JP2005035968A - Alicyclic dithiol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alicyclic dithiol having a high refractive index, Abbe number and transparency, and excellent heat resistance.
[MEANS FOR SOLVING PROBLEMS] It has a norbornane skeleton and has the following general formula (I)
HS-G ¹ -SH (I)
(In the formula, G ¹ represents an alicyclic hydrocarbon group having 3 or more ring structures, and the ring structure may contain an atom selected from a sulfur atom and an oxygen atom.)
It is an alicyclic dithiol represented by these.
[Selection figure] None

Description

  The present invention relates to an alicyclic dithiol, and in particular, has a high refractive index, Abbe number and transparency, and is excellent in heat resistance, etc., a monomer for plastic lenses, a raw material for polyurethane resins, a raw material for polycarbonate resins, an epoxy The present invention relates to an alicyclic dithiol suitable as a raw material for a curing agent, a coating curing agent, a vulcanizing agent for a synthetic resin, an intermediate of a methacrylate resin monomer, and the like.

Conventionally, 2,5-bis (mercaptomethyl) -1,4-dithiane is known as a dithiol having a cyclic structure (see, for example, Patent Document 1 and Non-Patent Document 1). This dithiol is a monomer for urethane resin, which is a thermoplastic resin having excellent optical properties, and is used as a monomer for spectacle lenses. However, although the above dithiol has a high refractive index, it has a low Abbe number of 35.2 and is not necessarily sufficient in terms of heat resistance and the like.
Moreover, although the polythiol compound excellent in the refractive index is also disclosed (for example, refer patent document 2), it cannot necessarily be said that Abbe number is enough. Furthermore, although 1,3-bis (mercaptomethyl) adamantane has also been reported (for example, see Non-Patent Document 2), the synthesis method is complicated, and optical properties such as refractive index have not been reported.

JP-A-3-236386 JP 2001-31675 A Journal of Applied Polymer Science, Vol.68, p1791-1799 (1998) Chem. Ber. 127, p2081 (1994)

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an alicyclic dithiol having a high refractive index, an Abbe number and transparency, and excellent heat resistance.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object is achieved by a specific alicyclic dithiol having three or more ring structures. The present invention has been completed based on such findings.
That is, the present invention has a norbornane skeleton and has the following general formula (I)
HS-G ¹ -SH (I)
(In the formula, G ¹ represents an alicyclic hydrocarbon group having 3 or more ring structures, and the ring structure may contain an atom selected from a sulfur atom and an oxygen atom.)
The alicyclic dithiol represented by these is provided.

  According to the present invention, the refractive index, Abbe number and transparency are high, and excellent in heat resistance, etc., monomers for plastic lenses, raw materials for polyurethane resins, raw materials for polycarbonate resins, epoxy curing agents, paint curing agents, An alicyclic dithiol suitable as a raw material for a synthetic resin vulcanizing agent, an intermediate of a methacrylate resin monomer, and the like can be obtained.

The alicyclic dithiol of the present invention has the following general formula (I)
HS-G ¹ -SH (I)
G ¹ is an alicyclic hydrocarbon group which has three or more ring structures, and may contain an atom selected from a sulfur atom and an oxygen atom in the ring structure. The alicyclic dithiol of the present invention has a norbornane skeleton, preferably a tricyclodecane skeleton. Examples of G ¹ include alicyclic hydrocarbon groups represented by the following general formulas (II) to (VIII).

（式中、Ａは単結合、酸素原子、硫黄原子、ＳＯ又はＳＯ₂ を示し、ｎは０、１又は２である。）

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO ₂ , and n is 0, 1 or 2.)

（式中、Ａは上記と同様である。Ｒは、各々独立して、水素原子、シアノ基、炭素数１〜６のアルコキシカルボニル基、炭素数１〜６のアルコキシ基、炭素数１〜６のアルキルチオ基又は炭素数１〜６のアルキル基を示し、該Ｒがアルキル基である場合、隣接するＲは互いに結合していてもよい。Ｇ² は酸素原子、硫黄原子、ＳＯ、ＳＯ₂ 、−ＯＣＨ₂ Ｏ−、−ＯＣＨ₂ ＣＨ₂ Ｏ−、−ＯＣＨ₂ ＣＨ₂ ＣＨ₂ Ｏ−、−ＯＣＨ₂ ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｏ−、−ＯＣＨ₂ ＣＨ₂ ＳＣＨ₂ ＣＨ₂ Ｏ−、−ＳＣＨ₂ Ｓ−、−ＳＣＨ₂ ＣＨ₂ Ｓ−、−ＳＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓ−を示す。i 、ｊ、ｋ及びｌは、０、１又は２であり、Ｒが互いに結合していない場合は、ｉ＋ｊ≧１である。ｎは０、１又は２である。）

(In the formula, A is the same as above. R is independently a hydrogen atom, a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms, and when R is an alkyl group, adjacent Rs may be bonded to each other, G ² may be an oxygen atom, a sulfur atom, SO, SO ₂ , _{-OCH 2 O -, - OCH 2} CH 2 O -, - OCH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 SCH 2 CH 2 O -, - SCH _{2 S -, - SCH 2 CH} 2 S -, - SCH 2 CH 2 CH 2 S- shown .i, j, k and l is 0, 1 or 2, when R is not bound to each other I + j ≧ 1, n is 0, 1 or 2.)

（式中、Ａは上記と同様である。ｎは０、１又は２、ｎ’は０〜５の整数であり、ｎ＋ｎ’＜６である。）

(In the formula, A is the same as above. N is 0, 1 or 2, n ′ is an integer of 0 to 5, and n + n ′ <6).

（式中、Ａ、Ｒ及びＧ² は上記と同様である。ｉ、ｊ、ｋ及びｌは、０、１又は２であり、Ｒが互いに結合していない場合は、ｉ＋ｊ≧１である。ｐ及びｐ’は０〜４の整数である。）

(In the formula, A, R and G ² are the same as described above. I, j, k and l are 0, 1 or 2, and when R is not bonded to each other, i + j ≧ 1). p and p ′ are integers of 0 to 4.)

（式中、Ａ及びＲは上記と同様である。Ｇ³ は、１個以上の環構造を有し、該環構造中に１〜６個の酸素原子、１〜６個の硫黄原子及び１〜４個のカルボニル基から選ばれる基を含んでいてもよい、炭素数３〜２４の構造を示す。ｉ、ｊ、ｋ及びｌは、０、１又は２であり、Ｒが互いに結合していない場合は、ｉ＋ｊ≧１である。ｐ及びｐ’は０〜４の整数である。）

(In the formula, A and R are the same as described above. G ³ has one or more ring structures, and 1 to 6 oxygen atoms, 1 to 6 sulfur atoms, and 1 Represents a structure having 3 to 24 carbon atoms, which may contain a group selected from ˜4 carbonyl groups, i, j, k and l are 0, 1 or 2, and R is bonded to each other; Otherwise, i + j ≧ 1 and p and p ′ are integers from 0 to 4.)

（式中、Ａは上記と同様であり、ｐ及びｐ’は０〜４の整数である。）

(In the formula, A is the same as described above, and p and p ′ are integers of 0 to 4.)

（式中、Ａは上記と同様である。ｉ及びｊは、０、１又は２であり、ｐ及びｐ’は０〜４の整数である。）

(In the formula, A is the same as described above. I and j are 0, 1 or 2, and p and p ′ are integers of 0 to 4.)

In the general formulas (III), (V), and (VI), examples of the alkoxycarbonyl group having 1 to 6 carbon atoms of R include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. Examples of the alkylthio group having 1 to 6 carbon atoms include a methylthio group, an ethylthio group, and a propylthio group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group.
In the general formula (VI), G ³ has one or more ring structures, and 1 to 6 oxygen atoms, 1 to 6 sulfur atoms, and 1 to 4 carbonyl groups in the ring structure Examples of the structure having 3 to 24 carbon atoms, which may contain a group selected from the following, include ring structures represented by the following formulae.

  Examples of the alicyclic dithiol represented by the general formula (I) include the following compounds.

  The alicyclic dithiol represented by the general formula (I) is, for example, the following scheme (A):

（式中、Ｇ¹ は上記と同様である。）

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

As shown in the above, it can be synthesized by reacting a halide (IX) with a mercapto agent. As a typical synthesis method according to the above-mentioned scheme (A), for example, the following methods (1) to (5) may be mentioned.
(1) A method of synthesizing an alicyclic dithiol (I) by reacting a halide (IX) with thiourea to synthesize an isothiuronium salt and hydrolyzing the isothiuronium salt.
The reaction between the halide (IX) and thiourea is usually carried out in a polar solvent. Examples of the polar solvent used here include water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol) and aprotic polar solvents (for example, dimethyl sulfoxide, N, N-dimethylformamide). Is water, alcohols, and a mixed solvent of both. The ratio of the solvent and halide (IX) used is not particularly limited, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, of halide (IX) per liter of the solvent. The use ratio of the halide (IX) and thiourea is preferably 1.0 to 10.0 mol of thiourea, more preferably 1.8 to 3.0 mol, relative to 1 mol of the halide (IX). .
The reaction temperature is not particularly limited, but a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable, and the reaction is usually performed under heating and reflux. This reaction is usually completed in 0.5 to 24 hours, and an isothiuronium salt is precipitated by the reaction between the halide (IX) and thiourea. Subsequent operations include a method of filtering the isothiuronium salt and a method of not filtering, but the latter method is preferable from the viewpoint of simplicity of operation and yield.

In order to hydrolyze the obtained isothiuronium salt to obtain alicyclic dithiol (I), a base is usually used. Preferred bases include alkali metal or alkaline earth metal hydroxides (eg, sodium hydroxide, calcium hydroxide), alkali metal or alkaline earth metal carbonates (eg, sodium carbonate) and amines (eg, aqueous ammonia, triethylamine). Among them, alkali metal or alkaline earth metal hydroxides are particularly preferable. 1.0-4.0 mol is preferable with respect to 1 mol of halides (IX), and, as for the usage-amount of a base, More preferably, it is 1.6-2.2 mol.
As a solvent for this reaction, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol), a mixed solvent of both, and an aprotic polar solvent (for example, dimethyl sulfoxide, N, N-dimethylformamide) are preferable, and particularly preferable. These are water, alcohols, and mixed solvents thereof. The use ratio of the solvent and the isothiuronium salt is not particularly limited, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, per liter of the solvent. Although the reaction temperature of this reaction is not particularly limited, it is usually carried out at the reflux temperature of the solvent. This reaction is usually completed in 0.5 to 24 hours, and alicyclic dithiol (I) is obtained by acidification with a mineral acid (for example, hydrochloric acid, sulfuric acid, nitric acid).

(2) A method for synthesizing an alicyclic dithiol (I) by reacting a halide (IX) with an alkali metal hydrosulfide.
As the alkali metal hydrosulfide used here, sodium hydrosulfide and potassium hydrosulfide are preferable. The use ratio of the halide (IX) to the alkali metal hydrosulfide is preferably 2.0 to 20.0 mol of the alkali metal hydrosulfide with respect to 1 mol of the halide (IX), more preferably 3 0.0-10.0 mol.
As the solvent used in this reaction, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol), a mixed solvent of both, and an aprotic polar solvent (for example, dimethyl sulfoxide, N, N-dimethylformamide) are preferable. Of these, water, alcohols, and a mixed solvent of both are particularly preferable. The use ratio of the solvent and the halide (IX) is not particularly limited, but is preferably 0.01 to 10 mol, and particularly preferably 0.1 to 5 mol, per liter of the solvent.
In this reaction, in order to suppress the formation of sulfide, it is preferable that the alkali metal hydrosulfide salt solution is saturated with hydrogen sulfide. Although the reaction temperature is not particularly limited, a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable, and the reaction is usually carried out under reflux with heating. This reaction is usually completed in 0.1 to 24 hours, and alicyclic dithiol (I) is obtained by acidifying with a mineral acid (for example, hydrochloric acid, sulfuric acid, nitric acid).

(3) By reacting halide (IX) with an alkali metal O-alkyldithiocarbonate to synthesize an O-alkyldithiocarbonate, and hydrolyzing the O-alkyldithiocarbonate with an alkali metal salt. This is a method for synthesizing alicyclic dithiol (I).
Examples of suitable alkyl groups in the alkali metal O-alkyldithiocarbonate include linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, with linear alkyl being particularly preferred. Group (for example, methyl group, ethyl group, propyl group). Moreover, sodium and potassium are mentioned as an example of the suitable alkali metal in O-alkyl dithio alkali-metal carbonate. The reaction between the halide (IX) and the alkali metal O-alkyldithiocarbonate is usually carried out in an organic solvent. Examples of the organic solvent used here include ketones (eg, acetone, methyl ethyl ketone), ethers (eg, diethyl ether, monoglyme), alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol), and aprotic polar solvents (eg, dimethyl). Sulfoxide, N, N-dimethylphonemamide) and the like. Among these, ketones and alcohols are preferable.
The use ratio of the solvent and the halide (IX) is not particularly limited, but is preferably 0.01 to 10 mol, and particularly preferably 0.1 to 5 mol, per liter of the solvent. The ratio of the halide (IX) to the alkali metal O-alkyldithiocarbonate used is 1.0 to 10.0 moles of the alkali metal O-alkyldithiocarbonate with respect to 1 mole of the halide (IX). Preferably, it is 1.8-3.0 mol.
The reaction temperature is not particularly limited, but a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable, and the reaction is usually performed under heating and reflux. This reaction is usually completed in 0.5 to 24 hours. In this way, an O-alkyldithiocarbonate is produced by reacting the halide (IX) with an alkali metal O-alkyldithiocarbonate.

To hydrolyze the O-alkyldithiocarbonate to obtain alicyclic dithiol (I), an acid or a base is used. Commonly used acids include mineral acids (eg hydrochloric acid, sulfuric acid, nitric acid). The amount of the acid used is preferably 0.01 to 2.0 mol, more preferably 0.1 to 0.5 mol, relative to 1 mol of the halide (IX). Further, bases that are usually used include alkali metal or alkaline earth metal hydroxides (for example, sodium hydroxide, calcium hydroxide), alkali metal or alkaline earth metal carbonates (for example, potassium carbonate), amines (for example, ammonia). Water, triethylamine, aniline). 1.0-4.0 mol is preferable with respect to 1 mol of halides (IX), and, as for the usage-amount of a base, More preferably, it is 1.6-2.2 mol.
As a solvent for this reaction, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol), a mixed solvent of both, and an aprotic polar solvent (for example, dimethyl sulfoxide, N, N-dimethylformamide) are preferable, and particularly preferable. Is water, alcohols and a mixed solvent of both. Although the usage-amount of a solvent and O-alkyl dithio carbonate is not specifically limited, 0.01-10 mol of O-alkyl dithio carbonate per liter of solvent is preferable, More preferably, it is 0.1-5 mol.
The temperature at which the O-alkyldithiocarbonate is hydrolyzed is not particularly limited, but a temperature in the range from 0 ° C. to the reflux temperature of the solvent is preferred, and a temperature in the range from 50 ° C. to the reflux temperature of the solvent is more preferred. is there. This reaction is usually completed in 0.1 to 24 hours. When an acid is used for hydrolysis of an O-alkyldithiocarbonate, the reaction is carried out as it is, and when a base is used, it is acidified with an acid. Cyclic dithiol (I) is obtained.

(4) A method of synthesizing an alicyclic dithiol (I) by reacting a halide (IX) with sodium thiosulfate to synthesize a Bunte salt and hydrolyzing the Bunte salt with an acid. .
The reaction between the halide (IX) and sodium thiosulfate is usually carried out in a polar solvent. Examples of the polar solvent used here include water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol) and aprotic polar solvents (for example, dimethyl sulfoxide, N, N-dimethylphonemamide). Water, alcohols, and a mixed solvent of both are preferable, and a mixed solvent of water and alcohols is particularly preferable. The use ratio of the solvent and the halide (IX) is not particularly limited, but is preferably 0.01 to 10 mol, and particularly preferably 0.1 to 5 mol, per liter of the solvent. The use ratio of the halide (IX) and sodium thiosulfate is preferably 1.0 to 10.0 mol of sodium thiosulfate and more preferably 1.8 to 3 with respect to 1 mol of the halide (IX). 0.0 mole.
The reaction temperature is not particularly limited, but a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable, and the reaction is usually carried out under reflux with heating. This reaction is usually completed in 0.5 to 24 hours. By reacting the halide (IX) with sodium thiosulfate in this way, a Bunte salt is formed.

In order to decompose the Bunte salt to obtain the alicyclic dithiol (I), an acid such as a mineral acid (for example, hydrochloric acid, sulfuric acid, nitric acid) is usually used. 1.0-4.0 mol is preferable with respect to 1 mol of halides (IX), and, as for the usage-amount of the acid used here, More preferably, it is 1.6-2.2 mol. As the solvent for this reaction, water, alcohols (for example, ethyl alcohol), a mixed solvent of them and an aprotic polar solvent (for example, dimethyl sulfoxide, N, N-dimethylformamide) are preferable, and water, alcohols are particularly preferable. And a mixed solvent of both. The use ratio of the solvent and Bunte salt is not particularly limited, but 0.01 to 10 mol of Bunte salt per liter of solvent is preferable, and more preferably 0.1 to 5 mol.
The reaction temperature is preferably in the range of 0 ° C. to the reflux temperature of the solvent, more preferably 20 to 70 ° C. This reaction is usually completed in 0.1 to 24 hours, and alicyclic dithiol (I) is obtained in an acidic state.

(5) A method of synthesizing an alicyclic dithiol (I) by reacting a halide (IX) with an alkali metal thiocarboxylic acid to synthesize a thiocarboxylic acid ester and hydrolyzing the thiocarboxylic acid ester with a base. It is.
Examples of suitable thiocarboxylic acids in the thiocarboxylic acid alkali metal salts include linear, branched or cyclic saturated or unsaturated thiocarboxylic acids having 1 to 8 carbon atoms, and particularly preferred are those having 2 to 2 carbon atoms. 4 saturated thiocarboxylic acids and thiobenzoic acids. Moreover, sodium and potassium are mentioned as an example of the suitable alkali metal in a thiocarboxylic acid alkali metal salt. The reaction between the halide (IX) and the alkali metal thiocarboxylate is usually carried out in an organic solvent. Examples of the organic solvent used here include halogenated hydrocarbons (eg, chloroform, dichloroethane), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, diethyl ether, monoglyme), alcohols (eg, methyl alcohol, ethyl alcohol, Ethylene glycol) and aprotic polar solvents (for example, dimethyl sulfoxide, N, N-dimethylphonemamide) and the like. Among these, ketones and alcohols are preferable. The use ratio of the solvent and the halide (IX) is not particularly limited, but is preferably 0.01 to 10 mol, and particularly preferably 0.1 to 5 mol, per liter of the solvent. The ratio of the halide (IX) to the alkali metal thiocarboxylate is preferably 1.0 to 10.0 mol of the alkali metal thiocarboxylate with respect to 1 mol of the halide (IX), more preferably 1.8. -3.0 mol.
The reaction temperature is not particularly limited, but a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable, and the reaction is usually carried out under reflux with heating. This reaction is usually completed in 0.5 to 24 hours. Thus, thiocarboxylic acid ester is produced | generated by making halide (IX) and thiocarboxylic acid alkali metal salt react.

In order to hydrolyze the thiocarboxylic acid ester to obtain the alicyclic dithiol (I), a base is usually used. Bases used here include alkali metal or alkaline earth metal hydroxides (for example, sodium hydroxide, calcium hydroxide), alkali metal or alkaline earth metal carbonates (for example, potassium carbonate), amines (for example, ammonia). Water, triethylamine, aniline). 1.0-4.0 mol is preferable with respect to 1 mol of halides (IX), and, as for the usage-amount of the base used here, More preferably, it is 1.6-2.2 mol. The temperature at which the thiocarboxylic acid ester is hydrolyzed is not particularly limited, but a temperature in the range from 0 ° C to the reflux temperature of the solvent is preferred, and more preferably 20 ° C to 50 ° C. This reaction is usually completed in 0.1 to 24 hours, and alicyclic dithiol (I) is obtained by acidification with an acid.
The alicyclic dithiol represented by the general formula (I) is, for example, the following scheme (B)

（式中、Ｇ¹ は上記と同様である。）

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

As shown by, it can be synthesized by reacting a hydroxy compound (X) with a mercapto agent. As a typical synthesis method according to the above scheme (B), for example, a hydroxy compound (X) is reacted with thiourea in the presence of odorous acid or hydrochloric acid to form an isothiuronium salt, and then hydrolyzed to obtain an alicyclic group. A method for synthesizing dithiol (I) is mentioned.
Odoric acid or hydrochloric acid may be in a gaseous state, or an aqueous solution or an acetic acid solution may be used. The reaction between the hydroxy compound (X) and thiourea is usually performed in a polar solvent. Examples of the polar solvent used here include water, acetic acid, and trifluoroacetic acid), but water, acetic acid, and a mixed solvent of both are preferable. Although the usage-amount of a solvent and hydroxy compound (X) is not specifically limited, 0.01-10 mol of hydroxy compound (X) is preferable per liter of solvent, More preferably, it is 0.1-5 mol. The use ratio of the hydroxy compound (X) and thiourea is preferably 1.0 to 10.0 mol, more preferably 1.8 to 4.0 mol, with respect to 1 mol of the hydroxy compound (X). .
The reaction temperature is not particularly limited, but a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable, and the reaction is usually performed under heating and reflux. This reaction is usually completed in 0.5 to 24 hours. In this way, by reacting the hydroxy compound (X) with thiourea, an isothiuronium salt is precipitated. Subsequent operations include a method of filtering the isothiuronium salt and a method of not filtering, but the latter method is preferred from the viewpoint of the convenience of the operation and the yield.

In order to hydrolyze the obtained isothiuronium salt to obtain alicyclic dithiol (I), a base is usually used. Preferred bases include alkali metal or alkaline earth metal hydroxides (eg, sodium hydroxide, calcium hydroxide), alkali metal or alkaline earth metal carbonates (eg, sodium carbonate) and amines (eg, aqueous ammonia, triethylamine). Among them, alkali metal or alkaline earth metal hydroxides are particularly preferable. 1.0-4.0 mol is preferable with respect to 1 mol of hydroxy compounds (X), and, as for the usage-amount of the base used here, More preferably, it is 1.6-2.2 mol. As a solvent for this reaction, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol), a mixed solvent of both, and an aprotic polar solvent (for example, dimethyl sulfoxide, N, N-dimethylformamide) are preferable, and particularly preferable. These are water, alcohols and their mixed solvents. The use ratio of the solvent and the isothiuronium salt is not particularly limited, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, per liter of the solvent. Although the reaction temperature of this reaction is not particularly limited, it is usually carried out at the reflux temperature of the solvent. This reaction is usually completed in 0.5 to 24 hours, and alicyclic dithiol (I) is obtained by acidification with a mineral acid (for example, hydrochloric acid, sulfuric acid, nitric acid).
Moreover, the alicyclic dithiol represented by the following general formulas (Ia) to (If) is, for example, the following schemes (C) to (H):

As shown in the above, it can be synthesized by reacting the diene compounds (XIa) to (XIf) with a mercapto agent. Here, the diene compounds (XIa) to (XIf) have three or more ring structures, and the ring structure may contain an atom selected from a sulfur atom and an oxygen atom. It is a diene compound having (G ¹ ). The diene double bond may be contained in the ring or may be outside the ring. The alicyclic dithiols (Ia) to (If) are alicyclic dithiols having the same alicyclic hydrocarbon groups as the diene compounds (XIa) to (XIf), and are included in the alicyclic dithiols (I). It is what
A typical method for synthesizing the alicyclic dithiol (Ia) according to the above scheme (C) includes, for example, a method of synthesizing the dithiol (Ia) by reacting the diene compound (XIa) with hydrogen sulfide. Further, a method of synthesizing dithiol (Ia) by reacting diene compound (XIa) with thioacetic acid to acetylthiolate and then hydrolyzing it can be mentioned. In the reaction with the diene compound (XIa), the reaction is promoted in the presence of a radical initiator as necessary, or the reaction is accelerated by irradiation with light. The same applies to the schemes (D) to (H).

  Examples of the radical initiator include azo radical initiators (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4′-dimethylvaleronitrile), 2,2′-azobis ( Methyl 2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4′-dimethyl-4-methoxyvaleronitrile), 4,4′-azobis Peroxide radical initiators such as (4-cyanopentanoic acid) such as lauroyl peroxide, benzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxy-2-ethyl Hexanoate, methyl ethyl ketone peroxide, etc. If necessary, irradiate with a high-pressure mercury lamp or UV (ultraviolet) lamp. Reaction is promoted with.

The reaction is carried out without solvent or in a solvent. Solvents used here include halogenated hydrocarbons (for example, carbon tetrachloride, chloroform, dichloroethane), aromatics (for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene), ketones (for example, acetone, methyl ethyl ketone), Ethers (eg, diethyl ether, tetrahydrofuran, dioxane, monoglyme), alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol) and aprotic polar solvents (eg, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile), carboxylic acids (For example, acetic acid, trifluoroacetic acid), water, and the like can be mentioned. Usually, the reaction is carried out without solvent or in a halogenated hydrocarbon. The use ratio of the solvent and the diene compounds (XIa) to (XIf) is not particularly limited, but 0.01 to 10 mol of the diene compounds (XIa) to (XIf) per liter of the solvent is preferable, more preferably 0.1 to 0.1 mol. 5 moles. The use ratio of the diene compounds (XIa) to (XIf) and thioacetic acid or hydrogen sulfide is 1.0 to 10.0 mol of thioacetic acid or hydrogen sulfide relative to 1 mol of the diene compounds (XIa) to (XIf). Preferably it is 1.8-4.0 mol.
The reaction temperature is not particularly limited, but a temperature in the range from 10 ° C. to the reflux temperature of the solvent is preferable. Usually, it is heated under reflux or the temperature of the radical initiator used is 10 hours half-life (for example, 2,2′-azo In the case of bisisobutyronitrile, it is carried out at 65 ° C.). This reaction is usually completed in 0.5 to 24 hours.

In order to obtain dithiols (Ia) to (If) by hydrolyzing the acetylthiolate obtained by the reaction of diene compounds (XIa) to (XIf) and thioacetic acid, a base is usually used. Preferred bases include alkali metal or alkaline earth metal hydroxides (eg, sodium hydroxide, calcium hydroxide), alkali metal or alkaline earth metal carbonates (eg, sodium carbonate) and amines (eg, aqueous ammonia, triethylamine). Among them, alkali metal or alkaline earth metal hydroxides are particularly preferable. 1.0-4.0 mol is preferable with respect to 1 mol of diene compounds (XIa)-(XIf), and, as for the usage-amount of a base, More preferably, it is 1.6-2.2 mol. As a solvent for this reaction, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol), a mixed solvent of both, and an aprotic polar solvent (for example, dimethyl sulfoxide, N, N-dimethylformamide) are preferable, and particularly preferable. These are water, alcohols and their mixed solvents. The use ratio of the solvent and the isothiuronium salt is not particularly limited, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, per liter of the solvent.
The reaction temperature is not particularly limited but is usually carried out at the reflux temperature of the solvent. This reaction is usually completed in 0.5 to 24 hours, and dithiols (Ia) to (If) are obtained by acidification with a mineral acid (for example, hydrochloric acid, sulfuric acid, nitric acid).
The alicyclic dithiol (I) obtained by the above schemes (A) to (H) is easily purified by usual means such as solvent extraction, chromatography and distillation. The alicyclic dithiol (I) of the present invention has a refractive index (nd) of 1.53 or more and an Abbe number (νd) of 42 or more.

  The alicyclic dithiol (I) of the present invention can be a constituent unit of a sulfur-containing polymer. Examples of the sulfur-containing polymer include at least one compound selected from the alicyclic dithiol (I) of the present invention, a polyisocyanate compound, a pothiisothiocyanate compound, and an isothiocyanate compound having an isocyanate group. A polymer obtained by reacting a sulfur-containing polymer (a) obtained by reacting with alicyclic dithiol (I) and a polycarbonate oligomer having a dihydric phenol or a functional group that reacts with a thiol group at the terminal. A thiocarbonate resin is mentioned. These sulfur-containing polymers have a refractive index (nd) of 1.53 or more and an Abbe number (νd) of 32 or more.

In the sulfur-containing polymer (a), at least one compound selected from a polyisocyanate compound, a pothiisothiocyanate compound, and an isothiocyanate compound having an isocyanate group, and an alicyclic dithiol (I) (other polythiols) The amount of [(NCO + NCS) / SH] (functional group) is usually 0.5 to 3.0, preferably 0.5 to 1.5. It is.
The amount of the alicyclic dithiol (I) used when the alicyclic dithiol (I) and another polythiol are used in combination is appropriately determined depending on the type of raw material monomer used and the required heat resistance. From the viewpoint of properties, 5 mol% or more of the total thiol compound is preferable, and more preferably 20 mol% or more.

The sulfur-containing polymer (a) is usually obtained by cast polymerization. Specifically, at least one compound selected from a polyisocyanate compound, a pothiisothiocyanate compound, and an isothiocyanate compound having an isocyanate group, and an alicyclic dithiol (I) (when other polythiol is used in combination) And the mixture is defoamed by an appropriate method as necessary, and then poured into a mold, and is usually polymerized while gradually raising the temperature from a low temperature to a high temperature, can get.
The polymerization temperature and polymerization time vary depending on the monomer composition, the type of additive, and the amount used, but generally start from about 20 ° C. and increase to about 120 ° C. over 8-24 hours. At this time, in order to facilitate the release property after polymerization, the mold may be subjected to a known release treatment. In addition, depending on the purpose, as in known molding methods, various agents such as internal mold release agents, chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, etc. Substances may be added. Furthermore, in order to adjust to a desired reaction rate, a known reaction catalyst used in the production of polyurethane can be appropriately added.

  The sulfur-containing polymer (a) is mainly composed of a thiocarbamic acid S-alkyl ester resin and / or a dithiourethane resin, and has a thiocarbamic acid S-alkyl ester bond formed by an isocyanate group and a mercapto group. It is mainly composed of a dithiourethane bond by an isothiocyanate group and a mercapto group. Depending on the intended use of the sulfur-containing polymer (a), other than these bonds, an allophanate bond, urea bond, thiourea bond, biuret bond, etc. may be contained. For example, the isocyanate group may be further reacted with the thiocarbamic acid S-alkyl ester bond, or the isothiocyanate group may be further reacted with the dithiourethane bond to increase the crosslinking density. Often gives. In this case, the reaction temperature is set to 100 ° C. or higher, and a large amount of isocyanate component and / or isothiocyanate component is used. Alternatively, it is also possible to use a urea bond or biuret bond by partially using an amine or the like. When using a compound other than the mercapto compound that reacts with the isocyanate compound or the isothiocyanate compound as described above, it is necessary to pay attention to the coloring point.

As described above, the polythiocarbonate resin which is a sulfur-containing polymer is obtained by reacting the alicyclic dithiol (I) with a polycarbonate oligomer having a dihydric phenol or a functional group which reacts with a thiol group at the terminal. It is. As the polycarbonate oligomer, for example, in the presence of a known acid acceptor in a solvent such as methylene chloride, the reaction between a dihydric phenol and a carbonate precursor such as phosgene, or in the presence or absence of a solvent, What was manufactured by transesterification with phenol and carbonate precursors, such as a carbonate ester compound, can be used.
Examples of dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,2-bis. Bis (4-hydroxyphenyl) alkane such as (4-hydroxyphenyl) ethane, bis (4-hydroxy) such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclodecane Phenyl) cycloalkane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4- Hydroxyphenyl) ketone and the like.
The reaction temperature and reaction time in the reaction between the alicyclic dithiol (I) and the above polycarbonate oligomer vary depending on the monomer composition, the type of additive, and the amount used, but in general, it is several minutes at 0 to 40 ° C. ~ Several days, preferably 10 to 30 ° C for 10 minutes to 5 hours. You may add a molecular regulator, a catalyst, antioxidant, etc. as needed.
In the polythiocarbonate resin, the copolymer composition is preferably 1 to 100% by mass.

The sulfur-containing polymer (a) or polythiocarbonate resin in which the alicyclic dithiol (I) of the present invention constitutes a structural unit may be a sulfur-containing polymer composition obtained by adding various additives to at least one of these. it can. Examples of the additive include a release agent, a heat stabilizer, an ultraviolet absorber, and a blue ink agent.
The above sulfur-containing polymer or sulfur-containing polymer composition comprising the alicyclic dithiol (I) of the present invention has no discomfort due to sulfur odor during handling of the monomer and no discomfort due to sulfur odor during post-processing, and physical properties It has extremely low dispersion, high refractive index, excellent heat resistance, is colorless and transparent, is lightweight, has excellent characteristics such as weather resistance, impact resistance, etc. Suitable as element material, glazing material, paint, adhesive material. Lenses made of the sulfur-containing polymer or sulfur-containing polymer composition comprising the alicyclic dithiol (I) of the present invention are antireflective, imparted with high hardness, improved wear resistance, and improved chemical resistance as necessary. In order to improve antifogging or fashionability, physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, anti-reflective coating treatment, dyeing treatment, and light control treatment may be applied. it can.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples. The refractive index and Abbe number were measured by the following methods.
<Measurement method of refractive index and Abbe number>
The refractive index and Abbe number were measured at 20 ° C. using an Abbe refractometer (manufactured by Atago Co., Ltd.). When the sample was resin, a test piece of length × width × thickness = 20 mm × 8 mm × 3 mm was prepared and measured using a sulfur-methylene iodide solution as an intermediate solution. When the sample is a solid powder at room temperature, the refractive index is obtained by extrapolation, and the Abbe number is obtained from this refractive index.

Example 1 [Synthesis of 4,8-bis (mercaptomethyl) tricyclo [5.2.1.0 ^2,6 ] decane (mixture of isomers)]
100 g (509 mmol) of 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (mixture of isomers), 154.2 g (1273 mmol) of dimethylaniline, 250 ml of dichloroethane, To the mixed solution, 93 ml (1723 mmol) of thionyl chloride was added dropwise and reacted at 70 ° C. for 5 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic phase was washed successively with aqueous hydrochloric acid, water and saturated brine, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel: hexane), and 98.0 g of 4,8-bis (chloromethyl) tricyclo [5.2.1.0 ^2,6 ] decane (yield). 83%).
Sodium hydrosulfide hydrate was added to a solution obtained by dissolving 50.0 g (214 mmol) of 4,8-bis (chloromethyl) tricyclo [5.2.1.0 ^2,6 ] decane in 200 ml of dimethylformamide. 66.0 g (1177 mmol) was added and reacted at 70 ° C. for 6 hours. The reaction mixture was poured into aqueous hydrochloric acid and extracted with hexane. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to obtain 4,8-bis (mercaptomethyl) tricyclo [5.2.1.0 ^{2, 6} ] 21.5 g (44% yield) of decane (isomer mixture) was obtained.
The measurement result by MS (mass spectrum) of 4,8-bis (mercaptomethyl) tricyclo [5.2.1.0 ^2,6 ] decane (mixture of isomers) was 228 (M +), and the refractive index (nd) was The Abbe number (νd) was 1.57 and 48.

Example 2 [Synthesis of bis (2-mercapto-octahydro-4,7-methano-inden-5-yl) ethylene glycol (isomer mixture)]
A mixture of 8.29 g (134 mmol) of ethylene glycol and 5.92 g (13.6 mmol) of boron trifluoride diethyl ether complex was heated to 120 ° C., and 50.0 g (378 mmol) of dicyclopentadiene was added to this mixture. The solution was added dropwise over a period of time and reacted at 120 ° C. for 6 hours. After cooling to room temperature, a saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (silica gel: hexane), and 34.3 g of bis (hexahydro-4,7-methano-inden-5-yl) ethylene glycol (isomer mixture) (yield) 79%).
The resulting bis (hexahydro-4,7-methano-inden-5-yl) ethylene glycol (isomer mixture) 30.0 g (91.8 mmol), thioacetic acid 17.4 g (229.5 mmol), and 2 , 2′-azobisbutyronitrile 1.2 g (7.3 mmol) in a solution of 90 ml of carbon tetrachloride was irradiated with light from a mercury lamp and reacted at room temperature for 12 hours. Furthermore, 8.7 g (115 mmol) of thioacetic acid was added, irradiated with light from a mercury lamp, and reacted at room temperature for 12 hours. Excess thioacetic acid and the solvent were distilled off from the reaction mixture under reduced pressure. The obtained residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to give bis (2-acetylthio-octahydro-4,7-methano-inden-5-yl). 29.6 g (yield 80%) of ethylene glycol (isomer mixture) was obtained.
The obtained bis (2-acetylthio-octahydro-4,7-methano-inden-5-yl) ethylene glycol (isomer mixture) 29.0 g (60.6 mmol), sodium hydroxide 9.69 g (242.3) Mmol), 100 ml of water, 100 ml of ethanol and 100 ml of tetrahydrofuran were reacted at room temperature for 4 hours. Concentrated hydrochloric acid was poured into the reaction mixture to make it acidic (pH = 1), and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is performed by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to obtain bis (2-mercapto-octahydro-4,7-methano-inden-5-yl). 12.2 g (51% yield) of ethylene glycol (isomer mixture) was obtained.
The organic phase was washed with saturated brine and then measured for bis (2-mercapto-octahydro-4,7-methano-inden-5-yl) ethylene glycol (isomer mixture). The measurement result by MS (mass spectrum) is 394 (M +), the measurement result by IR (infrared spectrophotometer) is 2550 cm ⁻¹ (SH), the refractive index (nd) is 1.55, and the Abbe number (νd) is 54. there were.

Example 3 [Synthesis of bis (2-mercapto-octahydro-4,7-methano-inden-5-yl) ether (mixture of isomers)]
A mixture of 30.0 g (200 mmol) of hydroxycyclopentadiene and 26.4 g (200 mmol) of dicyclopentadiene was heated to 70 ° C., and 3.0 g (21.3 mmol) of boron trifluoride diethyl ether complex was added to this mixture. The mixture was poured and reacted at 70 ° C. for 6 hours. After cooling to room temperature, a saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (silica gel: hexane), and 31.2 g of bis (hexahydro-4,7-methano-inden-5-yl) ether (isomer mixture) (yield 55 %).
The resulting bis (hexahydro-4,7-methano-inden-5-yl) ether (isomer mixture) 30.0 g (106.2 mmol), thioacetic acid 16.2 g (212.8 mmol) and carbon tetrachloride 90 ml of the mixture was irradiated with light from a mercury lamp and reacted at room temperature for 10 hours. Further, 16.2 g (212.8 mmol) of thioacetic acid and 0.9 g (5.6 mmol) of 2,2′-azobisbutyronitrile were added, irradiated with light from a mercury lamp, and reacted at room temperature for 36 hours. I let you. Excess thioacetic acid and the solvent were distilled off from the reaction mixture under reduced pressure. The obtained residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to give bis (2-acetylthio-octahydro-4,7-methano-inden-5-yl). 24.5 g (53% yield) of ether (isomer mixture) was obtained.
The obtained bis (2-acetylthio-octahydro-4,7-methano-inden-5-yl) ether (isomer mixture) 24.0 g (55.2 mmol), sodium hydroxide 8.83 g (220.8 mmol) ), A mixed solution of 100 ml of water and 100 ml of tetrahydrofuran was reacted at room temperature for 4 hours. Concentrated hydrochloric acid was poured into the reaction mixture to make it acidic (pH = 1), and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is performed by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to obtain bis (2-mercapto-octahydro-4,7-methano-inden-5-yl). 10.6 g (yield 55%) of ether (mixture of isomers) was obtained.
The organic phase was washed with saturated brine and then measured for bis (2-mercapto-octahydro-4,7-methano-inden-5-yl) ether (isomer mixture). The measurement result by MS (mass spectrum) is 350 (M +), the measurement result by IR (infrared spectrophotometer) is 2550 cm ⁻¹ (SH), the refractive index (nd) is 1.56, and the Abbe number (νd) is 52. there were.

Example 4 [Synthesis of 2- [2- (2-mercapto-ethylthio) -octahydro-4,7-methano-inden-5-yloxy] -ethanethiol (mixture of isomers)]
A mixture of 13.2 g (100 mmol) of dicyclopentadiene, 12.5 g (100 mmol) of bromoethanol and 0.3 g (2 mmol) of boron trifluoride diethyl ether complex was stirred at 70 ° C. for 10 hours to be reacted. It was. After cooling to room temperature, a saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 9/1 (volume ratio) to give 5- (2-bromoethoxy) -hexahydro-4,7-methano-indene (isomerism). Body mixture) 10.6 g (41% yield).
The resulting 5- (2-bromoethoxy) -hexahydro-4,7-methano-indene (isomer mixture) 8.0 g (33.1 mmol), mercaptoethanol 2.43 g (33.1 mmol), and 2 , 2′-Azobisbutyronitrile 0.1 g (0.7 mmol) dissolved in 90 ml of carbon tetrachloride was irradiated with light from a mercury lamp and reacted at room temperature for 24 hours.
To the obtained reaction liquid, 28.5 g (165.5 mmol) of 47% by mass odorous acid and 10.1 g (132.4 mmol) of thiourea were added, and the mixture was reacted by heating at 110 ° C. for 9 hours. The mixture was cooled to room temperature, 50 ml of toluene was added, 16.9 g (248 mmol) of 25% by mass aqueous ammonia was gradually added, and the mixture was reacted at 60 ° C. for 3 hours. Concentrated hydrochloric acid was added to the reaction mixture, and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to give 2- [2- (2-mercapto-ethylthio) -octahydro-4,7-methano. -Inden-5-yloxy] -ethanethiol (isomer mixture) 3.88 g (35% yield) was obtained.
The measurement result of 2- [2- (2-mercapto-ethylthio) -octahydro-4,7-methano-inden-5-yloxy] -ethanethiol by MS (mass spectrum) was 334 (M +), IR (infrared spectroscopy) The measurement result with a photometer was 2550 cm ⁻¹ (SH), the refractive index (nd) was 1.55, and the Abbe number (νd) was 47.

Example 5 Synthesis of mercaptopropoxy-mercapto-dodecahydro-dimethano-cyclopenta [b] naphthalene (mixture of isomers)
A mixture of 146.4 g (2.52 mol) of allyl alcohol and 20.0 g (0.14 mol) of boron trifluoride diethyl ether complex was heated to 75 ° C. to obtain 500.0 g (2.52 mol) of tricyclopentadiene. Was added dropwise over 1 hour and reacted at 70 ° C. for 2 hours. After cooling to room temperature, ice and saturated aqueous sodium hydrogen carbonate solution were poured into the reaction mixture, and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 516 g (yield 80%) of allyloxydecahydrodimethanocyclopenta [b] naphthalene (isomer mixture).
To the obtained allyloxydecahydrodimethanocyclopenta [b] naphthalene (isomer mixture) (495 g, 1.93 mol), 561 g (7.37 mol) of thioacetic acid was added dropwise and stirred at 50 to 70 ° C. for 2 hours. Reacted. Excess thioacetic acid was distilled off under reduced pressure to obtain 810 g of a crude product of acetylthiopropoxy-acetylthio-dodecahydro-dimethano-cyclopenta [b] naphthalene (isomer mixture).
To a mixed solution of 810 g of the obtained acetylthiopropoxy-acetylthio-dodecahydro-dimethano-cyclopenta [b] naphthalene (isomer mixture) crude product, 2.52 liters of ethanol and 300 ml of tetrahydrofuran, 317 g (7.93 of sodium hydroxide) was added. Mol) was dissolved in 3.17 liters of water, and reacted at room temperature for 2 hours. To the reaction mixture, 810 ml of concentrated hydrochloric acid was poured to make it acidic (pH = 1) and extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then with hexane / ethyl acetate = 50/1 (volume ratio), and 329 g of mercaptopropoxy-mercapto-dodecahydro-dimethano-cyclopenta [b] naphthalene (isomer mixture). (Yield 52.6%) was obtained.
Mercaptopropoxy-mercapto-dodecahydro-dimethano-cyclopenta [b] naphthalene (mixture of isomers) measured by MS (mass spectrum) is 324 (M +), measured by IR (infrared spectrophotometer) is 2550 cm ⁻¹ ( SH), the refractive index (nd) was 1.56, and the Abbe number (νd) was 50.

Example 6 [Synthesis of mercaptopropoxy-mercapto-octahydro-methano-indene (isomer mixture)]
A mixture of 439 g (7.56 mol) of allyl alcohol and 42.7 g (0.30 mol) of boron trifluoride diethyl ether complex was heated to 100 ° C., and 1000.0 g (7.56 mol) of dicyclopentadiene was added to 1 The solution was added dropwise over a period of time, reacted at 100 ° C. for 1 hour, and further reacted at 120 ° C. for 2 hours. After cooling to room temperature, ice and saturated aqueous sodium hydrogen carbonate solution were poured into the reaction mixture, and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 965 g (yield 67%) of allyloxyhexahydromethanoindene (isomer mixture).
To 516 g (2.01 mol) of the obtained allyloxyhexahydromethanoindene (isomer mixture), 612 g (8.04 mol) of thioacetic acid was added dropwise and reacted at 70 ° C. for 2 hours. Excess thioacetic acid was distilled off under reduced pressure to obtain 808 g of a crude product of (acetylsulfenyloctahydro-methano-indene-5-yloxy) propoxyhexahydromethanoindene (isomer mixture).
To a mixed solution of 808 g of the crude product (acetylsulfenyloctahydro-methano-inden-5-yloxy) propoxyhexahydromethanoindene (isomer mixture) and 800 ml of ethanol, 322 g (8.04 mol) of sodium hydroxide was added. ) Was dissolved in 1.60 liters of water and dropped at room temperature for 2 hours. The reaction mixture was acidified (pH = 1) by pouring 804 ml of concentrated hydrochloric acid and extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and 495 g (yield 81%) of mercaptopropoxy-mercapto-octahydro-methano-indene (isomer mixture) was obtained by distillation under reduced pressure.
Mercaptopropoxy-mercapto-octahydro-methano-indene (mixture of isomers) measured by MS (mass spectrum) is 258 (M +), measured by IR (infrared spectrophotometer) is 2550 cm ⁻¹ (SH), refraction The rate (nd) was 1.55 and the Abbe number (νd) was 50.

Example 7 [Synthesis of dimercapto-dodecahydro-dimethano-cyclopenta [b] naphthalene (mixture of isomers)]
To 30.0 g (151 mmol) of tricyclopentadiene, 23.0 g (303 mmol) of thioacetic acid was added dropwise, irradiated with light from a high-pressure mercury lamp at room temperature, and reacted for 40 hours. Excess thioacetic acid was distilled off under reduced pressure, purified by column chromatography (silica gel: hexane = 20: 1), bis (acetylthio) -dodecahydro-dimethano-cyclopenta [b] naphthalene (isomer mixture) 29. 1 g (55% yield) was obtained.
Mixing of the obtained bis (acetylthio) -dodecahydro-dimethano-cyclopenta [b] naphthalene (isomer mixture) 29.1 g, sodium hydroxide 13.2 g (331 mmol), methanol 60 ml, tetrahydrofuran 30 ml and water 40 ml The solution was allowed to react for 4 hours at room temperature. Concentrated hydrochloric acid was poured into the reaction mixture to make it acidic (pH = 1), and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then with hexane / ethyl acetate = 30/1 (volume ratio), and 19.6 g of dimercapto-dodecahydro-dimethano-cyclopenta [b] naphthalene (isomer mixture) ( Yield 89%).
The measurement result of dimercapto-dodecahydro-dimethano-cyclopenta [b] naphthalene (mixture of isomers) by MS (mass spectrum) is 266 (M +), the measurement result by IR (infrared spectrophotometer) is 2550 cm ⁻¹ (SH), The refractive index (nd) was 1.59, and the Abbe number (νd) was 48.

Example 8 [Synthesis of dimercapto-dodecahydro [1,4], [5,8] dimethanoanthracene (mixture of isomers)]
Octahydro [1,4], [5,8] dimethanoanthracene was synthesized by the method described in “Journal of Organic Chemistry Vol. 56, page 5253 (1991)”. A mixture of 30.0 g (125 mmol) of octahydro [1,4] [5,8] dimethanoanthracene, 22.8 g (300 mmol) of thioacetic acid and 150 ml of carbon tetrachloride was mixed at room temperature to 50 ° C. for 5 hours. Reacted. The precipitated solid was collected by filtration and washed with hexane to obtain 30.4 g of a crude product of bis (acetylthio) -dodecahydro [1,4], [5,8] dimethanoanthracene.
The obtained bis (acetylthio) -dodecahydro [1,4], [5,8] dimethanoanthracene crude product 30.4 g, sodium hydroxide 9.3 g (233 mmol), methanol 60 ml, tetrahydrofuran 30 ml and A mixed solution of 60 ml of water was reacted at room temperature for 4 hours. Concentrated hydrochloric acid was poured into the reaction mixture to make it acidic (pH = 1), and the mixture was extracted with hexane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification was performed by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 3/1 (volume ratio). Dimercapto-dodecahydro [1,4], [5,8] dimethanoanthracene (isomer) 2.2 g (9% yield) of the mixture was obtained.
Dimercapto-dodecahydro [1,4], [5,8] dimethanoanthracene (mixture of isomers) measured by MS (mass spectrum) was 308 (M +), and measured by IR (infrared spectrophotometer) was 2550 cm. ^-1 (SH), refractive index (nd) was 1.56, and Abbe number (νd) was 47.

Example 9 Synthesis of bis (mercaptoethylsulfenyl) -dodecahydro [1,4], [5,8] dimethanoanthracene (mixture of isomers)
Octahydro [1,4] [5,8] dimethanoanthracene 10.0 g (41) obtained by the same synthesis as in Example 9 was added to a solution of 15.0 g (167 mmol) of ethanediol in 20 ml of tetrahydrofuran. .6 mmol), 100 ml of tetrahydrofuran and 10 ml of dimethylformamide were gradually added at room temperature and reacted at 50 ° C. for 4 hours. Excess ethanediol was distilled off under reduced pressure and purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then with hexane / ethyl acetate = 2/1 (volume ratio) to obtain bis (mercaptoethylsulfenyl) -dodecahydro [1,4], [5,8]. 2.2 g (yield 13%) of dimethanoanthracene (isomer mixture) was obtained.
The measurement results of bis (mercaptoethylsulfenyl) -dodecahydro [1,4], [5,8] dimethanoanthracene (isomer mixture) by MS (mass spectrum) are 428 (M +), IR (infrared spectrophotometer) ) Was 2550 cm ⁻¹ (SH), refractive index (nd) was 1.56, and Abbe number (νd) was 44.

Example 10 [Synthesis of bis (2-mercapto-octahydro-4,7-methano-indene-5-yloxymethyl) -cyclohexane (mixture of isomers)]
To a mixture of 36.0 g (250 mmol) of 1,4-cyclohexanedimethanol and 100 ml of dichloroethane, 5 ml (39.8 mmol) of boron trifluoride diethyl ether complex was added, and dicyclopentadiene 66. 0 g (500 mmol) was added dropwise and reacted for 5 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with dichloromethane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, the residue was purified by column chromatography (silica gel: hexane = 20: 1), and 1,4-bis (octahydro-4,7-methano-inden-5-yloxymethyl) -cyclohexane ( The isomer mixture was obtained 82.0 g (yield 80%).
The obtained 1,4-bis (octahydro-4,7-methano-inden-5-yloxymethyl) -cyclohexane (isomer mixture) 54.0 g (132 mmol) and thioacetic acid 30 ml (420 mmol) A solution dissolved in 180 ml of carbon chloride was irradiated with light from a mercury lamp and reacted at room temperature for 9 hours. The resulting reaction mixture was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 20/1 (volume ratio) to obtain bis (2-acetylthio-octahydro-4,7-methano-inden-5-yloxy). 36.2 g (yield 49%) of methyl) -cyclohexane (isomer mixture) were obtained.
The obtained bis (2-acetylthio-octahydro-4,7-methano-inden-5-yloxymethyl) -cyclohexane (isomer mixture) 26.2 g (47.0 mmol), sodium hydroxide 10.0 g (250 Mmol), 100 ml of water, 100 ml of ethanol and 100 ml of tetrahydrofuran were reacted at room temperature for 1.5 hours. Concentrated hydrochloric acid was poured into the reaction mixture to make it acidic (pH = 1), and the mixture was extracted with dichloromethane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio) to give bis (2-mercapto-octahydro-4,7-methano-inden-5-yloxy). 16.0 g (yield 72%) of methyl) -cyclohexane (isomer mixture) was obtained.
The measurement result by MS (mass spectrum) of bis (2-mercapto-octahydro-4,7-methano-inden-5-yloxymethyl) -cyclohexane (mixture of isomers) is 476 (M +), IR (infrared spectrophotometry) The measurement result was 2550 cm ⁻¹ (SH), the refractive index (nd) was 1.53, and the Abbe number (νd) was 56.

Example 11
Synthesis of 3,6-bis (2-mercapto-hexahydro-4,7-methano-inden-5-yloxy) -hexahydro-furo [3,2-b] furan (mixture of isomers)
To a mixture of 7.3 g (50 mmol) of isosorbide and 20 ml of dichloroethane, 1 ml (8.0 mmol) of boron trifluoride diethyl ether complex was added, and 13.2 g (100 mmol) of dicyclopentadiene was added under heating and reflux. The solution was added dropwise and reacted for 3 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with dichloromethane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, the residue was purified by column chromatography (silica gel: hexane = 10: 1), and 3,6-bis (octahydro-4,7-methano-inden-5-yloxy) -hexahydro-furo [ 3,8.0 b of furan (isomer mixture) was obtained (88% yield).
18.0 g (44.0 mmol) of 3,6-bis (octahydro-4,7-methano-inden-5-yloxy) -hexahydro-furo [3,2-b] furan (isomer mixture) obtained and A solution obtained by dissolving 8 ml (112 mmol) of thioacetic acid in 50 ml of carbon tetrachloride was irradiated with light from a mercury lamp and reacted at room temperature for 12 hours. The resulting reaction mixture was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 5/1 (volume ratio), and 3,6-bis (2-acetylthio-octahydro-4,7-methano-indene- 12.6 g (45% yield) of 5-yloxy) -hexahydro-furo [3,2-b] furan (isomer mixture) were obtained.
The resulting 3,6-bis (2-acetylthio-octahydro-4,7-methano-inden-5-yloxy) -hexahydro-furo [3,2-b] furan (isomer mixture) 12.6 g (22. 4 mmol), 5.0 g (250 mmol) of sodium hydroxide, 50 ml of water, 50 ml of ethanol and 50 ml of tetrahydrofuran were reacted at room temperature for 1.5 hours. Concentrated hydrochloric acid was poured into the reaction mixture to make it acidic (pH = 1), and the mixture was extracted with dichloromethane. The organic phase was washed successively with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). The purification was carried out by eluting with hexane for a while and then with hexane / ethyl acetate = 10/1 (volume ratio), and 3,6-bis (2-mercapto-hexahydro-4,7-methano-indene- There were obtained 9.0 g (84% yield) of 5-yloxy) -hexahydro-furo [3,2-b] furan (isomer mixture).
Determination of 3,6-bis (2-mercapto-hexahydro-4,7-methano-inden-5-yloxy) -hexahydro-furo [3,2-b] furan (mixture of isomers) by MS (mass spectrum) The result was 478 (M +), the measurement result by IR (infrared spectrophotometer) was 2550 cm ⁻¹ (SH), the refractive index (nd) was 1.55, and the Abbe number (νd) was 51.

Example 12
[Synthesis of 4,8-dimercaptotricyclo [5.2.1.0 ^2,6 ] decane]
A solution obtained by dissolving 10 g (75.6 mmol) of cyclopentadiene and 11.5 g (151 mmol) of thioacetic acid in 50 ml of carbon tetrachloride was irradiated with light from a high-pressure mercury lamp and reacted at room temperature for 10 hours. The resulting reaction mixture was purified by column chromatography (filled with silica gel). Purification is performed by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 2/1 (volume ratio), and 4,8-bis (acetylthio) tricyclo [5.2.1.0 ^2,6 ] 4.5 g (21% yield) of decane was obtained.
Sodium hydroxide was added to a mixed solution of 4.5 g (15.8 mmol) of 4,8-bis (acetylthio) tricyclo [5.2.1.0 ^2,6 ] decane obtained, 20 ml of ethanol and 20 ml of water. 2.53 g (63.2 mmol) was added and reacted at 60 ° C. for 3 hours. The reaction mixture was poured into aqueous hydrochloric acid and extracted with hexane. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (filled with silica gel). Purification is carried out by eluting with hexane for a while and then eluting with hexane / ethyl acetate = 10/1 (volume ratio), and 4,8-dimercaptocyclo [5.2.1.0 ^2,6 ] decane. 1.4 g (45% yield) was obtained.
The measurement result of 4,8-dimercaptotricyclo [5.2.1.0 ^2,6 ] decane by MS (mass spectrum) is 200 (M +), refractive index (nd) is 1.58, Abbe number ( νd) was 46.

Reference example 1
2,2.8 g (0.10 mmol) of 4,8-bis (mercaptomethyl) tricyclo [5.2.1.0 ^2,6 ] decane obtained in Example 1 and 18.8 g of m-xylylene diisocyanate. (0.10 mmol), 0.05 g of dibutyltin dichloride, and 0.05 g of dioctyl phosphoric acid were mixed to form a homogeneous solution, defoamed at room temperature under reduced pressure, and then subjected to a mold release treatment. And poured into a mold comprising a gasket. Subsequently, it was heat-cured over 20 hours, gradually heating up to 40-120 degreeC. After completion of the polymerization, the mixture was gradually cooled, and the sulfur-containing polymer was taken out from the mold.
The obtained sulfur-containing polymer had a refractive index (nd) of 1.59 and an Abbe number (νd) of 38.

Claims (8)

It has a norbornane skeleton and has the following general formula (I)
HS-G ¹ -SH (I)
(In the formula, G ¹ represents an alicyclic hydrocarbon group having 3 or more ring structures, and the ring structure may contain an atom selected from a sulfur atom and an oxygen atom.)
An alicyclic dithiol represented by G ¹ in the above general formula (I) is the following general formula (II)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO ₂ , and n is 0, 1 or 2.)
Or the following general formula (III)

(In the formula, A is the same as above. R is independently a hydrogen atom, a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms, and when R is an alkyl group, adjacent Rs may be bonded to each other, and G ² represents an oxygen atom, a sulfur atom, SO, SO _{2. , -OCH 2 O -, - OCH} 2 CH 2 O -, - OCH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 SCH 2 CH 2 O -, - _{SCH 2 S -, - SCH 2} CH 2 S -, - SCH 2 CH 2 CH indicates ₂ S- a .i, j, k and l is 0, 1 or 2, when R is not bound to each other I + j ≧ 1 and n is 0, 1 or 2.)
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: G ¹ in the above general formula (I) is the following general formula (IV)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO _2. N is 0, 1 or 2, n ′ is an integer of 0 to 5, and n + n ′ <6.)
The following general formula (V)

(In the formula, A is the same as above. R is independently a hydrogen atom, a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms, and when R is an alkyl group, adjacent Rs may be bonded to each other, and G ² represents an oxygen atom, a sulfur atom, SO, SO _{2. , -OCH 2 O -, - OCH} 2 CH 2 O -, - OCH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 SCH 2 CH 2 O -, - _{SCH 2 S -, - SCH 2} CH 2 S -, - SCH 2 CH 2 CH indicates ₂ S- a .i, j, k and l is 0, 1 or 2, when R is not bound to each other I + j ≧ 1 and p and p ′ are integers of 0 to 4.)
The following general formula (VI)

(In the formula, A and R are the same as described above. G ³ has one or more ring structures, and 1 to 6 oxygen atoms, 1 to 6 sulfur atoms, and 1 Represents a structure having 3 to 24 carbon atoms, which may contain a group selected from ˜4 carbonyl groups, i, j, k and l are 0, 1 or 2, and R is bonded to each other; Otherwise, i + j ≧ 1 and p and p ′ are integers from 0 to 4.)
The following general formula (VII)

(In the formula, A is the same as described above, and p and p ′ are integers of 0 to 4.)
Or the following general formula (VIII)

(In the formula, A is the same as described above. I and j are 0, 1 or 2, and p and p ′ are integers of 0 to 4.)
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: G ¹ in the above general formula (I) is the following general formula (IV)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO _2. N is 0, 1 or 2, n ′ is an integer of 0 to 5, and n + n ′ <6.)
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: G ¹ in the general formula (I) is the following general formula (V)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO _2. R independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, 6 alkoxy group, an alkyl group having 1 to 6 alkylthio group carbon atoms or 1 to 6 carbon atoms, when said R is an alkyl group, the adjacent R are optionally bound to one another .G ² is oxygen atom, a sulfur _{atom, SO, SO 2, -OCH 2} O -, - OCH 2 CH 2 O -, - OCH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 CH 2 O -, - OCH 2 _{CH 2 SCH 2 CH 2 O -} , - SCH 2 S -, - SCH 2 CH 2 S -, - SCH 2 CH 2 CH 2 S- shown .i, j, k and l are 0, 1 or 2 Yes, when R is not bonded to each other, i + j ≧ 1, p and p ′ are integers from 0 to 4 )
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: G ¹ in the above general formula (I) is the following general formula (VI)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO _2. R independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, 6 alkoxy group, an alkyl group having 1 to 6 alkylthio group carbon atoms or 1 to 6 carbon atoms, when said R is an alkyl group, the adjacent R are optionally bound to one another .G ³ is Having 3 or more ring structures, the ring structure may contain a group selected from 1 to 6 oxygen atoms, 1 to 6 sulfur atoms and 1 to 4 carbonyl groups; Represents a structure of ˜24, i, j, k and l are 0, 1 or 2, and when R is not bonded to each other, i + j ≧ 1, p and p ′ are integers of 0 to 4 .)
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: G ¹ in the above general formula (I) is the following general formula (VII)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO ₂ , and p and p ′ are integers of 0 to 4.)
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: G ¹ in the above general formula (I) is the following general formula (VIII)

(In the formula, A represents a single bond, an oxygen atom, a sulfur atom, SO or SO ₂ , i and j are 0, 1 or 2, and p and p ′ are integers of 0 to 4.)
The alicyclic dithiol according to claim 1, which is an alicyclic hydrocarbon group represented by the formula: