0.3 hours.
Next, while maintaining the reactor pressure at 0.15 MPa and the reactor temperature at 40 ° C., 6 mL of the above benzene solution was injected, the benzene solution inlet of the autoclave was closed, and stirring was continued for 0.3 hours. Further, the same operation was repeated once. The total amount of benzene injected was 0.22 g, and the total amount of R-113 injected was 22 mL.
Further, stirring was continued for 1.0 hour while blowing 20% diluted fluorine gas at the same flow rate. Next, the pressure in the reactor was set to normal pressure, and nitrogen gas was blown in for 1.0 hour. As a result of analyzing the product by ¹⁹ F-NMR, it was confirmed that the title compound was contained in a yield of 87%.
¹⁹ F-NMR (282.7 MHz, solvent CDCl 3, standard: CFCl 3) δ (ppm): −73.8 (12 F), −80.5 (4 F), −118.6 (4 F), −123.6 ( 2F), -187.9 (2F).

[Example 2-3] Example of production of (CF ₃ ) ₂ CCFOF by ester bond decomposition reaction A distillation column, a distilling line equipped with a Liebig condenser capable of cooling with cold water, a receiver, and a dry ice trap were placed in a reaction vessel. A 20 ml reaction vessel provided at the top was charged with KF (0.7 g) and heated to 150 ° C. 9 g of a liquid from which R113 of the fluorination reaction product obtained in Example 7 was removed was slowly added to the reaction vessel. One hour after the end of the addition, the reaction was terminated when no more gas was generated. The receiver recovered 5.72 g of product. The products include FCO (CF ₂ ) ₃ COF (GC area 55%) and FCO (CF ₂ ) ₃ COOCF ₂ CH (CF ₃ ) ₂ (GC area 15%), (CF ₃ ) ₂ CFCOF (GC area 30 %). Further, (CF ₃ ) ₂ CFCOF (3.12 g) having a GC purity of 97% was recovered in the trap.

[Example 2-4] Esterification reaction of (CH ₃ ) ₂ CHCH ₂ OH and FCO (CF ₂ ) ₂ COF FCO (CF ₂ ) ₃ COF in Example 2-1 into FCO (CF ₂ ) ₂ COF (950 g) The reaction was conducted in the same manner as in Example 2-1, except that the change was made. As a result of GC analysis of the product, (CH ₃ ) ₂ CHCH ₂ OCO (CF ₂ ) ₂ COOCH ₂ CH (CH ₃ ) ₂ was 98.8%, (CH ₃ ) ₂ CHCH ₂ OCO (CF ₂ ) ₂ COF was 1.2% was formed, and unreacted isobutyl alcohol was not detected. This product was used in the following reaction without purification.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.98 (d, 6H), 2.05 (m, 1H), 4.13 (d, 2H).
¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −120.2.

Prepare Example 2-5] by fluorination reaction _{(CF 3) 2 CFCF 2 OCO} (CF 2) the same nickel autoclave reaction apparatus used in _{2 COOCF 2 CF (CF 3)} 2 of Preparation Example 1-2 Then, R-113 (312 g) was added, and the flow rate of the 20% diluted fluorine gas was changed to 12.16 L / h. The conditions were the same as in Example 1-2. A solution prepared by dissolving the product (5 g) obtained in Example 2-4 in R-113 (100 g) was poured into the autoclave over 5.7 hours.
Next, the pressure inside the autoclave is increased to 0.15 MPa while blowing 20% diluted fluorine gas at the same flow rate, and the R-113 solution having a benzene concentration of 0.01 g / mL is heated from 25 ° C. to 40 ° C. While injecting 9 mL, the benzene solution inlet of the autoclave was closed and stirring was continued for 0.3 hours.
Next, while maintaining the reactor pressure at 0.15 MPa and the reactor temperature at 40 ° C., 6 mL of the above benzene solution was injected, the benzene solution inlet of the autoclave was closed, and stirring was continued for 0.3 hours. Further, the same operation was repeated once. The total amount of benzene injected was 0.22 g, and the total amount of R-113 injected was 21 mL.
Further, stirring was continued for 1.0 hour while blowing 20% diluted fluorine gas at the same flow rate. Next, the pressure in the reactor was set to normal pressure, and nitrogen gas was blown in for 1.0 hour. As a result of analyzing the product by ¹⁹ F-NMR, it was confirmed that the title compound was contained in a yield of 90%.
¹⁹ F-NMR (282.7 MHz, solvent CDCl 3, standard: CFCl 3) δ (ppm): −73.8 (12 F), −80.4 (4 F), −119.2 (4 F), −187.8 ( 2F).

[Example 2-6] Production example of (CF ₃ ) ₂ CCFOF by ester bond decomposition reaction The fluorination reaction product in Example 2-3 was changed to the fluorination reaction product obtained in Example 2-5, and the fluorine The reaction was carried out in the same manner except that 8.1 g of the liquid from which R113 of the chemical reaction product was removed was slowly added. 1.02 g of product was recovered in the receiver. The products include FCO (CF ₂ ) ₂ COF (GC area 35%) and FCO (CF ₂ ) ₂ COOCF ₂ CH (CF ₃ ) ₂ (GC area 60%), (CF ₃ ) ₂ CFCOF (GC area 5 %). In addition, 6.94 g was recovered in the trap. The product contained FCO (CF ₂ ) ₂ COF (GC area 30%) and (CF ₃ ) ₂ CCFOF (GC area 70%).

As compound (1) which is a raw material for the production method of the present invention, various compounds having various carbon skeletons are commercially available and can be obtained at low cost. And according to the manufacturing method of this invention, the fluorine-containing compound which has various frame | skeleton can be freely manufactured from this raw material compound with a short process and a high yield.
In addition, by using the method of the present invention, it is possible to easily synthesize a low-molecular fluorine-containing compound or a complex structure fluorine-containing compound that has been difficult to obtain by conventional methods. Further, the production method of the present invention is not limited to the compounds described as specific examples above, and is a versatile method applicable to various compounds. Moreover, the method of this invention can be used as an efficient manufacturing method more industrially advantageous by employ | adopting methods, such as recycling a compound.

Claims (11)

The compound represented by the following formula (1) is the compound represented by the following formula (2) (however, the compound represented by the formula (2) is a compound represented by the formula (2) obtained from the decomposition reaction product of the ester bond. And an esterification reaction product containing one or more of the compounds represented by the following formula (3) to obtain an esterification reaction product, A compound fluorinated in such a ratio that at least one hydrogen atom of the compound represented by the formula (3) remains (however, the compound is obtained from the fluorination reaction product of the compound represented by the following formula (3)). And a compound having at least one -COOCH- moiety) by perfluorination by a fluorination reaction, thereby including at least one compound represented by the following formula (4): A reaction product is obtained and the fluorination reaction product By performing an ester bond decomposition reaction, a decomposition reaction product containing a compound represented by the following formula (5) and a compound represented by the following formula (2) is obtained, and the following formula is obtained from the decomposition reaction product. A method for producing a fluorinated carbonyl compound, comprising obtaining the fluorinated carbonyl compound represented by (5).
R ¹ CHR ² OH .. Formula (1)
Q ^f (COF) _n ·· Formula (2)
^{Q f (COOCHR 1 R 2)} m (COF) n-m ·· formula (3)
_{^{Q f (COOCFR 1f R 2f)}} m (COF) n-m ·· formula (4)
R ^{1 f} COR ^{2 f} .. Formula (5)
However, the symbol in a formula shows the following meanings.
R ^{1, R 2:} R ¹ represents a monovalent organic group which can be off Tsu fluorinated, R ² represents a monovalent organic group which can be fluorinated, R ¹ and R ² can be fluorinated jointly A divalent organic group may be formed.
R ^{1 f} , R ^{2 f} : R ^{1 f} is a monovalent organic group in which R ¹ is perfluorinated. R ^{2 f} is a monovalent organic group in which R ² is perfluorinated. However, when R ¹ and R ² jointly form a divalent organic group that can be fluorinated, R ^{1 f} and R ^{2 f} jointly form a perfluorinated group. To form a group.
Q ^f : a perfluorinated n-valent organic group.
n: An integer of 2 or more.
m: An integer of 2 or more and n or less.   The molecular weight of the compound represented by the formula (1) is 32-200, the average fluorine content of the esterification reaction product is 20-60% by mass, and the molecular weight of the esterification reaction product is 200-1100. The manufacturing method according to claim 1.   The production method according to claim 1 or 2, wherein the fluorination reaction is a liquid phase fluorination reaction. The compound represented by the formula (2) is a compound represented by the formula (2-1), the esterification reaction product essentially comprises the compound represented by the formula (3-1), and a fluorination reaction product. In which the compound represented by formula (4-1) is essential, the decomposition reaction product is essentially the compound represented by formula (5-1) and the compound represented by formula (2-1), and contains fluorine. The production method according to any one of claims 1 to 3, wherein the carbonyl compound is a compound represented by the formula (5-1).
FCOQ ^f2 COF .. Formula (2-1)
R ¹ CHR ² OCOQ ^f2 COOCHR ¹ R ² ..Formula (3-1)
R ^1f CFR ^2f OCOQ ^f2 COOCFR ^1f R ^2f .. Formula (4-1)
R ^1f COR ^2f .. Formula (5-1)
However, the symbols in the formulas have the following meanings.
R ¹ , R ² , R ^1f , R ^2f : same meaning as above.
Q ^f2 : Perfluorinated divalent organic group. The esterification reaction product includes a compound represented by formula (3-1H) together with a compound represented by formula (3-1), and the fluorination reaction product is represented by formula (4-1). The manufacturing method of Claim 4 containing the compound represented by a formula (4-1H) with a compound.
R ¹ CHR ² OCOQ ^f2 COF .. Formula (3-1H)
R ^1f CFR ^2f OCOQ ^f2 COF .. Formula (4-1H)
However, R ¹ , R ² , R ^1f , R ^2f and Q ^f2 in the formula have the same meaning as described above. The production method according to claim 4 or 5, wherein the esterification reaction product contains a compound represented by the following formula (3-2H) to perform a fluorination reaction.
R ¹ CHR ² OCOQ ^H2 COOCHR ¹ R ² Formula (3-2H)
However,
R ¹ , R ² : same meaning as above.
Q ^H2 : a divalent organic group that essentially ^{requires a} hydrogen atom, and a group that is perfluorinated to become Q ^f2 .   The fluorination reaction is performed according to claim 6, wherein the compound represented by the formula (3-1) is present in an amount of more than 0% by mass and 10% by mass or less of the compound represented by the formula (3-2H). Production method. R ¹ and R ² are —CH ₃ , R ^1f and R ^2f are —CF ₃ , Q ^f2 is — (CF ₂ ) _k — (wherein k represents an integer of 2 to 8), and Q ^H2 is - _{(CH 2) k} - in which method according to 請 Motomeko 6 or 7.   The liquid phase in liquid phase fluorination contains the compound represented by Formula (4-1) and / or the compound represented by Formula (5-1) as an essential component. Manufacturing method.   In the esterification reaction of the compound represented by the formula (1) with the compound represented by the formula (2), the amount of the compound represented by the formula (1) is set to 0. 0 of the compound represented by the formula (2). The manufacturing method according to any one of claims 1 to 9, wherein the molar amount is 5 to 1 times.   In the fluorination reaction of the compound represented by the formula (3), it has the same carbon skeleton corresponding to the compound represented by the formula (3) and contains more fluorine than the compound represented by the formula (3). The manufacturing method in any one of Claims 1-10 which perform a fluorination reaction in presence of a compound with little quantity.