JP5555919B2 - Novel sulfonium salt, production method thereof and use thereof - Google Patents

Description

  The present invention relates to a novel sulfonium salt, and more particularly to a sulfonium salt that can be used for the synthesis of various useful compounds containing a trifluoromethyl group, a production method thereof, and an application thereof.

The sulfonium salt is a compound that is mainly used as a synthetic intermediate for various organic compounds, and is an important compound that is used in an extremely wide range of organic syntheses including the pharmaceutical and agricultural chemical fields. Thus, because of its high utility value and wide range of utilization, many researchers are working on the synthesis of novel sulfonium salts. (For example, Non-Patent Document 1 to Non-Patent Document 6)
In recent years, organic compounds containing a trifluoromethyl group have attracted attention because of their useful properties. This is because, as a general property of an organic compound in which one or more hydrogen atoms contained in the organic compound are replaced with fluorine atoms, the chemical and physical properties such as high fat solubility and anti-degradability are significantly changed. This is because many of the compounds in which the methyl group contained in the organic compound is substituted with a trifluoromethyl group exhibit useful properties such as physiological activity. For example, a compound in which a trifluoromethyl group is introduced has been suggested to be useful as a pharmaceutical (see, for example, Patent Document 1).

  From such characteristics, organic compounds containing a trifluoromethyl group are widely used, including raw materials for pharmaceuticals or agricultural chemicals, or optical materials for liquid crystals or organic EL, and their application fields are further expanded.

  In order to introduce a trifluoromethyl group into an organic compound, a method of directly introducing the trifluoromethyl group into the organic compound is known, but there is a problem that the introduction operation is complicated.

  Because of these problems, a synthetic intermediate for building an organic compound (a so-called building block agent) is produced in advance in a state containing a trifluoromethyl group, and a reaction using the building block agent is performed. There is a method of introducing a trifluoromethyl group into an organic compound.

  For example, Non-Patent Document 7 discloses that a sulfone compound containing a trifluoromethyl group can be produced according to the following formula (A). Using this sulfone compound as a building block agent, the following (B It is disclosed that a trifluoromethyl group can be introduced into diethyl malonate as shown in the formula.

  According to the reaction of formula (A), a predetermined amount of 1-chloro-3,3,3-trifluoropropene and benzenethiol are put into an ethanol solution containing sodium hydroxide and stirred at 50 ° C. for one day. Then, by further stirring for one day at 100 ° C., a sulfide compound containing a trifluoromethyl group was obtained in a yield of about 80% as a mixture of a cis isomer and a trans isomer.

  Further, the obtained sulfide compound is put into an acetic acid solution in which a required amount of 30% hydrogen peroxide water is mixed and reacted at 40 ° C. for 40 hours, whereby a sulfone compound containing a trifluoromethyl group is obtained. The product was obtained in a yield of about 82% in a trans form.

  The sulfone compound thus obtained is fractionated in an appropriate amount, dissolved in a THF (tetrahydrofuran) solution as shown in the above formula (B), and an appropriate amount of malonic acid in the presence of 10 mol% NaOH. A partial structure containing a trifluoromethyl group was introduced into diethyl malonate by reacting with diethyl at room temperature for 5 minutes.

JP2008-525525

Angew. Chem. Int. Ed, 2006, 45, 7066-7069 Angew. Chem. Int. Ed, 2009, 47, 3784-3786 Synlett, 2008, 2191-2195 Chem. Lett, 2003, 392-393 Chem. Lett, 2003, 1192-1193 Arkivoc, 2004, 42-65 T. Taguchi, G. Tomizawa, M. Nakajima, Y. Kobayashi, "Chem. Pharm. Bull". 33 (9), 4077-4080 (1985)

However, as shown in the above document, when a conventional sulfonium salt is used as a building block agent, since the types of organic compounds that can introduce a trifluoromethyl group are limited, the versatility is low. In addition, as shown in the formula (B), there is a problem that functional groups (atomic groups) other than the trifluoromethyl group contained in the building block agent are also introduced into the final product and remain.
In particular, when the remaining functional group adversely affects the final product (for example, steric hindrance), an additional chemical reaction for removing the functional group needs to be additionally performed. There is a problem that the manufacturing cost is increased.

  An object of the present invention is to provide a new type of sulfonium salt that can be used as a building block agent or the like that can easily synthesize a wide variety of organic compounds containing a trifluoromethyl group.

  Thus, according to the present invention, there is provided a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the following general formula (I) and a method for producing the same, in order to solve the above problems. Furthermore, according to the present invention, there is also provided a method for synthesizing organic compounds containing various trifluoromethyl groups including aziridine, using the β- (trifluoromethyl) vinyldiarylsulfonium salt as a building block agent. The

  The β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be represented by the following general formula (I).

In the above formula (I), R ¹ and R ² each independently represent a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a hydroxyl group or an aryl group which may be substituted with a halogen atom.

Here, the aryl group represents a structure in which one hydrogen atom is eliminated from an aromatic hydrocarbon. In the above formula (I), the structures of R ¹ and R ² are derived from the structure of the aromatic thiol (represented by the general formula (VIb) described later) as the raw material, so that the aromatic thiol can be obtained. There is no particular limitation.

  However, when an aromatic thiol having a bulky aryl group and / or an aryl group having a bulky substituent is used, there are few advantages from the viewpoints of ease of synthesis, ease of handling, price, and the like. This indicates that, when the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention is used as a building block agent for the production of aziridine compounds and the like, the raw material β- (trifluoromethyl) vinyldiarylsulfonium salt is constituted. This is also true because the aryl group is a site that is removed without being contained in the final product such as an aziridine compound.

  For this reason, it is generally desirable that the aromatic ring constituting the aryl group comprises no more than two aromatic rings consisting of 5-membered or 6-membered rings. Further, the “lower” in the lower alkyl group, lower haloalkyl group and lower alkoxy group of the substituent which may be substituted on the aryl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Represents a thing.

From these points, the optionally substituted aryl group represented by R ¹ and R ² preferably includes the following. (1) a phenyl group, a naphthyl group, a thienyl group, pyridine group, a biphenyl group, an aryl group such as anthranyl group; (2) a tolyl group, a 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3, 6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,4 6-trimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, propylphenyl, butylphenyl, hexylphenyl, cyclo Hexylphenyl group, octylphenyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1- Naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5- Substituted by lower alkyl groups such as methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, 2-ethyl-1-naphthyl group (3) aryl groups substituted by lower haloalkyl groups such as trifluoromethylphenyl group and trifluoroethylphenyl group; (4) 3-methoxyphenyl group, 4-methoxyphenyl group, , 3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,6 -Dimethoxyphenyl group, 2,3,4-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,6-trimethoxyphenyl group, 2,4,5-trimethoxyphenyl group, 2 , 4,6-trimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, 2-methoxy-1-naphthyl group, 3-methoxy-1-naphthyl group, 4 -Methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1-naphthyl group, 7-methoxy-1-naphthyl group, 8-methoxy- -Naphthyl group, 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group, 4-methoxy-2-naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy-2-naphthyl group, 7 -Aryl groups substituted by lower alkoxy groups such as methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group, 2-ethoxy-1-naphthyl group; (5) phenol group, naphthol group, cresol group, etc. Aryl group substituted by hydroxyl group; (6) chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, iodophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group , Aryl groups substituted by halogen atoms such as pentafluorophenyl groups, etc. However, it is not limited to these.

R ¹ and R ² are preferably a phenyl group, a tolyl group, and a naphthyl group from the viewpoint of using the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention as a building block agent, and particularly preferred are a phenyl group and a tolyl Of these, a phenyl group is preferred.

In the above general formula (I) representing the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention, the aryl group represented by R ¹ and R ² is generally bonded to the carbon atom constituting the aromatic ring. It has a hand and is bonded to S (sulfur atom) through the bond.

  In the above general formula (I) representing the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention, X− represents an anionic group constituting a counter ion. Examples of the anionic group include a trifluoromethanesulfonyl group, a tetrafluoroborate group, a perfluoroalkanesulfonyl group, an alkanesulfonyl group, a tetraarylborate group, a perchloric acid group, a halogen (fluorine, chlorine, bromine, or iodine) ion, Or a hexafluorophosphate group etc. can be illustrated.

Examples of anion groups that are practically preferable include a trifluoromethanesulfonyl group (OTf ⁻ ) (Tf represents a triflate group) and a tetrafluoroborate group (BF ₄ ⁻ ).

  Thus, particularly preferred β- (trifluoromethyl) vinyldiarylsulfonium salts of the present invention include (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate, (3,3,3-triflate). Fluoropropen-1-yl) -diphenylsulfonium triflate, (3,3,3-trifluoropropen-1-yl)-(2-naphthyl) phenylsulfonium triflate, (3,3,3-trifluoropropene-1- Yl) -phenyl (2-pyridyl) sulfonium triflate, (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium tetrafluoroborate.

  The β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be produced using a reaction represented by the following reaction formula (VI) and reaction formula (VII).

In the above reaction scheme, R ¹ and R ² are the same as those already described in detail in connection with formula (I).
R ³ is independently selected from R ¹ and R ² and represents a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or an aryl group optionally substituted by a hydroxyl group. As the aromatic ring constituting the aryl group represented by R ³ , it is generally desirable that the aromatic ring consist of no more than two 5-membered or 6-membered aromatic rings. In relation to R ³ , “lower” in the lower alkyl group, lower haloalkyl group, and lower alkoxy group represents one having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Thus, practically, R ³ is preferably a phenyl group or a tolyl group, and a phenyl group is particularly preferable.

In the above reaction formula, X ⁻ represents an anion group constituting a counter ion, and Y represents a halogen group. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures.

  As represented by the above reaction formula (VI), 2-bromo-3,3,3-trifluoropropene represented by the formula (VIa) and an aromatic thiol represented by the general formula (VIb) Can be reacted at 80 ° C. to 150 ° C. under normal pressure to produce vinyl sulfide containing trifluoromethyl represented by the general formula (VIc).

  Further, as represented by the above reaction formula (VII), the produced vinyl sulfide and the diaryl halide represented by the general formula (VIIa) are halogenated at 80 ° C. to 150 ° C. under normal pressure. By reacting in a nonpolar solvent, the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention represented by the general formula (I) can be produced.

  More specifically, in the reaction formula (VI), β- (trifluoromethyl) vinyl diaryl sulfide is obtained as a mixture having the trans isomer as the main product (trans isomer: cis isomer = about 9: 1).

  Next, in the reaction formula (VII), the β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the formula (I) has a trans isomer from the vinyl sulfide of the trans isomer represented by the formula (VIc). A mixture of the trans isomer and the cis isomer can be obtained from the cis vinyl sulfide represented by the formula (VIc).

  Therefore, when reaction of reaction formula (VII) is performed using β- (trifluoromethyl) vinyl diaryl sulfide (trans form: cis = about 9: 1) represented by reaction formula (VI) The β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the formula (I) can be obtained with the trans isomer as the main component.

  The β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the formula (I) has almost no difference between the cis form and the trans form in terms of reactivity as a synthetic intermediate.

  In addition to this, in the case of synthesizing various compounds using the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention as a synthetic intermediate (for example, a building block agent), a trans isomer is mainly used. However, as will be understood from each of the following reaction formulas, the product to be obtained remains the same regardless of whether the cis isomer or the trans isomer is used.

  Although the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be used for various purposes, various useful compounds such as aziridine compounds, amide compounds, imide compounds, alkoxy compounds can be used as building block agents. The aziridine compound and the like that can be used for the production of a compound and a phosphorus compound contain a trifluoromethyl group, but the aryl group that constitutes the starting β- (trifluoromethyl) vinyldiarylsulfonium salt is It has a characteristic structure that it does not remain.

(Method for producing aziridine compound)
For example, an aziridine compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with a primary amine compound. . This production can be represented, for example, by the following formula (VIII).

  In the formula (VIII), the primary amine compound is represented by the general formula (VIIIa), and the resulting aziridine compound is represented by the general formula (VIIIb). As reaction conditions, the reaction can sufficiently proceed at normal temperature under normal pressure.

In the above reaction formula, R ¹ , R ² and X ⁻ are the same as those defined in the general formula (I). R ⁴ represents a functional group or an atomic group constituting various primary amines (amino compounds) derived from conventionally known synthetic or natural origin.

  That is, specific examples of the primary amine that can be used in the present invention are not particularly limited. For example, N, N-diethylethylenediamine, glycineethyl, methylamine, ethylamine, O-ethylhydroxylamine, 1 -Propylamine, 2-propylamine, 3-methoxypropylamine, n-butylamine, sec-butylamine, tert-butylamine, iso-butylamine, n-pentylamine, sec-pentylamine, neo-pentylamine, 3-pentylamine , Heptine, 2-methyl-1-butylamine, 1-hexylamine, 2-hexylamine, 3-hexylamine, 4-methyl-1-pentylamine, 4-methyl-2-pentylamine, 2-methyl-3- Pentylamine, 2-ethyl-1-but Ruamine, 2-ethyl-2-butylamine, 3-ethyl-2-butylamine, 3-ethyl-2-butylamine, n-heptylamine, 2-phenylethylamine, 2-phenylethylamine, 2-methyl-1-hexylamine, 3-methyl-1-hexylamine, 4-methyl-1-hexylamine, 5-methyl-1-hexylamine, 2-ethyl-1-pentylamine, 3-ethyl-1-pentylamine, 4-ethyl-1 -Pentylamine, n-octylamine, 2-methyl-1-heptylamine, 3-methyl-1-heptylamine, 4-methyl-1-heptylamine, 5-methyl-1-heptylamine, 6-methyl-1 -Heptylamine, 2-ethyl-1-hexylamine, 3-ethyl-1-hexylamine, 4-ethyl-1-hexyl Min, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, cycloheptaneamine, cyclopentylamine, cyclohexylamine, cyclooctylamine, tetrahydrofuran-2-methanamine, hydrogen thiosulfate S- (2-aminoethyl), 2 -Alkylamines containing or not containing heteroatoms in alkyl groups such as aminoethylphosphonic acid, midafluur, 3-aminopropylmethyldiethoxysilane; benzylamine, 2-phenylethanamine, 3,5- Dimethylbenzylamine, 3,5-bis (trifluoromethyl) benzylamine, 1-naphthalenemethylamine, p-toluenesulfonamide, o-toluidine, m-toluidine, aniline, 2,4-dimethylaniline, , 4-dimethylaniline, 3,5-bis (trifluoromethyl) aniline, 2-chloroaniline, 2,4,6-trichloroaniline, 2-methoxy-4-nitro-5-chloroaniline, methoxyaniline, ethoxyaniline 4- [2- (methylamino) propyl] aniline, 2-fluorobenzylamine, 4-bromobenzylamine, 3,4-dimethoxybenzylamine, 4-phenylbutylamine, 2-phenylcyclopropan-1-amine, 5 -Methyl-o-phenetidine, 4-chlorophenethylamine, 2-chlorobenzylamine, α-aminoacetophenone, α-amino-α-phenylacetophenone, 1-naphthylamine, 2-naphthylamine, 1-naphthylmethylamine, nafomin, 2- Aminobiphenyl, 4-aminobiphenyl , Pentrex, soamine, phentermine, chlorphentermine, chlortermine, 1,3-benzodioxol-5-methanamine, piperidine-1-ethanamine, 4-methoxy-1H-indole-3-ethanamine, 9- Aminoacridine, 2-aminopyrimidine, 4-methylthiazol-2-amine, 2-aminopurine, 2,6-dimethylpyrimidine-4-amine, 2-amino-4,6-dimethylpyrimidine, 3- (aminomethyl) Pyridine, adamantane-2-amine, 2-chloro-9-methyl-9H-purine-6-amine, furfurylamine, 9H-fluorene-3-amine, 4-amino-9H-fluorene, dibenzoylthiamine, 5-amino -1H-benzimidazole, 1H-benzimidazol-2-amine 2-aminoanthracene, 1-aminoanthracene, 1-aminopyrene, 2-aminothiophene, 1- (phenylazo) -2-naphthaleneamine, 9-aminoacridine, cipenamine, flunamine, halonamamine, 5-nitropyrimidin-2-amine, 4-aminobiphenyl, 2-aminothiazole, serotonin, histamine, triflutamine, tyramine, benzhydrylamine, adenine, primaquine, zoxazolamine, xylpropamine, betazole, tacrine, ethifermine, benanserin, norphenylephrine, chrysen-6-amine, 2-chrysenamine, quinazosin, xinomiline, 4-methylaminorex, 8-azaadenine, desmethylchlordiazepoxide, 1- (3-aminopropyl) silatrane, azepexol Acenaphthen-5-amine, 3-methylpyridin-2-amine, epinastine, riluzole, d-amphetamine, l-amphetamine, psicofuranine, d-sec-butylamine, noradrenaline, dimoxamine, fructosamine, memantine, norloline, folic acid, metallaminol, adenosine , Tubercidine, cordycepin, epihydrinamine, 6-aminopteridine and other aromatic rings containing a heteroatom or non-heteroatom such as glycine, tryptophan, methionine, phenylalanine , Threonine, L-valine, isoleucine, L-leucine, histidine, L-alanine, arginine, asparagine, aspartic acid, L-serine, cysteine, glutamine, L-glutamic acid, thi Such as amino acids, such as Shin and the like.

In particular, among the alkylamines, aromatic amines or amino acids as described above, primary amines having 12 or less carbon atoms constituting the functional group or atomic group represented by R ⁴ in the above formula (VIIIa) are generally used. From the viewpoint of being easily soluble in a typical solvent and easy to produce (synthesize), for example, benzylamine, 2-phenylethanamine, 3,5-dimethylbenzylamine, 3,5-bis (trifluoromethyl) Preferred examples include benzylamine, 1-naphthalenemethylamine, N, N-diethylethylenediamine, glycine ethyl, p-toluenesulfonamide, and the like.

  Moreover, if the primary amine as described above has optical activity, an optically active aziridine compound containing a trifluoromethyl group can be synthesized. That is, by using a primary amine having optical activity, it is possible to synthesize optically active aziridine compounds containing trifluoromethyl groups of R and S isomers.

As understood from the above formula (VIII), the aziridine compound obtained by the present invention is an aryl group constituting the β- (trifluoromethyl) vinyldiarylsulfonium salt as a raw material (that is, R ¹ and R ² ). Has a feature that none of them remain.

  For this reason, in conventional aziridine synthesis containing a trifluoromethyl group (for example, JP2009-512687, WO2006-71609, Izvestiya Akademii Nauk, Seriya Khimicheskaya, (2) 282-4, (1994), etc.) When a methyl group is introduced, functional groups (atomic groups) other than the trifluoromethyl group contained in the intermediate remain, but according to the present invention, an olefin moiety consisting of three carbons containing a trifluoromethyl group Can be introduced into other compounds all at once, and a completely new reaction that does not have a conventional example can be performed. Furthermore, the reaction can be carried out under normal and easy reaction conditions that the reaction proceeds sufficiently at normal temperature under normal pressure.

(Method for producing amide compound)
For example, an amide compound containing a trifluoromethyl group is obtained by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with an amide such as a carboxylic acid amide or a sulfonamide. Can be manufactured. This preparation can be represented, for example, by the following formulas (IX) and (X), each formula showing the case of a carboxylic acid amide and a sulfonamide as the amide.

  In the formula (IX), the carboxylic acid amide is represented by the general formula (IXa), and the resulting amide compound is represented by the general formula (IXb). In the formula (X), the sulfonamide is represented by the general formula (Xa), and the resulting amide compound is represented by the general formula (Xb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.

In the above reaction formula, R ¹ , R ² and X ⁻ are the same as those defined in the above general formula (I). R ⁴ , R ^5, and R ⁶ represent functional groups or atomic groups constituting various amides derived from conventionally known synthetic or natural sources.

  That is, specific examples of amides that can be used in the present invention are not particularly limited. For example, isatin, pivalamide, benzamide, N-phenylhexaneamide, N-phenylcyclohexanecarboxamide, 2-bromobenzamide, 4- Bromobenzamide, 3-chloropropionamide, N-methylpropionamide, 2-chloronicotinamide, 2-chloro-N- (4-chlorophenyl) acetamide, 6-chloronicotinamide, dibromoacetamide, 1-naphthaleneacetamide, N- (7-hydroxy-9H-fluoren-2-yl) acetamide, N- (5-hydroxy-9H-fluoren-2-yl) acetamide, N- (3-hydroxy-9H-fluoren-2-yl) acetamide, decanamide N-methyldecane Amide, N, N-dimethyldecanamide, dodecanamide, N, N-diethyldodecanamide, octadecanamide, N, N-dimethylstearoamide, lignoceramic acid amide, N, N-dimethyllignoceramide, N-hydroxy Methylcaprinamide, N-hydroxymethyldodecanamide, N-hydroxymethyl stearamide, N-hydroxymethyllignoceramide, N- [2- [bis (2-hydroxyethyl) amino] ethyl] dodecanamide, N- [2- [Bis (2-hydroxyethyl) amino] ethyl] stearic amide, N- (2-hydroxyethyl) decanamide, N- (2-hydroxyethyl) dodecanamide, N-cyclohexyl-5-nitro-2- Furanpropanamide, 2,2,2-trifluoro -N- [4- (5-nitro-2-furyl) -2-thiazolyl] acetamide, 2-phenyl-3- (5-nitro-2-furyl) acrylamide, N- [4- [2- (5- Nitro-2-furyl) vinyl] -2-thiazolyl] formamide, N-phenylbenzamide, N-[(ethylnitrosoamino) methyl] benzamide, N- (9H-fluoren-2-yl) -N- (tetradecanoyl) Oxy) tetradecanamide, (R) -N, N-diethyl-2- (1-naphthalenyloxy) propanamide, formamide, dimethylformamide, N-methylacetamide, salicylamide, chloroacetamide and other carboxylic acid amides; 2 Sulfonamides such as-(tosylamino) ethanol, sodium cyclamate, N-phenylbenzenesulfonamide N, N ', N' '- triphenyl triamide, phosphoric acid amides such as triamide phosphoric acid.

The amides represented by the above general formulas (IXa) and (Xa) may be either chain or cyclic, but cyclic amides are preferred from the viewpoint that they are generally easy to handle. Furthermore, among the amides as described above, amides having 12 or less carbon atoms constituting the functional groups or atomic groups represented by R ⁴ , R ⁵ and R ⁶ in the above formulas (IXa) and (Xa) From the viewpoint of being easily soluble in a typical solvent and easy to produce (synthesize), for example, isatin, 2- (tosylamino) ethanol and the like can be mentioned as preferred examples.

  In addition, if an amide having optical activity is used among the amides as described above, an optically active amide compound containing a trifluoromethyl group can be synthesized. That is, by using an amide having optical activity, it is possible to synthesize an optically active amide compound containing each trifluoromethyl group of R-form and S-form.

(Method for producing imide compound)
Moreover, for example, an imide compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with an imide. This manufacture can be represented by the following formula (XI), for example.

  In formula (XI), the imide is represented by general formula (XIa), and the resulting imide compound is represented by general formula (XIb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.

In the above reaction formula, R ¹ , R ² and X ⁻ are the same as those defined in the above general formula (I). R ⁴ and R ⁵ each represent a functional group or an atomic group constituting various conventionally known synthetic or natural imides. M represents a hydrogen atom or an alkali metal atom.

That is, specific examples of the imide that can be used in the present invention are not particularly limited. For example, iminodiacetic acid, acetyl (benzoyl) amine, bis (cyclohexanecarbonyl) amine, N-cyclopentyldiacetamide, acetyl ( Chain imides such as benzoyl) (3-chloropropanoyl) amine; phthalimide, naphthalimide, maleimide, N-potatiophthalimide, 4-nitrophthalimide, N-hydroxyphthalimide, 1,4,5,8-tetrahydro- 4a, 8a-naphthalene dicarboimide, 3,6-dihydroxyphthalimide, 2- (4-methylphenyl) -3- (4-chlorophenyl) maleimide, 2,3-diphenylmaleimide, 2- (3-methoxyphenyl) ) -3-Phenylmaleimide, 2- (4-chloro) Phenyl) -3-phenylmaleimide, 2- (3-chlorophenyl) -3-phenylmaleimide, 2- (4-bromophenyl) -3-phenylmaleimide, 2- (4-fluorophenyl) -3-phenyl Maleimide, 2- (3,5-dimethylphenyl) -3-phenylmaleimide, 3-methoxyphenanthrene-9,10-dicarboimide, 2-methoxyphenanthrene-9,10-dicarboimide, 3-chlorophenanthrene-9,10 -Dicarbimide, 2-chlorophenanthrene-9,10-dicarbomide, 3-bromophenanthrene-9,10-dicarbomido, 3-fluorophenanthrene-9,10-dicarbomido, 2,4-dimethylphenanthrene-9,10-dicarbomido, 3, -Methoxy-6- Chlorophenanthrene-9,10-dicarbimide, 3-methoxy-9,10-dihydrophenanthrene-9,10-dicarbomido, 2-methoxy-9,10-dihydrophenanthrene-9,10-dicarbomido, 3-chloro-9,10 -Dihydrophenanthrene-9,10-dicarbimide, 2-chloro-9,10-dihydrophenanthrene-9,10-dicarbomido, 3-bromo-9,10-dihydrophenanthrene-9,10-dicarbomido, 3-fluoro-9, 10-dihydrophenanthrene-9,10-dicarbimide, 2,4-dimethyl-9,10-dihydrophenanthrene-9,10-dicarbomide, 3-methoxy-6-chloro-9,10-dihydrophenanthrene-9,10-dicarboximide Succinimide, , 3-dibutylsuccinimide, 2-chloro-3-methylsuccinimide, 2,3-dichloro-2-methylsuccinimide, 2,2,3,3-tetrafluorosuccinimide, 2,2,3,3-tetramethylsuccinimide, Hexahydrophthalimide, 2,3-dichloromaleimide, 3-ethylglutazine, adipimide, 1,2,3,4-tetrahydrophthalimide, 3,4,5,6-tetrahydrophthalimide, 2- (m-fluorophenyl) Succinimide, N- (2,6-dioxopiperidin-3-yl) -5
, 6-Dihydro-1,4-dithiin-2,3-dicarbimide, 2- (α, α, α-trifluoro-m-tolyl) succinimide, 3,3-dimethylglutarimide, 2-methylsuccinimide, glutarimide 3,3,4-trimethylpyrrolidine-2,5-dione, 3,4-dibromo-3-pyrroline-2,5-dione, 3-methyl-4-vinyl-1H-pyrrole-2,5-dione, 6-amino-1H-benzo [de] isoquinoline-1,3 (2H) -dione, 3-methyl-4-ethyl-1H-pyrrole-2,5-dione, 3aα, 4,5,6,7,7aα -Hexahydro-2H-isoindole-1,3-dione, α-methyl-2-ethylsuccinimide, 9H-fluorene-4,5-dicarboximide, benzethimide, 2H-pyrrolo [3,4 c] pyridine-1,3-dione, pyrimidine-4,5-dicarbomide, 2,3-pyridinedicarboximide, 5,6-dihydro-1,4-dithiin-2,3-dicarboximide, 5,6 And cyclic imides such as -dihydro-1,4-dithiin-2,3-dicarboximide.

In addition, the imide represented by the general formula (XIa) may be either a chain or a ring, but a cyclic imide is generally preferable from the viewpoint of easy handling. Further, among the imides as described above, the imide having 12 or less carbon atoms constituting the functional group or atomic group represented by R ⁴ and R ⁵ in the formula (XIa) is less than a general solvent. It is preferable from the viewpoint that it is easily soluble and easy to manufacture (synthesize), and preferred examples include phthalimide and naphthalimide.

  Moreover, if what has optical activity among the imides mentioned above is used, the synthesis | combination of the optically active imide compound containing a trifluoromethyl group will be attained. That is, by using an imide having optical activity, it is possible to synthesize an optically active imide compound containing trifluoromethyl groups of R and S isomers.

(Method for producing alkoxy compound)
Further, for example, an alkoxy compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with an alcohol. This production can be represented, for example, by the following formula (XII).

  In the formula (XII), the alcohol is represented by the general formula (XIIa), and the resulting alkoxy compound is represented by the general formula (XIIb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.

In the above reaction formula, R ¹ , R ² and X ⁻ are the same as those defined in the above general formula (I). R ⁴ represents a functional group or an atomic group constituting various alcohols derived from conventionally known synthetic or natural origin.

  That is, specific examples of alcohols that can be used in the present invention are not particularly limited, and examples thereof include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol. 1-octanol, 1-nonanol, 1-decanol, 1-tridecanol, 1-eicosanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1 -Hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, 2,2-dimethyl-1-propanol, allyl alcohol, benzyl alcohol, phenethyl alcohol, cinnamon alcohol, 2 -Fluorobenzyl alcohol, 3-F Orobenzyl alcohol, 4-fluorobenzyl alcohol, 2-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 4-bromobenzyl alcohol, 4-methoxybenzyl alcohol, 4-acetylbenzyl alcohol, 2,2-dimethyl-1,3- Primary alcohols such as dioxolane-4-methanol, 2-methylbutanol, cyclohexylmethanol, 2-phenylethyl alcohol, 2-methyl-2- (tosylamino) propan-1-ol; 2-propanol, 2-butanol, 2 -Pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4 − Nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-tridecanol, 2-eicosanol, cyclobutanol, cyclopentyl alcohol, cyclohexyl alcohol, cycloheptanol, benzohydrol, pantolactone, Cyclooctanol, cyclododecanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2-tert-butylcyclohexanol, 3-tert-butylcyclohexanol, 4-tert-butylcyclohexanol, 1 -Phenylethanol, 1- (2-fluorophenyl) ethanol, 1- (3-fluorophenyl) ethanol, 1- (4-fluorophenyl) ethanol, 1- (2-chloro Enyl) ethanol, 1- (2-bromophenyl) ethanol, 1- (4-methoxyphenyl) ethanol, 1- (4-acetylphenyl) ethanol, benzoin, 1,3,5-tri-O-benzoyl-α- Secondary alcohols such as D-ribofuranose, 2,3: 4,5-di-O-isopropylidene-α-D-mannofuranose, menthol, 2-adamantanol; t-butanol, 2-methyl-2 -Butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl-2-pentanol 2,3-dimethyl-3-pentanol, 2,2,3-trimethyl-3-pentanol, 2-methyl-2-hexanol or 3-methyl-3-hex Such as tertiary alcohols Knoll and the like.

In particular, among the alcohols as described above, alcohols having 12 or less carbon atoms constituting the functional group or atomic group represented by R ⁴ in the above formula (XIIa) are soluble in general solvents. It is preferable from the viewpoint that it is easy to produce (synthesize) and, for example, 2-methyl-2- (tosylamino) propan-1-ol and the like can be mentioned as preferable examples.
Further, if an alkoxy compound having an optical activity is used among the alkoxy compounds as described above, an optically active alkoxy compound containing a trifluoromethyl group can be synthesized. That is, by using alkoxy having optical activity, it is possible to synthesize optically active alkoxy compounds containing trifluoromethyl groups of R and S isomers.

(Method for producing phosphorus compound)
For example, a phosphorus compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with a phosphorus compound. This production can be represented, for example, by the following formula (XIII).

  In the formula (XIII), the phosphorus compound is represented by the general formula (XIIIa), and the obtained phosphorus compound is represented by the general formula (XIIIb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.

In the above reaction formula, R ¹ , R ² and X ⁻ are the same as those defined in the above general formula (I). R ⁴ and R ⁵ represent functional groups or atomic groups constituting various conventionally known synthetic or natural phosphorus compounds. M represents a hydrogen atom or an alkali metal atom.

  That is, specific examples of the phosphorus compound that can be used in the present invention are not particularly limited. For example, diethylphosphonate, bis- (3-triethoxysilyl-1-propyl) methyldithiophosphonate; Bis- (3-triethoxysilyl-1-propyl) ethyldithiophosphonate, bis- (3-triethoxysilyl-1-propyl) methyltrithiophosphonate, bis- (3-triethoxysilyl- 1-propyl) ethyl trithiophosphonate, bis- (3-methyldimethoxysilyl-1-propyl) methyldithiophosphonate, bis- (3-methyldimethoxysilyl-1-propyl) ethyldithiophosphonate And so on.

In particular, among the phosphorus compounds as described above, the phosphorus compound having 12 or less carbon atoms constituting the functional group or atomic group represented by R ⁴ and R ⁵ in the above formula (XIIIa) From the viewpoint of easy dissolution and easy production (synthesis), for example, diethylphosphonate can be cited as a preferred example.

  Further, as shown in the following formula (XIV), in addition to the phosphorus compound represented by the formula (XIIIa), by using the phosphorus compound represented by the general formula (XIVa), the general formula (XIVb) The phosphorus compound represented can also be obtained. However, the phosphorus compound represented by the formula (XIVa) is very toxic, and it is preferable to use the phosphorus compound represented by the above formula (XIVa) in order to be subjected to various usage regulations.

In the above reaction formula, R ¹ , R ² and X ⁻ are the same as those defined in the above general formula (I). R ⁴ , R ⁵ and R ⁶ represent functional groups or atomic groups constituting various conventionally known synthetic or naturally derived phosphorus compounds. M represents a hydrogen atom or an alkali metal atom.

  Moreover, if what has optical activity among the phosphorus compounds as mentioned above is used, the synthesis | combination of the optically active phosphorus compound containing a trifluoromethyl group will be attained. That is, by using phosphorus having optical activity, it is possible to synthesize optically active phosphorus compounds containing trifluoromethyl groups of R and S isomers.

As understood from the above formulas (VIII) to (XIV), various useful compounds obtained by the present invention, such as aziridine compounds, amide compounds, imide compounds, alkoxy compounds, and phosphorus compounds, are the raw materials for β The aryl group (that is, R ¹ and R ² ) constituting the — (trifluoromethyl) vinyldiarylsulfonium salt has a feature that none remains.
For this reason, according to the present invention, it is possible to carry out a completely new reaction that is unprecedented in that an olefin moiety consisting of three carbons containing a trifluoromethyl group can be introduced into other compounds all at once.

  As can be seen from the above description, the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be used as a building block agent for the synthesis of various useful compounds as a preferred example of its use. Here, the building block agent means a synthetic intermediate for constructing an organic compound, as is well known.

  In addition, the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention, in another aspect, corresponds to a synthon represented by the following formula (XVa) or (XVb): It can also be used for reverse synthesis analysis. Here, as is well known, a synthon generally refers to a fragment generated when a compound bond is cleaved, and is usually in the form of an ion.

  For example, when the allyl (1-trifluoromethylvinyl) ether represented by the following formula (XVIa) is subjected to reverse synthesis analysis, the β- of the present invention corresponds to the synthon represented by the formula (XVa). (Trifluoromethyl) vinyldiarylsulfonium salts can be used. Moreover, as a thing corresponding to the synthon represented by a formula (XVIb), an allyl alcohol etc. are mentioned, for example.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
The analysis was conducted with the following equipment.
Melting point: MP-S3 from Yanako.
¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR: AL-300 manufactured by JEOL.
IR: SPECTRUM 2000 FT-IR from Perkin Elmer.
GC-MS: JMS-AWII15 manufactured by JEOL.
HRMS: JEOL JMS-HX100A.

(1. Production of β- (trifluoromethyl) vinyldiarylsulfonium salt)
Example 1
Preparation of tolyl β- (trifluoromethyl) vinyl sulfide

  Ethanol (30 mL) and potassium hydroxide (2.1 g, 37 mmol) were placed in a 100 mL round bottom flask equipped with a stir bar, and the temperature was adjusted to 0 ° C. with stirring. Then, 4-methylbenzene represented by the formula (XVIIa) was added thereto. Thiol (3.7 g, 30 mmol) and 3,3,3-trifluoro-2-bromopropene represented by formula (VIa) (3.7 mL, 36 mmol) were added, and the mixture was stirred overnight at room temperature.

After completion of the reaction, saturated aqueous ammonium chloride was added, the organic layer was separated, the aqueous layer was extracted three times with hexane, and the resulting organic layer and hexane extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure As a result, a crude product was obtained as an oily residue. The crude product was purified by silica gel column chromatography (eluent: hexane). As a result, tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) was a colorless oil (5.2 g of E form, E / Z body mixture = 0.8 g, Z body 0.4 g, total yield 98%).
E body
¹ H-NMR (CDCl ₃ , 300 MHz) d 2.38 (3H, s), 5.32 (1H, dq, J = 15.2, 6.4 Hz), 7.11 (1H, dq, J = 15.2 Hz, 2.0 Hz), 7.20- 7.40 (4H, m);
¹³ C-NMR (CDCl ₃ , 75 MHz) d 21.2, 112.6 (q, J = 34.3 Hz), 123.0 (q, J = 269.1 Hz),
126.3, 130.6, 133.6, 139.0 (q, J = 6.9 Hz), 139.7;
¹⁹ F-NMR (CDCl ₃ , 283 MHz) d -63.4 (dd, J = 6.6, 2.7 Hz);
IR (NaCl) 1619, 1300, 1279, 1119, 938, 832 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 218 (84, M ⁺ ), 217 (18), 134 (80), 123 (37), 91 (100), 77 (51), 69 (47) , 65 (79);
Elemental analysis C ₁₀ H ₉ F ₃ S Calculated value C; 55.03, H; 4.16 Measured value C; 55.12, H; 4.16.

(Example 2)
Preparation of 2-naphthyl β- (trifluoromethyl) vinyl sulfide

The 4-methylbenzenethiol represented by the formula (XVIIa) used in Example 1 was replaced with 2-naphthalenethiol represented by the formula (XVIIIa), and the same operation as in Example 1 was performed. As a result, the formula (XVIIIb) 2-naphthyl β- (trifluoromethyl) vinyl sulfide represented by the formula (1) was obtained as a colorless liquid (yield 60%).
E body
¹ H-NMR (CDCl ₃ , 300 MHz) d 5.44 (1H, dq, J = 15.2, 6.5 Hz), 7.24 (1H, dq, J = 15.2, 2.0 Hz), 7.48-7.58 (3H, m), 7.80 -7.89 (3H, m), 7.99 (1H, d, J = 1.7 Hz);
¹⁹ F-NMR (CDCl ₃ , 283 MHz) d -63.6 (d, J = 6.3 Hz).

(Example 3)
Preparation of 2-pyridyl β- (trifluoromethyl) vinyl sulfide

When 4-methylbenzenethiol represented by the formula (XVIIa) used in Example 1 was replaced with 2-pyridinethiol represented by the formula (XIXa) and the same operation as in Example 1 was performed, the formula (XIXb) 2-pyridyl β- (trifluoromethyl) vinyl sulfide was obtained as a pale yellow liquid (48% yield).
E / Z mixture
¹ H-NMR (CDCl ₃ , 300 MHz) d Z form: 5.83 (1H, dq, J = 16.0, 6.4 Hz), E form: 5.95 (1H, dq, J = 11.2, 8.4 Hz), 7.11-7.16 ( 1H, m), 7.22-7.27 (1H, m), 7.57-7.62 (1H, m), 8.05-8.12 (1H, m), 8.50-8.53 (1H, m);
¹⁹ F-NMR (CDCl ₃ , 283 MHz) d E form: -64.2 (dd, J = 6.4, 2.1 Hz), Z form: -61.74 (d, J = 8.5 Hz).

(Example 4)
Preparation of (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate

  In a 25 mL two-necked flask equipped with a stir bar, tolyl β- (trifluoromethyl) vinyl sulfide (514 mg, 2.36 mmol) represented by the formula (XVIIb) prepared in Example 1, tetrachloroethane (1.5 mL), formula Diphenyliodonium triflate (1.26 g, 2.83 mmol), copper (I) chloride (23.4 mg, 0.24 mmol) and a small amount of copper wire represented by (XXa) were added and reacted at 100 ° C. for 2 hours.

After cooling the reaction temperature to room temperature, the reaction mixture is directly purified by silica gel chromatography (eluent: first dichloromethane, then dichloromethane: acetone = 2: 1) to give (3,3,3) represented by the formula (IIa) -Trifluoropropen-1-yl) -phenyltoluylsulfonium triflate was obtained as a pale yellow oil (973 mg, 92% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 2.47 (3H, s), 6.97 (1H, dq, J = 14.7, 5.7 Hz), 7.51 (2H, d, J = 8.3 Hz), 7.67-7.79 (3H, m), 7.82 (2H, d, J = 8.4 Hz), 7.89-7.96 (3H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 21.6, 119.6, 120.2 (q, J = 273.4 Hz), 120.6 (q, J = 320.1 Hz), 124.0, 127.2 (q, J = 6.9 Hz), 130.7, 131.0 , 131.8, 132.6, 135.0, 136.6 (q, J = 37.4 Hz), 147.2;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -66.3 (d, J = 6.4Hz), -80.1 (s);
IR (NaCl) 3046, 1645, 1592, 1449, 1279, 1225, 1151, 1031, 872, 810, 749, 684, cm ^-1 ;
Elemental analysis C ₁₇ H ₁₄ F ₆ O ₃ S ₂ Calculated C; 45.94, H; 3.18 Measured C; 46.10, H; 3.33.

(Example 5)
Preparation of (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate

The tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) used in Example 4 was replaced with phenyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XXIa). When the same operation was performed, (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate represented by the formula (IIIa) was obtained as a white solid (yield 93%).
Melting point 68.1-70.5 ℃
¹ H NMR (CDCl ₃ , 300 MHz) δ 6.98 (1H, dq, J = 14.7, 5.7 Hz), 7.71-7.83 (6H, m), 7.88-7.93 (5H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 120.0 (q, J = 273.4 Hz), 120.6 (q, J = 320.1 Hz), 123.6, 126.7 (q, J = 6.9 Hz), 130.9, 131.8, 135.2, 137.3 (q, J = 37.4 Hz);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -66.3 (d, J = 6.5 Hz), -79.9 (s)
IR (NaCl) 3066, 3047, 1645, 1583, 1478, 1449, 1279, 1226, 1152, 1031, 999, 873, 748, 683, cm ^-1 ;
Elemental analysis C ₁₆ H ₁₂ F ₆ O ₃ S ₂ Calculated value C; 44.65, H; 2.81 Measured value C; 44.66, H; 2.92.

(Example 6)
Preparation of (3,3,3-trifluoropropen-1-yl)-(2-naphthyl) phenylsulfonium triflate

The tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) used in Example 4 was replaced with (2-naphthyl) β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIIb). When the same operation as in Example 4 was performed, (3,3,3-trifluoropropen-1-yl)-(2-naphthyl) phenylsulfonium triflate represented by the formula (IVa) was converted to a pale yellow oil (yield 93%).
¹ H NMR (CDCl ₃ , 300 MHz) δ 7.07 (1H, dq, J = 14.9, 5.7 Hz), 7.66-7.78 (6H, m), 7.92-7.97 (3H, m), 8.03 (1H, dq, J = 14.9, 1.8 Hz), 8.05-8.15 (2H, m), 8.72 (1H, d, J = 2.0 Hz);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -66.2 (d, J = 5.3 Hz), -79.9 (s).

(Example 7)
Preparation of (3,3,3-trifluoropropen-1-yl) -phenyl (2-pyridyl) sulfonium triflate

The tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) used in Example 4 was replaced with 2-pyridyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XIXb). When the same operation as 4 was performed, (3,3,3-trifluoropropen-1-yl) -phenyl (2-pyridyl) sulfonium triflate represented by the formula (Va) was converted into a pale yellow oil (yield 17 %).
¹ H NMR (acetone-d ₆ , 300 MHz) δ 6.73 (1H, dq, J = 15.2, 6.4 Hz), 7.69 (1H, dq, J = 15.2, 1.8 Hz), 7.79-7.89 (5H, m), 8.23-8.27 (1H, m), 8.53 (1H, d, J = 8.1 Hz), 8.78-8.84 (1H, m), 9.16-9.19 (1H, m);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -65.9 (d, J = 6.0 Hz), -79.8 (s).

(Example 8)
Preparation of (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium tetrafluoroborate

In a 25 mL two-necked flask equipped with a stir bar, (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate (109.7 mg, 0.247) represented by the formula (IIa) prepared in Example 4 was prepared. mmol), AgBF ₄ (66.2 mg, 0.34 mmol) represented by the formula (XXIVa) and dichloromethane (1 mL) are added, and the mixture is allowed to react in an ultrasonic cleaner for 1 hour, then removed from the ultrasonic cleaner and allowed to react at room temperature for 2 hours. It was.

The reaction mixture was filtered using short column chromatography packed with celite, and the filtrate was concentrated to obtain (3,3,3-trifluoropropen-1-yl) -phenyltoluyl represented by the formula (IIIb). Sulphonium tetrafluoroborate was obtained as a light brown oil. (Yield 79%)
¹ H NMR (CDCl ₃ , 300 MHz) δ 2.47 (3H, s), 6.95 (1H, dq, J = 14.7, 5.7 Hz), 7.52 (2H, d, J = 8.6 Hz), 7.67-7.77 (4H, m), 7.80 (2H, d, J = 8.4 Hz), 7.86-7.89 (2H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 21.5, 119.7, 120.1 (q, J = 273.4 Hz), 124.0, 126.5 (q, J = 6.9 Hz), 130.6, 131.0, 131.7, 132.5, 135.0, 136.9 (q , J = 37.4 Hz), 147.0; ¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -66.5 (d, J = 6.5 Hz), -151.3 (s);
IR (NaCl) 3065, 1645, 1592, 1494, 1478, 1449, 1303, 1283, 1151, 1059, 872, 811 cm ^-1 ;
Elemental analysis C ₁₆ H ₁₄ BF ₇ S Calculated value C; 50.29, H; 3.69 Measured value C; 50.36, H; 3.89.

(2. Production of aziridine compound)
Example 9
Preparation of 1-benzyl-2- (trifluoromethyl) aziridine

  A 25 mL two-necked flask equipped with a stir bar was charged with (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate (122.7 mg, 0.28) of the formula (IIa) prepared in Example 4. mmol), DMSO (1 mL), benzylamine (36 mL, 0.33 mmol) represented by the formula (XXVa), and tert-butylamine (87 mL, 0.83 mmol) were added and reacted at room temperature for 2.5 hours. Water was added to the reaction mixture, and a mixed solvent of hexane: ethyl acetate = 3/1 was added as an extraction solvent to separate the organic layer.

The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue. The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 10/1, then hexane: ethyl acetate = 3/1) to give 1-benzyl represented by the formula (XXVb). -2- (Trifluoromethyl) aziridine was obtained as a colorless oil (78% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.66 (1H, d, J = 5.9 Hz), 2.10-2.19 (2H, m), 3.78 (2H, s), 7.28-7.36 (5H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 30.0 (q, J = 2.5 Hz), 37.3 (q, J = 39.8 Hz), 63.4, 124.1 (q, J = 272.8 Hz), 127.5, 128.0, 128.5, 137.3 ;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.5 (d, J = 4.7 Hz);
IR (NaCl) 3067, 3033, 2935, 2843, 1498, 1456, 1362, 1286, 1142, 1070, 1028, 847, 736, 698 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 201 (0.4, M ⁺ ), 132 (1), 110 (2), 92 (9), 91 (100), 90 (9), 65 (13) , 51 (7);
Elemental analysis C ₁₀ H ₁₀ F ₃ N Calculated C; 59.70, H; 5.01, N; 6.96 Measured C; 59.81, H; 5.03, N; 7.08.

(Example 10)
Preparation of 2- (trifluoromethyl) -1-phenethylaziridine

The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 2-phenylethanamine represented by the formula (XXVIa). 2- (trifluoromethyl) -1-phenethylaziridine was obtained as a colorless oil (77% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.47 (1H, d, J = 6.2 Hz), 1.96-2.04 (1H, m), 2.08 (1H, d, J = 3.1 Hz), 2.52-2.66 (2H, m), 2.84-2.99 (2H, m), 7.18-7.29 ppm (5H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 30.2 (q, J = 2.3 Hz), 35.9, 37.4 (q, J = 39.5 Hz), 62.0, 124.1 (q, J = 272.5 Hz), 126.3, 128.5, 128.7 , 139.1;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.5 (d, J = 4.8 Hz);
IR (NaCl) 3060, 3027, 2940, 2833, 1497, 1453, 1363, 1286, 1143, 1074, 860, 748, 699 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 215 (1.8, M ⁺ ), 124 (100), 91 (28), 77 (20), 74 (23), 65 (17), 60 (35) , 51 (11);
Elemental analysis C ₁₁ H ₁₂ F ₃ N Calculated C; 61.39, H; 5.62, N; 6.51 Measured C; 61.59, H; 5.76, N; 6.59.

(Example 11)
Preparation of 2- (trifluoromethyl) -1- (3,5-dimethylbenzyl) aziridine

The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 3,5-dimethylbenzylamine represented by the formula (XXVIIa), and the formula (XXVIIb) 2- (trifluoromethyl) -1- (3,5-dimethylbenzyl) aziridine represented by the formula (1) was obtained as a colorless oil (yield 72%).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.65 (1H, brd, J = 5.9 Hz), 2.13-2.16 (2H, m), 2.311 (3H, s), 2.312 (3H, s), 3.42 (1H, d, J = 13.2 Hz), 3.55 (1H, d, J = 13.2 Hz), 6.93 (1H, s), 6.94 (2H, s);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 21.2, 29.9 (q, J = 1.9 Hz), 37.3 (q, J = 39.9 Hz), 63.4, 124.2 (q, J = 272.8 Hz), 125.9, 129.1, 137.1 , 138.0;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.5 (d, J = 4.8 Hz);
IR (NaCl) 3015, 2921, 2843, 1609, 1429, 1285, 1153, 1072, 1040, 961, 854, 827 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 229 (4, M ⁺ ), 132 (1), 120 (12), 119 (100), 118 (7), 104 (4), 91 (19) , 77 (9), 65 (3);
Elemental analysis C ₁₂ H ₁₄ F ₃ N Calculated C; 62.87, H; 6.16, N; 6.11 Measured C; 62.85, H; 6.25, N; 6.17.

(Example 12)
Preparation of 1- (3,5-bis (trifluoromethyl) benzyl) -2- (trifluoromethyl) aziridine

The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 3,5-bis (trifluoromethyl) benzylamine represented by the formula (XXVIIIa). 1- (3,5-bis (trifluoromethyl) benzyl) -2- (trifluoromethyl) aziridine represented by the formula (XXVIIIb) was obtained as a colorless oil (yield 40%).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.74 (1H, d, J = 6.4 Hz), 2.18-2.22 (1H, m), 2.28 (1H, d, J = 3.1 Hz), 3.64 (1H, d, J = 14.3 Hz), 3.71 (1H, d, J = 14.3 Hz), 7.82 (1H, s), 7.85 (2H, s);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 30.4 (q, J = 1.9 Hz), 37.9 (q, J = 39.9 Hz), 62.3, 121.5 (sep, J = 3.7 Hz), 123.8 (q, J = 272.7 Hz), 127.8, 131.8 (q, J = 33.4 Hz), 140.2;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.7 (d, J = 4.9 Hz);
IR (NaCl) 3006, 2933, 2853, 1624, 1433, 1386, 1351, 1280, 1246, 1136, 1076, 1040, 956, 911, 891, 837, 706, 683 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 336 (0.1, M ⁺ -1), 227 (13), 226 (4), 177 (2), 110 (100), 95 (2), 77 ( 2), 69 (4), 60 (15);
Elemental analysis C ₁₂ H ₈ F ₉ N Calculated C; 42.74, H; 2.39, N; 4.15 Measured C; 42.76, H; 2.45, N; 4.22.

(Example 13)
Preparation of 2- (trifluoromethyl) -1-((naphthalen-2-yl) methyl) aziridine

The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 1-naphthalenemethylamine represented by the formula (XXIXa). 2- (trifluoromethyl) -1-((naphthalen-2-yl) methyl) aziridine was obtained as a colorless oil (yield 86%).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.73 (1H, d, J = 5.9 Hz), 2.21-2.25 (2H, m), 3.90 (1H, d, J = 13.9 Hz), 4.14 (1H, d, J = 13.9 Hz), 7.43-7.57 (4H, m), 7.80 (2H, m), 8.08 (1H, d, J = 8.1 Hz);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 30.2 (q, J = 1.9 Hz), 37.6 (q, J = 39.9 Hz), 61.1, 123.5, 124.2 (q, J = 272.3 Hz), 125.3, 125.7, 125.8 , 126.8, 128.3, 128.6, 131.5, 133.0, 133.6;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.2 (d, J = 4.6 Hz);
IR (NaCl) 3051, 3011, 2849, 1599, 1510, 1430, 1287, 1239, 1152, 796, 775 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 251 (4, M ⁺ ), 154 (2), 141 (100), 139 (6), 127 (5), 115 (29), 89 (3) , 77 (3), 63 (3), 51 (2);
HRMS C ₁₄ H ₁₂ F ₃ N Calculated value 251.0943 Measured value 251.0922.

(Example 14)
Preparation of N, N-diethyl-2- (2- (trifluoromethyl) aziridin-1-yl) ethanamine

The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with N, N-diethylethylenediamine represented by the formula (XXXa). The indicated N, N-diethyl-2- (2- (trifluoromethyl) aziridin-1-yl) ethanamine was obtained as a colorless oil (63% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.10-1.06 (6H, m), 1.56 (1H, d, J = 6.2 Hz), 2.02-2.05 (1H, m), 2.09 (1H, d, J = 3.1 Hz), 2.34-2.40 (1H, m), 2.50-2.70 (6H, m), 2.76-2.81 (1H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 11.6, 29.7 (q, J = 1.9 Hz), 37.2 (q, J = 39.9 Hz), 47.3, 52.0, 58.6, 125.8 (q, J = 272.2 Hz);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.8 (d, J = 4.6 Hz);
IR (NaCl) 2972, 2933, 2873, 2806, 1431, 1383, 1336, 1287, 1240, 1196, 1141, 1066, 960, 853, 756 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 210 (0.1, M ⁺ ), 138 (1), 100 (2), 87 (10), 86 (100), 85 (14), 70 (2) , 58 (12), 56 (5).

(Example 15)
Preparation of ethyl 2- (2- (trifluoromethyl) aziridin-1-yl) acetate

To a 25 mL two-necked flask equipped with a stir bar, glycine ethyl hydrochloride (64.6 mg, 0.463 mmol), DMSO (1 mL), tert-butylamine (250 mL, 2.32 mmol) were added and stirred.
To this mixed solution, sodium hydride (62.7%, 32.4 mg, 0.556 mmol), (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate represented by the formula (IIIa) prepared in Example 5 (240.0 mg, 0.556 mmol) was added and reacted at room temperature for 10 hours.

  Water was added to the reaction mixture, and a mixed solvent of hexane: ethyl acetate = 3/1 was added as an extraction solvent to separate the organic layer. The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue.

The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3/1) to give ethyl 2- (2- (trifluoromethyl) aziridine- represented by the formula (XXXIb) 1-yl acetate was obtained as a colorless oil (54% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.30 (3H, t, J = 7.1 Hz), 1.68 (1H, d, J = 6.6 Hz), 2.19-2.24 (1H, m), 2.26 (1H, d, J = 3.1 Hz), 3.12 (1H, d, J = 15.8 Hz), 3.24 (1H, d, J = 16.0 Hz), 4.23 (1H, q, J = 7.2 Hz);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 13.9, 29.7 (q, J = 2.5 Hz), 37.3 (q, J = 39.9 Hz), 59.9, 61.0, 123.7 (q, J = 272.8 Hz), 168.7;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -72.9 (d, J = 4.6 Hz);
IR (NaCl) 2986, 2940, 2913, 1747, 1430, 1286, 1200, 1143, 1080, 1043, 956, 833 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 197 (1, M ⁺ ), 124 (100), 110 (21), 95 (4), 77 (3), 74 (9), 69 (2) , 60 (18), 55 (4).

(Example 16)
Preparation of 2- (trifluoromethyl) -1-tosylaziridine

  To a 25 mL two-necked flask equipped with a stir bar, p-toluenesulfonamide (689.8 mg, 4.03 mmol) represented by the formula (XXXIIa) and THF (13 mL) were added and stirred, and sodium hydride (62.7 %, 191.8 mg, 4.83 mmol) and stirred for 15 minutes.

  To this mixture was added (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate (1.839 g, 4.23 mmol) of the formula (IIIa) prepared in Example 5 and reacted at room temperature for 15 minutes. I let you. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and a hexane: ethyl acetate = 3/1 mixed solvent was further added as an extraction solvent to separate the organic layer.

The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue. The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 10/1, then hexane: ethyl acetate = 3/1) to give 2- (2) represented by the formula (XXXIIb). Trifluoromethyl) -1-tosylaziridine was obtained as a white solid (91% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 2.47 (3H, s), 2.52 (1H, d, J = 4.0 Hz), 2.82 (1H, d, J = 7.0 Hz), 3.23-3.31 (1H, m) , 7.38 (2H, d, J = 8.4 Hz), 7.85 (2H, d, J = 8.4 Hz);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 21.6, 28.9 (q, J = 2.5 Hz), 36.7 (q, J = 41.7 Hz), 122.1 (q, J = 274.0 Hz), 128.2, 129.9, 133.6, 145.6 ;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -73.3 (d, J = 4.6 Hz).

(3. Production of imide compound)
(Example 17)
Preparation of 2- (1,1,1-trifluoroprop-2-en-2-yl) isoindoline-1,3-dione

  In a 25 mL two-necked flask equipped with a stir bar, (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate of the formula (IIa) prepared in Example 4 (458 mg, 1.03 mmol) was added. ), Dichloromethane (2 mL), DMSO (1 mL), phthalimide (136 mg, 0.92 mmol) represented by the formula (XXXIIIa) and triethylamine (140 mL, 0.99 mmol) were added, and the mixture was reacted at room temperature for 3 hours.

  A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and ether was further added as an extraction solvent to separate the organic layer. The aqueous layer was extracted three times with ether, and the resulting organic layer and the ether extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oily residue.

The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3/1) to give 2- (1,1,1-trifluoroprop-propoxide represented by the formula (XXXIIIb). 2-En-2-yl) isoindoline-1,3-dione was obtained as a white solid (91% yield).
Melting point 92.2-93.9 ℃
¹ H NMR (CDCl ₃ , 300 MHz) δ 5.87-5.88 (1H, m), 6.42 (1H, q, J = 0.92 Hz), 7.80-7.92 (2H, m), 7.93-7.96 (2H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 120.3 (q, J = 274.7 Hz), 124.1, 126.3 (q, J = 3.7 Hz), 129.0 (q, J = 38.0 Hz), 131.5, 134.7, 166.0;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -69.9 (s);
IR (KBr) 3131, 1729, 1401, 1302, 1208, 1182, 1142, 1120, 886, 718, 637 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 241 (24, M ⁺ ), 197 (6), 172 (6), 144 (2), 118 (9), 104 (52), 76 (100) , 66 (20), 50 (38);
Elemental analysis C ₁₁ H ₆ F ₃ NO ₂ Calculated C; 54.78, H; 2.51, N; 5.81 Measured C; 55.03, H; 2.52, N; 5.81.

(Example 18)
Preparation of 2- (1,1,1-trifluoroprop-2-en-2-yl) -1,8-naphthalimide

The same operation as in Example 17 was performed by replacing the phthalimide represented by the formula (XXXIIIa) used in Example 17 with the naphthalimide represented by the formula (XXXIVa). 1,1,1-trifluoroprop-2-en-2-yl) -1,8-naphthalimide was obtained as a solid (yield 3%).
¹ H NMR (CDCl ₃ , 300 MHz) δ 5.90-5.93 (1H, m), 6.50-6.53 (1H, m), 7.81 (2H, dd, J = 8.4, 7.3 Hz), 8.29 (2H, d, J = 8.4 Hz), 8.66 (2H, d, J = 7.3 Hz);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -68.3 (s).

(4. Production of amide compound)
(Example 19)
Preparation of 1- (1,1,1-trifluoroprop-2-en-2-yl) indoline-2,3-dione

When phthalimide represented by the formula (XXXIIIa) used in Example 17 was replaced with isatin represented by the formula (XXXVa) and the same operation as in Example 17 was performed, 1- (1 represented by the formula (XXXVb) was obtained. , 1,1-trifluoroprop-2-en-2-yl) indoline-2,3-dione was obtained as a yellow solid (55% yield).
Melting point 93.2-94.5 ℃
¹ H NMR (CDCl ₃ , 300 MHz) δ 5.98-6.03 (1H, m), 6.49-6.51 (1H, m), 6.91 (1H, d, J = 8.1 Hz), 7.22 (1H, d, J = 7.5 Hz), 7.60-7.73 (2H, m);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 111.3 (t, J = 1.3 Hz), 117.4, 120.3 (q, J = 275.3 Hz), 124.8, 125.7, 126.9 (q, J = 3.7 Hz), 129.2 (q , J = 37.4 Hz), 138.8, 150.5, 157.2, 181.0;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -69.5 (s);
IR (KBr) 1790, 1770, 1732, 1714, 1694, 1621, 1615, 1589, 1574, 1480, 1409, 1278, 1189, 1134, 1089, 975, 816, 702 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 241 (3, M ⁺ ), 213 (31), 165 (15), 144 (40), 116 (100), 104 (13), 89 (92) , 63 (54)
Elemental analysis C ₁₁ H ₆ F ₃ NO ₂ Calculated C; 54.78, H; 2.51, N; 5.81 Measured C; 54.86, H; 2.56, N; 5.80.

(Example 20)
Preparation of 2- (N- (1,1,1-trifluoroprop-2-en-2-yl) -N-tosyl) aminoethanol

  A (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate of the formula (IIa) prepared in Example 4 (111.3 mg, 0.25 mmol) was prepared in a 25 mL two-necked flask equipped with a stir bar. ), Dichloromethane (1 mL), 2- (tosylamino) ethanol (66.3 mg, 0.30 mmol) represented by the formula (XXXIVa) and DBU (75 mL, 0.50 mmol) were added, and the mixture was reacted at room temperature for 2 hours.

  Water and dichloromethane were added to the reaction mixture, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the obtained organic layer and the extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product as an oily residue.

The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 1/1) to give 2- (N- (1,1,1-trimethyl) represented by the formula (XXXIVb). Fluoroprop-2-en-2-yl) -N-tosyl) aminoethanol was obtained as a colorless oil (78% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 2.12 (1H, t, J = 5.4 Hz), 2.44 (3H, s), 3.56 (2H, t, J = 5.3 Hz), 3.74 (2H, q, J = 5.4 Hz), 5.86 (1H, m), 6.15 (1H, t, J = 0.7 Hz), 7.32 (2H, d, J = 8.1 Hz), 7.73 (2H, d, J = 8.3 Hz);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 21.5, 51.7, 59.5, 120.9 (q, J = 276.5 Hz), 125.9 (q, J = 3.3 Hz), 127.8, 129.7, 133.7 (q, J = 34.7 Hz) , 135.3, 144.4;
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -60.1 (s);
IR (NaCl) 3542, 2930, 1598, 1354, 1165, 974, 684 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 245 (1), 214 (2), 155 (16), 124 (11), 91 (100), 77 (2), 65 (23), 54 ( 8).
Elemental analysis C ₁₂ H ₁₄ F ₃ NO ₃ S calculated C; 46.60, H; 4.56, N; 4.53 measured C; 46.74, H; 4.65, N; 4.65.

(5. Production of alkoxy compound)
(Example 21)
Preparation of 1- (1,1,1-trifluoroprop-2-en-2-yloxy) -2-methyl-N-tosylpropan-2-amine

The 2- (tosylamino) ethanol represented by the formula (XXXIVa) used in Example 20 was replaced with 2-methyl-2- (tosylamino) propan-1-ol represented by the formula (XXXVIIa). When the same operation was performed, 1- (1,1,1-trifluoroprop-2-en-2-yloxy) -2-methyl-N-tosylpropan-2-amine represented by the formula (XXXVIIb) Obtained as a white solid (65% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.27 (6H, s), 2.42 (3H, s), 3.53 (2H, s), 4.29 (1H, m, J = 1.9 Hz), 4.77 (1H, d, J = 4.0 Hz), 4.81 (1H, s), 7.28 (2H, d, J = 8.2 Hz),
7.76 (2H, d, J = 8.4 Hz);
¹³ C NMR (CDCl ₃ , 75 MHz) δ 21.4, 24.6, 55.7, 74.5, 88.0 (q, J = 3.7 Hz), 119.5 (q, J = 273.4 Hz), 126.9, 129.6, 139.8, 143.2, 146.6 (q , J = 34.9 Hz);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -73.8 (s);
IR (KBr) 3259, 1655, 1386, 1326, 1155, 985, 676 cm ^-1 ;
GC-MS (EI, m / z, 70 eV) 212 (30), 155 (44), 139 (2), 91 (100), 70 (2), 65 (15), 55
(Four).
HRMS C ₁₄ H ₁₈ F ₃ NO ₃ S Calculated 338.1059 Measured 338.1038.

(6. Production of phosphorus compound)
(Example 22)
Diethyl 1,1,1-trifluoroprop-2-ene? 2? Ilphosphonate

  In a 25 mL two-necked flask equipped with a stir bar, (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate (138.0 mg, 0.32 mmol) of the formula (IIIa) prepared in Example 5 was added. ), Molecular sieves 4A (155 mg) and dichloromethane (1.5 mL) were added and stirred for 30 minutes.

The mixture was cooled to 0 ° C., diethylphosphonate represented by the formula (XXXVIIIa) (24 mL, 0.19 mmol) and diisopropylethylamine (126 mL, 0.71 mmol) were added, and then the temperature was slowly raised to room temperature. The reaction was performed for 12 hours.
The reaction mixture was passed through a short column of celite to remove the precipitate. Water was added to the filtrate, and an organic layer was separated by adding a hexane: ethyl acetate = 3/1 mixed solvent as an extraction solvent.

  The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue.

The obtained crude product was purified by silica gel column chromatography (eluent: hexane, then ethyl acetate) to obtain diethyl 1,1,1-trifluoroprop-2-ene represented by the formula (XXXVIIIb)? 2? The ylphosphonate was obtained as a pale yellow oil (48% yield).
¹ H NMR (CDCl ₃ , 300 MHz) δ 1.36 (6H, t, J = 6.8 Hz), 4.06-4.28 (4H, m), 6.63 (1H, dq, J = 40.2, 1.7 Hz), 6.67 (1H, dm, J = 20.6 Hz);
¹⁹ F NMR (CDCl ₃ , 283 MHz) δ -64.4 (s);
GC-MS (EI, m / z, 70 eV) 232 (M +, 0.4), 205 (40), 177 '73), 164 (65), 159 (70), 157 (61), 105 (55), 81 (66), 65 (100).

Claims (10)

A β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the following general formula (I):

(In the formula, R ¹ and R ² each independently represent a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group , and X ⁻ represents an anion group constituting a counter ion. It is a body or trans isomer or a mixture thereof.) X ^- The β- (trifluoromethyl) vinyldiarylsulfonium salt according to claim 1, wherein is a trifluoromethanesulfonyl group or a tetrafluoroborate group. As represented by the following reaction formula (VI), 2-bromo-3,3,3-trifluoropropene represented by formula (VIa) and an aromatic thiol represented by general formula (VIb) To produce a vinyl sulfide containing trifluoromethyl represented by the general formula (VIc). Further, as represented by the reaction formula (VII), the produced vinyl sulfide and the general formula ( The β- (trifluoromethyl) vinyldiarylsulfonium represented by the general formula (I) according to claim 1, wherein the diaryl halide represented by VIIa) is reacted in a halogen-based nonpolar solvent. Method for producing salt.

(In the reaction formula, R ¹ And R ² Each independently represent a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^Three Represents a phenyl group and X ^- Represents an anionic group constituting a counter ion, and Y represents a halogen group. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (VIII), β- (trifluoromethyl) vinyldiarylsulfonium salt represented by general formula (I), benzylamine represented by general formula (VIIIa), 2- Of phenylethanamine, 3,5-dimethylbenzylamine, 3,5-bis (trifluoromethyl) benzylamine, 1-naphthalenemethylamine, N, N-diethylethylenediamine, glycine ethyl, or p-toluenesulfonamide Any primary amine compound is reacted to contain a trifluoromethyl group and R of the general formula (I) ¹ And R ² Producing an aziridine compound represented by the general formula (VIIIb), in which no residual remains.

(In the reaction formula, R ¹ And R ² Each independently represent a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ⁴ Is NH represented by the general formula (VIIIa) ₂ R formed by bonding with a group ⁴ -NH ₂ Is benzylamine, 2-phenylethanamine, 3,5-dimethylbenzylamine, 3,5-bis (trifluoromethyl) benzylamine, 1-naphthalenemethylamine, N, N-diethylethylenediamine, ethyl glycine, or p -Represents a functional group to be toluenesulfonamide, X ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (IX), an amide compound composed of β- (trifluoromethyl) vinyldiarylsulfonium salt represented by general formula (I) and isatin represented by formula (XXXVa) Are reacted to contain a trifluoromethyl group and R of the general formula (I) ¹ And R ² An amide compound represented by the formula (XXXVb) in which no amide remains is produced.

(In the reaction formula, R ¹ And R ² Each independently represents a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (X), β- (trifluoromethyl) vinyldiarylsulfonium salt represented by general formula (I) and 2- (tosylamino) ethanol represented by formula (XXXIVa) Is reacted with an amide compound comprising a trifluoromethyl group and R of the general formula (I) ¹ And R ² An amide compound represented by the formula (XXXIVb) in which no amide remains is produced.

(In the reaction formula, R ¹ And R ² Each independently represents a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (XI), a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) and an imide compound composed of a phthalimide represented by the formula (XXXIIIa) Are reacted to contain a trifluoromethyl group and R of the general formula (I) ¹ And R ² Producing an imide compound represented by the formula (XXXIIIb), wherein no amide remains.

(In the reaction formula, R ¹ And R ² Each independently represents a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (XI) ′, an imide comprising a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) and a naphthalimide represented by the formula (XXXIVa) Reacting with a compound containing a trifluoromethyl group and R of general formula (I) ¹ And R ² Producing an imide compound represented by the formula (XXXIVb), wherein no amide remains.

(In the reaction formula, R ¹ And R ² Each independently represents a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (XII), β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) and 2-methyl-2-methyl represented by the formula (XXXVIIa) Reaction with an alcohol comprising (tosylamino) propan-1-ol, containing a trifluoromethyl group and R of the general formula (I) ¹ And R ² Producing an alkoxy compound represented by the formula (XXXVIIb) in which no residual is present.

(In the reaction formula, R ¹ And R ² Each independently represents a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. ) As represented by the following reaction formula (XIII), a phosphor comprising β- (trifluoromethyl) vinyldiarylsulfonium salt represented by general formula (I) and diethylphosphonate represented by formula (XXXVIIIa) Reacting with a compound containing a trifluoromethyl group and R of general formula (I) ¹ And R ² Producing a phosphorus compound represented by the formula (XXXVIIIb), wherein no phosphorus remains.

(In the reaction formula, R ¹ And R ² Each independently represents a phenyl group, a tolyl group, a naphthyl group, or a pyridyl group; ^- Represents an anionic group constituting a counter ion. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures. )