TW200927888A - Method for producing pentafluorosulfanylbenzene compound and novel pentafluorosulfanylbenzene compound - Google Patents

Abstract

Disclosed is a commercially advantageous method for producing a pentafluorosulfanylbenzene compound represented by the formula (3) below, wherein a pentafluorosulfanylbenzene compound represented by the formula (1) below is reacted with one or more substances selected from R1OH, R1COOH, R1HC=CH2, R1X, R1C=CH (wherein R1 represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or the like) and the like. Also disclosed is a novel pentafluorosulfanylbenzene compound. (1) (In the formula (1), A represents a halogen atom, -OH, -COOH, -HC=CH2, -CH2X (wherein X represents a leaving group), -BY2 (wherein Y represents a hydroxy group or the like) or the like.) (3) (In the formula (3), Z represents a linking group such as -O-, -OCH2-, -CH2O-, -COO-, -OCO-, -HC=CH- and -C=C-, and n represents 0 or 1.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a sulfur pentafluoride-based compound and a novel sulfur oxysulfide compound. [Prior Art] The oxycarbonyl thiopentafluorobenzene compound can be used as a compound for use in, for example, a pharmaceutical or a liquid crystal material (for example, see Patent Document 1). In the past, a method for synthesizing an oxycarbonylthiopentafluorobenzene compound from a hydroxycarbonylthiopentafluorobenzene compound, for example, reacting thiopentabenzene carboxylic acid, methanol, and sulfinium chloride through pentafluorocarbon A method of producing thiophenylbenzenecarboxylic acid chloride to produce methyl thiosulfonate pentacarboxylate is known. However, since this method requires the use of a large amount of excess alcohol and sulfinium chloride, it is unsuitable for industrial processes (see, for example, Patent Documents 1 and 2). The 4-oxopentafluoropentafluorobenzene compound is also a compound which can be used as a Q such as a pharmaceutical or a liquid crystal material (see, for example, Patent Document 3 and Non-Patent Document 1). In the prior art, a method for preparing a 4-oxopentafluoropentafluorobenzene compound, for example, reducing 4-nitronitropentafluorobenzene-based benzene to 4-aminoafluorothiobenzene, and diazotizing the amine a method of hydrolyzing a 4-hydroxypentafluoropentabenzene compound (see, for example, Non-Patent Document 2), and a 4-chloropentafluoropentabenzene compound and a compound in the presence of potassium carbonate/fluorination at a high temperature The method of the reaction (see, for example, Non-Patent Document 3) is known. However, these methods - the law system requires a lot of reaction steps, and requires expensive reagents such as fluorinated planers, which are not suitable for the industrial process. -5-200927888 The 2-oxo-pentafluorobenzene-benzene compound is also a compound which can be used as a medicine or a liquid crystal material (see, for example, Non-Patent Document 4). In the past, a 2-oxopentafluoropentafluorobenzene compound is produced, for example, by reacting 2-fluoro-5-nitropentafluoropentabenzene, ethanol, and potassium hydroxide under heating under reflux to obtain 2-ethoxygen. A method of thio-5-nitropentafluorothiobenzene (Non-Patent Document 4). However, this method is apparently substituted by a nitro group at the 5 position, and the reaction is promoted by the electron attraction of the nitro group. Further, the production method of the unsubstituted 2-oxopentafluorothiobenzene compound has hitherto no production example. The alkenyl pentafluorothiobenzene compound is also a compound which can be used as a medicine or a liquid crystal material (see, for example, Non-Patent Document 5). In the past, an alkenyl pentasulfide benzene compound was prepared by mixing 3 or 4-iodopentafluoropentafluoride, methyl acrylate and triethylamine in the presence of palladium acetate and triphenylphosphine, and reacting under reflux. One night, a method of obtaining methyl 3-(3 or 4-pentafluorothiophenyl)acrylate in a yield of 65 to 59% (Non-Patent Document 5). However, this method has a problem that the reaction time is long, the compound obtained is colored, and the like, and only the examples of the ketone compound having a high activity of a methoxycarbonyl group are exemplified, and various alkenyl pentafluorobenzene compounds are required. The aryl thiopentafluoride benzene compound is also a compound which can be used as a medicine or a liquid crystal material (see, for example, Non-Patent Documents 1 and 5 and Patent Document 4). Mixing 3 or 4-iodopentafluoropentafluoride with phenylboronic acid or tris(η-butyl)phenyltin in the presence of tetrakis(triphenylphosphine)palladium, and reacting under reflux for 18 hours to A method of obtaining 3 or 4-biphenylpentafluoropentabenzene by a yield of 48 to 94% (200927888 Non-Patent Document 5). However, this method has a long reaction time and uses a tin reagent which is problematic in safety, and is only a production example of a phenyl group. Further, for example, there is a method of reacting a boronic acid derivative of a thiosulfonated benzene compound with a halogenated aryl group in the presence of a metal compound (Patent Document 4). However, the synthesis yield of the boronic acid derivatives of various kinds of sulfur pentafluoride compounds used in this method is low, and as a result, it is difficult to synthesize various aryl pentafluorothiobenzene compounds. The alkynyl thiosulfate benzene compound is also a compound which can be used as a medicine or a liquid crystal material (see, for example, Non-Patent Documents 1 and 5). Conventionally, a method for producing an alkynyl thiosulfate benzene compound is, for example, a method in which a halogenated thiobenzene benzene compound and an alkynyl compound are reacted in the presence of a metal compound. However, this method is low in yield and long in reaction time, and only an example of phenylacetylene is exemplified. The oxymethylpentafluorobenzene compound can also be expected as a compound which can be used as a medicine or a liquid crystal material. However, the preparation of the oxymethylpentafluorobenzene-based compound is still unknown. [Patent Document 1] International Publication No. 2005/047240 [Patent Document 2] US Patent Application Publication No. 2003/02 1 6476. [Patent Document 3] German Patent No. 10151491 (Patent Document 4) International Publication No. Specification No. 2005/1 23749 [Non-Patent Document 1] Eur. J. Org. Chem., 3095 (2005) [Non-Patent Document 2] J. Am. Chem. Soc. 84, 3 05 8 (1 962) [Non Patent Document 3] Chimia; Chemie Report, 58(3), 200927888 138 (2004) [Non-Patent Document 4] J. Fluorine Chem., 112, 287 (2001) [Non-Patent Document 5] Tetrahedron, 56, 3399 (2000) SUMMARY OF THE INVENTION [Disclosure of the Invention] The present invention solves the above problems, and provides an industrially applicable manufacturing method and novelty for obtaining a sulfur monofluoride benzene compound in a simple and safe manner by easily obtaining a raw material. The sulfur pentafluoride benzene compound is a problem. In other words, the present invention provides the following [1] to [6]. [1] A method for producing a sulfur pentafluoride-based benzene compound represented by the following general formula (3), characterized in that the sulfur pentafluoride-based compound represented by the following general formula (1) is selected from the following general formula (2) A compound of one or more compounds represented by the compound is reacted.

(wherein A is a halogen atom, an organic sulfonyloxy group, _〇h, _Ch2〇h

'-C^CH > -ChX (X is a base with detachment), -BY2 (γ is a radical or alkoxy group having a carbon number of 1 to 10, 2 oximes may be the same or different, γ is a hospital oxygen The base time 'may have a cyclic structure in which two alkyl groups on the alkoxy group are bonded to each other), and the hydrogen atom on the benzene ring may be substituted by a crypto atom, an alkyl group, a cycloalkyl group, a aryl group or an aryl group) -8 -

200927888 [Chem. 2] R1OH, r1ch2oh, r1sh, r1cooh, r1coor2, r1cox, (R^OfeO, R1HC=CH2, R1C5CH, R1CHO, R1NH2i R1x, (2) r1ch2x, r1by2 (wherein R1 may have a substituent Carbon number 1 to 20, alkane 3 number 3 to 25 cycloalkyl group, carbon number 7 to 20 aralkyl group, carbon number 6 to aryl group or carbon number 2 to 20 heteroaryl group, R 2 type carbon number 1~ 6 alkane: , Y system is the same as above) [Chemical 3]

R1—Z

(3)

(wherein R1 is the same as defined above, and Z is selected from the group consisting of -0, -OCH2-, -CH20-, -S-, -COO-'-OCO-, -CONH CH = N-, -N = CH -, -NHCO-, -HC = CH-, -C = C-link n is 0 or 1). [2] A pentafluorinated benzene compound represented by the following general formula (4) or (5). ❿ [Chemical 4]

Except for the case of propyl and η-pentyl) [3] Sulfonyl pentasulfide represented by the following general formula (6): S, X group of carbon 25, η - -9 of sulfur group (6) (wherein R1 is the same as defined above) [4] A sulfur pentafluoride-based benzene compound represented by the following general formula (7) or (8). [Chemical 6]

R1

Sf5 r1^CK^v^SF5 (7)

(wherein R1 is the same as defined above) [5] A thiosulfonium benzene compound represented by any one of the following formulas (9) to (13).

-10- 200927888 [化7]

C5H11

(11)

〇5Η11

SFs (13) (9) (10) (12) [6] A pentafluorobenzene compound which is not represented by any one of the following formulas (14) to (18). [化8]

(14)

(15)

(16)

(17)

(18) (wherein R4 represents an alkyl group having 2 to 12 carbon atoms) -11 - 200927888 According to the present invention, it is possible to provide a sulfur monofluoride benzene benzene by a simple and safe method by easily obtaining a raw material. The compounds are suitable for use in industrial manufacturing processes and novel sulfur oxysulfide compounds. [Best Mode for Carrying Out the Invention] The production method of the present invention is a method for producing a sulfur pentafluoride-based benzene compound represented by the following general formula (3), which is characterized by pentafluorination represented by the following general formula (1) The thiobenzene compound is reacted with one or more compounds selected from the group consisting of compounds represented by the following general formula (2). The sulfur pentafluoride-based benzene compound represented by the general formula (1) has the following chemical structure. [Chemistry 9]

In the formula, A represents a halogen atom, an organic sulfonyloxy group, -OH, -CH2OH, -SH, -NH2, -COOH, -CHO, -HC = CH2, -C = CH, -CH2X (X has The base of the detachment), -BY2 (the γ system represents a hydroxyl group or an alkoxy group having a carbon number of 1 to 10, and 2 Y may be the same or different, and when γ is an alkoxy group, it may have an alkyl group on 2 alkoxy groups. a ring structure bonded to each other). The hydrogen atom on the benzene ring may be a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 2 carbon atoms or Substituted by a heteroaryl group having 2 to 20 carbon atoms. The compound group represented by the general formula (2) is a compound having one of the following chemical structures-12-200927888 R10OH, R^HaOH, R1SH, R1COOH, R1COOR2, R1COX, (R1CO)z〇, R1HC=CH2 , R1C^H, R1CHO. R1NH2, R1X, (2) R1CH2X. r1by2 (wherein R1 may have an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 25 carbon atoms, and a carbon number of 7 a aralkyl group of -20, an aryl group having 6 to 25 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms, and X and Y are the same as defined above) & The "base having detachment" shown by X is not particularly limited as long as it is substantially detachable. Specific examples of X include a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; an aryl group such as an alkylsulfonyloxy group such as a methanesulfonyloxy group; a benzenesulfonyloxy group; and a p-toluenesulfoxy group. An organic sulfonyloxy group such as a sulfonyloxy group or a trifluoromethanesulfonyloxy group; an oxycarbonylalkyl group (—0C0R group, etc.), a trialkylcarbenyl group (-SiR3 group (R system represents a carbon number of 1 to 1) 〇 烷基 alkyl)) and so on. When the compound represented by the formula (2) is RiCOX, X is preferably a chlorine p atom 'R> X or WdX, and X is preferably a bromine atom or an iodine atom, more preferably an iodine atom.

In addition to the above, A may be an equivalent delocalization group (e.g., a halocarbonyl group, a halosulfonyl group, a diazo group, etc.) (see, for example, E. Negishi, "Handbook of ORGANOPALLADIUM CHEMISTRY for 〇rganic Synthesis" , Vo 1.1, WILEY INTERSCIENCE, ii 33 page, 2002). The sulfur pentafluoride-based benzene compound represented by the general formula (3) has the following chemical structure. R13 (wherein R1 is the same as defined above, and Z is selected from the group consisting of -Ο-, -OCH2-, -CH20-, -S-, -COO-, -OCO-, - Conjunction groups of CONH-, -CH=N-, -N=CH-, -NHCO-, -HC=CH-, -C^C·, n is 0 or 1).具体 Specific examples of the method for producing the pentafluorosulfide benzene compound represented by the general formula (3) of the present invention will be described below. (1) Production Example 1 Production Example 1 is characterized in that a hydroxypentafluorobenzene compound and a carbonyl compound are reacted in the presence of a dehydrating agent as shown in the following reaction formula. In other words, in the general formula (1), A is -OH, and the compound represented by the general formula (2) is selected from the group consisting of R^COOH'R^COX, (I^CCOzCKR1, 瘳

SF5 (3) X is one or more compounds of the same type as described above, and Z of the general formula (3) is a reaction of -COO-. [化 12]

HO (1a) SF« R1COOH, R1C0X. {^00)2〇 Dehydrating agent R1COO'

Sf5 (3a) In the general formula (la), any hydrogen atom on the benzene ring may be substituted by an alkyl group, a cycloalkyl group, an arylalkyl group or an aryl group. Further, the substrate may be substituted with a group other than the substituent (electron attracting group or electron donating group) as long as it does not affect the reactivity of the production example 1. -14- 200927888 The carbonyl compound used in the reaction of Production Example 1 is, for example, one or more selected from the group consisting of a carboxylic acid (Wcooh), a carboxylic acid halide (Ricox), and a carboxylic acid anhydride ((Ric(R) 2). R1 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, a carbon number of 3 to 25, preferably a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carbon number of 6~ 25, preferably an aryl group having 3 to 25 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, and X is a group having the above-mentioned detachability. The alkyl group has, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or the like having a carbon number of 1 to 20, preferably a carbon number of 1 to 1 〇. Alkyl group. The cycloalkyl group is, for example, a cycloalkyl group having a carbon number of 3 to 20, preferably a carbon number of 3 to 10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl 'cyclohexyl group, a cycloheptyl group or a cyclooctyl group. The cycloalkyl group which may have a substituent such as a dicyclohexyl group having a total carbon number of 12 to 25 and having a carbon number of 3 to 10 or a total of carbon having a carbon number of 3 to 10 A number of 12 to 25 phenylcyclohexyl groups. The aralkyl group has, for example, an aralkyl group having a carbon number of 7 to 20, preferably 7 to 10 carbon atoms, such as a benzyl group, a phenethyl group or a phenylpropyl group. The aryl group is, for example, an aryl group having a carbon number of 6 to 20, preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group or a fluorenyl group. The aryl group which may have a substituent is, for example, an alkylaryl group having a carbon number of 6 to 20, preferably a carbon number of 6 to 10, more specifically, for example, p-tolyl, p-xylyl, having a carbon number of 3 ～1〇〇 alkyl or alkoxy group having a total carbon number of 12 to 25, a biphenyl group having a carbon number of 3 to 10 or an alkoxy group having a total carbon number of 12 to -15-200927888 25 cyclohexylbenzene Base. The aforementioned heteroaryl group is, for example, a furyl group, a benzofuranyl group, a pyrrolyl group, a thiol group, a thienyl group, a benzothienyl group, an oxazoline group, a pyrazolinyl group, a pyridyl group, a quinolyl group, a pyrimidinyl group, The thiadiazole group or the like has a carbon number of 2 to 20, preferably a heteroaryl group having 2 to 10 carbon atoms. The substituent may, for example, be a substituent formed by a carbon atom, a substituent formed by an oxygen atom, a substituent formed by a nitrogen atom, a substituent formed by a sulfur atom, or a halogen atom. The substituent formed by the above carbon atom, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a ring; a cycloalkyl group such as heptyl; an alkenyl group such as a vinyl group, an allyl group, a propenyl group or a cyclopentenyl group; a heterocyclic ring such as a quinolyl group, a pyridyl group, a pyrrolidinyl group, a pyrrolyl group, a furyl group or a thienyl group; An aryl group such as a phenyl group, a tolyl group, a fluorophenyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group; an ethyl fluorenyl group, a propyl fluorenyl group, an acrylonitrile group, or a trimethyl ethane group; a mercapto group (which may be acetalized); a carboxyl group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a phenoxy group; a fluorenyl group such as a cyclohexylcarbonyl group, a benzamidine group, a naphthoquinone group or a tolylhydryl group; An aryloxycarbonyl group such as a carbonyl group; a halogenated alkyl group such as a trifluoromethyl group; and a cyano group. a substituent formed by the above oxygen atom, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group or a benzyloxy group; An aryloxy group such as a phenoxy group, a tolyloxy group or a naphthyloxy group. a substituent formed by the aforementioned nitrogen atom, for example, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a methylethylamino group, a methylpropylamino group a second amino group of methylbutylamino group, diphenylamino group, etc. - 200927888; N-methyl-N-methanesulfonyl fluorenylamine, N-methyl-N-acetamide a sulfhydryl group; a heterocyclic amine group such as morpholinyl, piperidinyl, piperazinyl, pyrazolidinyl, pyrrolidinyl, fluorenyl or the like; an imine group. a substituent formed by the aforementioned sulfur atom, for example, a thioalkoxy group such as a thiomethoxy group, a thioethoxy group or a thiopropoxy group; a thiophenoxy group, a thiotolyloxy group, A thioaryloxy group such as a thionaphthyloxy group. The above substituents contain various isomers (the same applies hereinafter). The above-mentioned group having a detachment property is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Further, the hydroxypentafluorobenzene benzene compound used in the reaction of Production Example 1 can be reacted with a hydroxy compound by, for example, the following reaction formula, and then reacted with a hydroxy compound. The resulting compound is obtained by a deprotection reaction. x1〇-sFs -^PO〇-sF5 ssi Η00"δΡ5 (1a) (wherein, X1 represents a halogen atom, and lanthanoid represents a protecting group. Any hydrogen atom on the benzene ring may be alkyl , a cycloalkyl group, an aralkyl group or an aryl group) The amount of the carbonyl compound used in the reaction of the production example 1 is 1 molar for the hydroxypentafluorobenzene compound, preferably 〇 5 to 20 moles. More preferably 0.9 to 10 moles, and especially preferably 1.0 to 5 moles. The dehydrating agent used in the reaction of Production Example 1 is a compound which promotes a condensation reaction of a carbonyl compound with an alcohol. The dehydrating agent to be used is preferably a dehydrating agent which does not affect the pentafluorosulfide group. The specific compound is, for example, a mineral acid such as hydrochloric acid, hydrogen bromide or sulfuric acid; a clay mineral such as acid clay; amberlite (trade name), dowex. (trade name), diaion. (trade name), and Deniolite (trade name). , an acid-expanding cation exchange resin such as Lewatit (trade name), Sumikaion (trade name); a fluorinated sulfonic acid resin such as nafion; an inorganic oxide such as cerium oxide alumina, zeolite, vanadium oxide or the like; a heteropoly acid; Halogenated sulfoniums such as sulfinium chloride and brominated sulfonium; organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, hexanesulfonic acid and trifluoromethanesulfonic acid; 2-methyl-6-nitro An acid anhydride such as benzoic anhydride; a phosphorus compound such as diphenylphosphine azide or diethyl cyanophosphate; 4-(4,6-dimethoxy-1,3,5-triazine-2- Triazine compound such as 4-methylmorpholine gun chlorine hydrate; dicyclohexylcarbodiimide, 1-ethyl-3-(dimethylaminopropyl)carbodiimide or a salt thereof A carbodiimide compound (which can be an acid salt) such as an acid salt. Among these, a sulfonic acid type cation exchange resin, a carbodiimide compound, an inorganic acid, more preferably a carbodiimide compound, and particularly preferably 1-ethyl-3-(dimethylaminopropyl group) is preferably used. Carbodiimide hydrochloride. These dehydrating agents can be used singly or in combination of two or more. The amount of the dehydrating agent used is 1 mM for the hydroxypentafluorothiobenzene compound, preferably 0.001 to 20 moles, more preferably 0.01 to 1 mole, and particularly preferably 〇. 1 to 5 moles. The reaction of Production Example 1 is preferably carried out in the presence of a solvent, and the solvent to be used is not particularly limited as long as it does not inhibit the reaction. For example, water: alcohols such as methanol, ethanol, isopropanol, t-butanol; tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, pyridine, a heterocyclic amine such as quinoline-18-200927888; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, a guanamine such as N-methylpyrrolidone; a urea such as 1,3-dimethyl-2-imidazolidone or 1,3-dimethylimidazolidin-2,4-dione; Sub-mills; mills such as butyl sulphate; nitriles such as acetonitrile and propionitrile; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane; benzene, An aromatic hydrocarbon such as toluene or xylene; a halogenated aromatic hydrocarbon such as chlorobenzene or dichlorobenzene; or a halogenated aliphatic hydrocarbon such as dichloromethane or chloroform. Among them, ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and halogenated aliphatic hydrocarbons are preferred, and ethers and halogenated aliphatic hydrocarbons are more preferred, and halogenated aliphatic hydrocarbons are particularly preferred. These solvents may be used singly or in combination of two or more. The solvent is used in an amount of preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, particularly preferably 1 to 30 m 1 ° for the hydroxypentafluorobenzene benzene compound lg. The reaction system of the production example 1 is, for example, a hydroxyl group. The reaction is carried out by mixing a sulfur pentafluoride benzene compound, a carbonyl compound, a dehydrating agent, and a solvent, and performing a reaction such as a reaction under stirring. The reaction temperature at this time is preferably -50 to 20 (TC, more preferably -20 to 150 ° C, particularly preferably -10 to 120 ° C, and the reaction pressure is not particularly limited, and is usually carried out under normal pressure or under pressure. In the reaction of Production Example 1, the by-product or the water present may be reacted by discharging the water out of the reaction system by, for example, azeotropic dehydration, etc. Further, an additive which improves the reaction rate of Production Example 1 may be contained ( For example, an organic amine such as 4-dimethylaminopyridine or triethylamine. -19- 200927888 The pentafluorination can be obtained by the reaction of Production Example 1 after the reaction is completed, for example, by neutralization, extractive distillation, Recrystallization, crystallization, sublimation, column chromatography, etc. Separation and purification. In the general formula of a thiosulfate-based benzene compound obtained by the reaction of Production Example 1, the 1-1 to the liquid crystal phase are useful. Compound, Example I-1, 3 compound. ❹ [Chemical 14]

(In the formula, R1 is the same as described above, except for the case of propyl group and η-pentyl group.) In general formulas (4) and (5), a particularly preferred carbon number is 2 to 12, preferably carbon number 3. ~10 yard compound. (2) Production Example 2 Production Example 2 was carried out in the presence of a dehydrating agent in the presence of a dehydrating agent as shown in the following reaction formula. In the general formula (1), hydrazine is -COOH, and -compound is R^OH. And Z of the general formula (3) is a thiobenzene compound, but the general method of filtering, concentrating, and steaming is carried out by (4) or (5) indicating that the compound of 7 is shown and the novelty of 5 to 12 is (4) (5) In (4), R1 is characterized in that the n-compound R1 is a reaction of thiopenta pentasulfonated pentafluorothiobenzenesulfonic acid. In other words, the general formula (2) represents the reaction of -0C0-. -20- 200927888 [化15]

Sf5

;^SF5^ri〇2C "1b> (3b) In the general formula (lb), any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. Further, as long as it is a group which does not affect the reactivity of Production Example 2, it can be substituted with a group other than the above substituent (electron attracting group or electron donating group). The hydroxy compound used in the reaction of Production Example 2 is represented by RhH. R1 is the same as that described in Production Example 1. Specific examples thereof include alkyl alcohols such as methanol, ethanol, isopropanol, η-butanol, t-butanol, tetracosyl alcohol, and (4'-pentyl-dicyclohexyl-4-yl)methanol; a cycloalkanol such as pentanol, cyclohexanol or 41-pentyl-dicyclohexyl-4-ol; benzyl alcohol, phenylethyl alcohol, [4-(4-pentyl-cyclohexyl)-phenyl]-methanol, Aryl alkanol such as (4.heptyl-biphenyl-4-yl)-methanol, (4·-decyloxy-biphenyl-4-yl)-methanol; phenol, cresol, 4-pentyl An aryl alcohol such as cyclohexylphenol. φ The thiosulfonylbenzene carboxylic acid compound used in the reaction of Production Example 2 can be obtained by, for example, a thiol pentafluorobenzene compound and a metal lithium reagent (for example, an alkyl group) as shown by the route a of the following formula: After the lithium is reacted, the obtained compound is reacted with carbon dioxide to obtain a reaction. Alternatively, a halogenated thiopentafluoride benzene compound is reacted with metallic magnesium to form a halogenated magnesium pentahafluoride benzene compound by reacting with carbon dioxide, as shown by path b of the following formula. -21 - 200927888 [Chem. 16] 雠a)

(path b) (wherein X1 represents a halogen atom, and R represents a hydrocarbon group. Any hydrogen atom on the benzene ring may be substituted by an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group). The amount of the hydroxy compound used is 1 mol of the thiosulfonate benzene carboxylic acid compound, preferably 0.5 to 20 mol, more preferably 0.9 to 10 mol, and particularly preferably 1. 〇~5. Moor. The dehydrating agent used in the reaction of Production Example 2 was the same as that of the user of Production Example 1. The dehydrating agent is used in an amount of from 0.001 to 20 mol, more preferably from 0.01 to 10 mol, particularly preferably from 0.1 to 5 mol, per mol of the thiosulfonylbenzene carboxylic acid compound. The reaction of Production Example 2 is preferably carried out in the presence of a solvent, and the solvent used is selected from those described in Production Example 1. Among them, ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and halogenated aliphatic hydrocarbons are preferred, and ethers and halogenated aliphatic hydrocarbons are more preferred, and halogenated aliphatic hydrocarbons are particularly preferred. These solvents may be used singly or in combination of two or more. The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, more preferably 1 to 3 Oml for the thiosulfonate benzenecarboxylic acid compound lg. The reaction system of the production example 2 is, for example, pentacene. The thiophenylene carboxylic acid compound, the hydroxy compound, the dehydrating agent and the solvent are mixed, and the reaction is carried out by a reaction such as a reaction in the state of -22-200927888 while stirring. The reaction temperature at this time is preferably -5 0 to 200 ° C, more preferably -2 0 to 150 ° C, particularly preferably -10 to 120 ° C, and the reaction pressure is not particularly limited, and is usually atmospheric or pressurized. Go on. In the reaction of Production Example 2, by-product or water present, for example, by azeotropic dehydration or the like, the water is discharged from the reaction system. Further, it may contain an additive (for example, an organic amine such as 4-dimethylaminopyridine or triethylamine) which increases the reaction rate of Production Example 2. After the completion of the reaction, the treatment can be carried out by the same method as that described in Production Example 1. Among the phosphorus pentafluoride benzene compounds represented by the general formula (6) obtained by the reaction of Production Example 2, the compounds of Examples II-1 to 3 are useful compounds which exhibit a liquid crystal phase, and the examples Π-1 to 7 are novel compounds. . [Chem. 17]

(wherein R1 is the same as defined above) In the general formula (6), a particularly preferred compound R1 is a thiosulfonium benzene compound having an alkyl group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms. . (3) Manufacturing Example 3

Production Example 3 is characterized in that a 2- or 4-difluoropentafluorobenzene compound and a hydroxy compound are reacted in the presence of a base as shown in the following reaction formula. In other words, in the general formula (1), A is a halogen atom substituted at the position of 2 or 4, and the compound represented by the general formula (2) is R1〇H 23-200927888 (R1 is the same as the above). Z of the general formula (3) is a reaction of -〇- which is substituted at the 2- or 4-position. [Chem. 18]

In the general formula (lc), 'X1 represents a quiescent atom, preferably a fluorine atom or a chlorine atom' is preferably a fluorine atom. Any hydrogen atom on the benzene ring is the same as the general formula (1), an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and carbon. The aryl group having 6 to 20 or the heteroaryl group having 2 to 20 carbon atoms is substituted. Specific examples of the 4-halopentafluoro-thiophenyl compound represented by the general formula (lc) are 4-fluoropentafluoropentabenzene, 4-chloropentafluorothiobenzene, 4-bromosulfur monosulfide. Benzobenzene, 4-iodopentafluorothiobenzene, and the like. Among these, 4-fluoropentafluorothiobenzene, 4-chloropentafluorothiobenzene, and more preferably 4-fluoropentafluorothiobenzene. Specific examples of the 2-halothiopentafluorobenzene compound represented by the general formula (lc) include 2-fluorothiopentafluorobenzene, 2-chloropentafluoropentabenzene, and 2-bromosulfur monosulfide. Benzobenzene, 2-iodopentafluoropentafluoride, and the like. Among these, 2-fluoropentafluoropentabenzene, 2-chloropentafluoropentabenzene, and more preferably 2-fluoropentafluorothiobenzene are preferable. The hydroxy compound used in the reaction of Production Example 3 is represented by Ι^ΟΗ. R1 is the same as that described in Production Example 1, and specific examples thereof are also the same. The amount of the hydroxy compound used in the reaction of Production Example 3 is 1 mol for the 2- or 4-halothiopentafluorobenzene compound, preferably 〇·8-20 mol-24-200927888, more preferably 0.9 to 15 moles, particularly preferably 1.0 to 10 moles. The base used in the reaction of Production Example 3 is, for example, an alkali metal hydroxide such as potassium hydroxide or the like; a salt such as sodium carbonate or potassium carbonate; sodium hydrogencarbonate or hydrogen carbonate; Alkali metal such as potassium, such as alkali hydrogen carbonate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, alkali metal alkoxide; lithium hydride, sodium hydride, Potassium hydride, hydrogenated or alkaline earth metal hydride; ethylamine, propylamine, butylamine, first amine, dimethylamine, diethylamine, dipropylamine, diamine, methylethylamine, methylpropylamine, diphenylamine The third, triethylamine, tributylamine, diisopropylethylamine or the like, a heterocyclic amine such as piperidine or pyridine. Among these, an alkali metal hydride is preferably used. These bases may be used singly or in combination of two or more kinds, and may also be used as a solution. The amount of the base used is 1 mol to 2- or 4-halopentafluoropentate, preferably 0.8 to 20 mol, more preferably 0 to 1.0 to 10 mol. The reaction of Production Example 3 was carried out in the presence of a solvent, and the specific examples were the same as those shown in Production Example 1. Preferably, it is a class of ureas, more preferably a guanamine or a urea. These are used in combination of two or more. The solvent is used in an amount of lg, preferably 0.5 to 100 ml, more preferably 0.7 to sodium, alkali metal hydroxide; phosphoric acid trisodium phosphate; methanol t - alkali metal aniline such as potassium butoxide or the like, isopropylamine such as benzylamine, dibutylamine, trimethylamine amine, pyrrolidine, preferably sodium hydride can be used as an organic solvent to dissolve thiobenzene. 9 to 15 moles Preferably, the solvent is ether, the guanamine solvent can be sulfonated alone or thiophenyl sulfonated 75ml, particularly preferably -25-200927888 1 ~ 5 0ml ° The reaction system of the production example 3, for example, 2- or 4-halogen The reaction is carried out by mixing a pentafluorosulfide-based benzene compound, a hydroxy compound, a base, and a solvent, and performing a reaction such as a reaction under stirring. The reaction temperature at this time is preferably -20 to 200 ° C, more preferably -10 to 150 ° C, particularly preferably 0 to 120 ° C, and the reaction pressure is not particularly limited. The 2- or 4-halothiosulfate benzene compound can be obtained by the reaction of Production Example 3, but after the reaction is completed, for example, by neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, The general method of sublimation, column chromatography, and the like is carried out for isolation and purification. The 4-oxopentafluoropentafluorobenzene compound obtained by the reaction of Production Example 3 is shown in the above general formula (3c), and the specific compound thereof is, for example, 4-methoxypentafluorothiobenzene, 4 -ethoxylated thiophenyl benzene, 4-propoxy thiosulfonyl benzene, 4-butoxy thiophenyl benzene, 4-cyclohexyloxy thiosulfonyl benzene, 4-benzyl Oxythiopentafluorobenzene, 4-phenoxypentafluoropentabenzene, 4-[4-(4-pentyl-cyclohexyl)-phenoxy]-pentafluorothiobenzene, 4- (4'-pentyl-dicyclohexyl-4-oxy)-thiosulfonylbenzene, 4-[4-(4-pentylcyclohexyl)benzyloxy]-thiosulfonate, 4- (4'-pentyl-dicyclohexyl-4-ylmethoxy)-thiosulfonylbenzene, 4-tetradecylpentafluoropentabenzene, 4-(4'-heptyl-linked Phenyl-4-ylmethoxy)-thiosulfonylbenzene, 4-(4'-nonyloxy-biphenyl-4-ylmethoxy)-thiosulfabenzene benzene, and the like. The 2-oxopentafluoropentafluorobenzene compound obtained by the reaction of the present invention is shown in the above general formula (3c), and specific compounds thereof are, for example, 2-methoxypentafluorothiobenzene, 2-B. Oxythiopentafluorobenzene, 2-propoxy-5-26- 200927888 benzene fluoro pentathiooxide fluorohexanyl-2-yl. phenylbenzene 2-yl, thiophenanyl fluorosulfurization Fluorooxo-penta-T-based 2 oxo, benzylbenzene 2-yl, thiophenoxy fluorothiophene, 2-[4-(4-pentyl-cyclohexyl)-phenoxy]-pentafluorothiobenzene , 2-( 4'-pentyl--•cyclohexyl-4-oxy)-penta-sulfurylbenzene, 2-[4-(4-pentylcyclohexyl)benzyloxy]-pentafluorosulfide Benzobenzene, 2-(V-pentyl-dicyclohexyl-4-ylmethoxy)-thiosulfabenzene benzene, 2-tetracosylpentafluoropentabenzene, 2- (4'· Heptyl-biphenyl-4-ylmethoxy)-thiosulfonylbenzene, 2-(4'-decyloxy-biphenyl-4-ylmethoxy)-thiosulfabenzene benzene Wait. Among the phosphorus pentafluorobenzene compounds represented by the general formula (7) or (8) obtained by the reaction of Production Example 3, the compounds of Examples III-8 and 11 are useful compounds which exhibit a liquid crystal phase, and Examples III-1 to 1 4 are novel compounds. [Chem. 19] Ο

(7) SF5 (8) (wherein R1 is the same as described above). In the general formulae (7) and (8), a particularly preferable compound R1 has a carbon number of 2 to 12, preferably a carbon number of 3 to 10. Alkyl thiosulfonate benzene compound. (4) Production Example 4 Production Example 4 is characterized by reacting a halogenated thiopentafluorobenzene compound with a vinyl compound in the presence of a metal compound as shown in the following reaction formula to 27-200927888. In other words, in the general formula (1), A is a halogen atom, and the compound represented by the general formula ( ) is RiHCzd, and the general formula (3) is a reaction of HC = CH- [Chem. 20]

The halogenated thiosulfate benzene compound of Production Example 4 is represented by the general formula. X1 is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or an iodine atom. Any hydrogen atom on the benzene ring may be substituted with a substituent, a cycloalkyl group, an aralkyl group or an aryl group. The vinyl compound used in the reaction of Production Example 4 is represented by F^HCsCHi. R1 is the same as that described in Production Example 1. The amount of the vinyl compound used in the reaction of Production Example 4 is preferably from 0.8 to 20 mol, more preferably from 0.9 to 15 mol, more preferably from 1.0 to 15 mol, more preferably from 1.0 to 20 mol, more preferably from 1.0 to 20 mol per mol of the thiopentafluorobenzene compound. ~10 m. The alkali used in the reaction of Production Example 4 was the same as that described in Production Example 3. Among them, an alkali metal carbonate or an amine is preferred, and potassium carbonate is more preferred, and triethylamine is particularly preferred. These bases may be used singly or in combination of two or more kinds, and may also be used as an aqueous solution or an organic solvent solution. The amount of the base to be used is preferably 0.5 to 5.0 moles, more preferably 0.7 to 4.0 moles, and particularly preferably 1.0 to 3.0 moles, to the halogenated thiosulfate benzene compound. The reaction of Production Example 4 is preferably carried out in the presence of a solvent, and the solvent used is the same as that described in Production Example 1. Among them, nitriles, cesium-28-200927888 amines, ethers, and more preferably acetonitrile, hydrazine, hydrazine-dimethylformamide, 1,4-dioxane, particularly preferably hydrazine, hydrazine- Dimethylformamide, 1,4-dioxane. These organic solvents may be used singly or in combination of two or more. The solvent is used in the amount of 5% of the halogenated thiosulfate benzene compound lg, preferably 0.1 to 5 〇 ml', more preferably 0.2 to 30 ml, particularly preferably 0.3 to 20 ml. Examples of the compound include palladium acetate, bis(acetate) bis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium or the like. Acid salt; palladium chloride such as palladium chloride; tetrakis(triphenylphosphine)palladium, tris(diphenylacetone)dipalladium, nitrogen-containing heterocyclic carnitene palladium complex (eg, dichloro{1,3- Bis(2,6-diisopropylphenyl)imidazol-2-ylidene} (3-chloropyridyl)palladium, allyl chloride {1,3-bis(2,6-diisopropylphenyl) Imidazol-2-ylidene}palladium, i,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, 1,3- a palladium complex of bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (1,4-naphthoquinone)palladium dimer; palladium/carbon, palladium/barium sulfate, palladium- a palladium-supporting compound such as platinum/carbon; a nickel compound of bis(cyclopentadienyl)nickel, dichlorobis(triphenylphosphine)nickel; a chlorine (monophenyl scale)己 院 ) 铭 铭 : : : : : : : : : : : : : : : : : : ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Among these, a palladium compound is preferred, a palladium complex is more preferred, and a nitrogen-containing heterocyclic carmine palladium complex is particularly preferred. More specifically, for example, dichloro {1,3_bis ( 2,6-diisopropylphenyl)imidazol-2-ylidene} (3-chloropyridyl) pin. These metal compounds may be used singly or in combination of two or more. -29- 200927888 (Triphenylphosphine) palladium can be used directly or in the reaction system by using palladium chloride and triphenylphosphine in the reaction system. The above metal compound can be used directly for the halogenated sulfur pentoxide. The benzene compound 1 mole, preferably 〇_1 mol %~100 mol%, more preferably 0.1 mol%~50 mol%, particularly preferably 0.1 mol%~20 mol%. ❹ ❹ The reaction of Production Example 4 may contain a phosphine ligand or a related mobile catalyst (for example, Tetrahedron, 52, 10113 (1 996 )) in order to control the reactivity. The ligand is, for example, a trialkylphosphine such as tri-n-butylphosphine, tri-t-butylphosphine or tricyclohexylphosphine; a triarylphosphine such as triphenylphosphine or trimethylphenylphosphine; or 1,4-double A diphosphine such as (diphenylphosphino)butane or 1,1'-bis(diphenylphosphino)ferrocene is preferably a trialkylphosphine, more preferably a tri-t-butylphosphine. Further, related mobile catalysts used are, for example, tetra-n-methylammonium chloride, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, Tetra-n-butylammonium tribromide, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylammonium nitrate, methane Tetra-n-butylammonium sulfonate, tetra-n-butylammonium trifluoromethanesulfonate, cyanotetra-n-butylammonium, hydroxytetra-n-butylsaurohydrate, hexa-amino acid tetra- Η-butyl form, tetra-n-butylammonium tetraruthenate, tetra-n-butylammonium perchlorate, and the like. These phosphine ligands or related mobile catalysts may be used singly or in combination of two or more, and each may also be a hydrate. Phosphine ligands can also be combined with related mobile catalysts. The use of the aforementioned phosphine ligand or related mobile catalyst is for the metallization -30-200927888 compound, particularly the palladium atom of the palladium compound, 1 mole, preferably 0 to 100 moles, more preferably 0 to 50. Moer, especially good for 0~10 m. The reaction of Production Example 4 is carried out, for example, by mixing a halogenated thiopentafluorobenzene compound, a vinyl compound, a metal compound, a base, and an organic solvent, and carrying out a reaction under stirring. The reaction temperature at this time is preferably from 0 to 200 ° C', more preferably from 20 to 150 ° C, and the reaction pressure is not particularly limited. 〇 After the reaction is completed, the treatment is carried out in the same manner as in Production Example 1. Among the five gasified thiobenzene compounds of the general formula (3d) table τκ obtained by the reaction of the production example 4, the compounds of the formulas (9) and (10) are useful novel compounds which exhibit liquid crystal phases (described in the implementation). Examples IV-1 and 2). [Chem. 21]

(5) Production Example 5 Production Example 5 is characterized in that a vinyl pentafluorothiobenzene compound is reacted with a compound having a leaving group, a metal compound and a base as shown in the following reaction formula. In other words, in the general formula (1), A is -HC = CH2, the compound represented by the general formula (2) is WX, and the general formula (3) is a reaction of -HC = CH-. -31 - 200927888 [化23⁄4 h2c=ch

Dd)

R'X metal compound r1|_IC=CH

(3d) In the general formula (Id), any hydrogen atom on the benzene ring may be an alkyl group, a ring-based group, a aryl group or an aryl group, a halogen atom (particularly a group which does not react with an alkenyl group) such as a fluorine atom. ) replaced. In addition, when it is a group which does not particularly affect the reactivity of Production Example 5, it can be substituted with a group other than the above substituent (electron attracting group or electron donating group).化合物 The compound having a leaving group used in the reaction of Production Example 5 is represented by the general formula Wx. In this Wx, Ri is the same as that described in Production Example 1. The X system indicates the above-mentioned group having detachability. The amount of the vinyl pentafluoride-based benzene compound used in the reaction of Production Example 5 is preferably from 0.8 to 20 mol, more preferably from 0.9 to 15 mol, to 1. 〇~1〇莫耳. The base used in the reaction of the present invention is the same as that described in Production Example 4. Among these, it is preferred to use an alkali metal carbonate or an amine, more preferably potassium carbonate or triethylamine. These bases may be used singly or in combination of two or more kinds, and may also be used as an aqueous solution or an organic solvent solution. The amount of the base used is preferably from 0.5 to 10 moles, more preferably from 0.8 to 5.0 moles, particularly preferably from 1.0 to 3.0 moles, per mole of the vinyl pentafluorobenzene compound. The reaction of Production Example 5 is preferably carried out in the presence of a solvent, and the solvent used is the same as that described in the production example. Preferably, a nitrile or a guanamine is used, more preferably acetonitrile, N,N-dimethylformamide, I,4-dioxane, or -32-200927888, preferably N,N-dimethyl Formamide, l, 4-dichotomy. These organic solvents may be used singly or in combination of two or more. The solvent is used in the reaction of the production example 5 with respect to the ethyl thiopentafluoride benzene compound lg, preferably 〇~l〇〇ml, more preferably 0.1 to 50 ml, particularly preferably 0.2 to 30 ml. Specific examples and preferred examples of the metal compound to be used are the same palladium compound or ruthenium compound as those described in Production Example 4, and more preferably a palladium compound. The metal compound is used in an amount of from 0.001 to 5 moles, more preferably from 0.005 to 1 mole, more preferably from 0.01 to 0.5 moles, per mole of the vinyl pentafluorobenzene compound. The reaction of Production Example 5 may contain a phosphine ligand or a related mobile catalyst in order to control the reactivity, and the phosphine ligand or the related mobile catalyst system used is the same as that described in Production Example 4. The phosphine ligand or the related mobile catalyst is used in an amount of 1 mole to the metallization compound, particularly the palladium atom of the palladium compound, preferably 0 to 100 Torr, more preferably 〇10 to 10 moles. . The reaction of Production Example 5 is carried out, for example, by mixing a vinyl pentafluorobenzene compound, a halogen compound, a palladium metal compound, a base, and a solvent, and carrying out a reaction under stirring. The reaction temperature at this time is preferably from 0 to 200 ° C, more preferably from 10 to 180 ° C, particularly preferably from 20 to 150 ° C. The reaction pressure is not particularly limited, and the treatment is the same as in Production Example 1 after the reaction is completed. The general method is to carry out. -33- 200927888 The compound of the formula (1 1 ) (Example V-2) is useful for exhibiting a liquid crystal phase in the sulfur pentafluoride benzene compound represented by the general formula (3d) obtained by the reaction of Production Example 5. The compounds, the compounds of Examples V-1 to 5, are novel compounds. [Chem. 23] C3H7

(11) 〇(6) Production Example 6 Production Example 6 is a boron compound, a trimer anhydride or an equilibrium mixture thereof, or a boron compound (le) such as a boric acid ester, and a halogenated pentafluoro group, as shown in the following formula. A thiolated benzene compound is a production example of an aryl-substituted thiosulfabenzene benzene characterized by a reaction in the presence of a metal compound and a base. In other words, in the general formula (1), A is a halogen atom, and the compound represented by the general formula (2) is a reaction of R^BY:' wherein the η of the general formula (3) is 0. [Chem. 24]

The specific example of the general formula (2a) is represented by the following formula, for example, (2a-1 and (2a-2) and (2a-3). [Chem. 25]

OH (2a-1)

The halogenated thiopentafluorobenzene compound of Production Example 6 is of the general formula (lc -34-

G

200927888) indicates that the same as those described in Production Example 4. The f3 group on the benzene ring is the same as the general formula (1), and may be a cycloalkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 7 to 20, a carbon number of 6 to 20 or a carbon number of 2 to 20. Heteroaryl substitution. The compound having a leaving group used in the reaction of Production Example 6 is represented by the formula i^BYa. In the r1by2, Ri is the same as the production example, and Y is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. γ can be an equilibrium mixture of terpolymer anhydrate of boric acid. Further, the system may be the same or different, and when Y is an alkoxy group, the two hospital groups may be bonded to each other and may have a ring structure. The amount of boric acid or ester used in the reaction of Production Example 6 is fluorinated thiobenzene 1 mol, preferably 0.5 to 20 mol, | 1 Torr, particularly preferably 1.0 to 5 mol. The reaction of Production Example 6 was carried out in the presence of a solvent, which was the same as that described in Production Example 1. Among them, preferred are hydrocarbons, guanamines, ureas, alcohols, flavonoids, waters, ethers, aromatic hydrocarbons, guanamines, ureas, alcohol ethers, and aromatic hydrocarbons. These solvents may be used singly or in combination. The solvent is used in an amount of 1 g to bromothiopentabenzene benzene, preferably 100 to 100 ml, more preferably 0.7 to 50 ml, particularly preferably 1 to 30 ml. The base used in the reaction of Production Example 6 and the production example 3 are preferably Phosphate, alkali metal carbonate, amine tripotassium phosphate, potassium carbonate, and triethylamine are used. These bases may be singly or in the form of a hydrogen atom S, an aryl group having 3 to 20 carbon atoms, and a compound having a hydroxyl group of 1 to 1 when the phase is a hydroxyl group. Preferably, it is 0.9~, and the ethers, aromas, ketones, and the like are more preferably used. It is better to use it in combination with -35- 200927888. It can also be used as an aqueous solution or an organic solvent solution. The amount of the base used is preferably 0.5 to 10.0 mol, more preferably 0.8 to 5.0 mol, and particularly preferably to 3.0 mol, for the halogenated thiosulfate compound. The metal compound used in the reaction of Production Example 6 was the same as that shown in Production Example 4. Among them, a palladium compound is preferred, and a palladium complex is more preferred. Tetrakis(triphenylphosphine)palladium and a nitrogen-containing heterocyclic carmine palladium complex are particularly preferred. A specific example of a nitrogen-containing heterocyclic carnation palladium complex is dichloro {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}(3-chloropyridyl)palladium. . These metal compounds may be used singly or in combination of two or more. The amount of the metal compound used is 1 mol for the halogenated thiosulfabenzene compound, preferably 0.1 mol% to 100 mol%, more preferably 0.1 mol% to 50 mol%, particularly preferably 0.1 mol% ~ 20 mol%. The reaction of Production Example 6 may contain a phosphine ligand or an associated mobile catalyst (see, for example, Tetrahedron, 52, 101 13 (1 996)) in order to control the reactivity. Specific examples are the same as in Production Example 4. The reaction of Production Example 6 is carried out, for example, by mixing a halogenated thiobenzenebenzene, a boric acid or an ester, a solvent, palladium, and a base, and performing a reaction under stirring. The reaction temperature at this time is preferably -50 to 200 ° C, more preferably -20 to 150 ° C, particularly preferably -10 to 1 Torr, and the reaction pressure is not particularly limited, and is usually under normal pressure or under pressure. get on. After the completion of the reaction, the treatment was carried out in the same manner as in Production Example 1. The compound of Examples VI_4 and 5, which is represented by the general formula (3e) obtained by the reaction of Production Example 6, is a useful compound of the liquid crystal phase. Examples VI_1 to 6 The compounds are novel compounds. (7) Production Example 7 Production Example 7 is a reaction of a compound of a thiopentaphenylbenzeneboronic acid or a terpolymer thereof or an equilibrium mixture thereof, or a boronic acid ester compound with a compound having a leaving group, as shown by the following formula A manufacturing example in which a substituted thiosulfate benzene compound is produced. In other words, 'A in the general formula (1) is -BY, and the compound represented by the general formula (2) is a reaction in which the general formula (3) has η of 0. R1 -X + y, bO~sf5 — rV〇^sfs (2b) Ϋ (le) (3e) The general example of the general formula (1 e ) is expressed by the following formula, for example (1 e- 1

(1e-2) In the reaction of Production Example 7, the compound WX having a leaving group was the same as in Production Example 5. The ΒΥ 2 system is the same as the manufacturing example 6. In the reaction of Production Example 7, the amount of the halogenated aryl group is preferably 0.5 to 20 moles, more preferably 0.6 to 10 moles, and particularly preferably 0.7 to 5. moles per mole of the boronic acid or ester. -37-200927888 The reaction of Production Example 7 is preferably carried out in the presence of a solvent, and the solvent used is the same as that described in Production Example 1. Among them, ethers, aromatic hydrocarbons, acid amines, ureas, alcohols, hydrazines, water, ketones, and more preferably ethers, aromatic hydrocarbons, guanamines, ureas, and the like are preferably used. Alcohols are particularly preferred as ethers and aromatic hydrocarbons. These solvents may be used singly or in combination of two or more. The solvent is used in an amount of 1 g to borneol-based thiosulfate benzene, preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, particularly preferably 1 to 30 ml. The base used in the reaction of Production Example 7 was the same as that shown in Production Example 3. Among them, preferred are phosphates, alkali metal carbonates, and amines, and more preferred are tripotassium phosphate, potassium carbonate, and triethylamine. These bases may be used singly or in combination of two or more, and may also be used as an aqueous solution or an organic solvent solution. The amount of the base to be used is preferably from 0.5 to 10.0 mol, more preferably from 0.8 to 5.0 mol, and particularly preferably from 1 to 0 to 3.0 m, for the borneol-based thiosulfate-based compound. q The metal compound used in the reaction of Production Example 7 was the same as that shown in Production Example 4. Among them, a palladium compound is preferred, and a palladium complex is more preferred, and tetrakis(triphenylphosphine)palladium is particularly preferred. These metal compounds may be used singly or in combination of two or more. The amount of the metal compound used is preferably from 0.1 mol% to 100 mol%, more preferably from 0. 1 mol% to 50 mol%, to the borneol-based thiosulfate-based benzene compound. It is especially good for 〇.丨莫耳. /. ~ 2 0 moles %. The reaction of Production Example 7 may contain a scaly ligand or an associated mobile catalyst (see, for example, Tetrahedron, 52, 10113 (-38-200927888 1 996)) in order to control the reactivity. Specific examples are the same as in Production Example 4. The reaction of Production Example 7 is carried out, for example, by a method in which a flavonoid-based sulfur pentafluoride is removed from a group, a solvent, a metal compound, and a base are reacted in a mixed state. The reverse is at -50 to 200 ° C, more preferably -20 to 150 ° C, and particularly preferably -10. There is no particular limitation on the pressure, and the reaction is usually carried out after the reaction at normal pressure or under pressure. Production Example 1 is described by a phase method. The novel compound of Example VII-1 was obtained from the general formula (3e) thiophenyl compound obtained by the reaction of Production Example 7. (8) Production Example 8 Production Example 8 was carried out by using a halogenated pentafluoride compound and an alkynyl compound in the presence of a metal compound and a base as shown in the following formula. In other words, in the general formula (1), A is a halogen atom, the compound represented by - is WCeCH, and the general formula (3) is Z. [Chem. 28] R1_H Ά% - (2c > (1c) R (3f) Production Example 8 The halogen-based thiosulfate-based benzene compound is represented by the same as that described in Production Example 4. The alkynyl compound used in the reaction of Production Example 8 is a base benzene having a mixture, and the reaction is preferably carried out at a suitable temperature, and the inversion is the same as the general expression of the pentafluoro compound. - General formula (2) | -C = the inverse general formula of C- (lc i^C^CH Table-39-200927888. wherein R1 is the same as that described in Production Example 1. The alkynyl group used in the reaction of Production Example 8 The amount of the compound is preferably from 0.5 to 10.0 mol, more preferably from 0.5 to 5.0 mol, particularly preferably from 〇5 to 2.0 mol, to the methoxysulfabenzene compound. The base used in the reaction is specifically the same as in Production Example 3. These tests may be used singly or in combination of two or more kinds, and may be used as an aqueous solution or an organic solvent solution. It is preferred to use an alkali metal carbonate or an organic base. More preferably, it is potassium carbonate, an organic amine, and particularly preferably a second-grade amine. The amount used in the foregoing test is 1 molar for the halogenated thiosulfate-based benzene compound, preferably 0.5 to 100 moles, more preferably It is 0.7 to 80 m, and particularly preferably 1.0 to 50 m. The reaction of Production Example 8 is carried out in the presence of a solvent. Specific examples are the same as in Production Example 1. Among these, it is preferred to use an amine, a nitrile or a guanamine 'more preferably a second-grade amine' acetonitrile, hydrazine, hydrazine-dimethylformamide. The solvent may be used singly or in combination of two or more. The solvent is used in an amount of 5% to 50 ml, more preferably 0.1 to 50 ml, particularly preferably 0.2 to 30 m, for the halogenated thiobenzene benzene compound lg. The metal compound used in the reaction of Production Example 8 is the same as that of Production Example 4. Among them, dichlorobis(triphenylphosphine)palladium, palladium chloride, palladium/carbon, dichlorobis(triphenylphosphine) is preferably used. Nickel, etc. The amount of the palladium compound used is 1 mM for the halogenated thiosulfabenzene compound, preferably 0.001 to 1 mol, more preferably 〇_〇〇2 to 0.3 mol. In order to control the reactivity, the phosphine coordination -40-200927888-based or related mobile catalyst, inorganic salt' specific example can be the same as in Production Example 4. In the reaction of Production Example 8, it is preferable to add as a touch The copper salt of the medium can be reacted for a short time at room temperature. The copper salt is, for example, copper iodide. I) 'Copper bromide (I), copper (I) chloride, copper (I) cyanide, copper (II) acetate. These copper salts may be used singly or in combination of two or more, each of which may be a hydrate. The phosphine ligand and the related mobile catalyst may be combined (refer to Non-Patent Documents 2 and 3). The phosphine ligand or the related mobile catalyst or copper salt is used in an amount of 1 mol to the palladium atom of the palladium compound. Preferably, it is 〇~1〇〇mol, more preferably 0~10 mol, and particularly preferably 0~5 mol. The reaction of the present invention is, for example, a halogenated thiosulfate benzene compound, an alkynyl compound, A method in which a palladium metal compound, a base, and a solvent are mixed and a reaction or the like is generated under stirring is carried out. The reaction temperature at this time is preferably from 0 to 200 ° C, more preferably from 20 to 150 ° C, and the reaction pressure is not particularly limited. After the completion of the reaction, the same general method as that described in Production Example 1 was carried out. In the sulfur pentafluoride-based benzene compound represented by the general formula (3f) obtained by the reaction of Production Example 8, the compound of Example VIII-4 is a useful compound showing a liquid crystal phase, and Examples VI-2 to 7, The compounds of 9 and 10 are novel compounds. (9) Production Example 9 Production Example 9 is represented by the following formula, and is characterized in that a halomethylene pentafluorobenzene benzene compound and a hydroxy compound are reacted in the presence of a base. For the general formula (1), 'A is a halomethyl group, and the compound represented by the general formula (2) is WOH'. The general formula (3) wherein Z is -〇CH2- 29]

R1OH (1f) 鹸

Sf5 (3g) In the general formula (If), X1 represents a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom. Any hydrogen atom on the benzene ring is the same as the specific example shown in Production Example 1. The hydroxy compound used in the reaction of Production Example 9 is represented by Ri 〇 H. The R1 system is the same as that shown in Production Example 1, and specific examples thereof are also the same. The amount of the hydroxy compound used in the reaction of Production Example 9 is preferably 0.5 to 20 moles, more preferably 0.8 to 10 moles, per mole of the halomethylene pentafluorobenzene compound. For 1 〇 ~ 5 〇 Mo Er. The base used in the reaction of Production Example 9 was the same as the specific example thereof and the production example 3. The base is used in an amount of from 1 to 20 moles, more preferably from 0.9 to 15 moles, more preferably from 1.0 to 10 moles, per mole of the halomethylpentafluorobenzenebenzene compound. The reaction of Production Example 9 is preferably carried out in the presence of a solvent, and the solvent used is the same as that described in Production Example 3. Among them, ethers, guanamines, and ureas are preferred, and ethers and guanamines are preferred, and ethers are particularly preferred. These solvents may be used singly or in combination of two or more. The solvent is preferably used in an amount of from 0.5 to 100 ml, more preferably from 1 to 50 ml, to the halomethylene pentafluorobenzene benzene compound. In order to promote the reaction of Production Example 9, it is preferred to use, as in Production Example 4, a related mobile catalyst or inorganic salt, and further to tetrabutylammonium iodide, potassium iodide or sodium iodide, and particularly preferably potassium iodide. These iodinated inorganic salts or related mobile catalysts may be used singly or in combination of two or more, each of which may be a hydrate. It is also possible to combine inorganic salts with related mobile catalysts. The inorganic salt or the related mobile catalyst is used in an amount of 1 mole to the halomethylidene pentafluoride benzene compound, preferably 0 to 100 moles, more preferably 0 to 50 moles, particularly preferably 0~1〇莫耳. The reaction of the present invention is carried out, for example, by mixing a halomethylpentafluorobenzene compound, a hydroxy compound, a base and a solvent, and reacting in a stirred state. The reaction temperature at this time is preferably 〇~200 °c, more preferably 20 to 150 °C, and the reaction pressure is not particularly limited. After the completion of the reaction, the treatment can be carried out in the same manner as in the description of Production Example 1. Further, among the pentafluorobenzene compounds represented by the general formula (3g) obtained by the reaction of Production Example IX, the compounds of Examples IX-1 to 6 are novel compounds. (10) Production Example 1 Production Example 1 The oxime system is characterized in that the amine thiopentafluorobenzene compound and the carboxylic acid are reacted in the presence of a dehydrating agent as shown in the following formula. In other words, in the general formula (1), 'A is -NH2, the compound represented by the general formula (2) is R^COOH, and the general formula (3) is a reaction of -CONH-. -43- 200927888

(wherein R1 represents a carbon number which may have a substituent: a fluorenyl group, a biphenyl group, a cyclohexylphenyl group, a dicyclohexyl group). In the general formula (lh), any hydrogen atom on the benzene ring may be ring-shaped. Alkyl, aralkyl or aryl substitution. Further, if it is a group which does not particularly affect the reactivity of the oxime, it may be substituted by an electron attracting group or an electron donating group other than the above substituent. In the general formula (3丨), a preferred example of R1 is p-tolyl, ρ· group, and has a carbon number of 2 to 12, preferably an alkyl group having 3 to 10 carbon atoms or a biphenyl group having carbon. The cyclohexylphenyl group having 2 to 12, preferably alkoxy group having 3 to 10 carbon atoms, and a bicyclohexyl group having 2 to 12 carbon atoms, preferably an alkyl group having 10 carbon atoms or an alkoxy group. The dehydrating agent used in the reaction of Production Example 10 was the same as that of the production example. The dehydrating agent is used in an amount of 1 mol to the thiosulfonate benzene carboxylate, preferably 0.001 to 20 mol, more preferably 0.01 Å, particularly preferably 0.1 to 5 mol. The reaction of Production Example 1 is carried out in the presence of a solvent. Specific examples of preferred solvents and preferred examples are the same as those described in Production Example 1. The solvent is used in an amount of lg, preferably from 0.5 to 100 ml, more preferably from 0.7 to 50 ml, particularly to 30 ml, for the ruthenium pentoxide ruthenium hydride. Production Example 1 The reaction of hydrazine is carried out, for example, by using a phenylalkyl group under an amine-based sulfur pentafluoride, a group of 10 (a xylene-oxyalkylene group or a number of 3 to 1 using an amidoxime~1 0 mo It is mixed with a amide compound, a carboxylic acid, a dehydrating agent and a solvent, and is produced under stirring.

The reaction is carried out by a method such as reaction. The reaction temperature at this time is preferably -50 to 200 ° C, more preferably -20 to 150 ° C, particularly preferably -10 to 120 ° C, and the reaction pressure is not particularly limited, and is usually carried out under normal pressure or under pressure. . In the reaction of Production Example 1, the by-product or the water present may be reacted by discharging the water out of the reaction system, for example, by azeotropic dehydration or the like. After the completion of the reaction, the treatment can be carried out in the same manner as in the general method described in Production Example 1. Among the carbonylaminothiopentafluorobenzene compounds represented by the general formulas (14) to (17) obtained by the reaction of Production Example 10, the compounds of Examples X-1 to 9 are novel compounds. [化31]

(In the formula, R4 represents an alkyl group having 2 to 12 carbon atoms) (1 1 ) Production Example 1 1 Production Example 1 1 is obtained by dehydrating an amine thiosulfate compound and an aldehyde compound as shown in the following formula The reaction is characterized by the presence of a agent. In other words, in the general formula (1), A is -NH2, and the compound represented by the general formula (2) is WCHO'. In the general formula (3), Z is -CH = N-. [化32]

(In the formula, R1 is the same as described above.) Production Example 11 is the same as Production Example 1 except that RiOOH is substituted with WCHO except for Production Example 10. The reaction conditions are also the same as in Production Example i. In the benzalkonium thiosulfate benzene compound represented by the general formula (18) obtained by the reaction of Production Example 11, the compound of the example 乂]: -!~2 is a novel compound. [化33]

(18)

(wherein R4 is the same as defined above) The compound of the present invention, particularly at least one selected from the group consisting of the above-mentioned formulas (9) to (i8), is contained in other liquid helium materials. And/or a non-liquid crystal material can be used as a liquid crystal display element such as a TN type, an STN type, an IPS type, an OC type, or a VA type. [Embodiment] [Embodiment] -46-200927888 Next, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited to the examples. The measurement of proton nuclear magnetic resonance (W-NMR) and chemical ionization mass spectrometry (CI-MS) was carried out under the following conditions. (!H-NMR) Measurement equipment: manufactured by JEOL Ltd., trade name: AL3 00 Measurement conditions: single pulse, room temperature (CI-MS)

Measuring machine: Hitachi, Ltd., a company established by the company, trade name: Μ8OB

Measurement conditions: double focusing type, reaction gas is isobutane, ion source temperature 180 ° C

Acceleration voltage 3kV, ionization voltage 70eV Example 1-1 (Synthesis of 4-{(trans,trans)-4'-ethylcyclohexyl-4-carbonyloxy}-thiosulphur pentoxide) To a 30 ml glass container, 4-hydroxypentafluoropentaphenyl hydrazine _22 g (1.0 mmol), (trans'trans)-4,-ethyl-dicyclohexyl-4-carboxylic acid 0.29 g ( 1.2 mmol), 1-ethyl-2-(dimethylaminopropyl)carbodiimide hydrochloride 〇.29g (丨·511111101), 4-dimethylaminopyridine 0.05g (0.4mmol) After 10 ml of dichloromethane, the mixture was reacted at room temperature overnight with stirring. After the reaction was completed, the reaction solution was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (Extension - 47-200927888 solvent; hexane / ethyl acetate = 95/5 (capacity ratio)) , 4-{〇1^118,4 3118)-4'-ethyl-dicyclohexyl-4-carbonyloxy}-pentafluorobenzene benzene 0.32 g of white solid (isolation yield; 73%) ). This compound is a novel compound represented by the following physical properties. 'H-NMR ( CDC13 ' δ ( ppm) ) ; 0_ 83 〜1.25 ( 14H,m ), 1.47~1.60(2H,m) , 1.71 〜1.88(6H,m) ' 2.12 〜2.17(2H,m ), 2.42 ~ 2.52 ( lH, m), 7.15 ~ 7.18 ( 2H, m), 7. 74 ~ 7.79 (2H, m) ❹ CI-MS ; 44 1 ( Μ ) Example 1-2 (4-{( Synthesis of 1^113,113118)-4'-11-propyl-dicyclohexyl-4-carbonyloxy}-thiosulfonylbenzene) (4&118,43113)-4'-11- 0.30 g (1.2 mmol) of benzyl-dicyclohexyl-4-residic acid was substituted for (trans,trans)-4'-ethyl-dicyclohexyl-4-carboxylic acid in Example 1-1, and Example 1 -1 was also reacted. As a result, 4-{(trans' trans)-4'-η-propyl-monocyclohexyl-4-carbonyloxy}-pentafluoropentabenzene was obtained as a white solid (yield: 61%). The physical properties of this compound are shown below. • H-NMR (CDCI3 ' δ (ppm) ); 0.85 〜1 .16 ( 14H,m ), 1.22~1.36(2H,m) , 1.47~1.59(2H,m) ' 1.70 〜1.88(6H,m) 2.12~2.17(2H,m), 2.42~2.52(lH,m), 7.15~7.18(2H,m), 7.74~7.79(2H,m) CI-MS; 455(M) -48- 200927888 Example Synthesis of 1-3(4-{(4&115,43115)-4,-11-butyl-dicyclohexyl-4-carbonyloxy}-thiosulfonylbenzene) using (trans,trans) - 4,-n-butyl-dicyclohexyl-4-carboxylic acid 0-32g (1.2mmol) is substituted for (trans,trans)-4'-ethyl-dicyclohexyl-4-carboxylic acid in the example i_i, Example ΐ-1 was reacted in the same manner. As a result, 4-{(trans,trans)-4'-η-butyl•dicyclohexyl-4-carbonyloxy}-thiopentafluorobenzoquinone.31 g (yield: 66%) was obtained as a white solid. ❿ )0 This compound is a novel compound represented by the following physical properties. j-NMR (CDC13, δ (ppm)); 0.84 to 1.29 (18H, m), 1.47~l_59 (2H, m), 1.70~1.88 (6H, m) ' 2.12 — 2.17 (2H, m), 2.42 ~ 2.52 ( lH,m) , 7.15 ~ 7.18 ( 2H,m) , 7.60~7.79 (2H,m) CI-MS ; 469 ( M )

G Example 1-4 (Synthesis of 4-{(trans,trans)-4'-n-pentyl-dicyclohexyl-4-carbonyloxy}-thiosulfonylbenzene) Content of the stirring device In a 30 ml glass container, (trans,trans)-4'-n-pentyl-dicyclohexyl-4-ruthenate ruthenium.76 g (2.7 mmol) and sulfinium chloride 16.3 g (137 mmol) were added to 70 After stirring at ° C for 2 hours, (trans,trans)-4'-η-pentyl-dicyclohexyl-4-indoleic acid chloride was formed. After the completion of the reaction, the sulfinium chloride was distilled off under reduced pressure, and the obtained residue was added with 4-hydroxypentafluoropentabenzene 0.5 g (2.3 mmol) and dichloromethane 10 ml -49-200927888, and stirred. Next, react at room temperature for one night. After the reaction was completed, the concentrate was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (solvent: hexane/ethyl acetate = 10/1 (volume ratio)) to give a white solid. 4-{(1:^118,1^118)-4'-11-pentyl-dicyclohexyl-4-carbonyloxy}-thiopentaphenyl quinone.8 2g (isolation yield; 75 %). The physical properties of this compound are as follows. ^-NMR ( CDC13 ' δ ( ppm) ) ; 0.8 3 〜1 · 3 3 ( 2 0 Η ' m ), 1.47 〜1_59 (2H, m), 1.70~1.88 (6H, m) ' 2.13 〜2.17 (2H,m), 2_42~2.52(lH,m), 7.15~7.18( 2H,m ) , 7.74 ~7.79 ( 2H,m ) CI-MS ; 483 ( M ) Example 1-5(4-(4 Synthesis of '-11-pentyloxy-biphenyl-4-carbonyloxy)-thiosulfonylbenzene) 4,-n-pentyloxybiphenyl-4-carboxylic acid hydrazine.34 g (l_2 mmol) The reaction was carried out in the same manner as in Example I-1 except for the (trans,trans)-4'-ethyl-cyclohexyl-4-carboxylic acid in Example 1-1. As a result, 4-( 4'-n-pentyloxy-biphenyl-4-carbonyloxy)-pentafluorothiobenzoquinone.26 g (yield: 53%) was obtained as a white solid. This compound is a novel compound represented by the following physical properties. *H-NMR (CDCI3 * δ (ppm)); 〇· 9 3 ～0.9 7 ( 3 Η ' m ), 1.39~1.53 (4H,m), 1.78 〜l·85 (2H,m), 4.00 ～4.04 (2H,m), 6.98~7.03(2H,m), 7.34~7.37( 2H,m), 7.58~7.61(2H,m), 7.68~7.73(2H,m) -50- 200927888,7.82~7.87 ( 2H,m), 8.20~8.24(2H,m) CI-MS; 487 ( Μ ) Example 1-6 (4-(4'-n-heptyloxy-biphenyl-4-carbonyloxy)· Synthesis of thiopentafluoride benzene) Using 4'-n-heptyloxybiphenyl-4-carboxylic acid hydrazine. 38 g (1.2 mmol) in place of (tΓans, trans)-4'- in Example 1-1 The reaction was carried out in the same manner as in Example I-1 except for ethyl-dicyclohexyl-4-carboxylic acid. As a result, 4-( 4'-η-heptyloxy-biphenyl-4-carbonyloxy)-thiosulfabenzene benzene 0 · 3 3 g (isolation yield; 63%) was obtained as a white solid. This compound is a novel compound represented by the following physical properties. 'H-NMR ( CDC13, δ (ppm ) ) ; 0 · 8 8 〜 0 · 9 3 ( 3 Η, m ), 1.26 〜 1.51 ( 8H, m) , 1.77~1.84 (2H, m) ' 4.00 ～4.04 (2H,m), 6.98 to 7.03( 2H,m) ' 7.34 ~ 7.3 7 ( 2H,m) , 7.58~7.61(2H,m) , 7.69~7.73(2H,m) ,7.82~7.87(2H'm ), 8.20 ~ 8_24 (2H, m) CI-MS; 5 15 (M) Example I-7 (4-(4,-n-decyloxy-biphenyl-4-carbonyloxy)-pentafluoro Synthesis of thiophenyl benzene) 4-hydroxypentafluoropentabenzene 0.5g (2.3mmol) and 4,-11-heptyloxybiphenyl-4 were added to a glass container containing a stirring device. -carboxylic acid 0.97 g (2.7 mmol), 1-ethyl-2-(dimethylaminopropyl) carbodiimide hydrochloride 0.65 g (3.4 mmol), 4-dimethylaminopyridine-51 - 200927888 0.05g (0.4mmol) and 1 Oml of dichloromethane, reacted at room temperature for one night with stirring. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hexane gel column chromatography (solvent: hexane / ethyl acetate = 20/1 (volume ratio)) to give a white solid. 4-(4, n-decyloxy-biphenyl-4-carbonyloxy)-thiosulfonylbenzene O.llg (isomeric yield; 9%). This compound is a novel compound represented by the following physical properties. 1 Η - NMR ( CD C13, δ (ppm ) ) ; 0 · 8 6 ～ 0.9 1 ( 3 η, ), 1.29 〜 1.49 ( 1 4H, m ), 1 · 7 7 〜 1. 8 4 ( 2 Η, m ), 4.00~4.04 (2H, m), 6.99~7_03 (2H, m), 7.34~ 7.37 ( 2H - m ), 7.58 ~ 7.61 ( 2H, m) ' 7.69 - 7.72 ( 2h , m) , 7.82 to 7.86 (2H, m), 8.20 to 8.25 (2H, m) CI-MS; 5 5 7 (M) Example 1-8 (3-tetracyclylcarbonyloxypentafluoride benzene a < 〇成 G ) Using 3-hydroxyl pentafluorophenyl phenyl hydrazine. 5g (2.3mmol) to replace 4-hydroxy thiosulfonylbenzene in the example 1-7, using twenty-four bases The reaction was carried out in the same manner as in Example 1-7 except that 1.00 g (2.7 mmol) of the acid was substituted for 4'-n-heptyloxybiphenyl-4-carboxylic acid. As a result, a white solid of 3.~~·tetradecylcarbonyloxypentafluorophenylphenylhydrazine.61 g (isolation yield; 47%) was obtained. This compound is a novel compound represented by the following physical properties. H-NMR (CDCI3 > δ (ppm) ); 0 · 8 6 〜0 · 9 0 ( q ^ ^ * m ), 1.26 〜 1.40 ( 40H , m ) , 1 · 7 1 〜1 .8 1 ( 2 Oh,

JX -52- 200927888 2.55~2.60(2H,m), 7.26~7.29 (1H,m) 7.51 (2H,m), 7.61~7.64 (1H,m) CI-MS ; 57i ( m ) Example 1-9 (Synthesis of 4-linoleoxime-oxypentafluoride benzene)

Substituting 3-hydroxypentafluorobenzoquinone. 5 g (2.3 mmol) for the 4-hydroxy pentafluorobenzene benzene in Example 7, using 4,5 g (2.7 mmoI) of linolenic acid to replace 4'-n-g The reaction was carried out in the same manner as in Example 7 except for the oxybiphenyl-4-carboxylic acid. As a result, 0.49 g of 4-linoleylpentafluoropentabenzene was obtained as a white solid (separation yield; 45 %). This compound is a novel compound represented by the following physical properties. 'H-NMR ( CDC13 - δ ( ppm ) ) ; 0 · 8 7 〜1 · 0 0 ( 3 Η,m ), l-27~l_42(9H,m) '1.71 ～1.78(2H,m) , 2.02 ~2.13(4H,m), 2.55~2.60( 2H,m) '2.76~2.86( 3H,m) , 5.27~5.44(6H,m) , 7.17~7.20(2H,m) ,7.75 to 7.80 ( 2H, m) CI-MS; 48 1 (M) Example 1-10 (Synthesis of 3-(4-n-butylphenyloxy)-thiosulfonylbenzene) Using 3-hydroxysulfuric acid Phenylhydrazine.5g (2.3mmol) was substituted for 4-hydroxypentafluoropentabenzene in Example 1-7, using 4-n-butylbenzoic acid 0.48g (2.7mmol) instead of 4'-η-heptyloxy The reaction was carried out in the same manner as in Example 1-7 except for the biphenyl-4-carboxylic acid. As a result, (4-η--53-200927888 butylbenzoquinoneoxy)-pentafluorosulfobenzene 0.59 g (isolation yield; 69%) was obtained as a white solid. Compound. !H-NMR (CDC13 > δ (ppm ) ) ; 0.92 〜0_97 ( 3H,m ), 1.34 〜1.41 (2H,m) , 1.60 〜1.70 ( 2H,m) ' 2.69 ～2.73 (2H,m ), 7.31~7.35(2H,m), 7.39~7.42(lH,m), 7.50~7.55(lH,m), 7.64~7.69(2H,m), 8.08~8. 12 ( 2H,m ) ❹ CI -MS; 38 1 (M + l ) Example 1-11 (Synthesis of 4-(thiophene-3-carbonyloxy)-pentafluorothiobenzene) Adding a glass container having a stirring capacity of 30 ml 4-hydroxypentafluoropentafluoride 0.62 g (2.8 mmol), thiophene-3-carboxylic acid hydrazine. 3 g (2.3 mmol), 1-ethyl-2-(dimethylaminopropyl)carbodiimide 0 hydrochloride 〇.65g (3.5mmol), 4 - dimethylaminopyridinium 〇 5 g (0.4mmol) and chloroform, l〇ml, reacted at room temperature with stirring late. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hexane gel column chromatography (eluent solvent; hexane/ethyl acetate = 9/1 (volume ratio)) to give a white solid. 4-(Thiophen-3-carbonyloxy)-thiosulfonyl quinone. 60 g (isolation yield; 79%). This compound is a novel compound represented by the following physical properties. W-NMR (CDC13, δ (ppm)); 7·43 ～7 · 45 ( 1 Η, m ), 7.49 ～7.51 ( lH, m) , 7.71 to 7.78 (4H'm) > 8.01 -54 - 200927888 ~8.03 ( 1 Η,m ) CI-MS ; 3 3 0 ( Μ ) Example 1-12 (2-{(& 3113,1^118)-4'-11-pentyl-cyclohexyl-4- Synthesis of carbonyloxy bromide benzene benzene) Adding (43118,4&115)-4'-11-pentyl-dicyclohexyl-4-indole to a glass container containing a stirring device Acid 0.2 § (0.7111111 〇 1 ), 2-hydroxy thiophenyl benzene 0.19 g (0.9 mmol), 1-ethyl-2-(dimethylaminopropyl) carbodiimide hydrochloride 〇. After 20 g (1.1 mmol), 4-dimethylaminopyridinium, 5 g (0.4 mmol) and dichloromethane (1 ml) were reacted at room temperature overnight with stirring. After the completion of the reaction, the reaction mixture was concentrated, and the obtained residue was purified by EtOAc EtOAc EtOAc EtOAc EtOAc 2-{(43113,1^115)-4'-11-pentyl-dicyclohexyl-4-oximeoxy}-thiophenylphosphonium pentoxide. 25 g (isolation yield; 59%). ^ This compound is a novel compound represented by the following physical properties. j-NMR (CDC13, δ (ppm)); 〇. 84 〜1 . 3 6 (20Η, m ), 1.48~1.60 (2H, m), 1.70~1.88 (6H, m) . 2.16 〜2.20 ( 2H, m), 2.46~2.56(lH,m), 7.11~7.26 (1H,m), 7.29~7.34 (1H,m), 7.49~7.55(lH,m), 7.79~7.82(lH,m)sai CI- MS; 483 (M) Example II-l (4-{(trans,trans)-4'-n-propyl-bicyclohexyl-55- 200927888 -4-yl-oxycarbonyl}-sulfur pentafluoride Synthesis of base benzene) In a glass container with a stirring device content of 30 ml, 'addition of 4-pentafluorothiobenzoic acid oxime. 2g (0.80mmol), (trans ' trans )-4,-n-propyl 2-dicyclohexyl-4-ol 0.22 g (〇.98 mmol), 1-ethyl-2-(dimethylaminopropyl)carbodiimide hydrochloride 0.23 g (1.2 mmol)' 4- Methylaminopyridinium, 5 g (0.4 mmol) and 1 ml of dichloromethane were reacted overnight at room temperature with stirring. After the completion of the reaction, the reaction mixture was concentrated, and the obtained residue was purified by chromatography on silica gel column chromatography (eluent solvent; hexane/ethyl acetate = 20/1 (capacity ratio)) to give a white solid. 4-five-concentrated thiobenzoic acid 4-{( trans,trans )-4'-n-propyl-dicyclohexyl-4-yl-oxycarbonyl}-thiosulphur pentabenzene 0.23g (single From yield; 6 2 %). This compound is a novel compound represented by the following physical properties. !H-NMR (CDC13 ' δ c ppm) ) ; 0.85 〜1 .35 ( 16H,m ), 1.40~1.51(2H,m) , 1.70~1.86(6H,m) ' 2.09 〜2.14(2H,m) , 4.85~4.96 (lH, m), 7.80~7.83 (2H'm), 8_l〇~8.13 (2H, m) CI-MS; 43 5 (M-19) Example II-2 (4-{ (trans ,trans) -4'-n-butyl-cyclohexyl-4-yl-oxycarbonyl}_sulfatobenzene benzene synthesis) using (trans,trans)-4,-η-butyl-dicyclohexyl The -4-ol 0.23 g (0.96 mmol) was reacted in the same manner as in Example II-1 except for the (trans,trans)-45-n-propyl-dicyclohexyl-4-ol in the Example ι.结-56- 200927888 Fruit 4-((trans,trans)-4'·η-butyl-cyclohexyl-4-yloxycarbonyl}-thiophenyl thiophenyl ruthenium benzoate. 16g Yield; 44%) This compound is a novel compound represented by the following physical properties. j-NMR (CDC13, δ (ppm)); Ο · 8 3 〜1 · 2 9 (1 8 Η, m ), 1.40~1.51 (2H, m),: 1.71 to 1.86 (6H, m) ' 2.09 〜 2.14 (2H, m), 4.85~4.96 (lH, m), 7.79~7.84 (2H, m), 8.1〇~8.13(2H,m) 〇CI-MS; 449 (M-1 9 ) Example II- Synthesis of 3 (4-{( trans,trans)-4'-n-pentyl-dicyclohexyl-4-yl-oxycarbonylsulfafluorobenzene) using (trans,trans ) -4'-n- 0.24 g (0.95 mmol) of pentyl-dicyclohexyl-4-ol was substituted for (trans,trans)-4'-n-propyl-dicyclohexyl-4-ol in Example II-1, and examples The same reaction was carried out in II-1. As a result, 4-{(trans,trans)-4'-n-pentyl-dicyclohexyl-4-yl-oxycarbonyl}-pentafluorothiobenzoquinone. 13 g (yield yield; 34) was obtained as a white solid. %) This compound is a novel compound represented by the following properties. j-NMR ( CDCh, δ ( ppm ) ) ; 〇 · 8 0 〜1 . 3 3 ( 2 Ο Η, m ), 1·40 ～ 1.51 (2H, m), 1·70 〜 1.85 (6H, m) ' 2.09 ～2.14(2H,m), 4.85~4.96(lH,m), 7.79~7.86( 2H > m ) , 8_10 ～8.13 ( 2H,m ) CI-MS ; 463 ( M-1 9 ) -57 - 200927888 Example 11-4 (Synthesis of 4-{(4'-11-decyloxy-biphenyl-4-yl-methyl)·oxycarbonyl}-thiosulfonylbenzene) (4' - η-decyloxybiphenyl-4-yl)methanol 0.33 g (0.97 mmol) in place of (trans,trans)-4'-n-propyl-dicyclohexyl-4-ol in Example II-1 Further, the reaction was carried out in the same manner as in Example 1-1. As a result, 4-{(4'-η-decyloxy-biphenyl-4-yl-methyl)-oxycarbonyl}-thiosulfabenzene benzene was obtained as a white solid (yield: 75%). ). This compound is a novel compound represented by the following physical properties. 'H-NMR (CDCI3 5 δ (ppm) ); 0.86~0.91 ( 3H,m ), 1_28~1·49(14Η,πι), 1.76~1.85( 2H,m), 3.97~4.02(2H,m) , 5.41 (2H, s), 6.94 to 6·99 (2Η, m), 7.46 to 7.59 (6H, m), 7.80 to 7.84 (2H, m), 8.15-8.18 (2H, m) CI-MS; 570 (M) Example II-5 (Synthesis of 3-(4-fluorobenzyloxycarbonyl)-thiosulfonylbenzene) Substituted with ruthenium 3-pentafluorobenzene benzoate. 2g (0.80mmol) 4-Tetrafluorosulfonylbenzenecarboxylic acid in Example II-1, using 4-fluorobenzyl alcohol 0.12 g (0.97 mmol) in place of (trans,trans)-4,-n-propyl-dicyclohexyl-4 The reaction was carried out in the same manner as in Example II-1. As a result, 0.18 g of 3-(4-fluorobenzyl-oxycarbonyl)-thiosulfabenzenebenzene (color yield; 6 3%) was obtained as a colorless liquid. -58- 200927888 This compound is a novel compound represented by the following physical properties. 'H-NMR (CDC13 > δ (ppm ) ); 5.36 ( 2H > s ), 7.04~7·12(2Η,ιη), 7.40~7.47(2H,m), 7.53 to 7.60 ( 1 Η > m), 7_93~7.96(lH,m), 8.18~8.21 "only, m), 8.43~8.44(lH,m) CI-MS; 356 ( M ) Example 11-6 ( 3_(cis-4_ Synthesis of phenyl-cyclohexyl-oxycarbonyl)-thiosulfanylbenzene) Substituting cis-4-phenylcyclohexane-bupropanol.17g (0.97mmo1) for 4-fluoro in Example Π-5 The reaction was carried out in the same manner as in Example 11-1 except for benzyl alcohol. As a result, 3-(cis-4-phenyl-cyclohexyl-oxycarbonyl)-thiosulfabenzene benzene 0.18 g (isomeric yield; 5 4%) was obtained as a white crystal. Novel compounds. iH-NMR (CDC13, δ (ppm)); 1 · 74 to 1.98 (6Η, m), 2.16 to 2.21 (2H, m), 2.62 to 2.71 (lH'm) ' 5.40 to 5.42 (lH, m), 7.19 ~ 7.36 ( 5H'm), 7.57 ~ 7.62 ( lH, m), 7_94 ~ 7.98 (lH'm), 8.22 ~ 8.24 (lH, m), 8.49 ~ 8.5 1 (1H, m) CI-MS; 406 (M) Example 11-7 (Synthesis of 3-(4-cyclohexyl-phenyl-oxy)-pentafluorobenzene-based benzene) A glass container having a stirring capacity of 300 ml was added to -59 - 200927888 3 - Sulfur pentafluoride basic residual acid 3.〇g (12.1mmol), 4-cyclohexylphenylhydrazine 2_55g (14.50mmol), i-ethyl_2_(dimethylaminopropyl)carbodiimide After 3.38 g (ulmni〇i) of amine hydrochloride, 0.74 g (6.0 mmol) of 4-dimethylaminopyridine, and i〇〇ml of dichloromethane, the mixture was stirred at room temperature overnight. After the completion of the reaction, the reaction mixture was concentrated, and the obtained residue was purified by EtOAc EtOAc EtOAc (EtOAc: EtOAc 3-(4-Cyclohexyl-phenyl-oxycarbonyl)-thiosulfanylbenzene 2.82 g (isolation yield; 5 7%) ° This compound is a novel compound represented by the following physical properties. • H-NMR (CDC13 > δ (ppm)); 1.22 ~ 1.55 (5H, m), 1.74 to 1.92 (5H, m), 2.50 to 2.57 (lH, m) ' 7.11 to 7.15 (2H , m), 7.25 to 7.29 (2H, m), 7.61 to 7.66 (lH, m), 8.00 to 8.03 (lH, m), 8.33 to 8.36 (lH, m), 8.57 to 8.59 (1H, m) CI- MS; 407 ( M+l ) Example III-1 (Synthesis of 4-n-butoxypentafluoropentabenzene) 4-Fluoropentafluoride was added to a glass vessel containing a stirring device and a thermometer of 30 ml Sulfurylbenzene 0.5g (2.3mmol), 60% sodium hydride 0.138g (3.5mmol), pre-dried η-butanol 0.32ml (3.5mmol) and pre-dried 1,3-dimethyl-2-imidazole After 5 ml of linoleone, it was reacted at room temperature for 12 hours under stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed 5 times with 30 ml of a saturated aqueous solution of sodium chloride. After filtration, the obtained filtrate was concentrated to obtain 4-η·butoxy thiopentafluoride phenyl hydrazine. 48 g (isomeric yield; 76%) of a colorless liquid. Compound. 'H-NMR ( CDC13, δ (ppm ) ) ; 0.98 ( 3H ' t, J = 7.3 Hz ) , 1.43 ～ 1.56 ( 2H, m) , 1.73 〜 1.83 (2H' m ), 3.99 ( 2H, t, J = 6.6 Hz), 6.8 7 to 6.9 0 ( 2 H,m ), 7.63 to 7,69 ( 2H,m ) 〇CI-MS ; 276 ( M) Example III-2 (4-phenoxypentafluoride Synthesis of thiobenzene) A glass vessel containing 30 ml of a stirring device and a thermometer was charged with 4-fluoropentafluoropentabenzene 0.5 g (2.3 mmol), 60% sodium hydride 0.276 g (6.9 mmol), and phenol 0.65. After g (6.9 mmol) and 5 ml of pre-dried 1,3-dimethyl-2-imidazolidinone, the mixture was stirred at room temperature for 1 2 hours at room temperature and reacted at 60 ° C for 4 hours. After the completion of the reaction, 30 ml of toluene was added to the reaction mixture, and the organic layer was washed with 30 ml of a saturated aqueous solution of sodium chloride and 1 mol/l aqueous sodium hydroxide solution (1 〇 m 1 ), and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated to give 0.25 g of 4-phenoxypentafluoropentabenzene as a colorless liquid (yield: 36%). This compound is a novel compound represented by the following physical properties. 1 H-NMR (CDCI3, δ (ppm ) ) ; 6.9 7 to 7.00 ( 2 Η, m ), 7.04 to 7.08 (2H, m), 7.18 to 7.25 ( lH, m) ' 7.36 to 7.43 (2H, m), 7.66~7.72(2H,m) -61 - 200927888 CI-MS ; 296 ( Μ ) Example in-3 (Synthesis of 4-cyclohexyloxypentafluoropentafluoride) Content of stirring device and thermometer 30 ml To the glass vessel, 0.5 g (2.3 mmol) of 4-fluoropentafluoropentabenzene, 0.138 g (3.5 mmol) of 60% sodium hydride, 0.36 ml (3.5 mmol) of cyclohexanol, and 1,3-pre-dried 1,3- After 5 ml of dimethyl-2-imidazolidinone, the mixture was reacted at 60 ° C for 3 hours while stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed five times with 30 ml of brine, and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated to give 4-cyclohexyloxypentafluoropentaphenyl benzoquinone. 76 g (yield: 99%). This compound is a novel compound represented by the following physical properties. !H-NMR ( CDC13 ' δ ( ppm ) ) ; 1.41 ~ 1.45 ( 2H, m ), 1.49~1.67 (4H, m) , 1.73~1.85(2H,m) ' 1.94 〜2.00(2H,m) > 4.26-4.3 5 ( 1 H « m ) , 6.88 (2H, d, J = 9.0 Hz), 7.63 to 7.66 ( 2H, m) CI-MS ; 3 02 ( M ) Example III-4 (4-Benzyloxy) Synthesis of thiopentafluoride-based benzene) A glass vessel containing 100 ml of a stirring device and a thermometer was charged with 4-fluoropentafluoropentabenzene 5.0 g (22.5 mmol) and 60% sodium hydride 1.35 g (33.8). Methyl), 3.65 g (33_8 mmol) of phenol, and 25 ml of pre-dried 1,3-dimethyl-2-imidazolidinone were reacted at room temperature for 12 hours with stirring. After the completion of the reaction, 50 ml of toluene and 50 ml of -62-200927888 ethyl acetate were added to the reaction mixture, and the organic layer was washed five times with 100 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and then added again to 200 ml of water, and filtered to remove the mixed 1,3-dimethyl-2-imidazolium. The obtained filtrate was dried under reduced pressure to give white crystals (yield: EtOAc, EtOAc, This compound is a novel compound represented by the following physical properties. W-NMR (CDC13, δ (ppm)); 5.10 (2H, s), 6.96 to 6_99 (2H, m), 7.29 to 7.43 (5H, m), 7.65 to 7.70 ( 2H, m ) CI-MS ; 1 0 ( M ) Example III-5 (Synthesis of 4-{4-( trans-4-n-pentyl-cyclohexyl)-phenoxy}-thiosulfonylbenzene) with stirring device and thermometer A glass container having a volume of 30 ml was charged with 4-fluoropentafluorobenzene benzene 0-5 g (2.3 mmol), 60% sodium hydride 0.135 g (3.5 mmol), and 4-n-pentylcyclohexyl phenylhydrazine. 832 g ( After 3.5 ml of 3.5 mmol) and pre-dried 1,3-dimethyl-2-imidazolidinone, the mixture was reacted at 60 ° C for 3 hours while stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed five times with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. After the mashing, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to obtain 4-{4- (trans-4-n-) as a white solid. Pentyl-cyclohexyl)-phenoxy}-thiophenylphosphonium pentoxide. 411 g (isolation yield; 40%). -63- 200927888 This compound is a novel compound represented by the following physical properties. H-NMR (CDC13, δ (ppm)); 0.8 7 to 0.9 2 (3 Η, m ), 1.03 to 1.11 (2Η, m), 1.25 to 1.51 (11H, m), 1.86 to 1.92 (4H, m ), 2.43~2.53(lH,m), 6.94~

6.99 (4H,m), 7.20 to 7.25 ( 2H,m) , 7.64 to 7.70 ( 2H ,m ) CI-MS ; 448 ( M) 实施 Example III-6 ( 4-{ ( trans,trans) -4' Synthesis of -n-pentyl-dicyclohexyl-4-yl-oxy}-thiosulphonium pentoxide. 4-Fluorofluorosulfate group was added to a glass vessel containing a stirring device and a thermometer of 30 ml. Benzene 0.22g (lmmol), 60% sodium hydride 0.060g (1.5mmol), 4-n-pentylcyclohexylcyclohexanol oxime. 3 79g (1.5mmol) and pre-dried 1,3-dimethyl-2 After 5 ml of the imidazolinone, the mixture was reacted at 60 ° C for 3 hours while stirring. After the completion of the reaction, toluene (50 m) was added to the reaction solution, and the organic layer was washed five times with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to give 4-{(trans,trans) -4'-n as a white solid. -Pentyl-dicyclohexyl-4-yl-oxy}-thiophenylphosphonium pentoxide. 244 g (isolation yield; 54%). This compound is a novel compound represented by the following physical properties. ^-NMR ( CDC13 ' δ ( ppm) ) ; 0 · 7 9 〜 2.0 4 ( 3 0 Η, m ), 4.56 (lH, brs), 6.87~6.90 (2H, m), 7.62~ 7.67 ( 2H, m ) -64 - 200927888 CI-MS; 454 ( Μ ) Example ΙΠ-7(Synthesis of 4-{4-(4-η-pentyl-cyclohexyl)-benzyloxy}-thiosulphur pentoxide) Adding 4-fluoropentafluoropentafluoride 0.22g (lmmol), 60% sodium hydride 0·0 6 0 g (1.5 mm ο 1 ), 4 in a glass container with a stirring device and a thermometer. After 0.40 g (1.5 mmol) of -n-pentylcyclohexyl sterol and 5 ml of 1,3-dimethyl-2-imidazolidinone previously dried, the mixture was reacted at 60 ° C for 3 hours while stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed five times with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to give 4-(4·(4-η-pentyl) as a white solid. Cyclohexyl)-benzyloxy}-thiopentaphenyl quinone. 310 g (isomeric yield; 67%). This compound is a novel compound represented by the following physical properties. !H-NMR ( CDC13 1 δ (ppm ) ) ; 0_ 87 〜0_92 ( 3H,m ), 1·02 ～1.10(2H,m) , 1.24 〜1.52 ( llH,m),

1.86 ~ 1.89 ( 4H, m) , 2.44 ~ 2.52 (lH, m), 5.06 (2H , s ), 6.97 ( 2H, d, J = 9.3Hz), 7.24 ( 2H, d, J = 8.8Hz ), 7.33 (2H,d,J = 8.3Hz), 7 · 6 5 〜7 · 6 9 ( 2 H,m) CI-MS ; 443 ( M-1 9 ) Example III-8 ( 4-[{ ( trans, Trans) Synthesis of -4'-n-pentyl-dicyclohexyl-4-yl}-methoxy]-thiosulfonyl benzene) -65- 200927888 Glass with a stirring device and a thermometer of 30 ml Add '2-fluoropentafluoropentabenzene 0.22g (1 mmol), 60% sodium hydride 0.060g (i.5mmol), { ( trans,trans) -4'-n-pentyl-dicyclohexyl After benzyl group-methanol 39. 39 ig (i. 5 mmol) and 5 ml of pre-dried 1,3 - dimethyl-2-imidazolidinone were reacted at 60 ° C for 3 hours while stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed five times with saturated brine (5 ml) and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to give 4-[{ (trans, trans) -4'-n as a white solid. -pentyl-dicyclohexyl-4-yl}-methoxy]-thiosulfabenzene benzene 0.25 7 g (isolation yield; 5 5 %). This compound is a novel compound represented by the following physical properties. *H-NMR (CDC13 * δ (ppm) ) ; Ο · 8 2 〜1 . 3 3 ( 2 2 Η,m ), 1.69 ～1.91 ( 9H > m ) , 3.77 ( 2H,d,J = 6.3Hz ), 6.86~6.90 (2H,m), 7.64~7·67 (2H,m) Win CI-MS; 468 ( Μ ) 实施 Example III-9 (4-Tetratetraoxypentafluoropentabenzene) Synthesis of a glass container containing a stirring device and a thermometer in a volume of 30 ml, adding 0.22 g (lmmol) of 4-fluoropentafluoropentabenzene, 60% sodium hydride 0.060 g (1.5 mmol), and twenty-four alcohol 0.532 g (1.5 mmol) and 5 ml of pre-dried 1,3-dimethyl-2-imidazolidinone were reacted at 60 ° C for 3 hours under stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed 5 times with 50 ml of a saturated aqueous solution of sodium sulfate, and dried over anhydrous magnesium sulfate - 66-200927888. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to give 4-tetrasyloxypentafluorothiobenzene as a white solid. 251.251g (isolation yield; 45%). This compound is a novel compound represented by the following physical properties. lH-NMR (CDC13, δ (ppm)); 0 · 8 5 ～0.90 ( 3 Η, m ), 1.21 〜 1.47 ( 42 Η, m ) , 1 · 74 〜 1 · 84 ( 2 Η, m ), 3.96 ～ 4.0 1 ( 2H,m ) , 6 8 7 to 6.9 0 ( 2 Η,m ) , 7.63 to 7.69 ( 2H,m) CI-MS ; 556 ( Μ ) Example ΙΙΙ-1〇(4-(4·-η- Synthesis of heptyl-biphenyl-4-yl-methoxy)-thiosulfanyl benzene) 4-fluoropentafluoropentafluoride 0.22 was added to a glass vessel containing a stirring device and a thermometer in a volume of 30 ml. g (1 mmol), 60% sodium hydride 0.060 g (1.5 mmol), 4-(4'-n-heptyl-biphenyl-4-yl)-methanol 0.424 g (1,5 mmol) and pre-dried 5 ml of 1,3-dimethyl-2-miprofenone was added to the mixture under stirring for 6 hours. After the reaction was completed, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed with 50 ml of saturated brine. After 5 times, it was dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and then subjected to hydrazine gel column chromatography (developing solvent; hexane/ethyl acetate = 9/1 (capacity ratio)) Purification to give 4-(4·-η-heptyl-biphenyl-4-yl-methoxy)-penta-sulfurized sulfur as a white solid Benzene 0.333 g (isomeric yield; 69%) This compound is a novel compound represented by the following physical properties: -67- 200927888 b-NMR (CDC13, δ (ppm)); 0.89 (3H, t, J = 6.9Hz), 1.28~1.35 (8H,m), 1.6 0 〜1 · 6 7 ( 2 H,m

) 2.65 ( 2H > t > J = 7.6Hz ) , 5.14 ( 2H, s) , 7.00 ( 2H , dJ = 9.2Hz ) , 7.23 ( 2H, d, J = 8.3Hz ) , 7.45 ~ 7.52 ( 4H , m), 7.59~7.63 (2H, m), 7.66 to 7.72 (2H, m) CI-MS; 48 5 (M+l) Example III-ll (4-(fn-decyloxy-biphenyl) Synthesis of -4-yl-methoxyindole)-thiosulfonylbenzene pentoxide) 0.22 g (lmmol) of 4-fluoropentafluoropentafluoride was added to a glass vessel containing a stirring device and a thermometer in an amount of 30 ml. 60% sodium hydride 0.060 g (l_5 mmol), 4-(4·-η-decyloxy-biphenyl-4-yl)-methanol 0.510 g (1.5 mmol) and pre-dried 1,3-dimethyl- After 5 ml of 2-imidazolinium, the mixture was reacted at 60 ° C for 3 hours with stirring. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed five times with saturated brine (50 ml) and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane/ethyl acetate = 9/1 (capacity ratio)) to give a white solid 4- (4"n-decyloxy-biphenyl-4-yl-methoxy)-thiophosphonium pentoxide. 3 5 8g (isomeric yield; 66%). This compound is the following properties 値A novel compound represented by 'H-NMR (CDC13 > δ (ppm)); 0.88 (3H, t, J = 6.3 Hz), 1.28 to 1.50 (14H, m), 1.76 to 1.85 (2H, m), 3.99 ( 2H > t, J = 6.6Hz ), 5.12 ( 2H, s) , 6.94 - -68- 200927888

6.98 ( 4H,m) , 7.44 ~ 7.60 ( 6H,m) , 7.67 ~ 7.70 ( 2H ,m ) CI-MS ; 542 ( Μ ) Example III-12 ( 2-n -pentyloxy-5- ( 4 -n-pentylphenyl)·Synthesis of thiosulfate benzene) 2-Fluoro-5- (4-η-pentylphenyl) was added to a glass container containing a stirring device and a thermometer ) _ pentafluorosulfide benzene l. 〇g ( 2.70 mmol), 60% sodium hydride 0.470 g (10. 8 mmol), pre-dried η-pentanol oxime. 97 g (10.8 mmol) and pre-dried 1,3- After 5 ml of dimethyl-2-imidazolidinone, the mixture was reacted at 10 ° C for 16 hours while stirring. After the reaction was completed, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed five times with 30 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to give 2-n-pentyloxy-5- (4-n as a colorless liquid. - 戊 pentylphenyl)-thiopentaphenyl quinone. 26 g (isolation yield; 21%). This compound is a novel compound represented by the following physical properties. !H-NMR ( CDC13 ' δ ( ppm) ) ; 0.88 ~ 0.97 ( 6H, m ), 1.26 ~ 1.89 ( 1 2H, m ) , 2 _ 6 4 ( 2 Η, t, J = 7 · 9Hz ), 4.08 ( 2H,t,J = 6.3Hz ) , 7.09 ( 1H,d,J = 8.8Hz ), 7.25 ( 2H,d,J = 8.5Hz ) , 7.43 ( 2H ' d ' J = 8.3Hz ) , 7.63 ( 1H , dd, J = 2.2 Hz > J = 8.5 Hz), 7.92 (1H, d, J = 2.4 Hz) CI-MS; 45 7 (M) -69- 200927888 Example 111-13 (2-phenoxy) - Synthesis of 5-(4-n-pentylphenyl)-thiosulfonium benzene hydride) 2-gas-5- (4-n) in a glass container with a stirring device and a thermometer -pentylphenyl)_penta-sulfurylbenzene l.〇g (2.7mmol), 60% sodium hydride 0.470g (10.8mmol), phenol 1.02g (10.8mmol) and pre-dried 1,3-dimethyl After 5 ml of the base-2-imidazolidinone, the mixture was reacted at 100 ° C for 4 hours with stirring. After the completion of the reaction, 30 ml of toluene was added to the reaction mixture, and the organic layer was washed 10 times with 30 ml of brine, and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane) to give 2-phenoxy-5- (4-n-pentyl) as a white liquid. Phenylphenyl)-thiosulfonylbenzene 0.25g (isolation yield; 21%) This compound is a novel compound represented by the following physical properties. 1 Η - N M R ( C D C13, δ ( p p m ) ) ; 0.8 8 〜 0 9 3 ( 3 Η, m ), 1.32~1.39 (4H, m), 1·60~l_70 (2H, m) ' 2.65

(2H,t,J = 7.7Hz), 7.03~7.48(l〇H,m), 7_59(1H ,dd » J = 2.2Hz > J = 8.8Hz ), 8.00 ( 1H,d,J = 2 · 2 H z ) CI-MS ; 296 ( M ) Example 111-14 (Synthesis of 2-benzyloxy-5-(4-n-pentylphenyl)-thiosulfonylbenzene) with stirring device 2-fluoro-5-(4-n-pentylphenyl)-pentafluorosulfonylbenzene l·84g (-70- 200927888 5.0 mm ο 1 ), 60% was added to a 30 ml glass container 0.8 70 g (2 Ommol) of sodium hydride, 2.1 6 g (20 mmol) of phenol, and 5 m 1 of 1,3-dimethyl-2-imidazolidinone previously dried, and reacted at 100 ° C under stirring hour. After the completion of the reaction, 50 ml of toluene was added to the reaction mixture, and the organic layer was washed 10 times with 30 ml of brine, and dried over anhydrous magnesium sulfate. After completion of the hydrazine, the obtained filtrate was concentrated to give a white liquid of 2-benzyloxy-5-(4-n-pentylphenyl)-pentafluorobenzene benzene 0.34 g (isolation yield; 15%) ). This compound is a novel compound represented by the following physical properties. • H-NMR (CDC13 > δ (ppm)); 0.88 to 0.93 (3H, m), 1.32 to 1.39 (4H, m), 1.62 to 1.70 (2H, m) ' 2.64 (2H, t, J = 7.7 Hz ) , 5.24 ( 2H, s) , 7 1 5 ( 1H, d, J = 8.8Hz ) , 7.24 ~ 7.49 ( 9H, m ) , 7.62 ( 1H, dd , J = 2.2Hz , J = 8.58Hz ) , 7.96 ( 1H,d,J = 2.2 Hz) CI-MS ; 457 ( M ) Example IV-1 (4-[2-{ (trans,trans) -4'-n-pentyl-dicyclohexyl-4 -Base}-Vinyl]-Synthesis of thiosulfate benzene) 0.71 g (2.50 mmol) of 4-bromopentafluoropentafluoride was added to a vessel containing a stirring apparatus, a thermometer and a reflux condenser. , 4-(4'-η-pentyldicyclohexyl)ethylene 0.72g ( 2.75mmol ), dichloro {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene }(3-chloropyridyl)palladium (trade name; PEPPSI (registered trademark)-IPr (made by Aldrich)) 0.03 5g (0.05mmol), potassium carbonate 1 · 0 3 g (7 · 4 8 mm ο 1 ) After 10 ml of 1,4-dioxane, the mixture was reacted at 10 ° C for 8 hours while stirring. -71 - 200927888 After the reaction was completed, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase 矽 gel chromatography (ODSC-18, developing solvent; acetonitrile/water = 90/10 - 94/6 (capacity ratio) )) purification to give 4-[2-{(trans,trans)-4'-n-pentyl-dicyclohexyl-4-yl}-ethylidene]-pentafluorosulfonylbenzene as a white solid. Llg (individual yield; 9%). This compound is a novel compound represented by the following physical properties. The compound was found to be an anti-oxime isomer from a coupling constant of 6.2 6 ppm and 6.35 pm (J値). h-NMR (CDC13, δ (ppm)); 0.83 to 1.33 (26H 'm), 1.70 to 1.87 (4Η, m), 2.05 to 2.11 (1Η' m), 6.26 (1H, dd, J = 6.2 Hz, J = 16.0 Hz), 6.35 (1H 'd, J = 16.1 Hz), 7.38 (2H, d, J = 8.3 Hz), 7.65 (2H > d, J = 8.3 Hz) CI-MS; 465 ( M )

Q Example IV-2 (Synthesis of 3-[2-{ ( trans,trans) -4·-η-pentyl-dicyclohexyl-4-yl}-vinyl]-thiosulphur pentoxide) Add 3-bromopentafluoropentafluoride.7lg (2.50mmo1), 4-(4,-η-pentyldicyclohexyl)vinyl hydrazine to the inner tank of the stirring device, thermometer and reflux cooler. .72g ( 2.75 mmol), dichloro {1,3-bis(2,6-diisopropylphenyl)imidazolidine}(3-chloroindole ratio steep) palladium (trade name; PEPPSI (registered trademark) -Ipr (made by Aldrich)) 0.03 5 g (0.05 mmol), potassium carbonate 1 · 〇3 g (7 · 4 8 mm ο 1 ) and -72- 200927888 1,4-dioxane l〇ml, stirred In the state, it was reacted at 100 ° C for 8 hours. After the completion of the reaction, the reaction solution was filtered. The filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reversed phase 矽 gel chromatography (0DSC·18, developing solvent; acetonitrile/water = 90/10 - 94/6 (capacity ratio) Purified to give 3-[2-{(48118,1 to 118)-4'-11-pentyl-dicyclohexyl-4-yl}-vinyl]-pentafluorothiobenzene 0.05 as a white solid g (isolation yield; 4%). This compound is a novel compound represented by the following physical properties. Further, the compound was confirmed to be a trans isomer by a coupling constant (J値) of 6.22 ppm and 6.35 pm. 1 Η-NM R ( CD C13, δ (ppm ) ) ; 0.8 3 〜1 · 4 3 ( 2 6 Η, m ), 1.69 〜 1.95 (4H, m) , 2.04 〜 2.08 ( 1H, m) ' 6.22 ( 1H, dd, J = 6.6 Hz, J = 15.9 Hz), 6.35 (1H &gt; d, J = 16.1 Hz), 7.33 to 7.56 (3H, m), 7.68 (1H, d, J = 1.7 Hz) CI- MS; 465 (M) Example Vl (Synthesis of 3-[2-{4-(trans-4-n-pentyl-cyclohexyl)-phenyl}-vinyl]-thiosulphur pentoxide) Add 3-vinyl pentasulfide thiobenzene 0.40g (1.74mm〇l), 4-(4-n-pentylcyclohexyl)bromophenylhydrazine to a 30ml container of the stirrer, thermometer and reflux cooler. .54g ( 1.74mmol ), dichloro U,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}(3-chloropyridyl)palladium (trade name; PEPPSI (registered trademark) -IPr (made by Aldrich -73-200927888)) 〇-136g (〇.19mmol), potassium carbonate 0 · 7 2 g (5.2 2 mmo 1 ) and 1,4-dioxane i〇mi, stirred It was reacted at 80 ° C for 12 hours. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by flash column chromatography (developing solvent; hexane) to give 3-[2-{4-(trans-4-n-pentyl-cyclohexyl)-phenyl} as a white solid. -Vinyl]· thiopentafluoride 0.25 g (isolation yield; 31%) ° This compound is a novel compound represented by the following physical properties. Further, the compound was confirmed to be a trans isomer by a coupling constant (J値) of 7.04 Ppm and 7.14 pm. 'H-NMR ( CDC13 5 δ (ppm) ) ; Ο · 8 8 〜1 · 5 2 ( 1 6 Η,m )' 1 .88 ( 4Η &gt; m ) , 2.44 〜2.52 ( lH,m) , 7.04 (1H, d &gt; J = 1 6.4 Hz), 7.14 (lH, d, J = 16.4 Hz), 7.22 (2H, d ' J = 8.1 Hz), 7.40 to 7_46 (3H, m), 7.5 9 to 7.6 3 ( 2 H, m ) , 7.84 ( 1H, dd, J = 1.9Hz, J = 1.9Hz ) CI-MS ; 45 8 ( M ) Example 乂-2(4-[2-{4-(& Synthesis of 31^-4-11-propyl-cyclohexyl)-phenyl}-vinyl]-thiosulphonium pentoxide. Add a 4-ml container with a stirrer, thermometer and reflux cooler. Vinyl pentasulfide benzene 0.40g (1.74mmol), 4-(4-propylcyclohexyl)iodobenzene 0.57§ (1.74111111〇1), two gas {1,3-double (2,6-diiso) Propylphenyl)imidazol-2-ylidene}(3-chloropyridinyl)palladium (trade name; PEPPSI (registered trademark)-IPr (made by Aldrich Co., Ltd. - 74-200927888)) 0.106g (0.156mmol), potassium carbonate After 0 · 7 2 g (5.2 2 mmo 1 ) and 10 ml of 1,4-dioxane, the mixture was reacted at 80 ° C for 12 hours while stirring. Further, 0.051 g (0.075 mmol) of the above fine compound and 74 g (0.23 mmol) of tetra-n-butylammonium bromide bromide were added, and the mixture was reacted at 80 ° C for 17 hours while stirring. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODSC-18, developing solvent ▲: acetonitrile / water = 70/3 0 - 85 / 15 (volume ratio)) was purified to give 4-[2-{4-(trans-4-n-propyl-cyclohexyl)-phenyl}-vinyl]-thiopentafluorobenzoquinone as a white solid. 21 g (isolation yield; 29%). This compound is a novel compound represented by the following physical properties. The compound was confirmed to be a trans isomer by a coupling constant (J値) of 7.〇4 ppm and 7.17 ppm. 'H-NMR (CDC13 &gt; δ (ppm)); 0.8 8 to 1.4 9 (1 2 Η, m ), l_88 (4H, m), 2.44~2.53 (lH, m), 7.04 (1H, ❹ d, J=16. 1 Hz ), 7.17 ( 1H, d, J = 16.4 Hz ), 7.21 to 7.26 (3H, m), 7.44 to 7.47 (2H, m), 7.53 - 7.56 (lH, m ), 7.70 to 7.73 (2H,m) CI-MS; 430 (M) Example V-3 (2-Fluoro-5-[2-{4_(trans-4-n-pentyl-cyclohexyl)-phenyl}-ethyl Synthesis of 5-sulfothiobenzene with a stirring device, thermometer and reflux cooler. Add 2-fluoro-5-vinylsulfurium thiobenzene 0.43g (-75-) to the inner volume of 30 ml. 200927888 1.73mmol ), 4. (4-n-pentylcyclohexyl)bromophenylhydrazine. 54g ( 1.75mmol), dichloro {1,3-bis(2,6-diisopropylphenyl)imidazole-2 - subunit} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) - IPr (manufactured by Aldrich)) 0.04 7 8 g (0 · 0 7 Omm ο 1 ), potassium carbonate 0.72 g (5_22 mmol) After 10 ml of 1,4-dioxane, the mixture was reacted at 60 ° C for 4 hours while stirring. Further, 0.1667 g (0.245 mmol) of the palladium compound and 0.0648 g (0.23 mmol) of tetra-n-butylene chloride were added, and the mixture was reacted at 80 ° C for 24 hours while stirring. After the reaction was completed, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODSC-18, developing solvent; acetonitrile/water = 85/15 - 95/5 ( The volume ratio)) was purified to give 2-fluoro-5-[2-{4-(trans-4-n-pentyl-cyclohexyl)-phenyl-vinyl]-thiopentafluorobenzoate as a white solid. .12g (isolation yield; 13%). This compound is a novel compound represented by the following physical properties. Further, it was confirmed that the compound was a trans isomer by a coupling constant (J値) of 6.98 ppm and 7.07 ppm. 'H-NMR (CDC13 &gt; δ (ppm) ) ; 〇· 8 8 〜1 · 4 9 (1 6 Η, m ), 1.88 (4H, m), 2.44 〜2.53 ( lH, m) , 6.98 (1H , d, J = 16.3 Hz), 7.07 (1H &gt; d' J = l6.3 Hz), 7.15 to 7.30 (3H &gt; m ), 7.43 (2H, m), 7.61 to 7.66 (lH, m), 7.79 ~7.82 ( 1H,m ) CI-MS ; 476 ( M ) -76- 200927888 Example V-4 (Synthesis of 2-Fluoro-5-(2-phenyl-vinyl)-thiosulfabenzene benzene) A vessel containing 30 ml of an internal volume of a stirring device, a thermometer and a reflux condenser was charged with 0.43 g (1.44 mmol) of 2-fluoro-5-vinylsulfurium pentoxide and phenyl trifluoromethanesulfonate. 3 7g ( 1.74mmο 1 ), dichloro {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}(3·chloropyridyl)palladium (trade name; PEPPSI (Login Trademark)-lpr (made by Aldrich)) 0.05 0g (〇.〇74mmol), potassium carbonate 0 · 7 2 g ( 5 · 2 2 mm ο I ) and 1,4-dioxane 10 ml, stirring The reaction was carried out at 80 ° C for 4 hours. Further, the above palladium compound 〇.50 g (0.736 mmol) and tetra-n-butylammonium chloride 0.108 7 g (0.39 mmol) were added, and the mixture was reacted at 80 ° C for 39 hours while stirring. After the completion of the reaction, the reaction solution was analyzed by chemical ionization to confirm the presence of 2-fluoro-5-(2-phenyl-ethylidene)-thiosulfate benzene (molecular weight 324). Example V-5 (Synthesis of 2-Fluoro-5-{2-(thiophen-3-yl)-vinyl}-thiosulphur pentoxide) 30 ml of the inner volume of a stirring device, a thermometer and a reflux cooler 2-Fluoro-5-vinylpentafluorobenzene benzoquinone.43g (1.74mmol), 3-bromothiophene ruthenium.29g (i.74mmol), palladium acetate 0.043g (0.17mmol), triphenylphosphine were added to the vessel. 〇_183g (0.6 8mmol), tetra-n-butylammonium chloride 0.483 8g ( 1.74mm〇l), potassium carbonate 0.72g (5.22mmol) and hydrazine, hydrazine-dimethylformamide 10ml, stirred state Under the reaction, react at 1 °C for 1 2 hours. After the end of the reaction, the reaction solution was confirmed by chemical ion-77-200927888 analysis to confirm the presence of 2-fluoro-5-{2-(thiophen-3-yl)-vinyl}-pentafluorothiobenzene (molecular weight 330). ). Example VI-1 (Synthesis of 3-(4-n-pentyl-phenyl)-thiosulfonylbenzene) Adding 3_bromine five to a container containing 30 ml of internal volume of a stirring device, a thermometer and a reflux cooler 1.42 g (5.00 mmol) of thiophenyl fluoride, 2.0 g (10.41 mmol) of 4-n-pentylboronic acid, dichloro {1,3-bis(2,6-diisopropylphenyl)imidazole-2- Subunit}(3-chloropyridinyl)palladium (trade name; PEPPSI (registered trademark)-IPr (manufactured by Aldrich)) 0.068 g (0.10 mmol), potassium carbonate 2.07 g (15.01 mmol) and 1,4-two After 10 ml of methane, the mixture was reacted at 60 ° C for 2 hours while stirring. After the reaction was completed, the reaction mixture was filtered, and ethyl acetate (50 ml) was added to the filtrate, and washed with water (20 ml χ2). The resulting organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by a flash column chromatography (developing solvent; hexane) to give a transparent liquid of 3-(4-n-pentyl-phenyl)-pentafluorosulfobenzene 0.40 g (individually separated) Yield; 23%) This compound is a novel compound represented by the following physical properties. h-NMR (CDC13, δ (ppm)): 〇·91 ( 3H, t ' J = 7.0 Hz), 1.26 to 1.39 ( 4H, m ) , 1. 6 1 to 1. 7 1 ( 2 H ' m ), 2.63 to 2.68 (2H, m), 7.26 to 7-31 (2H'm) ' 7.47 to 7.53 (3H, m), 7.68 to 7.72 (2H, m), 7.94 to 7.95 ( 1 H, m ) -78- 200927888 CI-MS ; 3 5 0 ( Μ ) Example VI-2 (Synthesis of 4-(4-n-pentyl-phenyl)-thiosulfabenzene benzene) with stirring device, thermometer and reflux Add 4.22g (5.00mmol) of 4-bromopentafluoropentabenzene, 2.0g (10.41mmol) of 4-n-pentylboronic acid, and dichloro{1,3-double (2) to the inner volume of the cooler. ,6-diisopropylphenyl)imidazole-2 -ylidene} (3-chloropyridyl)palladium (trade name; PEPPSI (registered trademark)-IPr (made by Aldrich)) 0.068 g (0.10 mmol), After 2.07 g (15.01 mmol) of potassium carbonate and 10 ml of 1,4-dioxane, the mixture was reacted at 60 ° C for 2 hours while stirring. After the completion of the reaction, the reaction mixture was filtered, and ethyl acetate (50 ml) was added to the filtrate and washed with water (20 ml χ2). The resulting organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by a flash column chromatography (developing solvent; hexane) to give 4-(4-n-pentyl-phenyl)-thiopentafluorobenzoquinone. Yield (33%) 〇 This compound is a novel compound represented by the following physical properties. 'H-NMR (CDC13 · δ (ppm)); 0.9 1 (3H &gt; t, J = 7.0Hz),: 1.32 to 1.39 (4H, m), 1.61 to 1.68 (2H, m), 2.63 to 2.68 ( 2H,m), 7.25~7.30(2H,m) ' 7.48 ~7.51(2H,m) , 7.62~7.65(2H,m) , 7.78 ~7.81( 2H,m ) CI-MS ; 3 5 0 ( M ) 79- 200927888 Example VI-3 (Synthesis of 3-{4-(4-n-pentyl-cyclohexyl)-phenyl})-thiosulfabenzene pentoxide) with stirring device, thermometer and reflux cooler 0.75 g (2.50 mmol) of 3-bromopentafluoropentabenzene, 1.07 g ( 3.00 mmol) of 4-(4-pentylcyclohexyl)-phenylboronic acid, and dichlorochloride were added to a 30 ml container. {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}(3-chloroindolyl)palladium (trade name; PEPPSI (registered trademark)-IPr (made by Aldrich) After 〇_ 〇3 5 g (0 · 0 5 4 mmol), potassium carbonate 1.03 5 g (7.50 mmol) and 1,4-dioxane 10 ml, the mixture was reacted at 60 ° C for 3 hours while stirring. After the completion of the reaction, the reaction solution was filtered, and toluene (50 ml) was added to the filtrate and washed with water (30 ml χ3). The resulting organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODSC-18, developing solvent; acetonitrile/water &amp; =75/25-90/ 1 0 (volume ratio)) purification, to obtain a transparent liquid of 3-{4-(4-η·pentyl-cyclohexyl)-phenyl})-thiophenylphosphonium pentoxide. 27 g (isolation yield; 2 5 % ). This compound is a novel compound represented by the following physical properties. !H-NMR ( CDC13 - δ ( ppm ) ) ; 0.90 ( 3H, t, J = 7.0Hz ) , 1·01 ～ 1.55 ( 13H, m) , 1.88 ～ 1.95 ( 4H, m ), 2.47~2.58 (lH , m), 7.30~7.33(2H,m) ' 7.48 ~7.53(3H,m) , 7_68~7.71(2H,m) , 7.93 ~7.94( 1 H,m ) -80- 200927888 CI-MS ; 432 ( Μ) Example VI-4 (Synthesis of 4-{4-(4-n-pentyl-cyclohexyl)-phenyl}-thiosulphur pentoxide) Internal volume with stirring device, thermometer and reflux cooler 0.71g (2.50mmol) of 4-bromopentafluoropentabenzene, 4-pinaline 4-(4-n-pentylcyclohexyl)-phenylborate i, 〇6g (3.00mm〇l) was added to a 30ml container. ^ ), Dichloro {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}(3-chloropyridyl)palladium (trade name; PEPPSI (registered trademark)-IPr ( After making (3636 g (0.054 mmol)), potassium carbonate 1.35 g (7.50 mmol) and 1,4-dioxane 10 m 1 , the reaction was carried out at 1 ° C for 8 hours. After the completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by flash column chromatography (developing solvent; hexane) to give 4-{4-(4-n-pentyl-cyclohexyl)phenyl]-pentafluoride as a white solid. Base benzene 0.69 g (isolation yield; 64% ❹). This compound is a novel compound represented by the following physical properties. W-NMR (CDC13, δ (ppm)); 0.90 (3H, t, J = 7.〇Hz), 1.0 1 to 1.56 (1 3H, m ) , 1 · 8 7 〜1 · 9 5 ( 4 H, m ), 2.49~2.57(lH,m), 7.32(2H,d,J = 8.0Hz), 7.5 1 ( 2H,d,J = 8.3Hz ), 7.64 ( 2H,d,J = 8.8Hz ), 7.80 (2H,d,J = 8.8 Hz) CI-MS; 43 2 (M) -81 - 200927888 Example 乂1-5(4_(41-11-heptyl-biphenyl-4-yl)-pentafluoro Synthesis of thiophenyl benzene) 0.75 g (2.50 mmol) of 4-bromopentafluoropentabenzene and 4-(4-n-heptylbenzene) were added to a 25 ml vessel containing a stirring device, a thermometer and a reflux condenser. Phenylboronic acid pinacol ester 1.13 g (3.00 mmol), dichloro {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene} (3-chloropyridyl) Palladium (trade name; PEPPSI (registered trademark) - IPr (made by Aldrich ▲)) 0.03 6g (0.054mmol), potassium carbonate l. 〇4g (7.50mmol) and 1,4-dioxane l〇ml, The mixture was stirred for 1 hour at TC. After the reaction was completed, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Then, the concentrate was subjected to boiling column chromatography (expanded solution). ; hexane) and reverse phase 矽 gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 8 5 / 15 - 1 00 / 0 (capacity ratio)), to obtain a white solid 4- (4'-n-heptyl-biphenyl-4-yl)-thiophosphonium pentoxide. 23g (isolation yield; 20%) II This compound is a novel compound represented by the following physical properties 4-(4'-η-Heptyl-biphenyl-4-yl)-pentafluorobenzene-based benzene is a novel compound represented by the following properties: ^-NMR (CDCI3 &gt; δ ( ppm ) ) ; 0_89 ( 3H,t, J = 6.9 Η z ) , 1 _ 2 6 〜1 . 3 4 ( 8 Η,m ) , 1 · 6 6 〜1 · 6 9 ( 2 Η,m ), 2.64 ～2.69 (2H , m), 7.28 (2H, d, J = 8.5Hz), 7.56 (2H, d, J = 8.3Hz), 7.64~7.72(6H,m), 7.84( 2H - d - J-8.8Hz ) CI- MS; 454 (M)-82-200927888 Example VI-6 (2,6-Difluoro-3-{4-(trans-4-n-propylcyclohexyl)-phenyl}-pentafluorosulfide Synthesis of benzene) 3-ethoxy-6-bromopentafluoropentaphenyl hydrazine _3 3 0g (1.0 mmol) was added to a vessel containing a stirring device, a thermometer and a reflux condenser. (4·η-pentylcyclohexyl)-benzene After stirring 0.53 g (1.50 mmol) of boronic acid pinacol ester, 0.124 g of tetrakis(triphenylphosphine)palladium (〇-l〇8 mmol), 0.430 g (2.02 mmol) of tripotassium phosphate and 5 ml of 1,4-dioxane, stirring The reaction was carried out at 1 ° C for 4 hours. After the completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Next, 'the concentrate was purified by a flash column chromatography (developing solvent; hexane-hexane/ethyl acetate = 70/30 (volume ratio)) to give a white solid 2,6-difluoro-3-{ 4-(trans-4-n-propylcyclohexyl)-phenyl}-pentafluorobenzene benzene 0.32 g (isolation yield; 40%, 4-(4-n-propylcyclohexyl)iodobenzene Based on the calculation, the yield is calculated as follows. This compound is a novel compound represented by the following physical properties. iH-NMR (CDC13, δ (ppm)); 0.91 (3H, t, J = 6.6 Hz), 1.05 to 1.54 (13H, m), 1.87 to 1.96 (4H, m), 2.47 to 2.55 (1 H, m ), 4.0 9 ( 2 H,q · J = 6.9 H z ), 7.25 to 7.48 ( 7H,m) CI-MS ; 476 ( M ) Example VII-l (2,6-difluoro-3-{4 -(trans-4-n-propylcyclohexyl)-phenyl thiopentafluoride benzene synthesis) -83- 200927888 Add 2,6- into the 30ml container with stirring device, thermometer and reflux cooler Difluoro-3-(4,4,5,5-tetramethyl-1,3-dioxaborolan-2-yl)·thiosulfonyl quinone.791g (2.20mmol), 4 -(4-n-propylcyclohexyl)iodobenzoquinone 591g (丨80mrn〇l), tetrakis(triphenylphosphine)palladium rhodium"24g (〇.l〇8mmol), tripotassium phosphate 0 · 7 6 4 g ( After 3 · 60 mm ο 1 ) and 1,4-dioxane 10 mi, the reaction was carried out for 4 hours under stirring with i〇〇°c. After the end of the reaction, the reaction solution was filtered, and the mash was concentrated under reduced pressure. Next, the concentrate was subjected to a boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 80/2 0-&gt; Purification of 5/5 (capacity ratio)) gave 2,6-difluoro-3-{4-(trans-4-n-propylcyclohexyl)-phenyl}-pentafluorosulfobenzene 0.3 as a white solid. 2 g (isolation yield; 40%, based on 4-(4-n-propylcyclohexyl)iodobenzene, the yield was calculated). This compound is a novel compound represented by the following physical properties. H-NMR (CDC13, δ (ppm)); 0.9 1 (3H, t, J = 7.1 Hz), 1.05 to 1.55 (9H, m), 1 · 8 7 〜1 · 9 5 ( 4 H, m ), 2.48~2_56(lH,m), 6.91~7.13(lH,m) ' 7.29 ~ 7.40(4H,m), 7.53~7.61(lH,m) CI-MS ; 440 ( M ) Example VIII- 1 (Synthesis of 4-(4-n-pentyl-phenylethynyl)-thiosulfonylbenzene) Addition of diisopropylamine 17 ml, acetic acid in a 30 ml container equipped with a stirring device, a thermometer and a reflux condenser Copper(II) monohydrate-84- 200927888 0.047g (0.23mmol), triphenylphosphine 0.2 Og (0.7 5 mmol), fine chloride 0.071g (0.40mmol), 4-bromopentafluorothiobenzene 1.42g (5.00 mmol), the mixture was stirred at room temperature until the reaction solution became homogeneous, and the reaction was carried out for 15 minutes. After 1.03 g (6 mmol) of 1-ethynyl-4-n-pentylbenzene was added to the reaction solution, the mixture was reacted at room temperature for 4 hours while stirring. After the reaction was completed, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by flash column chromatography (developing solvent; hexane) to give 4-(4-n-pentyl-phenylethynyl)-pentafluorosulfonylbenzene 0.5 lg as a white solid. Isolated yield; 27%). The physical properties of this compound are shown below. H-NMR (CDC13, δ (ppm)); 0.89 (3H, t, J = 7.0 Hz), 1.3 1 to 1.35 ( 4H,m ) ' 1 · 5 7 〜1 · 6 7 ( 2 H, m ), 2.62 ( 2H, t, J = 7.7Hz), 7.18 ( 2H &gt; d, J = 8.5Hz), 7.45 ( 2H &gt; d, J = 8,3Hz ), 7.57 ( 2H,d,J = 8.3 Hz), 7.72 (2H, d, J = 8.8 Hz) CI-MS; 374 (M) Example VIII-2 (3-(4-n-pentyl-phenylethynyl)-thiosulfate Synthesis of benzene) 17 ml of diisopropylamine, 0.047 g (0.23 mmol) of copper acetate (hydrate), and 0.20 g of triphenylphosphine ( (.) were placed in a 30 ml vessel equipped with a stirring device, a thermometer and a reflux condenser. 75 mmol), palladium chloride 0.071 g (0.40 mmol), and 3-bromothiopentabenzene benzene 1.42 g (5.00 mmol), and then stirred at 40 ° C until the reaction solution became homogeneous, and -85-200927888 was reacted for 15 minutes. . The reaction solution was cooled to room temperature under stirring, and 1.03 g (6 mm 〇l) of 1-ethynyl-4-n-pentylbenzene was added, and the mixture was reacted at room temperature for 4 hours while stirring. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODS C-1 8, developing solvent; acetonitrile / water = 90/1 0 (capacity) Purification gave a 3-(4-n-pentyl-phenylethynyl)-thiosulfabenzene benzene 0.72 g (yield: 38%) as a white solid. This compound is a novel compound represented by the following physical properties. iH-NMR (CDC13, δ (ppm)); 0.90 ( 3H, t ' J = 7.0 Hz ) , 1.28 ~ 1 .3 8 ( 4H, m ) , 1 · 5 8 to 1.6 8 ( 2 H ' m ), 2.62 ( 2H - t, J = 7.7Hz ), 7.18 ( 2H, d, J = 8.5Hz), 7.46 (3H, m), 7.60 to 7.71 ( 2H, m) , 7.90 to 7.91 ( 1 H, m CI-MS ; 3 74 ( M ) 实施 Example VIII-3 (Synthesis of 2-fluoro-5-(4-n-pentyl-phenylethynyl)-thiosulfabenzene benzene) 51 ml of diisopropylamine, copper (II) acetate monohydrate 141.141 g (0-71 mmol), triphenylphosphine 0.60 g (2.25 mmol), palladium chloride ruthenium.213 g (20 ml) were placed in a 30 ml container of the thermometer and reflux cooler. 1.20 mmol) and 5.22 g (15.00 mmol) of 2-fluoro-5-iodothiosulfabenzene were stirred at 40 ° C until the reaction solution became homogeneous, and the reaction was carried out for 15 minutes. The reaction solution was cooled to a temperature of -86 to 200927888 while stirring, and 3.09 g (18 mmol) of 1-ethynyl-4-n-pentylbenzene was added, and the mixture was reacted at room temperature for 4 hours while stirring. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODS C-1 8, developing solvent; acetonitrile/water = 80/20 (capacity ratio) () Purification gave 5.27 g of 2-fluoro-5-(4-n-pentyl-phenylethynyl)-pentafluorothiobenzene as a white solid (yield: 90%). This compound is a novel compound represented by the following physical properties. !H-NMR (CDC13 &gt; δ (ppm ) ) ; 0.90 ( 3H, t, J = 6.8 Hz ) , 1.2 8 〜1 .3 8 ( 4H,m ) , 1 · 57 〜1.67 ( 2H,m ), 2 · 62 ( 2 H,t,J = 7.6 Hz ), 7.1 5 to 7.22 ( 3 H,m ), 7.44 ( 2H - d &gt; J = 8.3Hz) , 7.61 to 7.66 ( 1H,m) , 7.89 ~ 7.92 ( 1 H &gt; m ) CI-MS ; 3 92 ( M ) Example: ¥111-4 (4-{4-(4-11-pentyl-cyclohexyl)-phenylethynyl}-pentafluoride Synthesis of thiobenzene) Adding isopropanol l〇ml, copper(II) acetate-hydrate 0.026g (0.13mmol), triphenylphosphine O with a stirring device, thermometer and reflux cooler .llg (0.42 mmol), palladium chloride 0.039 g (0.22 mmol), 4-bromothiopentaphenyl benzoquinone. 78 g ( 2.76 mmol), and then stirred at 40 ° C until the reaction solution became homogeneous, and the reaction was carried out. minute. After adding 1-ethynyl-4-(4-n-pentylcyclohexyl)phenylhydrazine.7〇g (2.75 mmol) to the reaction solution, the mixture was reacted under a stirring condition at room-87-200927888 for 4 hours. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by a flash column chromatography (developing solvent; hexane) to give 4-{4-(4-n-pentyl-cyclohexyl)-phenylethynyl}-pentafluoro Sulfuryl benzoquinone. 〇 8g (isolation yield; 6%). This compound is a novel compound represented by the following physical properties. j-NMR (CDC13, δ (ppm)); 0.90 (3H &gt; t ' J = 6.9 Hz), 1.03 〜1 _ 52 ( 13H,m ) , 1.89 ( 4H,m), 2.49 (lH,m) , 7.21 (2H, d, J = 8.1 Hz), 7.46 (2H, d, J = 8.3 Hz), 7.57 (2H, d, J = 8.8 Hz), 7.72 (2H, d, J = 8.8 Hz) CI-MS 45 6 ( M ) Example VIII-5 (Synthesis of 4-(thiophen-3-yl-ethynyl)-pentafluorothiobenzene) 容器 Container with 50 ml of internal volume of stirring device, thermometer and reflux cooler 3-ethynylthiophene 0.54g (5.0mmol), 2-propanol 10〇11, water 1〇1111, 4-iodopentafluoropentabenzene 1.65§(5.〇111111〇1), sodium phosphate ten Dihydrate 3.80 g (10 mmol), 1 Ο % P d/C Ο . 4 4 g (water content 51.3%, TYPE K, manufactured by NE Chemcat Co., Ltd.) was reacted at 80 ° C for 6 hours while stirring. After the completion of the reaction, the reaction mixture was subjected to hydrazine, and the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by flash column chromatography (developing solvent; hexane) to give 4-(thiophen-3-yl-ethynyl)-pentafluorosulfobenzene 0.5 Og as a white solid (single off Rate; -88- 200927888 3 2%). This compound is a novel compound represented by the following physical properties. • H-NMR (CDCI3 * δ (ppm)); 7.21 ( 1H ' dd ' J = 1 · 1Hz, J = 5 · 0Ηζ ), 7.33 ( 1H, dd, J = 2.9Hz, J = 4.9Hz ), 7.5 6-7.5 9 ( 3H,m ) , 7.7 3 ( 2 H,d,J = 9 · 0 H z ) CI-MS ; 3 10 ( M ) Example VIII-6 (4-(thiophen-3-yl-)乙快基)-Synthesis of five gasified thiobenzenes. Add 30 ml of diethylamine, copper iodide (I) O.OlOg (0.05 mmol), and a container containing 30 ml of a stirring device, a thermometer and a reflux condenser. Dichlorobis(triphenylphosphine)palladium 0 · 0 7 0 g (0 · 1 0 mm ο 1 ), 4-iodide, five gasified thiobenzene, 1.65 g (5.00 mmol), 3-ethynylthiophene 0.54 g (5.00 After mmol), the mixture was reacted at room temperature for 1.5 hours under stirring. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was purified by a flash column chromatography (developing solvent; hexane) to give 4-(thiophen-3-yl-ethynyl)-pentafluorosulfonylbenzene 1-34 g as a white solid. ;87%). Example VIII-7 (Synthesis of 4-(thiophen-3-yl-ethynyl)-pentafluorothiobenzene) A container containing a stirring device, a thermometer, and a reflux condenser was added to a container of 30 ml, and diethylamine 30 ml was added. Copper iodide (I ) 〇.〇l〇g ( 0 · 0 5 mm 01 ), dichlorobis(triphenylphosphine) nickel ruthenium 6 5 g (〇·1 〇mm 01 ), -89- 200927888 4 - 1.65 g (5.00 mmol) of iodine pentafluorobenzene and 0.54 g (5.00 mm 〇1) of 3-ethynylthiophene, and reacted at room temperature for 8 hours while stirring. After the completion of the reaction, the reaction solution was analyzed by chemical ionization to confirm the presence of 4-(thiophen-3-yl-ethynyl)-pentafluorothiobenzene (molecular weight 310). Example VIII-8 (Synthesis of 4-phenylethynylthiophenylbenzene) A vessel containing 100 ml of a stirring apparatus, a thermometer and a reflux condenser was charged with diethylamine 80 ml and copper (I) iodide. 〇41g (〇0.20mmol), dichlorobis(triphenylphosphine)palladium 0.280g (0.40mmol), 4-iodopentafluoropentabenzene 6.60g (20.00mmol), ethynylbenzene 2.04g (20.00mmol) Thereafter, the mixture was reacted at room temperature for 1.5 hours under stirring. After the completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Next, the concentrate was subjected to boiling column chromatography (developing solvent; hexane) and reverse phase gel column chromatography (ODS C-18, developing solvent; acetonitrile / water = 60/40 - 70/3) Purification by 0 (volume ratio)) gave 5. <RTIgt; </RTI> <RTIgt; </RTI> <RTIgt; </RTI> <RTIgt;物 The physical properties of this compound are as follows. h-NMR (CDC13, δ (ppm)); 7.33 to 7.40 (3H, m), 7.52 to 7.61 (4H, m), 7.73 (2H, d, J = 9.0 Hz) CI-MS; 304 (M) Example VIII-9 (Synthesis of 2-(4-n-pentyl-phenylethynyl)-thiosulfonylbenzene) Container with internal capacity of 30 ml -90 - 200927888 with stirring device, thermometer and reflux cooler Add diethylamine l〇ml, copper iodide (!) 〇 005g (0.025mmol), dichlorobis(triphenylphosphine) nickel 0.014g (0.02 2mmol), 2_(trifluoromethanesulfonyloxy)pentafluoro 35 g (0.99 mmol) of thiophenyl hydrazine, 18 g (i 04 mm 〇1) of 1-ethyl carbazyl 4-n-pentyl phenylhydrazine, and then reacted at room temperature for 24 hours under stirring. After the completion of the reaction, the reaction solution was analyzed by chemical ionization to confirm the presence of 2-(4-n-pentyl-phenylethynyl)-pentafluorothiobenzene (molecular weight 374). 〇

G Example VIII-10 (Synthesis of 3-ethoxy-6-(4-n-pentyl-phenylethynyl)-thiosulfabenzene pentoxide) Internal volume with stirring device, thermometer and reflux cooler 10 ml of diethylamine, 10% copper iodide (I) 0.006 g (0.0 3 mmo 1 ), dichlorobis(triphenylphosphine) 0_022g (0.03 mmol), 3-ethoxy-6-bromine five were added to a 25 ml vessel. After sulfurylbenzene benzene 0.49 g (1.50 mmol) and 1-ethynyl-4_n-pentyl phenylhydrazine. 52 g (3.02 mmol), the mixture was reacted at room temperature for 18 hours while stirring. After the end of the reaction, the reaction solution was filtered. The filtrate was concentrated under reduced pressure. Next, the concentrate was purified by a flash column chromatography (developing solvent; hexane, hexane/ethyl acetate = 10/1 (volume ratio)) to give 3-ethoxy-6- (4) as a yellow solid. -n-pentyl-phenylethynyl)-thiosulfonylbenzene 0.13 g (isolation yield; 21%) ° This compound is a novel compound represented by the following physical properties ° • H-NMR ( CDCla 1 5 ( ppm ) ) ; 0-89 ( 3H ' t ' J = 6.8 Hz), 1.24~1.34 ( 3H, m), I49 ～i·54 ( 4H ' m ), 1.57 ～1.67 (2H'm) , 2.62 (2H'm), 4.17 (2H'-91 - 200927888 q, J = 6.9Hz), 7.16 to 7.33 (4H, m), 7.44~7·53 (3Η' m) CI-MS; 4 18 ( M) Example IX-1 (Synthesis of 4-{(trans,trans)-4,-n-pentyl-dicyclohexyl-4-yl-oxymethylpentafluorophenyl) with stirring device and thermometer The content of 30 ml of glass was added to (trans,trans)-4'-η-pentyl-dicyclohexyl-4-ol 0.379 g (1,5 mmol), 60% sodium hydride 0.0 60 g (1 · 5 After mmo 1 ) and 5 ml of tetrahydrofuran, the mixture was reacted at 40 ° C for 15 minutes while stirring. After adding 0.024 g (0.14 mmol) of potassium iodide and 297 g (1.0 mmol) of 4-bromomethylpentafluoropentafluoride, the mixture was reacted at 60 ° C for 10 hours while stirring. After the completion of the reaction, 5 ml of 1 mol/1 hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution, and the mixture was separated. The organic layer was washed twice with brine (20 ml) and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by silica gel column chromatography (developing solvent; hexane-hexane/ethyl acetate = 85/15 (capacity ratio)) to give a white solid. 4-{( trans,trans)-4'-n-pentyl-dicyclohexyl-4-yloxymethyl}-thiosulphur pentabenzene 0.390 g (0.83 mmol) (83% yield) ). This compound is a novel compound represented by the following physical properties. !H-NMR (CDC13, δ (ppm)) ; Ο . 8 1 〜1 . 3 2 ( 2 2 Η, m ), 1.67 ～1.79 (6H, m), 2.08~2.12 (2H, m), 3.22 ~ 3.29 (lH, m), 4.59 (2H, s), 7_41 to 7.44 (2H, m), 7.69 to 7.73 (2H, m) -92- 200927888 CI-MS; 449 (Ml 9 ) Example IX-2 ( Synthesis of 4-{(trans,cis)-4'-n-pentyl-dicyclohexyl-4-yl-oxymethyl}-thiosulfonylbenzene) Glass with a stirring device and a thermometer of 30 ml (trans,cis) -4,-n-pentyl-dicyclohexyl-4-ol 0.379 g (1.5 mm ο 1 ), 60% sodium hydride 0.060 g (1.5 mmol) and tetrahydrofuran 5 ml were added to the vessel. The mixture was reacted at room temperature for 15 minutes while stirring. After adding 0.025 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluoropentabenzene, the mixture was reacted at 60 ° C for 3.5 hours while stirring. After the reaction was completed, 5 ml of 1 mol/1 hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution, and the mixture was separated. The organic layer was washed twice with saturated brine (20 ml) and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane-hexane/ethyl acetate = 95/5 (volume ratio)) to give a pale yellow color. Liquid 4-{( trans,cis)-4'-n-pentyl-dicyclohexyl-4-yl-oxymethyl}-thiosulphur pentabenzene 0.370 g (0.79 mmol) (isolation yield 79 %). This compound is a novel compound represented by the following physical properties. 'H-NMR ( CDC13 ' δ ( ppm) ) ; 0.82 ~ 1.45 ( 26H, m ), 1.73~1.76 (4H, m) , 1.91~1.94 (2H, m) ' 3.61 (1H, s), 4.53 ( 2H , s ) , 7 _ 4 2 〜 7 · 4 5 ( 2 H, m ), 7.70 ～ 7.73 ( 2H, m ) CI-MS ; 46 8 ( M) -93- 200927888 Example IX-3 (4-{ (trans,trans) Synthesis of -4'-n-butyl-dicyclohexyl-4-yl-oxymethyl}-sulfuryl benzene benzene) Glass container with a stirring device and thermometer content of 30 ml After adding (trans'trans) -4'-n-butyl-dicyclohexyl-4-ol 0.358 g (1.5 mmol), 60% sodium hydride 0.060 g (1.5 mmol) and tetrahydrofuran 5 ml, stirring In the state, it was reacted at room temperature for 15 minutes. After adding 0.025 g (0.14 mmol) of potassium iodide and 297 g (1.0 mmol) of 4-bromomethylpentafluoropentafluoride, the mixture was reacted at 60 ° C for 4 hours while stirring. After the reaction was completed, 5 ml of 1 mol/1 hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution, and the mixture was separated. The organic layer was washed twice with brine (20 ml) and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane-hexane/ethyl acetate = 90/10 (volume ratio)) to give a white solid. 4-{(trans,trans)-4'-n-butyl-dicyclohexyl-4-yl-oxymethyl}-thiosulfabenzene benzene 0.400 g (0.88 mmol) (88% yield) ). This compound is a novel compound represented by the following physical properties. iH-NMR (CDC13, δ (ppm)); 0 · 7 7 〜1 · 3 2 ( 2 0 Η, m ), 1.67 ～1.79 ( 6H, m) , 2.08~2.12 (2H, m) ' 3.21 ～3.31 (lH, m), 4.59 (2H, s), 7.41 to 7.44 (2H, m), 7·70 to 7.73 (2H, m) CI-MS; 43 5 (M-19) Example IX-4 (Synthesis of 4-octyloxymethyl thiosulfonylbenzene) A glass vessel containing a stirring device and a thermometer with a content of 30 ml -94- 200927888 was added with 4-octyloxyphenol 〇.3 3 3 g (1.5 After adding 60 ml of 60% sodium hydride, 0.060 g (1.5 mmol) and 4 ml of tetrahydrofuran, the mixture was reacted at room temperature for 15 minutes while stirring. After adding 25 g of potassium iodide, 〇25 g (0.14 mniol), and 4-bromomethylpentafluoride phenyl hydrazine. 29 7 g (1.0 mmol), the reaction was carried out for 6 hours under stirring for 6 hours. After the reaction was completed, the reaction was carried out. 5 ml of 1 mol/1 hydrochloric acid and 50 ml of ethyl acetate vinegar were added to the solution, and the mixture was separated, and the organic layer was washed twice with saturated brine (20 ml) and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated and concentrated. Purification by hydrazine gel column chromatography (developing solvent; hexane-hexane/ethyl acetate = 95/5 (volume ratio)) to give 4- octyl oxymethyl pent Benzene 0.410 g (0.94 mmol) (94% yield). This compound is a novel compound represented by the following physical properties.] H-NMR (CDC13, δ (ppm)); 0.88 (3H, t, J = 6.8 Hz), 1.25 to 1.46 (10H, m), 1.71 to 1.80 (2H 'm), 3.88 to 3.92 (2H, m), 5.06 (2H's), 6_80 to 6·96 (4H, m), 7_50 to 7.53 ( 2H'm), 7.74~7.77(2H'm) CI-MS; 43 8 (M) Example IX-5 (4-(trans-4-phenyl-cyclohexyl-oxymethyl)-sulfur pentafluoride Synthesis of base benzene) with stirring device and thermometer A glass container having a volume of 30 ml was charged with 4 &amp; 113-4-phenyl-cyclohexanol oxime. 264 liter (1.5111111 〇 1), 60% sodium hydride 0.060 g (1.5 mmol), and tetrahydrofuran 5 ml, and stirred. 95-200927888, react at room temperature for 15 minutes. Add potassium iodide 〇.〇25g (0.1 4 mm ο 1 ), 4-bromomethyl thiosulfate benzene 0.29 78 (1.〇111111〇1), stir In the state of the reaction, the reaction was carried out at 60 ° C for 7 hours. After the reaction was completed, 5 ml of 1 mol/1 hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution to carry out liquid separation, and the organic layer was washed twice with saturated brine (20 ml) to dryness. After drying over magnesium sulfate, the obtained filtrate was concentrated, and the concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane-hexane/ethyl acetate = 95/5 (volume ratio)). , 4- (trans-4-phenyl-cyclohexyl-oxomethyl)-pentafluorobenzene benzene 0.3 00 g (0.94 mmol) (isolation yield 7 6%) was obtained as a white solid. A novel compound represented by the physical properties. ^-NMR (CDCI3 ' δ (ppm ) ) ; 1.4 9 〜1 . 5 8 ( 4 Η, m ), 1.96 (2H, m), 2.24 (2H, m), 2.54~ 2.56 (1H, m), 3.42~3.44(lH,m), 4.64(2H,s), 7.17~7.32 (5H,m), 7.45~7.47(2H,m), 7.72~7.75(2H'm ❹) CI-MS ; 3 73 ( Ml 9 ) Example IX-6 (Synthesis of 4-(cis-4-phenyl-cyclohexyl-oxymethyl)-thiosulfonylbenzene) Glass with a stirring device and a thermometer of 30 ml After adding 264 mg (1.5 mmol) of cis-4-phenyl-cyclohexanol, 0.060 g (1.5 mmol) of 60% sodium hydride and 5 ml of tetrahydrofuran to the vessel, the reaction was carried out at room temperature under stirring. minute. After adding 0.025 g (4 mmo1) -96-200927888 of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluoropentabenzene, the reaction was carried out for 6 hours under stirring, and the reaction was completed. 5 ml of 1 mol/1 hydrochloric acid and 50 ml of ethyl acetate were added to the solution, and the liquid layer was separated, and the organic layer was washed twice with 20 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated. The concentrate was purified by hydrazine gel column chromatography (developing solvent; hexane-hexane/ethyl acetate = 95/5 (capacity ratio)) to give 4-(cis-4-phenyl-ring) as a clear liquid. Hexyl-oxymethyl)-penta-sulfurylbenzene 0.260 g (0.66 mmol) (66% yield) 〇 This compound is a novel compound represented by the following physical properties. 1 H-NMR (CDCI3, δ (ppm) ) ) ) 1 . 5 3 〜1 · 72 ( 4Η,m ), l_82~1.96(2H,m) , 2·08 ～2.13(2H,m) ' 2.52 〜2.62(lH,m) , 3.72 ～3.90 ( lH,m), 4.58(2H,s), 7.16~7.33(5H,m), 7.46~7_49(2H,m) &gt; 7.73~7.76 ( 2H,m ) CI-MS ; 392 ( M ) Example Xl (4-[4-(4-pentyl-cyclohexyl)-benzylideneamino] pentathylthio Synthesis of benzene) A glass container containing 30 ml of a stirring device was charged with 4-aminothiophene benzoquinone. 2 g (0-91 mmol), 4-(4-pentyl-cyclohexyl)benzoic acid 0.25 § ( 0.91111111〇1), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 〇.21g (1.〇9mmol), 4-dimethylaminopyridine O. After OlOg (0.08 mmol) and dichloromethane (5 ml), the mixture was stirred at room temperature for 20 hours under stirring -97-200927888. After the reaction was completed, the reaction liquid was concentrated, and the obtained concentrate was a gel column. Purification by hexane (hexane/ethyl acetate = 20/1 (volume ratio)) to give 4-[4-(4-pentyl-cyclohexyl)-benzamideamino] sulfur pentafluoride as white crystal Benzoquinone. 5g (yield 11.6%) This compound is a novel compound having the following physical properties: !H-NMR (CDC13 ' δ (ppm) ) ; 0.87 ~ 0.92 ( 3H, m ), 1· 01 to 1.12 (2H, m), 1.24 to 1.44 (6H, m) ' 1.45 to 1.54 (4H, m), 1.88 to 1.91 (2H, m), 2.51 to 2.59 (1 H &gt; m ), 7.33 to 7.35 (2H,m), 7.74~7.80(6H,m), 7.90 (1H &gt; s ) CI-MS ; 476 ( M+l ) Example X-2 (4-[(4'-pentyl-dicyclohexyl-4-carbonyl)amino]] Synthesis of thiophenyl benzene pentoxide) -Amino thiopentafluoride.2g (〇.91mmol), 4'-pentyl-dicyclohexyl-4-carboxylic acid 0.25§(0.91111111〇1), 1-ethyl-3-(3- Dimethylaminopropyl)carbodiimide hydrochloride 〇21g (1.〇9mmol), 4-dimethylaminopyridine 0.010g (0.08mmol) and dichloromethane 5ml, stirred, The reaction was carried out at room temperature for 20 hours. After the completion of the reaction, the reaction solution was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 2 0/1 (volume ratio)) to obtain white crystals. -[( 4'-pentyl-dicyclohexyl-4-carbonyl)amino]pentafluorobenzene benzene 0.08 g (from -98 to 200927888 rate of 18.2%). This compound is a novel compound having the following physical properties. !H-NMR (CDCb * δ (ppm)); 0.8 2 to 0.9 0 (3 Η, m ), 0.95 to 1.22 (15 Η, m), 1.25 to 1.33 (4H, m), 1.48 to 2.03 (8H, m ), 2.04 ~ 2.21 ( lH, m), 7.26 ~ 7.27 (2H, m), 7.60 ~ 7_71 (3H, m) CI-MS; 482 ( M + l ) Example X-3 ( 3-[4- ( 4-pentyl-cyclohexyl)-benzamide amino group) Synthesis of thiophene benzene pentoxide. 3-Amino thiophene quinone benzoquinone was added to a glass container with a stirring capacity of 30 ml. 2g (0.91 mmol), 4-(4-pentyl-cyclohexyl)benzoic acid hydrazine. 25 g (0-91 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride After 0.21 g (1.09 mmol) of the salt, 4-dimethylaminosuccinic O.OlOg (0.08 mmol) and 5 ml of dichloromethane, the mixture was reacted at room temperature for 20 hours under stirring. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 20/1 (volume ratio)) to give white crystals 3- [4-(4-Pentyl-cyclohexyl)-benzimidamide] thiopentaphenyl quinone. 3 lg (yield 7 2 _ 1%). This compound is a novel compound having the following physical properties. ^-NMR (CDC13 » δ (ppm)); 0.87 ~ 0·92 ( 3H, m ), 1.04 ~ 1 · 1 2 ( 2H, m ) , 1.22 ~ 1.55 ( 1 2H, m ), 1.88 ~ 1.91 ( 4H ' m) , 2.50~2.58 ( 1H,m) , 7-31~ -99- 200927888

7.33 (2H,m), 7.34~7.54(2H,m), 7.77~8.05(4H,m), 8.05~8.06 ( 1 H,m ) CI-MS ; 476 ( M+l ) Example X-4 ( Synthesis of 3-[(4'-pentyl-dicyclohexyl-4-carbonyl)amino) thiopentasulfonate) ❹

To a glass container containing 30 ml of a stirring device, 0.2 g (0.91 mmol) of 3-aminopentafluoropentabenzene and 0.25 g (0.9 lmmol) of 4'-pentyl-dicyclohexyl-4-carboxylic acid were added to a glass vessel containing 30 ml of a stirring apparatus. , 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 0.21 g (1.09 mmol), 4-dimethylaminosole 0.010 g (0.08 mmol) and two After 5 ml of the chloroform, the mixture was reacted at room temperature for 20 hours in a disturbing state. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 2 0/1 (volume ratio)) to obtain white crystals. [( 4, _ pentyl-dicyclohexyl-4-indenyl)amino] thiopentaphenyl quinone. 26 g (yield 5 9.1%). This compound is a novel compound having the following physical properties. iH-NMR (CDC13, δ (ppm)); 〇. 8 2 〜1 _ 2 8 (1 7 Η, m ), 1.30~2.20 (9H, m), 7·39 〜7_48 (2H, m), 7 · 71 to 7.73 (1Η, m), 7.95 to 7.96 (1Η, m) CI-MS; 482 ( M + l ) , Example X·5 ( 4·[ ( 4'-decyloxy-biphenyl- Synthesis of 4-carbonyl)amino] thiopentasulfonylbenzene) -100- 200927888 4-Amino thiophene pentoxide hydrazide. 5g ( 2.27 mmol) was added to a glass vessel containing 30 ml of a stirring device. , 4'-nonyloxy-biphenyl-4-carboxylic acid 0.97g ( 2.27mmol ), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. 65 g ( 3.41 mm 〇I ), 0.050 g (0.4 mmol) of 4-dimethylaminopyridine and 10 ml of dichloromethane were reacted at room temperature for 20 hours while stirring. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 9/1 (volume ratio)) to give white crystals 4- [( 4'-Methoxy-biphenyl-4-carbonyl)amino] thiopentaphenyl quinone. 〇 3 g (yield 2.24%). This compound is a novel compound having the following physical properties. 'H-NMR ( CDC13, δ (ppm ) ) ; 0 ' 8 3 〜 0 · 8 8 ( 3 Η, m ), 1.25 〜 1.42 ( 1 4 Η, m ) , 1.6 8 〜 1 7 7 ( 2 Η, m ), 4.02 ~ 4.04 ( 2H, m ), 7 · 0 3 ~ 7.0 6 ( 2 Η, m ), 7.63~

7.72 (2H,m), 7.79 to 7.82 ( 2H,m) , 7.89 to 7.93 ( 2H ,m ) , 8.02 to 8·06 ( 4H,m ) CI-MS ; 556 ( M + l ) Example X-6 (Synthesis of 4-[(4'-heptyl-biphenyl-4-carbonyl)amino]] thiopentafluoride benzene) 4-amino-5 with a content of 30 ml in a glass vessel equipped with a stirring device 0.5 g (2.77 mmol) of thiophenylbenzene, 0.81 g (2.77 mmol) of 4'-heptyl-biphenyl-4-indole, and 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide hydrochloride 〇.65g (3.41mmol), 4-dimethylamino-101 - · 200927888 pyridine 0.050g (0.4mmol) and dichloromethane l〇ml, stirring, room temperature The reaction was carried out for 20 hours. After the reaction was completed, the reaction mixture was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 9/1 (volume ratio)) to give white crystals 4- [(4'-Heptyl-biphenyl-4-sulfo)amino]pentasulfonylbenzoquinone. 82 g (yield 7 2.6%). This compound is a novel compound having the following physical properties. W-NMR (CDC13, δ (ppm)); Ο · 8 6 Ο . 9 1 ( 3 Η, m

), 1.29~1.33(6H,m),:1.58~1.68(4H,m) ^ 2.63~2.68(2H,m), 7.27~7.30(2H,m), 7.53~7.55( 2H,m) , 7.69~ 7.76(6H,m), 7.91~7_93(2H,m), 8.03 ( H,s )

Cl-MS; 498 (M + l ) Example X-7 (Synthesis of 3-[(4'-tert-butyl-biphenyl-4-indenyl)amino]thioperthiobenzene) The content of the stirring device was increased by 30% in a glass container. 3_Amino thiopentaphenyl quinone. 5g ( 2.27mmol), 4'-tert-butyl-biphenyl-4-carboxylic acid hydrazine. 69g (2.27mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 〇65g (3.41mmol), 4-dimethylamino group steep, 〇 After 50 g (0.4 mmol) and 10 ml of the dichlorocarbyl compound, the reaction was carried out at room temperature for 20 hours under the conditions of the sample. After the completion of the reaction, the reaction solution was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl-ethyl ester = 9/1 (capacity ratio)) to obtain white crystals ( -102- 200927888 4,-tert-butyl-biphenyl-4-ylcarbonyl)amino]sulfa pentafluoride was substantially 〇.44 g (yield 4 2.7 %). This compound is a novel compound having the following physical properties. W-NMR (CDC13, δ (PPm)); m ~ 141 ( 9H ' m ), 7.43 to 7.55 (6H, m), 7.69 to 7.73 (2H, m), 7.87 to 8.09 (5H, m CI-MS; 456 (M+l) Example X-8 (3-[(4'-decyloxy-biphenyl-carbonyl)amino)] Synthesis of sulfur pentabenzene benzene) 3-Amino thiopentaphenyl quinone, 5 g ( 2.27 mmol ) and 4'-decyloxy-biphenyl-4-carboxylic acid 0.97 g (2.77 mm 〇l) were added to a 30 ml glass container. , 1-ethyl_3·(3-dimethylaminopropyl)carbodiimide hydrochloride 〇.65g (3.41mmo1), 4·dimethylamino succinyl H 0.050g (0.4mmol) After being dilute in the chloroform, the reaction was carried out at room temperature for 20 hours in a disturbing state. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 9/1 (volume ratio)) to give white crystals 3- [( 4 '-Methoxy-biphenyl-4-carbonyl)amino]]pentafluorobenzene benzene 0.54 g (yield 4 2 8 %). This compound is a novel compound having the following physical properties. 1 Η - NMR ( CD C13, δ ( p pm ) ) ; 0.8 6 〜 0 · 9 0 ( 3 Η, m ), 1.28 〜 1.61 ( 14 Η, m ) , 1 · 7 6 〜 1. 8 5 ( 2 Η, m ), 3_98 to 4.03 (2H, m), 6.97 to 7.01 (2H, m), 7.43 to -103- 200927888 7.57 (3H, m), 7·65 to 7.68 (2H, m), 7.87 to 7.93 (3H , m), 8.03 ～8.09 ( 2H,m ) CI-MS ; 5 5 6 ( M+l ) Example X-9 (3-[(4'-heptyl-biphenyl-4-carbonyl)amino) Synthesis of sulfur pentafluoride benzene)

3_Amino-5-vaporized thiophenyl hydrazine. 5g (2.27mmol) and 4'-heptyl-biphenyl-4-indolinic acid 0.81g (2.27mmol) were added to a glass vessel containing a stirring device. , 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 0.65g (3.41 mmol), 4-dimethylaminopyridine 0.050 g (0.4 mmol) and two After the chloroform, i〇ml, it was reacted at room temperature for 20 hours under stirring. After the completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by hydrazine gel column chromatography (hexane/ethyl acetate = 9/1 (capacity ratio)) to obtain white crystals 3_[ (4'-Heptyl-biphenyl-4-carbonyl)amino] thiopentaphenyl quinone 51 g (yield 4 5.1%). This compound is a novel compound having the following physical properties. H-NMR (CDC13, δ (ppm)); 0.87 to 0.91 (3H, m), 1.28 to 1.35 (6H'm), ι·6〇~1.70 (2H, m), 7.27 to 7.43 (3H'm) , 7_46~7.55(3H,m), 7_68~7.71( 2H'm), 7·87 ～7.94(3H,m), 8·03 ～8·09(2Η,ηι) CI-MS ; 498 ( M+ l) Example XI-1 (3-[(4-propoxy-benzylidene)amino] thiosulfate-104-200927888 Synthesis of benzene) Adding a glass container containing 30 ml of a stirring device 3_Amino thiopentafluoride benzene l.〇g (4.55mmol), 4-propoxybenzoic acid 0.75g (4.55mmol), molecular sieve 4A (1/16) 3g and dichlorocarbyl 20ml, stirred state The reaction was carried out at room temperature for 20 hours. After the reaction is completed, the reaction solution is filtered and concentrated, and hexane is added to the obtained concentrate, and the vessel is cooled to -20 to 40 ° C with dry ice to cause crystallization to precipitate, and the crystal is filtered to obtain 3-4- of white crystals. (4-propoxy-benzylidene)amino]0.47 g of thiopentafluoride benzene (yield 28.3%). This compound is a novel compound having the following physical properties. H-NMR (CDC13, δ (ppm)) : 1.0 3 〜 1.0 8 ( 3 Η , m ), 1_79 〜 l_90 (2H, m) , 3.97~4.02 (2H, m) ' 6.97 ～7.01 (2H, m ), 7.29~7.48( 2H,m), 7.55~7.60( 2H,m) , 7.82~7.85(2H,m) , 8.35(lH,s) CI-MS ; 3 6 6 ( M + l ) 实施 Example Synthesis of XI-2 (3-[(4-octadecyl-benzylidene)amino]] thiopentafluoride benzene) 3-amino-based pentafluorination in a glass container containing 30 ml of a stirring device Sulfurylbenzene l.〇g (4.55mmol), 4- to 18-unit benzophenone awake 1.07g (4.55mmol), molecular shop 4A (1/16) 3g and 20ml of dichlorocarbyl, after stirring, The reaction was carried out at room temperature for 20 hours. After the completion of the reaction, the reaction solution was filtered and concentrated, and hexane was added to the obtained concentrate. The vessel was cooled to -20 to 40 ° C with dry ice to cause crystallization to precipitate, and the crystal was filtered-105-200927888 to obtain white crystals. 3-[(4-Octadecyl-benzylidene)amino]pentafluorobenzene Benzene 0 · 2 7 g (yield 1 3 · 6 %). This compound is a novel compound having the following physical properties. !H-NMR (CDCls J δ (ppm) ) ; 0.87~0.91 ( 3H,m ), 1.29 〜1 .58 ( 1 OH,m ) , 1.7 9 〜1 · 8 3 ( 2 H,m ), 4.00 〜 4.05 ( 2H,m ) , 6.9 6 〜6 · 9 9 ( 4 H,m ) , 7.28 ~

7.31 (2H,m), 7.45~7.45(2H,m), 7.55~7.59( 2H ,m) , 7.80 ~7.85(2H,m) , 8.35(lH,s) o CI-MS ; 43 6 ( M + l) [Observing the liquid crystal phase optically by a polarizing microscope (confirming the presence or absence of the liquid crystal phase)] Observing the compound synthesized in the above examples using a melting point measuring device equipped with two polarizing plates of 90 degrees orthogonally in the light source and the microscope section Optical appearance. As a result, in the compounds shown in Figs. 1 to 18, it was confirmed that a liquid crystal phase having a clear filamentous structure (shading pattern) in a temperature region above the melting point was obtained [industrial property] by the production method of the present invention. The sulfur pentafluoride-based benzene compound can be used in the field of liquid crystal materials or in the field of medicine. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows the compound of Example 1-1: 4-{( trans, -106- 200927888 trans ) -4'-ethyl-dicyclohexyl-4-carbonyloxy}- A diagram of the liquid crystal phase of sulfur pentafluoride benzene. [Fig. 2] shows the compound of Example 1-2: liquid crystal of 4-{( trans, trans ) -4'-η-propyl-dicyclohexyl-4-carbonyloxy}-pentafluorobenzene benzene The phase diagram [Fig. 3] shows the compound of Example 1-3: 4-{( trans, trans) -4'-II-butyl·cyclohexyl-4-mineoxy}-penta-sulfuryl group A diagram of the liquid crystal phase of benzene. ® [Fig. 4] shows the compound of Example 1-4: 4-{( trans ' trans ) -4,-η-pentyl-dicyclohexyl-4-carbonyloxybufluorosulfonylbenzene Phase diagram. Fig. 5 is a view showing the liquid crystal phase of the compound 4- 4-(4,-η-pentyloxy-biphenyl-4-mineooxy)-pentafluorothiobenzene. Fig. 6 is a view showing the liquid crystal phase of the compound of Example 1-6: (4'-η-heptylbiphenyl-4-tetracarbonyl)-pentafluorothiobenzene. Fig. 7 is a view showing the liquid crystal phase of the compound of Example I-7, 4_(4'-η-癸Oxy © 甘跑# lean 4-carbonyloxy)·thiosulfabenzene benzene. The base-binben s] is a compound of the example ΙΙ-1: 4-{ ( trans, [Fig δ ^

, η-propyl-dicyclohexyl-4-yl-oxycarbonyl pentafluorobenzene benzene trans ) -4 - n rJ of the liquid crystal phase Figure 1 ° 〇Ί shows the compound of Example 11-2: 4-{ ( trans ' [Fig. 9 J, you are less, butyl-dicyclohexyl-oxyindolyl thiosulfate benzene trans) -4 'n' of liquid crystal phase

ιλΊ represents the compound of Example H·3: (trans' [Fig. 1 UJ-107-200927888 trans) -4'-n-pentyl-dicyclohexyl-4_yl-oxycarbonylbupentafluorobenzene The picture of the liquid crystal phase. [Fig. 11] shows the compound of Example III-8: 4-[{ ( trans ,trans) -4'-n-pentyl-dicyclohexyl-4-yl}-methoxy]-pentafluoride A diagram of the liquid crystal phase of thiobenzene. [Fig. 12] shows the liquid crystal phase of the compound of the example in-: 4-(4,-n-decyloxy-biphenyl-4-yl-methoxy)-pentafluorosulfobenzene Figure 〇 [Fig. 13] shows the compound of Example IV_i: 4-[2-{( trans ' trans ) -4'-n-pentyl-dicyclohexyl-4-yl}-vinyl]-pentafluoride A diagram of the liquid crystal phase of thiobenzene. [Fig. 14] shows the compound of Example IV-2: 3-[2-{(trans' trans)-4, n-pentyl-dicyclohexyl-4-yl}-vinyl]-thiosulfabenzene benzene The picture of the liquid crystal phase. [Fig. 15] shows the compound of Example V-2: 4-[2-{4-(trans-4-n-propyl-cyclohexyl)-phenyl-vinyl]-thiosulphur pentabenzene A picture of the liquid crystal phase. Fig. 16 is a view showing the liquid crystal phase of the compound of Example VI-4: 4-{4-(4-n-pentyl-cyclohexyl)-phenyl}-pentafluorothiobenzene. Fig. 17 is a view showing the liquid crystal phase of the compound of Example VI-5: 4-(4·-η-heptyl-biphenyl-4-yl)-pentaoxide benzene. Fig. 18 is a view showing the liquid crystal phase of the compound of Example VIII-4: 4-(4-(4-n-pentyl-cyclohexyl)-phenylethynyl}-pentafluoropentabenzene. 108-

Claims (1)

200927888 X. Patent Application No. 1 A method for producing a sulfur pentafluoride-based benzene compound represented by the following general formula (3), which is characterized in that a five-vapor sulfur basic compound represented by the following general formula (1) is used. The reaction is carried out by one or more compounds of the compound group represented by the following general formula (2). [Chemical Formula 1] a SF5 (1) 〇 (wherein A-based halogen atom, organic sulfonyloxy group, 〇 〇 h, _CH2〇H, -SH, -NH2, -COOH '-CHO, -HC = CH2, _c = cH &gt; -CH2X (X is the base with detachment), -BY2 (Y system represents hydroxy or carbon number) 1 to 10 alkoxy groups, 2 Ys may be the same or different, and when γ is an alkoxy group, 'the ring structure having two 'yard groups bonded to each other on the oxy group') may be a hydrogen atom on the benzene ring. It may be substituted by a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.) [Right 2] Tortoise R1OH, r1ch2oh, r1sh, r1cooh, r1ccx&gt;r2, r1cox, V (R1CO)z〇, R1HC=CH2, R1C^CH, R1CHO, R1NH2i R1X. (2) r1ch2x, r1by2 (wherein R1 may have an alkyl group having a carbon number of from 1 to 20, a cycloalkyl group having a carbon number of from 3 to 25, and a carbon number of from 7 to 20 Aralkyl group, Aryl or heteroaryl group having a carbon number of 6~25 2~20 aryl group of 'R2 an alkyl group of 1~6 carbon atoms based' X, Y system and the same as defined above) [Chem 3] (3) -109- 200927888 (wherein R1 is the same as the above, and Z is selected from -〇-0CH2-, -CH20-, -S-, -C〇0-, -0C0-, -C0NH-- CH=N-, -N=CH-, -NHCO-, -HC=CH-, -C=C-, n is 0 or 1). 2. The method for producing a thiosulfonylbenzene according to the first aspect of the patent application, wherein in the general formula (1), A is -OH, and the compound represented by -) is one or more selected from the group consisting of RiOOH, R1 RkO) 2〇 The compound (R1, X is the same as the above), and Z of -) is -COO-. 3. A method for producing a thiosulfonylbenzene according to the first aspect of the patent application, wherein in the general formula (1), A is -COOH, and (2) is a compound represented by RbH (R1 is the same as the above) (3) Z is -OCO-. 4. The method for producing a sulfur fluoride compound according to the second or third aspect of the patent application, which is in the presence of a carbodiimide compound. 5. The method for producing sulfur thiobenzene based on the first item of the patent application scope In the general formula (1), A is a 2- or 4-substituted halogen atom, the compound represented by the general formula (2) is: the same as the above), and the general formula (3) is Z-substituted or 4-substituted. -Ο -. 6. The method for producing thiosulfonylbenzene according to item 5 of the patent application's method is carried out in the presence of a base. 1 A method for producing a sulfur tetrafluoride benzene according to item 6 of the patent application, wherein the base is an alkali metal hydride. The linking group, the compound of the general formula (2 cox, (--the general formula (3 compound is carried out in the general formula, the general formula is a benzene group. The position of the compound is in the position d〇H (the compound in the position of the R1 position - 110-200927888 8. A method for producing a sulfur thiobenzene compound according to the first aspect of the patent application, wherein in the general formula (1), A is a halogen atom, and the compound represented by the general formula (2) is RiHCzCH: , Z of the general formula (3) is -HC=CH-. 9. A method for producing a thiosulfate-based benzene compound according to the first aspect of the patent application, wherein in the general formula (1), A is -HC = CH2 The compound represented by the general formula (2) is RiX, and the z of the general formula (3) is -HC = CH-〇1 0. The manufacture of the sulfur thiobenzene compound as in the eighth or ninth aspect of the patent application The method is carried out in the presence of a metal compound and a base. 1 1 The method for producing a sulfur oxysulfide-based benzene compound according to the first aspect of the invention, wherein the metal compound is a palladium compound. The method for producing a sulfur pentafluoride-based benzene compound according to the first item, wherein the alkali is a base a metal carbonate, an amine or a mixture of these 〇13. A method for producing a fluorinated thiobenzene compound according to the first aspect of the patent application' wherein, in the general formula (1), A is a halogen atom, and the general formula (2) The compound represented by the formula is RiBY2, and the η of the general formula (3) is 〇. 1 4. The method for producing a thiosulfate-based benzene compound according to the first aspect of the patent application, wherein in the general formula (1), Α is - ΒΥ2, the compound represented by the general formula (2) is WX, and the η of the general formula (3) is 0. 1 5 · The method for producing a thiosulfonated benzene compound as described in claim 13 or 14 It is carried out in the presence of a metal compound and a base. 1 6 _ The method for producing a thiosulfonylbenzene compound-111 - 200927888 of the fifth aspect of the patent application, wherein the metal compound is a palladium compound. In the general formula (1), A is a tooth atom, and the compound represented by the general formula (2) is RiC = CH, and the general formula (3) is a method for producing a thiosulfonated benzene compound according to the first aspect of the patent application. Z is -C=C-. 18. As described in the first paragraph of the patent application, the thiosulfonated benzene compound In the general formula (1), A is a halomethyl group, the compound represented by the general formula (2) is RhH, and the general formula (3) is Z-OCH2-〇1 9 The method for producing a sulfur pentafluoride-based benzene compound wherein the halogen atom is a chlorine atom, a bromine atom or an iodine atom. 20) A method for producing a sulfur thiobenzene compound according to the first item of the patent application' In the formula, A is -NH2, and the compound represented by the general formula (2) is RkOOH (R1 may have a substituent having a carbon number of 20 or less, a phenyl group, a biphenyl group, a cyclohexylphenyl group or a dicyclohexyl group). Z of the formula (3) is -CONH-. 21. The method for producing a thiosulfonated benzene compound according to the i-th aspect of the patent application, wherein in the general formula (1), A is _Nh2, and the compound represented by the general formula (2) is RiCH0 (R) Same as above), the z of the general formula (3) is -CH = N_. A sulfur pentabenzene benzene compound characterized by the following general formula (4) or (5), -112-2, a thiopentafluorobenzene compound, 200927888 [化4] (In the formula, R1 is the same as defined above, except in the case of a propyl group or an η-pentyl group). (wherein R1 is the same as described above). A sulfur pentafluoride benzene compound represented by the formula (7) or (8), which is represented by the formula (7), R1^X]^〇-^SF5 ri〇OO^〇_^SF5 (wherein, R1 is related to The same as before). A thiophene pentoxide compound represented by any one of the formulae (9) to (11), wherein (4) (5) (4), R1 is an n-characteristic having the following general (6) characteristics as follows: General (7) (9) Characteristics are as follows -113- 200927888 [Chem. 7] (10) (11) 26. A sulfur pentabenzene benzene compound characterized by the following general formula (12), 化βΗ,ΥΛ/Λ/Λ-ΒΡ, (12, 27. A sulfur pentafluoride benzene compound characterized by the following general formula (13), [Chem. 9] csHiiOO*〇-sf5 ( 13) 〇 φ 28. A sulfur pentafluoride benzene compound characterized by any of the following general formulas (14) to (17) τρς, -114- 200927888 [化10] (wherein R4 is an alkyl group having 2 to 12 carbon atoms and a thiopentabenzene compound, and the formula (18) represents: R4〇^\-^sf (wherein the R4 system Same as above) (14) (15) (16) (17) ) ° The characteristics are as follows: general (18) -115- 200927888 The single simple number table is the map table : Case map of this book ' ' 代定一二^ (( No 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (3) SFs (3) R1—Z -4-