JPH10330352A - Thioanisole derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having a high refractive index, being a monomer suitable for synthesizing a resin with a small specific gravity, and capable of providing an optical material, a coating material, etc., having excellent physical properties. SOLUTION: This compound is a thioanisole derivative of formula I [(n) is an integer of 0-2], e.g. 2,4-bis(4-mercapto-2-thiabutyl)thioanisole, etc. For example, to obtain the compound of formula I, a 2,4-bis(halogenomethyl) thioanisole of formula II (X<1> and X<2> are each Cl, Br, or I) is reacted with a dithiol of formula III [(m) is an integer of 1 or 2] in the presence of a base. To obtain the 2,4-bis(halogenomethyl)thioanisole of formula II, for example, a formaldehyde derivative and an inorganic halogenated compound are reacted with the thioanisole in a fatty acid solvent in the presence of a mineral acid in the method for producing the thioanisole derivative. By using the compound, a hardened material having a high refractive index and excellent transparency can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thioanisole derivative and a method for producing the same, and 2,4-bis (halogenomethyl) thioanisole as an intermediate for producing the thioanisole derivative and a method for producing the same. More specifically, optical materials such as plastic lenses for glasses, Fresnel lenses, lenticular lenses, optical disk substrates, plastic optical fibers, prism sheets for LCDs, light guide plates, diffusion sheets, and raw materials for polymerization such as paints, adhesives, and encapsulants. And a particularly useful thioanisole derivative as a raw material (monomer) for polymerization of an optical material, a method for producing the same, an intermediate for producing the thioanisole derivative, and a method for producing the same.

[0002]

2. Description of the Related Art Resins for organic optical materials have been widely used in recent years as various materials because they are lighter in weight and easier to handle than glass and the like. Desirable characteristics of the resin for optical materials include high refractive index, low birefringence, low specific gravity, etc., and various attempts have been made for the purpose of producing a resin raw material having such characteristics.

As such resins for organic optical materials, polystyrene resins, polymethylmethacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate resins, etc. have been widely used.

However, such conventional resins for organic optical materials have drawbacks such as a low refractive index, a large birefringence and a high dispersibility, and are inferior in heat resistance and impact resistance, so that they are not always satisfactory. It wasn't something.

[0005] Particularly, diethylene glycol diallyl carbonate resin (CR-
39) and the like have the drawback that when used as a lens, the refractive index is as low as 1.50, so that the edge thickness and the center thickness become large, the appearance of the lens becomes poor, and the weight increases. .

[0006] In order to solve these drawbacks, various methods for mainly improving the refractive index have been studied. Examples of the method include a method of introducing a halogen atom into an aromatic ring in a resin raw material and a method of increasing the content of a sulfur atom having a high atomic refractive index in a monomer molecule of the resin raw material.

For example, Japanese Patent Publication No. 5-4404 discloses that
A resin having a halogen introduced into an aromatic ring is disclosed. However, although the resin obtained by this technique has a high refractive index of 1.60, it has a high specific gravity of 1.37,
It was not satisfactory in terms of the lightness of the lens, which is a characteristic of plastic lenses.

[0008] JP-A-2-270859 and JP-A-5-208950 disclose a method of increasing the content of sulfur atoms in monomer molecules of a resin material for the purpose of increasing the refractive index of a resin. Has been done. Here, a mercapto compound is generally used to increase the content of sulfur atoms. As the mercapto compound, for example, low-molecular-weight mercapto compounds such as methanethiol, ethanethiol, and ethanediol are widely known. However, these low-molecular-weight mercapto compounds have a peculiar odor based on the mercapto compound, and the use amount thereof is limited due to the composition ratio with other resin raw materials used for curing the resin. There is.

Therefore, instead of the low molecular weight mercapto compound, a polyfunctional compound having a large molecular weight used as an epoxy resin curing agent such as trimethylolpropane tris- (thioglycolate) or pentaerythritol tetrakis- (thioglycolate). The use of neutral mercapto compounds is contemplated. However, this type of mercapto compound has the advantage of low odor due to its high molecular weight and good handleability.However, since the content of sulfur atoms in the molecule is low, the content of sulfur atoms in the resin is reduced. There is a disadvantage that it is difficult to obtain a desired refractive index by increasing it ideally.

Further, Japanese Patent Publication No. 4-15249 and Japanese Patent Application Laid-Open No. 60-199016 disclose a technique for obtaining a resin by polymerization of an isocyanate compound and a polythiol. However, this resin also has a refractive index as large as 1.60, but has a specific gravity of 1.30 or more, a relatively low polymerization temperature, and a high polymerization rate, so that it is difficult to control heat during polymerization. There is a disadvantage that optical distortion is large.

[0011]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above-mentioned prior art, and produces a resin having desired characteristics of an optical material, that is, a resin having a high refractive index and a small specific gravity. To provide a thioanisole derivative, which is a suitable monomer. Another object of the present invention is to provide a method for producing the thioanisole derivative. Still another object of the present invention is to provide 2,4-bis (halogenomethyl) thioanisole which is a useful starting material for the thioanisole derivative. Still another object of the present invention is to provide a method for producing the 2,4-bis (halogenomethyl) thioanisole.

[0012]

That is, the present invention provides:
(1) General formula (I):

[0013]

[Chemical 10]

A thioanisole derivative represented by the formula (n represents an integer of 0 to 2), (2) the general formula (II):

[0015]

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Wherein X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom, and 2,4-bis (halogenomethyl) thioanisole represented by the general formula (III): HS (CH ₂ CH ₂ S) _m H (III) (wherein m represents an integer of 1 or 2), and reacted with a dithiol in the presence of a base, general formula (Ia):

[0017]

[Chemical 12]

(3) a process for producing a thioanisole derivative represented by the following formula: ## STR3 ##

[0019]

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(Wherein X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom) and 2,4-bis (halogenomethyl) thioanisole represented by the general formula (IV): HO (CH ₂ CH ₂ S) _m H (IV) (wherein m represents an integer of 1 or 2) is reacted in the presence of a base, and then thiourea is reacted in the presence of a mineral acid. A general formula (Ia) characterized by being hydrolyzed after being converted to an isothiuronium salt:

[0021]

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(4) a method for producing a thioanisole derivative represented by the following formula: ## STR4 ## (4) a general formula (II):

[0023]

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After the reaction of 2,4-bis (halogenomethyl) thioanisole represented by the formula (wherein X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom) with thiourea to give an isothiuronium salt Formula (Ib), characterized by being hydrolyzed:

[0025]

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A process for producing 2,4-bis (mercaptomethyl) thioanisole represented by

(5) General formula (IIa):

[0028]

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(In the formula, Y ¹ and Y ² represent a chlorine atom, a bromine atom or an iodine atom, except when both Y ¹ and Y ² are chlorine atoms.) 2,4-bis (halogeno) (Methyl) thioanisole, (6) Thioanisole is reacted with a formaldehyde derivative and an inorganic halogen compound in the presence of a mineral acid in a fatty acid solvent, represented by the general formula (II):

[0030]

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A method for producing 2,4-bis (halogenomethyl) thioanisole represented by the formula: wherein X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom, (7)
The production method according to (6) above, wherein the formaldehyde derivative is paraformaldehyde, trioxane or dimethoxymethane, (8) the inorganic halogen compound is sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide. (6) or (7), which is at least one member selected from the group consisting of
(9) The method according to the above (6), wherein the mineral acid is sulfuric acid.
(10) The method according to any one of (8) to (8), wherein the fatty acid is a lower fatty acid having 2 to 4 carbon atoms.
The production method according to any one of (9), (11) the production method according to (10) above, wherein the lower fatty acid is acetic acid.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The thioanisole derivative of the present invention has the general formula (I):

[0033]

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(Wherein n represents an integer of 0 to 2), and when n is 3 or more, synthesis is difficult. In the present invention, n is preferably in the range of 0 to 2 in terms of the refractive index, specific gravity, and the like.

The thioanisole derivative represented by the general formula (I) of the present invention can be suitably produced by the production method of the present invention described below, but the present invention is limited only by such a production method. Not a thing. Here, in the production method of the present invention, the first aspect and the second aspect are exemplified for the compound in which n is 1 or 2, and the third aspect is exemplified for the compound in which n is 0. Hereinafter, the production method of the present invention will be described in detail.

(1) First, the first embodiment will be described.

Among the thioanisole derivatives represented by the general formula (I) of the present invention, compounds in which n is 1 or 2 (general formula (Ia)
Can be synthesized by the following reaction scheme, for example.

[0038]

[Chemical 20]

(In the formula, X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom. M represents an integer of 1 or 2. In formula (Ia), two m's may be the same or different. That is, 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II) and the general formula (III)
The desired thioanisole derivative represented by the general formula (Ia) can be obtained by reacting with a dithiol represented by the formula (1) in the presence of a base. Here, X ¹ and X ² in the general formula (II) may be the same or different.
This point is the same in the following second and third embodiments.

Examples of the dithiol represented by the general formula (III) include 1,2-ethanedithiol, bis (2-mercaptoethyl) sulfide and the like.
The molar ratio to 2,4-bis (halogenomethyl) thioanisole of (II) is usually 3 to 30 times, preferably 6 to 2 times.
It is 0 times. When the molar ratio of the used amount is less than 3 times, the oligomer component tends to be by-produced, which is not preferable. Use of more than 30 times is not preferable because the effect corresponding thereto cannot be obtained and it is not economical.

Examples of the base that can be used include tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, Metal carbonates such as potassium carbonate, and metal alcoholates such as sodium methylate, sodium ethylate and potassium tert-butylate are exemplified. The amount of the base used is usually 2 in an equivalent ratio to 2,4-bis (halogenomethyl) thioanisole of the general formula (II).
˜5 times, preferably 2-3 times. 2 bases used
If it is less than twice, the yield is lowered, and even if it is used more than five times, the effect commensurate with it is not obtained and it is not economical.

The reaction temperature is -20 to 150 ° C, preferably -10 to 100 ° C. When the reaction temperature exceeds 150 ° C., byproducts increase, which not only decreases the yield of the desired thioanisole derivative represented by the general formula (Ia) but also increases the degree of coloring, which is not preferable. The reaction temperature is -20.
If the temperature is lower than 0 ° C., the reaction rate is undesirably reduced.

Further, in this reaction, an excess of dithiol also serves as a reaction solvent, but an organic solvent may be used, and usable organic solvents include hydrocarbons such as toluene, xylene, hexane and cyclohexane, and methylene chloride. , Halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, monochlorobenzene, and o-dichlorobenzene. In this case, good results are often obtained when a quaternary ammonium salt such as tetra-n-butylammonium bromide is used as the phase transfer catalyst.

The thioanisole derivative represented by the general formula (Ia) thus obtained can be isolated and purified by a conventional method such as column chromatography.

(2) Next, the second embodiment will be described.
The second embodiment is represented by the following reaction scheme.

[0046]

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(In the formula, X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom. M represents an integer of 1 or 2. Further, in the general formulas (Ia), (V) and (VI), 2
M may be the same or different. A represents an anion portion of a salt formed by a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid. ) That is, 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II) and the general formula (IV)
Is reacted with a mercapto alcohol represented by the following in the presence of a base, and then is reacted with thiourea in the presence of a mineral acid to give an isothiuronium salt, and then hydrolyzed to give the desired general formula (Ia). The thioanisole derivative represented can be obtained. Here, the base has the general formula (IV)
The salt may be present in the form of a salt with the mercapto alcohol represented by

First, 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II) is reacted with mercapto alcohol represented by the general formula (IV) in the presence of a base, The compound represented by (V) is obtained. Here, examples of the mercapto alcohol represented by the general formula (IV) include 2-mercaptoethanol and 2- (2-mercaptoethylthio) ethanol, and the amount used is represented by the general formula (II). 2,4-bis (halogenomethyl) thioanisole, usually 2 to 5 times in molar ratio,
It is preferably 2-3 times. If it is less than twice, the amount of unreacted raw materials increases and the yield decreases. Further, even if it is used more than 5 times, the effect corresponding to it cannot be obtained and it is not economical.

Examples of the base that can be used include the tertiary amine, metal hydroxide, metal carbonate, metal alcoholate and the like used in the first embodiment. The amount of the base used is usually 2 to 5 times, preferably 2 to 3 times, in terms of an equivalent ratio to 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II). If it is less than 2 times, the yield will be low, and if it is used more than 5 times, the effect corresponding to it will not be obtained and it will not be economical.

The reaction temperature is -20 to 150 ° C, preferably -10 to 100 ° C. When the reaction temperature exceeds 150 ° C., by-products increase, and not only the yield of the target thioanisole derivative represented by the general formula (Ia) decreases, but also the degree of coloring increases. On the other hand, when the temperature is lower than -20 ° C, the reaction rate is undesirably reduced.

Further, as the organic solvent which can be used at that time, the hydrocarbons and halogenated hydrocarbons described in the first embodiment can be similarly mentioned. As the phase transfer catalyst, for example, a quaternary ammonium salt such as tetra-n-butylammonium bromide can be used. The resulting compound of the general formula (V) may be subjected to the next step as it is, or the reaction solution may be subjected to the next step after isolation and purification by column chromatography or the like.

Next, the compound represented by the general formula (V) is reacted with thiourea in the presence of a mineral acid to obtain an isothiuronium salt represented by the general formula (VI). The amount of thiourea used in the production of the isothiuronium salt is usually 2 to 8 times, preferably 2 to 6 times the molar ratio of 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II). It is twice. If the amount used is less than twice, the amount of unreacted raw materials increases and the yield decreases. Further, even if it is used more than 8 times, the effect corresponding to it is not obtained and it is not economical. At this time, examples of the mineral acid that can be used include hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid and the like, and the amount used is 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II). The equivalent ratio is 2 to 12 times, preferably 2 to 8 times.
If it is less than twice, the reaction does not proceed completely and the yield decreases.
Further, even if it is used more than 12 times, the effect corresponding to it cannot be obtained and it is not economical. The reaction temperature in the production of isothiuronium salt is 20 to 120 ° C, preferably 40 to 110 ° C.
It is. When the reaction temperature is lower than 20 ° C., the reaction rate becomes slow. When the reaction temperature exceeds 120 ° C., by-products increase, which is not preferable.

Further, as the organic solvent which can be used at that time, the hydrocarbons and halogenated hydrocarbons described in the first embodiment are similarly mentioned. As for the obtained isothiuronium salt represented by the general formula (VI), the reaction solution may be usually subjected to the next step as it is.

Next, the desired thioanisole derivative represented by the general formula (Ia) is obtained by hydrolyzing the isothiuronium salt represented by the general formula (VI). Hydrolysis is usually performed in the presence of a base. Examples of the base used include the tertiary amine, metal hydroxide, and tertiary amine described in the first embodiment.
In addition to metal carbonates and metal alcoholates, primary amines such as ammonia, monomethylamine, monoethylamine and monobutylamine, and secondary amines such as dimethylamine, diethylamine and dibutylamine can also be mentioned. The amount of the base used is usually 2 in an equivalent ratio to 2,4-bis (halogenomethyl) thioanisole represented by the above general formula (II).
-12 times, preferably 2-8 times. When the equivalent ratio is less than twice, the reaction does not proceed completely and the yield decreases. Moreover, even if it is used more than 12 times, the effect corresponding to it cannot be obtained and it is not economical. The reaction temperature is from 20 to 120C, preferably from 30 to 110C. When the reaction temperature is lower than 20 ° C,
If the reaction rate is slow and exceeds 120 ° C., the amount of by-products increases and the degree of coloring increases, which is not preferable.

The thioanisole derivative represented by the general formula (Ia) thus obtained can be isolated and purified by a conventional method in the same manner as described in the first embodiment.

(3) Next, the third mode will be described.

Among the thioanisole derivatives represented by the general formula (I) of the present invention, 2,4-bis (mercaptomethyl) thioanisole represented by the formula (Ib) which is a compound in which n is 0 is synthesized. The following reaction scheme can be given as an example of the method.

[0058]

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That is, 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II) is reacted with thiourea to give an isothiuronium salt represented by the general formula (VII), and then hydrolyzed. 2,4-bis (mercaptomethyl) represented by the desired formula (Ib)
Thioanisole can be obtained.

The amount of the thiourea used for producing the isothiuronium salt represented by the general formula (VII) is 2,4-bis (halogenomethyl) represented by the general formula (II).
It is usually 2 to 8 times, preferably 2 to 6 times, the molar ratio to thioanisole. When the molar ratio is less than 2 times, the reaction does not proceed completely and the yield decreases. Further, even if it is used more than 8 times, the effect corresponding to it is not obtained and it is not economical.

The reaction temperature for producing the isothiuronium salt represented by the general formula (VII) is from 20 to 120 ° C., preferably from 40 to 110 ° C. When the reaction temperature is lower than 20 ° C, the reaction rate becomes slow, and when it exceeds 120 ° C, the amount of by-products increases and the degree of coloring increases, which is not preferable.

The organic solvents usable in this reaction include the hydrocarbons and halogenated hydrocarbons described in the first embodiment. The reaction can also be carried out using water as a solvent. The obtained compound of the general formula (VII) may be usually subjected to the next step as it is as a reaction solution.

Hydrolysis of the isothiuronium salt represented by the general formula (VII) is usually carried out in the presence of a base. Examples of the base used include tertiary amines, metal hydroxides, metal carbonates, metal alcoholates, primary amines and secondary amines as in the case of the second embodiment. The amount of the base used is usually 2 to 12 times, preferably 2 to 8 times the equivalent ratio of 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II). If the equivalence ratio is less than 2 times, the yield will decrease, and even if it is used in excess of 12 times,
It is not economical because there is no corresponding effect. The reaction temperature is 20 to 120 ° C, preferably 30 to 110 ° C. When the reaction temperature is lower than 20 ° C., the reaction rate decreases,
If the temperature exceeds ℃, the amount of by-products and the degree of coloring increase, which is not preferable.

The organic solvents usable in this reaction include the hydrocarbons and halogenated hydrocarbons described in the first embodiment.

The 2,4-bis (mercaptomethyl) thioanisole represented by the formula (Ib) thus obtained is isolated and purified by a conventional method in the same manner as described in the first embodiment. You can

The 2,4-bis (halogenomethyl) thioanisole represented by the general formula (II) used in the first to third embodiments is represented by the general formula (I) of the present invention. It is a compound useful as a starting material for producing a thioanisole derivative. In addition, among the compounds represented by the general formula (II), a compound excluding a compound in which X ¹ and X ² are both chlorine atoms, that is, a compound represented by the general formula (IIa) is a novel compound. . Therefore, the present invention also provides such a compound represented by the general formula (IIa).

2, represented by the general formula (II) of the present invention.
4-Bis (halogenomethyl) thioanisole can be produced by reacting thioanisole with a formaldehyde derivative and an inorganic halogen compound in a fatty acid solvent in the presence of a mineral acid.

Examples of the formaldehyde derivative used in the present invention include paraformaldehyde, trioxane, dimethoxymethane, diethoxymethane and the like, with paraformaldehyde, trioxane and dimethoxymethane being particularly preferred. The amount of the formaldehyde derivative used is usually 1.6 to 3.2 times mol, preferably 1.8 to 2.
It is 5 times mol. When the amount of formaldehyde derivative used is less than 1.6 times by mole, the amount of monohalogenomethyl compound increases and the yield decreases, and when it is more than 3.2 times by mole, the amount of trihalogenomethyl compound increases and the yield decreases. To do.

Examples of the inorganic halogen compound used in the present invention include sodium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, ammonium bromide, sodium iodide, potassium iodide and ammonium iodide. Is preferably sodium chloride,
Potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide. The amount of the inorganic halogen compound to be used is usually 1.7 to thioanisole.
It is 6.0 times mol, preferably 1.9 to 4.0 times mol. If the amount of the inorganic halogen compound used is less than 1.7 moles, the amount of by-products such as monohalogenomethyl is increased and the yield is reduced. If the amount is more than 6.0 moles, the yield is commensurate. The rate cannot be improved and it is not economical.

Mineral acids used in the present invention include sulfuric acid,
Nitric acid and the like can be mentioned, but sulfuric acid is preferable. The amount of mineral acid used is usually 1.0 to 20.0 times the equivalent amount of thioanisole,
The equivalent amount is preferably 1.5 to 14.0 times. If the amount of the mineral acid used is less than 1.0 equivalent, the reaction is not completed and the yield decreases, and if it is more than 20.0 equivalent, the corresponding improvement in yield cannot be expected and it is not economical.

Examples of the fatty acid used as the solvent in the present invention include lower fatty acids having 2 to 4 carbon atoms such as acetic acid, propionic acid, isobutyric acid and butyric acid, with acetic acid being preferred. The amount of fatty acid used is usually 1 to 15 parts by weight, preferably 1.2 to 10 parts by weight, based on 1 part by weight of thioanisole. When the amount of the fatty acid used is less than 1 part by weight, stirring becomes difficult, and even if it is more than 15 parts by weight, the corresponding improvement in yield cannot be expected and it is not economical.

The reaction temperature is 10 to 120 ° C., preferably 3
0-110 ° C. If the reaction temperature is lower than 10 ° C., the progress of the reaction is slow, and by-products are also generated.

The reaction time is 1 to 15 hours, preferably 2 to
12 hours. If the reaction time is shorter than 1 hour, the reaction is not completed, and if it is longer than 15 hours, it is not economical.

The above-mentioned general formula (II) thus obtained
The 2,4-bis (halogenomethyl) thioanisole represented by is extracted using an organic solvent such as toluene and methylene chloride, and then can be separated and purified through steps such as water washing and concentration. Further, it can be purified by column chromatography if necessary.

The thioanisole derivative of the present invention represented by the general formula (I) can be copolymerized to obtain a polymer used for an optical material, a paint, an adhesive, a sealing material, and the like.

In the present invention, the compound copolymerizable with the thioanisole derivative represented by the general formula (I) includes:
For example, a monomer having a polymerizable unsaturated bond, an oligomer having a polymerizable unsaturated bond, a monomer having an epoxy group, an oligomer having an epoxy group, a monomer having an isocyanate group, a monomer having an isothiocyanate group, and having a thioglycidyl group Examples thereof include monomers and oligomers having a thioglycidyl group. Depending on the purpose of use, not only monofunctional compounds but also polyfunctional compounds can be selected, and two or more of these compounds can be used in combination.

The composition containing the thioanisole derivative of the present invention represented by the above general formula (I) and a compound copolymerizable with the thioanisole derivative is prepared by an ordinary method.
It can be copolymerized by heat, light or the like. Further, a monomer or oligomer having a thiol group other than the thioanisole derivative represented by the general formula (I) can be added to these copolymer compositions.

Since the thioanisole derivative of the present invention represented by the general formula (I) has a refractive index of 1.60 or more, a cured product obtained by copolymerizing the composition is a monomer of the other party. A material having a high refractive index of 1.60 or more can be obtained by appropriately selecting

Further, the thiol group of the thioanisole derivative of the present invention represented by the above general formula (I) utilizes its high reactivity, for example, an acryloylthio group, a methacryloylthio group, a vinylthio group, a glycidylthio group. It can also be converted into a thioglycidylthio group or the like.

[0080]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 Production Example of 2,4-bis (bromomethyl) thioanisole 24.8 g of thioanisole was placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser.
(0.2 mol), 53.5 g (0.52 g) of sodium bromide
Mol), 13.1 g (0.2%) of 92% paraformaldehyde.
4 mol), 100 g of acetic acid, and then 77.6 g (0.76 mol) of 96% sulfuric acid at a reaction temperature of 80 to 85 ° C.
The solution was added dropwise over 1 hour while maintaining the above. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Then, water 120 was added to the reaction solution.
g, and extracted with 200 g of toluene, and separated into an organic layer and an aqueous layer. The obtained organic layer was washed twice with 120 g of water and then concentrated to obtain 59.5 g of a crude product. The crude product was purified by silica gel column chromatography to obtain a colorless transparent liquid.

Analysis was performed to determine the structure of this compound. The results are shown below.

Elemental analysis Theoretical value (%) C: 34.86, H: 3.25, S: 1
0.34 analytical value (%) C: 34.95, H: 3.35, S: 1
0.20 infrared absorption spectrum (NaClcm ^-1 ) 3018, 29
66, 2919, 2854, 2360, 2337, 16
00, 1477, 1434, 1234, 1211, 10
56, 972, 954, 898, 817, 746, 72
9 ¹ H- nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
(Reference) δ (ppm) 7.62 to 6.90 (m, 3H, -C ₆ H _3- ) 4.61 (S, 2H, 2-CH ₂ Br) 4.45 (S, 2H, 4- _{C H 2 Br) 2.51 (S} , 3H, SCH 3) molecular weight 310.0

From the above analysis results, the colorless transparent liquid was 2,4
-Identified as bis (bromomethyl) thioanisole.
The yield was 49.6 g, and the yield was 80% based on the raw material thioanisole.

Example 2 Production Example of 2,4-bis (4-mercapto-2-thiabutyl) thioanisole (Compound of the general formula (I) in which n = 1) (first embodiment) Stirrer, thermometer, 2,4-bis (bromomethyl) thioanisole 62 obtained in the same manner as in Example 1 was placed in a 1-liter four-necked flask equipped with a dropping funnel and a condenser.
g (0.2 mol), 1,2-ethanedithiol 282.
5 g (3.0 mol) and tetra-n-butylammonium bromide 3.2 g (0.01 mol) were charged, and then 2 hours were taken over 1.5 hours while maintaining the reaction temperature at 0 to 10 ° C.
96 g (0.48 mol) of 0% aqueous sodium hydroxide solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 20 to 25 ° C for 3 hours. After completion of the reaction, 20 g of 36% hydrochloric acid and 40
g was added to separate the organic layer and the aqueous layer. After the obtained organic layer was washed twice with 200 g of water, 1,2-ethanedithiol was distilled off to obtain 65.3 g of a concentrate. This concentrate was purified by column chromatography to obtain a colorless transparent liquid.

An analysis was performed to determine the structure of this compound. The results are shown below.

Refractive index (20 ° C.) n _D = 1.668 Elemental analysis Theoretical value (%) C: 46.38, H: 5.99, S: 4
7.63 Analytical value (%) C: 46.45, H: 6.05, S: 4
7.51 Infrared absorption spectrum (NaClcm ^-1 ) 2915, 28
44, 2543, 2349, 2283, 1596, 14
73, 1427, 1270, 1238, 1207, 11
37, 1053, 970, 819 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
Reference) δ (ppm) 7.34~7.08 (m , 3H, -C 6 H 3 -) 3.85 (S, 2H, 2-C 6 H 3 -C H 2 S) 3.70 (S _{, 2H, 4-C 6 H} 3 -C H 2 S) 2.78~2.64 (m, 8H, SC 2 H 4 S) 2.48 (S, 3H, SCH 3) 1.75~1. 63 (m, 2H, S H ) molecular weight 336.6

The refractive index was measured using an Abbe refractometer type 4T manufactured by Atago. The same applies to the following examples.

From the above analysis results, it was found that the colorless and transparent liquid was 2, 4
-Bis (4-mercapto-2-thiabutyl) thioanisole. The yield was 61.9 g, and the yield was 92% based on 2,4-bis (bromomethyl) thioanisole as a raw material.

Example 3 Production Example of 2,4-bis (4-mercapto-2-thiabutyl) thioanisole (n = 1 compound of general formula (I)) (second embodiment) Stirrer, thermometer, 2,4-bis (bromomethyl) thioanisole 62 obtained in the same manner as in Example 1 was placed in a 1-liter four-necked flask equipped with a dropping funnel and a condenser.
g (0.2 mol), 2-mercaptoethanol 35.9
g (0.46 mol), 3.2 g (0.01 mol) of tetra-n-butylammonium bromide, 200 ml of toluene
g, and then, while maintaining the reaction temperature at 20 to 40 ° C., a 20% aqueous sodium hydroxide solution 96 over 1.5 hours.
g (0.48 mol) was added dropwise. After completion of dropping, the mixture was further stirred at the same temperature for 1 hour, and then 93.2 g of 36% hydrochloric acid (0.92
Mol) and 52.5 g (0.69 mol) of thiourea were sequentially added, the temperature was raised to 88 ° C, and the mixture was stirred at 88 to 90 ° C for 6 hours. After cooling to room temperature, 92 g (0.92 mol) of 40% aqueous sodium hydroxide solution was added dropwise over 15 minutes while maintaining the reaction temperature at 50 ° C. or lower, and further at 60 to 65 ° C. for 1.
Stir for 5 hours. After the reaction is completed, 36% hydrochloric acid 30 is added to the reaction solution.
After adding g, the mixture was separated into an organic layer and an aqueous layer. After the obtained organic layer was washed twice with 200 g of water, toluene was distilled off to obtain 63.3 g of a concentrate. The concentrate was purified by column chromatography to give a colorless transparent liquid.

Analysis was performed to determine the structure of this compound, and the same analysis results as in Example 2 were obtained.

From the above analysis results, the colorless transparent liquid was 2,
4-bis (4-mercapto-2-thiabutyl) thioanisole. The yield was 60.6 g, and the yield was 90% based on the raw material 2,4-bis (bromomethyl) thioanisole.

Example 4 Example of Production of 2,4-bis (7-mercapto-2,5-dithiaheptyl) thioanisole (Compound of General Formula (I) wherein n = 2) (First Embodiment) In Example 2, , 1,2-ethanedithiol 282.
The reaction and purification were performed in the same manner as in Example 2 except that 462.9 g (3.0 mol) of bis (2-mercaptoethyl) sulfide was used instead of 5 g (3.0 mol), and a colorless transparent liquid was obtained. .

Analysis was performed to determine the structure of this compound. The results are shown below.

Refractive index (20 ° C.) n _D = 1.663 Elemental analysis Theoretical value (%) C: 44.69, H: 6.18, S: 4
9.13 Analytical value (%) C: 44.55, H: 6.15, S: 4
9.25 Infrared absorption spectrum (NaCl cm ^-1 ) 2916, 28
48, 2539, 2360, 2339, 1473, 14
19, 1265, 1197, 1053 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
Reference) δ (ppm) 7.37~7.09 (m , 3H, -C 6 H 3 -) 3.87 (S, 2H, 2-C 6 H 3 -C H 2 S) 3.71 (S _{, 2H, 4-C 6 H} 3 -C H 2 S) 2.87~2.59 (m, 16H, SC 2 H 4 SC 2 H
_{4 S) 2.49 (S, 3H} , SCH 3) 1.73~1.64 (m, 2H, S H) molecular weight 456.9

From the above analysis results, it was found that the colorless transparent liquid was 2,4
-Bis (7-mercapto-2,5-dithiaheptyl) thioanisole. The yield is 85.0 g,
The yield was 93% based on the raw material 2,4-bis (bromomethyl) thioanisole.

Example 5 2,4-bis (7-mercapto-2,5-dithiaheptyl) thioanisole (n = 2 compound of the formula (I))
Production Example (Second Aspect) In Example 3, 2-mercaptoethanol 35.9
The reaction and purification were carried out in the same manner as in Example 3 except that 63.6 g (0.46 mol) of 2- (2-mercaptoethylthio) ethanol was used instead of g (0.46 mol), and a colorless transparent liquid was obtained. Obtained.

Analysis was carried out to determine the structure of this compound, and the same analysis results as in Example 4 were obtained.

From the above analysis results, the colorless transparent liquid was 2,
4-bis (7-mercapto-2,5-dithiaheptyl)
Identified as thioanisole. The yield was 82.2 g, and the yield was 90% based on the starting material, 2,4-bis (bromomethyl) thioanisole.

Example 6 Production Example of 2,4-bis (mercaptomethyl) thioanisole (n = 0 compound of general formula (I)) (third embodiment) Stirrer, thermometer, dropping funnel, cooling tube In a 1-liter four-necked flask equipped with
3.0 g (0.3 mol), thiourea 57.1 g (0.7
5 mol), and 250 g of water.
The mixture was stirred for 10 hours while maintaining the temperature at 0 ° C. After completion of the reaction, the mixture was cooled to room temperature, 200 g of toluene was added, and then 66 g (0.66 mol) of 40% sodium hydroxide aqueous solution was added dropwise over 10 minutes while maintaining the reaction temperature at 20 to 30 ° C. After completion of the dropping, stirring was further continued for 2 hours while maintaining the reaction temperature at 60 to 65 ° C. After completion of the reaction, 25 g of 36% hydrochloric acid was added to the reaction solution, and the organic layer and the aqueous layer were separated. After the obtained organic layer was washed twice with 200 g of water, toluene was distilled off to obtain 58.4 g of a concentrate. This concentrate was purified by column chromatography to obtain a colorless transparent liquid. Analysis was performed to determine the structure of this compound. The results are shown below.

Refractive index (20 ° C.) n _D = 1.690 Elemental analysis Theoretical value (%) C: 49.96, H: 5.59, S: 4
4.46 Analysis value (%) C: 49.99, H: 5.50, S: 4
4.30 Infrared absorption spectrum (NaClcm ^-1 ) 2981, 29
17, 2850, 2553, 2360, 2339, 16
39, 1598, 1473, 1432, 1319, 12
45, 1166, 1056, 970, 894, 817,
734 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
Reference) δ (ppm) 7.23~7.07 (m , 3H, -C 6 H 3 -) 3.81 (d, J = 7.9Hz, 2H, 2-C 6 H 3 -
_{C H 2 S) 3.69 (d} , J = 7.5Hz, 2H, 4-C 6 H 3 -
C H ₂ S) 2.48 (S, 3H, SCH ₃ ) 2.02 (t, J = 7.9 Hz, 1H, 2-CH ₂ S
H ) 1.75 (t, J = 7.5 Hz, 1H, 4-CH ₂ S
H ) molecular weight 216.4

From the above analysis results, it was found that the colorless and transparent liquid was 2,4.
-Identified as bis (mercaptomethyl) thioanisole. The yield was 54.1 g, and the yield was 2,4 as the raw material.
-83% relative to bis (bromomethyl) thioanisole
Met.

[0103]

EFFECTS OF THE INVENTION The thioanisole derivative of the present invention can obtain a cured product having a high refractive index and excellent transparency by being copolymerized with various copolymerizable compounds.
Therefore, the thioanisole derivative of the present invention is an extremely useful monomer that provides optical materials, paints, adhesives, encapsulating materials and the like having excellent physical properties.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (72) Inventor Michio Suzuki 1 Sumitomo Seika Ltd. at 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Inside the company first research center

Claims (11)

[Claims] 1. A compound of the general formula (I): (In formula, n shows the integer of 0-2) The thioanisole derivative represented by these. 2. General formula (II): Wherein X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom, and 2,4-bis (halogenomethyl) thioanisole represented by the general formula (III): HS (CH ₂ CH ₂ S ) _m H (III) (formula which comprises reacting wherein the dithiol m is an integer of 1 or 2) in the presence of a base (Ia): ## STR3 ## (In the formula, m is the same as described above) A method for producing a thioanisole derivative. 3. General formula (II): Wherein X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom, and 2,4-bis (halogenomethyl) thioanisole represented by the general formula (IV): HO (CH ₂ CH ₂ S) ) _m H (IV) (wherein, m is 1 or a mercapto alcohol represented by 2 an integer of) in the presence of a base, followed by reacting thiourea in the presence of a mineral acid isothiouronium General formula (Ia) characterized in that it is converted into a salt and then hydrolyzed. (In the formula, m is the same as described above) A method for producing a thioanisole derivative. 4. A compound of the general formula (II): (Wherein, X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom), 2,4-bis (halogenomethyl) thioanisole is reacted with thiourea to give an isothiuronium salt, and then hydrolyzed. Formula (Ib) characterized by being decomposed: A method for producing 2,4-bis (mercaptomethyl) thioanisole represented by the formula: 5. A compound represented by the general formula (IIa): (Wherein, Y ¹ and Y ² represent a chlorine atom, a bromine atom or an iodine atom, except that both Y ¹ and Y ² are chlorine atoms) ) Thioanisole. 6. A general formula (II) characterized in that a thioanisole is reacted with a formaldehyde derivative and an inorganic halogen compound in a fatty acid solvent in the presence of a mineral acid. (In the formula, X ¹ and X ² represent a chlorine atom, a bromine atom or an iodine atom.) A method for producing 2,4-bis (halogenomethyl) thioanisole. 7. The method according to claim 6, wherein the formaldehyde derivative is paraformaldehyde, trioxane or dimethoxymethane. 8. The inorganic halogen compound according to claim 6, which is at least one selected from the group consisting of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, and potassium iodide. Production method. 9. The production method according to claim 6, wherein the mineral acid is sulfuric acid. 10. The method according to claim 6, wherein the fatty acid is a lower fatty acid having 2 to 4 carbon atoms. 11. The method according to claim 10, wherein the lower fatty acid is acetic acid.