WO2003002501A1 - Procédé de préparation de composés de carbonyle fluorés - Google Patents

Procédé de préparation de composés de carbonyle fluorés Download PDF

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Publication number
WO2003002501A1
WO2003002501A1 PCT/JP2002/006502 JP0206502W WO03002501A1 WO 2003002501 A1 WO2003002501 A1 WO 2003002501A1 JP 0206502 W JP0206502 W JP 0206502W WO 03002501 A1 WO03002501 A1 WO 03002501A1
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formula
compound
compound represented
reaction
reaction product
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PCT/JP2002/006502
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English (en)
Japanese (ja)
Inventor
Kazuya Oharu
Takashi Okazoe
Kunio Watanabe
Daisuke Shirakawa
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Asahi Glass Company, Limited
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Priority to JP2003508686A priority Critical patent/JP4362710B2/ja
Publication of WO2003002501A1 publication Critical patent/WO2003002501A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to a method for efficiently producing a fluorine-containing carbonyl compound having various structures. Background technology
  • the reaction for obtaining a polyethylene glycol having a triflate Ruo b methyl group at the end was fluorinated in a liquid phase after reacting the Torifuruoro acid polyethylene da recall molecular weight of at least 1000 is known (Kohyo 4 - No. 500520) .
  • Also known is a method of obtaining a perfluorinated polyethylene fluorinated difluoride by fluorinating a poly (ethylene dalicol) having a trifluoromethyl group produced by the method of JP-A-4-500520 in a liquid phase. Yes (US 5466877).
  • the method of WO 0 0/5 6 6 9 4 comprises the steps of:
  • the vapor pressure of the partially fluorinated ester increases, and a reaction in the gas phase may occur with the gas in the liquid phase fluorination reaction.
  • the reaction in the gas phase has a problem that it is difficult to control the reaction and the yield is reduced.
  • the method of using a high molecular weight partially fluorinated ester to reduce the vapor pressure of the partially fluorinated ester has problems such as a small number of kinds of partially fluorinated esters, high cost, and poor economic efficiency. is there.
  • the present invention provides the following manufacturing method which solves the above-mentioned problems.
  • a fluorination reaction product containing at least one compound represented by Formula 4 is obtained, and an ester bond is decomposed in the fluorination reaction product.
  • a decomposition reaction product containing the compound represented by the formula 5 and the compound represented by the formula 2 is obtained, and a fluorine-containing luponyl compound represented by the formula 5 is obtained from the decomposition reaction product.
  • a method for producing a fluorine-containing carbon compound which is a feature of the present invention.
  • R 1 , R 2 : R 1 is a hydrogen atom or a fluorinated monovalent organic group, R 2 is a fluorinated monovalent organic group, and R 1 and R 2 are fluorinated together It may form a divalent organic group.
  • R lf, R 2f 1 monovalent organic group R lf a fluorine atom, R lf where R 1 is a monovalent organic group which R 1 is Perufuruoro of R 1 is a hydrogen atom.
  • R 2 ⁇ is a monovalent organic group in which R 2 is perfluorinated. However, when R 1 and R 2 form a divalent organic group which can be fluorinated together, R lf and R 2f cooperate to form a perfluorinated divalent organic group. Form a group.
  • Q f a perfluorinated n-valent organic group.
  • n An integer of 2 or more.
  • n Integer not less than 2 and not more than n.
  • the molecular weight of the compound represented by the formula 1 is 32 to 200, the average fluorine content of the esterification reaction product is 20 to 60% by mass, and the molecular weight of the esterification reaction product is 200 to 1 3.
  • the compound represented by the formula 2 is a compound represented by the formula (2-1),
  • the reaction product must be a compound represented by the formula (3-1),
  • the fluorination reaction product must be a compound represented by the formula (4-1), and
  • the decomposition reaction product is a compound represented by the formula (5-1)
  • the compound represented by the formula (2-1) and the compound represented by the formula (2-1) are essential, and the fluorine-containing carbonyl compound is a compound represented by the formula (5-1). Manufacturing method.
  • the esterification reaction product includes the compound represented by the formula (3-1H) together with the compound represented by the formula (3-1), and the fluorination reaction product is represented by the formula (4_1) 6.
  • R 1 R 2 , R lf , R 2f and Q f2 in the formula have the same meaning as described above.
  • R ⁇ R 2 the same meanings as described above.
  • Q H2 a divalent organic group that essentially requires a hydrogen atom and is perfluorinated Group that becomes Q f2 .
  • R 1 and R 2 are one CH 3 , R lf and R 2f are one CF 3 , Q f2 is-(CF 2 ) k — (where k is an integer of 2 to 8). And Q H2 is — (CH 2 ) k — or R 1 is —H, R 2 is —CH (CH 3 ) 2 , R lf is one F, and R 2i is _CF (CF 3 ) 2 9.
  • Q H2 is — (CH 2 ) k —.
  • liquid phase in the liquid phase fluorination essentially comprises a compound represented by the formula (4-1) and a compound represented by the formula (5_1).
  • the manufacturing method of the description essentially comprises a compound represented by the formula (4-1) and a compound represented by the formula (5_1).
  • organic group refers to a group that essentially requires a carbon atom.
  • examples of the organic group that can be fluorinated include an organic group having a C-H portion and an organic group having a carbon-carbon unsaturated bond, and an organic group having a C-H portion is preferable.
  • a saturated organic group in which a carbon-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, a saturated hydrocarbon group containing an etheric oxygen atom, a partially halogenated saturated hydrocarbon group, or a partially halogenated (a saturated hydrocarbon group containing an etheric oxygen atom). ) Groups are preferred.
  • “partially halogenated” means that hydrogen atoms are halogenated at a remaining ratio.
  • 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 preferred.
  • a chlorine atom is preferable.
  • Examples of the monovalent saturated hydrocarbon group include an alkyl group, a cycloalkyl group, and a monovalent saturated hydrocarbon group having a ring portion (for example, a cycloalkyl group, a cycloalkinoalkyl group, or a group having these groups as a partial structure). And the like, and an alkyl group is preferable.
  • divalent saturated hydrocarbon group examples include an alkylene group, a cycloalkylene group, or a divalent saturated hydrocarbon group having a ring portion (for example, a divalent saturated hydrocarbon group having a cycloalkyl group, a bicycloalkyl group, or a cycloalkylene group as a partial structure).
  • An aliphatic hydrocarbon group), and the like, and an alkylene group is preferable.
  • the monovalent group of the etheric oxygen atom-containing saturated hydrocarbon group an alkyl group having an etheric oxygen atom inserted between carbon-carbon bonds, or an etheric oxygen atom being inserted between carbon-carbon bonds And a cycloalkyl group.
  • the divalent group among the etheric oxygen atom-containing saturated hydrocarbon groups includes a carbon-carbon bond, an alkylene group having an etheric oxygen atom inserted at the bond terminal of the group, or Examples thereof include a cycloalkylene group in which an etheric oxygen atom is interposed between carbon-carbon bonds, and particularly preferred is an oxyalkylene group or a group having a polyoxyalkylene moiety.
  • the number of etheric oxygen atoms may be one or two or more.
  • Perfluorination means that substantially all of the fluorinable moieties present in the fluorinable group are fluorinated. For example, in a group obtained by perfluorinating an organic group having a C—H portion, substantially all of the C—H portion becomes C—F, and an organic group having a carbon-carbon unsaturated bond is perfluorinated. In the group, substantially all unsaturated bonds have a fluorine atom attached.
  • perfluorinated monovalent organic group examples include a perfluoroalkyl group, specifically, —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF 2 CF 2 CF 2 CF 3 , One CF 2 CC 1 F 2 , one CF 2 CB r F 2 , or _ CF 2 CFC 1 CF 2 C 1, -CF (CF 3 ) 2 , -CF 2 CF (CF 3 ) 2 , —CF (CF 3 ) CF 2 CF 3 , 1 C
  • Examples of the perfluorinated divalent organic group include a perfluoroalkylene group, specifically, one CF 2 CF 2 CF 2 —, one CF (CF 3 ) CF 2 CF 2 —, — CF 2 CF (CF 3 ) CF 2 CF 2 — and the like.
  • Examples of the perfluorinated etheric oxygen atom-containing group include groups in which an etheric oxygen atom is inserted between carbon-carbon atoms of these groups.
  • the concept of the manufacturing method of the present invention can be represented by the following formula.
  • Rlf COR 2f In the production method of the present invention, an esterification reaction, a fluorination reaction, and a decomposition reaction of an ester bond are performed.
  • the method of the present invention is an advantageous method when the molecular weight of the compound (1) is small, so that the number of carbon atoms in the R 1 CHR 2 — moiety is 3 to 10. It is particularly preferable that it is 3 to 5.
  • the molecular weight of the compound (1) is preferably from 32 to 200, particularly preferably from 60 to 150, and particularly preferably from 60 to 120.
  • R 1 R 2 is a monovalent organic group that can be fluorinated, an alkyl group, a cycloalkyl group, or an alkoxy group is preferable.
  • R 1 and R 2 together form a divalent organic group that can be fluorinated, the divalent organic group is an alkylene group or one or more carbon atoms between carbon-carbon bonds of the alkylene group.
  • the group in which an etheric oxygen atom is inserted is preferable.
  • the compound (1) since alcohol compounds having various structures are commercially available and can be obtained at a low cost, compounds containing no fluorine atom (that is, compounds having a fluorine content of 0% by mass) are preferred. preferable.
  • a compound having a structure corresponding to the structure of the desired 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 in R lf and R 2f in the fluorine-containing carbonyl compound (5).
  • the fluorinated carbonyl compound (5) is used as a raw material for the fluorinated primary alcohol, it is preferable to use the compound (1) in which R 2 is a hydrogen atom.
  • R 2 is a monovalent organic group that can be fluorinated.
  • compound (1) undergoes an esterification reaction with compound (2).
  • the compound (2) is a compound in which n groups represented by —COF are bonded to the bond of a perfluorinated n-valent organic group (Q f ).
  • n represents an integer of 2 or more.
  • Q f is preferably a perfluorinated n-valent saturated hydrocarbon group or a perfluoro (n-valent saturated hydrocarbon containing an etheric oxygen atom) group.
  • the group (Q f ) is a divalent group (Q f2 )
  • a perfluoroalkylene group or a perfluoro (alkylene containing an etheric oxygen atom) group is particularly preferred.
  • the compound (2) is preferably FCO (CF 2 ) k C ⁇ F (k is an integer of 2 to 8) in terms of availability and low reaction yield.
  • the production method of the present invention is performed once, it is possible to obtain a fluorine-containing carbonyl compound (5) that is n-fold stoichiometric to the compound (2).
  • the compound (2) can be recovered, and the recovered compound (2) can be used any number of times. The method of recovering and using compound (2) will be described later. Specific examples of the compound (2) include a compound (2-1) in which n described later is 2.
  • the reaction between compound (1) and compound (2) can be carried out under known esterification reaction conditions.
  • the esterification reaction may be carried out in the presence of an esterification reaction solvent. It is preferably carried out in the absence of an esterification reaction solvent from the viewpoint of volumetric efficiency.
  • an esterification reaction solvent dichloromethane, chloroform, triethylamine, or a mixed solvent of triethylamine and tetrahydrofuran is preferred.
  • the esterification reaction solvent is used, the amount is preferably 50 to 500% by mass based on the total amount of the compound (1) and the compound (2).
  • hydrofluoric acid is generated, so that alkali metal fluoride (preferably NaF or KF) or trialkylamine is used as an HF scavenger in the reaction system. May be present.
  • the HF scavenger is preferably used when the compound involved in the reaction is an acid-labile compound. When an HF scavenger is not 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 together with a nitrogen gas stream.
  • the amount of the HF scavenger is preferably about 1 to 10 times the mol of the theoretical amount of HF generated.
  • the esterification reaction is an esterification reaction between a bifunctional or higher functional acid fluoride and a monofunctional alcohol.
  • both the reaction rate and the reaction result are higher when compared with the reaction between a highly polar bifunctional or higher-functional alcohol and a monofunctional acid fluoride. Further, it is not preferable that the alcohol remains in the product after the esterification reaction for the reason described later. From the above, the compounds used in the esterification reaction
  • the amount of (1) is n-fold molar with respect to compound (2) (n corresponds to the number (n) of groups represented by one COF in compound (2)). preferable.
  • the amount of (1) is preferably an amount that does not remain in the esterification reaction product, and the labor for purification of the esterification reaction product can be omitted.
  • the amount of the compound (1) is particularly preferably 0.5 n-fold to n-fold, more preferably 0.9 n-fold to n-fold. Especially preferred.
  • the advantage of the present invention using the compound (2) is exhibited particularly when the molecular weight of the compound (1) is low. Since the compound (2) has two or more acyl fluoride groups in the structure, two or more molecules of the compound (1) react with the compound (2). As a result, compared to the case where compound (1) is reacted with a compound having one acylfluoride group, the molecular weight of compound (3) is increased, so that the vapor pressure is reduced and the liquid phase fluorination reaction is performed. The reaction is more controllable, the yield is higher, and the volumetric efficiency is advantageous.
  • the lower limit of the reaction temperature of the esterification reaction is preferably 150 ° C.
  • the upper limit is preferably + 100 ° C., which is lower than the boiling point of the esterification solvent.
  • the reaction time of the reaction can be appropriately changed depending on the supply rate of the raw materials and the amount of the compound actually reacted.
  • the reaction pressure is preferably from normal pressure to 2 MPa (gauge pressure, hereinafter the pressure is described in gauge pressure).
  • 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 (one COOCHRiR 2 ) formed by the esterification reaction, and represents an integer of 2 or more and n or less.
  • N-m indicates the number of COF groups remaining without esterification.
  • (n_m) is 0, all of the COF groups of compound (2) are esterified. This means that one COF group does not exist in compound (3).
  • Compound (3) is a compound in which (nm) is 0, a compound in which n> m (that is, two or more COF groups of compound (2) are esterified, but all are esterified.
  • the compound ratio was not particularly limited.
  • the esterification reaction product in the present invention refers to all products formed in the esterification reaction, and may include compounds other than the compound (3).
  • esterification The reaction product also includes the following compound (3-10) in which only one of two or more C ⁇ F groups present in the compound (2) is esterified.
  • R 1 R 2 , Q and n in the compound (3-10) have the same meaning as described above.
  • the amount of the compound (3) is more than 50 mol% based on the total amount of the esterification reaction product. Is more preferable, and more preferably more than 60 mol%.
  • the product of the esterification reaction may be purified according to the purpose, or may be used as it is in the next reaction or the like, and is preferably purified from the viewpoint of smoothly performing the fluorination reaction in the next step.
  • 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 in which the product is treated with water and the like, and then separated, a method in which the product is extracted with an appropriate organic solvent and then distilled, silica gel column chromatography, and the like.
  • the esterification reaction product is fluorinated.
  • the fluorination reaction is preferably carried out by a liquid phase fluorination reaction described later.
  • the average fluorine content of the esterification reaction product (especially compound (3)) is 20 to 60 mass. It is preferably 25 to 55 mass. / 0 , preferably 30-55% by weight.
  • the average fluorine content is preferably adjusted the number of carbon structure Contact and the Q f of the compound (2) so as to the range.
  • the molecular weight of the esterification reaction product is preferably in the range of 200 to 1100, and particularly preferably in the range of 300 to 80 °.
  • esterification reaction products with an average fluorine content in a specific range For esterification reaction products with an average fluorine content in a specific range, the solubility in the liquid phase during the fluorination reaction is significantly improved, and the operability and reaction yield of the liquid phase fluorination reaction are improved.
  • the average fluorine content is in a certain range This also has the advantage of being economical.
  • the molecular weight of the esterification reaction product is equal to or more than a specific molecular weight, there is an advantage that a risk of a decomposition reaction caused by a gas-phase fluorination reaction can be avoided, and when the molecular weight is equal to or less than a specific molecular weight, There are advantages in handling compounds and purification of products.
  • the fluorination reaction can be carried out by a fluorination method using cobalt fluoride, an electrochemical fluorination method, a method of reacting with fluorine (electron talfluuorine), or the like.
  • a fluorination method using cobalt fluoride an electrochemical fluorination method, a method of reacting with fluorine (electron talfluuorine), or the like.
  • the liquid-phase fluorination method in which the reaction with fluorine in the liquid phase is preferable because the reaction can be carried out efficiently regardless of the structure of the substrate and the yield of the fluorination reaction is extremely high .
  • the fluorination reaction will be described using a liquid phase fluorination method as an example.
  • the liquid phase in the liquid phase fluorination method may be the substrate for the reaction itself, but is preferably a fluorination reaction solvent which does not normally participate in the product or the reaction.
  • fluorine gas it is or to use fluorine gas diluted with an inert gas.
  • an 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 Vo 1% or more from the viewpoint of efficiency, and particularly preferably 20 Vo 1% or more.
  • the fluorination reaction solvent a solvent inert to the fluorination reaction is preferable, and a solvent having high solubility of the esterification reaction product is particularly preferable.
  • the esterification reaction product is dissolved in 1% by mass or more. It is preferable to use a solvent that can dissolve, particularly a solvent that can dissolve at least 5% by mass.
  • fluorination reaction solvent examples include compound (2), compound (4) described below, a fluorine-containing carbonyl compound (5), perfluoroalkanes (trade name: FC-72, etc.), perfluorinated Loethers (trade names: FC_75, FC-77, etc.), Perfluoropolyethers (trade names: Crytotustus, Fomblin, Galden, Demunum, etc.) ), Black mouth full And polyfluoroethers, perfluoroalkylamines (for example, perfluorotrialkylamine, etc.), and inert fluids (trade name: Florinert).
  • the compound (2) or the fluorine-containing carbonyl compound (5) as a fluorination reaction solvent since there is an advantage that post-treatment is facilitated.
  • the reaction system of the fluorination reaction may be a batch system or a continuous system.
  • a fluorination reaction solvent and an esterification reaction product are charged into a reactor, stirred, and then reacted while continuously supplying fluorine gas into the fluorination reaction solvent.
  • a fluorination reaction solvent is charged into a reactor and stirred, and then a fluorine gas and an esterification reaction product are continuously supplied at a predetermined molar ratio into the fluorination reaction solvent.
  • 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.
  • the fluorine used in the fluorination reaction is preferably maintained such that the amount of fluorine relative to the amount of hydrogen atoms contained in the esterification reaction product is always excessively equivalent from the beginning to the end of the reaction. Is preferably maintained at 1.05 equivalents or more (that is, 1.05 times or more) from the viewpoint of selectivity, and more preferably at least 2 times equivalent (ie, at least 2 times the molar). It is more preferable to keep the ratio in terms of selectivity. Further, in order to make the amount of fluorine excessive even at the start of the reaction, it is preferable to dissolve a sufficient amount of fluorine in advance in the fluorination reaction solvent used at the beginning of the reaction.
  • the lower limit of the reaction temperature is preferably the lowest temperature among the boiling points of the esterification reaction products. .
  • the reaction temperature is particularly preferably from 150 ° C. to + 100 ° C., particularly preferably from 120 ° C. to 150 ° C., from the viewpoint of ease of implementation.
  • the reaction pressure of the fluorination reaction is not particularly limited, and is preferably from normal pressure to 2 MPa from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.
  • a compound containing a C-H bond 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 a later stage of the fluorination reaction. In the case where 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 satisfactorily fluorinated. These operations can efficiently fluorinate the esterification reaction product present in the reaction system, and can greatly improve the reaction rate.
  • the C—H bond-containing compound an aromatic hydrocarbon is preferable, and benzene, toluene and the like are particularly preferable.
  • the amount of the C—H bond-containing compound to be added is preferably from 0.1 to 10 mol%, particularly from 0.1 to 5 mol%, based on the total amount of hydrogen atoms in the esterification reaction product. Preferably it is.
  • the C—H bond-containing compound is preferably added to a reaction system in which fluorine is present. When a C—H bond-containing compound is added, it is preferable to pressurize the reaction system. When pressure is applied, the pressure is preferably 0.01 to 5 MPa. In the case of performing ultraviolet irradiation, it is preferable to perform irradiation for 0.1 to 3 hours.
  • esterification reaction product is perfluorinated to produce a compound
  • a fluorination reaction product containing one or more of (4) is produced.
  • Compound (4) is a compound
  • (3) is a perfluorinated compound.
  • the fluorination reaction product in the present invention includes all products obtained by fluorinating the esterification reaction product, and the compound (4) is essential. Composition of 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 be two or more.
  • R lf of the compound (4) is a perfluorinated monovalent organic group
  • a perfluorinated alkyl group, a perfluorocycloalkyl group, a perfluoroalkoxy group, or the like is preferable.
  • Alkyl groups are particularly preferred.
  • R 2f is a perfluorinated monovalent organic group
  • a perfluoroalkyl group is preferred.
  • the perfluorinated group may be a perfluorinated divalent saturated hydrocarbon group or a perfluorinated group.
  • a divalent saturated hydrocarbon group containing an etheric oxygen atom is preferable, and a perfluoroalkylene group or a group in which one or more etheric oxygen atoms are inserted between carbon-carbon bonds of an alkylene group is converted into a perfluoroalkyl group.
  • a perfluoroalkylene group or a group in which one or more etheric oxygen atoms are inserted between carbon-carbon bonds of an alkylene group is converted into a perfluoroalkyl group.
  • the esterification reaction product contains the compound (3-10)
  • the following compound (411) in which the compound is perfluorinated is also contained in the fluorination reaction product.
  • N, Q f , R 2f and R lf in the compound ( 4-110 ) correspond to the compound ( 3-10 ).
  • the fluorination reaction product may include one or more compounds in which the esterification reaction product is partially fluorinated (hereinafter, these partially fluorinated products are also referred to as hydrogen remaining compounds).
  • HF is by-produced.
  • a HF scavenger must coexist in the reaction system, the HF scavenger and the outlet gas come into contact at the reactor gas outlet, or the HF is condensed and recovered by cooling the outlet gas. Is preferred.
  • the HF scavenger the same one as described above is used, and NaF is preferable.
  • HF is added to an inert gas such as nitrogen gas. It is preferable to conduct the reaction to an outside of the reaction system and to perform an alkali treatment.
  • the amount is preferably 1 to 20 times, and particularly preferably 1 to 5 times, the mole of the total hydrogen atoms present in the esterification reaction product.
  • a cooler preferably kept at 10 ° C. to room temperature, particularly about 20 ° C.
  • NaF pellet packed bed And
  • the cooler preferably between 78 ° C and + 10 ° C, especially between -30 ° C and 0 ° C
  • a liquid return line for returning the condensed liquid from the cooler in (c) to the reactor may be installed.
  • the fluorination reaction product may be used as it is in the next step, or may be purified to high purity.
  • Examples of the purification method include a method of distilling the crude product as it is under normal pressure or reduced pressure.
  • an ester bond is further decomposed in the fluorination reaction product.
  • the decomposition reaction of the ester bond is a known reaction in which the ester bond present in the compound is cleaved to form the compound (2) and the fluorinated carbonyl compound (5).
  • the decomposition reaction of the ester bond is preferably 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 type of the thermal decomposition reaction is preferably selected depending on the boiling point of the fluorination reaction product and its stability.
  • the gas phase pyrolysis method is a method in which a decomposition reaction is continuously performed in the gas phase, and the resulting fluorinated carbonyl compound (5) and compound (2) are condensed from an outlet gas and recovered. Is preferred.
  • the reaction temperature of the gas phase pyrolysis method is preferably 50 to 350 ° C, more preferably 50 to 300 ° C. And more preferably 150 to 250 ° C.
  • a metal salt catalyst may be used, and an inert gas not directly involved in the reaction may coexist in the reaction system.
  • the inert gas include nitrogen gas and carbon dioxide gas.
  • the addition amount of the inert gas is preferably about 0.01 to 50 V o 1% based on the total amount of the fluorination reaction products. If the amount of inert gas added is too large, the amount of product recovered may be reduced.
  • 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 as it is.
  • the reaction pressure in the liquid phase pyrolysis is not limited.
  • the product of the decomposition reaction may be withdrawn from the reactor at one time.
  • the fluorination reaction is carried out using a reactor equipped with a distillation column, and the product is obtained. The reaction may be performed while extracting by distillation.
  • the reaction temperature of the liquid phase pyrolysis method is preferably from 50 to 300 ° C, particularly preferably from 100 to 250 ° C.
  • the liquid phase pyrolysis method may be performed without a solvent or in the presence of a decomposition reaction solvent, and is preferably performed without a solvent.
  • a decomposition reaction solvent it is preferable to use a solvent that is inert to the reaction and that is compatible with the fluorination reaction product. Further, it is preferable to use a decomposition reaction solvent that is easily separated from the product.
  • Specific examples of the decomposition reaction solvent include an inert solvent such as perfluorotrialkylamine and perfluoronaphthalene; And are preferred.
  • the amount of the decomposition reaction solvent is preferably 0.10 to 10 times the mass of the fluorination reaction product.
  • the reaction may be carried out without a solvent or in the presence of a decomposition reaction solvent. Is preferred. Performing the reaction without a solvent means that the fluorination reaction product itself This is particularly preferred because it acts even if it does not require the labor for separating the solvent from the reaction product.
  • the method using a nucleophile or an electrophile is also preferably performed while performing distillation in a reactor equipped with a distillation column.
  • F— is preferable, and F— derived from alkali metal fluoride is particularly preferable.
  • the alkali metal fluoride, Na F, NaHF 2, KF, is C s F
  • N a F in terms of economical efficiency, the KF is particularly preferred 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.
  • the amount of the nucleophile such as F— is preferably 1 to 500 mol%, more preferably:! To 100 mol%, particularly preferably 5 to 50 mol%, based on the fluorination reaction product.
  • the lower limit of the reaction temperature is preferably 130 ° C, and the upper limit is more preferably from 120 ° 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 requires the compound (2) and the fluorine-containing carbonyl compound (5). Since the compound formed by the decomposition reaction of the ester bond of the compound (4-110) is also the compound (2) and the fluorinated carbonyl compound (5), the compound (4-110) is combined with the compound (4) together with the ester bond. 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 a compound obtained by decomposing an ester bond of a residual hydrogen compound described later.
  • the fluorine-containing carbonyl compound (5) in the present invention is R 2f —COF or R lf —C ⁇ _R 2f . In the present invention, the compound
  • Fluorinated carbonyl compound obtained by the process of the present invention (5) is directly, or, as the conversion example to c other compounds are useful compounds that can be used in various applications by conversion to another compound , By introducing an unsaturated bond into the terminal by thermal decomposition Examples include a monomer for a fluororesin and an example of producing a fluorinated alcohol by converting a terminal into a hydroxyl group by a reduction reaction.
  • the method of recovering the compound (2) from the decomposition reaction product and reusing it is a method of continuously producing the fluorinated carbonyl compound (5) by adding the compound (1) into the reaction system.
  • the continuous production method is performed for one cycle, stoichiometrically, 1 mol to n mol of the fluorine-containing carbonyl compound (5) and 1 mol of the compound (2) can be produced.
  • the production method of the present invention is preferably carried out on a compound in which n is 2 because it is difficult to control the reaction and procure the compound (2).
  • n is 2 and Q f Is preferably carried out in the compound (2-1) in which is a perfluorinated divalent organic group (Q f2 ). That is, the compound (1) is subjected to an esterification reaction with the compound (2-1) to obtain an esterification reaction product containing at least one compound (3-1), and the esterification reaction product is fluorinated.
  • a fluorination reaction product containing at least one compound (4-1) is obtained, and by subjecting the fluorination reaction product to a decomposition reaction of an ester bond, the compound (4
  • a method for producing a fluorinated carbonyl compound comprising: obtaining a decomposition reaction product containing 1) and a compound (2-1); and obtaining a fluorinated carbonyl compound (5) from the decomposition reaction product.
  • RR 2 , R lf , R 2f , and Q f2 in the following formula have the same meaning as described above.
  • Specific examples of the compound (1) in the present invention include the following compounds. (CH 3 ) 2 CHOH,
  • Specific examples of the compound (2) include the following compounds.
  • Specific examples of the compound (3) include the following compounds.
  • CH 3 CH 2 CH 2 OCOCF 2 CF 2 CF 2 CF 2 COOCH 2 CH 2 CH 3o compound (3-10) include the following compounds.
  • Specific examples of the compound (4) include the following compounds.
  • CF 3 CF 2 CF 2 OCOCF 2 CF 2 CF 2 CF 2 COOCF 2 CF 2 CF 30 compound (4-110) include the following compounds.
  • fluorine-containing carbonyl compound (5) include the following compounds and perfluorocyclohexanone.
  • C Y f represents a perfluorocyclohexyl group.
  • n 2
  • R 1 and R 2 are CH 3
  • R lf is considered from the viewpoint of the usefulness of the product and the superiority over the conventional production method.
  • a preferred embodiment of the method for producing the compound (5-2) includes the following production method.
  • 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 subjected to an esterification reaction with the compound (2-2) to obtain an esterification reaction product containing the compound (3-2), and the esterification reaction containing the compound (3-2) is carried out.
  • the reaction product is perfluorinated by a fluorination reaction to obtain a fluorination reaction product containing the compound (4-2), and the compound (5-2) is subjected to a decomposition reaction of an ester bond in the fluorination reaction.
  • a decomposition reaction product containing the compound (2-2) and the compound (2-2) it is preferable to obtain a decomposition reaction product containing the compound (2-2) and the compound (2-2), and obtain the compound (5-2) from the decomposition reaction product. Further, a compound (5-2) is obtained from the decomposition reaction product, and is used as the compound (2_2) to be reacted with the compound (1-2). Preferably, it is manufactured continuously.
  • the compound (5_2) (that is, hexafluoroacetone; hereinafter, referred to as HFA) and the compound (5-3) are known compounds useful as various intermediates by themselves.
  • HF IP is also a known compound useful as a solvent and various intermediates. The concept of this manufacturing method can be represented by the following equation.
  • the production method of the present invention can be a more efficient production method by recycling the product.
  • An example of an efficient manufacturing method will be described below with a specific example.
  • the group whose definition is not described below has the same meaning as described above.
  • (I) a method of recycling the compound (2); a method of recovering the compound (2) generated in the reaction product of the decomposition of the ester bond, and using the compound (1) as the compound (2) for the esterification reaction; It is.
  • This method is economical and efficient in that compound (2) can be used many times.
  • to recover the F CO (CF 2) 4 COF produced in the decomposition reaction of the ester bond and examples of (CH 3) 2 CHOH and methods for esterification reaction.
  • (II) a method of recycling a partially fluorinated product into a fluorination reaction system when a partially fluorinated product is contained in the fluorination reaction product; May contain a partially fluorinated compound of the compound (3).
  • the partially fluorinated compound include a hydrogen remaining compound (that is, a compound fluorinated at a rate at which at least one hydrogen atom remains in compound (3)).
  • the partially fluorinated product can be converted into the compound (4) by returning it to the reaction system of the fluorination reaction and performing the fluorination reaction again.
  • compound (1) is S (CH 3 ) 2 CHOH and compound (2) is FCO (CF 2 ) k COF, then (CH 3 ) 2 CHOCO (CF 2 ) k COO CH (The following compounds as partially fluorinated CH 3 ) 2 may be included in the fluorination reaction product.
  • the following compound as a partially fluorinated product of (CH 3 ) 2 CHOCO (CF 2 ) k COF may also be contained in the fluorination reaction product.
  • the compound having one CFOCO- moiety is decomposed by a decomposition reaction of an ester bond, but the compound having one CHOCO- moiety is not decomposed. Regardless of whether the ester bond is decomposed or not, the partially fluorinated compound 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 esterification reaction system. By doing so, the partially fluorinated product can be converted into compound (4).
  • a compound that cannot be decomposed such as (CF 3 ) 2 CHOCO (CF 2 ) k COF is generated as a partially fluorinated product, this is separated and the fluorination reaction system is performed according to the method described in (2). May be recycled into the system, or may be included in the system of the ester bond decomposition reaction without being separated, and then, after the ester bond decomposition reaction, together with FCO (CF 2 ) k COF (CF 3 ) 2 CHOCO ( The CF 2 ) k COF may be recovered and used for the esterification reaction with (CH 3 ) 2 CHOH.
  • This method is particularly advantageous when the yields of the fluorination reaction and the ester decomposition reaction are low. This is because compound (2) is recovered and used for reaction with compound (1). In practice, it is usually difficult to achieve 100% recovery of compound (2) when attempting the process (1). That is, there is a problem that the amount of the compound (2) to be reacted with the compound (1) decreases as the continuous production is repeated.
  • a compound having a lower fluorine content than the compound (3) (the following compound (3H) is preferred) is present together with the compound (3). It is preferable to carry out a chemical reaction.
  • Q H is an n-valent organic radical essentially containing hydrogen atoms, and a group comprising a pair Rufuruoro reduction has been Q f.
  • the compound (3H) is hardly soluble in the liquid phase by itself, but the compound (3) having a similar structure coexists with the compound (3H), so that the solubility in the liquid phase is increased There is an advantage of improving.
  • Q H is a group having an ether bond
  • the solubility of the compound (3) or compound (3H) is advantageous to improve the further.
  • Compound (3H) is preferably a compound containing no fluorine from the viewpoint of economy.
  • Q H2 is preferably a fluorine-free divalent organic group having a carbon skeleton corresponding to Q f2 , particularly an alkylene group, a group having an etheric oxygen atom inserted between carbon-carbon bonds of the alkylene group. Is preferred.
  • the amount of the compound (3H) relative to the CF3COCF3 compound (3) is not particularly limited as long as it is not inconvenient in the fluorination reaction.
  • the amount 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 mole to 0.2 mole.
  • the total amount of the compound (3H) and the compound (3) is preferably 5% by weight or less, more preferably 0.5% by weight or less in the fluorinated solvent.
  • the compound (3H) may be a commercially available product or a compound synthesized separately and may be present in the system before the fluorination step. However, the esterification reaction is carried out in the presence of the following compound (2H) together with the compound (2). Is also good. However, the symbols in the formula have the same meanings as described above.
  • esterification reaction between the compound (2H) and the compound (1) can proceed similarly to the esterification reaction between the compound (2) and the compound (1).
  • Specific examples of the compound (2H) include the following compound (2H-1). Where X is Shows a halogen atom or a hydroxyl group.
  • fluorine-containing carbonyl compound (5) obtained by the production method of the present invention is not particularly limited.
  • the compound can be used for various applications as it is or by leading to other applications.
  • various useful fluorinated alcohols can be produced by reducing the fluorinated carbonyl compound (5).
  • 1,1,2-trichloro- mouth 1,2,2-trifluoroethane is indicated as R-113, and the pressure is indicated as gauge pressure.
  • gas chromatography is referred to as GC
  • GC analysis value gas chromatography mass spectrometry
  • GC-MS gas chromatography mass spectrometry
  • Example 1-2 Example of producing (CF 3 ) 2 CFOCO (CF 2 ) 4 COOC F (CF 3 ) 2 by fluorination reaction
  • R-113 200 g was added to a 50 OmL nickel autoclave, and the mixture was stirred and maintained at 25 ° C.
  • the autoclave gas outlet was kept at 20 ° C
  • a condenser, a packed bed of NaF pellets, and a condenser maintained at -10 ° C were installed in series.
  • a liquid return line was installed to return the condensed liquid from the cooler kept at -10 ° C to the autoclave.
  • fluorine gas diluted to 20% with nitrogen gas hereinafter referred to as 20% diluted fluorine gas
  • a solution prepared 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. did.
  • the pressure in the autoclave was increased to 0.15 MPa, and the R-113 solution with a benzene concentration of 0.1 g 9 mL was injected while the temperature was raised to ° C, the benzene solution injection port of the autoclave was closed, and stirring was continued for 0.3 hour.
  • Example 14 Example of production of (CF 3 ) 2 CF OCO (CF 2 ) 4 COOC F (CF 3 ) 2 by fluorination reaction
  • CF 3 (CF 2 ) 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COF (2534 g) as a fluorination reaction solvent was added to a 3 L nickel autoclave, and the mixture was stirred and kept at 25 ° C. .
  • a cooler maintained at 110 ° C was installed at the autoclave gas outlet.
  • fluorine gas diluted to 50% with nitrogen gas hereinafter referred to as 50% diluted fluorine gas
  • 50% diluted fluorine gas was blown at a flow rate of 94.89 L, h for 2 hours.
  • Example 1 Prepare the same autoclave made of nickel as the reactor used in 1-2, add R-113 (312 g), and adjust the flow rate of 20% diluted fluorine gas to 10.60 L / h. Except for this, the conditions were the same as in Example 1-2. A solution of the product obtained in Example 2-1 (5 g) in R-113 (95 g) was injected into the autoclave over 5.5 hours.
  • the pressure in 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 0.1 gZmL is cooled from 25 ° C to 40 ° C. 9 mL was injected while the temperature was raised to C, the benzene solution injection port of the autoclave was closed, and stirring was continued for 0.3 hour.
  • Example 2-3 Example of producing (CF 3 ) 2 CFC ⁇ F by decomposition reaction of ester bond Distillation tower, distillation line equipped with Liebig condenser that can be cooled by cold water, KF (0.7 g) was charged into a 2 Om 1 reaction vessel equipped with a receiver and a dry ice trap at the top of the reaction vessel, and heated to 150 ° C. 9 g of the liquid obtained by removing R 113 of the fluorination reaction product obtained in Example 7 was slowly added to the reaction vessel. One hour after the end of the addition, the reaction was terminated when no gas was generated. 5.72 g of the product was collected in the receiver.
  • 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%).
  • FCO (CF 2 ) 3 COF GC area 55%)
  • FCO (CF 2 ) 3 COOCF 2 CH CF 3 ) 2
  • CF 3 ) 2 CFCOF GC area 30%
  • (CF 3 ) 2 CF COF (3.12 g) with a GC purity of 97% was recovered in the trap.
  • Example 2-5 Example of producing (CF 3 ) 2 CFCF 2 OCO (CF 2 ) 2 CO OCF 2 CF (CF 3 ) 2 by fluorination reaction
  • Example 1 Prepare the same autoclave made of nickel as the reactor used in _2, add R-113 (31 2 g), and adjust the flow rate of the 20% diluted fluorine gas to 12.16 L / h. The conditions were the same as in Examples 1-2. A solution of the product (5 g) obtained in Example 2-4 in R-11 (100 g) was injected into the autoclave over 5.7 hours.
  • the pressure inside the autoclave was increased to 0.15 MPa, and the R-11 solution with a benzene concentration of 0.1 gZmL was removed from 25 ° C. 9 mL was injected while the temperature was raised to 40 ° C, the benzene solution injection port of the autoclave was closed, and stirring was continued for 0.3 hour.
  • Example 2-6 Production example of (CF 3 ) 2 CFCOF by decomposition reaction of ester bond
  • the fluorination reaction product in Example 2-3 was changed to the fluorination reaction product obtained in Example 2-5, and the fluorine was added.
  • the reaction was carried out in the same manner except that 8.1 g of the liquid from which the R113 reaction product was removed was slowly added. 1.02 g of product was collected in the receiver .
  • the products include FCO (CF 2 ) 2 COF ( ⁇ 35% area) and FCO (CF 2 ) 2 COOCF 2 CH (CF 3 ) 2 (GC area 60%), (CF 3 ) 2 CFCOF (GC area 5%) was included.
  • 6.94 g was collected in the trap.
  • the products contained FCO (CF 2 ) 2 COF (GC area 30%) and (CF 3 ) 2 CF COF (GC area 70%).
  • the compound (1) which is a raw material of the production method of the present invention various compounds having various carbon skeletons are commercially available and can be obtained at low cost. According to the production method of the present invention, a fluorine-containing compound having various skeletons can be freely produced from this raw material compound in a short step and at a high yield.
  • the production method of the present invention is not limited to the compounds described above as specific examples, and is a method having excellent versatility applicable to various compounds.
  • the method of the present invention can be a more industrially advantageous and efficient production method by employing a method of recycling a compound or the like.

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Abstract

Procédé de préparation de composés de carbonyle fluorés présentant diverses structures et de dérivés de ceux-ci, à partir d'alcools, notamment d'alcools de faible masse moléculaire. Le procédé comporte les étapes consistant à : estérifier R1CHR2OH (1) avec Qf(COF)n (2) pour obtenir un produit d'estérification contenant au moins un composé représenté par la formule générale : Q?f(COOCHR1R2)¿m (COF)n-m (3), perfluorer le produit d'estérification pour obtenir un produit de fluoration contenant au moins un composé représenté par la formule générale Q?f(COOCFR1fR2f)¿m (COF)n-m, soumettre le produit de fluoration à une coupure de liaison ester, et récupérer ensuite le composé (2) ainsi que les composés de carbonyle fluorés tels que R1fCOR2 (5) du mélange réactionnel obtenu ; R1 représentant hydrogène ou analogue ; R2 représentant alkyle ou analogue ; R1f représentant fluoro ou analogue ; R2f représentant perfluoroalkyle ou analogue ; Qf représentant alkylène perfluoré ou analogue ; n étant un nombre entier égal ou supérieur à 2 ; et m étant un nombre entier égal ou supérieur à 2 mais non supérieur à n.
PCT/JP2002/006502 2001-06-27 2002-06-27 Procédé de préparation de composés de carbonyle fluorés WO2003002501A1 (fr)

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Cited By (1)

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WO2019151267A1 (fr) * 2018-02-01 2019-08-08 Ａｇｃ株式会社 Procédés de production d'un composé 1,3-dioxolane et de perfluoro(2,2-diméthyl-1,3-dioxole)

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EP0271212A2 (fr) * 1986-11-07 1988-06-15 Tosoh Corporation Procédé pour la fabrication d'esters d'acide carboxylique contenant du fluor
WO1995025082A1 (fr) * 1994-03-15 1995-09-21 Minnesota Mining And Manufacturing Company Procede pour convertir des esters perfluores en fluorures d'acyles perfluores et/ou en cetones perfluorees
WO2000056694A1 (fr) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Procede de production d'un compose de fluor au moyen d'une fluoration en phase liquide

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JPS5340708A (en) * 1976-09-24 1978-04-13 Asahi Glass Co Ltd Preparation of acid fluorides having ester group
EP0271212A2 (fr) * 1986-11-07 1988-06-15 Tosoh Corporation Procédé pour la fabrication d'esters d'acide carboxylique contenant du fluor
WO1995025082A1 (fr) * 1994-03-15 1995-09-21 Minnesota Mining And Manufacturing Company Procede pour convertir des esters perfluores en fluorures d'acyles perfluores et/ou en cetones perfluorees
WO2000056694A1 (fr) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Procede de production d'un compose de fluor au moyen d'une fluoration en phase liquide

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CHEMICAL ABSTRACTS, vol. 48, 1954, Columbus, Ohio, US; abstract no. 1255G, FILLER R. ET AL.: "Fluorinated esters. II. Diesters of perfluorocarboxylic acids with alcohols and glycols" XP002957358 *
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019151267A1 (fr) * 2018-02-01 2019-08-08 Ａｇｃ株式会社 Procédés de production d'un composé 1,3-dioxolane et de perfluoro(2,2-diméthyl-1,3-dioxole)
JPWO2019151267A1 (ja) * 2018-02-01 2021-01-14 Ａｇｃ株式会社 １，３−ジオキソラン化合物及びペルフルオロ（２，２−ジメチル−１，３−ジオキソール）の製造方法
US10975053B2 (en) 2018-02-01 2021-04-13 AGC Inc. Production methods for 1,3-dioxolane compound and perfluoro(2,2-dimethyl-1,3-dioxole)
JP7184055B2 (ja) 2018-02-01 2022-12-06 Ａｇｃ株式会社 １，３－ジオキソラン化合物及びペルフルオロ（２，２－ジメチル－１，３－ジオキソール）の製造方法

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