JP5418226B2 - Method for producing pentafluorosulfanylbenzene compound and novel pentafluorosulfanylbenzene compound - Google Patents

Description

  The present invention relates to a method for producing a pentafluorosulfanylbenzene compound and a novel pentafluorosulfanylbenzene compound.

An oxycarbonylpentafluorosulfanylbenzene compound is a compound useful as, for example, a medicine or a liquid crystal material (see, for example, Patent Document 1).
Conventionally, as a method for synthesizing an oxycarbonylpentafluorosulfanylbenzene compound from a hydroxycarbonylpentafluorosulfanylbenzene compound, for example, pentafluorosulfanylbenzenecarboxylic acid chloride is reacted by reacting pentafluorosulfanylbenzenecarboxylic acid, methanol and thionyl chloride. A method for producing methyl pentafluorosulfanylbenzenecarboxylate is known. However, in this method, since a large excess of alcohol and thionyl chloride must be used, it is disadvantageous as an industrial production method such as complicated post-treatment (for example, see Patent Documents 1 and 2).

4-Oxypentafluorosulfanylbenzene compounds are also useful compounds as pharmaceuticals, liquid crystal materials, and the like (see, for example, Patent Document 3 and Non-Patent Document 1).
Conventionally, as a method for producing a 4-oxypentafluorosulfanylbenzene compound, for example, 4-nitropentafluorosulfanylbenzene is reduced to 4-aminopentafluorosulfanylbenzene, and the amino group is diazotized and then hydrolyzed. -A method of inducing a hydroxypentafluorosulfanylbenzene compound (for example, see Non-Patent Document 2), a method of reacting a 4-chloropentafluorosulfanylbenzene compound and a phenol compound at high temperature in the presence of potassium carbonate / cesium fluoride. (For example, refer nonpatent literature 3) etc. are known. However, these methods are disadvantageous as an industrial production method because many reaction steps are required and expensive cesium fluoride is required as a reagent.

A 2-oxypentafluorosulfanylbenzene compound is also a useful compound as a pharmaceutical or a liquid crystal material (see, for example, Non-Patent Document 4).
Conventionally, as a method for producing a 2-oxypentafluorosulfanylbenzene compound, 2-fluoro-5-nitropentafluorosulfanylbenzene, ethanol and potassium hydroxide are reacted under heating to reflux to give 2-ethoxy-5-nitropentafluoro. A method for obtaining sulfanylbenzene (Non-Patent Document 4) is disclosed. However, in this method, a nitro group is substituted at the 5-position, and it is clear that the reaction was promoted by the electron withdrawing property of the nitro group. In addition, there was no example until now as a manufacturing method of an unsubstituted 2-oxypentafluorosulfanylbenzene compound.

Alkenyl pentafluorosulfanylbenzene compounds are also useful compounds as pharmaceuticals, liquid crystal materials, and the like (see, for example, Non-Patent Document 5).
Conventionally, the alkenyl pentafluorosulfanylbenzene compound is prepared by mixing 3 or 4-iodopentafluorosulfanylbenzene, methyl acrylate and triethylamine in the presence of palladium acetate and triphenylphosphine, and heating under reflux overnight. A method of reacting and obtaining methyl 3- (3 or 4-pentafluorosulfanylphenyl) acrylate in a yield of 65 to 59% is disclosed (Non-Patent Document 5). However, this method has problems such as long reaction time and coloration of the obtained compound, and only examples of highly active alkenyl compounds having a methoxycarbonyl group are shown. There has been a need for sulfanylbenzene compounds.

Aryl pentafluorosulfanylbenzene compounds are also useful compounds as pharmaceuticals, liquid crystal materials, and the like (see, for example, Non-Patent Documents 1 and 5 and Patent Document 4).
Conventionally, arylpentafluorosulfanylbenzene compounds are produced by mixing 3 or 4-iodopentafluorosulfanylbenzene and phenylboronic acid or tris (n-butyl) phenyltin in the presence of tetrakis (triphenylphosphine) palladium. In addition, a method of obtaining 3 or 4-biphenylpentafluorosulfanylbenzene in a yield of 48 to 94% by reacting under heating under reflux for 18 hours (Non-Patent Document 5) is disclosed. However, this method only shows the use of a tin reagent having a long reaction time and a safety problem, and an example of a phenyl group.
In addition, a method of reacting a boronic acid derivative of a pentafluorosulfanylbenzene compound with an aryl halide in the presence of a metal compound (Patent Document 4) is known. However, the synthesis yield of boronic acid derivatives of various pentafluorosulfanylbenzene compounds used in this method is low, and as a result, synthesis development to various arylpentafluorosulfanylbenzene compounds is difficult.

Alkynylpentafluorosulfanylbenzene compounds are also useful compounds as pharmaceuticals and liquid crystal materials (see, for example, Non-Patent Documents 1 and 5).
Conventionally, as a method for producing an alkynylpentafluorosulfanylbenzene compound, a method in which a halogenopentafluorosulfanylbenzene compound and an alkynyl compound are reacted in the presence of a metal compound is known. However, in this method, the yield is low, the reaction time is long, and only examples of phenylacetylene are shown.
Oxymethylpentafluorosulfanylbenzene compounds are also expected to be useful as pharmaceuticals and liquid crystal materials. However, a method for producing an oxymethylpentafluorosulfanylbenzene compound is not known.

International Publication No. 2005/047240 Pamphlet US Patent Application Publication No. 2003/0216476 German Patent No. 10151491 International Publication No. 2005/123749 Pamphlet Eur.J.Org.Chem., 3095 (2005) J. Am. Chem. Soc. 84, 3058 (1962) Chimia; Chemie Report, 58 (3), 138 (2004) J. Fluorine Chem., 112, 287 (2001) Tetrahedron, 56,3399 (2000)

The present invention solves the above-mentioned problems, makes it possible to obtain a pentafluorosulfanylbenzene compound by a simple and safe method from readily available raw materials, and an industrially advantageous production method, and a novel pentafluorosulfanylbenzene It is an object to provide a compound.
That is, the present invention provides the following [1] to [6].
[1] A pentafluorosulfanylbenzene compound represented by the following general formula (1) is reacted with one or more compounds selected from the compound group represented by the following general formula (2): A method for producing a pentafluorosulfanylbenzene compound represented by the following general formula (3).

（式中、Ａは、ハロゲン原子、有機スルホニルオキシ基、−ＯＨ、−ＣＨ₂ＯＨ、−ＳＨ、−ＮＨ₂、−ＣＯＯＨ、−ＣＨＯ、−ＨＣ＝ＣＨ₂、−Ｃ≡ＣＨ、−ＣＨ₂Ｘ（Ｘは脱離性のある基を示す）、−ＢＹ₂（Ｙはヒドロキシ基又は炭素数１〜１０のアルコキシ基を示し、２つのＹは同一でも異なっていてもよく、Ｙがアルコキシの場合、２つのアルコキシ基上のアルキル基同士が結合した環状構造を有していてもよい。）を示し、ベンゼン環上の水素原子は、ハロゲン原子、アルキル基、シクロアルキル基、アラルキル基又はアリール基で置換されていてもよい。）

(In the formula, A represents a halogen atom, an organic sulfonyloxy group, —OH, —CH ₂ OH, —SH, —NH ₂ , —COOH, —CHO, —HC═CH ₂ , —C≡CH, —CH _2. X (X represents a leaving group), -BY ₂ (Y represents a hydroxy group or an alkoxy group having 1 to 10 carbon atoms, two Ys may be the same or different, and Y represents an alkoxy group. In this case, the alkyl group on the two alkoxy groups may have a cyclic structure in which the alkyl groups are bonded to each other.) The hydrogen atom on the benzene ring is a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. It may be substituted with a group.)

（式中、Ｒ¹は、置換基を有していてもよい、炭素数１〜２０のアルキル基、炭素数３〜２５のシクロアルキル基、炭素数７〜２０のアラルキル基、炭素数６〜２５のアリール基、又は炭素数２〜２０のヘテロアリール基を示し、Ｒ²は炭素数１〜６のアルキル基を示し、Ｘ、Ｙは前記と同じである。）

(In the formula, R ¹ may have a substituent, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 25 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 6 to 6 carbon atoms. 25 represents an aryl group or a heteroaryl group having 2 to 20 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and X and Y are as defined above.)

（式中、Ｒ¹は前記と同じであり、Ｚは、−Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＮＨＣＯ−、−ＨＣ＝ＣＨ−、−Ｃ≡Ｃ−から選ばれる連結基を示し、ｎは０又は１である。）
〔２〕下記一般式（４）又は（５）で表されるペンタフルオロスルファニルベンゼン化合物。

(In the formula, R ¹ is the same as defined above, and Z is —O—, —OCH ₂ —, —CH ₂ O—, —S—, —COO—, —OCO—, —CONH—, —CH═. A linking group selected from N-, -N = CH-, -NHCO-, -HC = CH-, -C≡C-, and n is 0 or 1.)
[2] A pentafluorosulfanylbenzene compound represented by the following general formula (4) or (5).

（式中、Ｒ¹は前記と同じである。但し、式（４）においては、Ｒ¹が、ｎ−プロピル基、ｎ−ペンチル基の場合を除く。）
〔３〕下記一般式（６）で表されるペンタフルオロスルファニルベンゼン化合物。

(In the formula, R ¹ is the same as described above, except that in Formula (4), R ¹ is an n-propyl group or an n-pentyl group.)
[3] A pentafluorosulfanylbenzene compound represented by the following general formula (6).

（式中、Ｒ¹は前記と同じである。）
〔４〕下記一般式（７）又は（８）で表されるペンタフルオロスルファニルベンゼン化合物。

(In the formula, R ¹ is the same as described above.)
[4] A pentafluorosulfanylbenzene compound represented by the following general formula (7) or (8).

（式中、Ｒ¹は前記と同じである。）
〔５〕下記式（９）〜（１３）のいずれかで表されるペンタフルオロスルファニルベンゼン化合物。

(In the formula, R ¹ is the same as described above.)
[5] A pentafluorosulfanylbenzene compound represented by any one of the following formulas (9) to (13).

〔６〕下記式（１４）〜（１８）のいずれかで表されるペンタフルオロスルファニルベンゼン化合物。

[6] A pentafluorosulfanylbenzene compound represented by any one of the following formulas (14) to (18).

（式中、Ｒ⁴は、炭素数２〜１２のアルキル基を示す。）

(In the formula, R ⁴ represents an alkyl group having 2 to 12 carbon atoms.)

  According to the present invention, an industrially advantageous production method capable of obtaining a pentafluorosulfanylbenzene compound from a readily available raw material by a simple and safe method, and a novel pentafluorosulfanylbenzene compound are provided. Can do.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the liquid crystal phase of the compound of Example I-1: 4-[(trans, trans) -4'-ethyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example I-2: 4-[(trans, trans) -4′-n-propyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example I-3: 4-[(trans, trans) -4′-n-butyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene. FIG. 4 shows a liquid crystal phase of the compound of Example I-4: 4-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene. FIG. 4 shows a liquid crystal phase of the compound of Example I-5: 4- (4′-n-pentyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene. FIG. 4 shows a liquid crystal phase of the compound of Example I-6: 4- (4′-n-heptyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene. FIG. 4 shows a liquid crystal phase of the compound of Example I-7: 4- (4′-n-decyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene. 1 is a diagram showing a liquid crystal phase of a compound of Example II-1: 4-[(trans, trans) -4′-n-propyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene. FIG. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example II-2: 4-[(trans, trans) -4′-n-butyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example II-3: 4-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example III-8: 4-[[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl] -methyloxy] -pentafluorosulfanylbenzene. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example III-11: 4- (4′-n-decyloxy-biphenyl-4-yl-methyloxy) -pentafluorosulfanylbenzene. FIG. 4 is a diagram showing a liquid crystal phase of the compound of Example IV-1: 4- [2-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl] -vinyl] -pentafluorosulfanylbenzene. . It is a figure which shows the liquid crystal phase of the compound of Example IV-2: 3- [2-[(trans, trans) -4'-n-pentyl-bicyclohexyl-4-yl] -vinyl] -pentafluorosulfanylbenzene. . It is a figure which shows the liquid crystal phase of the compound of Example V-2: 4- [2- [4- (trans-4-n-propyl-cyclohexyl) -phenyl] -vinyl] -pentafluorosulfanylbenzene. FIG. 4 is a diagram showing a liquid crystal phase of the compound of Example VI-4: 4- [4- (4-n-pentyl-cyclohexyl) -phenyl] -pentafluorosulfanylbenzene. It is a figure which shows the liquid crystal phase of the compound of Example VI-5: 4- (4'-n-heptyl-biphenyl-4-yl) -pentafluorosulfanylbenzene. FIG. 3 is a diagram showing a liquid crystal phase of the compound of Example VIII-4: 4- [4- (4-n-pentyl-cyclohexyl) -phenylethynyl] -pentafluorosulfanylbenzene.

The production method of the present invention comprises reacting a pentafluorosulfanylbenzene compound represented by the general formula (1) with one or more compounds selected from the compound group represented by the general formula (2). This is a method for producing a pentafluorosulfanylbenzene compound represented by the general formula (3).
The pentafluorosulfanylbenzene compound represented by the general formula (1) has the following chemical structure.

In the formula, A represents a halogen atom, an organic sulfonyloxy group, —OH, —CH ₂ OH, —SH, —NH ₂ , —COOH, —CHO, —HC═CH ₂ , —C≡CH, —CH ₂ X (X represents a leaving group), -BY ₂ (Y represents a hydroxy group or an alkoxy group having 1 to 10 carbon atoms, two Ys may be the same or different, and Y is alkoxy. It may have a cyclic structure in which alkyl groups on two alkoxy groups are bonded to each other.
The hydrogen atom on the benzene ring is 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 20 carbon atoms, or carbon. It may be substituted with a heteroaryl group of 2-20.

  The compound group represented by the general formula (2) is a group of compounds having the following chemical structure.

（式中、Ｒ¹は、置換基を有していてもよい、炭素数１〜２０のアルキル基、炭素数３〜２５のシクロアルキル基、炭素数７〜２０のアラルキル基、炭素数６〜２５のアリール基、又は炭素数２〜２０のヘテロアリール基を示し、Ｒ²は炭素数１〜６のアルキル基を示し、Ｘ、Ｙは前記と同じである。）

(In the formula, R ¹ may have a substituent, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 25 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 6 to 6 carbon atoms. 25 represents an aryl group or a heteroaryl group having 2 to 20 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and X and Y are as defined above.)

Here, the “leaving group” represented by X is not particularly limited as long as it is a substantially leaving group. Specific examples of X include halogen atoms such as chlorine atom, bromine atom and iodine atom; alkylsulfonyloxy groups such as methanesulfonyloxy group; arylsulfonyloxy groups such as benzenesulfonyloxy group and p-toluenesulfonyloxy group; trifluoro An organic sulfonyloxy group such as a lomethanesulfonyloxy group; an oxycarbonylalkyl group (—OCOR group, etc.), a trialkylsilyl group (—SiR ₃ group (R represents an alkyl group having 1 to 10 carbon atoms)), and the like. .
When the compound represented by the general formula (2) is R ¹ COX, X is preferably a chlorine atom, and when R ¹ X or R ¹ CH ₂ X is used, X is preferably a bromine atom or an iodine atom. And more preferably an iodine atom.
In addition to the above, A may be a group having an equivalent elimination action (for example, a halogenocarbonyl group, a halogenosulfonyl group, a diazo group, etc.) (for example, by E. Negishi). , “Handbook of Organopalladium Chemistry for Organic Synthesis”, Vol. 1, WILEY INTERSCIENCE, page 1133, 2002).

  The pentafluorosulfanylbenzene compound represented by the general formula (3) has the following chemical structure.

（式中、Ｒ¹は前記と同じであり、Ｚは、−Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｏ−−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＮＨＣＯ−、−ＨＣ＝ＣＨ−、−Ｃ≡Ｃ−から選ばれる連結基を示し、ｎは０又は１である。）

(In the formula, R ¹ is the same as above, and Z is —O—, —OCH ₂ —, —CH ₂ O——S—, —COO—, —OCO—, —CONH—, —CH═N A linking group selected from —, —N═CH—, —NHCO—, —HC═CH—, —C≡C—, and n is 0 or 1.

  Below, the specific example of the manufacturing method of the pentafluoro sulfanylbenzene compound represented by General formula (3) of this invention is demonstrated one by one.

(1) Production Example 1
Production Example 1 is characterized in that a hydroxypentafluorosulfanylbenzene compound and a carbonyl compound are reacted in the presence of a dehydrating agent, as shown in the following reaction formula. That is, in the general formula (1), A is —OH, and the compound represented by the general formula (2) is R ¹ COOH, R ¹ COX, (R ¹ CO) ₂ O (R ¹ , X is as defined above. It is one or more kinds of compounds selected from the same, and is a reaction in which Z in the general formula (3) is —COO—.

In the general formula (1a), any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. In addition, as long as the group does not particularly affect the reactivity of Production Example 1, the group may be substituted with a group other than the above-described substituent (an electron-withdrawing group or an electron-donating group).
The carbonyl compound used in the reaction of Production Example 1 includes at least one of carboxylic acid (R ¹ COOH), carboxylic acid halide (R ¹ COX), and carboxylic anhydride ((R ¹ CO) ₂ O). Can be mentioned.
R ¹ is an optionally substituted alkyl group having 1 to 20 carbon atoms, 3 to 25 carbon atoms, preferably a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, An aryl group having 6 to 25 carbon atoms, preferably 3 to 25 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and X represents a group having a leaving property.

Examples of the alkyl group include 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 nonyl group, and a decyl group. To 10 alkyl groups.
Examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. It is done.
Examples of the cycloalkyl group which may have a substituent include an alkyl group having 3 to 10 carbon atoms or a bicyclohexylyl group having 12 to 25 carbon atoms having an alkoxy group, an alkyl group having 3 to 10 carbon atoms, or an alkoxy group. And a phenylcyclohexyl group having 12 to 25 carbon atoms in total.
Examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group.
Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an anthryl group.
Examples of the aryl group which may have a substituent include alkylaryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more specifically, p-tolyl groups and p-xylyl groups. , A biphenylyl group having 12 to 25 carbon atoms having an alkyl group or an alkoxy group having 3 to 10 carbon atoms, a cyclohexylphenyl group having 12 to 25 carbon atoms having an alkyl group or an alkoxy group having 3 to 10 carbon atoms, and the like. It is done.
Examples of the heteroaryl group include carbon number 2 such as furyl group, benzofuryl group, pyrrolyl group, indolyl group, thienyl group, benzothienyl group, oxazolidyl group, pyrazolidyl group, pyridyl group, quinolyl group, pyrimidyl group, and thiadiazolidyl group. -20, preferably a C2-C10 heteroaryl group is mentioned.

Examples of the substituent include a substituent formed through a carbon atom, a substituent formed through an oxygen atom, a substituent formed through a nitrogen atom, a substituent formed through a sulfur atom, and a halogen atom.
Examples of the substituent formed through the carbon atom include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo Cycloalkyl groups such as heptyl group; Alkenyl groups such as vinyl group, allyl group, propenyl group and cyclopentenyl group; Heterocyclic groups such as quinolyl group, pyridyl group, pyrrolidyl group, pyrrolyl group, furyl group and thienyl group; Phenyl group Aryl groups such as tolyl group, fluorophenyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group; acetyl group, propionyl group, acryloyl group, pivaloyl group, cyclohexylcarbonyl group, benzoyl group, naphthoyl group, toluoyl Acyl group (aceta Carboxyl group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; aryloxycarbonyl group such as phenoxycarbonyl group; halogenated alkyl group such as trifluoromethyl group; cyano group It is done.

Examples of the substituent formed through the oxygen atom include an alkoxyl group such as a methoxyl group, an ethoxyl group, a propoxyl group, a butoxyl group, a pentyloxyl group, a hexyloxyl group, a heptyloxyl group, and a benzyloxyl group; a phenoxyl group And aryloxyl groups such as toluyloxyl group and naphthyloxyl group.
Examples of the substituent formed through the nitrogen atom include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a methylethylamino group, a methylpropylamino group, a methylbutylamino group, and a diphenylamino group. Secondary amino group; amide group such as N-methyl-N-methanesulfonylamide group and N-methyl-N-acetylamide group; morpholino group, piperidino group, piperazinyl group, pyrazolidinyl group, pyrrolidino group, indolyl group and the like Cyclic amino group; imino group.
Examples of the substituent formed through the sulfur atom include thioalkoxyl groups such as thiomethoxyl group, thioethoxyl group, and thiopropoxyl group; thioaryl groups such as thiophenoxyl group, thiotoluyloxyl group, and thionaphthyloxyl group. An oxyl group etc. are mentioned.
The above substituents include various isomers (the same applies below).
Examples of the leaving group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom.

  The hydroxypentafluorosulfanylbenzene compound used in the reaction of Production Example 1 was obtained after reacting a halogenopentafluorosulfanylbenzene compound with a hydroxy compound as shown in the following reaction formula, for example. It can be obtained by deprotecting the compound.

(In the formula, X ¹ represents a halogen atom and P represents a protecting group. Note that any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. .)
The amount of the carbonyl compound used in the reaction of Production Example 1 is preferably 0.5 to 20 mol, more preferably 0.9 to 10 mol, and particularly preferably 1. mol with respect to 1 mol of the hydroxypentafluorosulfanylbenzene compound. 0 to 5 moles.

The dehydrating agent used in the reaction of Production Example 1 refers to a compound that accelerates the condensation reaction between a carbonyl compound and an alcohol. As the dehydrating agent to be used, a dehydrating agent that does not affect the pentafluorosulfanyl group is suitably employed. Specific examples of the compound include inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid; clay minerals such as acidic clay; Amberlite (trade name), Dowex (trade name), Diaion (trade name) Sulphonic acid type cation exchange resins such as Deniolite (trade name), Levacit (trade name), Sumikaion (trade name); fluorinated sulfonic acid resins such as Nafion; inorganic oxides such as silica alumina, zeolite and vanadium oxide; Heteropolyacids; Halogenated sulfonyls such as thionyl chloride and sulfonyl bromide; Organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid; 2-methyl-6-nitrobenzoic anhydride, etc. Acid anhydrides; phosphorus compounds such as diphenylphosphonyl azide and diethyl cyanophosphate; 4- (4,6-dimethyl) Triazine compounds such as xy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride hydrate; dicyclohexylcarbodiimide, 1-ethyl-3- (dimethylaminopropyl) carbodiimide or its hydrochloride And a carbodiimide compound (which may be an acid salt). Among these, sulfonic acid type cation exchange resin, carbodiimide compound, inorganic acid, more preferably carbodiimide compound, particularly preferably 1-ethyl-3- (dimethylaminopropyl) carbodiimide hydrochloride is used. In addition, you may use these dehydrating agents individually or in mixture of 2 or more types.
The amount of the dehydrating agent to be used is preferably 0.001 to 20 mol, more preferably 0.01 to 10 mol, and particularly preferably 0.1 to 5 mol with respect to 1 mol of the hydroxypentafluorosulfanylbenzene compound. .

The reaction of Production Example 1 is desirably performed in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, water; alcohols such as methanol, ethanol, isopropyl alcohol and t-butyl alcohol; tertiary amines such as trimethylamine, triethylamine, tributylamine and diisopropylethylamine; heterocyclic amines such as pyrrolidine, pyridine and quinoline; acetone , Ketones such as methyl ethyl ketone and methyl isobutyl ketone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3 -Ureas such as dimethylimidazolidine-2,4-dione; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; nitriles such as acetonitrile and propionitrile; diethyl ether, diisopropyl ether, Ethers such as lahydrofuran, dimethoxyethane and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; halogenated aliphatic hydrocarbons such as dichloromethane and chloroform Is mentioned.
Among these, preferably ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, more preferably ethers, halogenated aliphatic hydrocarbons, particularly preferably halogens. Aliphatic hydrocarbons are used. In addition, you may use these solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, and particularly preferably 1 to 30 ml with respect to 1 g of the hydroxypentafluorosulfanylbenzene compound.

The reaction of Production Example 1 is performed by, for example, a method of mixing a hydroxypentafluorosulfanylbenzene compound, a carbonyl compound, a dehydrating agent, and a solvent and reacting them while stirring.
The reaction temperature at that 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, but is usually normal pressure or increased pressure. To do. The reaction of Production Example 1 can also be carried out while removing water from the reaction system by, for example, azeotropic dehydration of water produced as a by-product or present. Moreover, the additive (For example, organic amines, such as 4-dimethylamino pyridine and a triethylamine) which improves the reaction rate of manufacture example 1 may exist.
A pentafluorosulfanylbenzene compound is obtained by the reaction of Production Example 1. After the reaction is completed, for example, general methods such as neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, sublimation, column chromatography, etc. Isolated and purified by

In the pentafluorosulfanylbenzene compound represented by the general formula (4) or (5) obtained by the reaction of Production Example 1, the compounds of Examples I-1 to 7 are useful compounds exhibiting a liquid crystal phase, Example I-1,
3 and 5-12 are novel compounds.

(In the formula, R ¹ is the same as described above, except that in Formula (4), R ¹ is an n-propyl group or an n-pentyl group.)
In the general formulas (4) and (5), a particularly suitable compound is a pentafluorosulfanylbenzene compound in which R ¹ has an alkyl group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms.

(2) Production Example 2
Production Example 2 is characterized in that pentafluorosulfanylbenzenecarboxylic acid and a hydroxy compound are reacted in the presence of a dehydrating agent as shown in the following reaction formula. That is, in General Formula (1), A is —COOH, the compound represented by General Formula (2) is R ¹ OH, and Z in General Formula (3) is —OCO—.

In the general formula (1b), any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. In addition, as long as the group does not particularly affect the reactivity of Production Example 2, the group may be substituted with a group other than the above-described substituent (an electron-withdrawing group or an electron-donating group).
The hydroxy compound used in the reaction of Production Example 2 is represented by R ¹ OH. R ¹ is the same as described in Production Example 1. Specific examples thereof include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, tetracosanol, alkyl alcohols such as (4′-pentyl-bicyclohexyl-4-yl) methanol; cyclopentanol, Cyclohexanol such as cyclohexanol, 4′-pentyl-bicyclohexyl-4-ol; benzyl alcohol, phenethyl alcohol, [4- (4-pentyl-cyclohexyl) -phenyl] -methanol, (4′-heptyl-biphenyl-) Examples include aralkyl alcohols such as 4-yl) -methanol and (4′-decyloxy-biphenyl-4-yl) -methanol; and aryl alcohols such as phenol, cresol and 4-pentylcyclohexylphenol.

In addition, the pentafluorosulfanylbenzenecarboxylic acid compound used in the reaction of Production Example 2 includes, for example, a halogenopentafluorosulfanylbenzene compound and a metal lithium reagent (for example, alkyllithium) as shown by the route a in the following formula. After the reaction, it can be obtained by reacting the obtained compound with carbon dioxide.
Moreover, as shown by the route b of the following formula, it can be obtained by reacting a halogenopentafluorosulfanylbenzene compound with metal magnesium to form a halogenomagnesium pentafluorosulfanylbenzene compound and further reacting with carbon dioxide.

（式中、Ｘ¹はハロゲン原子を示し、Ｒは炭化水素基を示す。なお、ベンゼン環上の任意の水素原子は、アルキル基、シクロアルキル基、アラルキル基又はアリール基で置換されていてもよい。）

(In the formula, X ¹ represents a halogen atom and R represents a hydrocarbon group. Note that any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. Good.)

The amount of the hydroxy compound used in the reaction of Production Example 2 is preferably 0.5 to 20 mol, more preferably 0.9 to 10 mol, particularly preferably 1 with respect to 1 mol of the pentafluorosulfanylbenzenecarboxylic acid compound. 0.0-5.0 moles.
The dehydrating agent used in the reaction of Production Example 2 is the same as that used in Production Example 1. The amount of the dehydrating agent used is preferably 0.001 to 20 mol, more preferably 0.01 to 10 mol, and particularly preferably 0.1 to 5 mol with respect to 1 mol of the pentafluorosulfanylbenzenecarboxylic acid compound. .
The reaction of Production Example 2 is desirably performed in the presence of a solvent, but the solvent used is selected from those described in Production Example 1. Among these, preferably ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, more preferably ethers, halogenated aliphatic hydrocarbons, particularly preferably halogens. Aliphatic hydrocarbons are used. In addition, you may use these solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, and particularly preferably 1 to 30 ml with respect to 1 g of the pentafluorosulfanylbenzenecarboxylic acid compound.

The reaction of Production Example 2 is performed by, for example, a method of mixing a pentafluorosulfanylbenzenecarboxylic acid compound, a hydroxy compound, a dehydrating agent, and a solvent and reacting while stirring. The reaction temperature at that 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, but is usually normal pressure or increased pressure. To do. The reaction of Production Example 2 can also be performed while removing water from the reaction system by, for example, azeotropic dehydration of water produced as a by-product or present. Moreover, the additive (For example, organic amines, such as 4-dimethylamino pyridine and a triethylamine, etc.) which improves the reaction rate of manufacture example 2 may exist.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.

  In the pentafluorosulfanylbenzene compound represented by the general formula (6) obtained by the reaction of Production Example 2, the compounds of Examples II-1 to III-3 are useful compounds exhibiting a liquid crystal phase, and Example II-1 ~ 7 are novel compounds.

(In the formula, R ¹ is the same as described above.)
In the general formula (6), a particularly suitable compound is a pentafluorosulfanylbenzene compound in which R ¹ has an alkyl group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms.

(3) Production Example 3
Production Example 3 is characterized in that a 2- or 4-halogenopentafluorosulfanylbenzene compound and a hydroxy compound are reacted in the presence of a base, as shown in the following reaction formula. That is, in the general formula (1), A is a halogen atom substituted at the 2-position or 4-position, and the compound represented by the general formula (2) is R ¹ OH (R ¹ is the same as above). And Z in the general formula (3) is —O— substituted at the 2-position or 4-position.

In the general formula (1c), X ¹ represents a halogen atom, preferably a fluorine atom, a chlorine atom, more preferably a fluorine atom. Arbitrary hydrogen atoms on the benzene ring are similar to general formula (1) in that the alkyl group has 1 to 20 carbon atoms, the cycloalkyl group has 3 to 20 carbon atoms, the aralkyl group has 7 to 20 carbon atoms, and 6 carbon atoms. It may be substituted with ˜20 aryl groups or C2-C20 heteroaryl groups.
Specific examples of the 4-halogenopentafluorosulfanylbenzene compound represented by the general formula (1c) include 4-fluoropentafluorosulfanylbenzene, 4-chloropentafluorosulfanylbenzene, 4-bromopentafluorosulfanylbenzene, 4-iodo Examples include pentafluorosulfanylbenzene. Among these, 4-fluoropentafluorosulfanylbenzene and 4-chloropentafluorosulfanylbenzene are preferable, and 4-fluoropentafluorosulfanylbenzene is more preferable.
Specific examples of the 2-halogenopentafluorosulfanylbenzene compound represented by the general formula (1c) include 2-fluoropentafluorosulfanylbenzene, 2-chloropentafluorosulfanylbenzene, 2-bromopentafluorosulfanylbenzene, and 2-iodo. Examples include pentafluorosulfanylbenzene. Among these, 2-fluoropentafluorosulfanylbenzene and 2-chloropentafluorosulfanylbenzene are preferable, and 2-fluoropentafluorosulfanylbenzene is more preferable.

The hydroxy compound used in the reaction of Production Example 3 is represented by R ¹ OH. R ¹ 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 preferably 0.8 to 20 mol, more preferably 0.9 to 15 mol, relative to 1 mol of the 2- or 4-halogenopentafluorosulfanylbenzene compound. Most preferably, it is 1.0-10 mol.
Examples of the base used in the reaction of Production Example 3 include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate and potassium bicarbonate. Alkali metal hydrogen carbonates; phosphates such as trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, etc .; sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium alkali metal alkoxides such as t-butoxide and potassium t-butoxide; alkali metal or alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; ethylamine, propylamine, butylamine, aniline, Such as benzylamine Primary amine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, methylethylamine, methylpropylamine, diphenylamine and other secondary amines, trimethylamine, triethylamine, tributylamine, diisopropylethylamine and other tertiary amines, pyrrolidine And heterocyclic amines such as piperidine and pyridine.
Among these, preferably an alkali metal hydride, more preferably sodium hydride is used. In addition, these bases may be used individually or in mixture of 2 or more types, and may be used as an organic solvent solution.
The amount of the base used is preferably 0.8 to 20 mol, more preferably 0.9 to 15 mol, particularly preferably 1.0 to 1 mol with respect to 1 mol of the 2- or 4-halogenopentafluorosulfanylbenzene compound. 10 moles.

The reaction of Production Example 3 is desirably performed in the presence of a solvent, and specific examples of the solvent are the same as those shown in Production Example 1. Preferably ethers, amides and ureas are used, more preferably amides and ureas. In addition, you may use these solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 75 ml, and particularly preferably 1 to 50 ml with respect to 1 g of the 2- or 4-halogenopentafluorosulfanylbenzene compound.
The reaction of Production Example 3 is performed, for example, by a method of mixing a 2- or 4-halogenopentafluorosulfanylbenzene compound, a hydroxy compound, a base, and a solvent and reacting them while stirring. The reaction temperature at that 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.
A 2- or 4-oxypentafluorosulfanylbenzene compound is obtained by the reaction of Production Example 3. After completion of the reaction, for example, neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, sublimation, column chromatography. It is isolated and purified by a general method such as

  The 4-oxypentafluorosulfanylbenzene compound obtained by the reaction of Production Example 3 is represented by the general formula (3c). Specific examples of the compound include 4-methoxypentafluorosulfanylbenzene, 4- Ethoxypentafluorosulfanylbenzene, 4-propoxypentafluorosulfanylbenzene, 4-butoxypentafluorosulfanylbenzene, 4-cyclohexyloxypentafluorosulfanylbenzene, 4-benzyloxypentafluorosulfanylbenzene, 4-phenoxypentafluorosulfanylbenzene, 4- [4- (4-Pentyl-cyclohexyl) -phenoxy] -pentafluorosulfanylbenzene, 4- (4′-pentyl-bicyclohexyl-4-yloxy) -pentafluorosulfa Nylbenzene, 4- [4- (4-pentylcyclohexyl) benzyloxy] -pentafluorosulfanylbenzene, 4- (4′-pentyl-bicyclohexyl-4-ylmethoxy) -pentafluorosulfanylbenzene, 4-tetracosyloxypenta Examples thereof include fluorosulfanylbenzene, 4- (4′-heptyl-biphenyl-4-ylmethoxy) -pentafluorosulfanylbenzene, 4- (4′-decyloxy-biphenyl-4-ylmethoxy) -pentafluorosulfanylbenzene, and the like.

  The 2-oxypentafluorosulfanylbenzene compound obtained by the reaction of the present invention is represented by the general formula (3c). Specific examples of the compound include 2-methoxypentafluorosulfanylbenzene and 2-ethoxy. Pentafluorosulfanylbenzene, 2-propoxypentafluorosulfanylbenzene, 2-butoxypentafluorosulfanylbenzene, 2-cyclohexyloxypentafluorosulfanylbenzene, 2-benzyloxypentafluorosulfanylbenzene, 2-phenoxypentafluorosulfanylbenzene, 2- [ 4- (4-Pentyl-cyclohexyl) -phenoxy] -pentafluorosulfanylbenzene, 2- (4′-pentyl-bicyclohexyl-4-yloxy) -pentafluorosulfani Benzene, 2- [4- (4-pentylcyclohexyl) benzyloxy] -pentafluorosulfanylbenzene, 2- (4′-pentyl-bicyclohexyl-4-ylmethoxy) -pentafluorosulfanylbenzene, 2-tetracosyloxypenta Examples thereof include fluorosulfanylbenzene, 2- (4′-heptyl-biphenyl-4-ylmethoxy) -pentafluorosulfanylbenzene, 2- (4′-decyloxy-biphenyl-4-ylmethoxy) -pentafluorosulfanylbenzene, and the like.

  In the pentafluorosulfanylbenzene compound 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 exhibiting a liquid crystal phase, Examples III-1 to 14 are novel compounds.

(In the formula, R ¹ is the same as described above.)
In general formulas (7) and (8), a particularly suitable compound is a pentafluorosulfanylbenzene compound in which R ¹ has an alkyl group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms.

(4) Production Example 4
Production Example 4 is characterized in that a halogenopentafluorosulfanylbenzene compound and a vinyl compound are reacted in the presence of a metal compound, as shown in the following reaction formula. That is, in the general formula (1), A is a halogen atom, the compound represented by the general formula (2) is R ¹ HC═CH ₂ , and Z in the general formula (3) is —HC═CH—. It is a certain reaction.

The halogenopentafluorosulfanylbenzene compound of Production Example 4 is represented by the general formula (1c), and X ¹ represents 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 an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
The vinyl compound used in the reaction of Production Example 4 is represented by R ¹ HC═CH ₂ . Here, R ¹ 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 0.8 to 20 mol, more preferably 0.9 to 15 mol, and particularly preferably 1. mol per 1 mol of the halogenopentafluorosulfanylbenzene compound. 0 to 10 moles.

The base used in the reaction of Production Example 4 is the same as that described in Production Example 3. Among them, alkali metal carbonates, amines, more preferably potassium carbonate, particularly preferably triethylamine are used. In addition, these bases may be used individually or in mixture of 2 or more types, and may be used as aqueous solution or organic solvent solution.
The amount of the base used is preferably 0.5 to 5.0 mol, more preferably 0.7 to 4.0 mol, and particularly preferably 1.0 to 3.0 mol with respect to the halogenopentafluorosulfanylbenzene compound. Is a mole.
The reaction of Production Example 4 is desirably performed in the presence of a solvent, but the solvent used is the same as that described in Production Example 1. Among them, preferably nitriles, amides, ethers, more preferably acetonitrile, N, N-dimethylformamide, 1,4-dioxane, particularly preferably N, N-dimethylformamide, 1,4-dioxane. used. In addition, you may use these organic solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.1 to 50 ml, more preferably 0.2 to 30 ml, and particularly preferably 0.3 to 20 ml with respect to 1 g of the halogenopentafluorosulfanylbenzene compound.

Examples of the metal compound used in the reaction of Production Example 4 include palladium acetate, bis (acetate) bis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, bis (acetonitrile) dichloropalladium, and bis (benzonitrile). Palladium salts such as dichloropalladium; palladium chlorides such as palladium chloride; tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, nitrogen-containing heterocyclic carbenepalladium complexes (for example, dichloro {1,3- Bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium, allylchloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene Palladium, 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, 1,3-bis (2,4,6-trimethylphenyl) imidazol-2-ylidene Palladium complexes such as (1,4-naphthoquinone) palladium dimer; palladium-supported compounds such as palladium / carbon, palladium / barium sulfate, palladium-platinum / carbon; bis (cyclopentadienyl) nickel, dichlorobis (triphenylphosphine) nickel Nickel compounds such as: cobalt compounds such as dichloro (diphenylphosphinohexane) cobalt; rhodium compounds such as chloro (1,5-cyclooctadiene) rhodium dimer (for example, “Experimental Chemistry”, edited by the Chemical Society of Japan) Lecture ", 5th edition, 164-1 Among these, palladium compounds are preferable, palladium complexes are more preferable, nitrogen-containing heterocyclic carbene palladium complexes are particularly preferable, and more specifically, dichloro {1,3-bis (2,6 -Diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium These metal compounds may be used alone or in admixture of two or more.
Further, a commercially available product such as dichlorobis (triphenylphosphine) palladium can be used, or it can be prepared from palladium chloride and triphenylphosphine in a reaction system and used as it is regardless of whether or not it is isolated.
The amount of the metal compound to be used is preferably 0.1 mol% to 100 mol%, more preferably 0.1 mol% to 50 mol%, particularly preferably 0.1 mol%, based on 1 mol of the halogenopentafluorosulfanylbenzene compound. 1 mol% to 20 mol%.

In the reaction of Production Example 4, a phosphine ligand and a phase transfer catalyst may coexist in order to control the reactivity (see, for example, Tetrahedron, 52, 10113 (1996)).
Examples of the phosphine ligand used include trialkyl phosphines such as tri-n-butyl phosphine, tri-t-butyl phosphine, and tricyclohexyl phosphine; triaryl phosphines such as triphenyl phosphine and tri-o-tolyl phosphine. And diphosphines such as 1,4-bis (diphenylphosphino) butane and 1,1′-bis (diphenylphosphino) ferrocene, but are preferably trialkylphosphine, more preferably tri-t-butylphosphine. .
Examples of the phase transfer catalyst used include tetra-n-methylammonium chloride, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, and tribromide. Tetra-n-butylammonium, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylammonium nitrate, tetra-n-butylammonium methanesulfonate , Tetra-n-butylammonium trifluoromethanesulfonate, cyanotetra-n-butylammonium, hydroxytetra-n-butylammonium hydrate, tetra-n-butylammonium hexafluorophosphate, tetra-n-butylammonium tetrafluoroborate Moniumu include perchlorate tetra -n- butylammonium like. These phosphine ligands and phase transfer catalysts may be used alone or in combination of two or more, and each may be a hydrate. Further, a phosphine ligand and a phase transfer catalyst may be combined.
The amount of the phosphine ligand or phase transfer catalyst used is preferably 0 to 100 mol, more preferably 0 to 50 mol, particularly preferably 0 to 10 mol per 1 mol of the palladium atom of the metal compound, particularly the palladium compound. Is a mole.

The reaction of Production Example 4 is performed, for example, by a method of mixing a halogenopentafluorosulfanylbenzene compound, a vinyl compound, a metal compound, a base, and an organic solvent and reacting them with stirring. The reaction temperature at that time is preferably 0 to 200 ° C., more preferably 20 to 150 ° C., and the reaction pressure is not particularly limited.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.

  In the pentafluorosulfanylbenzene compound represented by the general formula (3d) obtained by the reaction of Production Example 4, the compounds of the formulas (9) and (10) are useful novel compounds exhibiting a liquid crystal phase (Examples) Described in IV-1 and 2).

(5) Production Example 5
As shown in the following reaction formula, Production Example 5 is characterized in that a vinylpentafluorosulfanylbenzene compound and a compound having a leaving group are reacted in the presence of a metal compound and a base. That is, in the general formula (1), A is —HC═CH ₂ , the compound represented by the general formula (2) is R ¹ X, and Z in the general formula (3) is —HC═CH—. It is a certain reaction.

In the general formula (1d), an arbitrary hydrogen atom on the benzene ring is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a halogen atom (particularly a group that does not react with an alkenyl group, and examples thereof include a fluorine atom). May be substituted). In addition, as long as the group does not particularly affect the reactivity of Production Example 5, the group may be substituted with a group other than the above-described substituent (an electron-withdrawing group or an electron-donating group).
The compound having a leaving group used in the reaction of Production Example 5 is represented by the general formula R ¹ X. In R ¹ X, R ¹ is the same as described in Production Example 1, and X represents the above-described group having a leaving property.
The amount of the vinylpentafluorosulfanylbenzene compound used in the reaction of Production Example 5 is preferably 0.8 to 20 mol, more preferably 0.9 to 15 mol, particularly preferably 1. 0 to 10 moles.

The base used in the reaction of the present invention is the same as that described in Production Example 4. Among them, alkali metal carbonates and amines are preferably used, more preferably potassium carbonate and triethylamine. In addition, these bases may be used individually or in mixture of 2 or more types, and may be used as aqueous solution or organic solvent solution.
The amount of the base used is preferably 0.5 to 10 mol, more preferably 0.8 to 5.0 mol, and particularly preferably 1.0 to 3.0 mol per mol of the vinylpentafluorosulfanylbenzene compound. Is a mole.
The reaction of Production Example 5 is desirably performed in the presence of a solvent, but the solvent used is the same as that described in Production Example 1. Among them, nitriles, amides, more preferably acetonitrile, N, N-dimethylformamide, 1,4-dioxane, particularly preferably N, N-dimethylformamide, 1,4-dioxane are used. . In addition, you may use these organic solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0 to 100 ml, more preferably 0.1 to 50 ml, and particularly preferably 0.2 to 30 ml with respect to 1 g of the vinylpentafluorosulfanylbenzene compound.
Specific examples and preferred examples of the metal compound used in the reaction of Production Example 5 include the same palladium compounds and rhodium compounds as described in Production Example 4, but palladium compounds are more preferred.
The amount of the metal compound used is preferably 0.001 to 5 mol, more preferably 0.005 to 1 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the vinylpentafluorosulfanylbenzene compound. It is.

In the reaction of Production Example 5, a phosphine ligand and a phase transfer catalyst may coexist in order to control the reactivity. The phosphine ligand and the phase transfer catalyst used are those described in Production Example 4. Is the same.
The amount of the phosphine ligand or phase transfer catalyst used is preferably 0 to 100 mol, more preferably 0 to 10 mol, per 1 mol of the palladium atom of the metal compound, particularly the palladium compound.
The reaction of Production Example 5 is performed by, for example, a method of mixing a vinylpentafluorosulfanylbenzene compound, a halogen compound, a palladium metal compound, a base and a solvent and reacting them with stirring. The reaction temperature at that time is preferably 0 to 200 ° C., more preferably 10 to 180 ° C., particularly preferably 20 to 150 ° C., and the reaction pressure is not particularly limited.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.

In the pentafluorosulfanylbenzene compound represented by the general formula (3d) obtained by the reaction of Production Example 5, the compound of the formula (11) (Example V-2) is a useful compound showing a liquid crystal phase, Example V-1
The compounds of -5 are novel compounds.

(6) Production Example 6
In Production Example 6, as shown by the following formula, a boron compound (1e) such as boronic acid, its trimer anhydride or its equilibrium mixture, or a boronic acid ester, and a halogenopentafluorosulfanylbenzene compound are converted into a metal compound and a base. Is a production example of aryl-substituted pentafluorosulfanylbenzene, which is characterized by reacting in the presence of. That is, in the general formula (1), A is a halogen atom, the compound represented by the general formula (2) is R ¹ BY ₂ , and n is 0 in the general formula (3).

  Specific examples of the general formula (2a) are represented by the following formulas, for example (2a-1), (2a-2) and (2a-3).

The halogenopentafluorosulfanylbenzene compound of Production Example 6 is represented by the general formula (1c) and is the same as that described in Production Example 4. Arbitrary hydrogen atoms on the benzene ring are similar to general formula (1) in that the alkyl group has 1 to 20 carbon atoms, the cycloalkyl group has 3 to 20 carbon atoms, the aralkyl group has 7 to 20 carbon atoms, and 6 carbon atoms. It may be substituted with ˜20 aryl groups or C2-C20 heteroaryl groups.
The compound having a leaving group used in the reaction of Production Example 6 is represented by the general formula R ¹ BY ₂ . In the R ¹ BY ₂ , R ¹ is the same as described in Production Example 1, and Y represents a hydroxy group or an alkoxy group having 1 to 10 carbon atoms. When Y is a hydroxy group, it may be an equilibrium mixture of boronic acid trimer anhydrides. Two Ys may be the same or different. When Y is alkoxy, the alkyl groups on the two alkoxy groups may be bonded to each other to have a cyclic structure.

  The amount of boronic acid or ester used in the reaction of Production Example 6 is preferably 0.5 to 20 mol, more preferably 0.9 to 10 mol, particularly preferably 1 with respect to 1 mol of halogenopentafluorosulfanylbenzene. 0.0 to 5 moles.

The reaction of Production Example 6 is desirably performed in the presence of a solvent, but the solvent used is the same as that described in Production Example 1. Among them, preferably ethers, aromatic hydrocarbons, amides, ureas, alcohols, sulfoxides, water, ketones, more preferably ethers, aromatic hydrocarbons, amides, ureas Alcohols, particularly preferably ethers and aromatic hydrocarbons are used. In addition, you may use these solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, and particularly preferably 1 to 30 ml with respect to 1 g of bromopentafluorosulfanylbenzene.
The base used in the reaction of Production Example 6 is the same as that shown in Production Example 3. Among them, preferably used are phosphates, alkali metal carbonates, amines, more preferably tripotassium phosphate, potassium carbonate, triethylamine. In addition, these bases may be used individually or in mixture of 2 or more types, and may be used as aqueous solution or 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 1.0 to 3.0 mol with respect to the halogenopentafluorosulfanylbenzene compound. Is a mole.

The metal compound used in the reaction of Production Example 6 is the same as that shown in Production Example 4. Among these, palladium compounds are preferable, palladium complexes are more preferable, and tetrakis (triphenylphosphine) palladium and nitrogen-containing heterocyclic carbene palladium complexes are particularly preferable. Specific examples of the nitrogen-containing heterocyclic carbene palladium complex include dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium. In addition, you may use these metal compounds individually or in mixture of 2 or more types.
The amount of the metal compound to be used is preferably 0.1 mol% to 100 mol%, more preferably 0.1 mol% to 50 mol%, particularly preferably 0.1 mol%, based on 1 mol of the halogenopentafluorosulfanylbenzene compound. 1 mol% to 20 mol%.
In the reaction of Production Example 6, a phosphine ligand or a phase transfer catalyst may coexist in order to control the reactivity (see, for example, Tetrahedron, 52, 10113 (1996)). A specific example is the same as in Production Example 4.

The reaction of Production Example 6 is performed by, for example, a method of mixing halogenopentafluorosulfanylbenzene, boronic acid or ester and a solvent, palladium, base and reacting while stirring. The reaction temperature at that time is preferably −50 to 200 ° C., more preferably −20 to 150 ° C., particularly preferably −10 to 100 ° C., and the reaction pressure is not particularly limited, but is usually normal pressure or increased pressure. To do.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.
In the pentafluorosulfanylbenzene compound represented by the general formula (3e) obtained by the reaction of Production Example 6, the compounds of Examples VI-4 and 5 are useful compounds exhibiting a liquid crystal phase, and Example VI-1 The compounds of -6 are novel compounds.

(7) Production Example 7
As shown in the following formula, Production Example 7 is a substituted pentafluorosulfurenylbenzene boronic acid or its trimer anhydride or its equilibrium mixture, or a substituted pentafluoro by reaction of a boronic ester compound with a compound having a leaving group. It is a manufacture example of a sulfanylbenzene compound. That is, in the general formula (1), A is —BY ₂ , the compound represented by the general formula (2) is R ¹ X, and n is 0 in the general formula (3).

  Specific examples of the general formula (1e) are represented by the following formulas, for example, (1e-1), (1e-2), and (1e-3).

The compound R ¹ X having a leaving group in the reaction of Production Example 7 is the same as in Production Example 5. -BY ₂ is the same as in Production Example 6.
In the reaction of Production Example 7, the amount of aryl halide is preferably 0.5 to 20 mol, more preferably 0.6 to 10 mol, particularly preferably 0.7 to 5 mol per mol of boronic acid or ester. 0.0 mole.

The reaction of Production Example 7 is desirably performed in the presence of a solvent, but the solvent used is the same as that described in Production Example 1. Among them, preferably ethers, aromatic hydrocarbons, amides, ureas, alcohols, sulfoxides, water, ketones, more preferably ethers, aromatic hydrocarbons, amides, ureas Alcohols, particularly preferably ethers and aromatic hydrocarbons are used. In addition, you may use these solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, and particularly preferably 1 to 30 ml with respect to 1 g of boronylpentafluorosulfanylbenzene.
The base used in the reaction of Production Example 7 is the same as that shown in Production Example 3. Among them, preferably, phosphate, alkali metal carbonate, amines, more preferably potassium phosphate, potassium carbonate, triethylamine are used. In addition, these bases may be used individually or in mixture of 2 or more types, and may be used as aqueous solution or 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 1.0 to 3. mol with respect to the boronylpentafluorosulfanylbenzene compound. 0 mole.
The metal compound used in the reaction of Production Example 7 is the same as that shown in Production Example 4. Among them, a palladium compound is preferable, a palladium complex is more preferable, and tetrakis (triphenylphosphine) palladium is particularly preferable. In addition, you may use these metal compounds individually or in mixture of 2 or more types.
The amount of the metal compound used is preferably 0.1 mol% to 100 mol%, more preferably 0.1 mol% to 50 mol%, particularly preferably 0, relative to 1 mol of the boronylpentafluorosulfanylbenzene compound. .1 mol% to 20 mol%.
In the reaction of Production Example 7, a phosphine ligand or a phase transfer catalyst may coexist in order to control the reactivity (see, for example, Tetrahedron, 52, 10113 (1996)). A specific example is the same as in Production Example 4.

The reaction of Production Example 7 is performed, for example, by a method such as mixing boronylpentafluorosulfanylbenzene, a compound having a leaving group and a solvent, a metal compound, and a base, and reacting with stirring. The reaction temperature at that time is preferably −50 to 200 ° C., more preferably −20 to 150 ° C., particularly preferably −10 to 100 ° C., and the reaction pressure is not particularly limited, but is usually normal pressure or increased pressure. To do.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.

In the pentafluorosulfanylbenzene compound represented by the general formula (3e) obtained by the reaction of Production Example 7, the compound of Example VII-1 is a useful novel compound.

(8) Production Example 8
Production Example 8 is characterized in that a halogenopentafluorosulfanylbenzene compound and an alkynyl compound are reacted in the presence of a metal compound and a base, as represented by the following formula. That is, a reaction in which A in the general formula (1) is a halogen atom, the compound represented by the general formula (2) is R ¹ C≡CH, and Z in the general formula (3) is —C≡C—. It is.

The halogenopentafluorosulfanylbenzene compound of Production Example 8 is represented by the general formula (1c) and is the same as that described in Production Example 4. .
The alkynyl compound used in the reaction of Production Example 8 is represented by R ¹ C≡CH. Here, R ¹ is the same as described in Production Example 1.
The amount of the alkynyl compound used in the reaction of Production Example 8 is preferably 0.5 to 10.0 mol, more preferably 0.5 to 5.0 mol, especially 0.5 mol to 1 mol of the halogenopentafluorosulfanylbenzene compound. Preferably it is 0.5-2.0 mol.
The base used in the reaction of Production Example 8 is specifically the same as in Production Example 3. In addition, these bases may be used individually or in mixture of 2 or more types, and may be used as aqueous solution or organic solvent solution. Preferably alkali metal carbonates, organic bases, more preferably potassium carbonate, organic amines, particularly preferably secondary amines are used.
The amount of the base used is preferably 0.5 to 100 mol, more preferably 0.7 to 80 mol, particularly preferably 1.0 to 50 mol, per 1 mol of the halogenopentafluorosulfanylbenzene compound.
The reaction of Production Example 8 is desirably performed in the presence of a solvent, and specific examples are the same as those of Production Example 1. Among them, preferably amines, nitriles, amides, more preferably secondary amines, acetonitrile, N, N-dimethylformamide are used. In addition, you may use these organic solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0 to 100 ml, more preferably 0.1 to 50 ml, particularly preferably 0.2 to 30 ml, based on 1 g of the halogenopentafluorosulfanylbenzene compound.

The metal compound used in the reaction of Production Example 8 is the same as in Production Example 4. Among them, dichlorobis (triphenylphosphine) palladium, palladium chloride, palladium / carbon, dichlorobis (triphenylphosphine) nickel and the like are preferably used. The amount of the palladium compound to be used is preferably 0.001 to 1 mol, more preferably 0.002 to 0.3 mol, per 1 mol of the halogenopentafluorosulfanylbenzene compound.
In the reaction of Production Example 8, a phosphine ligand, a phase transfer catalyst, and an inorganic salt may be allowed to coexist in order to control the reactivity, and a specific example is the same as in Production Example 4.
In the reaction of Production Example 8, it is desirable to add a copper salt as a co-catalyst, and the reaction can be performed at room temperature in a short time. Examples of the copper salt include copper (I) iodide, copper (I) bromide, copper (I) chloride, copper (I) cyanide, and copper (II) acetate. In addition, these copper salts may be used individually or in mixture of 2 or more types, and each may be a hydrate. Moreover, you may combine a phosphine ligand and a phase transfer catalyst (refer nonpatent literature 2, 3).
The amount of the phosphine ligand, phase transfer catalyst and copper salt used is preferably 0 to 100 mol, more preferably 0 to 10 mol, particularly preferably 0 to 5 mol, per 1 mol of the palladium atom of the palladium compound. It is.
The reaction of the present invention is performed, for example, by a method of mixing a halogenopentafluorosulfanylbenzene compound, an alkynyl compound, a palladium metal compound, a base and a solvent and reacting them with stirring. The reaction temperature at that time is preferably 0 to 200 ° C., more preferably 20 to 150 ° C., and the reaction pressure is not particularly limited.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.
In the pentafluorosulfanylbenzene 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 exhibiting a liquid crystal phase, and Examples VI-2 to 7-7 , 9 and 10 are novel compounds.

(9) Production Example 9
Production Example 9 is characterized in that a halogenomethylene pentafluorosulfanylbenzene compound and a hydroxy compound are reacted in the presence of a base, as represented by the following formula. That is, in the general formula (1), A is a halogenomethyl group, the compound represented by the general formula (2) is R ¹ OH, and Z in the general formula (3) is —OCH ₂ —. .

In the general formula (1f), X ¹ represents a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a bromine atom. Arbitrary hydrogen atoms on the benzene ring are 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 R ¹ OH. R ¹ is the same as that shown in Production Example 1, and the 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 mol, more preferably 0.8 to 10 mol, particularly preferably 1 with respect to 1 mol of the halogenomethylene pentafluorosulfanylbenzene compound. 0.0-5.0 moles.
The base used in the reaction of Production Example 9 and specific examples thereof are the same as those described in Production Example 3. The amount of the base used is preferably 0.8 to 20 mol, more preferably 0.9 to 15 mol, particularly preferably 1.0 to 10 mol, per 1 mol of the halogenomethylpentafluorosulfanylbenzene compound. .
The reaction of Production Example 9 is desirably performed in the presence of a solvent, but the solvent used is the same as that described in Production Example 3. Among them, ethers, amides, ureas, preferably ethers, amides, particularly preferably ethers are used. In addition, you may use these solvents individually or in mixture of 2 or more types.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 1 to 50 ml, with respect to 1 g of the halogenomethylene pentafluorosulfanylbenzene compound.

In order to promote the reaction of Production Example 9, preferably a phase transfer catalyst, an inorganic salt, more preferably tetrabutylammonium iodide, potassium iodide, sodium iodide, particularly preferably potassium iodide, as in Production Example 4. Is used. These inorganic iodide salts and phase transfer catalysts may be used alone or in combination of two or more, and each may be a hydrate. Moreover, you may combine an inorganic salt and a phase transfer catalyst.
The amount of the inorganic salt or phase transfer catalyst to be used is preferably 0 to 100 mol, more preferably 0 to 50 mol, particularly preferably 0 to 10 mol, relative to 1 mol of the halogenomethylene pentafluorosulfanylbenzene compound.
The reaction of the present invention is performed by, for example, a method of mixing a halogenomethylpentafluorosulfanylbenzene compound, a hydroxy compound, a base and a solvent and reacting them while stirring. The reaction temperature at that time is preferably 0 to 200 ° C., more preferably 20 to 150 ° C., and the reaction pressure is not particularly limited.
The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.
In the pentafluorosulfanylbenzene compound 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 10
Production Example 10 is characterized in that an aminopentafluorosulfanylbenzene compound and a carboxylic acid are reacted in the presence of a dehydrating agent as represented by the following formula. That is, in the general formula (1), A is —NH ₂ , the compound represented by the general formula (2) is R ¹ COOH, and Z in the general formula (3) is —CONH—.

（式中、Ｒ¹は、置換基を有していてもよい、炭素数２０以下のフェニル基、ビフェニルイル基、シクロヘキシルフェニル基、ビシクロヘキシルイル基を示す。）

(In the formula, R ¹ represents a phenyl group, a biphenylyl group, a cyclohexylphenyl group, or a bicyclohexylyl group having 20 or less carbon atoms, which may have a substituent.)

In the general formula (1h), any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. In addition, as long as the group does not particularly affect the reactivity of Production Example 10, the group may be substituted with a group other than the above-described substituent (an electron-withdrawing group or an electron-donating group).
In the general formula (3i), preferred examples of R ¹ include a p-tolyl group, a p-xylyl group, a biphenylyl group having an alkyl group or an alkoxy group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms, A cyclohexylphenyl group having an alkyl group or an alkoxy group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms, a bicyclohexylyl group having an alkyl group or an alkoxy group having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms Etc.
The dehydrating agent used in the reaction of Production Example 10 is the same as that used in Production Example 1. The amount of the dehydrating agent used is preferably 0.001 to 20 mol, more preferably 0.01 to 10 mol, particularly preferably 0.1 to 5 mol with respect to 1 mol of the pentafluorosulfanylbenzenecarboxylic acid amide compound. is there.
The reaction of Production Example 10 is desirably performed in the presence of a solvent, but specific examples and preferred examples of the solvent used are the same as those described in Production Example 1.
The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, and particularly preferably 1 to 30 ml with respect to 1 g of the pentafluorosulfanylbenzenecarboxylic acid amide compound.

  The reaction of Production Example 10 is performed, for example, by a method of mixing an aminopentafluorosulfanylbenzene compound, a carboxylic acid, a dehydrating agent, and a solvent and reacting them with stirring. The reaction temperature at that 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, but is usually normal pressure or increased pressure. To do. In addition, the reaction of Production Example 10 can also be performed while water is removed from the reaction system by, for example, azeotropic dehydration of water produced as a by-product or present. The post-treatment after completion of the reaction can be performed by the same general method as described in Production Example 1.

  In the carbonylaminopentafluorosulfanylbenzene 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.

（式中、Ｒ⁴は、炭素数２〜１２のアルキル基を示す。）

(In the formula, R ⁴ represents an alkyl group having 2 to 12 carbon atoms.)

(11) Production Example 11
Production Example 11 is characterized in that an aminopentafluorosulfanylbenzene compound and an aldehyde compound are reacted in the presence of a dehydrating agent as represented by the following formula. That is, in the general formula (1), A is —NH ₂ , the compound represented by the general formula (2) is R ¹ CHO, and Z in the general formula (3) is —CH═N—. is there.

（式中、Ｒ¹は前記と同じである。）

(In the formula, R ¹ is the same as described above.)

Production Example 11 is the same as Production Example 10 except that R ¹ COOH is replaced with R ¹ CHO in Production Example 10, and the reaction conditions are the same as in Production Example 10.
In the benzylideneaminopentafluorosulfanylbenzene compound represented by the general formula (18) obtained by the reaction of Production Example 11, the compounds of Examples XI-1 and XI-2 are novel compounds.

（式中、Ｒ⁴は前記と同じである。）

(In the formula, R ⁴ is the same as defined above.)

  A compound of the present invention, in particular, at least one selected from pentafluorosulfanylbenzene compounds represented by the above formulas (9) to (18) is contained in another liquid crystal material and / or a non-liquid crystal material to form a liquid crystal composition. Therefore, it can be effectively used as a liquid crystal display element of TN type, STN type, IPS type, OCB type, VA type or the like.

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
Measurements of proton nuclear magnetic resonance ( ¹ H-NMR) and chemical ionization mass spectrometry (CI-MS) were performed under the following conditions.
⁽¹ H-NMR)
Measuring instrument: manufactured by JEOL Ltd., trade name: AL300
Measurement conditions: single pulse, room temperature (CI-MS)
Measuring instrument: manufactured by Hitachi, Ltd., trade name: M80B
Measurement conditions: double focusing type, reaction gas is isobutane, ion source temperature 180 ° C
Acceleration voltage 3kV, ionization voltage 70eV

Example I-1 (Synthesis of 4-[(trans, trans) -4′-ethyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer, 0.22 g (1.0 mmol) of 4-hydroxypentafluorosulfanylbenzene, (trans, trans) -4′-ethyl-bicyclohexyl-4-carboxylic acid 0. 29 g (1.2 mmol), 1-ethyl-2- (dimethylaminopropyl) carbodiimide hydrochloride 0.29 g (1.5 mmol), 4-dimethylaminopyridine 0.05 g (0.4 mmol) and 10 ml of methylene chloride were added. Thereafter, the mixture was reacted overnight at room temperature with stirring. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 95/5 (volume ratio)) to give 4-[( trans, trans) Synthesis of 4′-ethyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene 0.32 g was obtained (isolation yield; 73%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.83 to 1.25 (14H, m), 1.47 to 1.60 (2H, m), 1.71 to 1.88 (6H, m), 2.12 to 2.17 (2H, m), 2.42 to 2.52 (1H, m), 7.15 to 7.18 (2H, m), 7.74 to 7.79 (2H, m)
CI-MS; 441 (M)

Example I-2 (Synthesis of 4-[(trans, trans) -4'-n-propyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene)
In Example 1-1, (trans, trans) -4'-n-propyl-bicyclohexyl-4-carboxylic acid was used instead of (trans, trans) -4'-ethyl-bicyclohexyl-4-carboxylic acid. The reaction was performed in the same manner as in Example I-1 except that 30 g (1.2 mmol) was used. As a result, 0.28 g of 4-[(trans, trans) -4′-n-propyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene was obtained as a white solid (isolation yield: 61% ).
The physical property values of this compound were as follows.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.85 to 1.16 (14H, m), 1.22 to 1.36 (2H, m), 1.47 to 1.59 (2H, m), 1.70 to 1.88 (6H, m), 2.12 to 2.17 (2H, m), 2.42 to 2.52 (1H, m), 7.15 to 7.18 (2H, m), 7.74 to 7.79 (2H, m)
CI-MS; 455 (M)

Example I-3 (Synthesis of 4-[(trans, trans) -4'-n-butyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene)
In Example I-1, (trans, trans) -4′-ethyl-bicyclohexyl-4-carboxylic acid was replaced with (trans, trans) -4′-n-butyl-bicyclohexyl-4-carboxylic acid. The reaction was performed in the same manner as in Example I-1 except that 32 g (1.2 mmol) was used. As a result, 0.31 g of 4-[(trans, trans) -4′-n-butyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene was obtained as a white solid (isolation yield; 66% ).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.84 to 1.29 (18H, m), 1.47 to 1.59 (2H, m), 1.70 to 1.88 (6H, m), 2.12 to 2.17 (2H, m), 2.42 to 2.52 (1H, m), 7,15 to 7.18 (2H, m), 7.60 to 7.79 (2H, m)
CI-MS; 469 (M)

Example I-4 (Synthesis of 4-[(trans, trans) -4'-n-pentyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.76 g (2.7 mmol) of (trans, trans) -4′-n-pentyl-bicyclohexyl-4-carboxylic acid and 16.3 g (137 mmol) of thionyl chloride were added. ) And stirred at 70 ° C. for 2 hours to produce (trans, trans) -4′-n-pentyl-bicyclohexyl-4-carboxylic acid chloride. After completion of the reaction, thionyl chloride was distilled off under reduced pressure, and 0.5 g (2.3 mmol) of 4-hydroxypentafluorosulfanylbenzene and 10 ml of methylene chloride were added to the resulting residue, followed by reaction overnight at room temperature with stirring. I let you. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 10/1 (volume ratio)) to give 4-[( trans, trans) -4′-n-pentyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene 0.82 g was obtained (isolation yield; 75%).
The physical property values of this compound were as follows.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.83 to 1.33 (20H, m), 1.47 to 1.59 (2H, m), 1.70 to 1.88 (6H, m), 2.13 to 2.17 (2H, m), 2.42 to 2.52 (1H, m), 7.15 to 7.18 (2H, m), 7.74 to 7.79 (2H, m)
CI-MS; 483 (M)

Example I-5 (Synthesis of 4- (4′-n-pentyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene)
In Example 1-1, 0.34 g (1.2 mmol) of 4′-n-pentyloxybiphenyl-4-carboxylic acid was used instead of (trans, trans) -4′-ethyl-bicyclohexyl-4-carboxylic acid. The reaction was performed in the same manner as in Example I-1 except that it was used. As a result, 0.26 g of 4- (4′-n-pentyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene was obtained as a white solid (isolation yield; 53%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.93 to 0.97 (3H, m), 1.39 to 1.53 (4H, m), 1.78 to 1.85 (2H, m), 4.00 to 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), 7.82-7.87 (2H, m), 8.20-8.24 (2H , m)
CI-MS; 487 (M)

Example I-6 (Synthesis of 4- (4′-n-heptyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene)
In Example 1-1, 0.38 g (1.2 mmol) of 4′-n-heptyloxybiphenyl-4-carboxylic acid was used instead of (trans, trans) -4′-ethyl-bicyclohexyl-4-carboxylic acid. The reaction was performed in the same manner as in Example I-1 except that it was used. As a result, 0.33 g of 4- (4′-n-heptyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene was obtained as a white solid (isolated yield; 63%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.88 to 0.93 (3H, m), 1.26 to 1.51 (8H, m), 1.77 to 1.84 (2H, m), 4.00 to 4.04 (2H, m), 6.98-7.03 (2H, m), 7.34-7.37 (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; 515 (M)

Example I-7 (Synthesis of 4- (4′-n-decyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer, 0.5 g (2.3 mmol) of 4-hydroxypentafluorosulfanylbenzene, 0.97 g (2.7 mmol) of 4′-n-heptyloxybiphenyl-4-carboxylic acid ), 1-ethyl-2- (dimethylaminopropyl) carbodiimide hydrochloride (0.65 g, 3.4 mmol), 4-dimethylaminopyridine (0.05 g, 0.4 mmol) and methylene chloride (10 ml) were added, followed by stirring. The reaction was allowed to proceed overnight at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 20/1 (volume ratio)) to give 4- (4 0.11 g of '-n-decyloxy-biphenyl-4-carbonyloxy) -pentafluorosulfanylbenzene was obtained (isolation yield; 9%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.86 to 0.91 (3H, m), 1,29 to 1.49 (14H, m), 1.77 to 1.84 (2H, m), 4.00 to 4.04 (2H, m ), 6.99 to 7.03 (2H, m), 7.34 to 7.37 (2H, m), 7.58 to 7.61 (2H, m), 7.69 to 7.72 (2H, m), 7.82 to 7.86 (2H, m), 8.20 to 8.25 (2H, m)
CI-MS; 557 (M)

Example I-8 (Synthesis of 3-tetracosylcarbonyloxypentafluorosulfanylbenzene)
In Example I-7, instead of 4-hydroxypentafluorosulfanylbenzene, 0.5 g (2.3 mmol) of 3-hydroxypentafluorosulfanylbenzene was replaced with 4′-n-heptyloxybiphenyl-4-carboxylic acid. The reaction was performed in the same manner as in Example I-7 except that 1.00 g (2.7 mmol) of tetracosylcarboxylic acid was used. As a result, 0.61 g of 3-tetracosylcarbonyloxypentafluorosulfanylbenzene was obtained as a white solid (isolation yield: 47%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.86 to 0.90 (3H, m), 1.26 to 1.40 (40H, m), 1.71 to 1.81 (2H, m), 2.55 to 2.60 (2H, m), 7.26-7.29 (1H, m), 7.45-7.51 (2H, m), 7.61-7.64 (1H, m)
CI-MS; 571 (M)

Example I-9 (Synthesis of 4-linolenoyloxypentafluorosulfanylbenzene)
In Example 7, instead of 4-hydroxypentafluorosulfanylbenzene, 0.5 g (2.3 mmol) of 3-hydroxypentafluorosulfanylbenzene was replaced with linolenic acid in place of 4′-n-heptyloxybiphenyl-4-carboxylic acid. The reaction was performed in the same manner as in Example I-7 except that 0.76 g (2.7 mmol) was used. As a result, 0.49 g of 4-linolenoyloxypentafluorosulfanylbenzene was obtained as a white solid (isolation yield; 45%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 1.00 (3H, m), 1.27 to 1.42 (9H, m), 1.71 to 1.78 (2H, m), 2.02 to 2.13 (4H, m), 2.55 to 2.60 (2H, m), 2.76 to 2.86 (3H, m), 5.27 to 5.44 (6H, m), 7.17 to 7.20 (2H, m), 7.75 to 7.80 (2H, m)
CI-MS; 481 (M)

Example I-10 (Synthesis of 3- (4-n-butylbenzoyloxy) -pentafluorosulfanylbenzene)
In Example I-7, instead of 4-hydroxypentafluorosulfanylbenzene, 0.5 g (2.3 mmol) of 3-hydroxypentafluorosulfanylbenzene was replaced with 4′-n-heptyloxybiphenyl-4-carboxylic acid. The reaction was conducted in the same manner as in Example I-7 except that 0.48 g (2.7 mmol) of 4-n-butylbenzoic acid was used. As a result, 0.59 g of 3- (4-n-butylbenzoyloxy) -pentafluorosulfanylbenzene was obtained as a white solid (isolation yield: 69%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.92 to 0.97 (3H, m), 1.34 to 1.41 (2H, m), 1.60 to 1.70 (2H, m), 2.69 to 2.73 (2H, m), 7.31-7.35 (2H, m), 7.39-7.42 (1H, m), 7.50-7.55 (1H, m), 7.64-7.69 (2H, m), 8.08-8.12 (2H, m)
CI-MS; 381 (M + 1)

Example I-11 (Synthesis of 4- (thiophene-3-carbonyloxy) -pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.62 g (2.8 mmol) of 4-hydroxypentafluorosulfanylbenzene, 0.3 g (2.3 mmol) of thiophene-3-carboxylic acid, 1-ethyl-2 -(Dimethylaminopropyl) carbodiimide hydrochloride (0.65 g, 3.5 mmol), 4-dimethylaminopyridine (0.05 g, 0.4 mmol) and methylene chloride (10 ml) were added, and the mixture was reacted overnight at room temperature with stirring. It was. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 9/1 (volume ratio)) to give 4- (thiophene) as a white solid. 0.60 g of (-3-carbonyloxy) -pentafluorosulfanylbenzene was obtained (isolation yield: 79%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 7.43 to 7.45 (1H, m), 7.49 to 7.51 (1H, m), 7.71 to 7.78 (4H, m), 8.01 to 8.03 (1H, m)
CI-MS; 330 (M)

Example I-12 (Synthesis of 2-[(trans, trans) -4'-n-pentyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer, 0.2 g (0.7 mmol) of (trans, trans) -4′-n-pentyl-bicyclohexyl-4-carboxylic acid, 2-hydroxypentafluorosulfanylbenzene 0.19 g (0.9 mmol), 1-ethyl-2- (dimethylaminopropyl) carbodiimide hydrochloride 0.20 g (1.1 mmol), 4-dimethylaminopyridine 0.05 g (0.4 mmol) and methylene chloride 10 ml. After the addition, the mixture was reacted overnight at room temperature with stirring. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 20/1 (volume ratio)) to give 2-[( trans, trans) -4′-n-pentyl-bicyclohexyl-4-carbonyloxy] -pentafluorosulfanylbenzene (0.25 g) was obtained (isolation yield: 59%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.84 to 1.36 (20H, m), 1.48 to 1.60 (2H, m), 1.70 to 1.88 (6H, m), 2.16 to 2.20 (2H, m), 2.46 ~ 2.56 (1H, m), 7.11 ~ 7.26 (1H, m), 7.29 ~ 7.34 (1H, m), 7.49 ~ 7.55 (1H, m), 7.79 ~ 7.82 (1H, m) sai
CI-MS; 483 (M)

Example II-1 (Synthesis of 4-[(trans, trans) -4′-n-propyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer, 0.2 g (0.80 mmol) of 4-pentafluorosulfanylbenzenecarboxylic acid, (trans, trans) -4′-n-propyl-bicyclohexyl-4-ol 0.22 g (0.98 mmol), 1-ethyl-2- (dimethylaminopropyl) carbodiimide hydrochloride 0.23 g (1.2 mmol), 4-dimethylaminopyridine 0.05 g (0.4 mmol) and methylene chloride 10 ml. After the addition, the mixture was reacted overnight at room temperature with stirring. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 20/1 (volume ratio)) to give 4-pentafluoro as a white solid. 0.23 g of sulfanylbenzenecarboxylic acid 4-[(trans, trans) -4′-n-propyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene was obtained (isolation yield: 62%) .
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.85 to 1.35 (16H, m), 1.40 to 1.51 (2H, m), 1.70 to 1.86 (6H, m), 2.09 to 2.14 (2H, m), 4.85 to 4.96 (1H, m), 7.80 to 7.83 (2H, m), 8.10 to 8.13 (2H, m)
CI-MS; 435 (M-19)

Example II-2 (Synthesis of 4-[(trans, trans) -4′-n-butyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene)
In Example II-1, (trans, trans) -4′-n-propyl-bicyclohexyl-4-ol was replaced with (trans, trans) -4′-n-butyl-bicyclohexyl-4-ol. The reaction was performed in the same manner as in Example II-1 except that 23 g (0.96 mmol) was used. As a result, 0.16 g of 4-[(trans, trans) -4′-n-butyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene was obtained as a white solid (isolation yield; 44%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.83 to 1.29 (18H, m), 1.40 to 1.51 (2H, m), 1.71 to 1.86 (6H, m), 2.09 to 2.14 (2H, m), 4.85 to 4.96 (1H, m), 7.79 to 7.84 (2H, m), 8.10 to 8.13 (2H, m)
CI-MS; 449 (M-19)

Example II-3 (Synthesis of 4-[(trans, trans) -4'-n-pentyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene)
In Example II-1, (trans, trans) -4′-n-propyl-bicyclohexyl-4-ol was replaced with (trans, trans) -4′-n-pentyl-bicyclohexyl-4-ol. The reaction was performed in the same manner as in Example II-1 except that 24 g (0.95 mmol) was used. As a result, 0.13 g of 4-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl-oxycarbonyl] -pentafluorosulfanylbenzene was obtained as a white solid (isolation yield; 34%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.80 to 1.33 (20H, m), 1.40 to 1.51 (2H, m), 1.70 to 1.85 (6H, m), 2.09 to 2.14 (2H, m), 4.85 to 4.96 (1H, m), 7.79 to 7.86 (2H, m), 8.10 to 8.13 (2H, m)
CI-MS; 463 (M-19)

Example II-4 (Synthesis of 4-[(4′-n-decyloxy-biphenyl-4-yl-methyl) -oxycarbonyl] -pentafluorosulfanylbenzene)
In Example II-1, instead of (trans, trans) -4′-n-propyl-bicyclohexyl-4-ol, 0.33 g of (4′-n-decyloxybiphenyl-4-yl) methanol The reaction was conducted in the same manner as in Example II-1 except that 97 mmol) was used. As a result, 0.34 g of 4-[(4′-n-decyloxy-biphenyl-4-yl-methyl) -oxycarbonyl] -pentafluorosulfanylbenzene was obtained as a white solid (isolated yield: 75%). .
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.86 to 0.91 (3H, m), 1.28 to 1.49 (14H, m), 1.76 to 1.85 (2H, m), 3.97 to 4.02 (2H, m), 5.41 (2H, s), 6.94 to 6.99 (2H, m), 7.46 to 7.59 (6H, m), 7.80 to 7.84 (2H, m), 8.15 to 8.18 (2H, m)
CI-MS; 570 (M)

Example II-5 (Synthesis of 3- (4-fluorobenzyl-oxycarbonyl) -pentafluorosulfanylbenzene)
In Example II-1, instead of 4-pentafluorosulfanylbenzenecarboxylic acid, 0.2 g (0.80 mmol) of 3-pentafluorosulfanylbenzenecarboxylic acid was added to (trans, trans) -4′-n-propyl- The reaction was conducted in the same manner as in Example II-1, except that 0.12 g (0.97 mmol) of 4-fluorobenzyl alcohol was used instead of bicyclohexyl-4-ol. As a result, 0.18 g of 3- (4-fluorobenzyl-oxycarbonyl) -pentafluorosulfanylbenzene was obtained as a colorless liquid (isolation yield; 63%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 5.36 (2H, s), 7.04 to 7.12 (2H, m), 7.40 to 7.47 (2H, m), 7.53 to 7.60 (1H, m), 7.93 to 7.96 (1H, m), 8.18 to 8.21 (1H, m), 8.43 to 8.44 (1H, m)
CI-MS; 356 (M)

Example II-6 (Synthesis of 3- (cis-4-phenyl-cyclohexyl-oxycarbonyl) -pentafluorosulfanylbenzene)
In Example II-5, instead of 4-fluorobenzyl alcohol, cis-4-phenylcyclohexane-
The reaction was conducted in the same manner as in Example II-1 except that 0.17 g (0.97 mmol) of 1-ol was used. As a result, 0.18 g of 3- (cis-4-phenyl-cyclohexyl-oxycarbonyl) -pentafluorosulfanylbenzene was obtained as white crystals (isolation yield; 54%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.74 to 1.98 (6H, m), 2.16 to 2.21 (2H, m), 2.62 to 2.71 (1H, m), 5.40 to 5.42 (1H, m), 7.19-7.36 (5H, m), 7.57-7.62 (1H, m), 7.94-7.98 (1H, m), 8.22-8.24 (1H, m), 8.49-8.51 (1H, m)
CI-MS; 406 (M)

Example II-7 (Synthesis of 3- (4-cyclohexyl-phenyl-oxycarbonyl) -pentafluorosulfanylbenzene)
In a glass container having a capacity of 300 ml equipped with a stirrer, 3.0 g (12.1 mmol) of 3-pentafluorosulfanylbenzenecarboxylic acid, 2.55 g (14.5 mmol) of 4-cyclohexylphenol, 1-ethyl-2- (Dimethylaminopropyl) carbodiimide hydrochloride (3.38 g, 18.1 mmol), 4-dimethylaminopyridine (0.74 g, 6.0 mmol) and methylene chloride (100 ml) were added, and the mixture was reacted overnight at room temperature with stirring. . After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 20/1 (volume ratio)) to give 3- (4 -Cyclohexyl-phenyl-oxycarbonyl) -pentafluorosulfanylbenzene 2.82 g was obtained (isolation yield: 57%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.22 to 1.55 (5H, m), 1.74 to 1.92 (5H, m), 2.50 to 2.57 (1H, m), 7.11 to 7.15 (2H, m), 7.25-7.29 (2H, m), 7.61-7.66 (1H, m), 8.00-8.03 (1H, m), 8.33-8.36 (1H, m), 8.57-8.59 (1H, m)
CI-MS; 407 (M + 1)

Example III-1 (Synthesis of 4-n-butoxypentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer and a thermometer, 0.5 g (2.3 mmol) of 4-fluoropentafluorosulfanylbenzene and 0.138 g (3.5 mmol) of 60% sodium hydride were previously dried. After adding 0.32 ml (3.5 mmol) of n-butanol and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance, the mixture was reacted at room temperature for 12 hours with stirring. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 times with 30 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated to obtain 0.48 g of 4-n-butoxypentafluorosulfanylbenzene as a colorless liquid (isolated yield; 76%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.98 (3H, t, J = 7.3 Hz), 1.43 to 1.56 (2H, m), 1.73 to 1.83 (2H, m), 3.99 (2H, t, J = 6.6Hz), 6.87-6.90 (2H, m), 7.63-7.69 (2H, m)
CI-MS; 276 (M)

Example III-2 (Synthesis of 4-phenoxypentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer, 0.5 g (2.3 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.276 g (6.9 mmol) of 60% sodium hydride, phenol 0.8 After adding 65 g (6.9 mmol) and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance, the mixture was reacted at room temperature for 12 hours and at 60 ° C. for 4 hours with stirring. After completion of the reaction, 30 ml of toluene was added to the reaction solution, and the organic layer was washed 10 times with 30 ml of saturated brine and 10 ml of 8 mol / l aqueous sodium hydroxide solution and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated to obtain 0.25 g of 4-phenoxypentafluorosulfanylbenzene as a colorless liquid (isolation yield: 36%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 6.97 to 7.00 (2H, m), 7.04 to 7.08 (2H, m), 7.18 to 7.25 (1H, m), 7.36 to 7.43 (2H, m), 7.66-7.72 (2H, m)
CI-MS; 296 (M)

Example III-3 (Synthesis of 4-cyclohexyloxypentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer and a thermometer, 0.5 g (2.3 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.138 g (3.5 mmol) of 60% sodium hydride, cyclohexanol 0 .36 ml (3.5 mmol) and 5 ml of 1,3-dimethyl-2-imidazolidinone previously dried were added, and the mixture was reacted at 60 ° C. for 3 hours with stirring. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 times with 30 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated to obtain 0.76 g of 4-cyclohexyloxypentafluorosulfanylbenzene as a pale yellow liquid (isolation yield: 99% or more).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.41 to 1.45 (2H, m), 1.49 to 1.67 (4H, m), 1.73 to 1.85 (2H, m), 1.94 to 2.00 (2H, m), 4.26-4.35 (1H, m), 6.88 (2H, d, J = 9.0Hz), 7.63-7.66 (2H, m)
CI-MS; 302 (M)

Example III-4 (Synthesis of 4-benzyloxypentafluorosulfanylbenzene)
In a 100 ml glass container equipped with a stirrer and a thermometer, 5.0 g (22.5 mmol) of 4-fluoropentafluorosulfanylbenzene, 1.35 g (33.8 mmol) of 60% sodium hydride, benzyl alcohol 3 .65 g (33.8 mmol) and 25 ml of 1,3-dimethyl-2-imidazolidinone previously dried were added, and the mixture was reacted at room temperature for 12 hours with stirring. After completion of the reaction, 50 ml of toluene and 50 ml of ethyl acetate were added to the reaction solution, and the organic layer was washed 5 times with 100 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated and then filtered again to remove 1,3-dimethyl-2-imidazolidinone mixed in 200 ml of water. The obtained residue was dried under reduced pressure to obtain 5.62 g of 4-benzyloxypentafluorosulfanylbenzene as a white solid (isolation yield: 81%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , 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; 310 (M)

Example III-5 (Synthesis of 4- [4- (trans-4-n-pentyl-cyclohexyl) -phenoxy] -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer and a thermometer, 0.5 g (2.3 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.135 g (3.5 mmol) of 60% sodium hydride, 4-n -After adding 0.832 g (3.5 mmol) of pentylcyclohexylphenol and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance, the mixture was reacted at 60 ° C. for 3 hours with stirring. After completion of the reaction, 50 ml of reaction solution toluene was added, and the organic layer was washed 5 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 silica gel column chromatography (developing solvent; hexane) to give 4- [4- (trans-4-n-pentyl-cyclohexyl) − as a white solid. 0.411 g of phenoxy] -pentafluorosulfanylbenzene was obtained (isolation yield: 40%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 0.92 (3H, m), 1.03 to 1.11 (2H, m), 1.25 to 1.51 (11H, m), 1.86 to 1.92 (4H, m), 2.43-2.53 (1H, m), 6.94-6.99 (4H, m), 7.20-7.25 (2H, m), 7.64-7.70 (2H, m)
CI-MS; 448 (M)

Example III-6 (Synthesis of 4-[(trans, trans) -4'-n-pentyl-bicyclohexyl-4-yl-oxy] -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer and a thermometer, 0.22 g (1 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.060 g (1.5 mmol) of 60% sodium hydride, 4-n-pentyl After adding 0.379 g (1.5 mmol) of cyclohexylcyclohexanol and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance, the mixture was reacted at 60 ° C. for 3 hours with stirring. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 times with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and then the concentrate was purified by silica gel column chromatography (developing solvent; hexane) to give 4-[(trans, trans) -4′-n-pentyl-biyl as a white solid. 0.244 g of cyclohexyl-4-yl-oxy] -pentafluorosulfanylbenzene was obtained (isolation yield; 54%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.79 to 2.04 (30H, m), 4.56 (1H, brs), 6.87 to 6.90 (2H, m), 7.62 to 7.67 (2H, m)
CI-MS; 454 (M)

Example III-7 (Synthesis of 4- [4- (4-n-pentyl-cyclohexyl) -benzyloxy] -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer and a thermometer, 0.22 g (1 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.060 g (1.5 mmol) of 60% sodium hydride, 4-n-pentyl After adding 0.40 g (1.5 mmol) of cyclohexylbenzyl alcohol and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance, the mixture was reacted at 60 ° C. for 3 hours with stirring. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 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 silica gel column chromatography (developing solvent; hexane) to give 4- [4- (4-n-pentyl-cyclohexyl) -benzyloxy as a white solid. ] 0.310 g of pentafluorosulfanylbenzene was obtained (isolation yield; 67%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 0.92 (3H, m), 1.02 to 1.10 (2H, m), 1.24 to 1.52 (11H, m), 1.86 to 1.89 (4H, m), 2.44-2.52 (1H, 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) ), 7.65-7.69 (2H, m)
CI-MS; 443 (M-19)

Example III-8 (Synthesis of 4-[[(trans, trans) -4'-n-pentyl-bicyclohexyl-4-yl] -methyloxy] -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer and a thermometer, 0.22 g (1 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.060 g (1.5 mmol) of 60% sodium hydride, [(trans, trans ) -4'-n-pentyl-bicyclohexyl-4-yl] -methanol (0.391 g, 1.5 mmol) and 5 ml of 1,3-dimethyl-2-imidazolidinone previously dried were added and stirred. The reaction was carried out at 60 ° C. for 3 hours. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 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 silica gel column chromatography (developing solvent; hexane) to give 4-[[((trans, trans) -4′-n-pentyl-] as a white solid. Bicyclohexyl-4-yl] -methyloxy] -pentafluorosulfanylbenzene (0.257 g) was obtained (isolation yield; 55%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.82 to 1.33 (22H, m), 1.69 to 1.91 (9H, m), 3.77 (2H, d, J = 6.3 Hz), 6.86 to 6.90 (2H, m), 7.64-7.67 (2H, m)
CI-MS; 468 (M)

Example III-9 (synthesis of 4-tetracosyloxypentafluorosulfanylbenzene)
In a glass container equipped with a stirrer and a thermometer and having a content of 30 ml, 0.22 g (1 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.060 g (1.5 mmol) of 60% sodium hydride, 0. After adding 532 g (1.5 mmol) and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance, the mixture was reacted at 60 ° C. for 3 hours with stirring. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 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 silica gel column chromatography (developing solvent: hexane) to obtain 0.251 g of 4-tetracosyloxypentafluorosulfanylbenzene as a white solid ( Isolated yield; 45%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.85 to 0.90 (3H, m), 1.21 to 1.47 (42H, m), 1.74 to 1.84 (2H, m), 3.96 to 4.01 (2H, m), 6.87-6.90 (2H, m), 7.63-7.69 (2H, m)
CI-MS; 556 (M)

Example III-10 (Synthesis of 4- (4′-n-heptyl-biphenyl-4-yl-methyloxy) -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer, 0.22 g (1 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.060 g (1.5 mmol) of 60% sodium hydride, 4- (4 ′ -N-heptyl-biphenyl-4-yl) -methanol (0.424 g, 1.5 mmol) and pre-dried 1,3-dimethyl-2-imidazolidinone (5 ml) were added, followed by stirring at 60 ° C. The reaction was performed for 3 hours. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 times with 50 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated and then purified with a silica gel column chromatography developing solvent; hexane / ethyl acetate = 9/1 (volume ratio)) to give 4- (4′-n-heptyl-) as a white solid. Biphenyl-4-yl-methyloxy) -pentafluorosulfanylbenzene 0.333 g was obtained (isolation yield; 69%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.89 (3H, t, J = 6.9 Hz), 1.28 to 1.35 (8H, m), 1.60 to 1.67 (2H, 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), 7.66-7.72 (2H, m)
CI-MS; 485 (M + 1)

Example III-11 (Synthesis of 4- (4′-n-decyloxy-biphenyl-4-yl-methyloxy) -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer, 0.22 g (1 mmol) of 4-fluoropentafluorosulfanylbenzene, 0.060 g (1.5 mmol) of 60% sodium hydride, 4- (4 ′ -N-decyloxy-biphenyl-4-yl) -methanol (0.510 g, 1.5 mmol) and pre-dried 1,3-dimethyl-2-imidazolidinone (5 ml) were added, followed by stirring at 60 ° C. The reaction was performed for 3 hours. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 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 silica gel column chromatography (developing solvent; hexane / ethyl acetate = 9/1 (volume ratio)) to give 4- (4′- n-decyloxy-biphenyl-4-yl-methyloxy) -pentafluorosulfanylbenzene (0.358 g) was obtained (isolation yield; 66%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , 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), 6.94-6.98 (4H, m), 7.44-7.60 (6H, m), 7.67-7.70 (2H, m)
CI-MS; 542 (M)

Example III-12 (Synthesis of 2-n-pentoxy-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer and a thermometer, 1.0 g (2.70 mmol) of 2-fluoro-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene, 60% sodium hydride 0.470 g (10.8 mmol), 0.97 g (10.8 mmol) of n-pentanol dried in advance and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance were added with stirring. The reaction was carried out at 100 ° C. for 16 hours. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 5 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 silica gel column chromatography (developing solvent; hexane) to give 2-n-pentoxy-5- (4-n-pentylphenyl) -penta as a colorless liquid. 0.26 g of fluorosulfanylbenzene was obtained (isolation yield; 21%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.88 to 0.97 (6H, m), 1.26 to 1.89 (12H, m), 2.64 (2H, t, J = 7.9 Hz), 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 = 2.2Hz, J = 8.5Hz), 7.92 (1H, d, J = 2.4Hz)
CI-MS; 457 (M)

Example III-13 (Synthesis of 2-phenoxy-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer, 1.0 g (2.7 mmol) of 2-fluoro-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene, 60% sodium hydride 0.470 g (10.8 mmol), 1.02 g (10.8 mmol) of phenol and 5 ml of 1,3-dimethyl-2-imidazolidinone dried in advance were added, followed by reaction at 100 ° C. for 4 hours with stirring. It was. After completion of the reaction, 30 ml of toluene was added to the reaction solution, and the organic layer was washed 10 times with 30 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and then the concentrate was purified by silica gel column chromatography (developing solvent: hexane) to give 2-phenoxy-5- (4-n-pentylphenyl) -pentafluorosulfanyl as a white liquid. 0.25 g of benzene was obtained (isolation yield; 21%)
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.88 to 0.93 (3H, m), 1.32 to 1.39 (4H, m), 1.60 to 1.70 (2H, m), 2.65 (2H, t, J = 7.7 Hz), 7.03 to 7.48 (10H, m), 7.59 (1H, dd, J = 2.2Hz, J = 8.8Hz), 8.00 (1H, d, J = 2.2Hz)
CI-MS; 296 (M)

Example III-14 (Synthesis of 2-benzyloxy-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer and a thermometer, 1.84 g (5.0 mmol) of 2-fluoro-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene, 60% sodium hydride After adding 0.870 g (20 mmol), 2.16 g (20 mmol) of benzyl alcohol and 5 ml of 1,3-dimethyl-2-imidazolidinone previously dried, the mixture was reacted at 100 ° C. for 4 hours with stirring. After completion of the reaction, 50 ml of toluene was added to the reaction solution, and the organic layer was washed 10 times with 30 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated to obtain 0.34 g of 2-benzyloxy-5- (4-n-pentylphenyl) -pentafluorosulfanylbenzene as a white liquid (isolation yield; 15%). .
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , 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), 7.15 (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 = 2.2Hz)
CI-MS; 457 (M)

Example IV-1 (Synthesis of 4- [2-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl] -vinyl] -pentafluorosulfanylbenzene)
To a container having a volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.71 g (2.50 mmol) of 4-bromopentafluorosulfanylbenzene, 4- (4′-n-pentylbicyclohexyl) ethylene 72 g (2.75 mmol), dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich) )) 0.035 g (0.05 mmol), 1.03 g (7.48 mmol) of potassium carbonate and 10 ml of 1,4-dioxane were added, and the mixture was reacted at 100 ° C. for 8 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under source pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel chromatography (ODSC-18, developing solvent; acetonitrile / water = 90/10 → 94/6 (volume ratio)), and white As a solid, 0.11 g of 4- [2-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl] -vinyl] -pentafluorosulfanylbenzene was obtained (isolation yield; 9 %).
This compound is a novel compound represented by the following physical property values. In addition, from the coupling constant (J value) of 6.26 ppm and 6.35 pm, the compound is considered to be a trans isomer.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.83 to 1.33 (26H, m), 1.70 to 1.87 (4H, m), 2.05 to 2.11 (1H, m), 6.26 (1H, dd, J = 6.2 Hz, J = 16.0Hz), 6.35 (1H, d, J = 16.1Hz), 7.38 (2H, d, J = 8.3Hz), 7.65 (2H, d, J = 8.3Hz)
CI-MS; 465 (M)

Example IV-2 (Synthesis of 3- [2-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl] -vinyl] -pentafluorosulfanylbenzene)
In a container having a volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.71 g (2.50 mmol) of 3-bromopentafluorosulfanylbenzene, 4- (4′-n-pentylbicyclohexyl) ethylene 72 g (2.75 mmol), dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich) )) 0.035 g (0.05 mmol), 1.03 g (7.48 mmol) of potassium carbonate and 10 ml of 1,4-dioxane were added, and the mixture was reacted at 100 ° C. for 8 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel chromatography (ODSC-18, developing solvent; acetonitrile / water = 90/10 → 94/6 (volume ratio)), and white As a solid, 0.05 g of 3- [2-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl] -vinyl] -pentafluorosulfanylbenzene was obtained (isolation yield; 4 %).
This compound is a novel compound represented by the following physical property values. In addition, from the coupling constant (J value) of 6.22 ppm and 6.35 pm, the compound is considered to be a trans isomer.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.83 to 1.43 (26H, m), 1.69 to 1.95 (4H, m), 2.04 to 2.08 (1H, m), 6.22 (1H, dd, J = 6.6 Hz, J = 15.9Hz), 6.35 (1H, d, J = 16.1Hz), 7.33-7.56 (3H, m), 7.68 (1H, d, J = 1.7Hz)
CI-MS; 465 (M)

Example V-1 (Synthesis of 3- [2- [4- (trans-4-n-pentyl-cyclohexyl) -phenyl] -vinyl] -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.40 g (1.74 mmol) of 3-vinylpentafluorosulfanylbenzene, 0.54 g of 4- (4-n-pentylcyclohexyl) bromobenzene (1.74 mmol), dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich) ) 0.136 g (0.19 mmol), 0.72 g (5.22 mmol) of potassium carbonate and 10 ml of 1,4-dioxane were added, followed by reaction at 80 ° C. for 12 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane), and 3- [2- [4- (trans-4-n-pentyl-cyclohexyl) -phenyl] -vinyl] -penta was obtained as a white solid. 0.25 g of fluorosulfanylbenzene was obtained (isolation yield; 31%).
This compound is a novel compound represented by the following physical property values. In addition, from the coupling constant (J value) of 7.04 ppm and 7.14 pm, the compound is considered to be a trans isomer.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.88 to 1.52 (16H, m), 1.88 (4H, m), 2.44 to 2.52 (1H, m), 7.04 (1H, d, J = 16.4 Hz) 7.14 (1H, d, J = 16.4Hz), 7.22 (2H, d, J = 8.1Hz), 7.40-7.46 (3H, m), 7.59-7.63 (2H, m), 7.84 (1H, dd, J = 1.9Hz, J = 1.9Hz)
CI-MS; 458 (M)

Example V-2 (Synthesis of 4- [2- [4- (trans-4-n-propyl-cyclohexyl) -phenyl] -vinyl] -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.40 g (1.74 mmol) of 4-vinylpentafluorosulfanylbenzene, 0.57 g of 4- (4-propylcyclohexyl) iodobenzene (1 .74 mmol), dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich)) 0 .106 g (0.156 mmol), potassium carbonate 0.72 g (5.22 mmol) and 1,4-dioxane 10 ml were added, and the mixture was reacted at 80 ° C. for 12 hours with stirring. Furthermore, 0.051 g (0.075 mmol) of the palladium compound and 0.074 g (0.23 mmol) of tetra-n-butylammonium bromide were added, and the mixture was reacted at 80 ° C. for 17 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 70/30 → 85/15 (volume ratio)), As a white solid, 0.21 g of 4- [2- [4- (trans-4-n-propyl-cyclohexyl) -phenyl] -vinyl] -pentafluorosulfanylbenzene was obtained (isolated yield; 29%).
This compound is a novel compound represented by the following physical property values. In addition, from the coupling constant (J value) of 7.04 ppm and 7.17 ppm, it is thought that the said compound is a trans body.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.88 to 1.49 (12H, m), 1.88 (4H, m), 2.44 to 2.53 (1H, m), 7.04 (1H, d, J = 16.1 Hz) 7.17 (1H, d, J = 16.4Hz), 7.21-7.26 (3H, m), 7.44-7.47 (2H, m), 7.53-7.56 (1H, m), 7.70-7.73 (2H, m)
CI-MS; 430 (M)

Example V-3 (Synthesis of 2-fluoro-5- [2- [4- (trans-4-n-pentyl-cyclohexyl) -phenyl] -vinyl] -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.43 g (1.73 mmol) of 2-fluoro-5-vinylpentafluorosulfanylbenzene, 4- (4-n-pentylcyclohexyl) bromo 0.54 g (1.75 mmol) of benzene, dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr ( Aldrich)) 0.0478 g (0.070 mmol), potassium carbonate 0.72 g (5.22 mmol) and 1,4-dioxane 10 ml were added, and the mixture was reacted at 60 ° C. for 4 hours with stirring. Further, 0.1667 g (0.245 mmol) of the palladium compound and 0.0648 g (0.23 mmol) of tetra-n-butylammonium chloride were added, and the mixture was reacted at 80 ° C. for 24 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 85/15 → 95/5 (volume ratio)), As a white solid, 0.12 g of 2-fluoro-5- [2- [4- (trans-4-n-pentyl-cyclohexyl) -phenyl] -vinyl] -pentafluorosulfanylbenzene was obtained (isolation yield; 13%).
This compound is a novel compound represented by the following physical property values. In addition, from the coupling constant (J value) of 6.98 ppm and 7.07 ppm, the said compound is considered to be a trans body.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.88 to 1.49 (16H, m), 1.88 (4H, m), 2.44 to 2.53 (1H, m), 6.98 (1H, d, J = 16.3 Hz) 7.07 (1H, d, J = 16.3Hz), 7.15-7.30 (3H, m), 7.43 (2H, m), 7.61-7.66 (1H, m), 7.79-7.82 (1H, m)
CI-MS; 476 (M)

Example V-4 (Synthesis of 2-fluoro-5- (2-phenyl-vinyl) -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.43 g (1.74 mmol) of 2-fluoro-5-vinylpentafluorosulfanylbenzene and 0.37 g of trifluoromethanesulfonic acid phenyl ester (1 .74 mmol), dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich)) 0 0.050 g (0.074 mmol), 0.72 g (5.22 mmol) of potassium carbonate and 10 ml of 1,4-dioxane were added, and the mixture was reacted at 80 ° C. for 4 hours with stirring. Further, 0.50 g (0.736 mmol) of the palladium compound and 0.1087 g (0.39 mmol) of tetra-n-butylammonium chloride were added, and the mixture was reacted at 80 ° C. for 39 hours with stirring. After completion of the reaction, the reaction solution was analyzed by chemical ionization. As a result, the presence of 2-fluoro-5- (2-phenyl-vinyl) -pentafluorosulfanylbenzene was confirmed (molecular weight 324).

Example V-5 (Synthesis of 2-fluoro-5- [2- (thiophen-3-yl) -vinyl] -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, a thermometer, and a reflux condenser, 0.43 g (1.74 mmol) of 2-fluoro-5-vinylpentafluorosulfanylbenzene and 0.29 g (1.74 mmol) of 3-bromothiophene were added. ), Palladium acetate 0.043 g (0.17 mmol), triphenylphosphine 0.183 g (0.68 mmol), tetra-n-butylammonium chloride 0.4838 g (1.74 mmol), potassium carbonate 0.72 g (5.22 mmol) ) And 10 ml of N, N-dimethylformamide were added, followed by reaction at 100 ° C. for 12 hours with stirring. After completion of the reaction, the reaction solution was analyzed by a chemical ionization method. As a result, the presence of 2-fluoro-5- [2- (thiophen-3-yl) -vinyl] -pentafluorosulfanylbenzene was confirmed (molecular weight 330).

Example VI-1 (Synthesis of 3- (4-n-pentyl-phenyl) -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, thermometer and reflux condenser, 1.42 g (5.00 mmol) of 3-bromopentafluorosulfanylbenzene and 2.0 g (10.41 mmol) of 4-n-pentylboronic acid , 0.068 g of dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich)) 0.100 mmol), 2.07 g (15.01 mmol) of potassium carbonate and 10 ml of 1,4-dioxane were added, followed by reaction at 60 ° C. for 2 hours with stirring. After completion of the reaction, the reaction solution was filtered, ethyl acetate (50 ml) was added to the filtrate, and washed with water (20 ml × 2). The obtained organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) to obtain 0.40 g of 3- (4-n-pentyl-phenyl) -pentafluorosulfanylbenzene as a transparent liquid (isolated yield). 23%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.91 (3H, t, J = 7.0 Hz), 1.26 to 1.39 (4H, m), 1.61 to 1.71 (2H, m), 2.63 to 2.68 (2H, m), 7.26-7.31 (2H, m), 7.47-7.53 (3H, m), 7.68-7.72 (2H, m), 7.94-7.95 (1H, m)
CI-MS; 350 (M)

Example VI-2 (Synthesis of 4- (4-n-pentyl-phenyl) -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, thermometer and reflux condenser, 1.42 g (5.00 mmol) of 4-bromopentafluorosulfanylbenzene and 2.0 g (10.41 mmol) of 4-n-pentylboronic acid , 0.068 g of dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (manufactured by Aldrich)) 0.100 mmol), 2.07 g (15.01 mmol) of potassium carbonate and 10 ml of 1,4-dioxane were added, followed by reaction at 60 ° C. for 2 hours with stirring. After completion of the reaction, the reaction solution was filtered, ethyl acetate (50 ml) was added to the filtrate, and washed with water (20 ml × 2). The obtained organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) to obtain 0.58 g of 4- (4-n-pentyl-phenyl) -pentafluorosulfanylbenzene (isolated yield) as a white solid. 33%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.91 (3H, t, J = 7.0 Hz), 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; 350 (M)

Example VI-3 (Synthesis of 3- [4- (4-n-pentyl-cyclohexyl) -phenyl])-pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.71 g (2.50 mmol) of 3-bromopentafluorosulfanylbenzene, 4- (4-pentylcyclohexyl) -phenylboronic acid pinacol ester 1 0.07 g (3.00 mmol), dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr (Aldrich) Manufactured)) After adding 0.035 g (0.054 mmol), potassium carbonate 1.035 g (7.50 mmol) and 1,4-dioxane 10 ml, the mixture was reacted at 60 ° C. for 3 hours with stirring. After completion of the reaction, the reaction solution was filtered, and toluene (50 ml) was added to the filtrate, followed by washing with water (30 ml × 3). The obtained organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 75/25 → 90/10 (volume ratio)), As a transparent liquid, 0.27 g of 3- [4- (4-n-pentyl-cyclohexyl) -phenyl])-pentafluorosulfanylbenzene was obtained (isolation yield: 25%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.90 (3H, t, J = 7.0 Hz), 1.01 to 1.55 (13H, m), 1.88 to 1.95 (4H, m), 2.47 to 2.58 (1H, m), 7.30-7.33 (2H, m), 7.48-7.53 (3H, m), 7.68-7.71 (2H, m), 7.93-7.94 (1H, m)
CI-MS; 432 (M)

Example VI-4 (Synthesis of 4- [4- (4-n-pentyl-cyclohexyl) -phenyl] -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.71 g (2.50 mmol) of 4-bromopentafluorosulfanylbenzene, 4- (4-n-pentylcyclohexyl) -phenylboronic acid pinacol 1.06 g (3.00 mmol) of ester, dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr ( Aldrich))) 0.036 g (0.054 mmol), potassium carbonate 1.035 g (7.50 mmol) and 1,4-dioxane 10 ml were added, followed by reaction at 100 ° C. for 8 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) to obtain 0.69 g of 4- [4- (4-n-pentyl-cyclohexyl) -phenyl] -pentafluorosulfanylbenzene as a white solid. (Isolation yield; 64%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.90 (3H, t, J = 7.0 Hz), 1.01 to 1.56 (13H, m), 1.87 to 1.95 (4H, m), 2.49 to 2.57 (1H, m), 7.32 (2H, d, J = 8.0Hz), 7.51 (2H, d, J = 8.3Hz), 7.64 (2H, d, J = 8.8Hz), 7.80 (2H, d, J = 8.8Hz)
CI-MS; 432 (M)

Example VI-5 (Synthesis of 4- (4′-n-heptyl-biphenyl-4-yl) -pentafluorosulfanylbenzene)
In a container having an internal volume of 25 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.71 g (2.50 mmol) of 4-bromopentafluorosulfanylbenzene, 4- (4-n-heptylphenyl) -phenylboronic acid pinacol 1.13 g (3.00 mmol) of ester, dichloro {1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene} (3-chloropyridyl) palladium (trade name; PEPPSI (registered trademark) -IPr ( Aldrich)) 0.036 g (0.054 mmol), potassium carbonate 1.04 g (7.50 mmol) and 1,4-dioxane 10 ml were added, followed by reaction at 100 ° C. for 4 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 85/15 → 100/0 (volume ratio)), As a white solid, 0.23 g of 4- (4′-n-heptyl-biphenyl-4-yl) -pentafluorosulfanylbenzene was obtained (isolation yield; 20%).
This compound is a novel compound represented by the following physical property values.
4- (4′-n-heptyl-biphenyl-4-yl) -pentafluorosulfanylbenzene is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.89 (3H, t, J = 6.9 Hz), 1.26 to 1.34 (8H, m), 1.66 to 1.69 (2H, m), 2.64 to 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)

Example VI-6 (Synthesis of 2,6-difluoro-3- [4- (trans-4-n-propylcyclohexyl) -phenyl] -pentafluorosulfanylbenzene)
To a 30-ml container equipped with a stirrer, a thermometer and a reflux condenser, 0.330 g (1.00 mmol) of 3-ethoxy-6-bromopentafluorosulfanylbenzene, 4- (4-n-pentylcyclohexyl)- 0.53 g (1.50 mmol) of phenylboronic acid pinacol ester, 0.124 g (0.108 mmol) of tetrakis (triphenylphosphine) palladium, 0.430 g (2.02 mmol) of tripotassium phosphate and 5 ml of 1,4-dioxane After the addition, the mixture was reacted at 100 ° C. for 4 hours with stirring. After 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 → hexane / ethyl acetate = 70/30 (volume ratio)), and 2,6-difluoro-3- [4- (trans- 0.32 g of 4-n-propylcyclohexyl) -phenyl] -pentafluorosulfanylbenzene was obtained (isolation yield; 40%, yield calculated based on 4- (4-n-propylcyclohexyl) iodobenzene) .
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , 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 (1H, m), 4.09 (2H, qJ = 6.9Hz), 7.25-7.48 (7H, m)
CI-MS; 476 (M)

Example VII-1 (Synthesis of 2,6-difluoro-3- [4- (trans-4-n-propylcyclohexyl) -phenyl] -pentafluorosulfanylbenzene)
2,6-Difluoro-3- (4,4,5,5-tetramethyl-1,3-dioxaborolan-2-yl)-was added to a 30-ml container equipped with a stirrer, a thermometer and a reflux condenser. Pentafluorosulfanylbenzene 0.791 g (2.20 mmol), 4- (4-n-propylcyclohexyl) iodobenzene 0.591 g (1.80 mmol), tetrakis (triphenylphosphine) palladium 0.124 g (0.108 mmol), After adding 0.764 g (3.60 mmol) of tripotassium phosphate and 10 ml of 1,4-dioxane, the mixture was reacted at 100 ° C. for 4 hours with stirring. After 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) and reverse phase silica gel column chromatography (ODSC-18, developing solvent; acetonitrile / water = 80/20 → 95/5 (volume ratio)), As a white solid, 0.32 g of 2,6-difluoro-3- [4- (trans-4-n-propylcyclohexyl) -phenyl] -pentafluorosulfanylbenzene was obtained (isolation yield; 40%, 4- (Yield was calculated based on (4-n-propylcyclohexyl) iodobenzene).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.91 (3H, t, J = 7.1 Hz), 1.05 to 1.55 (9H, m), 1.87 to 1.95 (4H, m), 2.48 to 2.56 (1H, m), 6.91 to 7.13 (1H, m), 7.29 to 7.40 (4H, m), 7.53 to 7.61 (1H, m)
CI-MS; 440 (M)

Example VIII-1 (Synthesis of 4- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, thermometer and reflux condenser, 17 ml of diisopropylamine, 0.047 g (0.23 mmol) of copper (II) acetate monohydrate, 0.20 g (0. 75m
mol), 0.071 g (0.40 mmol) of palladium chloride and 1.42 g (5.00 mmol) of 4-bromopentafluorosulfanylbenzene were added, and the mixture was allowed to react for 15 minutes while stirring at room temperature until the reaction solution became homogeneous. After adding 1.03 g (6 mmol) of 1-ethynyl-4-n-pentylbenzene to the reaction solution, the mixture was reacted at room temperature for 4 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) to obtain 0.51 g of 4- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene (isolated product) as a white solid. Rate; 27%).
The physical property values of this compound were as follows.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.89 (3H, t, J = 7.0 Hz), 1.31 to 1.35 (4H, m), 1.57 to 1.67 (2H, m), 2.62 (2H, t, J = 7.7Hz), 7.18 (2H, d, J = 8.5Hz), 7.45 (2H, d, J = 8.3Hz), 7.57 (2H, d, J = 8.3Hz), 7.72 (2H, d, J = (8.8Hz)
CI-MS; 374 (M)

Example VIII-2 (Synthesis of 3- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, thermometer and reflux condenser, 17 ml of diisopropylamine, 0.047 g (0.23 mmol) of copper (II) acetate monohydrate, 0.20 g (0. 75m
mol), 0.071 g (0.40 mmol) of palladium chloride and 1.42 g (5.00 mmol) of 3-bromopentafluorosulfanylbenzene, and then stirred for 15 minutes while stirring at 40 ° C. until the reaction solution becomes homogeneous. I let you. The reaction solution was cooled to near room temperature with stirring, and 1.03 g (6 mmol) of 1-ethynyl-4-n-pentylbenzene was added, followed by reaction at room temperature for 4 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) and reverse phase silica gel column chromatography (ODS C-18, developing solvent; acetonitrile / water = 90/10 (volume ratio)) as a white solid. , 3- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene 0.72 g was obtained (isolation yield; 38%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.90 (3H, t, J = 7.0 Hz), 1.28 to 1.38 (4H, m), 1.58 to 1.68 (2H, m), 2.62 (2H, t, J = 7.7Hz), 7.18 (2H, d, J = 8.5Hz), 7.46 (3H, m), 7.60-7.71 (2H, m), 7.90-7.91 (1H, m)
CI-MS; 374 (M)

Example VIII-3 (Synthesis of 2-fluoro-5- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, a thermometer and a reflux condenser, 51 ml of diisopropylamine, 0.141 g (0.71 mmol) of copper (II) acetate monohydrate, 0.60 g of triphenylphosphine (2. 25mm
ol), 0.213 g (1.20 mmol) of palladium chloride and 5.22 g (15.00 mmol) of 2-fluoro-5-iodopentafluorosulfanylbenzene are added, and the reaction solution becomes homogeneous while stirring at 40 ° C. The reaction was continued for 15 minutes. The reaction solution was cooled to near room temperature while stirring, and 3.09 g (18 mmol) of 1-ethynyl-4-n-pentylbenzene was added, followed by reaction at room temperature for 4 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent: hexane) and reverse phase silica gel column chromatography (ODS C-18, developing solvent; acetonitrile / water = 80/20 (volume ratio)) as a white solid. , 5.27 g of 2-fluoro-5- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene was obtained (isolation yield; 90%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.90 (3H, t, J = 6.8 Hz), 1.28 to 1.38 (4H, m), 1.57 to 1.67 (2H, m), 2.62 (2H, t, J = 7.6Hz), 7.15-7.22 (3H, m), 7.44 (2H, d, J = 8.3Hz), 7.61-7.66 (1H, m), 7.89-7.92 (1H, m)
CI-MS; 392 (M)

Example VIII-4 (Synthesis of 4- [4- (4-n-pentyl-cyclohexyl) -phenylethynyl] -pentafluorosulfanylbenzene)
In a 30-ml container equipped with a stirrer, a thermometer and a reflux condenser, 10 ml of diisopropylamine, 0.026 g (0.13 mmol) of copper (II) acetate monohydrate, 0.11 g of triphenylphosphine (0. 42m
mol), 0.039 g (0.22 mmol) of palladium chloride, and 0.78 g (2.76 mmol) of 4-bromopentafluorosulfanylbenzene, and then stirred for 15 minutes while stirring at 40 ° C. until the reaction solution becomes homogeneous. I let you. After adding 0.70 g (2.75 mmol) of 1-ethynyl-4- (4-n-pentylcyclohexyl) benzene to the reaction solution, the mixture was reacted at room temperature for 4 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane), and 0.08 g of 4- [4- (4-n-pentyl-cyclohexyl) -phenylethynyl] -pentafluorosulfanylbenzene was obtained as a white solid. Obtained (isolation yield; 6%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.90 (3H, t, J = 6.9 Hz), 1.03 to 1.52 (13H, m), 1.89 (4H, m), 2.49 (1H, m), 7.21 (2H, d, J = 8.1Hz), 7.46 (2H, d, J = 8.3Hz), 7.57 (2H, d, J = 8.8Hz), 7.72 (2H, d, J = 8.8Hz)
CI-MS; 456 (M)

Example VIII-5 (Synthesis of 4- (thiophen-3-yl-ethynyl) -pentafluorosulfanylbenzene)
In a 50 ml internal volume container equipped with a stirrer, a thermometer and a reflux condenser, 3-ethynylthiophene 0.54 g (5.0 mmol), 2-propanol 10 ml, water 10 ml, 4-iodopentafluorosulfanylbenzene 1.65 g (5.0 mmol), sodium phosphate dodecahydrate 3.80 g (10 mmol), 10% Pd / C 0.044 g (moisture content 51.3%, manufactured by TYPE K, NE Chemcat) Then, the mixture was reacted at 80 ° C. for 6 hours with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) to obtain 0.50 g of 4- (thiophen-3-yl-ethynyl) -pentafluorosulfanylbenzene (isolated yield) as a white solid. 32%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 7.21 (1H, dd, J = 1.1 Hz, J = 5.0 Hz), 7.33 (1H, dd, J = 2.9 Hz, J = 4.9 Hz), 7.56- 7.59 (3H, m), 7.73 (2H, d, J = 9.0Hz)
CI-MS; 310 (M)

Example VIII-6 (Synthesis of 4- (thiophen-3-yl-ethynyl) -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 30 ml of diethylamine, 0.010 g (0.05 mmol) of copper (I) iodide, 0.07 of dichlorobis (triphenylphosphine) palladium.
0 g (0.10 mmol), 4-iodopentafluorosulfanylbenzene 1.65 g (5.00 mmol), 3-ethynylthiophene 0.54 g (5.00 mmol) was added, followed by reaction at room temperature for 1.5 hours with stirring. I let you. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane) to obtain 1.34 g of 4- (thiophen-3-yl-ethynyl) -pentafluorosulfanylbenzene (isolated yield) as a white solid. 87%).

Example VIII-7 (Synthesis of 4- (thiophen-3-yl-ethynyl) -pentafluorosulfanylbenzene)
In a container with an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 30 ml of diethylamine, 0.010 g (0.05 mmol) of copper (I) iodide, 0.065 g of dichlorobis (triphenylphosphine) nickel
g (0.10 mmol), 4-iodopentafluorosulfanylbenzene (1.65 g, 5.00 mmol) and 3-ethynylthiophene (0.54 g, 5.00 mmol) were added, followed by reaction at room temperature for 8 hours with stirring. . After completion of the reaction, the reaction solution was analyzed by a chemical ionization method. As a result, the presence of 4- (thiophen-3-yl-ethynyl) -pentafluorosulfanylbenzene was confirmed (molecular weight 310).

Example VIII-8 (Synthesis of 4-phenylethynylpentafluorosulfanylbenzene)
In a container having a volume of 100 ml equipped with a stirrer, a thermometer and a reflux condenser, 80 ml of diethylamine, 0.041 g (0.20 mmol) of copper (I) iodide, 0.2% of dichlorobis (triphenylphosphine) palladium
After adding 80 g (0.40 mmol), 6.60 g (20.00 mmol) of 4-iodopentafluorosulfanylbenzene and 2.04 g (20.00 mmol) of ethynylbenzene, the mixture was reacted at room temperature for 1.5 hours with stirring. . After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent: hexane) and reverse phase silica gel column chromatography (ODS C-18, developing solvent: acetonitrile / water = 60/40 → 70/30 (volume ratio)). To obtain 5.50 g of 4-phenylethynylpentafluorosulfanylbenzene (isolated yield; 90%) as a white solid.
The physical property values of this compound were as follows.
¹ H-NMR (CDCl ₃ , 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) -pentafluorosulfanylbenzene)
In a container having an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 10 ml of diethylamine, 0.005 g (0.025 mmol) of copper (I) iodide, 0.01% of dichlorobis (triphenylphosphine) nickel
After adding 4 g (0.022 mmol), 2- (trifluoromethanesulfonyloxy) pentafluorosulfanylbenzene 0.35 g (0.99 mmol), 1-ethynyl-4-n-pentylbenzene 0.18 g (1.04 mmol) The mixture was reacted for 24 hours at room temperature with stirring. After completion of the reaction, the reaction solution was analyzed by a chemical ionization method. As a result, the presence of 2- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene was confirmed (molecular weight 374).

Example VIII-10 (Synthesis of 3-ethoxy-6- (4-n-pentyl-phenylethynyl) -pentafluorosulfanylbenzene)
In a container with an internal volume of 25 ml equipped with a stirrer, a thermometer and a reflux condenser, 10 ml of diethylamine, 0.006 g (0.03 mmol) of copper (I) iodide, 0.02 of dichlorobis (triphenylphosphine) palladium
After adding 2 g (0.03 mmol), 3-ethoxy-6-bromopentafluorosulfanylbenzene 0.49 g (1.50 mmol), 1-ethynyl-4-n-pentylbenzene 0.52 g (3.02 mmol), The reaction was allowed to proceed for 18 hours at room temperature with stirring. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, the concentrate was purified by flash column chromatography (developing solvent; hexane, hexane / ethyl acetate = 10/1 (volume ratio)), and 3-ethoxy-6- (4-n-pentyl-phenyl) was obtained as a yellow solid. 0.13 g of ethynyl) -pentafluorosulfanylbenzene was obtained (isolation yield; 21%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.89 (3H, t, J = 6.8 Hz), 1.24 to 1.34 (3H, m), 1.49 to 1.54 (4H, m), 1.57 to 1.67 (2H, m), 2.62 (2H, m), 4.17 (2H, q, J = 6.9Hz), 7.16 to 7.33 (4H, m), 7.44 to 7.53 (3H, m)
CI-MS; 418 (M)

Example IX-1 (Synthesis of 4-[(trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl-oxymethyl] -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer, 0.379 g (1.5 mmol) of (trans, trans) -4′-n-pentyl-bicyclohexyl-4-ol, 60% sodium hydride After adding 0.060 g (1.5 mmol) and 5 ml of tetrahydrofuran, the mixture was reacted at 40 ° C. for 15 minutes with stirring. After adding 0.024 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluorosulfanylbenzene, the mixture was reacted at 60 ° C. for 10 hours with stirring. After completion of the reaction, 5 ml of 1 mol / l hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution for liquid separation, 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, and then the concentrate was purified by silica gel column chromatography (developing solvent; hexane → hexane / ethyl acetate = 85/15 (volume ratio)) to give 4-[( trans, trans) -4′-n-pentyl-bicyclohexyl-4-yl-oxymethyl] -pentafluorosulfanylbenzene 0.390 g (0.83 mmol) was obtained (isolation yield 83%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.81 to 1.32 (22H, m), 1.67 to 1.79 (6H, m), 2.08 to 2.12 (2H, m), 3.22 to 3.29 (1H, m), 4.59 (2H, s), 7.41-7.44 (2H, m), 7.69-7.73 (2H, m)
CI-MS; 449 (M-19)

Example IX-2 (Synthesis of 4-[(trans, cis) -4′-n-pentyl-bicyclohexyl-4-yl-oxymethyl] -pentafluorosulfanylbenzene)
(Trans, cis) -4′-n-pentyl-bicyclohexyl-4-ol 0.379 g (1.5 mmol), 60% sodium hydride in a 30 ml glass container equipped with a stirrer and a thermometer After adding 0.060 g (1.5 mmol) and 5 ml of tetrahydrofuran, the mixture was reacted at room temperature for 15 minutes with stirring. After adding 0.025 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluorosulfanylbenzene, the mixture was reacted at 60 ° C. for 3.5 hours with stirring. After completion of the reaction, 5 ml of 1 mol / l hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution for liquid separation, 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, and the concentrate was purified by silica gel column chromatography (developing solvent; hexane → hexane / ethyl acetate = 95/5 (volume ratio)) to give 4- [ 0.370 g (0.79 mmol) of (trans, cis) -4′-n-pentyl-bicyclohexyl-4-yl-oxymethyl] -pentafluorosulfanylbenzene was obtained (isolation yield 79%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.82 to 1.45 (26H, m), 1.73 to 1.76 (4H, m), 1.91 to 1.94 (2H, m), 3.61 (1H, s), 4.53 ( 2H, s), 7.42-7.45 (2H, m), 7.70-7.73 (2H, m)
CI-MS; 468 (M)

Example IX-3 (Synthesis of 4-[(trans, trans) -4'-n-butyl-bicyclohexyl-4-yl-oxymethyl] -pentafluorosulfanylbenzene)
(Trans, trans) -4′-n-butyl-bicyclohexyl-4-ol 0.358 g (1.5 mmol), 60% sodium hydride in a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer After adding 0.060 g (1.5 mmol) and 5 ml of tetrahydrofuran, the mixture was reacted at room temperature for 15 minutes with stirring. After adding 0.025 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluorosulfanylbenzene, the mixture was reacted at 60 ° C. for 4 hours with stirring. After completion of the reaction, 5 ml of 1 mol / l hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution for liquid separation, 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, and the concentrate was purified by silica gel column chromatography (developing solvent; hexane → hexane / ethyl acetate = 90/10 (volume ratio)) to give 4-[(( trans, trans) -4′-n-butyl-bicyclohexyl-4-yl-oxymethyl] -pentafluorosulfanylbenzene (0.400 g, 0.88 mmol) was obtained (isolation yield 88%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.77 to 1.32 (20H, m), 1.67 to 1.79 (6H, m), 2.08 to 2.12 (2H, m), 3.21 to 3.31 (1H, m), 4.59 (2H, s), 7.41-7.44 (2H, m), 7.70-7.73 (2H, m)
CI-MS; 435 (M-19)

Example IX-4 (Synthesis of 4-octyloxymethylpentafluorosulfanylbenzene)
4-Octyloxyphenol 0.333 g (1.5 mmol), 60% sodium hydride 0.060 g (1.5 mmol), and tetrahydrofuran 5 ml were added to a glass container equipped with a stirrer and a thermometer. Then, it was made to react at room temperature for 15 minutes, stirring. After adding 0.025 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluorosulfanylbenzene, the mixture was reacted at 60 ° C. for 4 hours with stirring. After completion of the reaction, 5 ml of 1 mol / l hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution for liquid separation, 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, and the concentrate was purified by silica gel column chromatography (developing solvent; hexane → hexane / ethyl acetate = 95/5 (volume ratio)) to give 4-octyloxy as a white solid. 0.410 g (0.94 mmol) of methylpentafluorosulfanylbenzene was obtained (isolation yield 94%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , 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 to 7.77 (2H, m)
CI-MS; 438 (M)

Example IX-5 (Synthesis of 4- (trans-4-phenyl-cyclohexyl-oxymethyl) -pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer and a thermometer, trans-4-phenyl-cyclohexanol 0.264 g (1.5 mmol), 60% sodium hydride 0.060 g (1.5 mmol) and tetrahydrofuran 5 ml. Then, the mixture was reacted at room temperature for 15 minutes with stirring. After adding 0.025 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluorosulfanylbenzene, the mixture was reacted at 60 ° C. for 7 hours with stirring. After completion of the reaction, 5 ml of 1 mol / l hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution for liquid separation, 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, and the concentrate was purified by silica gel column chromatography (developing solvent; hexane → hexane / ethyl acetate = 95/5 (volume ratio)) to give 4- (trans 0.300 g (0.94 mmol) of -4-phenyl-cyclohexyl-oxymethyl) -pentafluorosulfanylbenzene was obtained (isolation yield 76%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.49 to 1.58 (4H, m), 1.96 (2H, m), 2.24 (2H, m), 2.54 to 2.56 (1H, m), 3.42 to 3.44 ( 1H, m), 4.64 (2H, s), 7.17-7.32 (5H, m), 7.45-7.47 (2H, m), 7.72-7.75 (2H, m)
CI-MS; 373 (M-19)

Example IX-6 (Synthesis of 4- (cis-4-phenyl-cyclohexyl-oxymethyl) -pentafluorosulfanylbenzene)
In a glass container having a capacity of 30 ml equipped with a stirrer and a thermometer, 0.264 g (1.5 mmol) of cis-4-phenyl-cyclohexanol, 0.060 g (1.5 mmol) of 60% sodium hydride and 5 ml of tetrahydrofuran. Then, the mixture was reacted at room temperature for 15 minutes with stirring. After adding 0.025 g (0.14 mmol) of potassium iodide and 0.297 g (1.0 mmol) of 4-bromomethylpentafluorosulfanylbenzene, the mixture was reacted at 60 ° C. for 7 hours with stirring. After completion of the reaction, 5 ml of 1 mol / l hydrochloric acid and 50 ml of ethyl acetate were added to the reaction solution for liquid separation, 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, and the concentrate was purified by silica gel column chromatography (developing solvent; hexane → hexane / ethyl acetate = 95/5 (volume ratio)) to give 4- (cis -4-Phenyl-cyclohexyl-oxymethyl) -pentafluorosulfanylbenzene 0.260 g (0.66 mmol) was obtained (isolation yield 66%).
This compound is a novel compound represented by the following physical property values.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.53 to 1.72 (4H, m), 1.82 to 1.96 (2H, m), 2.08 to 2.13 (2H, m), 2.52 to 2.62 (1H, m), 3.72 to 3.90 (1H, m), 4.58 (2H, s), 7.16 to 7.33 (5H, m), 7.46 to 7.49 (2H, m), 7.73 to 7.76 (2H, m)
CI-MS; 392 (M)

Example X-1 (Synthesis of 4- [4- (4-pentyl-cyclohexyl) -benzoylamino] pentafluorosulfanylbenzene)
4-Aminopentafluorosulfanylbenzene 0.2 g (0.91 mmol), 4- (4-pentyl-cyclohexyl) benzoic acid 0.25 g (0.91 mmol), in a 30 ml glass container equipped with a stirrer, 1 After adding 0.21 g (1.09 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.010 g (0.08 mmol) of 4-dimethylaminopyridine and 5 ml of methylene chloride, the mixture was stirred at room temperature. For 20 hours. After completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (volume ratio)). As a result, 4- [4 0.05 g (yield 11.6%) of-(4-pentyl-cyclohexyl) -benzoylamino] pentafluorosulfanylbenzene was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 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 (1H, m), 7.33 to 7.35 (2H, m), 7.74 to 7.80 (6H, m), 7.90 (1H, s)
CI-MS; 476 (M + 1)

Example X-2 (Synthesis of 4-[(4′-pentyl-bicyclohexyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.2 g (0.91 mmol) of 4-aminopentafluorosulfanylbenzene, 0.25 g (0.91 mmol) of 4′-pentyl-bicyclohexyl-4-carboxylic acid, While adding 0.21 g (1.09 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.010 g (0.08 mmol) of 4-dimethylaminopyridine and 5 ml of methylene chloride, the mixture was stirred. The reaction was allowed to proceed for 20 hours at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (volume ratio)). As a result, 4-[(( 4'-pentyl-bicyclohexyl-4-carbonyl) amino] pentafluorosulfanylbenzene (0.08 g, yield 18.2%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.82 to 0.90 (3H, m), 0.95 to 1.22 (15H, m), 1.25 to 1.33 (4H, m), 1.48 to 2.03 (8H, m), 2.04 to 2.21 (1H, m), 7.26 to 7.27 (2H, m), 7.60 to 7.71 (3H, m)
CI-MS; 482 (M + 1)

Example X-3 (Synthesis of 3- [4- (4-pentyl-cyclohexyl) -benzoylamino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.2 g (0.91 mmol) of 3-aminopentafluorosulfanylbenzene, 0.25 g (0.91 mmol) of 4- (4-pentyl-cyclohexyl) benzoic acid, 1 After adding 0.21 g (1.09 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.010 g (0.08 mmol) of 4-dimethylaminopyridine and 5 ml of methylene chloride, the mixture was stirred at room temperature. For 20 hours. After completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (volume ratio)) to give 3- [4 as white crystals. 0.31 g (yield 72.1%) of-(4-pentyl-cyclohexyl) -benzoylamino] pentafluorosulfanylbenzene was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 0.92 (3H, m), 1.04 to 1.12 (2H, m), 1.22 to 1.55 (12H, m), 1.88 to 1.91 (4H, m), 2.50 to 2.58 (1H, m), 7.31 to 7.33 (2H, m), 7.34 to 7.54 (2H, m), 7.77 to 8.05 (4H, m), 8.05 to 8.06 (1H, m)
CI-MS; 476 (M + 1)

Example X-4 (Synthesis of 3-[(4'-pentyl-bicyclohexyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
In a glass container having an internal volume of 30 ml equipped with a stirrer, 0.2 g (0.91 mmol) of 3-aminopentafluorosulfanylbenzene, 0.25 g (0.91 mmol) of 4′-pentyl-bicyclohexyl-4-carboxylic acid, While adding 0.21 g (1.09 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.010 g (0.08 mmol) of 4-dimethylaminopyridine and 5 ml of methylene chloride, the mixture was stirred. The reaction was allowed to proceed for 20 hours at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (volume ratio)). As a result, 3-[(( 4'-pentyl-bicyclohexyl-4-carbonyl) amino] pentafluorosulfanylbenzene (0.26 g, yield 59.1%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.82 to 1.28 (17H, m), 1.30 to 2.20 (9H, m), 7.39 to 7.48 (2H, m), 7.71 to 7.73 (1H, m), 7.95-7.96 (1H, m)
CI-MS; 482 (M + 1)

Example X-5 (Synthesis of 4-[(4′-decyloxy-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
4-aminopentafluorosulfanylbenzene 0.5 g (2.27 mmol), 4′-decyloxy-biphenyl-4-carboxylic acid 0.97 g (2.27 mmol), -0.63 g (3.41 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.050 g (0.4 mmol) of 4-dimethylaminopyridine and 10 ml of methylene chloride were added, followed by stirring at room temperature. For 20 hours. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1 (volume ratio)). As a result, 4-[(( 4'-decyloxy-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene (0.03 g, yield 2.24%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.83 to 0.88 (3H, m), 1.25 to 1.42 (14H, m), 1.68 to 1.77 (2H, m), 4.02 to 4.04 (2H, m), 7.03 to 7.06 (2H, m), 7.63 to 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 + 1)

Example X-6 (Synthesis of 4-[(4′-heptyl-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
4-Aminopentafluorosulfanylbenzene 0.5g (2.27mmol), 4'-heptyl-biphenyl-4-carboxylic acid 0.81g (2.27mmol), in a 30ml glass container equipped with a stirrer, 1 -0.63 g (3.41 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.050 g (0.4 mmol) of 4-dimethylaminopyridine and 10 ml of methylene chloride were added, followed by stirring at room temperature. For 20 hours. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1 (volume ratio)). As a result, 4-[(( 4'-Heptyl-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene 0.82 g (yield 72.6%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.86 to 0.91 (3H, m), 1.29 to 1.33 (6H, m), 1.58 to 1.68 (4H, m), 2.63 to 2.68 (2H, m), 7.27 to 7.30 (2H, m), 7.53 to 7.55 (2H, m), 7.69 to 7.76 (6H, m), 7.91 to 7.93 (2H, m), 8.03 (H, s)
CI-MS; 498 (M + 1)

Example X-7 (Synthesis of 3-[(4′-tert-butyl-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.5 g (2.27 mmol) of 3-aminopentafluorosulfanylbenzene, 0.69 g (2.27 mmol) of 4′-tert-butyl-biphenyl-4-carboxylic acid , 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 0.65 g (3.41 mmol), 4-dimethylaminopyridine 0.050 g (0.4 mmol) and methylene chloride 10 ml were added and stirred. For 20 hours at room temperature. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1 (volume ratio)). As a result, 3-[(( 4'-tert-butyl-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene (0.44 g, yield 42.7%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.33 to 1.41 (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 + 1)

Example X-8 (Synthesis of 3-[(4′-decyloxy-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.5 g (2.27 mmol) of 3-aminopentafluorosulfanylbenzene, 0.97 g (2.27 mmol) of 4′-decyloxy-biphenyl-4-carboxylic acid, 1 -0.63 g (3.41 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.050 g (0.4 mmol) of 4-dimethylaminopyridine and 10 ml of methylene chloride were added, followed by stirring at room temperature. For 20 hours. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1 (volume ratio)). As a result, 3-[(( 4'-decyloxy-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene 0.54 g (yield 42.8%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.86 to 0.90 (3H, m), 1.28 to 1.61 (14H, m), 1.76 to 1.85 (2H, m), 3.98 to 4.03 (2H, m), 6.97 to 7.01 (2H, m), 7.43 to 7.57 (3H, m), 7.65 to 7.68 (2H, m), 7.87 to 7.93 (3H, m), 8.03 to 8.09 (2H, m)
CI-MS; 556 (M + 1)

Example X-9 (Synthesis of 3-[(4′-heptyl-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 0.5 g (2.27 mmol) of 3-aminopentafluorosulfanylbenzene, 0.81 g (2.27 mmol) of 4′-heptyl-biphenyl-4-carboxylic acid, 1 -0.63 g (3.41 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.050 g (0.4 mmol) of 4-dimethylaminopyridine and 10 ml of methylene chloride were added, followed by stirring at room temperature. For 20 hours. After completion of the reaction, the reaction mixture was concentrated, and the resulting concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1 (volume ratio)). As a result, 3-[(( 4'-Heptyl-biphenyl-4-carbonyl) amino] pentafluorosulfanylbenzene 0.51 g (yield 45.1%) was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 0.91 (3H, m), 1.28 to 1.35 (6H, m), 1.60 to 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 (2H, m)
CI-MS; 498 (M + 1)

Example XI-1 (Synthesis of 3-[(4-propoxy-benzylidene) amino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 1.0 g (4.55 mmol) of 3-aminopentafluorosulfanylbenzene, 0.75 g (4.55 mmol) of 4-propoxybenzaldehyde, molecular sieves 4A (1/16) After adding 3 g and 20 ml of methylene chloride, the mixture was reacted at room temperature for 20 hours with stirring. After completion of the reaction, the reaction solution was filtered and concentrated. Hexane was added to the concentrate, and the container was cooled to -20 to 40 ° C. with dry ice. As a result, crystals were precipitated. 0.47 g (yield 28.3%) of [(4-propoxy-benzylidene) amino] pentafluorosulfanylbenzene was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.03 to 1.08 (3H, m), 1.79 to 1.90 (2H, m), 3.97 to 4.02 (2H, m), 6.97 to 7.01 (2H, m), 7.29 to 7.48 (2H, m), 7.55 to 7.60 (2H, m), 7.82 to 7.85 (2H, m), 8.35 (1H, s)
CI-MS; 366 (M + 1)

Example XI-2 (Synthesis of 3-[(4-octadecyl-benzylidene) amino] pentafluorosulfanylbenzene)
In a 30 ml glass container equipped with a stirrer, 1.0 g (4.55 mmol) of 3-aminopentafluorosulfanylbenzene, 1.07 g (4.55 mmol) of 4-octadecylbenzaldehyde, Molecular Sieves 4A (1/16) After adding 3 g and 20 ml of methylene chloride, the mixture was reacted at room temperature for 20 hours with stirring. After completion of the reaction, the reaction solution was filtered and concentrated. Hexane was added to the concentrate, and the container was cooled to -20 to 40 ° C. with dry ice. As a result, crystals were precipitated. 0.27 g (yield 13.6%) of [(4-octadecyl-benzylidene) amino] pentafluorosulfanylbenzene was obtained.
This compound is a novel compound having the following physical properties.
¹ H-NMR (CDCl ₃ , δ (ppm)); 0.87 to 0.91 (3H, m), 1.29 to 1.58 (10H, m), 1.79 to 1.83 (2H, m), 4.00 to 4.05 (2H, m), 6.96 to 6.99 (4H, m), 7.28 to 7.31 (2H, m), 7.45 to 7.45 (2H, m), 7.55 to 7.59 (2H, m), 7.80 to 7.85 (2H, m), 8.35 (1H, s )
CI-MS; 436 (M + 1)

[Liquid crystal phase optical observation with a polarizing microscope (confirmation of liquid crystal phase)]
An optical pattern was observed for the compounds synthesized in the above examples using a melting point measuring device in which two polarizing plates orthogonal to 90 degrees were attached to the light source and the microscope. As a result, it was confirmed that the compounds shown in FIGS. 1 to 18 have a liquid crystal phase exhibiting a clear filamentous structure (Schlieren pattern) in a temperature range higher than the melting point.

  The pentafluorosulfanylbenzene compound obtained by the production method of the present invention is useful in the fields of liquid crystal materials and medicine.

Claims (13)

And pentafluorosulfanylbenzene compound represented by the following general formula (1), the general formula R ¹ HC = CH ₂ (wherein, R ¹ represents an alkyl group having a carbon number of 1 to 20, a cycloalkyl of 3 to 25 carbon atoms One or more compounds selected from a group of compounds represented by: a group, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 25 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms). A method for producing a pentafluorosulfanylbenzene compound represented by the following general formula (3), characterized by reacting.

(In the formula, A is a halogen atom, and the hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)

(In the formula, R ¹ is the same as above, Z represents a linking group consisting of —HC═CH—, and n is 1. ) And pentafluorosulfanylbenzene compound represented by the following general formula (1), the general formula R ¹ X (wherein, R ¹ is an alkyl group having a carbon number of 1 to 20, a cycloalkyl group having 3 to 25 carbon atoms, carbon An aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 25 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and X represents a detachable group. A method for producing a pentafluorosulfanylbenzene compound represented by the following general formula (3), comprising reacting with one or more compounds.

(In the formula, A is —HC═CH ₂ , and the hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.)

(In the formula, R ¹ is the same as above, Z represents a linking group consisting of —HC═CH—, and n is 1. )   The manufacturing method of the pentafluoro sulfanylbenzene compound of Claim 1 or 2 performed in presence of a metal compound and a base.   The method for producing a pentafluorosulfanylbenzene compound according to claim 3, wherein the metal compound is a palladium compound.   The method for producing a pentafluorosulfanylbenzene compound according to claim 3, wherein the base is an alkali metal carbonate, an amine or a mixture thereof. And pentafluorosulfanylbenzene compound represented by the following general formula (1), the general formula R ¹ OH (wherein, R ¹ is an alkyl group having a carbon number of 1 to 20, a cycloalkyl group having 3 to 25 carbon atoms, carbon (Represents an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 25 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms). A process for producing a pentafluorosulfanylbenzene compound represented by the following general formula (3):

(In the formula, A is a halogenomethyl group, and the hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)

(In the formula, R ¹ is the same as above, Z represents a linking group consisting of —OCH ₂ —, and n is 1. ) And pentafluorosulfanylbenzene compound represented by the following general formula (1), the general formula R ¹ COOH (wherein, R ¹ is carbon number of 20 or less phenyl group, biphenylyl group, phenyl group, bicyclohexyl-yl group A method for producing a pentafluorosulfanylbenzene compound represented by the following general formula (3), wherein one or more compounds selected from the group of compounds represented by formula (3) are reacted.

(In the formula, A is —NH ₂ , and the hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)

(Wherein R ¹ is the same as above, Z represents a linking group consisting of —CONH—, and n is 1. ) And pentafluorosulfanylbenzene compound represented by the following general formula (1), the general formula R ¹ CHO (wherein, R ¹ represents an alkyl group having a carbon number of 1 to 20, a cycloalkyl group having 3 to 25 carbon atoms, carbon (Represents an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 25 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms). A process for producing a pentafluorosulfanylbenzene compound represented by the following general formula (3):

(In the formula, A is —NH ₂ , and the hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)

(In the formula, R ¹ is the same as above, Z represents a linking group consisting of —CH═N—, and n is 1. ) A pentafluorosulfanylbenzene compound represented by the following general formula (5).

(In the formula, R ¹ is an alkyl group having a carbon number of 1 to 20, a cycloalkyl group having 3 to 25 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 25 carbon atoms, or 2 carbon atoms Represents 20 heteroaryl groups.) A pentafluorosulfanylbenzene compound represented by the following general formula (7) or (8).

(In the formula, R ¹ is an alkyl group having a carbon number of 1 to 20, a cycloalkyl group having 3 to 25 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 25 carbon atoms, or 2 carbon atoms Represents 20 heteroaryl groups.) A pentafluorosulfanylbenzene compound represented by the following formula (9) or (10).

A pentafluorosulfanylbenzene compound represented by any one of the following formulas (14) to (17).

(In the formula, R ⁴ represents an alkyl group having 2 to 12 carbon atoms.) A pentafluorosulfanylbenzene compound represented by the following formula (18).

(In the formula, R ⁴ represents an alkyl group having 2 to 12 carbon atoms.)

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