JP2003261502A - Method for producing perfluoro(3-methoxypropionyl fluoride) - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce CF<SB>3</SB>O(CF<SB>2</SB>)<SB>2</SB>COF useful as an intermediate for a fluororubber by simple method. <P>SOLUTION: A compound represented by formula (3) Q(COO(CH<SB>2</SB>)<SB>3</SB>OCHX<SP>1</SP>X<SP>2</SP>)<SB>n</SB>; (Q is an n-functional fluorine-containing organic group, n is an integer of ≥1; X<SP>1</SP>and X<SP>2</SP>are each a hydrogen atom or a fluorine atom) is fluorinated in a liquid phase to give a compound represented by formula (4) Q<SP>f</SP>(COO(CF<SB>2</SB>)<SB>3</SB>OCF<SB>3</SB>)<SB>n</SB>; (Q<SP>f</SP>is a perfluorinated n-functional organic group) and decomposition reaction of an ester bond is carried out to give perfluoro(3-methoxypropionyl fluoride) represented by formula (5) CF<SB>3</SB>O(CF<SB>2</SB>)<SB>2</SB>COF. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to perfluoro (3-
Methoxypropionyl fluoride).

[0002]

2. Description of the Related Art CF_ThreeO (CF_Two)_TwoCOF (Perfuru
Oro (3-methoxypropionyl fluoride))
It is a useful compound as an intermediate for raw materials of fluorine rubber. Servant
Come CF _ThreeO (CF_Two)_TwoCOF is CH_ThreeOCH_TwoC
H_TwoManufactured by electrolytic fluorination of COCl
It was

[0003]

However, the above method requires a special electrolyzer which can be operated by pressurization because the boiling point of the product is low, and a branched isomer characteristic of electrolytic fluorination is produced as a by-product. There was a problem to do.

On the other hand, as a method using the liquid phase fluorination method, it is known to react an organic compound having a hydrogen atom bonded to a carbon atom with fluorine in the liquid phase to perfluorinate it (WO90 / 03353). The present inventors intend to apply the method to a method for producing perfluoro (3-methoxypropionyl fluoride), and have CH ₃ O (CH ₂ ) which has a corresponding carbon skeleton and is easily available.
_{A method} of obtaining ₂ COOCH ₃ and subjecting this to liquid phase fluorination and then decomposing the ester bond was investigated. However, in this method, since the boiling point of CH ₃ O (CH ₂ ) ₂ COOCH ₃ is low, the fluorination reaction in the gas phase also occurs during the liquid phase fluorination reaction, and the compound is decomposed, resulting in a significant decrease in yield. Was recognized. To avoid fluorination in the gas phase,
We also examined the method of liquid phase fluorination by pressurizing the reaction system, but fluorination under pressure requires a special device, and it is special to handle highly reactive fluorine under pressure. It has been recognized that fluorination by this method is difficult and difficult to employ as an industrial production method because it requires special consideration and the reaction operation is difficult.

[0005]

The present invention has been made for the purpose of solving the above problems, and produces perfluoro (3-methoxypropionyl fluoride) from an easily available raw material by an economically advantageous method. Provide a way to do. That is, the present invention provides a compound represented by the following formula (4) by subjecting a compound represented by the following formula (3) to liquid phase fluorination and perfluorination to obtain a compound represented by the following formula (4) The method for producing perfluoro (3-methoxypropionylfluoride) represented by the following formula (5) is characterized in that the ester bond decomposition reaction is carried out.

Q (COO (CH ₂ ) ₃ OCHX ¹ X ² ) _n ··· Formula (3), Q ^f (COO (CF ₂ ) ₃ OCF ₃ ) _n ··· Formula (4), CF ₃ O (CF ₂₎ ) ₃ COF ... Formula (5).

However, the symbols in the formulas have the following meanings. Q: n-valent fluorine-containing organic group. Q ^f : Perfluorinated n-valent organic group. n: an integer of 1 or more. X ¹ and X ² : each independently a hydrogen atom or a fluorine atom.

The present invention also provides the following compound useful as an intermediate for the production of perfluoro (3-methoxypropionyl fluoride). Where X ¹ , X ² , and k
Has the same meaning as above.

[0009]   CHX¹X^TwoO (CH_Two)_ThreeOCO (CF_Two)_FourCOO (CH_Two)_ThreeOCHX ¹ X^Two..Formula (3-1a)   CF_ThreeO (CF_Two)_ThreeOCO (CF_Two)_FourCOO (CF_Two)_ThreeOCF_Three··formula (4-1a)   CHX¹X^TwoO (CH_Two)_ThreeOCOCF (CF_Three) [OCF_TwoCF (CF_Three) ]_kOCF_TwoCF_TwoCF_Three..Formula (3-2)   CF_ThreeO (CF_Two)_ThreeOCOCF (CF_Three) [OCF_TwoCF (CF_Three)]_kO CF_TwoCF_TwoCF_Three..Formula (4-2)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The organic group in the present specification means a group in which a carbon atom is essential. Examples of the fluorinated organic group 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 preferable, and among these groups, a carbon group is preferred. A saturated organic group in which the carbon bond is composed of only a single bond is preferable.

Examples of the organic group having a C--H moiety include a saturated hydrocarbon group, an etheric oxygen atom-containing saturated hydrocarbon group,
A partially halogenated saturated hydrocarbon group or a partially halogenated (etheric oxygen atom-containing saturated hydrocarbon) group may be mentioned. Here, the partial halogenation means that the hydrogen atoms are halogenated at a rate 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 these groups having a partial structure). Groups, etc.) and the like, and an alkyl group is preferable.

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

The monovalent group of the saturated hydrocarbon group containing an etheric oxygen atom is an alkyl group in which an etheric oxygen atom is inserted between carbon-carbon bonds, or an etheric oxygen atom between carbon-carbon bonds. And a cycloalkyl group in which is inserted. In addition, the divalent group of the etheric oxygen atom-containing saturated hydrocarbon group may be a carbon-carbon bond or an alkylene group having an etheric oxygen atom inserted at the bond end of the group, or a carbon-carbon bond. Examples thereof include a cycloalkylene group having an etheric oxygen atom inserted therein, and an oxyalkylene group or a group having a polyoxyalkylene moiety is particularly preferable. In a group containing an etheric oxygen atom, the number of etheric oxygen atoms is 1
The number may be one or two or more.

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

As a perfluorinated monovalent organic group
Is a perfluoroalkyl group, and specifically-
CF_TwoCF_Three, -CF_TwoCF_TwoCF_Three, -CF_TwoCF_Two
CF_TwoCF_Three, -CF_TwoCClF_Two, -CF_TwoCBrF
_Two, Or -CF_TwoCFClCF_TwoCl, -CF (CF
_Three)_Two, -CF_TwoCF (CF_Three)_Two, -CF (CF_Three)
CF_TwoCF_Three, -C (CF_Three)_ThreeEtc. Pell
Perfluorinated divalent organic groups include
And a alkylene group, specifically,-(CF_Two) _a−
(A represents an integer of 1 to 8), -CF (CF_Three) CF
_TwoCF_TwoCF_Two-, -CF_TwoCF (CF_Three) CF_TwoCF
_Two-And the like. Also, perfluorinated a
Examples of the telluric oxygen atom-containing group include carbon-carbon of these groups.
Examples include groups in which an etheric oxygen atom is inserted between elementary atoms.
For example, as a monovalent group, -CF (CF_Three)
[OCF_TwoCF (CF_Three)]_bOCF_TwoCF_TwoCF
_Three(B represents an integer of 1 to 5),-(CF_Two)_dOC
F_Three(D represents an integer of 1 to 8).

In the present invention, the compound (3) is fluorinated in the liquid phase. The compound (3) has (—COO (CH ₂ ) ₃ OCHX ^{1 on} the bond of the fluorine-containing n-valent organic group (Q).
X ² ) is a compound in which n groups are bonded. n represents an integer of 1 or more, and n is 1 because of the availability of the compound.
Alternatively, it is preferably 2. The n-valent fluorine-containing organic group (Q) may be a partially fluorinated organic group or a perfluorinated organic group, and may be a fluorine-containing n-valent saturated hydrocarbon group or a fluorine-containing (ether-containing oxygen group). Atom-containing n-valent saturated hydrocarbon) groups are preferred. Further, the n-valent fluorine-containing organic group (Q) is preferably a perfluorinated group, and when it is a monovalent group, a perfluoroalkyl group or a perfluoro (etheric oxygen atom-containing alkyl) group is preferable, When it is a divalent group, a perfluoroalkylene group and a perfluoro (etheric oxygen atom-containing alkylene) group are preferable.

Further, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom. The -CHX ¹ X ² _moiety, -CH 3, CHF _2, or CH ₂ F may be mentioned, -CH ₃ from the viewpoint of ready availability of the compound ^{(i.e., X 1,} X ² is a hydrogen atom. ) Is preferred.

The compound (3) in the present invention includes n
Compounds in which is 1 or 2 are preferred. The compound in which n is 1 is advantageous in that the compound is easily available and can be continuously produced as described later, and the compound (3) in which n is 2 or more has a large molecular weight of the compound (3). Further, the vapor pressure becomes small, the reaction of the liquid phase fluorination reaction becomes easy to control, the yield becomes high, and it is also advantageous in terms of volume efficiency.

In the present invention, the compound represented by the compound (3) is fluorinated in the liquid phase. In order for the liquid phase fluorination reaction to proceed smoothly, the fluorine content of the compound (3) should be 2
It is preferably from 0 to 60% by mass, and particularly preferably from 25 to 55% by mass. The molecular weight of the compound (3) is preferably in the range of 200 to 1100, particularly 3
It is preferably in the range of 00 to 800. The compound (3) having a fluorine content in a specific range has the advantage that the solubility in the liquid phase during the fluorination reaction is markedly improved, and the operability of the liquid phase fluorination reaction and the reaction yield are improved. There is also an advantage that the fluorine content is in a specific range, which is excellent in economic efficiency. Further, when the molecular weight of the compound (3) is not less than the specific molecular weight, there is an advantage that the risk of causing a decomposition reaction due to the gas phase fluorination reaction can be avoided. When the molecular weight is not more than the specific amount, the compound Has the advantage that it is easy to handle and to purify the product.

The compound (3) in the present invention is preferably prepared by a method of esterifying the compound (1) with the compound (2) to obtain the compound (3). However, Q, n, X ¹ and X ² have the same meanings as described above.

CHX ¹ X ² O (CH ₂ ) ₃ OH .. Formula (1), Q (COF) _n .. Formula (2).

The compound (1) is a known compound and can be produced by a known method. The esterification reaction between the compound (1) and the compound (2) can be carried out under known esterification reaction conditions. The lower limit of the reaction temperature is usually -50.
C. is preferred, and the upper limit is preferably + 100.degree. Further, the reaction time of the reaction can be appropriately changed depending on 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; hereinafter, the pressure is described as gauge pressure). Since hydrofluoric acid (HF) is generated in the esterification reaction, an alkali metal fluoride (NaF, KF or the like is preferable), a trialkylamine or the like may be present in the reaction system as an HF scavenger. The amount of the HF scavenger is preferably about 0.1 to 10 times the molar amount of the generated HF. When the HF scavenger is not used, it is preferable to carry out the reaction at a reaction temperature at which HF can be vaporized, to cause HF to be entrained in the nitrogen stream and to be discharged out of the reaction system.

The amount of the compound (1) is not more than n times the molar amount of the compound (2) (n corresponds to the number (n) of the groups represented by —COF in the compound (2)). Preferably. By adjusting the amount of the compound (1) to n times or less, unreacted compound (1) remains in the reaction product of the esterification reaction, and the compound (1) is not preferable in the next fluorination reaction. You can avoid problems that cause reactions, and
The labor of purification of the compound (3) can be omitted. In particular, the amount of the compound (1) is particularly preferably 0.5n times to n times the molar amount of the compound (2), and particularly preferably 0.9n times to the n times molar amount.

When n is 2 or more, the following compound (3-A) in which an unreacted --COF group remains in the esterification reaction
May be present in the reaction product. This compound (3-A) may be subjected to the next fluorination reaction while remaining in the esterification reaction product. However, n, Q, X in the following formula
¹ and X ² have the same meanings as described above, and m is 1 or more and n.
Indicates an integer less than. When n is 2, m is 1. _{Q (COO (CH 2) 3} OCHX 1 X 2) nm (COF) m ·· formula (3-A).

From the viewpoint of smoothly carrying out the fluorination reaction, the product of the esterification reaction is preferably purified. Particularly when the product of the esterification reaction 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 in which the product is treated with water or the like and then separated, a method in which the product is extracted with an appropriate organic solvent and then distilled, a silica gel column chromatography and the like.

Since HF is generated in the esterification reaction, an HF scavenger may be present, but in the absence of the HF scavenger, HF is entrained in a nitrogen stream and discharged out of the reaction system. It is preferable because the crude liquid can be used as it is in the next fluorination step. When the HF scavenger is used, the amount thereof is preferably 1n to 10n times mol based on the compound (1).

The following compounds may be mentioned as specific examples of the compound (3). However, Q ^2f has a carbon number of 1 to which an etheric oxygen atom may be inserted between carbon-carbon bonds.
18 represents a perfluoroalkylene group, and k represents an integer of 0 to 5.

CHX ¹ X ² O (CH ₂ ) ₃ OCOQ ^2f COO (CH ₂ ) ₃ OCHX ¹ X ² ··· Formula (3-1), CHX ¹ X ² O (CH ₂ ) ₃ OCOCF (CF ₃ ) [ OCF ₂ CF (CF ₃ )] _k OCF ₂ CF ₂ CF ₃ ... Formula (3-2).

As a specific example of Q ^2f ,-(CF ₂ ) _j
-(J represents an integer of 1 to 18),-(CF ₂ CF _{2
O) p CF (CF 3)} - (p is an integer of 1-9), and the like.

In the present invention, the liquid phase fluorination reaction of the compound (3) is carried out. To fluorinate compound (3),
Although a fluorination method using cobalt fluoride, an electrochemical fluorination method, or a liquid phase fluorination method can be adopted, since the yield of the fluorination reaction is remarkably high, in the present invention,
Fluorination is performed by a liquid-phase fluorination method of reacting with fluorine in a liquid phase.

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 the fluorine, it is preferable to use the fluorine gas as it is or the 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 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 it is particularly preferable to use a solvent having a high solubility of the compound (3). Particularly, the compound (3) is dissolved at 1% by mass or more. Possible solvents, especially 5% by weight
It is preferable to use a solvent that can dissolve the above.

Examples of the fluorination reaction solvent include the compound (2F), the compound (4) described later, and perfluoro (3-methoxypropionylfluoride) which is the object compound of the present invention, as well as a solvent for liquid phase fluorination. A known solvent used as is. Among them, as the fluorination reaction solvent, the compound (2F) or perfluoro (3-methoxypropionyl fluoride) (provided that the compound (2
When F) and perfluoro (3-methoxypropionyl fluoride) are compounds having the same structure, any of them may be used. Is preferred as a fluorination reaction solvent because it has the advantage of facilitating post-treatment. The amount of the fluorination reaction solvent is based on the total mass of the compound (3).
5 times or more mass is preferable, and in particular, 1 × 10 ¹ to 1 × 10 ⁵
Double mass is preferred.

The reaction system of the fluorination reaction may be a batch system or a continuous system. For example, a reaction vessel is charged with the fluorination reaction solvent and the compound (3), stirred,
Next, there may be mentioned a method of reacting while supplying fluorine gas continuously into the fluorination reaction solvent. Further, there may be mentioned a method in which a fluorination reaction solvent is charged into a reactor and stirred, and then fluorine gas and the compound (3) are continuously fed into the fluorination reaction solvent at a predetermined molar ratio. this house,
The fluorination reaction is preferably carried out by the latter method from the viewpoint of reaction yield and selectivity. The fluorine gas used in the method is preferably diluted with an inert gas such as nitrogen gas before use.

Fluorine used in the fluorination reaction is such that the amount of fluorine relative to the amount of hydrogen atoms contained in the compound (3) is
It is preferable to always maintain an excess equivalent amount from the beginning to the end of the reaction.
From the viewpoint of selectivity, it is preferable to keep it at 5 times equivalent or more (that is, 1.05 times mol or more), and it is preferable to keep it at 2 times equivalent or more (that is, 2 times mol or more). It is more preferable from the point of view. Further, in order to make the amount of fluorine excessive even at the start of the reaction, it is preferable to dissolve sufficient amount of fluorine in the fluorination reaction solvent used at the beginning of the reaction in advance.

Further, the liquid phase fluorination reaction is carried out by the compound (3)
Since it is necessary to carry out without cleaving the ester bond therein, it is preferable that the lower limit of the reaction temperature is −60 ° C. and the lowest boiling point of the compound (3).
In the usual case, the reaction temperature is −50 ° C. to + 100 ° C. from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.
Is particularly preferable, and −20 ° C. to + 50 ° C. is particularly preferable. The reaction pressure of the fluorination reaction is not particularly limited, and may be normal pressure to
The pressure of 2 MPa is particularly preferable from the viewpoint of reaction yield, selectivity, and industrial ease of implementation.

Further, in order to allow the fluorination reaction to proceed efficiently, C--H such as benzene or toluene is added to the reaction system.
It is preferable to carry out operations such as adding a bond-containing compound, allowing the compound (3) to stay in the reaction system for a long time, or irradiating with ultraviolet light. These operations are preferably performed in the latter stage of the fluorination reaction.

In the fluorination in the liquid phase, hydrogen atoms are replaced by fluorine atoms to produce HF as a by-product. For the purpose of removing this HF, an HF scavenger (NaF is preferable) is made to coexist in the reaction system, the HF scavenger is brought into contact with the outlet gas at the reactor gas outlet, or the outlet gas is cooled to condense the HF. It is preferable to collect and recover. In addition, HF may be entrained in an inert gas such as nitrogen gas and led to the outside of the reaction system for alkali treatment. When using the HF scavenger, the amount is
1-2 with respect to the total amount of hydrogen atoms present in compound (3)
A 0-fold molar amount is preferable, and a 1- to 5-fold molar amount is particularly preferable.

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

In the fluorination reaction, compound (3) is perfluorinated to produce compound (4). In compound (4), n corresponds to compound (3). Q
^f is a perfluorinated n-valent organic group, and when Q is a fluorinated group, it is a perfluorinated group, and Q is a non-fluorinated group (for example,
When it is a perfluoro n-valent organic group),
It is the same group as Q.

In the present invention, the ester bond decomposition reaction is further carried out in compound (4). The decomposition reaction of the ester bond is a known reaction. The reaction is a reaction in which the ester bond existing in the compound is cleaved to produce perfluoro (3-methoxypropionyl fluoride).

The decomposition reaction of the ester bond is a thermal decomposition reaction,
Alternatively, the decomposition reaction is preferably performed in the presence of a nucleophile or an electrophile. The thermal decomposition reaction is preferably carried out by a gas phase reaction or a liquid phase reaction.

For example, the thermal decomposition reaction of the compound (4) having a low boiling point is preferably carried out by a gas phase thermal decomposition method. The gas-phase thermal decomposition method is a perfluoro (3-methoxypropionyl fluoride) produced by continuously performing decomposition reaction in the gas phase.
Is preferably condensed from the outlet gas and recovered. The reaction temperature in the gas phase pyrolysis method is 50 to 35.
0 degreeC is preferable, 50-300 degreeC is especially preferable, and 100-250 degreeC is especially preferable. In the gas-phase thermal decomposition 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. If the addition amount of the inert gas is too large, the recovery amount of the product may be reduced.

The decomposition reaction of the ester bond of the compound (4) having a high boiling point is preferably carried out by the liquid phase thermal decomposition method. The liquid phase decomposition method is preferably carried out by heating the liquid compound (4). The products of the decomposition reaction may be withdrawn from the reactor at once. Further, since perfluoro (3-methoxypropionyl fluoride) usually has a lower boiling point than that of the compound (4), a reaction is carried out using a reactor equipped with a distillation column, and the product is distilled. You may go out while pulling out. The reaction temperature of the liquid phase thermal decomposition method is preferably 50 to 300 ° C, particularly 100 to 250 ° C.
Is preferred. The reaction pressure in the liquid phase pyrolysis method is not limited.

The liquid phase thermal decomposition method may be carried out without solvent or in the presence of a decomposition reaction solvent, and is preferably carried out without solvent. When the decomposition reaction solvent is used, it is preferable to use the solvent in an amount of 0.1 to 10 times the mass of the compound (4).

When the decomposition reaction of the ester bond is carried out by reacting with a nucleophile or an electrophile in a liquid phase,
It may be solventless or in the presence of a decomposition reaction solvent, and is preferably carried out without solvent. Performing the reaction without a solvent means that the fluorination reaction product itself also acts as a solvent,
It is particularly preferable because the trouble of separating the solvent from the reaction product can be omitted. The method using a nucleophile or an electrophile is also
It is preferable to carry out the distillation while using a reactor equipped with a distillation column.

As the nucleophile, F ⁻ is preferable, and F ⁻ derived from an alkali metal fluoride is particularly preferable. Alkali metal fluorides include NaF, NaHF ₂ , KF and C
sF is preferable, NaF is preferable from the viewpoint of economy, and KF is particularly preferable from the viewpoint of reaction activity. The amount of the nucleophile at the beginning of the reaction may be a catalytic amount or an excess amount. F
^- The amount of the nucleophilic agent such as 1 to 5 with respect to the fluorination reaction product
00 mol% is preferable, 1 to 100 mol% is particularly preferable, and 5 to 50 mol% is particularly preferable. The lower limit of the reaction temperature is preferably -30 ° C, and the upper limit is preferably -20 ° C to 250 ° C.

In the decomposition reaction of the ester bond of compound (4), perfluoro (3-methoxypropionyl fluoride) and compound (2F) are produced. In the present invention,
It is preferably obtained by separating perfluoro (3-methoxypropionyl fluoride) and compound (2F) from the decomposition reaction product. As a separation method, a distillation method is preferable.

Perfluoro (3 obtained by the method of the present invention
-Methoxypropionyl fluoride) is a compound useful as an intermediate for fluororubber raw materials. For example, perfluoro (3-methoxypropionyl fluoride) is
After reacting with hexafluoropropylene oxide,
Introducing an unsaturated bond at the molecular end by a thermal decomposition reaction to produce CF ₃ O.
It can be led to CF ₂ CF ₂ CF ₂ OCF = CF ₂ .

Further, a part or all of the compound (2F) contained in the decomposition reaction product of the ester bond can be reused in the production of the compound (3) described below to obtain a continuous production method of the compound (5). Can be implemented.

Preferred embodiments of the production method of the present invention include the following embodiments. [Aspect 1] Compound (3)
Is the compound (3-1), and the compound (4) is the compound (4
-1) The manufacturing method which is it. However, Q ^2f represents a C 1-18 perfluoroalkylene group in which an etheric oxygen atom may be inserted between carbon-carbon bonds, and X ¹ and X ² have the same meanings as described above. _{^{CHX 1 X 2 O (CH 2}} ) 3 OCOQ 2f COO (CH 2) 3 OCHX 1 X 2 ·· formula ^{_{(3-1), CF 3 O (}} CF 2) 3 OCOQ 2f COO (CF 2) 3 OCF 3 · -Formula (4-1).

[Aspect 2] Compound (3) is compound (3-
2) and the compound (4) is the compound (4-2). Here, k represents an integer of 0 to 5, ^{X 1} and ^{X 2} are as defined above. _{^{CHX 1 X 2 O (CH 2}} ) 3 OCOCF (CF 3) [OCF 2 CF (CF 3)] k OCF 2 CF 2 CF 3 ·· formula _{(3-2), CF 3 O (} CF 2) 3 OCOCF ( _{CF 3) [OCF 2 CF (} CF 3)] k O CF 2 CF 2 CF 3 ·· formula (4-2).

[Aspect 3] The compound (3) is the following compound (3
In the case of -3), the decomposition reaction product of the ester bond is essentially only perfluoro (3-methoxypropionylfluoride) of the present invention, and thus the target is obtained without performing a special separation operation. It is particularly preferable because a compound is obtained. That is, the compound (3) is the compound (3-3)
In the case where the compound (4) is the compound (4-3), perfluoro (3-methoxypropionyl fluoride) can be obtained without substantially separating the ester bond decomposition reaction product. . ^{_{CHX 1 X 2 O (CH 2}} ) 3 OCO (CF 2) 2 OCF 3 ·· formula _{(3-3), CF 3 O (} CF 2) 3 OCO (CF 2) 2 OCF 3 ·· formula (4-3 ).

[Aspect 4] Further, the compound (2F) [Q produced in the decomposition reaction of the ester bond in the present invention is used.
^f (COF) _n ] is a compound that can be used for the preparation of compound (3). That is, as described in the method for preparing the compound (3), a part or all of the compound (2) produced by the decomposition reaction of the ester bond is used as the compound (2F) for reacting with the compound (1) to give a perfluoro compound. A continuous production method of (3-methoxypropionyl fluoride) can be carried out.

The following examples can be given as specific examples of the compound used in the above-mentioned production method of the present invention.

Examples of compound (2) in which n is 1; Cy ^f COF (wherein Cy ^f represents a perfluorocyclohexyl group), CF ₂ ClCFClCF ₂ CO
_{F, (CF 3) 2 CFCOF} , CF 3 CF 2 COF, C
F ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF, CF ₃ CF
₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CO
_{F, CF 3 CF 2 CF 2} OCF 2 CF 2 COF.

Examples of compound (2) in which n is 2; FCOCF ₂ CF ₂ COF, FCOCF ₂ CF ₂ CF ₂
CF ₂ COF, FCOCF (CF ₃ ) OCF ₂ CF ₂ C
F ₂ COF, FCOCF (CF ₃ ) OCF ₂ CF ₂ OC
F (CF ₃ ) COF, FCOCF (CF ₃ ) OCF ₂ C
F ₂ CF ₂ CF ₂ OCF (CF ₃ ) COF, FCOCF
(CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ COF, FCO
CF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ CO
F, FCOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂
CF ₂ CF ₂ COF.

[0059]

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

[Example 1] FCO (CF_Two)_FourWith COF
CF_ThreeO (CF_Two)_TwoCOF manufacturing example (Example 1-1) CH by esterification reaction_ThreeO (CH_Two)
_ThreeOCO (CF_Two)_FourCOO (CH_Two)_ThreeOCH_ThreeMade of
Example CH in Hastelloy C 2L autoclave_ThreeO (C
H_Two)_ThreeOH (595g) was charged. Cool the reactor
Slowly so that the internal temperature is kept below 30 ° C under normal pressure.
And FCO (CF_Two)_FourIntroduce COF (1000g)
It was Bubbling nitrogen gas at the same time with sufficient stirring
Then, HF generated by the reaction was driven out of the system. FC
O (CF_Two)_FourAfter adding the total amount of COF, further at 50 ℃
The reaction was carried out for 5 hours to obtain a product. The product was analyzed by GC
As a result, CH_ThreeO (CH_Two)_ThreeOCO (CF_Two)_FourCOO
(CH_Two)_ThreeOCH_ThreeIs 97.8%, CH_ThreeO (C
H_Two)_ThreeOCO (CF_Two)_Four1.2% COF is generated
And unreacted CH_ThreeO (CH_Two) _ThreeOH is not detected
won. This product was used in the following reaction without purification.
used.

¹ H-NMR (300.4 MHz, solvent:
CDCl ₃ , reference: TMS) δ (ppm): 1.33,
1.46, 3.24, 3.37. ¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , reference: CFCl ₃ ) δ (ppm): 119.5, 123.
1.

(Example 1-2) CF ₃ O by fluorination reaction
_{(CF 2) 3 OCO (CF} 2) 4 COO (CF 2) 3 O
Production Example of CF _{3 In} a 500 mL nickel autoclave, R-113 was added.
After (312 g) was added, the mixture was stirred and kept 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. Further, a liquid returning line for returning the condensed liquid from the cooler maintained at -10 ° C to the autoclave was installed. After nitrogen gas was blown into the autoclave at room temperature for 1 hour, fluorine gas diluted with nitrogen gas to 20% (hereinafter referred to as 20% diluted fluorine gas) was blown at room temperature at a flow rate of 8.69 L / h for 1 hour. Next 20
Example 1-while injecting% diluted fluorine gas at the same flow rate
A solution of the product obtained in 1 (5 g) in R-113 (100 g) was injected over 5.4 hours.

Next, while blowing 20% diluted fluorine gas at the same flow rate, the pressure inside the autoclave was adjusted to 0.15MP.
The pressure is increased to a (gauge pressure) and the benzene concentration is 0.01.
9 mL of the R-113 solution of g / mL was injected while the temperature was raised from 25 ° C to 40 ° C, the benzene solution injection port of the autoclave was closed, and stirring was continued for 0.3 hours.

Next, while maintaining the reactor internal pressure at 0.15 MPa (gauge pressure) and the reactor internal temperature at 40 ° C., 6 mL of the benzene solution was injected, and the benzene solution injection port of the autoclave was closed to 0.3 Stirring was continued for hours. 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, 20% diluted fluorine gas is added at the same flow rate.
The stirring was continued for 1 hour while blowing. Next, in the reactor
The pressure was set to normal pressure, and nitrogen gas was blown in for 1 hour. Generate
Things ¹⁹As a result of F-NMR analysis, the yield of the title compound was 6
It was confirmed that the content was 4%.

¹⁹ F-NMR (282.7 MHz, solvent C
DCl3, reference: CFCl3) delta (ppm): -54.
9 (6F), -86.7 (4F), -119.2 to -1
27.5 (16F).

[0067] in (Example _{1-3) CF 3 O (CF 2} ) due to decomposition reaction of the ester bond flask 2 COF 2L equipped with reflux condenser of Preparation 10 ° C. of, _CF 3 O
_{(CF 2) 3 OCO (CF} 2) 4 COO (CF 2) 3 O
CF ₃ (2000 g) was charged, and potassium fluoride (4
5.9 g) was added, and the heat medium temperature was maintained at 100 to 130 ° C. and the mixture was heated and stirred. The generated gas was collected by a stainless steel (SUS316) trap cooled to −78 ° C., and the reaction was terminated when the reaction proceeded and the generation of gas was not observed. After the reaction, the weight of the trap was measured and the result of GC analysis showed that CF ₃ O (CF ₂ ) ₂ CO
Formation of F (purity 98%, 1224 g, yield: 98%) was observed.

[Example 2] FCOCF (CF_Three) OCF_TwoC
F_TwoCF_ThreeCF using_ThreeO (CF _Two)_TwoCOF manufacturing
An example (Example 2-1) CH by esterification reaction_ThreeO (CH_Two)
_ThreeOCOCF (CF_Three) OCF_TwoCF_TwoCF_ThreeManufacturing example CH of Example 1-1_ThreeO (CH_Two)_ThreeOH (595g) as C
H_ThreeO (CH_Two)_ThreeChange to OH (342g), FCO
(CF_Two)_FourCOF (1000 g) to FCOCF (CF
_Three) OCF_TwoCF_TwoCF_ThreeChange to (1300g),
A similar reaction was performed. As a result of GC analysis of the product, CH
_ThreeO (CH_Two)_ThreeOCOCF (CF_Three) OCF_TwoCF_Two
CF_Three99.0% is produced, and unreacted CH_ThreeO
(CH_Two) _ThreeNo OH was detected. This product is
Used in the reaction of Example 2-2 without preparation.

¹ H-NMR (300.4 MHz, solvent:
CDCl ₃ , reference: TMS) δ (ppm): 1.33,
1.46, 3.24, 3.37. ¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , reference: CFCl ₃ ) δ (ppm): 26.6, −80.
0, -81.8, -82.2, -87.5, -130.
2, -131.1.

(Example 2-2) CF ₃ O by fluorination reaction
_{(CF 2) 3 OCOCF (CF} 3) OCF 2 CF 2 CF
Production Example ₃ of Example ₃ The flow rate of the diluted fluorine gas of Example 1-2 was set to a flow rate of 7.63 L / h.
To the product obtained in Example 1-1 (5 g) to the product obtained in Example 2-1 (5 g), and
The reaction was carried out in the same manner except that the solution dissolved in 13 (100 g) was injected over 4.0 hours. Product ¹⁹
As a result of F-NMR analysis, it was confirmed that the title compound was contained in a yield of 75%.

¹⁹ F-NMR (282.7 MHz, solvent C
DCl3, reference: CFCl3) delta (ppm): -54.
3 (3F), -79.7 (1F), -81.9 to -8
2.4 (6F), -86.3 to -89.3 (3F),-
120.2--127.5 (4F), -130.1 (2
F), -132.2 (1F).

Example 2-3 Production Example of CF ₃ O (CF ₂ ) ₂ COF by Decomposition Reaction of Ester Bond In Example 1-3, CF ₃ O (CF ₂ ) ₃ OCO (CF
₂ ) ₄ COO (CF ₂ ) ₃ OCF ₃ (2000 g) as C
_{F 3 O (CF 2) 3} OCOCF (CF 3) OCF 2 CF
₂ CF ₃ (2000 g) was changed, the amount of potassium fluoride was changed to 30.9 g, and the same reaction was carried out. As a result, CF ₃
O (CF ₂ ) ₂ COF (purity 99%, 814 g, yield:
98%) was observed.

[0073]

According to the method of the present invention, CF ₃ O (CF ₂ ) ₂ COF, which is useful as an intermediate for fluororubber raw materials, can be produced in a high yield and a high purity by a simpler method than the conventional method. it can.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA02 AC30 AC47 AC48 BA02                       BA37 BA92 BB17 BC10 BC11                       BC31 BC34 BE53 BM10 BM71                       BP10 BS10                 4H039 CA65 CE90

Claims (7)

[Claims] 1. A compound represented by the following formula (3) is obtained by subjecting a compound represented by the following formula (3) to liquid phase fluorination and perfluorination to obtain a compound represented by the following formula (4). In the method for producing perfluoro (3-methoxypropionyl fluoride) represented by the following formula (5), a decomposition reaction of an ester bond is carried out. _{Q (COO (CH 2) 3} OCHX 1 X 2) n ·· formula ^{_{(3) Q f (COO (}} CF 2) 3 OCF 3) n ·· formula _{(4) CF 3 O (CF} 2) 2 COF ·· Formula (5) However, the symbol in a formula shows the following meanings. Q: n-valent fluorine-containing organic group. Q ^f : Perfluorinated n-valent organic group. n: an integer of 1 or more. X ¹ and X ² : each independently a hydrogen atom or a fluorine atom. 2. A compound represented by the formula (3) has the following formula (1):
The production method according to claim 1, which is a compound obtained by subjecting a compound represented by the formula (1) to an esterification reaction with a compound represented by the following formula (2). However, Q, n, X ¹ and X ² have the same meanings as described above. CHX ¹ X ² O (CH ₂ ) ₃ OH ... Formula (1) Q (COF) _n ... Formula (2) 3. The compound represented by the formula (2) which is reacted with the compound represented by the formula (1) is a compound represented by the following formula (2F) obtained from a decomposition reaction product of an ester bond. The manufacturing method according to claim 2. However, Q ^f and n have the same meanings as described above. Q ^f (COF) _n ··· Formula (2F) 4. The fluorine content of the compound represented by formula (3) is 20 to 60 mass%, and the molecular weight is 200 to 1100.
The manufacturing method according to any one of claims 1 to 3. 5. A compound represented by the formula (3) is represented by the following formula (3-
The compound represented by 1), wherein the compound represented by the formula (4) is a compound represented by the following formula (4-1):
The manufacturing method in any one of -4. However, Q ^2f represents a C 1-18 perfluoroalkylene group in which an etheric oxygen atom may be inserted between carbon-carbon bonds, and X ¹ and X ² have the same meanings as described above. ^{_{CHX 1 X 2 O (CH 2}} ) 3 OCOQ 2f COO (CH 2) 3 OCHX 1 X 2 ·· formula ^{_{(3-1) CF 3 O (CF}} 2) 3 OCOQ 2f COO (CF 2) 3 OCF 3 ·· Formula (4-1) 6. A compound represented by formula (3) is represented by formula (3-2):
It is a compound represented by these, The compound represented by Formula (4) is a compound represented by Formula (4-2), The manufacturing method in any one of Claims 1-4. Here, k represents an integer of ^0-5, respectively X 1, ^{X 2} are independently a hydrogen atom or a fluorine atom. ^{_{CHX 1 X 2 O (CH 2}} ) 3 OCOCF (CF 3) [OCF 2 CF (CF 3)] k OCF 2 CF 2 CF 3 ·· formula _{(3-2) CF 3 O (CF} 2) 3 OCOCF (CF _{3) [OCF 2 CF (CF} 3)] k O CF 2 CF 2 CF 3 ·· formula (4-2) 7. Any of compounds selected from the following formulas:
That compound. However, k shows the integer of 0-5, X¹,
X^TwoAre each independently a hydrogen atom or a fluorine atom.
Show.   CHX¹X^TwoO (CH_Two)_ThreeOCO (CF_Two)_FourCOO (CH_Two)_ThreeOCHX ¹ X^Two..Formula (3-1a)   CF_ThreeO (CF_Two)_ThreeOCO (CF_Two)_FourCOO (CF_Two)_ThreeOCF_Three··formula (4-1a)   CHX¹X^TwoO (CH_Two)_ThreeOCOCF (CF_Three) [OCF_TwoCF (CF_Three) ]_kOCF_TwoCF_TwoCF_Three..Formula (3-2)   CF_ThreeO (CF_Two)_ThreeOCOCF (CF_Three) [OCF_TwoCF (CF_Three)]_kO CF_TwoCF_TwoCF_Three..Formula (4-2)