JP5998948B2 - Compound having bis (trifluoromethylsulfonyl) methyl group, process for producing the same, and use thereof as acid catalyst - Google Patents

Description

The present invention relates to a compound having a bis (trifluoromethylsulfonyl) methyl group [—CH (SO ₂ CF ₃ ) ₂ group] and a method for producing the same. Furthermore, the present invention relates to a method for using the compound as an acid catalyst.

  Reactions using conventional acid catalysts, such as Bronsted acids such as fuming sulfuric acid, Lewis acids such as aluminum chloride and titanium tetrachloride, require a stoichiometric amount of catalyst for the reaction. May occur, and the reaction solvent may be limited. For example, the Beckmann rearrangement reaction with fuming sulfuric acid and the Friedel-Crafts acylation reaction with aluminum chloride do not proceed catalytically, and the product and catalyst produce a stable adduct. It is necessary to decompose the sum or adduct to remove the product, which consumes a stoichiometric amount of acid or higher.

  Therefore, with the aim of changing to a more environmentally harmonious synthesis process, aiming to reduce waste and improve reaction efficiency, construction of continuous production processes using solid acid catalysts and organometallic complexes that are easily soluble in organic solvents Reactions using organic acid catalysts have been developed.

Among them, an organic acid substituted with a trifluoromethylsulfonyl group (—SO ₂ CF ₃ group, abbreviation: trifuryl group) is known as a compound exhibiting unique properties. The trifluoromethylsulfonyl group is known as one of the strongest electron withdrawing groups, and is a bis (trifluoromethylsulfonyl) methyl group [—CH (SO ₂ CF ₃ ) containing two trifluoromethylsulfonyl groups. _[ Group ₂ ] is highly acidic due to the strong electron withdrawing property of the trifluoromethylsulfonyl moiety, and exhibits high acidity. For example, bis (trifluoromethylsulfonyl) methane _{[CH 2 (SO 2 CF 3} ) 2; pK a (H 2 O) = - 1] ( Non-Patent Document 1) and phenyl bis (trifluoromethylsulfonyl) methane [PhCH _{(SO 2 CF 3) 2;} pK a (MeCN) = 7.83] ( non-Patent Document 2) is known as strong acids without oxidizing power.

  Non-patent document 3, Non-patent document 4, Patent document 1, and Patent document 2 disclose a compound having a bis (trifluoromethylsulfonyl) group, an acid catalyst, and a production method thereof.

Non-Patent Document 3 includes octanol (C ₈ H ₁₇ OH), trifluoromethanesulfinyl chloride (CF ₃ SOCl) and trifluoromethanesulfonic anhydride [(CF ₃ SO ₂ ) ₂ O] as starting compounds, A process for the preparation of 1-bis (trifluoromethylsulfonyl) octane is described. However, a multi-step reaction that takes time and effort to control the reaction is performed using an uncommon active reagent, and there is a problem that 1,1-bis (trifluoromethylsulfonyl) octane cannot be obtained in a high yield.

  Non-Patent Document 4 describes a method for introducing a bis (trifluoromethylsulfonyl) methyl group into an aliphatic epoxide compound, which comprises reacting an aliphatic epoxide compound with bis (trifluoromethylsulfonyl) methane. ing. The aliphatic epoxide compound is prepared by reacting a Grignard reagent prepared from methylmagnesium chloride with an epoxide to extend the alkyl side chain. However, this method has problems such as the use of epoxides having high degradability as a raw material compound and the dehydration conditions when using the Grignard reagent are limited, and it is not necessarily practical.

In Patent Document 1, as a polymer-supported catalyst, the general formula [RCH (SO ₂ R _f ) (SO ₂ R _f ′)] (R represents a substituted or unsubstituted aryl group, and R _f and R _f ′ Represents a perfluoroalkyl group independently of each other), and polymer-supported arylbis (perfluoroalkylsulfonyl) methane represented by

  However, in order to obtain polymer-supported arylbis (perfluoroalkylsulfonyl) methane, the active compound such as trifluoromethanesulfinate and trifluoromethanesulfonic acid anhydride, in which the raw material compound is limited to the highly active aryl halide, is excessive. There were problems such as requiring a complicated synthesis route in multiple steps under low temperature and strongly basic conditions.

For the purpose of improving the complexity of the production of compounds having these bis (trifluoromethylsulfonyl) methyl groups and the low generality of the substrate, Patent Document 2 describes that bis (( A method for introducing a trifluoromethylsulfonyl) methyl group is disclosed. 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane [(CF ₃ SO ₂ ) ₂ CHCH ₂ CH (SO ₂ CF ₃ ) ₂ ] is used to convert the phenol derivative or aniline derivative to bis (trifluoro Methylsulfonyl) methyl group is introduced. In this reaction, highly active bis (trifluoromethylsulfonyl) ethylene [(CF ₃ SO ₂ ) ₂ C═CH ₂ generated from 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane in the reaction system. ], It is possible to produce a compound having a bis (trifluoromethylsulfonyl) methyl group in a wide range of substrates with a good yield under mild conditions. In addition, the phenol derivative having a bis (trifluoromethylsulfonyl) methyl group obtained by this production method expresses high catalytic activity in the Mukaiyama aldol reaction and esterification reaction.

  However, in the production of 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane, it is necessary to use 2 molar equivalents of bis (trifluoromethylsulfonyl) methane and to synthesize the compound separately. Further, when bis (trifluoromethylsulfonyl) ethylene is generated, there is a problem that 1 molar equivalent of bis (trifluoromethylsulfonyl) methane is by-produced and is not efficient.

  As described above, a compound having a bis (trifluoromethylsulfonyl) methyl group has high acidity and is useful for an acid catalyst or the like, but the production of a compound having a bis (trifluoromethylsulfonyl) methyl group is There was a problem that the synthesis of the raw material compound was not easy, a multi-step reaction was required, and the reaction reagent to be reacted with the raw material compound was unstable and had to be used excessively.

On the other hand, Patent Documents 3 to 5 disclose a method for producing a bis (trifluoromethylsulfonyl) ethylene compound as a simple method for producing a compound having a structure similar to a bis (trifluoromethylsulfonyl) methyl group. ing. In the production method, a bis (trifluoromethylsulfonyl) ethylene compound can be obtained in good yield under mild conditions by subjecting bis (trifluoromethylsulfonyl) methane to a condensation reaction with an easily available aldehyde compound. The raw material compound in this production method is an aromatic aldehyde, conjugated aldehyde, acetaldehyde or paraformaldehyde, and the following bis (perfluoroalkylsulfonyl) ethylene compound is synthesized.

(In the above compounds, the wavy line represents an E-type or Z-type bond, and Et represents an ethyl group.)

  In this production method, a bis (trifluoromethylsulfonyl) ethylene compound can be obtained in good yield by using 1 to 2 molar equivalents of an easily available aldehyde compound under mild conditions. However, the resulting bis (trifluoromethylsulfonyl) ethylene compound does not have an acidic proton and is difficult to use as an acid catalyst.

A. R. Siedle et al., J. Am. Chem. Soc., 106, 1510-1511 (1984) I. Leito et al., J. Org. Chem., 63, 7868-7874 (1998) H. Yamamoto and K. Ishihara et al., Bull. Chem. Soc. Jpn., 78, 1401-1410 (2005) R. J. Koshar and R. A. Mitsch, J. Org. Chem., 38, 3358-3363 (1973)

JP 2002-338539 A JP 2012-126688 A U.S. Pat. No. 3,932,526 U.S. Pat. No. 3,962,346 US Pat. No. 4,053,519

  Provided are a compound having a bis (trifluoromethylsulfonyl) methyl group having high acid catalyst activity and a simple production method thereof.

  The present inventors have intensively studied to solve the above problems. As a result, it was found that a compound having a bis (trifluoromethylsulfonyl) methyl group can be obtained in high yield by reducing the bis (trifluoromethylsulfonyl) ethylene compound using a hydride reducing agent.

  Furthermore, the present inventors have found that the compound having a bis (trifluoromethylsulfonyl) methyl group can be used as an acid catalyst having high activity, and completed the present invention.

  That is, the present invention is as follows.

[Invention 1]
Formula (1)

[In Formula (1), A represents a monovalent organic group. ]
The compound represented by formula (2) is contacted with a hydride reducing agent.

[In Formula (2), A represents a monovalent organic group. ]
A method for producing a compound represented by the formula (2), wherein the compound represented by the formula (2) is obtained.

[Invention 2]
A is the formula (3)

[In Formula (3), Ar represents an aryl group, a heteroaryl group, an aryl group having a substituent, or a heteroaryl group having a substituent. n represents an arbitrary integer of 0 to 5. ]
The manufacturing method of the invention 1 which is the monovalent organic group represented by these.

[Invention 3]
A is the formula (4)

[In Formula (4), Ar represents an aryl group, a heteroaryl group, an aryl group having a substituent, or a heteroaryl group having a substituent. ]
The manufacturing method of the invention 1 or the invention 2 which is the monovalent organic group represented by these.

[Invention 4]
A is the formula (5) or (6)

[In Formula (5) or Formula (6), each R ¹ and each R ² are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a sulfo group, a cyano group, 20 aliphatic hydrocarbon groups or C6-C20 aromatic hydrocarbon groups are represented.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or a sulfo group. The cyano group may be substituted.
Even if a part of carbon atoms in an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in an aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom Good.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms may include a carbonyl group or a sulfonyl group in the group.
p represents an arbitrary integer of 0 to 5.
q represents an arbitrary integer of 0 to 3. ]
The manufacturing method in any one of the invention 1 which is a monovalent organic group represented by these.

[Invention 5]
The manufacturing method in any one of invention 1-4 whose hydride reducing agent is a borohydride reducing agent or an aluminum hydride reducing agent.

[Invention 6]
The manufacturing method of the invention 5 whose borohydride reducing agent is a borane complex or a borohydride metal.

[Invention 7]
The production method of Invention 6, wherein the metal borohydride is lithium borohydride, sodium borohydride or potassium borohydride.

[Invention 8]
Formula (2)

[In Formula (2), A represents Formula (5) or Formula (6)

(In Formula (5) or Formula (6), each R ¹ and each R ² are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a sulfo group, a cyano group, or a C ¹ -C 1 group. 20 aliphatic hydrocarbon groups or C6-C20 aromatic hydrocarbon groups are represented.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or a sulfo group. The cyano group may be substituted.
Even if a part of carbon atoms in an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in an aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom Good.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms may include a carbonyl group or a sulfonyl group in the group.
p represents an arbitrary integer of 0 to 5.
q represents an arbitrary integer of 0 to 3. )
The monovalent organic group represented by these. ]
A compound represented by

[Invention 9]
The use method of the compound represented by Formula (2) of the invention 8 as an acid catalyst.

  In the production method of the present invention, a compound having a bis (trifluoromethylsulfonyl) methyl group can be obtained in a high yield by a simple synthesis reaction.

Moreover, the compound which has a bis (trifluoromethylsulfonyl) methyl group obtained by this manufacturing method shows high acid catalyst activity in various reaction.

  Configurations and combinations thereof in the following embodiments are examples, and additions, omissions, substitutions, and other modifications of the configurations can be made without departing from the spirit of the present invention. Further, the present invention is not limited by the embodiments, and is limited only by the scope of the claims.

1. Compound having bis (trifluoromethylsulfonyl) methyl group

[Compound (2) having bis (trifluoromethylsulfonyl) methyl group]
The compound having a bis (trifluoromethylsulfonyl) methyl group according to the present invention has the formula (2)

[In Formula (2), A is a monovalent organic group. ]

It is represented by

The compound has the formula (1)

[In Formula (1), A is a monovalent organic group. ]

It can be obtained by reducing a bis (trifluoromethylsulfonyl) ethylene compound represented by the formula below using a hydride reducing agent.

In the compound (2), A in the compound (2) is represented by the formula (3) from the viewpoint of the stability of the compound and the availability of the raw material compound.

[In Formula (3), Ar represents an aryl group, a heteroaryl group, an aryl group having a substituent, or a heteroaryl group having a substituent. n represents an arbitrary integer of 0 to 5. ]

(7) which is a monovalent organic group represented by

[In Formula (7), Ar and n are synonymous with Ar and n in Formula (3), respectively. ]

Is preferred.

  In Formula (3) or Formula (7), the “aryl group” means an aromatic hydrocarbon group having 6 to 60 carbon atoms. The aromatic hydrocarbon group may be a single ring or a condensed ring.

  The “heteroaryl group” means a 5- to 10-membered heteroaromatic ring group having 3 to 60 carbon atoms and containing one or more heteroatoms selected from an oxygen atom or a sulfur atom. The heteroaromatic ring group may be a single ring or a condensed ring.

  “Substituent” of “aryl group having substituent” or “heteroaryl group having substituent” is a fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, sulfo group, cyano group, carbon number 1 Means an aliphatic hydrocarbon group having -20 carbon atoms or an aromatic hydrocarbon group having 6-20 carbon atoms.

  The “substituent” may be singular or plural, and in the case of plural, each may have a different substituent.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, sulfo group. Group and a cyano group may be substituted.

  A part of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in the aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom. May be.

  The C1-C20 aliphatic hydrocarbon group or the C6-C20 aromatic hydrocarbon group may contain a carbonyl group or a sulfonyl group in the group.

  Examples of "aryl group" or "heteroaryl group" include phenyl group, naphthyl group, anthracenyl group, tetracenyl group, phenanthrenyl group, perylenyl group, fluorenyl group, indenyl group, furyl group, thienyl group, benzofuryl group, benzothienyl group Etc.

Examples of an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group Group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, tert-pentyl group, neopentyl group, 2-pentyl group, 3-pentyl group 2-hexyl group, tert-octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, undecyl Xyl group, isopropyloxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, cyclopropyloxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, 2-cyclohexylethoxy group, 1- Adamantyloxy group, 2-adamantyloxy group, 1-adamantylmethyloxy group, 2- (1-adamantyl) ethyloxy group, trifluoromethoxy group, allyloxy group, benzyloxy group, phenoxy group, 1-naphthyloxy group, 2- Naphthyloxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, cyclopropylthio, cyclobutylthio, cyclope Tylthio group, cyclobutylthio group, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, undecyl Sulfonyl group, dodecylsulfonyl group, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, benzoyl group, naphthoyl group Group, formyloxy group, acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy Group, hexanoyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, benzoyloxy group, naphthoyloxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group Group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, allyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group Phenyl group, indenyl group, naphthyl group, fluorenyl group, 1-phenylvinyl group, 2-phenylvinyl group, biphenyl group, o-terphenyl group, m-terphenyl group, p-ta _{Phenyl, -CH = C (H) CO} 2 CH 3 _{group, -CH = C (H) CO} 2 C 2 H 5 _{group, -CH = C (H) CO} 2 C 3 H 7 group, -CH = C _{(H) CO 2 CH (CH} 3) 2 group, -CH = C (H) CO 2 C (CH 3) such as ₃ group can be mentioned.

In the compound (7), A in the compound (1) is represented by the formula (8) or the formula (9) from the viewpoint of the stability of the corresponding product.

[In formula (8) or formula (9), each R ¹ and each R ² are each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, sulfo group, cyano group, 20 aliphatic hydrocarbon groups or C6-C20 aromatic hydrocarbon groups are represented.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or a sulfo group. The cyano group may be substituted.
Even if a part of carbon atoms in an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in an aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom Good.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms may include a carbonyl group or a sulfonyl group in the group.
p represents an arbitrary integer of 0 to 5.
q represents an arbitrary integer of 0 to 3.
r represents an arbitrary integer of 0 to 5.
s represents an arbitrary integer of 0 to 5. ]

Is particularly preferred.

Specifically, the following compounds can be exemplified.

(In the above compounds, Et represents an ethyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.)

2. Bis (trifluoromethylsulfonyl) ethylene compound (1)

[Bis (trifluoromethylsulfonyl) ethylene compound (1)]
In the compound (1), A in the compound (1) is represented by the formula (3) from the viewpoint of the stability of the corresponding product and the availability of the raw material compound.

[In Formula (3), Ar represents an aryl group, a heteroaryl group, an aryl group having a substituent, or a heteroaryl group having a substituent. n represents an arbitrary integer of 0 to 5. ]

(10) which is a monovalent organic group represented by

[In Formula (10), Ar and n are synonymous with Ar and n in Formula (3), respectively. ]

Is preferred. Among these, from the viewpoint of the stability of the compound, A in the compound (1) is represented by the formula (11) or the formula (12).

[In formula (11) or formula (12), each R ¹ and each R ² are each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, sulfo group, cyano group, 20 aliphatic hydrocarbon groups or C6-C20 aromatic hydrocarbon groups are represented.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or a sulfo group. The cyano group may be substituted.
Even if a part of carbon atoms in an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in an aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom Good.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms may include a carbonyl group or a sulfonyl group in the group.
p represents an arbitrary integer of 0 to 5.
q represents an arbitrary integer of 0 to 3.
r represents an arbitrary integer of 0 to 5.
s represents an arbitrary integer of 0 to 5. ]

Is particularly preferred.

Specifically, the following compounds can be exemplified.

(In the above compounds, Et represents an ethyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.)

[Method for Producing Bis (trifluoromethylsulfonyl) ethylene Compound (1)]
The bis (trifluoromethylsulfonyl) ethylene compound (1) can be obtained by a known method or a method analogous thereto. For example, it can be obtained by performing a condensation reaction of an aldehyde compound represented by formula (13) and bis (trifluoromethylsulfonyl) methane represented by formula (14) (see Patent Documents 3 to 5).

[In Formula (13), A is synonymous with A in Formula (1). ]

Examples of compound (13) include the following compounds.

(In the above compounds, Et represents an ethyl group, and t-Bu represents a tert-butyl group.)

A method for producing the bis (trifluoromethylsulfonyl) ethylene compound (1) will be briefly described. First, an aldehyde compound represented by the formula (13) and bis (trifluoromethylsulfonyl) methane represented by the formula (14) are brought into contact with each other in a predetermined reaction vessel and reacted at a predetermined temperature for a predetermined time. Thereafter, the bis (trifluoromethylsulfonyl) ethylene compound (1) can be obtained by performing a predetermined post-treatment.

  The reaction can be carried out using a solvent.

  The reaction can be carried out with stirring. From the viewpoint of reaction efficiency, stirring is preferred.

  Further, the reaction may be performed while circulating an inert gas such as nitrogen gas or argon gas.

  The amount of aldehyde compound (13) and bis (trifluoromethylsulfonyl) methane (14) used in the reaction is usually bis (trifluoromethylsulfonyl) methane (14) relative to aldehyde compound (13). Although it may be used for the reaction in the range of 1-fold mole to 10-fold mole, those skilled in the art can appropriately adjust it outside this range depending on the reaction. From the viewpoint of reaction yield, it is preferably used for the reaction in the range of 1 to 3 moles.

  The reaction vessel is not particularly limited, and a reaction vessel that can withstand the pressure used during the reaction or a material that does not affect the reaction can be used. The reaction may be at normal pressure or under pressure, and can be appropriately adjusted by those skilled in the art depending on the type of reaction.

  The reaction temperature is preferably 0 ° C. to 120 ° C., and can be appropriately adjusted within the temperature range according to the boiling point of the reaction solvent and the progress of the reaction.

  The reaction time is not particularly limited, but it may be usually in the range of 1 minute to 24 hours. The reaction time may be measured by an analytical means such as gas chromatography measurement, liquid chromatography measurement, or nuclear magnetic resonance spectrum (NMR spectrum) measurement. It is preferable to follow the progress and set the end point when the raw material substrate has almost disappeared.

  The reaction solvent is not particularly limited as long as it does not participate in the reaction, and aliphatic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, alcohols, ketones, aprotic polar solvents Can be used. Specifically, n-pentane, n-hexane, n-heptane, n-octane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dichloromethane, 1,2-dichloroethane, chloroform, methanol, ethanol , Isopropanol, acetone, methyl ethyl ketone, acetonitrile, N, N-dimethylformamide (abbreviation: DMF), dimethyl sulfoxide (abbreviation: DMSO), hexamethylphosphoric triamide (abbreviation: HMPA), and the like. Of these, 1,2-dichloroethane is particularly preferred from the viewpoint of the solubility of the reaction substrate and the reaction temperature.

  For purification of the compound (1), a purification method generally used in organic synthesis can be used, and examples thereof include recrystallization, distillation, column chromatography and the like. By these means, the compound (1) can be obtained.

  In addition, compound (1) may be used as a reaction substrate for a reduction reaction using a hydride reducing agent, which is the next reaction, after removing the solvent used for the reaction under reduced pressure conditions without performing a special purification operation. .

  When distillation is performed, the pressure may be normal pressure (in particular, the pressure when no pressure is applied or reduced, usually about 0.1 MPa. The same applies hereinafter), but preferably the pressure is reduced. There are no restrictions on the material of the distillation tower, and it is made of glass, stainless steel, tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass, etc. Can be used. A filler can also be packed in the distillation column. Distillation is preferred because it can be accomplished at a relatively low temperature under reduced pressure.

3. Method for producing compound (2) having bis (trifluoromethylsulfonyl) methyl group

A method for producing the compound (2) having a bis (trifluoromethylsulfonyl) methyl group according to the present invention will be described.

  First, bis (trifluoromethylsulfonyl) ethylene compound (1) is added to a predetermined reaction vessel, and then a hydride reducing agent is added at a predetermined temperature, and the reaction is performed at the same temperature or an appropriately adjusted temperature for a predetermined time. Thereafter, a compound having a bis (trifluoromethylsulfonyl) methyl group can be obtained by performing a predetermined post-treatment.

  The order of adding the bis (trifluoromethylsulfonyl) ethylene compound (1) and the hydride reducing agent can be reversed. That is, a hydride reducing agent is added to a predetermined reaction vessel, and then a bis (trifluoromethylsulfonyl) ethylene compound (1) is added at a predetermined temperature, followed by reaction at the same temperature or an appropriately adjusted temperature. A compound having a bis (trifluoromethylsulfonyl) methyl group can also be obtained by performing post-treatment.

  The reaction can be carried out using a solvent. When both the bis (trifluoromethylsulfonyl) ethylene compound (1) and the hydride reducing agent are solid, it is preferable to use a solvent. In the case of using a solvent, it is preferable that the bis (trifluoromethylsulfonyl) ethylene compound (1) and / or the hydride reducing agent is dissolved in the solvent and then used for the reaction.

  The reaction can be carried out with stirring. From the viewpoint of reaction efficiency, stirring is preferred.

  Further, the reaction may be performed while circulating an inert gas such as nitrogen gas or argon gas.

  The amount of the bis (trifluoromethylsulfonyl) ethylene compound (1) and hydride reducing agent used in the reaction is usually 1% relative to the bis (trifluoromethylsulfonyl) ethylene compound (1). What is necessary is just to use for reaction in the range of double mole-10 times mole, and it is preferable to use for reaction in the range of 2 times mole-3 times mole from the point of reaction yield.

  The reaction vessel is not particularly limited, and a reaction vessel that can withstand the pressure used during the reaction or a material that does not affect the reaction can be used. The reaction may be at normal pressure or under pressure, and can be appropriately adjusted by those skilled in the art depending on the type of reaction.

  The reaction temperature is preferably room temperature (in particular, an atmospheric temperature not heated or cooled, usually about 15 ° C. to 30 ° C., the same applies hereinafter), more preferably −150 ° C. to + 10 ° C., and more preferably about − It is particularly preferable to carry out at 78 ° C. Moreover, it can adjust suitably in the range of -150 degreeC-room temperature according to progress of reaction.

  The reaction time is not particularly limited, but it may be usually in the range of 1 minute to 24 hours. The reaction time may be measured by an analytical means such as gas chromatography measurement, liquid chromatography measurement, or nuclear magnetic resonance spectrum (NMR spectrum) measurement. It is preferable to follow the progress and set the end point when the raw material substrate has almost disappeared.

  A hydride reducing agent means a reagent that reduces a compound by nucleophilic hydrogen donation.

  Specific examples of the hydride reducing agent in the present invention include a borohydride reducing agent and an aluminum hydride reducing agent.

  Examples of the borohydride reducing agent include diborane, borane complex, borohydride metal, and the like.

  Specific examples of the borane complex include borane-N, N-dimethylaniline complex, borane-dimethylamine complex, borane-dimethylsulfide complex, borane-ethylamine complex, borane-morpholine complex, borane-pyridine complex, borane-2- Examples include a picoline complex, a borane-tetrahydrofuran complex, a borane-triethylamine complex, a borane-trimethylamine complex, and a borane-triphenylphosphine complex.

  Specific examples of the metal borohydride include lithium borohydride, potassium borohydride, sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, and the like.

  Specific examples of the aluminum hydride reducing agent include aluminum hydride compounds such as aluminum hydride, lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, alkoxyaluminum hydride, and diisobutylaluminum hydride. It is done.

  Of the hydride reducing agents, sodium borohydride, lithium borohydride, borane-2-picoline complex, lithium aluminum hydride, diisobutylaluminum hydride are particularly preferred because of the high yield of reaction products and the simplicity of the reaction. preferable.

  A hydride reducing agent can also be used for reaction combining several types.

  When using the hydride reducing agent, a Lewis acid may be used as an activator. Examples of the Lewis acid include aluminum chloride, iron trichloride, gallium trichloride, boron trifluoride diethyl ether complex, and the like. In this case, the amount of Lewis acid used may generally be about 0.1 to 1 mole relative to the hydride reducing agent.

  The reaction solvent is not particularly limited as long as it does not inhibit the reaction. For example, when a borohydride reducing agent is used, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, alcohols, esters, aprotic polar solvents, or a mixed solvent thereof Etc. can be preferably used, but ethers, halogenated hydrocarbons, alcohols and esters are particularly preferred.

  In the case of using an aluminum hydride reducing agent, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, or a mixed solvent thereof can be preferably used, but ethers, halogenated hydrocarbons, etc. Are particularly preferred.

  Aliphatic hydrocarbons include n-pentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, n-undecane, n-dodecane, Examples include cyclopentane, cyclohexane, methylcyclohexane, tert-butylcyclohexane, petroleum ether and the like.

  Aromatic hydrocarbons include benzene, toluene, ethylbenzene, isopropylbenzene, tert-butylbenzene, xylene, mesitylene and the like.

  Examples of ethers include tetrahydrofuran (abbreviation: THF), methyltetrahydrofuran, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, di-n-hexyl ether, di-n-heptyl ether, Examples include di n-octyl ether, tert-butyl methyl ether (abbreviation: MTBE), cyclopentyl methyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, anisole, and diphenyl ether.

  Examples of halogenated hydrocarbons include dichloromethane, chloroform, 1,2-dichloroethane, monochlorobenzene, monofluorobenzene, α, α, α-trifluoromethylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene and the like can be mentioned.

  Alcohols include methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, isopentyl alcohol, 1-hexanol, 2- Hexanol, isohexyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, isopeptyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol Mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n- butyl ether, diethylene glycol mono isobutyl ether, and the like diethylene glycol tert- butyl ether.

  Examples of the esters include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, and isoamyl acetate.

  Examples of aprotic polar solvents include dimethyl sulfoxide, sulfolane, N, N-dimethylformamide (abbreviation: DMF), N, N-dimethylacetamide, N, N-dimethylpropionamide, N-methylpyrrolidone, γ-butyrolactone, Examples include dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyridinone, and the like. .

  Among them, when a borohydride reducing agent is used in the hydride reducing agent, tetrahydrofuran, diethyl ether, methanol, ethanol, ethyl acetate, and dichloromethane are particularly preferable. When an aluminum hydride reducing agent is used, tetrahydrofuran, diethyl ether Dichloromethane is particularly preferred.

  About the post-processing method in this manufacturing method, it is preferable to process an excess hydride reducing agent using the aqueous solution of an acid. As the acid to be used, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as acetic acid and methanesulfonic acid can be used, but dilute hydrochloric acid or dilute sulfuric acid is preferably used from the viewpoint of separation from the product. . Further, when an aluminum hydride reducing agent is used as the hydride reducing agent, it is particularly preferable to use dilute sulfuric acid because of the problem of solubility of by-product aluminum hydroxide.

  There is no restriction | limiting in particular about the purification method of the compound (2) in this manufacturing method, The purification method currently generally performed by the organic synthesis can be used. For example, recrystallization, distillation, column chromatography and the like can be mentioned. By these means, the compound (2) can be obtained.

  When distillation is performed, normal pressure may be used, but reduced pressure is preferable. There are no particular restrictions on the material of the distillation tower, glass, stainless steel, tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, etc. Can be used. A filler can also be packed in the distillation column. Distillation is preferred because it can be achieved at a relatively low temperature when performed under reduced pressure.

4). Method of using bis (trifluoromethylsulfonyl) methyl group-containing compound (2) as an acid catalyst

Since compound (2) has high acidity due to the bis (trifluoromethylsulfonyl) methyl group, it is useful as an acid catalyst in various organic synthesis reactions. Although the compound (2) is acidic, the conjugate base has a low nucleophilicity, so that it does not easily cause a decomposition reaction, and can be easily separated from the target compound after the acid-catalyzed reaction.

  Compound (2) can be used as an acid catalyst in various organic synthesis reactions such as aldol-type reaction, Friedel-Crafts-type reaction, Diels-Alder reaction, Michael reaction, ene reaction, esterification reaction, acetalization reaction. is there.

  Compound (2) is a highly active acid catalyst compared to conventionally known Bronsted acids such as fuming sulfuric acid, Lewis acids such as aluminum chloride, titanium tetrachloride, and boron trifluoride.

  About the addition amount as an acid catalyst of a compound (2), it is not necessary to use a stoichiometric amount, and even when using a small amount, a desired organic reaction advances. Specifically, it is usually 0.001 times to 10 times mol, preferably 0.01 times to 7 times mol, more preferably 0.03 times to 5 times the amount of the reaction substrate. Is a mole. If it is less than 0.001 mol, it is too dilute and impractical, and if it exceeds 10 mol, it is not economical.

  When used as an acid catalyst in various organic synthesis reactions, the reaction temperature varies depending on the amount of the reaction substrate and the catalyst to be added, but may be usually in the range of −50 ° C. to + 100 ° C.

  About the use of the acid catalyst in various organic synthesis reactions, it is good to carry out by a liquid phase reaction like the case of using a normal solid catalyst.

  The solvent is not particularly limited as long as it does not participate in the reaction. For example, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, alcohols, ketones, aprotic polarity And solvents. Specifically, n-pentane, n-hexane, n-heptane, n-octane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, dichloromethane, dichloroethane, chloroform, acetone, acetonitrile, N, N-dimethylformamide (Abbreviation: DMF), dimethyl sulfoxide (abbreviation: DMSO), hexamethylphosphoric triamide (abbreviation: HMPA), and the like.

  However, when the reaction raw materials or reaction reagents are liquid at room temperature or melt at the reaction temperature, they themselves also serve as a solvent, so that it is not necessary to use a separate solvent, which is industrially burdensome. However, it is economically preferable.

  There is no restriction | limiting in particular as a reaction container, The thing which can endure the pressure used at the time of reaction and the material which does not influence reaction can be used. The reaction may be at normal pressure or under pressure, and can be appropriately adjusted by those skilled in the art depending on the type of reaction.

  Further, the reaction may be performed while circulating an inert gas such as nitrogen gas or argon gas.

The reaction time is not particularly limited, but usually it can be performed within 24 hours, and the progress of the reaction is traced by analytical means such as gas chromatography measurement, liquid chromatography measurement, and nuclear magnetic resonance spectrum (NMR) measurement. In addition, it is preferable that the end point is when the reaction raw material is almost lost.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

  The following measuring apparatus was used for identification of the compound obtained in the present Example.

Infrared absorption spectrum (IR): Bruker ALPHA FT-IR spectrometer Nuclear magnetic resonance spectrum (NMR): Bruker ANANCE III 400 spectrometer Mass spectrometry spectrum (MS): Micromass LCT spectrometer (ESI-TOF) or Varian CP-3800 gas chromatograph TOGRAPH 1200 Quadrupole MS / MS system (EI)

[Example 1]
[Production of (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene (2a) using sodium borohydride as a reducing agent]
The reaction formula is shown below (in the reaction formula, Et represents an ethyl group and Ac represents an acetyl group. The same applies hereinafter in the examples).

  118 mg of 1,1-bis (trifuryl) alkadiene (1a) as compound (1) was dissolved in 9.0 ml of ethyl acetate, and then cooled to -78 ° C. Next, 22.7 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 1.5 hours. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under the conditions of a temperature of 160 ° C. and a pressure of 6.57 Pa to obtain (E)-(4,4-bis (tri 95.4 mg of fluoromethylsulfonyl) but-1-enyl) benzene was obtained with a yield of 80%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. IR (ATR) v 2943, 1389, 1374, 1206, 1114, 1098, 970, 759, 692, 660, 485 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ3. 38-3.44 (2H, m), 4.97 (1H, t, J = 5.8 Hz), 6.24 (1H, dt, J = 15.7, 7.3 Hz), 6.70. (1H, d, J = 15.7 Hz), 7.28-7.41 (5H, m); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 29.0, 77.6, 119.2 (q, J _C-F = 327.0 Hz), 119.3, 126.5, 128.5, 128.7, 135.5, 137.3; ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ-10.2 (6F) , S); MS (ESI-TOF) m / z 419 [M + Na] ⁺ ; HRMS calcd for C ₁₂ H ₁₀ F ₆ NaO ₄ S ₂ [M + Na] ⁺ , 418.9822; found, 418.9821; Anal. _{Calcd for C 12 H 10 F 6} O 4 S 2: C, 36.37; H, 2.54. Found: C, 36.47; H, 2.76.

[Example 2]
[Production of (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene (2a) using borane-2-picoline complex as reducing agent]
The reaction formula is shown below.

  118 mg of 1,1-bis (trifuryl) alkadiene (1a), which is the compound (1), was dissolved in 9.0 ml of ethyl acetate, and then cooled to -10 ° C. Next, 31.8 mg of borane-picoline complex as a reducing agent was slowly added, followed by stirring at the same temperature for 5 minutes. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under the conditions of a temperature of 160 ° C. and a pressure of 6.57 Pa to obtain (E)-(4,4-bis (tri Fluoromethylsulfonyl) but-1-enyl) benzene 83.7 mg was obtained with a yield of 71%.

[Example 3]
[Production of (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene (2a) using diisobutylaluminum hydride as a reducing agent]
The reaction formula is shown below.

  After dissolving 197.4 mg of 1,1-bis (trifuryl) alkadiene (1a) as compound (1) in 1.5 ml of dichloromethane, it was cooled to -78 ° C. Next, 0.55 ml of diisopropylaluminum hydride (1.0 M hexane solution) as a reducing agent was slowly added, and the mixture was stirred at room temperature for 4 hours. To the reaction solution after stirring, 5 ml of 10% sulfuric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under conditions of a temperature of 140 to 150 ° C. and a pressure of 5 mmHg, and (E)-(4,4-bis (tri 172.6 mg of fluoromethylsulfonyl) but-1-enyl) benzene was obtained with a yield of 87%.

[Example 4]
[Production of (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene (2a) using lithium aluminum hydride as a reducing agent]
The reaction formula is shown below.

  To 20.9 mg of lithium aluminum hydride as a reducing agent, 1.0 ml of diethyl ether was added to form a suspension, and then cooled to 0 ° C. Next, a solution of 197.2 mg of 1,1-bis (trifuryl) alkadiene (1a) as the compound (1) in 0.5 ml of diethyl ether was slowly added, followed by stirring at room temperature for 2.5 hours. To the reaction solution after stirring, 5 ml of 10% sulfuric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under conditions of a temperature of 140 to 150 ° C. and a pressure of 5 mmHg, and (E)-(4,4-bis (tri 136.5 mg of fluoromethylsulfonyl) but-1-enyl) benzene was obtained with a yield of 65%.

[Comparative Example 1]
[Catalytic reduction using palladium carbon as a catalyst in a hydrogen atmosphere]
Instead of sodium borohydride used in Example 1, reduction was performed using palladium carbon as a catalyst in a hydrogen atmosphere. The reaction formula is shown below.

  After dissolving 119.1 mg of 1,1-bis (trifuryl) alkadiene (1a) as the compound (1) in 1.0 ml of ethyl acetate, 47.6 mg of 5% palladium carbon (about 55% water-wet product) was added at room temperature. Added in. Next, the reaction solution was subjected to a hydrogen atmosphere and stirred at room temperature for 30 minutes. The reaction mixture was filtered using Celite (registered trademark, manufactured by Celite Corporation) and then concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography and eluted with a developing solvent of hexane / ethyl acetate = 20: 1. In the above reaction formula, (4-trifluoromethylsulfonyl) butylbenzene represented by the formula (15) was used. 56.3 mg was obtained with a yield of 70%. The measurement results of the nuclear magnetic resonance spectrum of the obtained product are shown below.

Colorless liquid; IR (neat) _v 2938, 1446, 1360, 1194, 1119 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.79-1.88 (2H, m), 1.92-2.03 (2H, m), 2.69 (2H, t, J = 7.4 Hz), 3.21 (2H, t, J = 8.0 Hz), 7.17 (2H, d, J = 8.2) Hz), 7.19-7.25 (1H, m), 7.27-7.34 (2H, m); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 20.3, 30.0, 35.1. 49.5, 119.5 (q, J _C-F = 327.0 Hz), 126.3, 128.3, 128.6, 140.6; ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ-15 .5 (3F, s); MS (ESI-TOF) m / z 289 [M + N a] ⁺ ; HRMS calcd for C ₁₁ H ₁₃ F ₃ NaO ₂ S [M + Na] ⁺ , 289.0486; found, 289.0476.

  When the reaction is carried out using catalytic reduction conditions instead of the hydride reducing agent according to the present invention, an excessive reduction reaction of the reaction substrate and product proceeds, and the target compound (2) (E)-(4, 4-Bis (trifluoromethylsulfonyl) but-1-enyl) benzene (2a) was not obtained.

[Example 5]
[Production of (E) -1- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) -4-methylbenzene (2b) using sodium borohydride as a reducing agent]
The reaction formula is shown below.

  Compound (1) (E) -1- (4,4-bis (trifluoromethyl) sulfonyl) buta-1,3-dienyl) -4-methylbenzene (1b) 119.6 mg in 9.0 ml of ethyl acetate Was dissolved, and then cooled to -78 ° C. Next, 22.2 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 1.5 hours. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under the conditions of a temperature of 160 ° C. and a pressure of 6.57 Pa to obtain (E) -1- (4,4-bis as the compound (2). 119.6 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) -4-methylbenzene (2b) was obtained with a yield of 99%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. 69.0-71.0 ° C .; IR (ATR) _v 2942, 1514, 1377, 1203, 1168, 1103, 698, 642, 592, 470 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 2.32. (3H, s), 3.32-3.39 (2H, m), 4.92 (1H, t, J = 5.8 Hz), 6.14 (1H, dt, J = 15.7, 7.). ¹³ C), 6.63 (1H, d, J = 15.7 Hz), 7.12 (2H, d, J = 8.0 Hz), 7.25 (2H, d, J = 8.0 Hz); ¹³ C _{-NMR (100MHz, CDCl 3) δ2.11,29.0,77.7,118.3,119.3} (q, J C-F = 328.0Hz), 124.2,129.4,132. ^{7,137.3,138.7; 19 F-NMR (376MHz} , C _{Cl 3) δ-10.2 (6F} , s); MS (ESI-TOF) m / z 433 [M + Na] +; HRMS calcd for C 15 H 12 F 6 NaO 4 S 2 [M + Na] +, 432.9979 Found, 432, 9981. Anal. _{Calcd for C 15 H 12 F 6} O 4 S 2: C, 38.05; H, 2.95. Found: C, 37.84; H, 3.09.

[Example 6]
[Production of (E) -1- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) -3-ethoxybenzene (2c) using sodium borohydride as a reducing agent]
The reaction formula is shown below.

  Compound (1) (E) -1- (4,4-bis (trifluoromethyl) sulfonyl) buta-1,3-dienyl) -3-ethoxybenzene (1c) 135.4 mg in 9.0 ml of ethyl acetate Was dissolved, and then cooled to -78 ° C. Next, 23.4 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 1 hour. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. To the obtained organic layer, 500 mg of sodium sulfate was added, dehydrated and dried, followed by filtration. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under conditions of a temperature of 190 ° C. and a pressure of 6.57 Pa, and (E) -1- (4,4-bis as the compound (2). 135.5 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) -3-ethoxybenzene (2c) was obtained with a yield of 99%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. 56.0-57.5 ° C .; IR (ATR) _v 2930, 1581, 1377, 1205, 1106, 686, 664, 578, 520, 495 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.43 (3H, t, J = 7.0 Hz), 3.36-3.41 (2H, m), 4.05 (2H, q, J = 7.0 Hz), 4.96 (1H, t, J = 5.8 Hz), 6.21 (1H, dt, J = 15.7, 7.3 Hz), 6.66 (1H, d, J = 15.7 Hz), 6.85 (1H, dd, J = 8.1, 2.2 Hz), 6.91 (1 H, brs) 6.96 (1 H, d, J = 7.7 Hz), 7.21-7.30 (1 H, m); ¹³ C-NMR ( 100MHz, CDCl ₃₎ δ14.7,29.0,63.5,77.7,112.7,114.3,119. _{, 119.3 (q, J C-} F = 330.0Hz), 119.6,129.7,136.9,137.3,159.3; 19 F-NMR (376MHz, CDCl 3) δ-10 MS (ESI-TOF) m / z 463 [M + Na] ⁺ ; HRMS calcd for C ₁₄ H ₁₄ F ₆ NaO ₅ S ₂ [M + Na] ⁺ , 463.0085; found, 463.0074 . Anal. _{Calcd for C 14 H 14 F 6} O 5 S 2: C, 38.18; H, 3.20. Found: C, 38.23; H, 3.20.

[Example 7]
[Production of (E) -1- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) -4-chlorobenzene (2d) using sodium borohydride as a reducing agent]
The reaction formula is shown below.

  Dissolve 86.3 mg of compound (1) (E) -1- (4,4-bis (trifluoromethylsulfonyl) buta-1,3-dienyl) -4-chlorobenzene (1d) in 6.0 ml of ethyl acetate. And then cooled to -78 ° C. Next, 15.2 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 1 hour. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under conditions of a temperature of 170 ° C. and a pressure of 5.23 Pa, and (E) -1- (4,4-bis as the compound (2). 76.5 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) -4-chlorobenzene (2d) was obtained with a yield of 88%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. IR (ATR) _v 2943, 1492, 1377, 1205, 1102, 970, 590, 470 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.30-3.39 (71.5-72.5 ° C.) 2H, t, J = 7.0 Hz), 4.89 (1H, t, J = 5.6 Hz), 6.16 (1H, dt, J = 15.6, 7.2 Hz), 6.60 (1H , D, J = 15.6 Hz), 7.27-7.31 (4H, m); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 29.0, 77.3, 119.2 (q, J _{C- F} = 328.0 Hz), 120.0, 127.8, 128.9, 134.0, 134.4, 136.2; ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ-10.1 (6F, s ); MS (ESI-TOF) m / z 475 [M ^{H + 2Na] +, 477 [} M + 2-H + 2Na] +; HRMS calcd for C 12 H 8 ClF 6 Na 2 O 4 S 2 [M-H + 2Na] +, 474.9252; found, 474.9241. Anal. _{Calcd for C 12 H 9 ClF 6} O 4 S 2: C, 33.46; H, 2.11. Found: C, 33.69; H, 2.28.

[Example 8]
[(E) -1- (4,4-bis ((trifluoromethyl) sulfonyl) but-1-en-1-yl) -4-bromobenzene (2e) using sodium borohydride as a reducing agent] Manufacturing]
The reaction formula is shown below.

  To 4.7 ml of ethyl acetate, 94.7 mg of (E) -1- (4,4-bis (trifluoromethylsulfonyl) buta-1,3-dienyl) -4-bromobenzene (1e) (1) is added. After dissolving, it was cooled to -78 ° C. Next, after slowly adding 15.1 mg of sodium borohydride as a reducing agent, the mixture was stirred at the same temperature for 1.5 hours. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under conditions of a temperature of 210 ° C. and a pressure of 6.57 Pa, and (E) -1- (4,4-bis as the compound (2). 68.7 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) -4-bromobenzene (2e) was obtained with a yield of 72%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. IR (ATR) _v 2943, 1487, 1424, 1396, 1203, 1102, 645, 587 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.35-3.42 (81.8-83.5 ° C.) 2H, m), 4.93 (1H, t, J = 5.6 Hz), 6.23 (1H, dt, J = 15.7, 7.7 Hz), 6.63 (1H, d, J = 15) 7 Hz), 7.23 (2H, d, J = 8.4 Hz), 7.46 (2H, d, J = 8.4 Hz); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 29.0, 77. 3, 119.2 (q, J _C-F = 328.0 Hz), 120.1, 122.6, 128.1, 131.9, 134.4, 136.3; ¹⁹ F-NMR (376 MHz, CDCl _{3) δ-10.1 (6F,} s); MS (E ^{I-TOF) m / z 519} [M-H + 2Na] +, 521 [M + 2-H + 2Na] +; HRMS calcd for C 12 H 8 BrF 6 Na 2 O 4 S 2 [M-H + 2Na] +, 518.8747; found , 5188.8734. Anal. _{Calcd for C 12 H 9 BrF 6} O 4 S 2: C, 30.33; H, 1.91. Found: C, 30.56; H, 2.20.

[Example 9]
[Production of (E) -1- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) -2-bromobenzene (2f) using sodium borohydride as a reducing agent]
The reaction formula is shown below.

  Compound (1) (E) -1- (4,4-bis (trifluoromethyl) sulfonyl) buta-1,3-dienyl) -2-bromobenzene (1f) 87.8 mg in 6.0 ml of ethyl acetate Was dissolved, and then cooled to -78 ° C. Next, 14.0 mg of sodium borohydride as a reducing agent was slowly added, followed by stirring at the same temperature for 1 hour. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under the conditions of a temperature of 160 ° C. and a pressure of 6.57 Pa to obtain (E) -1- (4,4-bis as the compound (2). 79.5 mg of (trifluoromethyl) sulfonyl) but-1-en-1-yl) -2-bromobenzene (2f) was obtained with a yield of 97%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. IR (ATR) _v 2931, 1376, 1202, 1105, 694, 660, 592, 491 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.42-3.48 (57.8-59.5 ° C.) 2H, m), 4.96 (1H, t, J = 5.7 Hz), 6.19 (1H, dt, J = 15.6, 7.6 Hz), 7.05 (1H, d, J = 15) .6 Hz), 7.16 (1 H, dt, J = 7.8, 1.4 Hz), 7.30 (1 H, t, J = 7.8 Hz), 7.48 (1 H, brd, J = 7. 8 Hz), 7.57 (1H, brd, J = 7.8 Hz); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 29.1, 77.3, 119.2 (q, J _C-F = 330.0 Hz) ), 122.5, 123.6, 127.3, 127.7, 129.8, 1 ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ-10.1 (6F, s); MS (ESI-TOF) m / z 497 [M + Na] ⁺ , 499 [33.0, 135.6, 136.2; M + 2 + Na] ⁺ ; HRMS calcd for C ₁₂ H ₉ BrF ₆ NaO ₄ S ₂ [M + Na] ⁺ , 4968.828; found, 4968.828. Anal. _{Calcd for C 12 H 9 BrF 6} O 4 S 2: C, 30.33; H, 1.91. Found: C, 30.46; H, 2.17.

[Example 10]
[Production of (E) -1- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) -4-nitrobenzene (2 g) using sodium borohydride as a reducing agent]
The reaction formula is shown below.

  Dissolve 118.9 mg of (E) -1- (4,4-bis (trifluoromethylsulfonyl) buta-1,3-dienyl) -4-nitrobenzene (1 g) as compound (1) in 9.0 ml of ethyl acetate. And then cooled to -78 ° C. Next, 22.4 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 2 hours. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under conditions of a temperature of 210 ° C. and a pressure of 6.57 Pa, and (E) -1- (4,4-bis as the compound (2). 118.9 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) -4-nitrobenzene (2 g) was obtained with a yield of 91%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Colorless crystals; Mp. IR (ATR) _v 2924, 1598, 1517, 1382, 1343, 1202, 1101, 588, 485 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.49-3. 50 (2H, m), 5.09 (1H, t, J = 4.6 Hz), 6.44 (1H, dt, J = 15.8, 7.7 Hz), 6.77 (1H, t, J = 15.8 Hz), 7.51 (2H, d, J = 8.8 Hz), 8.17 (2H, d, J = 8.8 Hz); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 29.1. 77.3, 119.2 (q, J _CF = 328.0 Hz), 124.1, 124.2, 127.3, 135.2, 141.8, 147.5; ¹⁹ F-NMR (376 MHz) , CDCl ₃ ) δ-10.1 (6F, s); MS (ESI-TOF) m / z 486 [M-H + 2Na] ⁺ ; HRMS calcd for C ₁₂ H ₈ F ₆ NNaO ₆ S ₂ [M-H + 2Na] ⁺ , 485.9493; found, 485.9482. Anal. _{Calcd for C 12 H 9 F 6} NO 6 S 2: C, 32.66; H, 2.06; N, 3.17. Found: C, 33.03; H, 2.33; N, 3.21.

[Example 11]
[(E) -2- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) -1-bromo-4-fluorobenzene (2h using sodium borohydride as a reducing agent] )Manufacturing of]
The reaction formula is shown below.

  Compound (1) (E) -2- (4,4-bis (trifluoromethylsulfonyl) buta-1,3-dienyl) -1-bromo-4-fluorobenzene (1h) was added to 15.0 ml of ethyl acetate. After 245.9 mg was dissolved, it was cooled to 0 ° C. Next, 22.4 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 1.5 hours. 10 ml of 10% hydrochloric acid was added to the reaction solution after stirring, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation under the conditions of a temperature of 210 ° C. and a pressure of 3.94 Pa using a Kugelrohr distillation apparatus, and (E) -2- (4,4-bis as the compound (2). 198.7 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) -1-bromo-4-fluorobenzene (2h) was obtained with a yield of 80%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), and mass spectrometry (MS) are shown below.

Colorless crystals; Mp. IR (ATR) _v 2938, 1465, 1394, 1203, 1099, 969, 808, 703, 661, 578, 484, 471 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) 53.0-54.8 ° C. δ 3.41-3.48 (2H, m), 4.97 (1H, t, J = 5.6 Hz), 6.19 (1H, dt, J = 15.6, 7.6 Hz), 6.91 (1H, td, _JH-F = 8.6 Hz, _JH-H = 8.6, 3.0 Hz), 7.00 (1H, d, J = 15.6 Hz), 7.18 (1H, dd , J _H-F = 9.9 Hz, J _H-H = 3.0 Hz), 7.52 (1H, dd, J _H-H = 8.5 Hz, J _H-F = 5.3 Hz); ¹³ C- _{NMR (100MHz, CDCl 3) δ29.0,77.0,114.1} (d, J C- _{= 23.6Hz), 117.1 (d,} J C-F = 22.7Hz), 118.5 (d, J C-F = 3.2Hz) 119.3 (2C, q, J C-F = 330.0 Hz), 123.7, 134.3 (d, J _C-F = 8.1 Hz), 135.5, 137.3 (d, J _C-F = 7.9 Hz), 162.1 (d , J _C-F = 246.0 Hz); ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ-51.3 (1F, m) -10. 1 (6F, s); MS (ESI-TOF) m / z 537 [M-H + 2Na] ⁺ , 539 [M + 2-H + 2Na] ⁺ ; HRMS calcd for C ₁₂ H ₇ F ₇ Na ₂ O ₄ S ₂ [M-H + 2Na] ⁺ , 536.8653; found, 536.8632.

[Example 12]
[(E) -Methyl-3- (2-((E)-(4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) phenyl using sodium borohydride as a reducing agent] ) Production of acrylate (2i)]
The reaction formula is shown below.

  Compound (1) (E) -methyl-3- (2-((E)-(4,4-bis (trifluoromethylsulfonyl) buta-1,3-dienyl) phenyl) in 6.0 ml of ethyl acetate After dissolving 93.2 mg of acrylate (1i), the mixture was cooled to −78 ° C. Next, 15.1 mg of sodium borohydride as a reducing agent was slowly added, followed by stirring at the same temperature for 3 hours. The reaction solution was warmed to room temperature, 10 ml of 10% hydrochloric acid was added to separate the organic layer and the aqueous layer, and the separated aqueous layer was extracted three times with 15 ml of diethyl ether. After dehydrating and drying with 500 mg of sodium sulfate, the filtrate was concentrated under reduced pressure, and then purified by distillation using a Kugelrohr distillation apparatus at a temperature of 210 ° C. and a pressure of 6.57 Pa as compound (2). ( ) -Methyl-3- (2-((E)-(4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) phenyl) acrylate (2i) 52.0 mg 55% yield Measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), and mass spectrometry (MS) are shown below.

Colorless crystals; Mp. IR (ATR) _v 2097, 1702, 1631, 1383, 1319, 1194, 1101, 959, 644, 585, 483 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ3. 42-3.50 (2H, m), 3.82 (3H, s), 5.03 (1H, t, J = 5.5 Hz), 6.13 (1H, dt, J = 15.5, 7) .6 Hz), 6.34 (1 H, d, J = 15.9 Hz), 7.04 (1 H, d, J = 15.5 Hz), 7.30-7.40 (2 H, m), 7.42 (1H, d, J = 7.5 Hz), 7.54 (1H, d, J = 7.4 Hz), 7.95 (1H, d, J = 15.9 Hz); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 29.3, 51.8, 77.1, 119.2 (q, J _C−F = 328.1 Hz), 120.5, 123.5, 127.2, 127.5, 128.7, 130.2, 132.8, 134.8, 135.8, 141.9, 167.1; ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ-10.1 (6F, s); MS (ESI-TOF) m / z 481 [M + H] ⁺ ; HRMS calcd for C ₁₆ H ₁₅ F ₆ O ₆ S ₂ [M + H ] ⁺ , 481.0214; found, 481.0201.

[Example 13]
[Production of (E) -2- (4,4-bis (trifluoromethylsulfonyl) but-1-en-1-yl) furan (2j) using sodium borohydride as a reducing agent]
The reaction formula is shown below.

  To 6.0 ml of ethyl acetate, 113.6 mg of (E) -2- (4,4-bis (trifluoromethylsulfonyl) but-1,3-dien-1-yl) furan (1j), which is the compound (1), was added. After dissolving, it was cooled to -78 ° C. Next, 22.7 mg of sodium borohydride as a reducing agent was slowly added, and the mixture was stirred at the same temperature for 1.5 hours. The temperature of the stirred reaction solution was raised to room temperature, 10 ml of 10% hydrochloric acid was added, and the organic layer and the aqueous layer were separated. The separated aqueous layer was extracted three times with 15 ml of diethyl ether. The obtained organic layer was dehydrated and dried with 500 mg of sodium sulfate and then filtered. After concentrating the filtrate under reduced pressure, it was purified by distillation using a Kugelrohr distillation apparatus under the conditions of a temperature of 160 ° C. and a pressure of 6.57 Pa to obtain (E) -2- (4,4-bis as the compound (2). 80.7 mg of (trifluoromethylsulfonyl) but-1-en-1-yl) furan (2j) was obtained with a yield of 71%. The measurement results of infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrometry (MS), and elemental analysis are shown below.

Yellow crystals; Mp. IR (ATR) _v 2945, 1373, 1201, 1100, 961, 747, 587, 494, 469 cm ⁻¹ ; ¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.32-3-3. 40 (2H, m), 4.90 (1H, t, J = 5.6 Hz), 6.13 (1H, dt, J = 15.6, 7.7 Hz), 6.32 (1H, d, J = 3.3 Hz), 6.39 (1H, dd, J = 3.3, 1.4 Hz), 6.49 (1H, d, J = 15.6 Hz), 7.38 (1H, d, J = 1.4 CHz); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ 28.9, 77.5, 109.8, 111.5, 117.7, 119.2 (q, J _CF = 328.0 Hz) ^{, 125.2,142.9,151.0; 19 F-NMR (} 376MH _{, CDCl 3) δ-10.1 (} 6F, s); MS (ESI-TOF) m / z 409 [M + Na] +; HRMS calcd for C 10 H 8 F 6 NaO 5 S 2 [M + Na] +, 408. 9615; found, 408.99610. Anal. _{Calcd for C 10 H 8 F 6} O 5 S 2: C, 31.09; H, 2.09. Found: C, 31.36; H, 2.36.

[Example 14]
[Acetalization of 3-phenylpropionaldehyde using (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene as an acid catalyst]
The reaction formula is shown below.

  After 132.9 mg of 3-phenylpropionaldehyde was dissolved in 1.0 ml of trimethyl formate, 15.5 mg of (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene was added at room temperature. It was. After stirring at the same temperature for 1 hour, the reaction mixture was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with a developing solvent of hexane / ethyl acetate = 30: 1 to obtain 169.2 mg of the intended 3-phenylpropionaldehyde dimethyl acetal in a yield of 95%. The measurement results of the nuclear magnetic resonance spectrum of the obtained product are shown below. The product structure was determined by comparison with known spectra.

Colorless ^{liquid; 1 H-NMR (400MHz,} CDCl 3) δ1.95-2.03 (2H, m), 2.74 (2H, t, J = 7.9Hz), 3.39 (6H, s), 4.42 (1H, t, J = 5.7 Hz), 7.20-7.29 (3H, m), 7.30-7.37 (2H, m); ¹³ C-NMR (100 MHz, CDCl ₃ ) 30.9, 34.2, 52.8, 104.0, 125.9, 128.4 (4C), 141.7.

[Example 15]
[Mukoyama aldol reaction of 2-methylcyclohexanone using (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene as an acid catalyst]
The reaction formula is shown below (in the reaction formula, TBS represents a tert-butyldimethylsilyl group).

After 10.9 mg of 2-methylcyclohexanone was dissolved in 1.5 ml of dichloromethane, 19.1 mg of (E)-(4,4-bis (trifluoromethylsulfonyl) but-1-enyl) benzene was added at 0 ° C. . Next, a solution of tert-butyl (1-ethoxyvinyloxy) dimethylsilane (303.0 mg) in dichloromethane (0.5 ml) was added at 0 ° C. over 1 hour using a syringe pump. After stirring at the same temperature for 2 hours, the reaction mixture was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with a developing solvent of hexane / ethyl acetate = 50: 1 to obtain the desired ((1S ^* , 2S ^* )-1- (tert-butyldimethylsiloxy) -2-methylcyclohexyl. 293.8 mg of ethyl acetate was obtained with a yield of 95%, and the results of measurement of the nuclear magnetic resonance spectrum of the obtained product are shown below: The structure of the product was determined by comparison with a known spectrum.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.08 (3H, s), 0.10 (3H, s), 0.87-0.93 (3H, m), 0.89 (9H, s), 1.18 (1H, qt, J = 12.8, 3.9 Hz), 1.24 (3H, t, J = 7.1 Hz), 1.27-1.78 (8H, m), 2.35 (1H, d, J = 12.8 Hz), 2.77 (1 H, d, J = 12.8 Hz), 4.03-4.16 (2H, m); ¹³ C-NMR (100 MHz, CDCl ₃ ) δ-2.2, -1.8, 14.2, 15.6, 18.8, 21.8, 25.9, 26.0, 30.5, 37.7, 38.8, 46.4, 60.1, 76.3, 170.8.

  The compound having a bis (trifluoromethylsulfonyl) methyl group targeted in the present invention can be used as an acid catalyst in various organic synthesis reactions.

Claims (7)

Formula (1)

[In the formula (1), A represents the following formula (3)

[In Formula (3), Ar represents an aryl group, a heteroaryl group, an aryl group having a substituent, or a heteroaryl group having a substituent. n represents an arbitrary integer of 0 to 5. ]
The monovalent organic group represented by these is represented. ]
The compound represented by formula (2) is contacted with a borohydride reducing agent or an aluminum hydride reducing agent.

[In Formula (2), A is synonymous with A in Formula (1). ]
A method for producing a compound represented by the formula (2), wherein the compound represented by the formula (2) is obtained. A is the formula (4)

[In Formula (4), Ar represents an aryl group, a heteroaryl group, an aryl group having a substituent, or a heteroaryl group having a substituent. ]
In a monovalent organic group represented by The process according to claim 1. A is the formula (5) or (6)

[In formula (5) or formula (6), each R ¹ and each R ² are each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, sulfo group, cyano group, 20 aliphatic hydrocarbon groups or C6-C20 aromatic hydrocarbon groups are represented.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or a sulfo group. The cyano group may be substituted.
Even if a part of carbon atoms in an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in an aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom Good.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms may include a carbonyl group or a sulfonyl group in the group.
p represents an arbitrary integer of 0 to 5.
q represents an arbitrary integer of 0 to 3. ]
The manufacturing method of Claim 1 or Claim 2 which is a monovalent organic group represented by these. The production method according to claim 1 , wherein the borohydride reducing agent is a borane complex or a borohydride metal. The production method according to claim 4 , wherein the metal borohydride is lithium borohydride, sodium borohydride or potassium borohydride. Formula (2)

[In Formula (2), A represents Formula (5) or Formula (6)

(In Formula (5) or Formula (6), each R ¹ and each R ² are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a sulfo group, a cyano group, 20 aliphatic hydrocarbon groups or C6-C20 aromatic hydrocarbon groups are represented.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may contain an unsaturated bond, and any number of hydrogen atoms in the group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or a sulfo group. The cyano group may be substituted.
Even if a part of carbon atoms in an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a part of carbon atoms in an aromatic hydrocarbon group having 6 to 20 carbon atoms is substituted with an oxygen atom or a sulfur atom Good.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms may include a carbonyl group or a sulfonyl group in the group.
p represents an arbitrary integer of 0 to 5.
q represents an arbitrary integer of 0 to 3. )
The monovalent organic group represented by these. ]
A compound represented by The use method of the compound represented by Formula (2) of Claim 6 as an acid catalyst.