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WO2002026693A1 - Procede de preparation d'un compose fluoroamine - Google Patents

Procede de preparation d'un compose fluoroamine Download PDF

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Publication number
WO2002026693A1
WO2002026693A1 PCT/JP2001/008257 JP0108257W WO0226693A1 WO 2002026693 A1 WO2002026693 A1 WO 2002026693A1 JP 0108257 W JP0108257 W JP 0108257W WO 0226693 A1 WO0226693 A1 WO 0226693A1
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Prior art keywords
compound represented
compound
formula
group
reaction
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PCT/JP2001/008257
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English (en)
Japanese (ja)
Inventor
Masahiro Ito
Kunio Watanabe
Daisuke Shirakawa
Takashi Okazoe
Shin Tatematsu
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2002531079A priority Critical patent/JPWO2002026693A1/ja
Priority to AU2001290260A priority patent/AU2001290260A1/en
Publication of WO2002026693A1 publication Critical patent/WO2002026693A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • the present invention relates to a process for producing a fluorine-containing amine compound such as a fluorine-containing trialkylamine which is industrially useful as a solvent or an inert fluid.
  • a fluorine-containing amine compound such as a fluorine-containing trialkylamine which is industrially useful as a solvent or an inert fluid.
  • the present invention also provides a novel compound useful as a fluorine-containing trialkylamine or a fluorine-containing ester.
  • a method of fluorinating all of the C-H portion in a C-H-containing compound to C-F a method of using cobalt trifluoride, a method of directly fluorinating using fluorine gas, or an electrolytic cell Among them, a method of performing a fluorination reaction by electrolysis of hydrogen fluoride (hereinafter referred to as an ECF method) is known.
  • ECF method a method of performing a fluorination reaction by electrolysis of hydrogen fluoride
  • the reaction is performed by a gas-solid reaction at a high temperature, and there is a problem that isomerization and bond cleavage occur, and various by-products are generated.
  • Fluorine-containing tri-substituted amine compounds such as fluorinated trialkylamine compounds are soluble in It is useful as an agent.
  • fluorinated trialkylamines have been industrially produced by fluorinating a hydrocarbon compound having the same skeleton as the intended fluorinated trialkylamine by the + ECF method.
  • fluorination involves isomers and it is difficult to separate the isomers, the resulting fluorinated trialkylamine is a mixture of isomers. That is, the method has a problem that it is difficult to obtain only a target compound.
  • the present invention as a result of various investigations of the causes of the problems of the conventional method, first, when an attempt was made to produce a fluorine-containing amine compound by a fluorination reaction in a liquid phase using fluorine gas, if the boiling point of the raw material was low, It was found that the raw materials react in the gas phase to cause a decomposition reaction. Therefore, a raw material compound that can be obtained at low cost is selected, and this is converted into a compound having a specific structure that has a high molecular weight to such an extent that a gas phase reaction hardly occurs and that is soluble in a solvent used in the fluorination reaction.
  • fluorination can be performed while preventing decomposition reaction by performing fluorination in the liquid phase. Furthermore, they have found that the desired fluorinated amine compound can be produced by cleaving the bonding group after fluorination. Furthermore, they have found that an industrially useful and efficient continuous process can be achieved by recycling the produced compounds.
  • the present invention has the following configurations.
  • a compound represented by the following formula (1) is reacted with a compound represented by the following formula (2) to obtain a compound represented by the following formula (3) or a salt thereof, and the compound represented by the formula (3): Wherein the compound or a salt thereof is fluorinated by reacting the compound or a salt thereof with fluorine in a liquid phase.
  • R A and R AF are each a monovalent organic group which may be the same or different, and when R A is different from R A A is a fluorinated monovalent organic group
  • R B and R BF are each a monovalent organic group which may be the same or different, and when R B and R BF are different, R BF is R B It is a fluorinated monovalent organic group.
  • R A and R B may form a divalent organic group bonded to each other, R AF and R BF when the are bonded to form a divalent organic group with one another, R A and R may be the divalent organic group formed divalent organic group and which is formed with a R BF from B are identical or different, divalent organic group formed from R AF and R BF when different, R divalent organic group formed by a and R B are fluorinated groups.
  • R c is a single bond or a divalent organic group; when R c is a single bond, R c F is a single bond; when R c is a divalent organic group, R CF is the same as R c Alternatively, R CF in different cases is a divalent organic group in which R c is fluorinated.
  • R E and R EF is a monovalent organic group which may have the same as or different from each other, R EF when the R E and R EF are different is a monovalent organic group R E is fluorinated.
  • E 1 and E 2 is a reactive group capable of reacting with each other respectively, E is a divalent linking group formed by reaction between E 1 and E 2, E F is E and the same 2 A valent linking group or a divalent linking group in which E is fluorinated;
  • R AF at least one group R BF, is selected from R CF, R EF, and E F is a group formed by fluorinated.
  • the compound represented by the formula (1) is a compound represented by the following formula (la)
  • the compound represented by the formula (2) is a compound represented by the following formula (2a)
  • the compound represented by the formula (3) or a salt thereof is a compound represented by the following formula (3a) or an HX salt of the compound represented by the formula (3a)
  • R A , R B , R c , R E , R AF , R BF , R CF , and R EF each have the same meaning as described above, and X represents a halogen atom.
  • the compound represented by the formula (4) obtained by the above method is subjected to a decomposition reaction to cleave the divalent linking group (E F ) in the compound represented by the formula (4).
  • E Fi Oyo E F2 are each independently E F was formed by cleaving group.
  • R AF , R BF , R CF and R EF each have the same meaning as described above. 7.
  • R AFF is a monovalent organic group in which RA in formula ( 3a ) is completely fluorinated
  • R BFF is a monovalent organic group in which R B is completely fluorinated in formula ( 3a ).
  • CFF is a single bond or a divalent linking group
  • R c in Formula (3a) represents a fully fluorinated divalent linking group
  • REFF represents a fully fluorinated monovalent organic group.
  • reaction between the compound represented by the formula (la) and the compound represented by the formula (2a) is carried out without or in the presence of a neutralizing agent, or after the reaction, neutralization or desalination is performed.
  • a neutralizing agent or after the reaction, neutralization or desalination is performed.
  • the above manufacturing method to be performed without any.
  • the organic group in the present specification refers to a group having a carbon atom as essential, and may be saturated or unsaturated.
  • the fluorinated group refers to a group in which an atom that can be substituted with a fluorine atom such as a hydrogen atom bonded to a carbon atom or an atomic group that can be substituted with a fluorine atom is substituted with a fluorine atom.
  • the monovalent organic group includes a monovalent hydrocarbon group, a heteroatom-containing monovalent hydrocarbon group, a halogenated monovalent hydrocarbon group, or a halogenated (heteroatom-containing monovalent hydrocarbon group).
  • a hydrogen) group is preferred.
  • Divalent organic groups include divalent hydrocarbon groups, heteroatom-containing divalent hydrocarbon groups, halogenated divalent hydrocarbon groups, and halogenated
  • the organic group preferably has 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, from the viewpoint of solubility in the liquid phase used during the fluorination reaction.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. Further, a single bond, a double bond, or a triple bond may be present as a carbon-carbon bond in the aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group may have any of a linear structure, a branched structure, a ring structure, and a structure partially having a ring structure.
  • the organic group is preferably a saturated group among the above groups.
  • a saturated group refers to a group in which a carbon-carbon bond consists of only a single bond.
  • examples of the monovalent saturated hydrocarbon group include an alkyl group.
  • examples of the divalent saturated hydrocarbon group include an alkylene group.
  • the saturated group is preferably a linear structure, a branched structure, a ring structure, or a structure having a ring portion.
  • the alkyl group or the alkylene group preferably has 1 to 10 carbon atoms.
  • Examples of the alkyl group having a straight-chain structure include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • alkyl group having a branched structure examples include an isopropyl group, an isobutyl group, a sec-butyl group, a t-tert-butyl group, and the like.
  • alkyl group having a ring structure examples include a cycloalkyl group, a bicycloalkyl group, a group having an alicyclic spiro structure, and a 3- to 6-membered cycloalkyl group is preferable, and a cyclopentyl group or a cycloalkyl group is preferred.
  • Xyl groups and the like examples include an isopropyl group, an isobutyl group, a sec-butyl group, a t-tert-butyl group, and the like.
  • alkyl group having a ring structure examples include a cycloalkyl group, a bicycloalkyl group, a group having an alicyclic spiro structure, and a 3-
  • Particularly preferred are a hexylethyl group, a hexylmethyl hexylmethyl group and the like.
  • alkyl group having a ring portion examples include an alkyl group having an aromatic ring (for example, an aralkyl group such as a benzyl group and a phenethyl group) and an alkyl group having a heterocyclic ring (for example, a pyridylmethyl group, a furfuryl group, and the like).
  • alkylene group examples include groups in which one hydrogen atom of the above-mentioned alkyl group is a bond, and a linear or branched alkylene group is preferable.
  • the hetero atom may be the hetero atom itself, or may be present in the group as a hetero atom in which the hetero atoms are bonded to each other or a hetero atom is formed by bonding a hetero atom to another atom. Further, it is preferable that neither the hetero atom nor the heteroatom group is changed by the angle-of-reaction of the group (E).
  • the heteroatom-containing saturated hydrocarbon group preferably has 1 to 20 carbon atoms.
  • the heteroatom-containing saturated hydrocarbon group include a group in which a divalent heteroatom or a divalent heteroatom atomic group is inserted between carbon and carbon atoms of the saturated hydrocarbon group, or a group in the saturated hydrocarbon group. And a group in which a divalent hetero atom or a divalent heteroatom is bonded to a carbon atom at the bonding end of the saturated hydrocarbon group.
  • an etheric oxygen atom-containing group is particularly preferred in view of the usefulness of the compound.
  • the monovalent group is preferably an alkyl group containing an etheric oxygen atom (for example, an alkoxyalkyl group, etc.), and a divalent group.
  • an alkylene group containing an etheric oxygen atom for example, a polyoxyalkylene group
  • Examples of the monovalent aliphatic hydrocarbon group having an etheric oxygen atom inserted between carbon-carbon atoms and having a ring portion include an alkyl group having a dioxolane skeleton.
  • alkoxyalkyl group a group in which one of the hydrogen atoms present in the alkyl group described above for the monovalent aliphatic hydrocarbon group is substituted with an alkoxy group is preferable.
  • the alkoxy group preferably has 1 to 10 carbon atoms. Examples of the alkoxyalkyl group include an ethoxymethyl group, a 1-propoxyshetyl group, and a 2-propoxyshetyl group.
  • Halogenation means that one or more hydrogen atoms have been replaced by halogen atoms.
  • the halogen atom in the halogenated group include a fluorine atom, a chlorine atom, and a odor.
  • a fluorine atom, a chlorine atom, or a bromine atom is preferable, and a fluorine atom, or a fluorine atom and a chlorine atom are particularly preferable from the viewpoint of the usefulness of the compound.
  • Partial halogenation in halogenation means that part of a hydrogen atom has been replaced by a halogen atom.
  • a hydrogen atom is present in the c- halogenation, and perno and lipogenation mean that all of the hydrogen atoms are fluorinated. That is, there is no hydrogen atom in the perhalogenated group.
  • the number of halogen atoms present in the halogenated group or perhalogenated group may be one or more.
  • the meanings of the terms halogenation, partial halogenation, and perhalogenation are the same as the meanings of the terms such as fluoro, partial fluoro, and perfluoro.
  • the halogenated saturated hydrocarbon group refers to a group in which one or more of the hydrogen atoms present in the above saturated hydrocarbon group has been replaced by a halogen atom.
  • a hydrogen atom may or may not be present in the halogenated saturated hydrocarbon group.
  • the halogen atom in the halogenated saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a fluorine atom and a chlorine atom.
  • the partially halogenated saturated hydrocarbon group refers to a group in which a part of the hydrogen atoms present in the above-mentioned saturated hydrocarbon group has been replaced by a halogen atom.
  • a hydrogen atom is present in the partially halogenated saturated hydrocarbon group.
  • the perhalogenated saturated hydrocarbon group is a group in which all of the hydrogen atoms present in the saturated hydrocarbon group have been replaced by Happagen atoms. There is no hydrogen atom in the perno and lipogenated saturated hydrocarbon groups.
  • the halogenated saturated hydrocarbon group may have a linear structure or a branched structure, may have a ring structure, or may have a ring portion.
  • halogenated monovalent saturated hydrocarbon groups fluoroalkyl groups or fluoro (partially alkyl) groups
  • examples of the halogenated divalent saturated hydrocarbon group include a fluoroalkylene group and a fluoro (partial cycloalkylene) group.
  • the halogenated saturated hydrocarbon group preferably has 1 to 20 carbon atoms.
  • a perfluoroalkyl group or a perfluoro (partial alkyl group) group ie, a group in which all of the hydrogen atoms in the partial alkyl group are fluorinated
  • a perfluoroalkylene group or a perfluoro (partially chloroalkylene) group that is, a group in which all of the hydrogen atoms in the partial cycloarylene group are fluorinated
  • the perfluoro (partially fluoroalkyl) group is the same as the perfluoroalkyl group, and the perfluoro (partially fluoroarylene) group is the same as the perfluoroalkylene group.
  • the number of carbon atoms in the halogenated saturated hydrocarbon group is preferably 1 to 20.
  • the halogenated (heteroatom-containing saturated hydrocarbon) group preferably has 1 to 20 carbon atoms, and preferably has a linear structure, a branched structure, or a structure having a ring portion.
  • a fluoro (hetero atom-containing saturated hydrocarbon) group or a fluoro (partial chroma (hetero atom-containing saturated hydrocarbon)) group is preferable, and a perfluoro (hetero atom-containing monovalent saturated hydrocarbon) group or perfluoro group is preferred.
  • a (partial chroma (hetero atom-containing saturated hydrocarbon)) group is particularly preferred, and a fluoro (hetero atom-containing alkyl) or fluoro (partial cyclo (hetero atom-containing alkyl)) group is particularly preferred. Alkoxyl) groups or perfluoro (partial cyclo (alkoxyl)) groups are more preferred.
  • the perhalogenated (heteroatom-containing divalent saturated hydrocarbon) group is a group in which one of the halogen atoms in the perhalogenated (heteroatom-containing monovalent saturated hydrocarbon) group is a bond, Perfluoro (polyoxyalkylene) groups are preferred. Examples of these groups are specifically shown in the specific compounds described below.
  • R A , R B and R c various compounds having different structures of R A , R B and R c can be used as the compound (1). That is, the compound of interest (4), compound (5) in R AF, R BP, and R CF group corresponding to (R A, R B, and R c) a compound having a
  • the compound (4) By carrying out the reaction of the present invention using (1) and a compound (2) having a group (R E ) corresponding to R EF , the compound (4), which was difficult to obtain by conventional methods, (5) can be manufactured.
  • Examples of compound (4) and compound (5), which were difficult to obtain by conventional methods, include compounds with complicated structures of R AF , R BF , R CF, and R EF , and various types due to fluorination reactions.
  • examples of c latter fluorinated can be mentioned low molecular weight products occurs, the molecular weight of 200 or less, preferably a molecular weight include fluorides of 50-200 der Ru amine compound.
  • Compound (1) in E 1 is a reactive group capable of forming a bivalent connecting group (E) reacts with E 2.
  • E is —CH 2 OCO—
  • each of E 1 and E 2 is a case where one is one CH 2 OH and the other is one COX (X is a halogen atom).
  • the divalent linking group (E) is —CH 2 ⁇ CO— will be described in detail.
  • the following compound (la) wherein E 1 is one CH 2 OH is preferable.
  • R A and R B are monovalent organic groups, each of which is a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated group.
  • RG is a single bond, a divalent saturated hydrocarbon group, a partially halogenated divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group containing an etheric oxygen atom, or a partial halogen radical (a divalent compound containing an ethereal oxygen atom) (Saturated hydrocarbon) group.
  • R c -CH (R D ) 1 (where R D represents a hydrogen atom or a monovalent organic group, and R D is a hydrogen atom, a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon.
  • RD is particularly preferably a hydrogen atom, an alkyl group, an alkoxyalkyl group, a partially halogenated alkyl group, or a partially halogenated (alkoxyalkynole) group.
  • R A and R B are each an alkyl group, an alkoxyalkyl group, moiety halogenation alkyl group or a partially halogenated (alkoxyalkyl) group is particularly favorable preferable.
  • R A and R B are particularly preferably bonded to each other to form an alkylene group, an alkyleneoxyalkylene group, a partially halogenated alkylene group, or a partially halogenated (alkylenoxyanorylene) group. .
  • R c is particularly preferably a single bond, an alkylene group, an alkoxyalkylene group, a partially halogenated alkylene group, or a partially halogenated, or halogenated (alkoxyalkylene) group.
  • the compound (1) and the compound (la) are preferably compounds containing no fluorine atom, and particularly preferably compounds containing no halogen atom, because various structures are easily available. That is, the groups in the compound (1) and the compound (1a) are preferably non-nodogenated groups.
  • Specific examples of the compound (la) include the following compounds.
  • Compound (la) is a compound that is easily available or can be easily synthesized by a known method.
  • dialkylamino alcohols can be easily synthesized by a known method described in JP-A-9-511497.
  • R E is a monovalent organic group
  • E 2 is a reactive group capable of reacting with E 1 of the compound (1)
  • E 1 and E 2 reacts with each other to form a divalent linking group (E) in compound (3).
  • compound (2) a commercially available product may be used, or the compound (6) produced by the method of the present invention described later may be used.
  • Compound (2) E 2 in is appropriately changed by the combination of E 1, E 1 gar CH 2 one COX or a E 2 is the case where the OH S o 2 x (X is a halogen atom , A chlorine atom or a fluorine atom is preferable, and when a continuous process is carried out, X is preferably a fluorine atom.) Is preferable, and particularly, one COX is preferable.
  • the compound (3) is preferably a compound containing a fluorine atom.
  • the fluorine content (the ratio of fluorine atoms in the molecule) is preferably 10% by mass or more. It is particularly preferred to be from 86 to 86% by mass, particularly preferably from 10 to 76% by mass, and more preferably from 30 to 76% by mass.
  • R E in the compound (2) is not that preferred for a fluorine-containing monovalent organic group. Also, R E in the compound (2) may be easily performed a continuous process which will be described later Therefore, a perhalogenated group is preferable, and a perfluoro group is particularly preferable.
  • the compound (2) is preferable because the compound (2a) in which E 2 is one COF is easy to carry out the continuous process described later.
  • R E is a monovalent organic group, preferably a perfluoro monovalent organic group, a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, And a group in which all of the hydrogen atoms present in the group selected from the group consisting of a halogenated (etherified oxygen atom-containing monovalent saturated hydrocarbon) group are substituted with fluorine atoms are preferable. Particularly preferred is an alkyl group or a perfluoro (alkoxyalkyl) group.
  • CF 3 CF 2 CF 2 OCF (CF 3 ) COF is readily available as an intermediate for perfluoro (alkyl vinyl ether).
  • the reaction of the compound (1) and the compound (2) can be carried out by applying known reaction methods and conditions depending on the structure you Yopi combinations thereof E 1 and E 2.
  • the reaction between the compound (la) in which E 1 is —CH 2 OH and the compound (2a) in which E 2 is —C OX can be carried out under known reaction conditions.
  • the reaction may be carried out in the presence of a solvent (hereinafter referred to as solvent 1), but is preferably carried out in the absence of solvent 1 from the viewpoint of volumetric efficiency.
  • solvent 1 dichloromethane, chloroform, triethylamine, or a mixed solvent of triethylamine and tetrahydrofuran is preferable.
  • the amount of the solvent 1 to be used is preferably 50 to 500% by mass based on the total amount of the compound (la) and the compound (2a).
  • the reaction temperature between the compound (la) and the compound (2a) is preferably not lower than 50 ° C, more preferably not higher than + 100 ° C or not higher than the boiling point of the 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 used for the reaction.
  • the reaction pressure gauge pressure, the same applies hereinafter is preferably from 0 to 2 MPa.
  • the reaction of compound (1) with compound (2) produces compound (3) or a salt thereof (hereinafter collectively referred to as compound (3)).
  • a to R E are their respective, the same groups corresponding to these groups in the compound (1) and the compound (2).
  • E is a divalent linking group formed by the reaction of E 1 and E 2 and includes the groups described above.
  • the molecular weight of the compound (3) is preferably from 200 to 1,000, since the fluorination reaction in the liquid phase can be carried out smoothly. If the molecular weight is too small, the compound (3) is likely to evaporate, so that the decomposition reaction in the gas phase during the fluorination reaction in the liquid phase May occur. On the other hand, if the molecular weight is too large, it may be difficult to handle the compound (3).
  • the fluorine content in the compound (3) is preferably the above-mentioned amount.
  • a compound (3a) formed by reacting the compound (la) with the compound (2a) or an HX salt thereof (hereinafter, collectively referred to as compound (3a)) is preferable. .
  • R A , R B , R c , and R E have the same meaning as described above, and preferred embodiments are also the same.
  • Specific examples of the compound (3) include the following compounds.
  • the novel compound among the compounds (3) is useful as an intermediate of a fluorinated trialkylamine, and can be led to a fluorinated trialkylamine by a reaction described later (the compound (1) and the compound (2) )),
  • the crude product containing the compound (3) may be purified according to the purpose or used as it is for the next reaction, etc., and the fluorination reaction in the next step is safely performed. From the viewpoint of performing, it is usually desirable to purify.
  • the compound (3) is reacted with fluorine in a liquid phase to form a compound.
  • the fluorination reaction of the compound (3) can be theoretically carried out even by the cobalt fluorination method, the ECF method, or the gas phase fluorination method.
  • the chemical method is a particularly advantageous method.
  • the fluorination in the liquid phase is carried out by reacting compound (3) with fluorine in the liquid phase.
  • fluorine fluorine gas may be used as it is, or may be diluted with an inert gas and used.
  • the inert gas nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic reasons.
  • the amount of fluorine gas in the nitrogen gas is not particularly limited, and is preferably 10 vol% or more in view of efficiency, and particularly preferably 2 Ovol% or more.
  • the liquid phase may be a liquid phase formed from the compounds involved in the reaction itself, but may be a solvent (hereinafter, referred to as solvent 2).
  • the solvent 2 is preferably a solvent which does not contain a C—H bond and requires a C-F bond, and is preferably a perfluoroalkane or at least one selected from a chlorine atom, a nitrogen atom, and an oxygen atom
  • An organic solvent obtained by perfluorinating a known organic solvent having the following formula in its structure is preferable.
  • the solvent 2 it is preferable to use a solvent having high solubility of the compound (3), particularly a solvent capable of dissolving the compound (3) by 1% by mass or more, particularly a solvent dissolving the compound (3) by 5% by mass or more. It is preferred to use
  • the amount of the solvent 2 is preferably at least 5 times the mass of the compound (3), particularly preferably 10 to 100 times the mass.
  • the liquid phase in the fluorination reaction of the compound (3a) or its salt includes perfluoroalkanes (e.g., 172), perfluoroethers (e.g., FC-75, FC-177), Fluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), black mouth fluorocarbons (trade name: CFC), black mouth fluoropolyethers, inert fluids (trade name: (Florinite).
  • perfluoroalkanes e.g., 172
  • perfluoroethers e.g., FC-75, FC-177
  • Fluoropolyethers trade names: Krytox, Fomblin, Galden, Demnum, etc.
  • black mouth fluorocarbons trade name: CFC
  • black mouth fluoropolyethers black mouth fluoropolyethers
  • inert fluids trade name: (Florinite).
  • R AFF is a monovalent organic group R A in formula (3 a) is fully fluorinated
  • R BFF is a monovalent organic group in which R B in the formula (3 a) are fully fluorinated
  • R CFF represents a single bond or a divalent organic group
  • R c represents a completely fluorinated divalent organic group
  • R EFF represents a completely fluorinated monovalent organic group.
  • the reaction system of the fluorination reaction is preferably a batch system or a continuous system.
  • the fluorine gas may be diluted with an inert gas such as nitrogen gas, regardless of whether the method is performed in a batch mode or in a continuous mode.
  • [Fluorination method 2] Charge solvent 2 into the reactor and start stirring. A method in which compound (3) and fluorine gas are continuously and simultaneously supplied at a predetermined molar ratio at a predetermined reaction temperature and reaction pressure.
  • the compound (3) When the compound (3) is supplied in the fluorination method 2, the compound (3) may be supplied as it is without being diluted with the solvent 2.
  • the amount of solvent 2 is preferably at least 5 times the mass of compound (3), particularly It is preferably at least 10 times the mass.
  • the amount of fluorine used in the fluorination reaction whether the reaction is performed in a batch mode or in a continuous mode, the amount of fluorine is always excessive with respect to the hydrogen atoms in compound (3). It is preferable to carry out the reaction while maintaining the state in which fluorine is present in an equivalent amount, and in particular, the use of fluorine in an amount of 1.5 times equivalent (ie, 1.5 times mol) or more is the selectivity. Preferred from the point.
  • the amount of fluorine is preferably such that an excess equivalent is maintained from the beginning to the end of the reaction.
  • the reaction temperature of the fluorination reaction can be changed depending on the structure of the divalent linking group (E). However, in the fluorination reaction of the compound (3a), it is not lower than 160 ° C and not higher than the boiling point of the compound (3a). From the viewpoints of reaction yield, selectivity, and the ease of industrial implementation, the temperature is particularly preferably from 150 ° C to 110 ° C, and particularly preferably from 120 ° C to 150 ° C. .
  • the reaction pressure of the fluorination reaction is not particularly limited, and is particularly preferable from the viewpoint of 0 to 2 MPa power, reaction yield, selectivity, and ease of industrial implementation.
  • a C—H bond-containing compound to the reaction system or to perform ultraviolet irradiation.
  • a C—H bond-containing compound to the reaction system in the latter stage of the fluorination reaction, or to perform ultraviolet irradiation.
  • the ultraviolet irradiation time is preferably from 0.1 to 3 hours.
  • the C—H bond-containing compound is an organic compound other than the compound (3), particularly preferably an aromatic hydrocarbon, particularly preferably benzene, toluene and the like.
  • the addition amount of the C one H bond-containing compound, the 0. 1 is preferably 1 0 mol 0/0 to hydrogen atoms in the compound (3), in particular 0. 1 5 mol% Is preferred.
  • the C-H bond-containing compound is preferably added in a state where fluorine is present in the reaction system. Furthermore, when a compound containing a C--H bond is added, the reaction system must be pressurized. Is preferred. The pressure at the time of pressurization is preferably 0.01 to 5 MPa.
  • R REF and E F in the compound (4) is a group corresponding to R A to R E and E in the compound (3).
  • RR B a group R C, is R ⁇ and E is fluorinated, in and when the fluorine has reacted, the corresponding R BF, R CF, R EF , and E F will fluorinated groups .
  • R A , R B , R C , R E , and E are non-fluorinated groups but do not react with fluorine even if they are fluorinable groups, the corresponding 1, R BF , R CF , R EF, becomes the same group as Oyopi E F.
  • Examples of the same group include a case where a hydrogen atom is not subjected to fluorination even if a hydrogen atom is present in R A , R B , RG, R e , or E, or R A , R B , R G , R E or E is a compound (3) in which the compound is a perhalogenated group.
  • BF , rCF , and F are preferably a fluorine-substituted group, and an unsubstituted hydrogen atom may be present in the group.
  • the amount of hydrogen atoms in the group can be appropriately changed by adjusting the degree of fluorination.
  • R C of compound (3) is a group having a structure represented by —CH (R D ) — (where R D has the same meaning as described above)
  • compound (4) groups (R E F) is _ CF corresponding portions (R DF) - preferably (where that is a group having, is preferably the R DF are groups R D is fluorinated, a fluorine atom And particularly preferably a group in which all of the hydrogen atoms present in an alkyl group, an alkoxyalkyl group, a partially halogenated alkyl group, or a partially halogenated (alkoxyalkyl) group are substituted with fluorine atoms, and particularly preferably a fluorine atom. ).
  • E is a divalent linking group.
  • the compound (4), E is one CH 2 OCO- der Ru compound (3 a) fluorinated by E F is one CF 2 ⁇ CO- in Natsuta following compounds of (4 a) is preferred.
  • R A is Ri Oh a group all the hydrogen atoms present in R A is substituted by a fluorine atom, a group in which all of the hydrogen atoms R BP is present in R B substituted by fluorine atoms,
  • the group formed from R AF , R BF and the force is preferably a group in which all of the hydrogen atoms in the group formed from R A and R B have been substituted with fluorine atoms.
  • R EF is a monovalent saturated hydrocarbon group, partially halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing an etheric oxygen atom, and partially halogenated (monovalent saturated hydrocarbon containing an etheric oxygen atom) It is preferable that all of the hydrogen atoms present in the group selected from the groups are substituted with fluorine atoms.
  • RBF and RBF are groups in which all of the hydrogen atoms present in an alkyl group, an alkoxyalkyl group, a partially halogenated alkyl group, or a partially halogenated (alkoxyalkyl) group are substituted with fluorine atoms. Particularly preferred. Or, when and R BF are bonded to each other to form a divalent group, an alkylene group, an alkyleneoxyalkylene group, a partially halogenated alkylene group, or a partially halogenated (alkyleneoxyalkylene) group It is particularly preferred that all of the hydrogen atoms present therein are substituted with fluorine atoms.
  • R CF is all hydrogen atoms present in the alkylene, alkoxyalkylene, partially halogenated alkylene, or partially halogenated (alkoxyalkylene) groups Is particularly preferably a group in which is substituted by a fluorine atom.
  • R EF is a phenolic alkyl group, or a perno, logen (alkoxyalkyl) group.
  • Specific examples of the compound (4) include the following compounds.
  • the amount is preferably 1 to 20 times, and more preferably 1 to 5 times, the molar amount of the total hydrogen atoms present in the compound (3).
  • a cooler preferably maintained at 10 ° C. to room temperature, particularly preferably maintained at about 20 ° C.
  • a cooler preferably between 78 ° C and 110 ° C, preferably between 30 ° C and 0 ° C
  • a liquid return line for returning the condensed liquid to the reactor from the cooler (I I I) may be installed.
  • the crude product containing the compound (4) obtained by the fluorination reaction 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.
  • the conversion reaction is the reaction that cleaves E F in the compound (4).
  • R EF- I E F2 (6)
  • R AF, R BF, R CF, R EF is the same as defined above, E "and E F2 are in their respective independently a group E F is formed by cutting.
  • the conversion reaction is a decomposition reaction of an ester bond cleaving one CF 2 ⁇ CO— represented by the following formula.
  • the ester bond decomposition reaction of the compound (4a) is preferably performed by a thermal decomposition reaction or a decomposition reaction performed in the presence of a nucleophile or an electrophile.
  • the reaction produces compound (5a) and compound (6a).
  • R BF , R CF , and R EF are as defined above.
  • the thermal decomposition reaction can be carried out by heating compound (4a). It is preferable to select the reaction type of the thermal decomposition reaction based on the boiling point of the compound (4a) and its stability. For example, when the compound (4a), which is easily vaporized, is thermally decomposed, it is continuously decomposed in the gas phase, and the outlet gas containing the compound (5a) is condensed and recovered. Can be adopted.
  • the reaction temperature of the gas phase pyrolysis method is preferably from 50 to 350 ° C, particularly preferably from 50 to 300 ° C, particularly preferably from 150 to 250 ° C.
  • an inert gas not directly involved in the reaction may be allowed to coexist in the reaction system.
  • the inert gas include nitrogen gas and carbon dioxide gas. It is preferable to add about 0.01 to 50 V o 1% of the inert gas to the compound (4a). Large amounts of inert gas may reduce the amount of product recovered.
  • reaction temperature of this liquid phase pyrolysis method is preferably from 50 to 300 ° C, particularly preferably from 100 to 250 ° C.
  • the thermal decomposition may be performed without a solvent or in the presence of a solvent (hereinafter, referred to as solvent 3).
  • the solvent 3 is not particularly limited as long as it does not react with the compound (4a), is compatible with the compound (4a), and does not react with the compound (5a) to be produced.
  • the solvent 3 include an inert solvent such as perfluorotrialkylamine, perfluoronaphthylene, and a chlorofluoroethylene oligomer having a high boiling point among chlorofluorocarbons (for example, trade name : Freon loop) and are preferred.
  • the amount of the solvent 3 is preferably 10 to 1000% by mass based on the compound (4a).
  • the reaction may be performed without a solvent or in the presence of a solvent 3.
  • Solvent 3 is as described above.
  • F— is preferable, and F— derived from an alkali metal fluoride is particularly preferable.
  • F— nucleophilically adds to the carbonyl group present in the ester bond of compound (4a), and R AF R BF N— R CF — CF -Is eliminated and acid fluoride [compound (6a)] is formed.
  • R RBFN- R CF - - CF 2 0- from more F- apart is de-fluorinated Amin compound '[compound (5 a)] is produced.
  • the eliminated F— reacts in the same way as another compound (4a) molecule. But Thus, the nucleophile used at the beginning of the reaction may be in catalytic amount or in excess.
  • the reaction temperature is preferably from 30 ° C to the boiling point of the solvent 3 or the compound (4a), and particularly preferably from 20 ° C to 250 ° C. This method is also preferably carried out using a reactor equipped with a reflux tower.
  • R AF R AF , R BF , R CF , and R EF have the same meanings as above.
  • specific examples of the compound (6a) include the same compounds as the compound (2a).
  • compounds having a partial structure of “CiF—C 2 —COF” at the molecular terminal are known reactions.
  • a new compound (5 a) is a compound useful as a precursor of a fluorine-containing amine compound.
  • novel compounds provided by the present invention can lead to useful perfluorotrialkylamines, for example, in the following manner. That is, the formula (CH 3 C) 2 NC CH 2 CH 2 a compound represented by 0H and formula FCOCF (0CF 2 CF 2 CF 3 ) reacting the compound represented by CF 3 and Formula
  • the compound represented by (CF 3 CF 2 ) 2 NCF 2 CF 2 CF 2 0C0CF (0CF 2 CF 2 CF 3 ) CF 3 has the formula (CF 3 CF 2 ) 2 NCF by performing an ester bond decomposition reaction.
  • FCOCF (0CF 2 CF 2 CF 3 )
  • the compound represented by the formula (CF 3 CF 2 ) 2 NCF 2 COF produced by the above method is a compound represented by the formula (CF 3 CF 2 ) 2 NCF 2 C00H by a water-splitting reaction. Then, the compound can be led to a compound represented by the formula (CF 3 CF 2 ) 2 NCHF 2 by a decarboxylation reaction.
  • Compound (6) may be present together with compound (5) in the reaction product of the conversion reaction of compound (4).
  • the target compound may be any one of the compound (5) alone, the compound (6) alone, and both the compound (5) and the compound (6).
  • the process may omit the step of separating the product.
  • Specific example of the process 1 Is illustrated in Process 3.
  • a process in which the compound (5) and the compound (6) to be formed have the same structure, and a group is selected so that the compound (2) has the same structure. This process is particularly preferred because it is not necessary to separate the product, and a part or all of the produced compound can be used again for the reaction with the compound (1).
  • a compound (lb) is reacted with a compound (2b) to give a compound (3b), and the compound (3b) is fluorinated in a liquid phase to give a compound '(4b).
  • R A to and R AF to R CF in the following formula have the same meaning as described above.
  • the compound (5b-1) is reacted with the compound (2b-1) to give a compound (3b-1), and the compound (3b-1) is fluorinated in a liquid phase to give a compound (4b-1). l), and then the compound (5b-1) is produced from the reaction product obtained by decomposing the ester bond of the compound (4b-1). Way. And some or all of the compound (5b-l)
  • various fluorine-containing compounds can be produced using compound (1) and compound (2), which are raw materials that can be obtained at low cost.
  • compound (1) and the compound (2) various compounds having different R A , R B , R c , R E , and E 1 are commercially available and can be obtained at low cost.
  • a fluorinated amide compound can be produced from this raw material compound in a short step and at a high yield. Further, by using the method of the present invention, it is possible to easily synthesize a low-molecular-weight fluorinated amine compound or a fluorinated amine compound having a complicated structure, which was difficult to obtain by a conventional method.
  • the production method of the present invention is not limited to the compounds described as specific examples above, and is a method with excellent versatility that can be applied to various compounds. Can be manufactured freely. Also, by selecting the structure of the group, the method of the present invention can be a continuous process.
  • a novel acid fluoride compound or an intermediate thereof which can be used as a fluorine-containing trialkylamine compound.
  • the use of the fluorinated trialkylamine compound is not particularly limited, but is useful, for example, as an inert fluid, and is applied to various reaction solvents, refrigerants, and the like.
  • Example> Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
  • NMR yield the yield determined from the peak area ratio of the NMR spectrum is referred to as NMR yield.
  • TMS tetramethylsilane
  • CC 1 2 FCC 1 F 2 the R- 1 1 3.
  • the values of the NMR spectrum data are shown as apparent chemical shift ranges. In the quantification by 19 F-NMR, C 6 F 6 was used as an internal standard.
  • FC0CF (CF 3) 0CF 2 CF 2 CF 3 was dropped for one hour or only by keeping the (12. 8 g) and the internal temperature below 10 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. Thereafter, nitrogen was bubbled while maintaining the internal temperature at 30 ° C. to obtain a crude liquid containing the title compound from which excess FC0CF (CF 3 ) 0CF 2 CF 2 CF 3 was removed out of the system. The obtained crude liquid was used in the next step without purification.
  • Example 2 Example of producing (CF 3 CF 2 ) 2 NCF 2 CF 2 CF 2 0C0CF (CF 3 ) 0CF 2 CF 2 CF 3 by fluorination reaction
  • R-113 140 g was added to a 200 mL nickel autoclave, and the mixture was stirred and maintained at 25 ° C. After blowing nitrogen gas for 1 hour, fluorine gas diluted to 20% with nitrogen gas was blown at a flow rate of 8.69 LZh for 1 hour while the internal pressure of the autoclave was increased to 0.15 MPa. While blowing the diluted fluorine gas at the same flow rate, the crude liquid containing the HF salt of (C3 ⁇ 4CH 2 ) 2 NCH 2 CH 2 CH 2 0C0CF (CF 3 ) 0CF 2 CF 2 CF 3 obtained in Example 1 with a purity of 88% (4 A solution of 99 g) in R-113 (100 g) was injected over 6.1 hours.
  • the total amount of benzene injected was 0.21 g and the total amount of R-113 injected was 2 lmL.
  • stirring was continued for 1.1 hour while blowing diluted fluorine gas at the same flow rate.
  • the pressure in the reactor was adjusted to normal pressure, and nitrogen gas was blown for 1.2 hours to obtain a compound.
  • the measurement result of the mass spectrum of the compound was 712 (M + — F), and the measurement result of the IR spectrum showed that strong absorption was observed at 1780 to 1850 cm -1 derived from the ester bond. The formation of the title compound was confirmed.
  • Example 2 The compound (0.5) obtained in Example 2 was charged into a flask together with 0.01 g of NaF powder, and heated at 120 ° C for 10 hours in an oil bath with vigorous stirring. A reflux condenser adjusted to 20 ° C was installed above the flask. After cooling, 0.4 g of a liquid sample was recovered. GC-MS confirmed that CF 3 CF (0CF 2 CF 2 CF 3 ) C0F and the title compound were the main products. NMR yield was 60 ° / 0 .
  • a fluorine-containing amine compound which has been conventionally difficult to synthesize and a fluorine-containing amine compound which has been synthesized by an economically disadvantageous method can be obtained by shortening the compound (1) from the compound (1). And can be produced with high yield.
  • Compound (1) is generally easily available, easy to synthesize, inexpensive, and compounds of various structures are available. Further, by selecting the structure of the group in the compound (3), the compound can be easily dissolved in the liquid phase at the time of fluorination, and the fluorination reaction in the liquid phase can be carried out with high yield.

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Abstract

L'invention concerne un procédé industriel par lequel une fluoroamine peut être efficacement préparée à faible coût. R?ARBN-RC-E1¿ (1) est mis en réaction avec RE-E2 (2) afin de produire R?ARBN-RC-E-RE¿ (3), et ensuite fluoré pour produire un composé fluoro-amine représenté par R?AFRBFN-RCF-CF¿2-E?F-REF (4). RAF à REF¿ représentent éventuellement des groupes organiques fluorés correspondant à R?A à RE. E1 et E2¿ représentent des groupes réactifs l'un avec l'autre. E représente un groupe de liaison divalent formé par la réaction de E?1 avec E2. EF¿ est égal à E ou représente un groupe formé par fluoration.
PCT/JP2001/008257 2000-09-27 2001-09-21 Procede de preparation d'un compose fluoroamine Ceased WO2002026693A1 (fr)

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AU2001290260A AU2001290260A1 (en) 2000-09-27 2001-09-21 Process for producing fluoroamine compound

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586626B2 (en) 1999-03-23 2003-07-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6956138B2 (en) 2000-07-11 2005-10-18 Asahi Glass Company, Limited Method for producing a fluorine-containing compound
WO2015019809A1 (fr) * 2013-08-09 2015-02-12 ユニマテック株式会社 Ester bis(acide perfluoroétheralkylcarboxylique)amino et procédé pour le fabriquer
WO2016125257A1 (fr) * 2015-02-03 2016-08-11 ユニマテック株式会社 Ester d'aminoalkyle d'acide éther monocarboxylique contenant du fluor et son procédé de fabrication
JP2018193373A (ja) * 2012-07-18 2018-12-06 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ フッ素化界面活性剤
WO2021033649A1 (fr) 2019-08-20 2021-02-25 Ａｇｃ株式会社 Procédé de production d'un composé contenant du fluor contenant de l'azote

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EP0077114A1 (fr) * 1981-09-08 1983-04-20 Green Cross Corporation Produits perfluorochimiques, procédé de leur préparation et leur utilisation à titre de succédané du sang
JPH01259188A (ja) * 1988-04-08 1989-10-16 Agency Of Ind Science & Technol ペルフルオロ（３‐ジアルキルアミノプロピオン酸フルオリド）の製造方法

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EP0077114A1 (fr) * 1981-09-08 1983-04-20 Green Cross Corporation Produits perfluorochimiques, procédé de leur préparation et leur utilisation à titre de succédané du sang
JPH01259188A (ja) * 1988-04-08 1989-10-16 Agency Of Ind Science & Technol ペルフルオロ（３‐ジアルキルアミノプロピオン酸フルオリド）の製造方法

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6951957B2 (en) 1999-03-23 2005-10-04 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US7083705B2 (en) 1999-03-23 2006-08-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6586626B2 (en) 1999-03-23 2003-07-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6956138B2 (en) 2000-07-11 2005-10-18 Asahi Glass Company, Limited Method for producing a fluorine-containing compound
JP2018193373A (ja) * 2012-07-18 2018-12-06 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ フッ素化界面活性剤
WO2015019809A1 (fr) * 2013-08-09 2015-02-12 ユニマテック株式会社 Ester bis(acide perfluoroétheralkylcarboxylique)amino et procédé pour le fabriquer
CN105593207A (zh) * 2013-08-09 2016-05-18 优迈特株式会社 二(全氟醚羧酸烷基)氨基酯及其制备方法
JPWO2015019809A1 (ja) * 2013-08-09 2017-03-02 ユニマテック株式会社 ビス（パーフルオロエーテルカルボン酸アルキル）アミノエステルおよびその製造法
US9758470B2 (en) 2013-08-09 2017-09-12 Unimatec Co., Ltd. Bis(perfluoroether carboxylic acid alkyl)amino ester and method for producing the same
WO2016125257A1 (fr) * 2015-02-03 2016-08-11 ユニマテック株式会社 Ester d'aminoalkyle d'acide éther monocarboxylique contenant du fluor et son procédé de fabrication
JPWO2016125257A1 (ja) * 2015-02-03 2017-11-02 ユニマテック株式会社 含フッ素エーテルモノカルボン酸アミノアルキルエステルおよびその製造法
US10000444B2 (en) 2015-02-03 2018-06-19 Unimatec Co., Ltd. Fluorine-containing ether monocarboxylic acid aminoalkyl ester and a method for producing the same
CN107207410A (zh) * 2015-02-03 2017-09-26 优迈特株式会社 含氟醚单羧酸氨基烷基酯及其制造方法
WO2021033649A1 (fr) 2019-08-20 2021-02-25 Ａｇｃ株式会社 Procédé de production d'un composé contenant du fluor contenant de l'azote

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