JP2007091613A - Sulfide compound and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfide compound that has a high refractive index and a high Abbe number, is excellent in heat resistance, weather resistance and transparency and is therefore suitable as a raw material for manufacturing optical products such as plastic lenses, prisms, optical fibers, substrates for information recording media, colored filters, infrared ray-absorbing filters or the like, and its manufacturing method. <P>SOLUTION: The sulfide compound is represented by general formula (1) (wherein R<SP>1</SP>is an alkane residue, thioalkane residue, cycloalkane residue, heterocyclic compound residue or aromatic compound residue; and n is 0 or 1). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel sulfide compound and a method for producing the same. More specifically, the present invention relates to a novel sulfide compound useful as a raw material for optical products having a high refractive index and high Abbe number and an efficient production method thereof.

  In recent years, plastics are used in various optical applications such as lenses because they are lighter than glass and are difficult to break and can be easily dyed. As an optical plastic material, poly (diethylene glycol bisallyl carbonate) (CR-39) or poly (methyl methacrylate) is generally used. However, since these plastics have a refractive index of 1.50 or less, when they are used, for example, as a lens material, the lens becomes thicker as the power increases, and the superiority of the plastic, which is advantageous in terms of light weight, is impaired. . In particular, a concave lens having an intensity number is not preferable because the periphery of the lens is thick and birefringence and chromatic aberration occur. In addition, thick lenses in eyeglass applications tend to degrade aesthetics. In order to obtain a thin lens, it is effective to increase the refractive index of the material. In general, in glass and plastic, the Abbe number decreases as the refractive index increases, and as a result, their chromatic aberration increases. Therefore, a plastic material having a high refractive index and Abbe number is desired.

As plastic materials having such performance, 1,6-bis (2,3-epithiopropyl) -1,2,5,6-tetrathiahexane, 1,5-bis (2,3-epithiopropyl) ) -1,2,4,5-tetrathiapentane, 1,7-divinyl-4- (1,2-dithia-3-butenyl) -1,2,6,7-tetrathiaheptane An optical product using the above has been proposed (see Patent Document 1).
The refractive index (n _D ) of 1,6-bis (2,3-epithiopropyl) -1,2,5,6-tetrathiahexane in Reference Example 1 of the same document is 1.666, Reference Example of the same document 1,5-bis (2,3-epithiopropyl) -1,2,4,5-tetrathiapentane has a refractive index (n _D ) of 1.681 and 1,7- Divinyl-4- (1,2-dithia-3-butenyl) -1,2,6,7-tetrathiaheptane has a refractive index (n _D ) of 1.646, and an optical product using these compounds Can produce an optical product with a high refractive index. However, on the other hand, it is desired to provide an optical product having a higher refractive index and a higher Abbe number.
JP 2002-131502 A

  The present invention has been made in order to solve the above-mentioned problems, and a novel sulfide compound capable of providing an optical product having a high refractive index and an Abbe number and excellent in heat resistance, weather resistance, and transparency, and its production It is intended to provide a method.

  As a result of intensive studies to achieve the above object, the present inventors have obtained an essential monomer component of a sulfide compound containing an epithioethyl group and having a structure in which the epithioethyl group is directly linked to a monosulfide (epithioethylthio structure). As a result, it was found that the polymer obtained by using the polymer as an optical product can provide an optical product having a high refractive index and an Abbe number and excellent in heat resistance, weather resistance and transparency, and completed the present invention.

（式中、Ｒ¹は、炭素数１〜７のアルカン残基、炭素数２〜４のチアアルカン残基、炭素数４〜７のシクロアルカン残基、ヘテロ原子が酸素、窒素もしくは硫黄原子である炭素数３〜７のヘテロ環式化合物残基又は炭素数６〜１０の芳香族化合物残基を示し、各残基は置換基を有していてもよく、ｎは０又は１を示す。）
さらに本発明は、上記一般式（１）で表されるスルフィド化合物の製造方法を提供する。 That is, the present invention provides a sulfide compound having one or more epithioethylthio structures represented by the following general formula (1).

(In the formula, R ¹ is an alkane residue having 1 to 7 carbon atoms, a thiaalkane residue having 2 to 4 carbon atoms, a cycloalkane residue having 4 to 7 carbon atoms, and the hetero atom is an oxygen, nitrogen or sulfur atom. A C3-C7 heterocyclic compound residue or a C6-C10 aromatic compound residue is shown, each residue may have a substituent, and n shows 0 or 1.)
Furthermore, this invention provides the manufacturing method of the sulfide compound represented by the said General formula (1).

  By using the sulfide compound of the present invention, an optical product having a high refractive index and Abbe number, and excellent heat resistance and transparency can be obtained. Moreover, the sulfide compound of the present invention can be produced efficiently by using thiol compounds and haloacetaldehyde as starting materials.

式中、Ｒ¹は、炭素数１〜７のアルカン残基、炭素数２〜４のチアアルカン残基、炭素数４〜７のシクロアルカン残基、ヘテロ原子が酸素、窒素もしくは硫黄原子である炭素数３〜７のヘテロ環式化合物残基又は炭素数６〜１０の芳香族化合物残基を示す。各残基は置換基を有していてもよい。ｎは０又は１を示す。 The sulfide compound of the present invention is represented by the following general formula (1).

In the formula, R ¹ is an alkane residue having 1 to 7 carbon atoms, a thiaalkane residue having 2 to 4 carbon atoms, a cycloalkane residue having 4 to 7 carbon atoms, or a carbon whose hetero atom is an oxygen, nitrogen or sulfur atom. A heterocyclic compound residue having 3 to 7 carbon atoms or an aromatic compound residue having 6 to 10 carbon atoms is shown. Each residue may have a substituent. n represents 0 or 1.

Examples of the alkane residue of R ¹ include linear or branched methane residues, ethane residues, propane residues, butane residues, pentane residues, hexane residues, heptane residues and the like. , A methane residue, an ethane residue and the like are preferable.
Examples of the R ¹ thiaalkane residue include 2-thiapropane residue, 2-thiabutane residue, 3-thiapentane residue and the like.
Examples of the cycloalkane residue of R ¹ include a cyclobutane residue, a cyclopentane residue, a cyclohexane residue, and the like, and a cyclopentane residue, a cyclohexane residue, and the like are preferable.
As the heterocyclic compound residue of R ¹ , those in which the hetero atom is a sulfur atom are particularly preferable. For example, 1,3-dithiolane residue, 1,3-dithiane residue, 1,4-dithiane residue 1,3-dithiolane residue, 1,4-dithiane residue and the like are preferable.
Examples of the aromatic compound residue of R ¹ include a benzene ring residue and a naphthalene ring residue, and a benzene ring residue and the like are preferable.
In addition, examples of the substituent for each of these residues include halogen atoms such as bromine, chlorine, and iodine, alkyl groups such as methyl, ethyl, n-propyl, and isopropyl groups, and aromatic groups such as phenyl and naphthyl groups. Groups and the like.

  The sulfide compound represented by the general formula (1) contains sulfur having a high atomic refraction in a high proportion, and greatly increases the refractive index of a polymer obtained using this sulfide compound. Moreover, since the episulfide group which is a polymerizable functional group contributes to the introduction of sulfur atoms into the polymer main chain, the refractive index of the polymer obtained using this sulfide compound is further increased. Usually, the Abbe number of an amorphous material tends to decrease as the refractive index increases. In the case of a polymer containing a high ratio of sulfur, the electron resonance of sulfur becomes remarkable and a large decrease in Abbe number is often observed, but this is not the case with the sulfide compound of the present invention. Another cause of the increase in the refractive index is a decrease in molecular volume. In the case of a polymer obtained from the sulfide compound of the present invention, it is expressed by a high crosslinking density and a strong intermolecular force. The sulfide compound of the general formula (1) has a plurality of polymerizable functional groups, and the refractive index of the polymer is increased particularly by the former effect.

Examples of the sulfide compound represented by the general formula (1) of the present invention include bisepithioethyl sulfide, bisepithioethylthiomethane, 1,1-bisepithioethylthioethane, and 1,2-bisepithioethyl. Thioethane, 1,1-bisepithioethylthiopropane, 1,2-bisepithioethylthiopropane, 1,3-bisepithioethylthiopropane, 2,2-bisepithioethylthiopropane, 1,2 -Bisepithioethylthiobutane, 1,3-bisepithioethylthiobutane, 1,4-bisepithioethylthiobutane, 1,2-bisepithioethylthioheptane, 1,3-bisepithioethylthio Heptane, 1,4-bisepithioethylthioheptane, 1,5-bisepithioethylthioheptane, 1,3-bis (epithioethylthio)- -Thiapropane, 1,4-bis (epithioethylthio) -2-thiabutane, 1,5-bis (epithioethylthio) -3-thiapentane, 1,2-bisepithioethylthiocyclopentane, 1,3 -Bisepithioethylthiocyclopentane, 1,1-bisepithioethylthiocyclohexane, 1,2-bisepithioethylthiocyclohexane, 1,3-bisepithioethylthiocyclohexane, 1,4-bisepithioethyl Thiocyclohexane, 1,2-bisepithioethylthiobenzene, 1,3-bisepithioethylthiobenzene, 1,4-bisepithioethylthiobenzene, 1,2-bis (epithioethylthiomethyl) benzene, 1,3-bis (epithioethylthiomethyl) benzene, 1,4-bis (epithioethylthiomethyl) benzene 4,5-bisepithioethylthio-1,3-dithiolane, 2,3-bisepithioethylthio-1,4-dithiane, 3,4-bisepithioethylthio-bicyclo [4.3.0 ] -2,5,7,9-tetrathianonane, 2,3-bisepithioethylthio-1,4-benzodithiane, 2,5-bisepithioethylthio-1,4-dithiane and the like. When R ¹ is an aliphatic cyclic group, the sulfide compound of the present invention includes cis- and trans-isomers with respect to the epithioethylthio group.
In addition to the above, the sulfide compound represented by the general formula (1) of the present invention includes a compound represented by the following formula.

（式中、Ｒ¹は前記と同様）で表されるスルフィド化合物は、下記の工程（ａ）〜（ｄ）により製造することが出来る。
（ａ）下記一般式（４）：
ＸＣＨ₂ＣＨＯ （４）
（式中、Ｘはハロゲン原子を示す）で表されるハロアセトアルデヒドと、下記一般式（５）：
Ｒ¹（ＳＨ）₂ （５）
（式中、Ｒ¹は前記と同様である）で表されるポリチオール化合物とを反応させ、得られた生成物をアシル化して下記一般式（６）：

（式中、Ｒ¹及びＸは前記と同様であり、Ｒ²は炭素数１〜６のアルキル基を示す）で表されるジアシルオキシ化合物を得る工程；
（ｂ）該ジアシルオキシ化合物を下記一般式（７）：

（式中、Ｒ¹及びＸは前記と同様であり、Ｒ³は炭素数１〜６のアルキル基を示す）で表されるジアシルチオ化合物にする工程；
（ｃ）該ジアシルチオ化合物を下記一般式（８）：

（式中、Ｒ¹及びＸは前記と同様）で表されるジチオール化合物にする工程；及び
（ｄ）該ジチオール化合物の１−メルカプト−２−ハロエチル基をエピスルフィド化する工程。 The sulfide compound of the present invention can be produced by the following production method characterized by using a thiol compound and haloacetaldehyde as raw material compounds.
The following general formula (2) in which n = 1 in the general formula (1):

(Wherein R ¹ is as defined above) can be produced by the following steps (a) to (d).
(A) The following general formula (4):
XCH ₂ CHO (4)
(Wherein X represents a halogen atom) and the following general formula (5):
R ¹ (SH) ₂ (5)
(Wherein R ¹ is the same as above) and the resulting product is acylated to give the following general formula (6):

(Wherein, R ¹ and X are as defined above, and R ² represents an alkyl group having 1 to 6 carbon atoms) to obtain a diacyloxy compound represented by:
(B) The diacyloxy compound is represented by the following general formula (7):

(Wherein, R ¹ and X are the same as defined above, and R ³ represents an alkyl group having 1 to 6 carbon atoms);
(C) The diacylthio compound is represented by the following general formula (8):

(Wherein R ¹ and X are as defined above); and (d) a step of episulfiding the 1-mercapto-2-haloethyl group of the dithiol compound.

Step (a)
Step (a) is a step of reacting the haloacetaldehyde (4) with the polythiol compound (5) and acylating the resulting product to obtain the diacyloxy compound represented by the general formula (6).
Specific examples of the haloacetaldehyde (4) include chloroacetaldehyde and bromoacetaldehyde, and chloroacetaldehyde is preferably used.
Specific examples of the polythiol compound (5) include dimercaptomethane, 1,1-dimercaptoethane, 1,2-dimercaptoethane, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3. -Dimercaptopropane, 2,2-dimercaptopropane, 1,1-dimercaptobutane, 1,2-dimercaptobutane, 1,3-dimercaptobutane, 1,4-dimercaptobutane, 2,2-dimer Mercaptobutane, 2,3-dimercaptobutane, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-dimercaptoxylene, 1,3-dimercaptoxylene 1,4-dimercaptoxylene, 2,5-dimercaptomethyl-1,4-dithiane, 4,5-dimercaptomethyl-1,3 Dithian, 2,5-dimercapto-1,4-dithian, 4,5-dimercapto-1,3-dithiane, 4,5-dimercaptomethyl-1,3-dithiolane, 4,5-dimercapto-1,3- Although dithiol compounds, such as dithiolane, are mentioned, it is not limited only to these exemplary compounds.

The haloacetaldehyde (4) and the polythiol compound (5) are -20 to 20 in a solvent such as dichloromethane, chloroform, toluene, hexane, 2-butanone and acetone in the presence of an alkali such as pyridine, aniline, quinoline, ammonia and triethylamine. React at 40 ° C. The polythiol compound (5) is preferably used in an amount of 0.8 to 1.3 mol per 1 mol of haloacetaldehyde (4). The obtained product is acylated using pyridine and carboxylic anhydride ((R ² CO) ₂ O; R ² is the same as above) at −20 to 50 ° C. to obtain the diacyloxy compound of the general formula (6). . In the acylation reaction, it is preferable to use 0.8 to 2.0 mol of pyridine and 0.8 to 2.0 mol of carboxylic anhydride with respect to 1 mol of haloacetaldehyde (4).

Step (b)
In the step (b), the acyloxy group (—OCOR ² ) of the diacyloxy compound (6) is converted into an acylthio group (—SCOR ³ ) with a thiocarboxylic acid (R ³ COSH; R ³ is the same as described above), In this step, a diacylthio compound of formula (7) is obtained. The reaction is preferably performed at −40 to 20 ° C. in the presence of a Lewis acid catalyst such as boron trifluoride / ethyl ether adduct. The thiocarboxylic acid is preferably used in an amount of 0.9 to 2.5 mol per mol of the acyloxy group (—OCOR ² ).

Step (c)
Step (c) is a step of obtaining the dithiol compound of the general formula (8) by converting the acylthio group (—SCOR ³ ) of the diacylthio compound (7) into a mercapto group. The reaction is carried out by adding an acid such as hydrogen chloride, hydrogen bromide or sulfuric acid to the diacylthio compound (7) and stirring at 0 to 100 ° C. The amount of the acid used is preferably 0.9 to 10 equivalents relative to 1 equivalent of the acylthio group (—SCOR ³ ).

Step (d)
Step (d) is a step of obtaining the sulfide compound (2) as the target compound by episulfiding the 1-mercapto-2-haloethyl group of the dithiol compound (8). In the reaction, dithiol compound (8) is dissolved in dichloromethane, chloroform, toluene, normal hexane, cyclohexane, acetone, in the presence of a basic compound such as sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate, ammonium carbonate. It is carried out by stirring at -40 to 40 ° C. in a solvent such as 2-butanone, acetonitrile, methanol, and ethanol. It is preferable that the usage-amount of a basic compound is 0.8-4.0 equivalent with respect to 1 equivalent of 1-mercapto-2-haloethyl groups.

で表されるスルフィド化合物は、下記の工程（ａ’）〜（ｄ’）により製造することが出来る。
（ａ’）前記一般式（４）のハロアセトアルデヒドと、下記一般式（９）：

（式中、Ｒ⁴は炭素数１〜６のアルキル基を示し、Ｘ²はハロゲン原子を示す）で表されるチオール化合物とを反応させ、得られた生成物をアシル化して下記一般式（１０）：

（式中、Ｒ⁴、Ｘ及びＸ²は前記と同様であり、Ｒ⁵は炭素数１〜６のアルキル基を示す）で表されるアルコキシアシルオキシ化合物を得る工程；
（ｂ’）該アルコキシアシルオキシ化合物を下記一般式（１１）：

（式中、Ｘ及びＸ²は前記と同様であり、Ｒ⁶は炭素数１〜６のアルキル基を示す）で表されるジアシルチオ化合物にする工程；
（ｃ’）該ジアシルチオ化合物を下記一般式（１２）：

（式中、Ｘ及びＸ²は前記と同様）で表されるジチオール化合物にする工程；及び
（ｄ’）該ジチオール化合物の１−メルカプト−２−ハロエチル基をエピスルフィド化する工程。 The following general formula (3) in which n = 0 in the general formula (1):

Can be produced by the following steps (a ′) to (d ′).
(A ′) the haloacetaldehyde of the general formula (4) and the following general formula (9):

(Wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom), and the resulting product is acylated to give the following general formula ( 10):

(Wherein R ⁴ , X and X ² are as defined above, and R ⁵ represents an alkyl group having 1 to 6 carbon atoms) to obtain an alkoxyacyloxy compound represented by:
(B ′) The alkoxyacyloxy compound is represented by the following general formula (11):

(Wherein, X and X ² are the same as defined above, and R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms);
(C ′) The diacylthio compound is represented by the following general formula (12):

(Wherein X and X ² are as defined above); and (d ′) a step of episulfiding the 1-mercapto-2-haloethyl group of the dithiol compound.

Step (a ′)
Step (a ′) is a step of reacting the haloacetaldehyde (4) with the thiol compound (9) and acylating the obtained product to obtain the alkoxyacyloxy compound represented by the general formula (10). Specific examples of the haloacetaldehyde (4) include chloroacetaldehyde and bromoacetaldehyde, and chloroacetaldehyde is preferably used. The haloacetaldehyde (4) and the thiol compound (9) are -20 to 20 in a solvent such as dichloromethane, chloroform, toluene, hexane, 2-butanone and acetone in the presence of an alkali such as pyridine, aniline, quinoline, ammonia and triethylamine. React at 40 ° C. The thiol compound (9) is preferably used in an amount of 0.8 to 1.3 mol with respect to 1 mol of the haloacetaldehyde (4). The obtained product is acylated using pyridine and carboxylic anhydride ((R ⁵ CO) ₂ O; R ⁵ is the same as above) at −20 to 50 ° C. to obtain the alkoxyacyloxy compound of the general formula (10). . In the acylation reaction, it is preferable to use 0.8 to 2.0 mol of pyridine and 0.8 to 2.0 mol of carboxylic anhydride with respect to 1 mol of haloacetaldehyde (4).

Step (b ′)
Step (b '), the alkoxy acyl acyloxy group (-OCOR ⁵⁾ alkoxy group (-OR ⁴⁾ a thiocarboxylic acid of the oxy-compound (10); acylthio group by (R ⁶ COSH same and R ⁶ above) (- This is a step of converting to SCOR ⁶ ) to obtain the diacylthio compound of the general formula (11). The reaction is preferably performed at −40 to 20 ° C. in the presence of a Lewis acid catalyst such as boron trifluoride / ethyl ether adduct. The thiocarboxylic acid is preferably used in an amount of 0.9 to 2.5 mol per mol of the total amount of acyloxy group (—OCOR ⁵ ) and alkoxy group (—OR ⁴ ).

Step (c ′)
Step (c ′) is a step of obtaining the dithiol compound of the general formula (12) by converting the acylthio group (—SCOR ⁶ ) of the diacylthio compound (11) into a mercapto group. The reaction can be carried out in the same manner as in the step (c).

Step (d ′)
Step (d ′) is a step of obtaining the sulfide compound (3) as the target compound by episulfiding the 1-mercapto-2-haloethyl group of the dithiol compound (12). The reaction can be carried out in the same manner as in the step (d).

  The sulfide compound represented by the general formula (1) of the present invention is useful as a raw material for optical products, and can be used as a polymer by using one or a combination of two or more types to obtain an optical product. This optical product preferably contains 10 to 100% by weight, more preferably 50 to 100% by weight, in total of at least one of the sulfide compounds of the present invention. Furthermore, (i) episulfide compounds, (ii) epoxy compounds, thiourethane raw materials, and (iii) polyisopropylene as optional components for appropriately improving the physical properties of polymers obtained using the sulfide compounds of the present invention as essential monomer components. A polymerizable composition may be prepared by appropriately blending (thio) cyanate and (iv) a mixture of polythiol, polythiol and (v) a homopolymerizable vinyl monomer. Thereby, refractive index, Abbe number, heat resistance, weather resistance, transparency, etc. can be further improved. Polyiso (thio) cyanate means both polyisocyanate and polyisothiocyanate.

(I) Episulfide compound Examples of the episulfide compound include bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio). ) Propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β- Epithiopropylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5- Bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) ) Hexane, 1- (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthio) Chain organic compounds such as ethyl) thio] ethane, 1- (β-epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethane, tetrakis (β- Epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) ) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio)- 2, -Bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis ( β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bi (Β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β- Epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3 , 6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11- Bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5 , 7-[(2-β-epithio Propylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6 Branched organic compounds such as 9-trithiaundecane, and compounds in which at least one of the hydrogen in the episulfide group of these compounds is substituted with a methyl group;
1,3- and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3- and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithio Propylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β -Cycloaliphatic organic compounds such as epithiopropylthiomethyl) -1,4-dithiane and 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane and episulfide groups of these compounds A compound in which at least one of the hydrogens is substituted with a methyl group;
1,3- and 1,4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropyl) Thio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epi Aromatic organic compounds such as thiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl, and compounds in which at least one of the hydrogens in the episulfide group of these compounds is substituted with a methyl group Etc. You may use these individually or in combination of 2 or more types.
The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the sulfide compound of the present invention which is an essential component.

(Ii) Epoxy compounds Examples of epoxy compounds include condensation of epihalohydrins with polyhydric phenol compounds such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, and novolac resin. Phenolic epoxy compounds produced by:
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, tri Methylolpropane trimethacrylate, pentaerythritol, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene Alcohol-based epoxy compounds produced by condensation of polyhydric alcohol compounds such as oxide adducts and epihalohydrins;
Adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, het acid, nadic Glycidyl ester system produced by condensation of polyhalogen carboxylic acid compounds such as acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid and epihalohydrin Epoxy compounds;
Ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane 1,7-diaminoheptane, 1,8-diaminooctane, bis (3-aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2 , 2'-dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisamino Ethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, isophoronediamine, 1 4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4 , 4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, primary diamines such as 2,2- (4,4′-diaminodiphenyl) propane, N, N′-dimethylethylenediamine, N, N′-dimethyl-1 , 2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1,6-diaminohexane, N, N′-dimethyl Til-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2-diaminopropane, N, N'-diethyl-1,3-diaminopropane, N, N'- Diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N′-diethyl-1,6-diaminohexane Piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di (4-piperidyl) methane, 1,2-di (4-piperidyl) ethane, 1,3 An amine-based epoxy compound produced by condensation of a secondary diamine such as di (4-piperidyl) propane or 1,4-di (4-piperidyl) butane with an epihalohydrin;
3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, bis Alicyclic epoxy compounds such as (3,4-epoxycyclohexyl) adipate;
An epoxy compound produced by epoxidation of an unsaturated compound such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide;
Examples thereof include urethane-based epoxy compounds produced from the above-mentioned polyhydric alcohols, phenol compounds, diisocyanates, glycidols, and the like. You may use these individually or in combination of 2 or more types.
The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the sulfide compound of the present invention which is an essential component.

(Iii) Polyiso (thio) cyanate Examples of polyiso (thio) cyanate include xylylene di (thio) cyanate, 3,3'-dichlorodiphenyl-4,4'-diiso (thio) cyanate, 4,4'- Diphenylmethane diiso (thio) cyanate, hexamethylene diiso (thio) cyanate, 2,2 ′, 5,5′-tetrachlorodiphenyl-4,4′-diiso (thio) cyanate, tolylene di (thio) cyanate, bis ( Iso (thio) cyanatemethyl) cyclohexane, bis (4-iso (thio) cyanatecyclohexyl) methane, bis (4-iso (thio) cyanatemethylcyclohexyl) methane, cyclohexanediiso (thio) cyanate, isophorone diiso (thiol) ) Cyanate, 2,5-bis (iso (thio) cyanate methyl) Cyclo [2.2.2] octane, 2,5-bis (iso (thio) cyanatemethyl) bicyclo [2.2.1] heptane, 2-iso (thio) cyanatemethyl-3- (3-iso (thio ) Cyanatepropyl) -5-iso (thio) cyanatemethyl-bicyclo [2.2.1] -heptane, 2-iso (thio) cyanatemethyl-3- (3-iso (thio) cyanatepropyl) -6-iso (Thio) cyanatemethyl-bicyclo [2.2.1] heptane, 2-iso (thio) cyanatemethyl-2- [3-iso (thio) cyanatepropyl] -5-iso (thio) cyanatemethyl-bicyclo [2] 2.1] Heptane, 2-iso (thio) cyanate methyl-2- (3-iso (thio) cyanatepropyl) -6-iso (thio) cyanate methyl-bicyclo [2 2.1] Heptane, 2-iso (thio) cyanatemethyl-3- (3-iso (thio) cyanatepropyl) -6- (2-iso (thio) cyanateethyl) -bicyclo [2.2.1] heptane 2-iso (thio) cyanatemethyl-3- (3-iso (thio) cyanatepropyl) -6- (2-iso (thio) cyanateethyl) -bicyclo [2.2.1] heptane, 2-iso ( Thio) cyanatemethyl-2- (3-iso (thio) cyanatepropyl) -5- (2-iso (thio) cyanateethyl) -bicyclo [2.2.1] heptane, 2-iso (thio) cyanatemethyl- 2- (3-iso (thio) cyanatepropyl) -6- (2-iso (thio) cyanateethyl) -bicyclo [2.2.1] heptane and the like. You may use these individually or in combination of 2 or more types.
The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the sulfide compound of the present invention which is an essential component.

  In addition, in the polyiso (thio) cyanate component, a compound component having a vinyl group may be copolymerized in order to appropriately improve the physical properties of the polymer. Specifically, divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane-modified (meth) acrylate containing at least two (meth) acryloxy groups in one molecule, epoxy-modified (Meth) acrylate, polyester-modified (meth) acrylate and the like may be mentioned, and these may be used alone or in combination of two or more. The (meth) acrylate means both acrylate and methacrylate, and the (meth) acryloxy group means both acryloxy group and methacryloxy group.

(iv) Polythiol Examples of polythiol include 1,2-ethanedithiol, 1,3-propanedithiol, tetrakismercaptomethylmethane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakismercaptoacetate, 2,3-dimercaptopropanol , Dimercaptomethane, trimercaptomethane, 1,2-benzenedithiol, 1,3-benzenedithiol, 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,4-benzenedithiol, 1,3, 5-benzenetrithiol, 1,2-dimercaptomethylbenzene, 1,3-dimercaptomethylbenzene, 1,4-dimercaptomethylbenzene, 1,3,5-trimercaptomethylbenzene, toluene-3,4- Dithiol, 1 2,3- tri mercapto propane, 1,2,3,4-mercaptobutanoic the like. You may use these individually or in combination of 2 or more types.
The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the sulfide compound of the present invention which is an essential component.

(v) Homopolymerizable vinyl monomer Examples of the homopolymerizable vinyl monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neo Pentyl glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2 , 2-bis [4- (acryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy / polyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetrameth Esters of monohydric or higher alcohols such as acrylate, hexaacrylate of bis (2,2,2-trimethylolethyl) ether, hexamethacrylate of bis (2,2,2-trimethylolethyl) ether, acrylic acid and methacrylic acid A compound having a structure;
Allyl compounds such as allyl sulfide, diallyl phthalate and diethylene glycol bisallyl carbonate; vinyl compounds such as acrolein, acrylonitrile and vinyl sulfide;
Aromatic vinyl compounds such as styrene, α-methyl styrene, methyl vinyl benzene, ethyl vinyl benzene, α-chloro styrene, chloro vinyl benzene, vinyl benzyl chloride, paradivinyl benzene, metadivinyl benzene, and the like. You may use these individually or in combination of 2 or more types.
The amount of these used is preferably 0.01 to 20 mol% with respect to the total amount of the sulfide compound of the present invention which is an essential component.

In order to improve the refractive index of an optical product obtained using the sulfide compound of the present invention as an essential component, an inorganic compound containing sulfur or a sulfur atom may be appropriately added. Examples of inorganic compounds containing a sulfur atom include hydrogen sulfide, carbon disulfide, carbon selenosulfide, ammonium sulfide, sulfur dioxide, sulfur trioxide and other sulfide oxides, thiocarbonate, sulfuric acid and its salts, hydrogen sulfate, sulfite. Persulfates, thiocyanates, thiosulfates, halides such as sulfur dichloride, thionyl chloride, thiophosgene, boron sulfide, nitrogen sulfide, silicon sulfide, phosphorus sulfide, selenium sulfide, metal sulfide, metal hydrosulfide, etc. Is mentioned. You may use these individually or in combination of 2 or more types.
The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the sulfide compound of the present invention which is an essential component.

In the polymerizable composition containing the sulfide compound of the present invention, an ultraviolet absorber, an antioxidant, an anti-coloring agent, a fluorescent dye are optionally added for improving the weather resistance as long as the object of the present invention is not impaired. Additives such as may be added as appropriate.
Further, a catalyst for improving the polymerization reactivity may be appropriately used. Examples of the catalyst that can be used include amines in the polymerization of a polymerizable composition containing an episulfide compound (i) and an epoxy compound (ii), Phosphins, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid, vinyl monomers (v In the polymerization of a polymerizable composition containing), a radical generator such as azobisbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, and the like, and a polymerizable composition containing polyiso (thio) cyanate (iii) and polythiol (iv) Dimethyltin dichloride, dilauryltin dichloride, amines and the like are effective in polymerizing the product.

An optical product obtained by using the sulfide compound of the present invention can be produced, for example, according to the following method.
First, a uniform composition containing at least one sulfide compound of the present invention and various additives used as necessary is prepared, and this composition is made of glass or metal using a known casting polymerization method. Is poured into a mold in which a mold and a resin gasket are combined, and cured by heating. At this time, in order to facilitate the removal of the resin after molding, the mold may be subjected to a mold release treatment in advance, or a mold release agent may be mixed with the composition. The polymerization temperature varies depending on the compound used, but is generally from -20 to + 150 ° C, and the polymerization time is from about 0.5 to 72 hours. The cast molded article released after polymerization can be easily dyed in water or an organic solvent using a normal disperse dye. At this time, in order to further facilitate dyeing, a carrier may be added to the dye dispersion, or it may be heated.
The use of the optical product thus obtained is not limited. Here, examples of the optical product include a plastic lens, an optical fiber, an information recording substrate, an infrared absorption filter, and a colored filter, and are particularly preferably used as a plastic lens.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. In addition, the physical property of the compound obtained in the Example and the physical property of the optical product which consists of the polymer obtained by the application example and the application comparative example were measured in accordance with the method shown below.
<Physical properties of sulfide compounds>
Refractive index (n _D ), Abbe number (ν _D ): Measured at 25 ° C. using a precision refractometer KPR-200 manufactured by Kalnew.
<Physical properties of polymer>
(A) Refractive index (n _D ), Abbe number (ν _D ): measured in the same manner as described above.
(B) Appearance: The transparency of the polymer obtained by the naked eye was observed.
(C) Heat resistance: TMA measurement was performed with a load of 98 mN (10 gf) using a pin with a diameter of 0.5 mm by a TMA apparatus manufactured by Rigaku Corporation, and the peak temperature of the chart obtained at a temperature increase of 10 ° C./min. evaluated.

Example 1
Synthesis of bisepithioethylthiomethane (1) Synthesis of bis (2-chloro-1-acetoxyethylthio) methane 40% chloroacetaldehyde aqueous solution 98 g (0.50 mol), dimercaptomethane 20 g (0.25 mol), dichloromethane 300 ml Was placed in a 1000 ml three-necked flask and cooled to -2 ° C. After adding 50 g of anhydrous magnesium sulfate in 4 portions, 0.5 g of pyridine was added. After stirring for 18 hours, the organic layer was filtered, and the solid was washed with dichloromethane (50 ml (3). To this filtrate were added 76.4 g (0.75 mol) of acetic anhydride and 59.2 g (0.75 mol) of pyridine. The mixture was stirred at 0 ° C. for 2 hours and then aged at 20 ° C. for 6 hours. (2) the. yellow oily substance concentration of the solution of bis (2-chloro-1-acetoxyethyl thio) methane 77 g (96.0%) was obtained. ¹ H-NMR for the specific structure of this compound The analysis results of (solvent: CDCl ₃ ) are shown below.
(: 6.10-6.20 (2H, m, -SCHOAc), 3.95-4.22 (2H, m, -SCH 2 S -), 3.75-3.90 (4H, m, - _{CH 2 Cl), 2.15 (6H} , s, -COCH 3)
(2) Synthesis of bis (2-chloro-1-thioacetoxyethylthio) methane 20 g (0.062 mol) of bis (2-chloro-1-acetoxyethylthio) methane and 11.4 g (0.15 mol) of thioacetic acid The flask was placed in a 100 ml three-necked flask and cooled to 0 ° C. Boron trifluoride ether solution 1.3 g (0.01 mol) was slowly added dropwise, and after completion of the addition, the reaction was allowed to proceed for 24 hours. After completion of the reaction, the reaction solution was added to 100 ml of cold water and extracted with dichloromethane (100 ml (2). The organic layer was washed with 20% aqueous potassium carbonate solution to remove acetic acid and thioacetic acid, then washed with water and neutralized. dried over anhydrous magnesium sulfate, orange oil of the concentrated bis (2-chloro-1-thio-acetoxyethyl thio) methane 21.2 g (96.4%) was obtained. ¹ for the particular structure of this compound The analysis results of 1 H-NMR (solvent: CDCl ₃ ) are shown below.
(: 5.00-5.10 (2H, m, -SCHSAc), 3.80-4.00 (6H, m, -SCH 2 S -, - CH 2 Cl), 2.40 (6H, s, -COCH ₃₎
(3) Synthesis of bis (2-chloro-1-mercaptoethylthio) methane 50 ml of a 2% hydrogen chloride methanol solution was added to 21.2 g (0.060 mol) of bis (2-chloro-1-thioacetoxyethylthio) methane. For 24 hours at room temperature. After completion of the reaction, 100 ml of cold water was added and the mixture was extracted with dichloromethane (50 ml (2). It was dried over anhydrous magnesium sulfate and concentrated to 14.7 g (90.7%) of bis (2-chloro-1-mercaptoethylthio) methane. The analysis result of ¹ H-NMR (solvent: CDCl ₃ ) for specifying the structure of this compound is shown below.
(: 4.35-4.45 (2H, m, -SCHSH), 4.12 and 4.14 (each _{1H, s, -SCH 2 S -} ), 3.90-4.00 (4H, m, -CH ₂ Cl), 2.42 and 2.46 (each 1H, d, J = 8.1Hz, -SH)
(4) Synthesis of bisepithioethylthiomethane 14.7 g of bis (2-chloro-1-mercaptoethylthio) methane, 100 ml of dichloromethane, and 30 g of sodium hydrogen carbonate were placed in a 200 ml three-necked flask. After stirring for 23 hours, inorganic substances were filtered and removed, and concentrated to obtain 9 g of a product. When the column was formed, 1.70 g (15.9%) of colorless bisepithioethylthiomethane was obtained. The analysis result of ¹ H-NMR (solvent: CDCl ₃ ) for specifying the structure of this compound is shown below.
(: Isomer 1: 4.21 (2H, dd, J = 6.2, 5.1 Hz, episulfide-CH), 4.06 (2H, s, -SCH ₂ S-), 2.88 (2H, dd , J = 6.2, 1.6 Hz, episulfide-CH ₂ ), 2.66 (2H, dd, J = 5.1, 1.6 Hz, episulfide-CH ₂ )
(: Isomer 2: 4.15 (2H, dd, J = 6.2, 5.1 Hz, episulfide-CH), 4.12 (1H, d, J = 13.5 Hz, -SCH ₂ S-), 4 .02 (1H, d, J = 13.5Hz, -SCH 2 S -), 2.83 (2H, dd, J = 6.2,1.6Hz, episulfide-CH 2), 2.61 (2H, dd, J = 5.1, 1.6 Hz, episulfide-CH ₂ )
This compound had a refractive index (n _D ) of 1.681 and an Abbe number (ν _D ) of 31.0.
The route of the above reaction is shown below.

Example 2
Synthesis of 4,5 -bisepithioethylthio-1,3-dithiolane (1) Synthesis of 4,5-bis (2-chloro-1-acetoxyethylthio) -1,3-dithiolane 40% chloroacetaldehyde aqueous solution 39 .2 g (0.20 mol), 4,5-dimercapto-1,3-dithiolane 17.0 g (0.10 mol) and dichloromethane 200 ml were placed in a 1000 ml three-necked flask and cooled to -2 ° C. After adding 30 g of anhydrous magnesium sulfate in 4 portions, 0.5 g of pyridine was added. After stirring for 18 hours, the organic layer was filtered, and the solid was washed with dichloromethane (50 ml (3). To this filtrate was added 30.6 g (0.30 mol) of acetic anhydride and 23.7 g (0.30 mol) of pyridine. The mixture was stirred for 2 hours at 0 ° C. and then aged for 6 hours at 20 ° C. After completion of the reaction, the solution was washed with water (100 ml (2), washed with 2% sulfuric acid aqueous solution (100 ml (2), then further washed with water (100 ml Concentrating the solution gave 40.2 g (97.8%) of a yellow oily substance, 4,5-bis (2-chloro-1-acetoxyethylthio) -1,3-dithiolane. The analysis results of ¹ H-NMR (solvent: CDCl ₃ ) for specifying the structure of the compound are shown below.
(: 6.05-6.30 (2H, m, -SCHOAc), 5.10-5.30 (2H, m, -SCHOAc), 4.04 (2H, s, -SCH 2 S -), 3 _{.75-3.85 (4H, m, -CH 2} Cl), 2.18 (6H, s, -COCH 3)
(2) Synthesis of 4,5-bis (2-chloro-1-thioacetoxyethylthio) -1,3-dithiolane 4,5-bis (2-chloro-1-acetoxyethylthio) -1,3-dithiolane 40.0 g (0.097 mol) and 17.8 g (0.233 mol) of thioacetic acid were placed in a 100 ml three-necked flask and cooled to 0 ° C. Boron trifluoride ether solution 1.3 g (0.01 mol) was slowly added dropwise, and after completion of the addition, the reaction was allowed to proceed for 24 hours. After completion of the reaction, the reaction solution was added to 100 ml of cold water and extracted with dichloromethane (100 ml (2). The organic layer was washed with 20% aqueous potassium carbonate solution to remove acetic acid and thioacetic acid, then washed with water and neutralized. Drying over anhydrous magnesium sulfate and concentration gave 40.5 g (94.0%) of an orange oily substance, 4,5-bis (2-chloro-1-thioacetoxyethylthio) -1,3-dithiolane. The analysis result of ¹ H-NMR (solvent: CDCl ₃ ) for specifying the structure of this compound is shown below.
(: 4.90-5.10 (4H, m, -SCHSAc, -SCHS -), 4.05-4.10 (2H, m, -SCH 2 S -), 3.70-3.90 (4H , M, —CH ₂ Cl), 2.41 (6H, s, —COCH ₃ )
(3) Synthesis of 4,5-bis (2-chloro-1-mercaptoethylthio) -1,3-dithiolane 4,5-bis (2-chloro-1-thioacetoxyethylthio) -1,3-dithiolane To 40.0 g (0.090 mol), 60 ml of a 2% hydrogen chloride methanol solution was added and reacted at room temperature for 24 hours. After completion of the reaction, 100 ml of cold water was added and extracted with dichloromethane (80 ml (2). It was dried over anhydrous magnesium sulfate and concentrated to 4,5-bis (2-chloro-1-mercaptoethylthio) -1,3-dithiolane. 29.0 g (89.7%) was obtained, and the results of ¹ H-NMR (solvent: CDCl ₃ ) analysis for specifying the structure of this compound are shown below.
(: 5.05-5.25 (2H, m, -SCHS-), 4.35-4.45 (2H, m, -SCHSH), 4.05-4.15 (2H, m, -SCH ₂ S -), 3.8-4.0 (4H, m, -CH 2 Cl), 2.50 and 2.60 (2H, m, -SH)
(4) Synthesis of 4,5-bisepithioethylthio-1,3-dithiolane 4,5-bis (2-chloro-1-mercaptoethylthio) -1,3-dithiolane 18.0 g (0.05 mol) And 100 ml of dichloromethane and 42.0 g (0.5 mol) of sodium hydrogen carbonate were placed in a 200 ml three-necked flask. After stirring for 23 hours, inorganic substances were filtered and removed, and concentrated to obtain 12.1 g of a product. When the column was formed, 1.3 g (9.1%) of colorless 4,5-bisepithioethylthio-1,3-dithiolane was obtained. The analysis result of ¹ H-NMR (solvent: CDCl ₃ ) for specifying the structure of this compound is shown below.
(: 5.00-5.20 (2H, m, -SCHS-), 4.10-4.35 (2H, m, episulfide-CH), 4.05-4.12 (2H, m, -SCH) ₂ S-), 2.70-2.90 (2H, m, episulfide-CH ₂ ), 2.40-2.60 (2H, m, episulfide-CH ₂ )
This compound had a refractive index (n _D ) of 1.713 and an Abbe number (ν _D ) of 31.0.

Example 3
Synthesis of bisepithioethyl sulfide (1) Synthesis of 1-acetoxy-1- (2-chloro-1-methoxyethylthio) -2-chloroethane 6.20 g of 1-mercapto-1-methoxy-2-chloroethane (0. 049 mol), 9.61 g (0.049 mol) of 40% chloroacetaldehyde and 100 ml of dichloromethane were put into a 1000 ml flask and cooled to 0 ° C. 20 g of anhydrous magnesium sulfate and then 0.3 g of pyridine were added and stirred for 20 hours. The organic layer was filtered and the solid was washed with 100 ml dichloromethane. To the filtrate, 7.5 g (0.073 mol) of acetic anhydride and 5.8 g (0.073 mol) of pyridine were added dropwise, stirred at 0 ° C. for 2 hours, and further stirred at 20 ° C. for 8 hours. After completion of the reaction, the solution was washed with water (100 ml (2), neutralized with 2% aqueous sulfuric acid (100 ml (2) and further washed with water (100 ml (2). The organic layer was concentrated to 11.0 g of a yellow oily product). The results of ¹ H-NMR (solvent: CDCl ₃ ) analysis for specifying the structure of this compound are shown below.
(: (2 isomers): 6.05-6.2 (1H, m, -SCHOAc), 4.76 and 4.89 (1H, dd, -SCHOCH _3- ), 3.75-3.9 (4H _{, m, -CH 2 Cl),} 3.47 and 3.49 (3H, s, OCH 3), 2.14 (3H, s, -COCH 3)
(2) Synthesis of bis (2-chloro-1-thioacetoxyethyl) sulfide 10.9 g (0.044 mol) of 1-acetoxy-1- (2-chloro-1-methoxyethylthio) -2-chloroethane and acetic anhydride 4.50 g (0.044 mol) and 6.70 g (0.088 mol) thioacetic acid were placed in a 250 ml flask and cooled to 0 ° C. Boron trifluorolide ether solution 1.0 g (0.007 mol) was slowly added dropwise. It stirred for 18 hours after completion | finish of dripping. After completion of the reaction, 100 ml of cold water was added and extracted with dichloromethane (100 ml (2). The organic layer was washed with 20% aqueous potassium carbonate solution to remove acetic acid and thioacetic acid, washed with water and neutralized. 10 g of anhydrous magnesium sulfate Was added to remove water and concentrated to obtain 11.2 g (82.6%) of the product, which was analyzed by ¹ H-NMR (solvent: CDCl ₃ ) for the identification of the structure of this compound. Show.
(: (2 isomers): 5.00 and 4.91 (2H, t, J = 5.4Hz, -SCHSAc), 3.85-3.90 (4H, m, -CH 2 Cl), 2.40 (6H, -COCH ₃₎
(3) Synthesis of bis (2-chloro-1-mercaptoethyl) sulfide 11.0 g of bis (2-chloro-1-thioacetoxyethyl) sulfide and 40 ml of a 2% hydrogen chloride / methanol solution were added and the mixture was stirred at 5 ° C. for 48 hours. Stir. 100 ml of cold water was added, extracted with dichloromethane (100 ml (2) and dried over anhydrous magnesium sulfate. The solution was concentrated to give 6.3 g (78.8%) of product. The analysis result of ¹ H-NMR (solvent: CDCl ₃ ) is shown below.
(: 4.4-4.5 (2H, m, -SCHSH), 3.75-3.9 (4H, m, -CH 2 Cl), 2.49 and 2.56 (2H, d, J = 8.0Hz, -SH)
(4) Synthesis of bisepithioethyl sulfide 6.3 g (0.028 mol) of bis (2-chloro-1-mercaptoethyl) sulfide, 300 ml of dichloromethane, and 30 g of sodium hydrogen carbonate were added to a 500 ml flask. After stirring at room temperature for 10 hours, the inorganics were filtered and concentrated to give 1.70 g (40%) of product. A diastereoisomer was obtained from the NMR peak. The analysis result of ¹ H-NMR (solvent: CDCl ₃ ) for specifying the structure of this compound is shown below.
(: Isomer 1: 4.13 (2H, dd, J = 6.0, 5.3 Hz, episulfide-CH), 2.84 (2H, dd, J = 6.0, 1.6 Hz, episulfide-CH ₂ ), 2.62 (2H, dd, J = 5.3, 1.6 Hz, episulfide-CH ₂ )
(: Isomer 2: 4.10 (2H, dd, J = 6.0, 5.3 Hz, episulfide-CH), 2.81 (2H, dd, J = 6.0 1.6 Hz, episulfide-CH ₂ ) , 2.56 (2H, dd, J = 5.3, 1.6 Hz, episulfide-CH ₂ )
This compound had a refractive index (n _D ) of 1.663 and an Abbe number (ν _D ) of 32.2.
The route of the above reaction is shown below.

Application example 1
Production of optical product made of polymer A mixture of 0.05 mol of bisepithioethylthiomethane obtained in Example 1 and 5 × 10 ⁻⁵ mol of dicyclohexylmethylamine as a polymerization catalyst was uniformly stirred. The polymer was poured into a lens-molding glass mold and heated and polymerized at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 100 ° C. for 3 hours to obtain a lens-shaped polymer. Table 1 shows various physical properties of the obtained polymer. As can be seen from Table 1, the obtained polymer is transparent, has a refractive index (n _D ) of 1.76, an Abbe number (ν _D ) of 32, a high refractive index, low dispersion, and heat resistance. (95 ° C.). Therefore, the obtained polymer was suitable as an optical product.

Application example 2
Production of optical product comprising polymer Mixture of 0.05 mol of 4,5-bisepithioethylthio-1,3-dithiolane obtained in Example 2 and 5 × 10 ⁻⁵ mol of dicyclohexylmethylamine as a polymerization catalyst Were uniformly stirred and poured into two lens-molding glass molds, followed by heat polymerization at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 100 ° C. for 3 hours to obtain a lens-shaped polymer. Table 1 shows various physical properties of the obtained polymer. As can be seen from Table 1, the obtained polymer is transparent, has a refractive index (n _D ) of 1.77, an Abbe number (ν _D ) of 31, a high refractive index, low dispersion, and heat resistance. (110 ° C.). Therefore, the obtained polymer was suitable as an optical product.

Application example 3
Production of optical product made of polymer A mixture of 0.05 mol of bisepithioethyl sulfide obtained in Example 3 and 5 × 10 ⁻⁵ mol of dicyclohexylmethylamine as a polymerization catalyst was uniformly stirred to obtain two lenses. The polymer was poured into a molding glass mold and polymerized by heating at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 100 ° C. for 3 hours to obtain a lens-shaped polymer. Table 1 shows various physical properties of the obtained polymer. As can be seen from Table 1, the obtained polymer is transparent, has a refractive index (n _D ) of 1.75, an Abbe number (ν _D ) of 33, a high refractive index, low dispersion, and heat resistance. (100 ° C.). Therefore, the obtained polymer was suitable as an optical product.

Application comparison example 1
Production of optical product comprising polymer As shown in Table 1, 0.1 mol of pentaerythritol tetrakismercaptopropionate (RM1), 0.2 mol of m-xylylene diisocyanate (RM2) and 1.0 × 10 10 of dibutyltin dichloride ^-4 moles of the mixture is stirred uniformly, poured into two lens molding glass molds, and heated and polymerized at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 120 ° C. for 3 hours. Coalescence was obtained. Table 1 shows various physical properties of the obtained polymer. As can be seen from Table 1, the obtained polymer was colorless and transparent, and no optical distortion was observed, but n _D / ν _D was 1.59 / 36, the refractive index was low, and the heat resistance was inferior at 86 ° C. It was.

Application Comparative Example 2 and Application Comparative Example 3
Manufacture of optical product made of polymer Except that the raw material composition shown in Table 1 was used, the same operation as in Application Comparative Example 1 was performed to obtain a lens-shaped polymer. Table 1 shows the physical properties of these polymers. As can be seen from Table 1, the polymer of this application comparative example 2 has a low n _D / ν _D of 1.67 / 28 and has a relatively good heat resistance (94 ° C.), but it is colored. And optical distortion was observed. In addition, the polymer of this comparative application example 3 had a relatively high ν _D of 36, was colorless and transparent, and no optical distortion was observed, but the n _D was not so high as 1.70, and the polymer was fragile. Met.

The abbreviations shown in Table 1 represent the following.
E1: Bisepithioethylthiomethane E2: 4,5-bisepithioethylthio-1,3-dithiolane E3: Bisepithioethyl sulfide RM1: Pentaerythritol tetrakismercaptopropionate RM2: m-xylylene diisocyanate RM3: 1,3,5-trimercaptobenzene RM4: 2,3-epithiopropyl sulfide CT1: dicyclohexylmethylamine CT2: dibutyltin dichloride CT3: tetra (n-butyl) phosphonium bromide

Since the sulfide compound of the present invention has a high sulfur content and a specific structure as represented by the general formula (1), it has a high refractive index and Abbe number, and is an optical product excellent in heat resistance and transparency. Suitable as a raw material. For example, it is suitable as a raw material for optical products such as information recording medium substrates, colored filters, infrared absorption filters, and the like used for lenses such as eyeglass lenses and camera lenses, prisms, optical fibers, optical disks, and magnetic disks.
Moreover, the manufacturing method of this invention can manufacture efficiently the sulfide compound represented by General formula (1) by using a thiol compound and a haloacetaldehyde as a starting material.

Claims (7)

The following general formula (1):

(In the formula, R ¹ is an alkane residue having 1 to 7 carbon atoms, a thiaalkane residue having 2 to 4 carbon atoms, a cycloalkane residue having 4 to 7 carbon atoms, and the hetero atom is an oxygen, nitrogen or sulfur atom. A heterocyclic compound residue having 3 to 7 carbon atoms or an aromatic compound residue having 6 to 10 carbon atoms, each residue may have a substituent, and n represents 0 or 1) The sulfide compound represented. The following general formula (2):

The sulfide compound according to claim 1, wherein R ¹ is as defined above. The following general formula (3):

The sulfide compound of Claim 1 represented by these. (A) The following general formula (4):
XCH ₂ CHO (4)
(Wherein X represents a halogen atom) and the following general formula (5):
R ¹ (SH) ₂ (5)
(Wherein R ¹ is the same as above) and the resulting product is acylated to give the following general formula (6):

(Wherein, R ¹ and X are as defined above, and R ² represents an alkyl group having 1 to 6 carbon atoms) to obtain a diacyloxy compound represented by:
(B) The diacyloxy compound is represented by the following general formula (7):

(Wherein, R ¹ and X are the same as defined above, and R ³ represents an alkyl group having 1 to 6 carbon atoms);
(C) The diacylthio compound is represented by the following general formula (8):

(Wherein R ¹ and X are as defined above); and (d) a step of episulfiding the 1-mercapto-2-haloethyl group of the dithiol compound. A method for producing the sulfide compound as described. (A) The following general formula (4):
XCH ₂ CHO (4)
(Wherein X represents a halogen atom) and the following general formula (9):

(Wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom), and the resulting product is acylated to give the following general formula ( 10):

(Wherein R ⁴ , X and X ² are as defined above, and R ⁵ represents an alkyl group having 1 to 6 carbon atoms) to obtain an alkoxyacyloxy compound represented by:
(B) The alkoxyacyloxy compound is represented by the following general formula (11):

(Wherein, X and X ² are the same as defined above, and R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms);
(C) The diacylthio compound is represented by the following general formula (12):

(Wherein X and X ² are as defined above); and (d) episulfiding the 1-mercapto-2-haloethyl group of the dithiol compound. A method for producing the sulfide compound as described.   The method for producing a sulfide compound according to claim 4 or 5, wherein the haloacetaldehyde is chloroacetaldehyde.   An optical product containing a polymer obtained by polymerizing at least one sulfide compound according to claim 1.