Process for producing vinyl bisfluoroalkanesulfonylimide

Abstract

To provide a method for readily producing vinylbisfluoroalkane sulfonylimide.SOLUTION: A method for producing vinylbisfluoroalkane sulfonylimide includes reacting an alkyne compound represented by formula (I) with bisfluoroalkane sulfonylimide represented by formula (II) (where R1 is an optionally substituted, chain hydrocarbon group, an optionally substituted, aromatic hydrocarbon group, or the like; R2 is H, an optionally substituted, chain hydrocarbon group or the like; Rf independently represents a C1-C10 fluoroalkyl group or the like).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel method for producing vinyl bis(fluoroalkanesulfonyl)imide using an alkyne compound as a starting material.

Background Art

[0002] Organic fluorine compounds have effects derived from the characteristic size and electronic properties of fluorine atoms, such as the mimic effect (mimicking effect) of steric molecular recognition on the biological side, which is due to the fact that the atomic radii of fluorine and hydrogen are almost the same, the block effect, which enables protection of metabolic sites and avoidance of associated toxicity because the C-F bond is stronger than the C-H bond, and the lipophilicity effect, which promotes absorption and transport in the living body due to improved lipophilicity. Through chemical modifications that utilize these effects, many pharmaceuticals and agricultural chemicals have been developed. And the development of methods for introducing a fluoroalkyl group, which is a mimic substituent of an alkyl group, has been carried out.

[0003] By the way, sulfonamide compounds are also compounds widely used in herbicides and fungicides. Patent Document 1 discloses a method for producing vinyl trifluoromethanesulfonamide into which a fluoroalkyl group has been introduced. On the other hand, although vinyl bis(fluoroalkanesulfonyl)imide, which is an analog thereof, is expected to be applied as an agricultural chemical intermediate, no reports on its synthesis have been made until recently. Recently, it has been clarified that vinyl bis(phenylsulfonyl)imide can be synthesized by reacting an alkyne compound with dibenzenesulfonimide (Non-Patent Document 1). In addition, Non-Patent Document 2 discloses that vinyl bis(trifluoromethanesulfonyl)imide could be synthesized by reacting an alkyne compound with lithium bis(trifluoromethanesulfonyl)imide.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Non-Patent Document

[0005]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the method described in Non-Patent Document 2 has problems in that lithium hexafluorophosphate and tetrabutylammonium hexafluorophosphate must be added as additives to the reaction system, resulting in a large variety of residual additives, and the reaction time is as long as 20 hours or more. In addition, in Non-Patent Document 2, only (CF3SO2)2NLi is used as the starting material, and it is unclear whether the reaction proceeds in the same manner when other sulfonimide compounds are used and whether a wide range of vinyl bis(fluoroalkanesulfonyl)imides can be produced. In view of the above problems, an object of the present invention is to provide a method for producing vinyl bis(fluoroalkanesulfonyl)imide and its analogs more simply, inexpensively, and efficiently.

Means for Solving the Problems

[0007] The present inventor has conducted intensive studies to solve the above problems. Although Non-Patent Document 2 disclosed that bis(trifluoromethanesulfonyl)imide has weak nucleophilicity and the reaction with an alkyne compound does not proceed, the present inventor, daringly using an alkyne compound and bis(trifluoromethanesulfonyl)imide as starting materials and reacting them at room temperature without adding an additive, unexpectedly found that the reaction proceeded and vinyl bis(trifluoromethanesulfonyl)imide could be produced. Furthermore, when reacting using bisfluoroalkanesulfonylimide other than bis(trifluoromethanesulfonyl)imide, it was found that the corresponding vinyl bisfluoroalkanesulfonylimide could be obtained simply and efficiently, leading to the completion of the present invention.

[0008] That is, the present invention relates to the following. [1] An alkyne compound represented by formula (I) [Chemical formula] (In the formula, R1 is a linear hydrocarbon group which may have a substituent; a cyclic aliphatic hydrocarbon group which may have a substituent; an aromatic hydrocarbon group which may have a substituent; or a heterocyclic group which may have a substituent, and R2 is a hydrogen atom; a linear hydrocarbon group which may have a substituent; a cyclic aliphatic hydrocarbon group which may have a substituent; a trialkylsilyl group; an allyldialkylsilyl group; an alkyldiallylsilyl group; or a triallylsilyl group.) and a bisfluoroalkanesulfonylimide represented by formula (II) [Chemical formula] (In the formula, each Rf is independently a C1-C10 fluoroalkyl group or together a C3-C10 cyclofluoroalkyl group.) are reacted, and is characterized in that a compound represented by formula (III) [Chemical formula] (In the formula, R1, R2, and Rf are the same groups as R1, R2, and Rf in the above formula (I) and formula (II).) A method for producing vinyl bis(fluoroalkanesulfonyl)imide represented by 〔2〕The method for producing vinyl bis(fluoroalkanesulfonyl)imide according to 〔1〕 above, wherein R1 in formula (I) is an aromatic hydrocarbon group which may have a substituent. 〔3〕The method for producing vinyl bis(fluoroalkanesulfonyl)imide according to 〔1〕 or 〔2〕 above, wherein the fluoroalkyl group in formula (II) is an alkyl group in which 60% or more of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. 〔4〕The method for producing vinyl bis(fluoroalkanesulfonyl)imide according to any one of 〔1〕 to 〔3〕 above, wherein the fluoroalkyl group in formula (II) is a perfluoroalkyl group. 〔5〕A vinyl bis(fluoroalkanesulfonyl)imide compound represented by formula (III).

Chemical formula

Advantages of the Invention

[0009] According to the production method of the present invention, the target vinyl bis(fluoroalkanesulfonyl)imide can be efficiently obtained by a simple and short-time reaction under mild conditions without the need for an additive.

Embodiments for Carrying Out the Invention

[0010] The method for producing vinyl bis(fluoroalkanesulfonyl)imide of the present invention comprises reacting an alkyne compound represented by formula (I)

Chemical formula

[0011] In the alkyne compound represented by formula (I) used in the production method of the present invention, R1 is a linear hydrocarbon group which may have a substituent; a cyclic aliphatic hydrocarbon group which may have a substituent; an aromatic hydrocarbon group which may have a substituent; or a heterocyclic group which may have a substituent, and R2 is a hydrogen atom; a linear hydrocarbon group which may have a substituent; a cyclic aliphatic hydrocarbon group which may have a substituent; a trialkylsilyl group; an allyldialkylsilyl group; an alkyldiallylsilyl group; or a triallylsilyl group.

[0012] As the "linear hydrocarbon group" in the above-mentioned "linear hydrocarbon group which may have a substituent", specifically, an alkyl group, an alkenyl group, an alkynyl group, etc. can be exemplified, and also a group in which 2 to 3 carbon-carbon bonds in the alkyl group are converted into double bonds, such as an alkadienyl group, an alkatrienyl group, etc., may be used.

[0013] The above alkyl group may be linear or branched, and specifically, a C1-C10 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, etc. can be exemplified.

[0014] The term "C1-C10" indicates that the number of carbon atoms in the parent nucleus group is 1 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group. Hereinafter, the same meaning is used in this specification.

[0015] The alkenyl group may be linear or branched. Specifically, examples thereof include C2-C10 alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group, 1-decenyl group, and the like.

[0016] The alkynyl group may be linear or branched. Specifically, examples thereof include C2-C10 alkynyl groups such as ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 1-hexynyl group, 1-heptynyl group, 1-octynyl group, 1-nonynyl group, and the like.

[0017] Specific examples of the "group in which 2 to 3 carbon-carbon bonds in the alkyl group are converted into double bonds" include C4-C6 alkadienyl groups such as 1,3-butadienyl group, which is a group in which 2 to 3 carbon-carbon bonds in the alkyl group having 1 to 10 carbon atoms are converted into double bonds, and alkatrienyl groups such as 1,3,5-hexatriene group.

[0018] Specific examples of the "cyclic aliphatic hydrocarbon group" in the "cyclic aliphatic hydrocarbon group which may have a substituent" include monocyclic aliphatic hydrocarbon groups or condensed cyclic aliphatic hydrocarbon groups having 3 to 10 members. Specific examples of the monocyclic aliphatic hydrocarbon group include cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, etc., which are saturated or unsaturated cyclic aliphatic hydrocarbon groups.

[0019] Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and the like.

[0020] Specific examples of the above cycloalkenyl group include a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 1-cyclohexenyl group, a 1-cyclobutenyl group, a 1-cycloheptenyl group, and the like.

[0021] Specific examples of the above cycloalkadienyl group include a 2,4-cyclopentadienyl group, a 2,4-cyclohexadienyl group, a 2,5-cyclohexadienyl group, and the like.

[0022] The "aromatic hydrocarbon group" in the above "optionally substituted aromatic hydrocarbon group" may be monocyclic or condensed polycyclic. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-azulenyl group, a 3-indenyl group, a 1-indanyl group, a 5-tetralinyl group, and the like.

[0023] Specific examples of the "heterocyclic group" in the above "optionally substituted heterocyclic group" include a monocyclic heterocyclic group having 5 to 10 members, a monocyclic aromatic heterocyclic group having 5 to 10 members, or a condensed aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. The condensed aromatic heterocyclic group includes those in which a monocyclic heterocyclic group containing at least one heteroatom selected from the group consisting of a benzene ring and a nitrogen atom, an oxygen atom, and a sulfur atom is condensed.

[0024] As the above-mentioned complex ring group, specifically, 1-piperidinyl group, 1-morpholinyl group, 2-pyrrolyl group, 2-imidazolyl group, 2-benzimidazolyl group, 3-pyrazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 2-oxazolyl group, 3-isoxazolyl group, 4-furazanyl group, 2-pyridinyl group, 2-pyrazinyl group, 2-pyrimidinyl group, 3-pyridazinyl group, 2-furanyl group, 2-pyranyl group, 2-thienyl group, 2-benzothiophenyl group, 2-thiopyranyl group, 1-isothiochromenyl group, 2-thiochromenyl group, 9-thioxanthenyl group, 1-thianthrenyl group, 1-phenoxathiinyl group, 1-pyrrolidinyl group, 5H-1-pyrindin-5-yl group, indolizine-1-yl group, 1-isoindolyl group, 1-indolyl group, 1-indazolylinyl group, 2-purinyl group, 1-quinolizinyl group, 1-isoquinolinyl group, 2-quinolinyl group, 2,6-naphthyridin-1-yl group, 2,7-naphthyridin-1-yl group, 1-phthalazinyl group, 2-quinoxalinyl group, 2-quinazolinyl group, 3-cinnolinyl group, 2-pteridinyl group, 9-carbazolyl group, 9-β-carbolinyl group, 10-phenanthridinyl group, 9-acridinyl group, 2-perimidinyl group, 1,10-phenanthroline-2-yl group, 1-phenazinyl group, 1-phenothiazinyl group, 1-phenoxazinyl group, 2-antiridinyl group, 1-isobenzofuranyl group, 2-benzofuranyl group, 1-isochromenyl group, 2-chromenyl group, 9-xanthenyl group, parathiazinyl group, 1,2,4-triazol-3-yl group, 1,2,3-triazol-1-yl group, 5-tetrazolyl group, etc. can be exemplified.

[0025] In the above-mentioned "chain hydrocarbon group which may have a substituent", "cyclic aliphatic hydrocarbon group which may have a substituent", "aromatic hydrocarbon group which may have a substituent", and "complex ring group which may have a substituent", the "substituent" is chemically acceptable and is not particularly limited as long as it has the effects of the present invention.

[0026] Specifically, A C1-10 alkyl group such as a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group; A C2-6 alkenyl group such as a vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group or 2-methyl-2-propenyl group; A C2-6 alkynyl group such as an ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group or 1-methyl-2-propynyl group;

[0027] A C3-8 cycloalkyl group such as a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group or cubanyl group; A C6-10 aryl group such as a phenyl group or 1-naphthyl group; A C6-10 aryl C1-6 alkyl group such as a benzyl group or phenethyl group; A 3-6 membered heterocyclyl group; A 3-6 membered heterocyclyl C1-6 alkyl group;

[0028] A hydroxyl group; A C1-6 alkoxy group such as a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group or t-butoxy group; A C2-6 alkenyloxy group such as a vinyloxy group, allyloxy group, propenyloxy group or butenyloxy group; A C2-6 alkynyloxy group such as an ethynyloxy group or propargyloxy group; A C6-10 aryloxy group such as a phenoxy group or 1-naphthoxy group; A C6-10 aryl C1-6 alkoxy group such as a benzyloxy group or phenethyloxy group; A 5-6 membered heteroaryloxy group such as a 2-thiazolyloxy group or 2-pyridyloxy group; A 5- to 6-membered heteroaryl C1-6 alkyloxy group such as a 2-thiazolylmethyloxy group or a 2-pyridylmethyloxy group;

[0029] A formyl group; A C1-6 alkylcarbonyl group such as an acetyl group or a propionyl group; A formyloxy group; A C1-6 alkylcarbonyloxy group such as an acetyloxy group or a propionyloxy group; A C6-10 arylcarbonyl group such as a benzoyl group; A C6-10 arylcarbonyloxy group such as a benzoyloxy group; A C1-6 alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, or a t-butoxycarbonyl group; a C1-6 alkoxycarbonyloxy group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, or a t-butoxycarbonyloxy group; A carboxyl group;

[0030] A halogeno group such as a fluoro group, a chloro group, a bromo group, or an iodo group; A C1-6 haloalkyl group such as a chloromethyl group, a chloroethyl group, a trifluoromethyl group, a 1,2-dichloro-n-propyl group, a 1-fluoro-n-butyl group, or a perfluoro-n-pentyl group; A C2-6 haloalkenyl group such as a 2-chloro-1-propenyl group or a 2-fluoro-1-butenyl group; A C2-6 haloalkynyl group such as a 4,4-dichloro-1-butynyl group, a 4-fluoro-1-pentynyl group, or a 5-bromo-2-pentynyl group; A C1-6 haloalkoxy group such as a trifluoromethoxy group, a 2-chloro-n-propoxy group, or a 2,3-dichlorobutoxy group; A C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group or a 3-bromobutenyloxy group; A C1-6 haloalkylcarbonyl group such as a chloroacetyl group, a trifluoroacetyl group or a trichloroacetyl group;

[0031] An amino group; A C1-6 alkyl-substituted amino group such as a methylamino group, a dimethylamino group or a diethylamino group; A C6-10 arylamino group such as an anilino group or a 1-naphthylamino group; A C6-10 arylC1-6 alkylamino group such as a benzylamino group or a phenethylamino group; A formylamino group; A C1-6 alkylcarbonylamino group such as an acetylamino group, a propanoylamino group, a butyrylamino group or an i-propylcarbonylamino group; A C6-10 arylcarbonylamino group such as a benzoylamino group; A C1-6 alkoxycarbonylamino group such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group or an i-propoxycarbonylamino group;

[0032] An unsubstituted or substituted aminocarbonyl group such as an aminocarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group or an N-phenyl-N-methylaminocarbonyl group; An iminoC1-6 alkyl group such as an iminomethyl group, a 1-iminoethyl group or a 1-imino-n-propyl group; An unsubstituted or substituted N-hydroxyiminoC1-6 alkyl group such as an N-hydroxy-iminomethyl group, a 1-(N-hydroxyimino)ethyl group, a 1-(N-hydroxyimino)-n-propyl group, an N-methoxyiminomethyl group or a 1-(N-methoxyimino)ethyl group;

[0033] An aminocarbonyloxy group; A C1-6 alkyl-substituted aminocarbonyloxy group such as an ethylaminocarbonyloxy group or a dimethylaminocarbonyloxy group;

[0034] Mercapto group; C1-C6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group or t-butylthio group; C1-C6 haloalkylthio groups such as trifluoromethylthio group or 2,2,2-trifluoroethylthio group; C6-C10 arylthio groups such as phenylthio group or 1-naphthylthio group; 5- to 6-membered heteroarylthio groups such as 2-thiazolylthio group or 2-pyridylthio group; C1-C6 alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group or t-butylsulfinyl group; C1-C6 haloalkylsulfinyl groups such as trifluoromethylsulfinyl group or 2,2,2-trifluoroethylsulfinyl group; C6-C10 arylsulfinyl groups such as phenylsulfinyl group or 1-naphthylsulfinyl group; 5- to 6-membered heteroarylsulfinyl groups such as 2-thiazolylsulfinyl group or 2-pyridylsulfinyl group; C1-C6 alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group or t-butylsulfonyl group; C1-C6 haloalkylsulfonyl groups such as trifluoromethylsulfonyl group or 2,2,2-trifluoroethylsulfonyl group; C6-C10 arylsulfonyl groups such as phenylsulfonyl group or 1-naphthylsulfonyl group; 5- to 6-membered heteroarylsulfonyl groups such as 2-thiazolylsulfonyl group or 2-pyridylsulfonyl group; C1-C6 alkylsulfonyloxy groups such as methylsulfonyloxy group, ethylsulfonyloxy group or t-butylsulfonyloxy group; C1-C6 haloalkylsulfonyloxy groups such as trifluoromethylsulfonyloxy group or 2,2,2-trifluoroethylsulfonyloxy group;

[0035] A tri-C1-6 alkyl-substituted silyl group such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, or a t-butyldimethylsilyl group; A tri-C1-6 alkyl-substituted silyloxy group such as a trimethylsilyloxy group, a triethylsilyloxy group, or a t-butyldimethylsilyloxy group; A tri-C6-10 aryl-substituted silyl group such as a triphenylsilyl group; A tri-C6-10 aryl-substituted silyloxy group such as a triphenylsilyloxy group; Examples thereof include a cyano group or a nitro group.

[0036] In addition, any of the hydrogen atoms in these "substituents" may be substituted with a group having a different structure. Specific examples of the "substituent" in that case include a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a halogeno group, a cyano group, or a nitro group.

[0037] In addition, the above-mentioned "3- to 6-membered heterocyclyl group" contains, for example, 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a boron atom as ring-constituting atoms. The heterocyclyl group may be either monocyclic or polycyclic. In the case of a polycyclic heterocyclyl group, as long as at least one ring is a heterocycle, the remaining rings may be any of a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring. Specific examples of the "3- to 6-membered heterocyclyl group" include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, a 5- to 6-membered partially unsaturated heterocyclyl group, and the like.

[0038] Specific examples of the above-mentioned 3- to 6-membered saturated heterocyclyl group include a 2-aziridinyl group, a 2-epoxy group, a 2-pyrrolidinyl group, a 2-tetrahydrofuranyl group, a 2-thiazolidinyl group, a 2-piperidyl group, a 2-piperazinyl group, a 1-morpholinyl group, a 2-dioxolanyl group, a 2-dioxanyl group, a pinacoloniylboronyl group, and the like.

[0039] Specific examples of the above five-membered heteroaryl group include a 2-pyrrolyl group, a 2-furyl group, a 2-thienyl group, a 2-imidazolyl group, a 3-pyrazolyl group, a 2-oxazolyl group, a 3-isoxazolyl group, a 2-thiazolyl group, a 3-isothiazolyl group, a 1,2,4-triazol-3-yl group, a 1,2,4-oxadiazol-3-yl group, a 1,2,4-thiadiazol-3-yl group, a 5-tetrazolyl group, and the like.

[0040] Specific examples of the above six-membered heteroaryl group include a 2-pyridyl group, a 3-pyrazinyl group, a 2-pyrimidinyl group, a 2-pyridazinyl group, a 1,3,5-triazin-2-yl group, and the like.

[0041] Specific examples of the above five- to six-membered partially unsaturated heterocyclyl group include a 2-oxazolinyl group or a 3-isoxazolinyl group, and the like.

[0042] Specific examples of the C1-C6 alkyl group of the above three- to six-membered heterocyclyl include a 2-aziridinylmethyl group, a glycidyl group, a 2-pyrrolidylmethyl group, a 2-tetrahydrofuranylmethyl group, a 2-thiazolidinylmethyl group, a 2-pyrrolylmethyl group, a 2-furylmethyl group, a 2-imidazolylmethyl group, a 2-pyridylmethyl group, or a 4-pyridylmethyl group, and the like.

[0043] In a preferred embodiment, R1 is an optionally substituted aromatic hydrocarbon group or an optionally substituted heterocyclic group, more preferably an optionally substituted aromatic hydrocarbon group, and even more preferably an optionally substituted phenyl group. Further, the number of substituents on the optionally substituted phenyl group may be 1 or 2 or more, and the position of the substituent may be any of the ortho, meta, and para positions with respect to the substitution position with the triple bond.

[0044] Specific examples of the compound represented by formula (I) include the compounds listed in the following formula.

[0045] [Chemical formula]

[0046] In addition, the fluoroalkyl group represented by Rf in formula (II) may be the same or different, and may be an alkyl group in which all hydrogen atoms are substituted by fluorine atoms (perfluoroalkyl group), or an alkyl group in which some hydrogen atoms are substituted by fluorine atoms. The number of carbon atoms is not particularly limited, but a range of C1 to C10 is preferable and can be exemplified. Specifically, CF3, C2F5, C3F7, C4F9, C5F 11 , C6F 13 , C7F 15 Or C8F 17 And other perfluoroalkyl groups such as CF2H, CFH2, CF2CF2H, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9 or CH2CH2C4F9 and other partially fluorinated alkyl groups can be exemplified. Among them, an alkyl group in which 60% or more of the hydrogen atoms in the alkyl group are substituted by fluorine atoms is preferable, and 70% or more, 80% or more, 90% or more are more preferable. Furthermore, among them, a fluoroalkyl group of C1 to C6 is preferable, and further a fluoroalkyl group of C1 to C3 is preferable, and particularly CF 3、 CF2CF2H is preferable. Also, two Rf's in formula (II) may combine to form a cyclofluoroalkyl group, which may be a cycloalkyl group in which all hydrogen atoms are substituted by fluorine atoms (percyclofluoroalkyl group), or a cycloalkyl group in which some hydrogen atoms are substituted by fluorine atoms. The number of carbon atoms is not particularly limited, but a range of C3 to C10 is preferable and can be exemplified. Specifically, C3F6, C4F8, C5F 10 , C6F 12 , C7F 14 Or C8F 16Examples thereof include perfluorinated alkyl groups such as etc., and partially fluorinated alkyl groups such as CH2CH2CF2, CH2C2F4, CH2CH2C2F4, CH2C3F6, CH2CH2C3F6, CH2C4F8 or CH2CH2C4F8. Among them, an alkyl group in which 60% or more of the hydrogen atoms in the alkyl group are substituted with fluorine atoms is preferable, and 70% or more, 80% or more, and 90% or more are more preferable. Further, among them, a C3-C8 perfluorinated alkyl group is preferable, and more preferably a C3-C5 perfluorinated alkyl group, and particularly preferably C3F6.

[0047] In the production method of the present invention, an alkyne compound represented by formula (I) is reacted with a bisfluoroalkanesulfonylimide represented by formula (II) in an organic solvent. Here, as the organic solvent to be used, specifically, organic halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, bromobenzene, iodobenzene, trifluoromethylbenzene, fluorobenzene, or difluorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene or mesitylene; aprotic polar solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diethyl ether, diisopropyl ether, di(n-butyl) ether, monoglyme, diglyme, triglyme, tetrahydrofuran, 1,4-dioxane, anisole, veratrole, diethyl sulfide, di(n-butyl) sulfide, acetonitrile, propionitrile or benzonitrile; aliphatic hydrocarbons such as pentane, hexane, cyclopentane or cyclohexane can be exemplified. Among them, organic halogen solvents are preferable, and further, dehydrated dichloromethane or dehydrated 1,2-dichloroethane, more preferably dehydrated dichloromethane or dehydrated 1,2-dichloroethane can be suitably used.

[0048] The amount of these organic solvents used is not particularly limited, but is preferably in the range of 0.5 to 20 times by weight with respect to the alkyne compound represented by formula (I).

[0049] The usage amount of the bisfluoroalkanesulfonylimide represented by the formula (II) with respect to the alkyne compound represented by the formula (I) is preferably in the range of 1.0 to 2.0 equivalents in terms of molar ratio.

[0050] The reaction temperature in the production method of the present invention is not particularly limited, but is usually -100°C to 150°C, preferably 0°C to 100°C, more preferably 10°C to 50°C, and even more preferably 15°C to 30°C. The reaction can also be carried out at room temperature. The reaction pressure can be carried out under normal pressure or under pressure, but normal pressure is preferred. The reaction time is usually 1 minute to 200 hours, preferably 1 hour to 10 hours, more preferably 1 hour to 5 hours, and even more preferably 1 hour to 3 hours. In addition, it is desirable that the reaction be carried out under sufficient stirring. After the reaction, vinyl bisfluoroalkanesulfonylimide can be isolated by purification such as known distillation methods, extraction, crystallization, recrystallization, chromatography, etc.

[0051] By the production method of the present invention, vinyl bisfluoroalkanesulfonylimide represented by the following formula (III) can be synthesized.

Chemical formula

Examples

[0052] The present invention will be explained in more detail using the following examples, but the present invention is not limited to the scope of these examples. [Example 1]

[0053] In Examples 1 to 12, 1-ethynylbenzene and bis(trifluoromethanesulfonyl)imide (HNTf2) were used as starting materials, and the equivalent number of starting materials and the amount of solvent were investigated.

[0054]

Chemical formula

[0055] A stir bar was placed in a 100 mL two-necked flask and purged with nitrogen. After that, dehydrated dichloromethane (24.5 mL), 1-ethynylbenzene (51.3 mg), and 1 M HNTf2 solution (0.50 mL) were added in this order, and then stirred at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product (172.6 mg). CHCl2CCl2 was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (99%). [Example 2]

[0056]

Chemical formula

[0057] A stir bar was placed in a 10 mL two-necked flask and purged with nitrogen. After that, dehydrated dichloromethane (9.5 mL), 1-ethynylbenzene (52.2 mg), and 1 M HNTf2 solution (0.51 mL) were added in this order, and then stirred at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product (179.5 mg). CHCl2CCl2 was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (99%). [Example 3]

[0058]

Chemical formula

[0059] After placing a stir bar in a 10 mL two-necked flask and performing nitrogen substitution, dehydrated dichloromethane (4.5 mL), 1-ethynylbenzene (51.7 mg), and 1 M HNTf2 solution (0.51 mL) were added in this order, followed by stirring at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product (194.6 mg). CHCl2CCl2 was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (93%). [Example 4]

[0060]

Chemical Formula

[0061] After placing a stir bar in a 10 mL two-necked flask and performing nitrogen substitution, dehydrated dichloromethane (2.0 mL), 1-ethynylbenzene (50.8 mg), and 1 M HNTf2 solution (0.50 mL) were added in this order, followed by stirring at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product (193.0 mg). CHCl2CCl2 was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (93%). [Example 5] - [Example 12]

[0062] The reaction was carried out in the same manner as in Examples 1 to 4, except that the equivalent number of starting materials, the type and amount of the solvent, and the reaction temperature were as shown in Table 1. The results are shown in Table 1. From the results of Examples 1 to 12, it was found that by using CH2ClCH2Cl or CH2Cl2 as the solvent, adding 1 equivalent or more of HNTf2 to 1-ethynylbenzene, and reacting at room temperature for 2 hours, the product vinyl bis(trifluoromethanesulfonyl)imide can be obtained in a high yield without an additive.

[0063]

Table 1

[0064] In this example, it was confirmed that vinyl bis(trifluoromethanesulfonyl)imide could be similarly synthesized using 10 mmol of 1-ethynylbenzene and an equivalent amount of HNTf2.

[0065] [ka] A 200 mL two-neck flask was fitted with a stir bar and purged with nitrogen. Anhydrous dichloromethane (90 mL), 1-ethynylbenzene (1.0223 g), and 1 M HNTf2 solution (10.0 mL) were added in that order and stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography (SiO2 = 95 g, Φ = 6.0 cm, packed solvent: hexane, eluent: hexane / ethyl acetate = 50%) to obtain the product (3.2 g, 84%). 1H-NMR(500MHz,CHLOROFORM-D)δ7.54-7.52(m,2H),7.45-7.42(m,3H),6.18(d,J=2.9Hz,1H),5.76(d,J=2.3Hz,1H);13C-NMR(126MHz ,CHLOROFORM-D)δ140.57,133.60,130.23,128.77,126.72,123.671119.17(q,J=325.5Hz);19F-NMR(471MHz,CHLOROFORM-D)δ-69.55 [Example 14]

[0066] In Examples 14 to 23, vinylbisfluoroalkanesulfonylimides were produced using starting materials other than 1-ethynylbenzene and HNTf2.

[0067] [ka] A stirrer was placed in a 10 mL two-neck flask and the inside of the flask was replaced with nitrogen. Then, dehydrated dichloromethane (4.5 mL), ethyl 4-[2-(trimethylsilyl)ethynyl]benzoate (113.3 mg), and a 1 M HNTf2 solution (0.50 mL) were added in that order, and the mixture was stirred at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product. CHCl2CCl2 (42.8 mg) was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (96%). The crude product was isolated and purified by silica gel column chromatography (SiO2 = 35 g, Φ = 3.2 cm, packing solvent: hexane, developing solvent: hexane / ethyl acetate = 50) to obtain a product (191.6 mg, 87%). 1H-NMR (500 MHz, CHLOROFORM-D) δ 7.44 (d, J = 2.3 Hz, 4H), 6.15 (d, J = 2.3 Hz, 1H), 5.69 (d, J = 2.3 Hz, 1H), 1.33 (s, 9H); 13C-NMR (126 MHz, CHLOROFORM-D) δ 153.71, 140.44, 130.61, 126.34, 125.73, 122.57, 119.15 (q, J = 325.9 Hz), 34.77, 31.07; 19F-NMR (471 MHz, CHLOROFORM-D) δ -69.54 [Example 15]

[0068]

Chemical formula

[0069] A stir bar was placed in a 10 mL two-necked flask and purged with nitrogen. After that, dehydrated dichloromethane (4.5 mL), 1-(tert-butyl)-4-[2-(trimethylsilyl)ethynyl]-benzene (146.5 mg), and 1M HNTf2 solution (0.60 mL) were added in this order, and then stirred at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product (247.2 mg). CHCl2CCl2 (38.8 mg) was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (63%). 1H-NMR (500 MHz, CHLOROFORM-D) δ 8.10 (dt, J = 8.6, 2.0 Hz, 2H), 7.58 - 7.62 (m, 2H), 6.30 (d, J = 2.3 Hz, 1H), 5.87 (d, J = 2.9 Hz, 1H), 4.40 (q, J = 7.5 Hz, 2H), 1.42 (t, J = 7.5 Hz, 3H); 19F-NMR (471 MHz, CHLOROFORM-D) δ -69.47 [Example 16]

[0070] [Chemical formula]

[0071] A stir bar was placed in a 10 mL two-necked flask and the flask was purged with nitrogen. After that, dehydrated dichloromethane (4.0 mL), ethyl 4-[2-(trimethylsilyl)ethynyl]benzoate (138.5 mg, 0.56 mmol), and a 1 M solution of HNTf2 (1.12 mL) were added in this order, and then the mixture was stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain a crude product (390.5 mg). CHCl2CCl2 (39.6 mg) was added as an internal standard, and NMR measurement was carried out. The yield was calculated from the integration ratio (72%). [Example 17]

[0072] [Chemical formula]

[0073] A stir bar was placed in a 10 mL two-necked flask and the flask was purged with nitrogen. After that, dehydrated dichloromethane (4.5 mL), 1-chloro-3-[2-(trimethylsilyl)ethynyl]-benzene (103.2 mg, 0.49 mmol), and a 1 M solution of HNTf2 (0.50 mL) were added in this order, and then the mixture was stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain a crude product (186.6 mg). CHCl2CCl2 (45 mg) was added as an internal standard, and NMR measurement was carried out. The yield was calculated from the integration ratio (78%). 1H-NMR(500MHz,CHLOROFORM-D)δ7.51(t,J=2.0Hz,1H),7.35-7.43(m,3H),6.20(d,J=2.3Hz,1H),5.81(d,J=2.3Hz,1H);19F-NMR(471MHz,CHLOROFORM-D)δ-69.44 [Example 18]

[0074] [ka]

[0075] A stirrer was placed in a 10 mL two-neck flask and the inside of the flask was replaced with nitrogen. Then, dehydrated dichloromethane (4.5 mL), 4-[2-(trimethylsilyl)ethynyl]-1,1'-biphenyl (124.9 mg, 0.5 mmol), and 1 M HNTf2 solution (0.50 mL) were added in that order, and the flask was stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain a crude product (218.7 mg). CHCl2CCl2 (45 mg) was added as an internal standard, and NMR measurement was performed. The yield was calculated from the integral ratio (97%). 1H-NMR(500MHz,CHLOROFORM-D)δ7.66(dt,J=8.6,2.0Hz,2H),7.60(tt,J=8.7,1.9Hz,4H),7.47(tt,J=7.9,2.1Hz,2H ),7.39(tt,J=7.4,1.7Hz,1H),6.24(d,J=2.9Hz,1H),5.77(d,J=2.9Hz,1H);19F-NMR(471MHz,CHLOROFORM-D)δ-69.48 [Example 19]

[0076] [ka]

[0077] A 10 mL two-neck flask was charged with a stir bar and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (143.5 mg, 0.49 mmol). After purging with nitrogen, anhydrous dichloromethane (5 mL) and ethynylbenzene (50.1 mg, 0.49 mmol) were added and stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain the crude product. NMR analysis was performed using CHCl2CCl2 (38.9 mg) as an internal standard, and the yield was calculated from the integral ratio (>99%). The crude product was purified by silica gel column chromatography (SiO2 = 35 g, Φ = 3.2 cm, packed solvent: hexane, eluent: hexane / ethyl acetate = 40) to obtain the product (175 mg, 90%). 1 H-NMR(500MHz,CHLOROFORM-D)δ7.77-7.75(m,2H),7.69-7.67(m,3H),6.41(d,J=2.9Hz,1H),5.90(d,J=2.9Hz,1H); 19 F-NMR(471MHz,CHLOROFORM-D)δ-113.31--111.10(m,2F),-118.40--115.81(m,1F),-121.30--119.25(m,2F),-131.79--130.21(m,1F) [Example 20]

[0078] [ka]

[0079] A 10 mL two-neck flask was charged with a stir bar and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (143.5 mg, 0.49 mmol). After purging with nitrogen, dehydrated dichloromethane (5 mL) and 4-[2-(trimethylsilyl)ethynyl]-1,1'-biphenyl (124.6 mg) were added in that order and stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain the crude product. CHCl2CCl2 (39.7 mg) was added as an internal standard, and NMR measurements were performed. The yield (94%) was calculated from the integral ratio. 1H-NMR (500 MHz, CHLOROFORM-D) δ 7.69 (dt, J = 8.6, 2.0 Hz, 2H), 7.59 - 7.64 (m, 4H), 7.47 (tt, J = 7.7, 1.6 Hz, 2H), 7.40 (tt, J = 7.4, 1.5 Hz, 1H), 6.24 (d, J = 2.9 Hz, 1H), 5.70 (d, J = 2.9 Hz, 1H); 19F-NMR (471 MHz, CHLOROFORM-D) δ -113.60--111.57 (m, 2F), -117.71--115.58 (m, 1F), -121.90--119.70 (m, 2F), -132.08--130.38 (m, 1F) [Example 21]

[0080] [Chemical formula]

[0081] A stir bar and 1,1,2,2,3,3 - hexafluoropropane - 1,3 - disulfonimide (148.2 mg) were placed in a 10 mL two - necked flask. After purging with nitrogen, dehydrated dichloromethane (5.0 mL) and 1 - chloro - 3 - [2 - (trimethylsilyl)ethynyl] - benzene (105 mg) were added, and then the mixture was stirred at room temperature for 2 hours. The volatile components of the filtrate were distilled off using a rotary evaporator to obtain a crude product. CHCl2CCl2 (34.7 mg) was added as an internal standard, and NMR measurement was carried out, and the yield was calculated from the integration ratio (79%). 1H-NMR (500 MHz, CHLOROFORM-D) δ 7.53 - 7.54 (m, 1H), 7.40 - 7.44 (m, 3H), 6.21 (d, J = 2.9 Hz, 1H), 5.75 (d, J = 2.9 Hz, 1H); 19F-NMR (471 MHz, CHLOROFORM-D) δ -114.10--111.43 (m, 2F), -117.98--116.09 (m, 1F), -121.38--119.21 (m, 2F), -131.35--129.49 (m, 1F) [Example 22]

[0082] [Chemical formula]

[0083] A 10 mL two-neck flask was charged with a stir bar and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (139.2 mg), and the atmosphere was purged with nitrogen. Anhydrous dichloromethane (5.0 mL) and 1-chloro-3-[2-(trimethylsilyl)ethynyl]-Benzene (96.6 mg) were added, followed by stirring at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain the crude product. CHCl2CCl2 (45.7 mg) was added as an internal standard, and NMR measurements were performed. The yield (96%) was calculated from the integral ratio. 1H-NMR(500MHz,CHLOROFORM-D)δ7.48(td,J=6.0,3.8Hz,2H),6.97(td,J=6.2,3.6Hz,2H),6.05(d,J=2.3Hz,1H),5.55(d,J=2.9Hz,1H),3.85(s ,3H);19F-NMR(471MHz,CHLOROFORM-D)δ-113.94--111.24(m,2F),-118.06--116.30(m,1F),-121.46--119.62(m,2F),-131.99--130.10(m,1F) [Example 23]

[0084] [ka]

[0085] A 10 mL two-neck flask was charged with a stir bar and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (148.2 mg), and the atmosphere was purged with nitrogen. Anhydrous dichloromethane (5.0 mL) and 1-methyl-4-[2-(trimethylsilyl)ethynyl]benzene (96.5 mg) were added and stirred at room temperature for 2 hours. The volatile components of the filtrate were removed using a rotary evaporator to obtain the crude product. CHCl2CCl2 (52.8 mg) was added as an internal standard, and NMR measurements were performed. The yield was calculated from the integral ratio (<100%). 1H-NMR (500 MHz, CHLOROFORM-D) δ 7.44 (d, J = 8.6 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 6.14 (d, J = 2.3 Hz, 1H), 5.61 (d, J = 2.3 Hz, 1H), 2.39 (s, 3H); 19F-NMR (471 MHz, CHLOROFORM-D) δ -110.28--113.99 (2F), -115.46--118.43 (1F), -119.35--121.57 (2F), -129.28--132.99 (1F)

Industrial Applicability

[0086] According to the production method of the present invention, the target vinyl bis(fluoroalkanesulfonyl)imide can be efficiently obtained under mild conditions with no need for additives and in a short reaction time. Further, according to the production method of the present invention, a novel vinyl bis(fluoroalkanesulfonyl)imide that could not be synthesized by conventional production methods can be synthesized, which can contribute to the development of pharmaceuticals, agricultural chemicals, etc. Therefore, the applicability of the present invention in the fields of pharmaceuticals and agricultural chemicals is extremely high.

Claims

**Claim 1**: A vinyl bisfluoroalkanesulfonylimide compound represented by formula (III). 【Chemical Formula 1】 (In the formula, R1 is an aromatic hydrocarbon group which may have a substituent; or a heterocyclic group which may have a substituent, R2 is a hydrogen atom; a chain hydrocarbon group which may have a substituent; a cyclic aliphatic hydrocarbon group which may have a substituent; a trialkylsilyl group; an allyldialkylsilyl group; an alkyldiallylsilyl group; or a triallylsilyl group, and two Rf together form a C3-C5 pericyclic fluoroalkyl group)

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