WO2011108668A1 - 置換された含フッ素オレフィンの製造方法 - Google Patents
置換された含フッ素オレフィンの製造方法 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/2632—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving an organo-magnesium compound, e.g. Grignard synthesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4233—Kumada-type, i.e. RY + R'MgZ, in which Ris optionally substituted alkyl, alkenyl, aryl, Y is the leaving group and Z is halide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Definitions
- the present invention relates to a method for producing a fluorine-containing olefin substituted with an organic group. Specifically, by using a transition metal complex such as palladium (Pd) or nickel (Ni) as a catalyst and selectively substituting the fluorine atom (F) on the sp2 hybrid carbon atom of the fluorinated olefin with an organic group. And a method for producing a fluorine-containing olefin substituted with an organic group.
- a transition metal complex such as palladium (Pd) or nickel (Ni)
- Non-Patent Document 1 discloses that a carbon-halogen (C—X) bond of CF 2 ⁇ CFX (X: a halogen atom other than a fluorine atom) is converted into a carbon-lithium (C—Li) bond by butyl lithium. , A method for performing a C—C bond formation reaction is described.
- Non-Patent Documents 2 and 3 describe a method in which the C—Li bond Li generated above is further reconverted into a metal such as Sn or Si, and then a CC bond generation reaction is performed. Yes.
- Non-Patent Documents 4 to 6 describe a method of selectively replacing one fluorine atom by reacting tetrafluoroethylene (TFE) with an organolithium reagent or an arylmagnesium reagent.
- TFE tetrafluoroethylene
- Ph represents a phenyl group.
- TFE TFE
- Non-Patent Document 7 alkyl lithium is reacted with HFC134a (CF 3 CFH 2 ), and fluorine-containing vinyl lithium is generated by an elimination reaction. Further, this fluorine-containing vinyl lithium is subjected to a coupling reaction using a vinyl zinc reagent produced by metal exchange with zinc.
- TFE tetrafluoroethylene
- HFP hexafluoropropene
- 1-substituted fluorine-containing olefin such as 1,1,2-trifluorostyrene is a compound useful as a raw material for polymer electrolyte, for example, and 1,1-difluoro-2,2-diphenylethylene is also used.
- 1,1-disubstituted fluorine-containing olefins such as, for example, are useful compounds as raw materials for pharmaceuticals such as enzyme inhibitors and ferroelectric materials.
- a method for easily and efficiently producing these compounds has not been established.
- 1,1-disubstituted fluorine-containing olefins can be produced by a difluoromethylene reaction by a Wittig reaction of a carbonyl compound (Non-patent Document 8).
- the carbonyl compound is a ketone
- the yield is low even when an excess amount (4-5 equivalents or more) of Wittig reagent is used, and further, carcinogenic hexamethyl phosphite triamide is used as the phosphorus compound. This method is problematic because it is essential.
- a substituted fluorine-containing olefin for example, 1-substituted fluorine-containing olefin, 1,1-disubstituted fluorine-containing olefin, etc.
- TFE fluorine-containing olefin
- An object of the present invention is to provide a production method in which fluorine atoms bonded to sp2 hybrid carbon atoms of fluorine-containing olefins such as TFE can be efficiently substituted with organic groups.
- this invention relates to the manufacturing method of the following substituted fluorine-containing olefins.
- Item 1 A method for producing a fluorine-containing olefin substituted with an organic group, which comprises reacting a fluorine-containing olefin with an organomagnesium compound in the presence of a catalyst containing nickel or palladium.
- Item 2 The production method according to Item 1, wherein at least one fluorine atom bonded to the sp2-hybridized carbon atom of the fluorine-containing olefin is substituted with an organic group derived from an organomagnesium compound.
- Item 3. The method according to Item 1 or 2, wherein a fluorine affinity compound is further added and / or heated to react.
- Item 4. The production method according to any one of Items 1 to 3, wherein the catalyst is a catalyst containing palladium.
- the catalyst containing palladium is a zero-valent palladium complex; a zero-valent palladium complex generated from a II-valent palladium complex; or these and at least one compound selected from the group consisting of diketone, phosphine, diamine and bipyridyl.
- Item 2 The production method according to Item 1, which is a complex obtained.
- the zero-valent palladium complex is Pd 2 (DBA) 3 (DBA is dibenzylideneacetone), Pd (COD) 2 (COD is cycloocta-1,5-diene), Pd (DPPE) (DPPE is 1,2- At least one selected from the group consisting of bisdiphenylphosphinoethane), Pd (PCy 3 ) 2 (Cy is a cyclohexyl group), Pd (Pt-Bu 3 ) 2 and Pd (PPh 3 ) 4 (Ph is a phenyl group) Item 6.
- Item 7 The organomagnesium compound is represented by formula (7a) and / or formula (7b): RMgX (7a) R 2 Mg (7b) (In the formula, R represents an aryl group which may have a substituent or an alkyl group which may have a substituent. X represents Cl, Br or I.) Item 7.
- R is a monocyclic, bicyclic or tricyclic aryl group which may be substituted with at least one group selected from the group consisting of a lower alkyl group, a lower alkenyl group, a lower alkoxy group and an aryl group, or Item 8.
- Item 9 The production method according to Item 3, wherein the fluorine affinity compound is added and reacted, and the fluorine affinity compound is lithium halide, magnesium halide, or zinc halide.
- R represents an aryl group which may have a substituent or an alkyl group which may have a substituent.
- item 1 characterized by making the organomagnesium compound represented by these react.
- R and R ′ are the same or different and each represents an aryl group which may have a substituent or an alkyl group which may have a substituent.
- R represents an aryl group which may have a substituent or an alkyl group which may have a substituent.
- the manufacturing method characterized by making the organomagnesium compound represented by these react.
- the fluorine atom bonded to the sp2 hybrid carbon atom of the fluorinated olefin can be efficiently substituted with an organic group such as an aryl group or an alkyl group.
- an organic group such as an aryl group or an alkyl group.
- Non-Patent Documents 4 and 6 only 1,2-disubstituted fluorinated olefins are obtained in the addition / elimination reaction of an alkyl metal reagent to TFE, and 1,1-disubstituted fluorinated olefins are obtained. Cannot be obtained.
- a 1,1-disubstituted fluorinated olefin can be selectively produced.
- the production method of the present invention can efficiently produce a fluorine-containing olefin substituted with an organic group by reacting a fluorine-containing olefin with an organic magnesium compound in the presence of a catalyst containing nickel or palladium.
- examples of the fluorine-containing olefin used as a substrate include compounds in which at least one fluorine atom is bonded to two sp2 hybrid carbon atoms forming the olefin.
- Specific examples include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoroethylene, 1,1-difluoroethylene (vinylidene fluoride), 1,2-difluoroethylene, and the like. From the viewpoint of versatility in fluorine chemistry, TFE, trifluoroethylene and the like are preferable.
- the catalyst containing nickel or palladium examples include a nickel complex and a palladium complex, respectively. These complexes mean both those charged as reagents and those generated during the reaction (catalytically active species).
- the palladium complex a zero-valent palladium complex; a zero-valent palladium complex generated during the reaction from a divalent palladium complex; or at least one compound selected from the group consisting of diketone, phosphine, diamine and bipyridyl (ligand) ) And a complex obtained by mixing.
- the zero-valent palladium complex is not particularly limited.
- Pd 2 (DBA) 3 (DBA is dibenzylideneacetone)
- Pd (COD) 2 (COD is cycloocta-1,5-diene)
- Pd (DPPE) (DPPE is 1,2-bisdiphenylphosphinoethane)
- Pd (PCy 3 ) 2 (Cy is a cyclohexyl group)
- Pd (Pt-Bu 3 ) 2 and Pd (PPh 3 ) 4 (Ph is a phenyl group)
- Pd 2 (DBA) 3 DBA is dibenzylideneacetone
- Pd (COD) 2 COD is cycloocta-1,5-diene
- Pd (DPPE) DPPE is 1,2-bisdiphenylphosphinoethane
- PCy 3 Cy is a cyclohexyl group
- divalent palladium complex examples include palladium chloride, palladium bromide, palladium acetate, bis (acetylacetonato) palladium (II), dichloro ( ⁇ 4 -1,5-cyclooctadiene) palladium (II), or these And a complex in which a phosphine ligand such as triphenylphosphine is coordinated.
- phosphine ligand such as triphenylphosphine
- the zero-valent palladium complex produced by reduction from the above-mentioned zero-valent palladium complex or II-valent palladium complex acts in the reaction with a compound (ligand) such as diketone, phosphine, diamine, or bipyridyl added as necessary. Thus, it can be converted into a zero-valent palladium complex involved in the reaction. In the reaction, it is not always clear how many of these ligands are coordinated to the zero-valent palladium complex.
- ligand such as diketone, phosphine, diamine, or bipyridyl
- examples of the diketone include ⁇ diketones such as acetylacetone, 1-phenyl-1,3-butanedione, and 1,3-diphenylpropanedione.
- trialkylphosphine As the phosphine, trialkylphosphine or triarylphosphine is preferable.
- Specific examples of the trialkylphosphine include tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, tritexylphosphine, triadamantylphosphine, tricyclopentylphosphine, di-t-butylmethylphosphine, tribicyclo [2,2, 2] Tri (C3-20 alkyl) phosphine such as octylphosphine and trinorbornylphosphine.
- triarylphosphine examples include tri (monocyclic aryl) phosphine such as triphenylphosphine, trimesitylphosphine, and tri (o-tolyl) phosphine.
- triphenylphosphine, tricyclohexylphosphine, tri-t-butylphosphine and the like are preferable.
- bidentate ligands such as 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) propane, and 1,1′-bis (diphenylphosphino) ferrocene Is also effective.
- diamine examples include tetramethylethylenediamine and 1,2-diphenylethylenediamine.
- ligands such as phosphine, diamine, and bipyridyl are preferable, triarylphosphine is more preferable, and triphenylphosphine is particularly preferable.
- the target substituted fluorine-containing olefin can be obtained in a higher yield by using a palladium complex having a bulky ligand such as phosphine.
- the nickel complex may be a zero-valent nickel complex; a zero-valent nickel complex generated during the reaction from a II-valent nickel complex; or at least one compound selected from the group consisting of diketone, phosphine, diamine and bipyridyl And a complex obtained by mixing a ligand.
- the zero-valent nickel complex is not particularly limited.
- Ni (COD) 2 Ni (CDD) 2 (CDD is cyclodeca-1,5-diene), Ni (CDT) 2 (CDT is cyclodeca-1, 5,9-triene), Ni (VCH) 2 (VCH is 4-vinylcyclohexene), Ni (CO) 4 , (PCy 3 ) 2 Ni—N ⁇ N—Ni (PCy 3 ) 2 , Ni (PPh 3 ) 4 etc. are mentioned.
- II-valent nickel complex examples include nickel chloride, nickel bromide, nickel acetate, bis (acetylacetonato) nickel (II), and a complex in which a phosphine ligand such as triphenylphosphine is coordinated. It is done.
- II-valent nickel complexes are reduced by, for example, reducing species (phosphine, zinc, organometallic reagents, etc.) coexisting during the reaction to form zero-valent nickel complexes.
- the zero-valent nickel complex produced by reduction from the above-mentioned zero-valent nickel complex or II-valent nickel complex acts in the reaction with a ligand that is added as necessary to form a zero-valent nickel complex involved in the reaction. It can also be converted. It is not always clear how many of these ligands are coordinated to the zerovalent nickel complex during the reaction.
- the nickel complex one having a high function of stabilizing the zero-valent nickel complex generated in the system is desirable. Specifically, those having a ligand such as phosphine, diamine and bipyridyl are preferred, and those having phosphine are particularly preferred.
- trialkylphosphine is preferable as the phosphine, trialkylphosphine or triarylphosphine.
- specific examples of the trialkylphosphine include tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, tritexylphosphine, triadamantylphosphine, tricyclopentylphosphine, di-t-butylmethylphosphine, tribicyclo [2,2, 2] Tri (C3-20 alkyl) phosphine such as octylphosphine and trinorbornylphosphine.
- triarylphosphine examples include tri (monocyclic aryl) phosphine such as triphenylphosphine, trimesitylphosphine, and tri (o-tolyl) phosphine.
- triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine and the like are preferable.
- diamine examples include tetramethylethylenediamine and 1,2-diphenylethylenediamine.
- the target substituted fluorine-containing olefin can be obtained in a higher yield by using a nickel complex having a bulky ligand such as triarylphosphine.
- a catalyst containing palladium, further a palladium complex, particularly a zero-valent palladium phosphine complex (In particular, a triphenylphosphine complex) is preferable.
- the amount of palladium or nickel catalyst (or palladium or nickel complex) used is not particularly limited, but the amount of zero-valent or II-valent palladium complex or nickel complex used as a reagent is determined as organomagnesium compound 1
- the amount is usually about 0.001 to 1 mol, preferably about 0.01 to 0.2 mol, relative to mol.
- the amount of the ligand used is usually about 0.002 to 2 mol, preferably about 0.02 to 0.4 mol, per 1 mol of the organomagnesium compound. .
- the molar ratio of the ligand to be added and the catalyst is usually 2/1 to 10/1, preferably 2/1 to 4/1.
- the organomagnesium compound used in the production method of the present invention is a compound having an organic group that can be substituted with a fluorine atom on the sp2 hybridized carbon atom of the fluorinated olefin, and functions as a nucleophile.
- Typical examples of the organomagnesium compound include formula (7a) and / or formula (7b): RMgX (7a) R 2 Mg (7b) (In the formula, R represents an aryl group which may have a substituent or an alkyl group which may have a substituent. X represents Cl, Br or I.) The compound represented by these is mentioned. These compounds may form a solvate with the solvent to be used in the reaction system.
- Examples of the aryl group that may have a substituent represented by R include monocyclic, bicyclic, and tricyclic aryl groups such as phenyl, naphthyl, anthracenyl, and phenanthryl groups.
- Examples of the substituent on the aryl group include lower (particularly C1-6) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl; lower (particularly vinyl, allyl and crotyl).
- alkenyl groups lower (particularly C1-6) alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy; aryl groups such as phenyl and naphthyl; The aryl group may be substituted with 1 to 4 (especially 1 to 2) of the above substituents.
- R is preferably a phenyl group.
- alkyl group which may have a substituent represented by R examples include, for example, lower (particularly C1-6) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl. Is mentioned.
- substituent on the alkyl group include lower (particularly C1-6) alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy; aryl groups such as phenyl and naphthyl.
- the alkyl group may be substituted with 1 to 3 (especially 1 to 2) of the above substituents.
- X is preferably Br or Cl.
- a Grineer reagent obtained by reacting an organic halide and magnesium metal (Mg) in an inert solvent such as THF can be used.
- the magnesium compound represented by the formula (7b) is prepared by adding a poor solvent to the Grineer reagent solution, precipitating an insoluble salt (for example, MgX 2 ), filtering, and drying the filtrate as necessary. can do. Any known method can be employed.
- the amount of fluorine-containing olefin and organomagnesium compound used can be appropriately set according to the number of fluorine atoms that undergo substitution reaction in the fluorine-containing olefin.
- the amount of fluorine-containing olefin used is usually about 0.1 to 100 moles, preferably about 0.5 to 10 moles per mole of the organomagnesium compound.
- a fluorine-affinity compound is further added to the reaction system and / or the reaction system is heated and reacted to form the formula (1) from the reaction intermediate ( ⁇ complex).
- the reaction intermediate ( ⁇ complex) to 2) can be promoted, and the oxidative addition reaction to the C—F bond can be facilitated. Therefore, the catalytic reaction can be promoted.
- the fluorine affinity compound examples include a metal halide having Lewis acidity composed of a metal (hard metal) having affinity with a fluorine atom and a halogen atom.
- a metal halide having Lewis acidity composed of a metal (hard metal) having affinity with a fluorine atom and a halogen atom.
- lithium halide, magnesium halide, zinc halide and the like can be mentioned.
- lithium halides such as lithium chloride, lithium bromide and lithium iodide
- magnesium halides such as magnesium bromide and magnesium iodide
- zinc halides such as zinc chloride, zinc bromide and zinc iodide, etc. Is mentioned.
- Lithium halide such as lithium iodide is preferable.
- the amount used is usually about 0.5 to 10 moles, preferably about 1 to 1.5 moles per mole of the organomagnesium reagent used. .
- the reaction temperature is not particularly limited, but is usually ⁇ 100 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., more preferably room temperature (about 20 ° C.) to 100 ° C. From the viewpoint of promoting the oxidative addition reaction of nickel or palladium catalyst to the C—F bond, heating conditions of 40 ° C. to 150 ° C., preferably 50 ° C. to 100 ° C. can be mentioned. In addition, since dimerization of the product trifluorovinyl derivative may proceed at high temperatures, the upper limit reaction temperature can be set within a range in which dimerization does not proceed.
- reaction time is not particularly limited, but it may be about 10 minutes to 72 hours.
- the reaction atmosphere is not particularly limited, but is usually performed in an inert gas atmosphere such as argon or nitrogen in consideration of the activity of a catalyst containing nickel or palladium.
- the reaction pressure may be under pressure, normal pressure, or reduced pressure. In general, it is preferably carried out under pressure, in which case it is about 0.1 to 10 MPa, preferably about 0.1 to 1 MPa.
- the solvent to be used is not particularly limited as long as it does not adversely affect the reaction.
- aromatic hydrocarbon solvents such as benzene, toluene and xylene
- aliphatic hydrocarbon solvents such as hexane and cyclohexane
- tetrahydrofuran Ether solvents such as (THF), dioxane, diethyl ether, glyme and diglyme
- THF tetrahydrofuran Ether solvents
- benzene, toluene, diethyl ether, dioxane, THF and the like are preferable, and THF is particularly preferable.
- a catalyst containing nickel or palladium, a fluorinated olefin, and an organomagnesium compound can be mixed and reacted simultaneously.
- a fluorine-containing vinyl complex of nickel or palladium is once prepared or isolated from a catalyst containing nickel or palladium and a fluorine-containing olefin, and the fluorine-containing olefin can be reacted with an organomagnesium compound using this.
- TFE which is a typical example of the present invention
- TFE which is a typical example of the present invention
- the compound represented by the formula (4) and / or (5) (monosubstituted and / or 1,1-disubstituted) reacts with TFE and an organomagnesium compound in the presence of a catalyst containing nickel or palladium. Can be manufactured.
- the reaction conditions described above can be employed.
- the compound (1,1-disubstituted product) represented by the formula (5 ′) is obtained by reacting TFE with an organomagnesium compound in the presence of a catalyst containing (i) nickel or palladium. And (ii) in the presence of a catalyst containing nickel or palladium, the compound represented by formula (4) and an organomagnesium compound can be reacted.
- organomagnesium compounds used in steps (i) and (ii) may be the same or different.
- examples of the organomagnesium compound in the step (i) include compounds represented by the above formula (7a) and / or formula (7b).
- the organomagnesium compound in step (ii) is, for example, formula (7a ′) and / or formula (7b ′): R'MgX '(7a') R ′ 2 Mg (7b ′) (In the formula, X ′ represents Cl, Br or I. R ′ is the same as above.)
- the compound represented by these is mentioned.
- R and R ′ may be the same or different.
- reaction conditions in the steps (i) and (ii) are not particularly limited as long as a desired target product is obtained, and may be the same or different.
- the compound represented by the formula (4) is subjected to the step (ii) and represented by the formula (5 ′).
- the steps (i) and (ii) are carried out in one pot from TFE.
- 1-substituted fluorine-containing olefins, 1,1-disubstituted fluorine-containing olefins and the like can be easily produced from readily available fluorine-containing olefins such as TFE.
- 1,1-disubstituted fluorine-containing olefins can be easily produced.
- the production method of the present invention is an effective method for producing a 1,1-disubstituted fluorine-containing olefin from a 1,1-difluoroolefin such as TFE.
- the compound represented by the formula (4a) can be produced by reacting trifluoroethylene with an organomagnesium compound in the presence of a catalyst containing nickel or palladium.
- the reaction conditions described above can be employed.
- the fluorine-containing olefin having a substituent thus obtained includes, for example, fluororubber, antireflection membrane material, ion exchange membrane, fuel cell electrolyte membrane, liquid crystal material, piezoelectric element material, enzyme inhibitor, insecticide, etc. It is useful as a raw material.
- Example 1 In a glove box, a solution of Ni (cod) 2 (5.5 mg, 0.02 mmol) and PPh 3 (10.6 mg, 0.04 mmol) in THF (0.4 mL) was put in a pressure tube (capacity 2 ml, the same applies hereinafter). Prepared, and an ether solution of PhMgBr (3M, 0.067 mL, 0.2 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (14 ⁇ L, 0.114 mmol: internal standard for 19 F-NMR measurement) were added thereto. Further, TFE (0.313 mmol: calculated from the above container capacity of 2 ml and the introduction pressure of 0.35 MPa) was added thereto.
- PhMgBr 3M, 0.067 mL, 0.2 mmol
- ⁇ , ⁇ , ⁇ -trifluorotoluene 14 ⁇ L, 0.114 mmol: internal standard for 19 F-NMR measurement
- 1,1-difluoro-2,2-diphenylethylene 19 F-NMR (C 6 D 6 ): ⁇ -91.5 (s). MS m / z 216 (M + ), 166 (M-CF 2), 50 (CF 2).
- 1,2-difluoro-1,2-diphenylethylene 19 F-NMR (C 6 D 6 ): ⁇ trans form-154.8 (s), cis form-130.5 (s).
- Example 2 In a glove box, a solution of Ni (cod) 2 (5.5 mg, 0.02 mmol), PPh 3 (10.6 mg, 0.04 mmol) in THF (0.4 mL) was prepared in a pressure tube, to which PhMgBr was added. An ether solution (3 M, 0.133 mL, 0.4 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (14 ⁇ L: internal standard for 19 F-NMR measurement) were added. Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction solution was left at room temperature for 48 hours. The reaction was followed by 19 F-NMR.
- Example 3 In a glove box, Pd 2 (dba) 3 (5 mg, 0.005 mmol), PPh 3 (5.3 mg, 0.02 mmol), LiI (16.1 mg, 0.12 mmol) in THF (0.4 mL) / C 6 D 6 (0.1 mL) solution was prepared in a pressure tube, and PhMgBr ether solution (3M, 0.038 mL, 0.115 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (14 ⁇ L: at the time of 19 F-NMR measurement) Internal standard). Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction solution was heated at 60 ° C. for 2 hours.
- Example 4 In a glove box, Pd 2 (dba) 3 (5 mg, 0.005 mmol), PCy 3 (5.6 mg, 0.02 mmol), LiI (16.1 mg, 0.12 mmol) in THF (0.4 mL) / C 6 D 6 (0.1 mL) solution was prepared in a pressure tube, and PhMgBr ether solution (3M, 0.038 mL, 0.115 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (14 ⁇ L: at the time of 19 F-NMR measurement) Internal standard). Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction solution was heated at 60 ° C. for 2 hours.
- Example 5 In the glove box, Pd 2 (dba) 3 (5 mg, 0.005 mmol), PPh 3 (5.3 mg, 0.02 mmol), LiI (16.1 mg, 0.12 mmol), Ph 2 Mg (THF) 2 (37 0.1 mg, 0.115 mmol) of C 6 D 6 (0.5 mL) solution was prepared in a pressure tube, and ⁇ , ⁇ , ⁇ -trifluorotoluene (14 ⁇ L: internal standard for 19 F-NMR measurement) was added thereto. It was. Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction solution was left at room temperature for 72 hours. The reaction was followed by 19 F-NMR.
- ⁇ , ⁇ , ⁇ -trifluorostyrene was 21% (based on the number of moles of Ph 2 Mg (THF) 2 used), 1,1- It was confirmed that difluoro-2,2-diphenylethylene was obtained in a yield of 10% and 1,2-difluoro-1,2-diphenylethylene in a yield of 2%.
- Example 6 In the glove box, Pd 2 (dba) 3 (5 mg, 0.005 mmol), PPh 3 (5.3 mg, 0.02 mmol), LiI (16.1 mg, 0.12 mmol), Ph 2 Mg (THF) 2 (37 0.1 mg, 0.115 mmol) in THF (0.4 mL) / C 6 D 6 (0.1 mL) was prepared in a pressure tube, and ⁇ , ⁇ , ⁇ -trifluorotoluene (14 ⁇ L: 19 F-NMR measurement) Internal standard). Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction solution was left at room temperature for 27 hours. The reaction was monitored by 19 F-NMR.
- ⁇ , ⁇ , ⁇ -trifluorostyrene was 86% (same basis based on the number of moles of Ph 2 Mg (THF) 2 used), 1,1- It was confirmed that difluoro-2,2-diphenylethylene was obtained in a yield of 2% and 1,2-difluoro-1,2-diphenylethylene in a yield of 4%.
- the conversion rate was 3% at a reaction time of 15 minutes, the conversion rate was 62% at a reaction time of 5 hours, and the conversion rate was 89% at a reaction time of 12 hours.
- Example 7 In a pressure tube, Ni (cod) 2 (2.6 mg, 0.01 mmol), PPh 3 (5.3 mg, 0.02 mmol) C 6 D 6 -THF-d 8 (1: 1, 0.5 mL) A solution was prepared and to this was added Ph 2 Mg (THF) 2 (32.2 mg, 0.10 mmol). Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction was followed by 1 H-NMR as in Reference Example 2.
- the conversion rate was 95% at a reaction time of 15 minutes, and the conversion rate was 99% at a reaction time of 1 hour.
- Example 8 Synthesis of 1,1-difluoro-2-phenylethylene from trifluoroethylene
- trifluoroethylene 0.313 mmol
- Ni (cod) 2 2.6 mg, 0.01 mmol
- PPh 3 5.3 mg, 0.02 mmol
- Ph 2 Mg (THF) 2 32 .2 mg, 0.10 mmol
- THF-d 8 0.5 mL
- the reaction was monitored by 19 F-NMR to confirm the formation of 1,1-difluoro-2-phenylethylene.
- Example 9 In a glove box, a solution of Pd 2 (dba) 3 (5 mg, 0.005 mmol), PPh 3 (5.3 mg, 0.02 mmol) in THF (0.4 mL) / C 6 D 6 (0.1 mL) was pressure-resistant tube. Into this, an ether solution of MeMgBr (3M, 0.033 mL, 0.100 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (12.3 ⁇ L, 0.100 mmol: internal standard for 19 F-NMR measurement) were prepared. added. Further, TFE (0.313 mmol, sealed up to 0.35 MPa) was added thereto. The reaction solution was heated at 60 ° C. for 2 hours. The reaction was monitored by 19 F-NMR, and it was confirmed that 1,1,2-trifluoro-1-propene and 1,1-difluoro-2-methyl-1-propene were obtained from the internal standard.
- MeMgBr 3M, 0.033 m
- 1,1,2-trifluoro-1-propene 19 F-NMR (C 6 D 6 -THF-d 8 ): ⁇ -109.8 (ddq, 1F), -129.4 (ddq, 1F), -170.2 (m, 1F).
- 1 H-NMR (C 6 D 6 -THF-d 8 ): ⁇ 1.56 (d, J 3.1 Hz)
- PhMBr solution in THF 2.0 M, 0.100 mL, 0.200 mmol
- Pd 2 (dba) 3 in THF 0.5 mM, 20.0 ⁇ L, 1.0 ⁇ 10 ⁇ 5 mmol
- ⁇ , ⁇ , ⁇ -trifluorotoluene (12.3 ⁇ L, 0.100 mmol: internal standard for 19 F-NMR measurement) were added, and the resulting solution was transferred to an NMR tube.
- TFE 3.5 atm, 0.313 mmol
- the reaction mixture was kept at 40 ° C. until the reaction was complete (4 hours). The reaction was observed by 19 F-NMR, and it was confirmed that ⁇ , ⁇ , ⁇ -trifluorostyrene was obtained in a yield of 145% (in terms of mole of zinc reagent used).
- a THF solution (1.0 M, 0.200 mL, 0.200 mmol) of p-Me-C 6 H 4 -MgBr, a THF solution of Pd 2 (dba) 3 (0.5 mM, 20.0 ⁇ L, 1.0 ⁇ 10 ⁇ 5 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (12.3 ⁇ L, 0.100 mmol: internal standard for 19 F-NMR measurement) were added, and the resulting solution was added to an NMR tube. Moved. After degassing, TFE (3.5 atm, 0.313 mmol) was introduced into the NMR tube. The reaction mixture was kept at 40 ° C. until the reaction was complete (6 hours).
- Example 15 Synthesis of 1-methoxy-4- (1,2,2-trifluoroethenyl) benzene
- the catalytic reaction was carried out by observing a 19 F-NMR spectrum using a pressure-resistant NMR tube (Wilmad-LabGlass, 524-PV-7).
- a pressure-resistant NMR tube Wang-LabGlass, 524-PV-7.
- LiI 32.1 mg, 0.240 mmol
- the resulting solution was added to a THF solution (1.0 M, 0.200 mL, 0.200 mmol) of pF—C 6 H 4 —MgBr, a THF solution of Pd 2 (dba) 3 (0.5 mM, 20.0 ⁇ L, 1.0 ⁇ 10 ⁇ 5 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (12.3 ⁇ L, 0.100 mmol: internal standard for 19 F-NMR measurement) were added, and the resulting solution was added to an NMR tube. Moved. After degassing, TFE (3.5 atm, 0.313 mmol) was introduced into the NMR tube. The reaction mixture was kept at 40 ° C. until the reaction was complete (4 hours).
- Example 22 Synthesis of 2- (1,2,2-trifluoroethenyl) naphthalene
- the catalytic reaction was carried out by observing a 19 F-NMR spectrum using a pressure-resistant NMR tube (Wilmad-LabGlass, 524-PV-7).
- a pressure-resistant NMR tube Wang-LabGlass, 524-PV-7.
- LiI 32.1 mg, 0.240 mmol
- Example 24 (Synthesis of ⁇ , ⁇ , ⁇ -trifluorostyrene) Under a nitrogen atmosphere, a THF (60 ml) solution of ZnCl 2 (5.44 g, 40 mmol) and LiI (10.7 g, 80 mmol) was prepared in a pressure-resistant glass container having an internal volume of 150 mL, and then PhMgCl in THF under stirring. The solution (2M, 40 mL, 80 mmol) was slowly added dropwise. After this solution was allowed to stir for 1 hour, Pd 2 (dba) 3 (4 mg, 0.01 mol%) was further added thereto as a THF solution.
- Pentane (200 mL) and water (200 mL) were added to the reaction solution, and insolubles were removed by Celite filtration. The insoluble material was washed with pentane (100 mL). The combined organic layers were washed twice with water (200 mL) and once with saturated brine (30 mL). After drying over anhydrous magnesium sulfate, anhydrous magnesium sulfate was removed by filtration. The reaction solution obtained here was concentrated at normal pressure using a distillation apparatus equipped with a 20 cm Vigreux column and then distilled under reduced pressure (boiling point: 58 ° C./65 mmHg; yield 2.8 g, yield 44%).
- a THF solution (1.0 M, 0.200 mL, 0.200 mmol) of p-CH 3 C 6 H 4 —MgBr, a THF solution (0.5 mM, 20.0 ⁇ L, Pd 2 (dba) 3 , 1.0 ⁇ 10 ⁇ 5 mmol) and ⁇ , ⁇ , ⁇ -trifluorotoluene (12.3 ⁇ L, 0.100 mmol: internal standard for 19 F-NMR measurement) were added, and the resulting solution was added to an NMR tube. Moved. After degassing, HFP (0.313 mmol) was introduced into the NMR tube. The reaction mixture was kept at 40 ° C. until the reaction was complete (20 hours).
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Abstract
Description
PhMgBr+CF2=CF2→PhCF=CF2(非特許文献5、6)
TFEを原料として、既存方法で目的物を選択性良く得るためには、反応を低温で行うと共に、原料のTFEを大過剰に用いる必要がある。反応温度が上がると反応の進行が制御出来なくなり、1,2-付加体、更なる多置換体等との混合物となる。そのため、目的物の収率は大きく低下する。
RMgX (7a)
R2Mg (7b)
(式中、Rは置換基を有しても良いアリール基又は置換基を有しても良いアルキル基を示す。XはCl、Br又はIを示す。)
で表される化合物である項1~6のいずれかに記載の製造方法。
で表される化合物の製造方法であって、ニッケル又はパラジウムを含む触媒の存在下、テトラフルオロエチレンと、式(7a)及び/又は式(7b):
RMgX (7a)
R2Mg (7b)
(式中、XはCl、Br又はIを示す。Rは前記に同じ。)
で表される有機マグネシウム化合物を反応させることを特徴とする項1に記載の製造方法。
で表される化合物の製造方法であって、
(i)ニッケル又はパラジウムを含む触媒の存在下、テトラフルオロエチレンと、式(7a)及び/又は式(7b):
RMgX (7a)
R2Mg (7b)
(式中、XはCl、Br又はIを示す。Rは前記に同じ。)
で表される有機マグネシウム化合物とを反応させて、式(4):
で表される化合物を製造する工程、及び
(ii)ニッケル又はパラジウムを含む触媒の存在下、式(4)で表される化合物と、式(7a’)及び/又は式(7b’):
R’MgX’ (7a’)
R’2Mg (7b’)
(式中、X’はCl、Br又はIを示す。R’は前記に同じ。)
で表される有機マグネシウム化合物とを反応させて、式(5’)で表される化合物を製造する工程、を含む製造方法。
で表される化合物の製造方法であって、ニッケル又はパラジウムを含む触媒の存在下、トリフルオロエチレンと、式(7a)及び/又は式(7b):
RMgX (7a)
R2Mg (7b)
(式中、XはCl、Br又はIを示す。Rは前記に同じ。)
で表される有機マグネシウム化合物とを反応させることを特徴とする製造方法。
RMgX (7a)
R2Mg (7b)
(式中、Rは置換基を有しても良いアリール基又は置換基を有しても良いアルキル基を示す。XはCl、Br又はIを示す。)
で表される化合物が挙げられる。なお、これらの化合物は反応系内において、用いる溶媒と溶媒和物を形成していてもよい。
また、式(5’)で表される化合物(1,1-二置換体)は、(i)ニッケル又はパラジウムを含む触媒の存在下、TFEと有機マグネシウム化合物とを反応させて、式(4)で表される化合物を製造し、さらに(ii)ニッケル又はパラジウムを含む触媒の存在下、式(4)で表される化合物と有機マグネシウム化合物とを反応させることにより製造することができる。
工程(i)及び(ii)で用いられる有機マグネシウム化合物は同一又は異なっていても良い。具体的には、工程(i)における有機マグネシウム化合物は、上述した式(7a)及び/又は式(7b)で表される化合物が挙げられる。工程(ii)における有機マグネシウム化合物は、例えば、式(7a’)及び/又は式(7b’):
R’MgX’ (7a’)
R’2Mg (7b’)
(式中、X’はCl、Br又はIを示す。R’は前記に同じ。)
で表される化合物が挙げられる。R及びR’は同一又は異なっていてもよい。
本反応では、トリフルオロエチレンから式(4a)で表される化合物のみが生成し、他の位置のフッ素原子の置換は進行しない。この点が本発明の遷移金属触媒と有機マグネシウム試薬を用いる利点でもある。これまでに、(4a)で表される化合物の合成報告は極めて少ない。そのため、本発明の方法は(4a)で表される化合物の有効な製造方法である。
Cy: シクロヘキシル(cyclohexyl)
TFE: テトラフルオロエチレン(tetrafluoroethylene)
THF: テトラヒドロフラン(tetrahydrofuran)
PhMgBr: フェニルマグネシウムブロマイド(phenyl magnesium bromide)
dba: ジベンジリデンアセトン(dibenzylideneacetone)
グローブボックス中、Ni(cod)2(5.5mg、0.02mmol)、PPh3(10.6mg、0.04mmol)のTHF(0.4mL)溶液を耐圧チューブ(容量2ml、以下同じ)中に調製し、これにPhMgBrのエーテル溶液(3M、0.067mL、0.2mmol)とα,α,α-trifluorotoluene(14μL、0.114mmol:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol:上述の容器容量2mlと導入圧力0.35MPaから算出した。)を加えた。この反応溶液を室温(20℃、以下同じ)で8時間放置した。反応を19F-NMRで追跡し、内部標準より、α,β,β-トリフルオロスチレンが49%、1,1-ジフルオロ-2,2-ジフェニルエチレンが58%、1,2-ジフルオロ-1,2-ジフェニルエチレンが5%の収率で得られたことを確認した。
1H-NMR(C6D6):δ 7.16(tt,J=7.5,1.5Hz,1H),7.47(dd,J=8.5,7.5Hz,2H),7.59(dd,J=8.5,1.5Hz,2H).
19F-NMR(C6D6):δ -103.5(dd,J=72,32Hz,1F),-118.0(dd,J=72,107Hz,1F),-179.2(dd,J=107,32Hz,1F).
1,1-ジフルオロ-2,2-ジフェニルエチレン:
19F-NMR(C6D6):δ -91.5(s).MS m/z 216(M+),166(M-CF2),50(CF2).
1,2-ジフルオロ-1,2-ジフェニルエチレン:
19F-NMR(C6D6):δ trans体-154.8(s)、cis体-130.5(s).
グローブボックス中、Ni(cod)2(5.5mg,0.02mmol),PPh3(10.6mg,0.04mmol)のTHF(0.4mL)溶液を耐圧チューブ中に調製し、これにPhMgBrのエーテル溶液(3M,0.133mL,0.4mmol)とα,α,α-trifluorotoluene(14μL:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を室温で48時間放置した。反応を19F-NMRで追跡し、内部標準より、α,β,β-トリフルオロスチレンが43%、1,1-ジフルオロ-2,2-ジフェニルエチレンが26%、1,2-ジフルオロ-1,2-ジフェニルエチレンが6%の収率で得られたことを確認した。
グローブボックス中、Pd2(dba)3(5mg,0.005mmol),PPh3(5.3mg,0.02mmol),LiI(16.1mg,0.12mmol)のTHF(0.4mL)/C6D6(0.1mL)溶液を耐圧チューブ中に調製し、これにPhMgBrのエーテル溶液(3M,0.038mL,0.115mmol)とα,α,α-trifluorotoluene(14μL:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を60℃で2時間加熱した。反応を19F-NMRで追跡し、内部標準より、α,β,β-トリフルオロスチレンが49%、1,1-ジフルオロ-2,2-ジフェニルエチレンが15%の収率で得られたことを確認した。
グローブボックス中、Pd2(dba)3(5mg,0.005mmol),PCy3(5.6mg,0.02mmol),LiI(16.1mg,0.12mmol)のTHF(0.4mL)/C6D6(0.1mL)溶液を耐圧チューブ中に調製し、これにPhMgBrのエーテル溶液(3M,0.038mL,0.115mmol)とα,α,α-trifluorotoluene(14μL:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を60℃で2時間加熱した。反応を19F-NMRで追跡し、内部標準より、α,β,β-トリフルオロスチレンが18%、1,1-ジフルオロ-2,2-ジフェニルエチレンが6%、1,2-ジフルオロ-1,2-ジフェニルエチレンが6%の収率で得られたことを確認した。
PhMgBrの1M THF溶液(Aldrich社購入品)に1,4-Dioxaneを加え、MgBr2を沈殿させた。この際、MgBr2の析出量が進まなくなったところで、1,4-Dioxaneの滴下を終了した。グローブボックス内で、析出したMgBr2を濾別し、目的物が溶解した濾液を乾燥することで、Ph2Mg(THF)2を得た。得られたPh2Mg(THF)2はガラス容器内に密封し、グローブボックス内で保管した。
グローブボックス中、Pd2(dba)3(5mg,0.005mmol),PPh3(5.3mg,0.02mmol),LiI(16.1mg,0.12mmol),Ph2Mg(THF)2(37.1mg,0.115mmol)のC6D6(0.5mL)溶液を耐圧チューブ中に調製し、これにα,α,α-trifluorotoluene(14μL:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を室温で72時間放置した。反応を19F-NMRで追跡し、内部標準より、α,β,β-トリフルオロスチレンが21%(用いたPh2Mg(THF)2のモル数を基準、以下同様)、1,1-ジフルオロ-2,2-ジフェニルエチレンが10%、1,2-ジフルオロ-1,2-ジフェニルエチレンが2%の収率で得られたことを確認した。
グローブボックス中、Pd2(dba)3(5mg,0.005mmol),PPh3(5.3mg,0.02mmol),LiI(16.1mg,0.12mmol),Ph2Mg(THF)2(37.1mg,0.115mmol)のTHF(0.4mL)/C6D6(0.1mL)溶液を耐圧チューブ中に調製し、これにα,α,α-trifluorotoluene(14μL:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を室温で27時間放置した。反応を19F-NMRで追跡し、内部標準より、α,β,β-トリフルオロスチレンが86%(用いたPh2Mg(THF)2のモル数を基準、以下同様)、1,1-ジフルオロ-2,2-ジフェニルエチレンが2%、1,2-ジフルオロ-1,2-ジフェニルエチレンが4%の収率で得られたことを確認した。
耐圧チューブ中に、Ph2Mg(THF)2(22.6mg,0.07mmol)のC6D6-THF-d8(1:1,0.5 mL)溶液を調製し、TFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を室温で放置しつつ、1H-NMRにて反応を追跡した。反応系内に存在するTHFのβ水素を基準としたプロトンの積分比から、Ph2Mg(THF)2の転化率を見積もった。
耐圧チューブ中に、Ni(cod)2(2.6mg,0.01mmol),PPh3(5.3mg,0.02mmol)のC6D6-THF-d8(1:1,0.5mL)溶液を調製し、これにPh2Mg(THF)2(32.2mg,0.10mmol)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。参考例2と同様に1H-NMRにて反応を追跡した。
耐圧チューブ中に、トリフルオロエチレン(0.313mmol)、Ni(cod)2(2.6mg,0.01mmol),PPh3(5.3mg,0.02mmol),Ph2Mg(THF)2(32.2mg,0.10mmol)のTHF-d8(0.5mL)溶液を調製し、60℃で放置した。反応を19F-NMRにて反応を追跡し、1,1-ジフルオロ-2-フェニルエチレンの生成を確認した。これ以外は、原料のトリフルオロスチレンであり、トリフルオロスチレンのジフルオロメチレン基(CF2=)側のフッ素が置換した生成物は検出できなかった。
19F-NMR(THF-d8):δ -86.5(dd,J=37.0,29.2Hz,1F),-83.4(dd,J=37.0,4.4Hz,1F).
グローブボックス中、Pd2(dba)3(5mg,0.005mmol),PPh3(5.3mg,0.02mmol)のTHF(0.4mL)/C6D6(0.1mL)溶液を耐圧チューブ中に調製し、これにMeMgBrのエーテル溶液(3M,0.033mL,0.100mmol)とα,α,α-trifluorotoluene(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を加えた。さらにここにTFE(0.313mmol、0.35MPaまで封入した)を加えた。この反応溶液を60℃で2時間加熱した。反応を19F-NMRで追跡し、内部標準より、1,1,2-トリフルオロ-1-プロペンと、1,1-ジフルオロ-2-メチル-1-プロペンが得られたことを確認した。
19F-NMR(C6D6-THF-d8):δ -109.8(ddq,1F),-129.4(ddq,1F),-170.2(m,1F).
1,1-ジフルオロ-2-メチル-1-プロペン:
19F-NMR(C6D6-THF-d8):δ -98.41(septet,J=3.1Hz).
1H-NMR(C6D6-THF-d8):δ 1.56(d,J=3.1Hz)
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にPhMgBrのTHF溶液(2.0M,0.100mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(4時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、α,β,β-トリフルオロスチレンが145%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-179.0(dd,JFF=32.7,110.3Hz,1F,F1),-118.5(dd,JFF=73.5,110.3Hz,1F,F3),-104.2(dd,JFF=32.7,73.5Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にPhMgClのTHF溶液(2.0M,0.100mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(2時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、α,β,β-トリフルオロスチレンが162%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-Me-C6H4-MgBrのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(6時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-メチル-4-(1,2,2-トリフルオロエテニル)ベンゼンが150%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-178.6(dd,JFF=32.0,109.3Hz,1F,F1),-119.4(dd,JFF=76.0,109.3Hz,1F,F3),-105.2(dd,JFF=32.0,76.0Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にm-Me-C6H4-MgClのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(4時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-メチル-3-(1,2,2-トリフルオロエテニル)ベンゼンが144%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-178.7(dd,JFF=31.9,109.3Hz,1F,F1),-118.6(dd,JFF=74.0,109.3Hz,1F,F3),-104.4(dd,JFF=31.9,74.0Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にo-Me-C6H4-MgClのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(8時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-メチル-2-(1,2,2-トリフルオロエテニル)ベンゼンが113%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-163.8(dd,JFF=29.4,117.1Hz,1F,F1),-121.4(dd,JFF=77.6,117.1Hz,1F,F3),-107.1(dd,JFF=29.4,77.6Hz,1F,F2).
ZnCl2(136mg,1.00mmol)とLiI(321mg,2.40mmol)との固体混合物にTHF(5.0mL)を添加した。得られた溶液にo-Me-C6H4-MgClのTHF溶液(1.0M,2.00mL,2.00mmol)、Pd2(dba)3のTHF溶液(0.5mM,0.20mL,1.0×10-4mmol)を添加し、得られた溶液をオートクレーブ反応器に移した。その後、TFE(3.5気圧)を反応器に導入し、反応混合物を8時間40℃に保持した。未反応のTFEを反応器から取り除いた後、反応混合物を脱イオン水(20mL)で急冷した。その後、水相をペンタン(15mL)で3回抽出した。一方、有機相はMgSO4で乾燥した。ペンタン及びTHFを蒸留で取り除き、単離収率33%で1-メチル-2-(1,2,2-トリフルオロエテニル)ベンゼンを得た。
1H-NMR(400MHz,C6D6,rt,δ/ppm):2.07(s,3H,CH3),6.80-6.90(m,2H,C6H4),6.92-7.00(m,1H,C6H4),7.00-7.08(m,1H,C6H4).
13C{1H}-NMR(100.6MHz,C6D6,rt,δ/ppm):19.6(s,CH3),126.3(s,C4),126.4(dd,JCF=19.2,4.6Hz,C2),128.6(ddd,JCF=233.3,51.4,19.1Hz,-CF=CF2),130.3(apparent dd,JCF=3.1,2.3Hz,C3),130.3(d,JCF=2.3Hz,C5),131.1(s,C6),138.7(d,JCF=3.1Hz,C1),154.1(ddd,JCF=306.7,292.9,54.5Hz,-CF=CF2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-MeO-C6H4-MgBrのTHF溶液(0.5M,0.400mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(2.5時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-メトキシ-4-(1,2,2-トリフルオロエテニル)ベンゼンが126%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-177.2(dd,JFF=31.2,110.3Hz,1F,F1),-121.2(dd,JFF=79.1,110.3Hz,1F,F3),-106.7(dd,JFF=31.2,79.1Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-F-C6H4-MgBrのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(4時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-フルオロ-4-(1,2,2-トリフルオロエテニル)ベンゼンが110%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-177.8(dd,JFF=31.2,110.3Hz,1F,F1),-119.0(dd,JFF=74.9,110.3Hz,1F,F3),-114.2(br d,JHF=4.1Hz,1F,C6H4F),-104.6(ddd,JHF=4.1Hz,JFF=31.2,74.9Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液に(4-stylyl)MgBrのTHF溶液(0.71M,0.282mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(4時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-エテニル-4-(1,2,2-トリフルオロエテニル)ベンゼンが129%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-179.2(dd,JFF=32.8,110.3Hz,1F,F1),-118.0(dd,JFF=72.3,110.3Hz,1F,F3),-103.9(dd,JFF=32.8,72.3Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-CF3-MgBrのTHF溶液(0.42M,0.476mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(18時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-トリフルオロメチル-4-(1,2,2-トリフルオロエテニル)ベンゼンが62%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-179.8(dd,JFF=32.8,109.2Hz,1F,F1),-115.0(dd,JFF=65.5,109.2Hz,1F,F3),-100.8(dd,JFF=32.6,65.1Hz,1F,F2),-65.5(s,3F,CF3).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-MeS-MgBrのTHF溶液(0.5M,0.400mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(21時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-メチルチオ-4-(1,2,2-トリフルオロエテニル)ベンゼンが81%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-178.8(dd,JFF=31.2,109.2Hz,1F,F1),-118.9(dd,JFF=74.9,109.2Hz,1F,F3),-104.8(dd,JFF=31.2,74.9Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-Cl-MgClのEt2O溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(28時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-クロロ-4-(1,2,2-トリフルオロエテニル)ベンゼンが73%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-179.1(dd,JFF=32.8,110.3Hz,1F,F1),-117.2(dd,JFF=70.8,110.3Hz,1F,F3),-103.1(dd,JFF=32.8,70.8Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-Me2N-MgBrのTHF溶液(0.5M,0.400 mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(2時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-(N,N-ジメチルアミノ)-4-(1,2,2-トリフルオロエテニル)ベンゼンが60%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-176.1(dd,JFF=29.8,110.3Hz,1F,F1),-123.0(dd,JFF=85.2,110.3Hz,1F,F3),-108.6(dd,JFF=29.8,85.2Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液に(2-naphthyl)MgBrのTHF溶液(0.5M,0.400mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(4時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、2-(1,2,2-トリフルオロエテニル)ナフタレンが122%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-178.4(dd,JFF=32.0,108.8Hz,1F,F1),-118.0(dd,JFF=72.3,108.8Hz,1F,F3),-103.4(dd,JFF=31.0,72.3Hz,1F,F2).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液に(2-thienyl)MgBrのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、TFE(3.5気圧,0.313mmol)をNMRチューブに導入した。反応が終了するまで(75時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、2-(1,2,2-トリフルオロエテニル)チオフェンが67%の収率(使用した亜鉛試薬のモル数換算)で得られたことを確認した。
19F-NMR(372MHz,in THF/THF-d8,rt,δ/ppm):-171.9(dd,JFF=31.2,110.3Hz,1F,F1),-117.7(dd,JFF=72.3,110.3Hz,1F,F3),-106.5(dd,JFF=31.2,72.3Hz,1F,F2).
窒素雰囲気下で、内容量150mLの耐圧ガラス容器中に、ZnCl2(5.44g,40mmol)及びLiI(10.7g,80mmol)のTHF(60ml)溶液を調製した後、撹拌下でPhMgClのTHF溶液(2M,40mL,80mmol)をゆっくり滴下した。この溶液を1時間撹拌させた後、さらにここにPd2(dba)3(4mg,0.01mol%)をTHF溶液として加えた。容器内を微減圧にした後、TFE(3気圧)を仕込み、オイルバス中40℃で18時間撹拌させた。室温まで冷却後、脱圧し、反応容器内部を窒素置換した。反応溶液にα,α,α-トリフルオロトルエン(4mmol)を内標として滴下し、19F-NMRによって反応収率を求めた(使用した亜鉛試薬のモル数換算で99%収率)。
GLC分析条件
カラム:DB-5、液層0.25μm、径0.25φ;長さ30m
気化室温度:150℃
検出器温度:200℃
恒温槽温度:50℃、5分一定-昇温10℃/min-200℃、10分保持
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にC6H5-MgBrのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、ヘキサフルオロプロペン(HFP:0.313mmol)をNMRチューブに導入した。反応が終了するまで(27時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-フェニル-1,2,3,3,3-ペンタフルオロ-1-プロペン(E/Z=2:1)が44%(使用した亜鉛試薬のモル数換算)の収率で得られたことを確認した。
1H-NMR(THF-d8):δ7.26~7.37(3H),7.38~7.45(2H).
19F-NMR(THF-d8):δ -174.1(dq,JFF=11,133Hz,1F),-148.0(dq,JFF=22,133Hz,1F),-69.6(dd,JFF=11,22Hz,3F).
(Z)-1-フェニル-1,2,3,3,3-ペンタフルオロ-1-プロペン:
1H-NMR(THF-d8):δ7.26~7.37(3H),7.38~7.45(2H).
19F-NMR(THF-d8):δ -159.3(dq,JFF=12,13Hz,1F),-109.9(dq,JFF=12,8Hz,1F),-68.5(dd,JFF=8,13Hz,3F).
触媒反応は、耐圧NMRチューブ(Wilmad-LabGlass, 524-PV-7)を用い、19F-NMRスペクトルを観察することにより行った。ZnCl2(13.6mg,0.100mmol)とLiI(32.1mg,0.240mmol)との固体混合物にTHF-d8/THF溶液(0.4mL;体積比=3/1)を添加した。得られた溶液にp-CH3C6H4-MgBrのTHF溶液(1.0M,0.200mL,0.200mmol)、Pd2(dba)3のTHF溶液(0.5mM,20.0μL,1.0×10-5mmol)及びα,α,α-トリフルオロトルエン(12.3μL,0.100mmol:19F-NMR測定時の内部標準)を添加し、得られた溶液をNMRチューブに移した。その後脱気し、HFP(0.313mmol)をNMRチューブに導入した。反応が終了するまで(20時間)、反応混合物を40℃に保持した。19F-NMRで反応を観察し、1-(3-メチルフェニル)-1,2,3,3,3-ペンタフルオロ-1-プロペン(E/Z=3:2)が42%(使用した亜鉛試薬のモル数換算)の収率で得られたことを確認した。
19F-NMR(THF-d8):δ -69.6(dd,J=11,22Hz,3F),-148.2(dq,J=131,22Hz,1F),-174.1(dq,J=131,11Hz,1F).
(Z)-1-(3-メチルフェニル)-1,2,3,3,3-ペンタフルオロ-1-プロペン:
19F-NMR(THF-d8):δ -68.4(dd,J=13,8Hz,3F),-109.9(dq,J=9,8Hz,1F),-159.3(dq,J=9,13Hz,1F).
Claims (12)
- 有機基で置換された含フッ素オレフィンの製造方法であって、ニッケル又はパラジウムを含む触媒の存在下、含フッ素オレフィンと有機マグネシウム化合物とを反応させることを特徴とする製造方法。
- 前記含フッ素オレフィンのsp2混成炭素原子に結合した少なくとも1個のフッ素原子が、有機マグネシウム化合物に由来する有機基で置換される請求項1に記載の製造方法。
- さらにフッ素親和性化合物を添加して及び/又は加熱して反応させる請求項1又は2に記載の製造方法。
- 前記触媒がパラジウムを含む触媒である請求項1~3のいずれかに記載の製造方法。
- 前記パラジウムを含む触媒が、0価パラジウム錯体;II価パラジウム錯体から発生した0価パラジウム錯体;又はこれらとジケトン、ホスフィン、ジアミン及びビピリジルよりなる群から選ばれる少なくとも1種の化合物とを混合して得られる錯体である請求項1に記載の製造方法。
- 前記0価のパラジウム錯体が、Pd2(DBA)3(DBAはジベンジリデンアセトン)、Pd(COD)2(CODはシクロオクタ-1,5-ジエン)、Pd(DPPE)(DPPEは1,2-ビスジフェニルホスフィノエタン)、Pd(PCy3)2(Cyはシクロヘキシル基)、Pd(Pt-Bu3)2及びPd(PPh3)4(Phはフェニル基)よりなる群から選ばれる少なくとも1種であり、ホスフィンが、トリアリールホスフィン又はトリアルキルホスフィンである請求項5に記載の製造方法。
- 前記有機マグネシウム化合物が、式(7a)及び/又は式(7b):
RMgX (7a)
R2Mg (7b)
(式中、Rは置換基を有しても良いアリール基又は置換基を有しても良いアルキル基を示す。XはCl、Br又はIを示す。)
で表される化合物である請求項1~6のいずれかに記載の製造方法。 - 前記Rが、低級アルキル基、低級アルケニル基、低級アルコキシ基、及びアリール基からなる群より選ばれる少なくとも1種の基で置換されていても良い単環、二環又は三環のアリール基、又は、低級アルコキシ基及びアリール基からなる群より選ばれる少なくとも1種の基で置換されていても良いアルキル基である請求項7に記載の製造方法。
- 前記フッ素親和性化合物を添加して反応させる場合であって、該フッ素親和性化合物がハロゲン化リチウム、ハロゲン化マグネシウム、又はハロゲン化亜鉛である請求項3に記載の製造方法。
- 式(5’):
で表される化合物の製造方法であって、
(i)ニッケル又はパラジウムを含む触媒の存在下、テトラフルオロエチレンと、式(7a)及び/又は式(7b):
RMgX (7a)
R2Mg (7b)
(式中、XはCl、Br又はIを示す。Rは前記に同じ。)
で表される有機マグネシウム化合物を反応させて、式(4):
で表される化合物を製造する工程、及び
(ii)ニッケル又はパラジウムを含む触媒の存在下、式(4)で表される化合物と、式(7a’)及び/又は式(7b’):
R’MgX’ (7a’)
R’2Mg (7b’)
(式中、X’はCl、Br又はIを示す。R’は前記に同じ。)
で表される有機マグネシウム化合物を反応させて、式(5’)で表される化合物を製造する工程、を含む製造方法。
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