Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/78—Halides of sulfonic acids
  • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
  • C07C309/84—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by carboxyl groups

Definitions

• the present invention relates to a method for producing a compound having a fluorosulfonyl group and a novel compound.
• the present invention relates to a method for producing a compound having a fluorosulfonyl group and a novel compound.
• R f indicates 1 CF, 1 CF, 1 CF or 1 CF. ;
• Non-Patent Document 1 Chem. Soc., Chem. Comm., 1974, 323-324
• Non-Patent Document 2 J. Chem. Soc., Perkin Trans. I, 1978, 202—209
• Non-Patent Document 3 Tetrahedron, Vol. 47, 1991, 555-562
• R f in the perfluorocarboxylic acid described in Non-Patent Document 1 and Non-Patent Document 2 is only a chemically stable perfluoroalkyl group such as CF, CF, CF, and CF.
• the inventors of the present invention have prepared a reaction product having a fluorosulfonyl group retained when an electrode reaction is carried out between an ethylenic compound and a polyfluorocarboxylic acid having a fluorosulfonyl group. And a novel fluorine-containing compound having a fluorosulfonyl group, and a reaction of an electrode reaction between fluoroethylenes and polyfluorocarboxylic acid or a salt thereof.
• the present invention provides the following inventions.
• X, ⁇ , ⁇ Independently, an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbonyl group, a fluoroalkoxycarbonyl group, an alkylcarbonyloxy Or a fluoroalkylcarbonyloxy group having 1 to C carbon atoms: L0 ( ⁇ ), carboxyl group, cyan group, chlorine atom, fluorine atom or Hydrogen atom.
• a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group.
• a group represented by the formula C (O) —, a group represented by the formula C (O) 2 O 3, or a group represented by the formula oc (o) 1 may be inserted.
• a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
• the compound (2) is a compound (21) represented by the formula CR (SO F) (C (O) OH).
• R a fluorine atom or a trifluoromethyl group.
• n l, 2, or 3.
• X a , Y a each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxy carbo group, a fluoro alkoxy carbo ol group, an alkyl carbo oxy group, or a fluoro It is a loalkylcarboxoxy group, which is a carbon number of 1 to: L0 group (A), carboxyl group, cyano group, chlorine atom, or hydrogen atom.
• the alkyl group moiety having 2 or more carbon atoms which may contain a fluorine atom in the group (A).
• a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
• x al an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
• Y 31 an alkyl group, an alkoxy carbo group, or an alkyl carbo oxy group, a group having 1 to 10 carbon atoms (A a ) or a carboxyl group.
• Y b , z b each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbon group, a fluoroalkoxycarbol group, an alkyl A chlorocarboxoxy group or a fluoroalkylcarboxoxy group, which has a carbon number of 1 to: an L0 group (A), a carboxyl group, a cyano group, a chlorine atom, a fluorine atom, or a hydrogen atom;
• a group represented by the formula O is present between the carbon atom and carbon atom bond in the alkyl group.
• a group represented by the formula C (O) —, a group represented by the formula C (O) O 2, or a group represented by the formula oc (o) 1 may be inserted.
• a group represented by the formula O may be inserted between the carbon atom and the carbon atom bond in Q.
• Y bl an alkyl group, an alkoxycarbo group, or an alkylcarboxoxy group, a group having 1 to 10 carbon atoms (A b ) or a carboxyl group.
• z bl a hydrogen atom or a fluorine atom.
• a compound represented by the following formula (ll 2 ) (wherein Z 1 represents a hydrogen atom or a methyl group, R 1 represents a fluorine atom or a trifluoromethyl group.) O
• a compound having a fluorosulfonyl group can be produced efficiently. Further, according to the present invention, a novel compound having a fluorosulfol group useful as a functional material such as a raw material of fluoromonomer and a surfactant is provided.
• Electrode reaction is performed with the compound (2) represented by OH) or a salt thereof.
• salt of the compound (2) and the compound (2) may be used alone or the compound (2) alone may be used alone (the following may be used) .
• salt 2 is sodium salt of the compound (2): Q (SO F ) (C (O) 0 "Na +), or compound (2
• X and Y forces are each independently an alkyl group, a closed alkyl group, a fluoroalkyl group, a hydroxyalkyl group, an alkoxycarbo group, A fluoroalkoxycarbol group, an alkylcarboxoxy group, or a fluoroalkylcarboxoxy group, which is a group having 1 to 10 carbon atoms (A), a carboxyl group, a cyano group, a chlorine atom, or
• Z is a hydrogen atom
• Y and Z are each independently an alkyl group, a closed alkyl group, a fluorinated alkyl group, a hydroxyalkyl group, an alkoxycarbo group, a fluoroalkoxycarbonyl Group, an alkylcarbonyloxy group or a fluoroalkylcarbonyloxy group, the group having 1 to C carbon atom
• the group (A) may contain a fluorine atom, and when an alkyl group part having 2 or more carbon atoms is present, between the carbon atom and carbon atom bond in the alkyl group, OC ( O) — — C (O) O or — OC (O)-is inserted!
• M in the compound (2) is preferably 1.
• Q is particularly preferably a difluoromethylene group, preferably a perfluoroalkylene group having 1 to 3 carbon atoms!
• the fluorosulfonyl group in the compound (2) is considered to be an unstable group in the electrode reaction, and the elimination of the fluorosulfonyl group was expected even in the electrode reaction in the present invention. Therefore, a compound (11), a compound (12), a compound (13) or a compound (14) which is a reaction product in which a fluorosulfol group is retained in an electrode reaction using the compound (2) can be obtained. Was an unexpected effect.
• Compound (2) is preferably compound (21) represented by the formula CR (SO F) (C (O) OH).
• the compound (211) represented by the formula CFR ⁇ SO F) (C (O) OH) is particularly preferred (the same applies hereinafter).
• R and R 1 are a fluorine atom or a trifluoromethyl group, and a fluorine atom is particularly preferable.
• n is preferably 1. In addition, when n is 1, the Rs may be the same or different.
• Compound (21) and Compound (211) are each a fluorine-containing carboxylic acid having a fluorophore group at the a- position of the carboxyl group, and a reaction in which the ⁇ -position fluorosulfonyl group is retained in the electrode reaction. It was a particularly unexpected effect that the product was obtained.
• compound (2) include CF (SO F) (C (O) OH) CF (CF) (SO F) (C (O)
• the amount of the compound (3) relative to the total amount of the compound (2) and the salt of the compound (2) is preferably 0.25-1.
• the current density in the electrode reaction is preferably 0.015 OA Zcm 2 from the viewpoint of reaction control and reaction efficiency.
• the total amount of current in the electrode reaction is compound (2), compound (2) 0.1 to 5. OFZmol is preferable with respect to the total amount of the salt and the compound (3).
• the reaction temperature in the electrode reaction is preferably -20 ° C to + 100 ° C, particularly preferably -20 ° C to + 60 ° C.
• the reaction pressure in the electrode reaction may be atmospheric pressure, reduced pressure, or increased pressure, and atmospheric pressure is preferable.
• the electrode reaction is preferably performed in the presence of a solvent which may be performed in the absence of a solvent or in the presence of a solvent.
• the solvent is not particularly limited as long as it is a solvent that dissolves compound (3) and compound (2) or a salt thereof.
• the solvent is preferably an aprotic solvent.
• Non-protonic solvents include tetrahydrofuran, 1,2-dimethoxyethane, propylene carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane and the like.
• the electrode reaction is preferably performed in the presence of a supporting electrolyte.
• the supporting electrolyte is particularly preferably an alcohol (methanol, ethanol, etc.) or water for which a protic solvent is preferred.
• the reaction vessel used for the electrode reaction is preferably a known electrolytic cell. From the viewpoint of good insulation of the battery case, a glass battery case or a fluorine resin battery case is preferred V ,. Also, let the battery case function as an anode or cathode.
• the anode and cathode in the electrode are preferably electrodes having a high acid reduction potential.
• the electrode is particularly preferably an electrode made of platinum or a carbon material, preferably an electrode made of magnesium, copper, aluminum, platinum, and an electrode material made of at least one kind of electrode material that is also selected as a group force.
• post-treatment is preferably performed to obtain compound (11), compound (12), compound (13), or compound (14) having a purity suitable for the purpose.
• the post-treatment method include water washing, extraction, chromatography, distillation, recrystallization and the like.
• the post-treatment may be performed by combining these two or more methods.
• the electrode reaction may be performed by a batch method that is performed after the reaction substrate is collectively supplied to the battery case, or may be performed by a continuous reaction method that is performed while the reaction substrate is continuously supplied to the battery case.
• the reason why the compound (13) is formed is considered to be that the radical (I 1 ) and the proton undergo a radical coupling reaction.
• radical (2 1 ) and radical (I 1 ) undergo a radical coupling reaction.
• a compound (3 a ) represented by the formula CX a Y a CH,
• X a in the compound (3 a ) is preferably an alkyl group having 1 to carbon atoms or a hydrogen atom, particularly preferably a methyl group or a hydrogen atom, from the viewpoint of reaction yield.
• Y a in the compound (3 a ) is an alkyl group, an alkoxy carbo yl group, or an alkyl carbo oxy group in which the group (A) or the carboxyl group is preferable from the viewpoint of the reaction yield, and has 1 carbon atom.
• Methoxyca is particularly preferred for groups of ⁇ 10 (A a ) or carboxyl groups. Most preferred is a sulfonyl group, a hydroxymethyl group or a carboxy group.
• the group (A a ) contains a fluorine atom! /, May! /, An alkyl group part having 2 or more carbon atoms is present, and a carbon atom in the alkyl group is bonded between carbon atom bonds, and OC (O) C
• the number of inserted groups is preferably 1 to 4, particularly preferably 1.
• the number of carbon atoms in the group (A a ) is preferably 2 to 10 and particularly preferably 2 to 8.
• Preferred embodiments of Y 3 include C (0) OCH, -CH OH CH OC (0) CH,-
• the compound (2) is particularly preferably the compound (211) preferred by the compound (21).
• the compound (3 a ) and the compound (2) or a salt thereof are electrode-reacted to produce the following compound (ll a ), the following compound (12 a ), and the following compound:
• An embodiment of obtaining any one compound selected from ( 13a ) is mentioned.
• the configuration of compound ( 12a ) may be either cis or trans! /.
• the compound (3 a ) in which X a is a group (A), a carboxyl group, a cyano group, or a chlorine atom is used, the compound (12 a ) and the compound (13 a ) are Since the compound can be obtained with high selectivity, it is preferable to obtain the compound (12 a ) or the compound (13 a ).
• the compound (3 a ) in which X a is a hydrogen atom is used, the compound (1 l a ) can be obtained with high selectivity. Therefore, it is preferable to obtain the compound (ll a ).
• the amount of the compound (3 a ) relative to the total amount of the compound (2) and the salt of the compound (2) is preferably 0.4 to 1.0 times monoreca, preferably 0.5 to 0.8. Double monore power is especially preferred!
• the current density in the electrode reaction from the viewpoint of reaction control and reaction efficiency, 0. 01 ⁇ 5.
• OA Zcm 2 is preferably tool 0. 05 ⁇ 2. 5AZcm 2 more preferably tool 0. 1 ⁇ 1. OAZcm 2 Is particularly preferred.
• OFZmol is preferred instrument 0.2 ⁇ 2.5 F / mol force, more preferably 0.3 to 1. OFZmol is particularly preferred.
• the above conditions are preferably applied to the reaction temperature, reaction pressure, presence / absence of solvent, type of reactor, and type of anode and cathode in the electrode reaction.
• the reason why the compound (ll a ), the compound (12 a ), or the compound (13 a ) is efficiently produced is not necessarily clear, but is considered to be due to the following reasons, respectively. It is done.
• the reason why the compound (ll a ) is generated is that the electrode ( 1 ) generates a radical (2 1 ) due to the electrode reaction, and then the radical (2 1 ) is converted into a radical (2 a) into the compound (3 a ). This is thought to be because the following radical (1 ⁇ was generated by the addition reaction, and two radicals (I 31 ) were further radical-coupled.
• the following compound (ll al ), the following compound (12 al ), and the following compound (13 al ) are prepared by subjecting the compound (3 al ) and the compound (21) or a salt thereof to an electrode reaction.
• it is a method for producing any one selected compound.
• the configuration of the compound (12 al ) may be cis or trans! /. [0050] [Chemical 16] x a1
• (211) or a salt thereof is particularly preferably a method for producing any one compound selected from the following compounds (11, the following compounds (12), and the following compounds (13 1 ).
• the configuration of the compound (12 1 ) may be cis or trans.
• the compound (II 1 ) is a characteristic novel compound having two fluorosulfol groups and two groups represented by the formula C (0) OZ 1 .
• the compound (II 1 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant.
• Specific examples of the compound (II 1 ) include the following compounds.
• the CH 3 CH 3 compound (12 1 ) is a novel ethylenic compound having a characteristic structure having a fluorosulfol group and a group represented by the formula C (O) OZ 1 .
• the compound (12 1 ) is useful as a functional material such as a fluoromonomer or a surfactant. Specific examples of the compound (12 1 ) include the following compounds.
• the compound (13 1 ) is a novel compound having a characteristic structure having a fluorosulfol group and a group represented by the formula C (O) OZ 1 .
• the compound (13 1 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (13 1 ) include the following compounds.
• Y b in the compound (3 b ) is an alkyl group, an alkoxy carbo yl group, or an alkyl carbo oxy group in which the group (A) or the carboxyl group is preferable from the viewpoint of the reaction yield, A methoxycarbonyl group, a hydroxymethyl group or a carboxy group is most preferred, and a group having 1 to 10 carbon atoms (A b ) or a carboxyl group is particularly preferred.
• the group (A b ) may contain a fluorine atom, but there may be an alkyl group part having 2 or more carbon atoms, and a carbon atom in the alkyl group may be bonded with an O 1 or a C (O ) —, 1 C (O) 0—, or 1 OC (O) — is inserted, the number of inserted groups is preferably 1 to 4, and particularly preferably 1. When these groups are inserted between carbon atoms in carbon atoms in the alkyl group, the number of carbon atoms in the group (A bl ) is preferably from 2 to 10, and particularly preferably from 2 to 8.
• Preferred embodiments of Y b include one C (0) OCH, one CH OH, one CH OC (0) CH,-
• Z b in the compound (3 b ) is preferably a hydrogen atom or a fluorine atom.
• the compound (3 b ) was oc fluoroethylenes, and the carbon atom in the compound (3 b ) had a low activity, so it was considered that no electrode reaction occurred. Therefore, it is an unexpected effect that the compound (3 b ) undergoes an electrode reaction, and the formation of the compound (14 b ) at a high selectivity in the electrode reaction is a particularly unexpected effect. It was.
• Compound (2) is particularly preferably compound (211), more preferably compound (21).
• the compound (3 b ) and the compound (2) or a salt thereof are electrode-reacted to produce the following compound (ll b ), the following compound (12 b ), and the following compound. Any one compound selected from ( 14b ) is obtained.
• the configuration of the compound ( 12a ) may be cis type or trans type.
• the amount of the compound (3 b ) relative to the total amount of the salt of the compound (2) and the compound (2) is preferably 0.25 to 0.5 times the monoreaction power, preferably 0.3 to 0. 4 times monore power is especially preferred!
• the current density in the electrode reaction is preferably 0.01 to 5.
• OA / cm 2 from the viewpoint of reaction control and reaction efficiency, and particularly preferably 0.1 to 1.
• OA / cm 2 The total amount of electric current in the electrode reaction is preferably 0.1 to 5.
• the above conditions are preferably applied to the reaction temperature, reaction pressure, presence / absence of solvent, type of reactor, and type of anode and cathode in the electrode reaction.
• the reason why the compound (ll b ), the compound (12 b ), or the compound (14 b ) is efficiently produced is not necessarily clear, but is considered to be due to the following reasons, respectively.
• the following compound (ll bl ), the following compound (12 bl ), and the following compound (14 bl ) are prepared by subjecting the compound (3 bl ) to the compound (21) or a salt thereof.
• the method for producing any one compound selected from (1) is preferred.
• the configuration of the compound (12 bl ) may be cis or trans.
• the compound (14 bl ) is preferably obtained because the compound (14 bl ) can be obtained with high selectivity.
• the method is a method for producing one kind of compound.
• the configuration of the compound (12 2 ) may be cis or trans. In the production method, since the compound (14 2 ) can be obtained with high selectivity, it is preferable to obtain the compound (14 2 ).
• the compound (ll 2 ) is a novel fluorine-containing compound having a characteristic structure having a fluorosulfol group and a group represented by the formula ⁇ ⁇ ⁇ 1 .
• the compound (II 2 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant.
• the compound (12 2 ) has a fluorosulfol group and the formula C (O) A novel ethylenic fluorine-containing compound having a characteristic structure having a group represented by OZ 1 .
• the compound (12 2 ) is useful as a functional material such as a fluoromonomer or a surfactant. Specific examples of the compound (12 2 ) include the following compounds.
• Compound (14 2 ) has two fluorosulfol groups and It is a unique novel compound having a group represented by one formula (1).
• the compound (14 2 ) is useful as a functional material such as a raw material for fluoromonomers and a surfactant. Specific examples of the compound (14 2 ) include the following compounds.
• GC gas chromatography and GC-M for gas chromatography mass spectrometry S
• EI—MS electron ionization mass spectrometry
• CI MS chemical ionization mass spectrometry
• GC yield for the yield determined from the peak area ratio of GC
• mF millifaradaic
• a stirring blade was installed in a battery tank (made of glass, internal volume 50 mL) equipped with a refrigerant distribution jacket and a discharge valve at the bottom, and 0 ° C refrigerant was circulated.
• Two platinum nets (length 3 cm x width 3 cm, 80 mesh) were installed in the battery case as anodes and anodes so as not to interfere with the stirring blades.
• the platinum mesh was used in a polyethylene mesh bag to prevent short circuit.
• Acetonitrile (30 mL) as a solvent and ion-exchanged water (5 mL) as a supporting electrolyte were placed in a battery case.
• a stirring blade was installed in a battery tank (made of glass, internal volume 50 mL) equipped with a refrigerant distribution jacket and a discharge valve at the bottom, and 0 ° C refrigerant was circulated.
• Two platinum nets (length 3 cm x width 3 cm, 80 mesh) were installed in the battery case as anodes and anodes so as not to interfere with the stirring blades.
• the platinum mesh was used in a polyethylene mesh bag to prevent short circuit.
• Acetonitrile (30 mL) as a solvent and ion-exchanged water (5 mL) as a supporting electrolyte were placed in a battery case.
• fluorine-containing compounds having various structures particularly compounds having a fluorosulfol group can be easily produced.
• the compound of the present invention is useful as a functional material such as a raw material of a fluoromonomer, a fluoromonomer, and a surfactant.

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  • 2006-11-07 WO PCT/JP2006/322199 patent/WO2007055212A1/ja active Application Filing
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