JP5989464B2 - Sulfur-containing bicyclic compound, method for producing the same, and composition containing sulfur-containing bicyclic compound - Google Patents

Description

  The present invention relates to a sulfur-containing bicyclic compound, a method for producing the same, and a composition containing the sulfur-containing bicyclic compound.

  Transparent resins such as (meth) acrylic resins such as polymethylmethacrylate, polycarbonate resins, transparent epoxy resins, and transparent silicone resins are lighter than glass and have excellent processability. Widely used in transparent containers and transparent coating agents. Furthermore, in recent years, transparent resins are frequently used in the field of optical parts such as glasses, and in the field of electronic materials, antireflection coating agents for liquid crystal displays, transparent coating agents for solar cells, light emitting diodes, CCDs, CMOS sensors, etc. Transparent resins are being widely used for optical electronic materials such as light receiving parts.

  Among the above uses, particularly in the use of optical materials, a high refractive index may be required in order to improve light extraction efficiency and light collection in addition to transparency. With conventional transparent resins, it was possible to improve the mechanical properties to some extent by a technique such as crosslinking, but it was difficult to improve the optical properties, particularly the refractive index.

Patent Documents 1 and 2 disclose a method for improving the refractive index by bonding a large amount of heavy atoms such as bromine and sulfur to an organic resin.
The methods of Patent Documents 1 and 2 have a problem that various resins that have already been put into practical use and are inexpensive cannot be used because a resin including heavy atoms is used as a base resin. In addition, in the methods of Patent Documents 1 and 2, since the base resin is generally unstable with respect to heat and light, it is liable to cause deterioration such as discoloration when used for a long period of time. There is also concern about electrode corrosion.

Patent Documents 3 and 4 disclose a method for improving the refractive index by dispersing high refractive index inorganic oxide fine particles in an organic resin.
In the methods of Patent Documents 3 and 4, there is a problem in the long-term storage stability of the obtained fine particle dispersed resin, and a large amount of dispersion stabilizer is used to improve the dispersion stability of the inorganic oxide fine particles in the resin. Therefore, it is difficult to balance the refractive index and dispersion stability.

JP 05-164901 A JP 2005-350531 A JP 2007-27099 A JP 2007-308631 A

An object of the present invention is to provide a sulfur-containing polycyclic compound capable of expressing a high refractive index even when a known inexpensive resin is combined as a base resin.
Another object of the present invention is to provide a composition comprising a sulfur-containing polycyclic compound having a high refractive index and a high Abbe number.

According to the present invention, the following sulfur-containing polycyclic compounds and the like are provided.
1. A sulfur-containing polycyclic compound represented by the following formula (1).
(In the formula, each R ₁ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —R′—R _a . , At least one R ₁ is a group represented by —R′—R _a .
R _a is a hydrogen atom, a carboxyl group, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, two substituted or unsubstituted fats Or a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group. However, when R _a is a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group, R ′ is 1,3,5 , 7-Tetramethyl-2,4,6,8,9,10-bonds to the carbon atom constituting the methyl group of the hexathiaadamantyl group.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents two or more groups selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group, and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group. )
2. 2. The sulfur-containing polycyclic compound according to 1, which is represented by the following formula (2).
(R ₂ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _c , respectively. R ₂ is a group represented by —S—R _c .
R _c represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. It is. )
Of the 3.12 one of _{R 2,} 1 to 3 one of _{R 2} is a sulfur-containing-cyclic compounds according to 2 is a group represented by _{-S-R c,} respectively.
4). The sulfur-containing polycyclic compound according to 1, which is represented by the following formula (3).
(Wherein R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _e , respectively.
R _e is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. is there.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group. )
5. 2. The sulfur-containing bicyclic compound represented by the following formula (4):
(In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _d , respectively. At least one R ₃ is a group represented by —S—R _d .
R _d represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. It is. )
6). 2. The sulfur-containing polycyclic compound according to 1, which is represented by the following formula (5).
(Wherein R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _e , respectively.
R _e is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. is there.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats A group hydrocarbon group is bonded by an ester bond. )
7). The manufacturing method of the sulfur containing bicyclic compound which makes the compound represented by following formula (6) and the thiol compound represented by following formula (7) react on basic conditions.
(Wherein R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic carbon groups. A hydrogen group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats Group hydrocarbon group bonded by an ester bond.
n is an integer of 1 or 2. )
8). The manufacturing method of the sulfur containing bicyclic compound which makes the compound represented by following formula (6), and the thiol compound represented by following formula (8) react on basic conditions.
(Wherein R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic carbon groups. A hydrogen group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
R ″ represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a divalent group represented by —S—, or —S—. And a divalent group obtained by combining two or three groups selected from a substituted or unsubstituted divalent aliphatic hydrocarbon and a substituted or unsubstituted divalent aromatic hydrocarbon group. )
9. The manufacturing method of the sulfur containing bicyclic compound which makes the compound represented by following formula (9) and the thiol compound represented by following formula (7) react on basic conditions.
(Wherein R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic groups A hydrocarbon group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats Group hydrocarbon group bonded by an ester bond.
n is an integer of 1 or 2. )
10. A high refractive index material which is the sulfur-containing polycyclic compound according to any one of 10.1 to 6, or 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane .
11. Abbe number improving material which is the sulfur-containing bicyclic compound according to any one of 1 to 6 or 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane .
12. A composition comprising the sulfur-containing bicyclic compound according to any one of 1 to 6 or 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane.
13. An optical member comprising the composition according to 13.12.

According to the present invention, it is possible to provide a sulfur-containing polycyclic compound that can exhibit a high refractive index even when a known inexpensive resin is combined with a base resin.
According to the present invention, a composition containing a sulfur-containing polycyclic compound having a high refractive index and a high Abbe number can be provided.

2 is a diagram showing an LC-MS chart of the mixture obtained in Example 1. FIG. 3 is a diagram showing an LC-MS chart of a mixture obtained in Example 2. FIG. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 8. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 9. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 10. FIG. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 11. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 12. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 13. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained by the comparative example 1. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 14. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 15. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 16. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 17. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 18. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 19. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained by the comparative example 2. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 20. 6 is a graph showing the refractive index of the thin film obtained in Example 21 in the wavelength range of 200 nm to 1700 nm. FIG. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 22. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained by the comparative example 3. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 23. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 24. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained in Example 25. It is a figure which shows the refractive index in the wavelength range of 200 nm-1700 nm of the thin film obtained by the comparative example 4.

[Sulfur-containing polycyclic compounds]
The sulfur-containing bicyclic compound of the present invention is a compound represented by the following formula (1).
(In the formula, each R ₁ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —R′—R _a . , At least one R ₁ is a group represented by —R′—R _a .
R _a is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, two substituted or unsubstituted aliphatic hydrocarbons The group is a group bonded by an ester bond, or a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group. However, when R _a is a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group, R ′ is 1,3,5 , 7-Tetramethyl-2,4,6,8,9,10-bonds to the carbon atom constituting the methyl group of the hexathiaadamantyl group.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group. )

The sulfur-containing polycyclic compound of the present invention is a compound containing a 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane (TMHTA) structure, When a specific substituent is further bonded to the structure, optical properties (high refractive index and high Abbe number) higher than those of TMHTA can be exhibited.
In addition, 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane is a compound having the following structure.

  The sulfur-containing bicyclic compound represented by the formula (1) is preferably a sulfur-containing bicyclic compound represented by any of the following formulas (2) to (5).

The sulfur-containing bicyclic compound represented by the formula (2) is the following compound.
In the compound represented by the formula (2), more preferably, out of 12 R ₂ , 1 to 3 R ₂ are groups represented by —S—R _c , respectively.
(R ₂ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _c , respectively. R ₂ is a group represented by —S—R _c .
R _c represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. It is. )

The sulfur-containing polycyclic compound represented by the formula (3) is the following compound containing a dimer structure of TMHTA. In Formula (1), at least one R ₁ is a group represented by —R′—R _a , but in Formula (3), the dimer linking moiety and one TMHTA structure are —R′—R _a. Corresponds to the group represented by Accordingly, the limitation that “at least one R ₁ is represented by —R′—R _a ” in Formula (1) does not include Formula (3).
(Wherein R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _e , respectively.
R _e is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. is there.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group. )

The sulfur-containing polycyclic compound represented by the formula (4) is the following compound.
(R ₃ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _d , respectively. R ₃ is a group represented by —S—R _d .
R _d represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. It is. )

The sulfur-containing bicyclic compound represented by the formula (5) is the following compound.
(Wherein R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _e , respectively.
R _e is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. is there.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats Group hydrocarbon group bonded by an ester bond. )

Each substituent of the compounds of formulas (1) to (5) will be described.
Examples of the halogen atom for R ₁ , R ₂ , R ₃ and R ₄ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkali metal atoms of _Ra and A include a lithium atom, a sodium atom, a potassium atom, a rubidium atom, a cesium atom, and a francium atom.
Examples of the alkaline earth metal atoms of _Ra and A include a beryllium atom, a magnesium atom, a calcium atom, a strontium atom, a barium atom, and a radium atom.

The aliphatic hydrocarbon groups of R ₁ , R ₂ , R ₃ , R ₄ , R _a , R _c , R _d, R _e and A include a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.
Examples of the saturated aliphatic hydrocarbon group include an alkyl group, and examples of the unsaturated aliphatic hydrocarbon group include an alkenyl group.
Specific examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, isobutyl group, various pentyl groups, various hexyl groups, and various types. Heptyl, various octyl, various nonyl, various decyl, various undecyl, various dodecyl, various tridecyl, various tetradecyl, various pentadecyl, various hexadecyl, various heptadecyl, various octadecyl, neopentyl, Alkyl groups such as 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, 3-methylpentyl group; vinyl group, allyl group, propenyl group, various types Butenyl group, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups And an alkenyl group such as various tetradecenyl.
Carbon number of an aliphatic hydrocarbon group is 1-20, for example, Preferably it is 1-10, More preferably, it is 1-5.
Examples of the divalent aliphatic hydrocarbon group for R _b and R ″ include a divalent residue corresponding to the aliphatic hydrocarbon group.

Examples of the aromatic hydrocarbon group for R ₁ , R ₂ , R ₃ , R ₄ , R _a , R _c , R _d, R _e and A include an aryl group.
Specific examples of the aryl group include phenyl group, naphthyl group, anthracenyl group, naphthacenyl group, triphenylyl group, phenanthryl group, chrysenyl group, benzphenanthryl group, benzanthranyl group, pyrenyl group, fluorenyl group, indenyl group, acenaphthylenyl group. Fluoranthenyl group, perylenyl group and the like, and phenyl group and naphthyl group are preferable.
Examples of the divalent aromatic hydrocarbon group for R _b and R ″ include a divalent residue corresponding to the aromatic hydrocarbon group.

A group in which two substituted or unsubstituted aliphatic hydrocarbon groups of R _a are bonded by an ester bond —C (O) —O—, the two substituted or unsubstituted aliphatic hydrocarbon groups may be the same or different; Good.
The “substituted or unsubstituted aliphatic hydrocarbon group” to be bonded includes the same substituents as described above.

  When the aliphatic hydrocarbon group and the aromatic hydrocarbon group have a substituent, examples of the substituent include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, a hydroxyl group, and a carboxyl group. , Mercapto group, halogen atom, cyano group, nitro group and the like. Specific examples of the saturated aliphatic hydrocarbon group, the unsaturated aliphatic hydrocarbon group, and the aromatic hydrocarbon group are as described above.

For _a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group of Ra, when the TMHTA group has a substituent, the substituent is The hydrogen atom of the methyl group of TMHTA group is substituted.
Examples of the substituent substituted on the TMHTA group include a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, and a group represented by —S—R _e .

A divalent group in which two or more linking groups selected from a divalent group represented by -S- of R _b, a divalent aliphatic hydrocarbon group, and a divalent aromatic hydrocarbon group are combined is, for example, _{-S-C 6 H 4 -,} - S-CH 2 -, - S-S -, - CH 2 -C 6 H 4 - , and the like.
Similarly, a group formed by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group of R _d and R _e is, for example, an alkyl group of the aliphatic hydrocarbon group and an aryl group of the aromatic hydrocarbon group. Examples thereof include a bonded arylalkyl group.

Specific examples of the sulfur-containing bicyclic compound of the present invention are shown below.
In addition, it is not limited to the specific example of the sulfur containing polycyclic compound of this invention.

[Method for producing sulfur-containing polycyclic compound]
The sulfur-containing bicyclic compound of the present invention can be produced by reacting a TMHTA derivative bromide with a thiol compound under basic conditions.
For example, the sulfur-containing polycyclic compound of the present invention reacts a compound represented by formula (6) and a thiol compound represented by formula (7) under basic conditions as shown below: Reacting the compound represented by formula (8) with the thiol compound represented by formula (8) under basic conditions; or reacting the compound represented by formula (9) and the thiol compound represented by formula (7) under basic conditions. Can be manufactured.
(In the formula, A is the same as A in formula (5).
R ₁₁ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic carbon groups. A hydrogen group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
R ″ represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a divalent group represented by —S—, or —S—. And a divalent group obtained by combining two or three linking groups selected from a substituted or unsubstituted divalent aliphatic hydrocarbon and a substituted or unsubstituted divalent aromatic hydrocarbon group.
n is an integer of 1 or 2. )

In addition, the sulfur-containing polycyclic compound of the present invention is not limited to the above-described production method, and for example, even if it is a compound in which part or all of R _{11 in} formulas (6) and (9) is R ₁ Can do.

The compound represented by A (SH) _n of formula (7) which is a thiol compound is preferably anhydrous sodium hydrosulfide (NaSH), methyl mercaptan, thiophenol, benzyl mercaptan, 2-mercaptoethanol, 4-hydroxybenzenethiol. is there. When anhydrous sodium hydrosulfide is used, a compound in which A is sodium in the above formula is generated as an intermediate, and this intermediate causes a coupling reaction, or a plurality of anhydrous sodium sulfide reacts to form sulfur- By causing a coupling reaction through an intermediate that has produced a sulfur bond, a mixture of a sulfide compound, a disulfide compound, and a trisulfide compound is obtained.
The compound represented by HS-R ″ -SH of the formula (8) which is a thiol compound is preferably 4,4′-thiobisbenzenedithiol, biphenyl-4,4′dithiol, benzene-1,2-dithiol, Benzene-1,3-dithiol.

  The blending ratio of the TMHTA derivative bromide and the thiol compound is, for example, 1: 1 (molar ratio) in the case of the reaction of formula (6) and formula (7), and 2 in the case of the reaction of formula (6) and formula (8). 1 (molar ratio), and in the case of the reaction of formula (9) and formula (7), it is 1: 2 (molar ratio). Further, either one of the TMHTA derivative bromide and the thiol compound used in combination or the reaction conditions may be used in excess. When it is used in excess, it is generally 1 to 1.5 times the equimolar amount.

In order to facilitate the reaction between the TMHTA derivative bromide and the thiol compound, these are reacted under basic conditions. The basic condition can be obtained by adding an inorganic base or an organic base.
Examples of inorganic bases include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates. Examples of the salt include potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydroxide, and sodium hydroxide.
Examples of the organic base include amine organic bases including a pyridine compound, and specifically, triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0]. And undeca-7-ene and 1,4-diazabicyclo [2.2.2] octane.
The said inorganic base and organic base may be used individually by 1 type, respectively, and may be used as a 2 or more types of mixture. Moreover, the addition amount of an inorganic base and an organic base is, for example, TMHTA derivative bromide used, or TMHTA derivative bromide or thiol compound is used in an amount of 1 to 1.5 molar equivalents relative to the thiol compound. When used in excess, it is preferably used in the range of the smaller one molar equivalent to the larger 1.5 molar equivalent. If it exceeds 1.5 molar equivalents, the basicity in the reaction system becomes unnecessarily high, and in the case where active hydrogen is present in the produced sulfur-containing polycyclic compound of the present invention, the elimination and subsequent to it. A rearrangement reaction or the like of the proceeding cyclic structure proceeds. In the case where no active hydrogen is present, when an inorganic base is used, the metal cation acts on the sulfur site as an electrophile, and the anion site acts on the adjacent carbon of sulfur as a nucleophile. -Destabilize bonds between sulfur and give unintended by-products such as decomposition products. Similarly, when an organic base is used in the absence of active hydrogen, an unintended by-product such as a decomposition product is provided.

The reaction between the TMHTA derivative bromide and the thiol compound can be carried out in the presence or absence of an organic solvent. When an organic solvent is used, the concentration of the TMHTA derivative bromide is about 0.1 to 10 mol / L. It is preferable to adjust so that it becomes. When the concentration is 0.1 mol / L or more, a sufficient amount is generated even in a normal reactor, which is economically preferable. When the concentration is 10 mol / L or less, the temperature of the reaction solution can be easily controlled. It is preferable.
Usable organic solvents include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene; ethers such as diethyl ether, dibutyl ether, THF (tetrahydrofuran), dioxane, DME (dimethoxyethane), etc. Solvents: Halogen solvents such as carbon tetrachloride, chloroform, dichloromethane; DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), NMP (N-methyl-2-pyrrolidone), HMPA (hexamethyl phosphate triamide) ), HMPT (hexamethyl phosphite triamide), aprotic polar solvents such as carbon disulfide, etc., and these may be used alone or in combination.

The reaction temperature is usually −200 ° C. to 200 ° C., preferably room temperature to 100 ° C. When the reaction temperature is within this range, the reaction time can be moderated and side reactions can be suppressed, so that production efficiency can be improved.
The reaction pressure is usually 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. If the pressure is too high, special equipment is required and it is not economical.
The reaction time is usually 1 minute to 5 days, preferably 2 to 10 hours. When the reaction time is within the range, the reaction smoothly proceeds and the production efficiency can be improved. That is, if the reaction time is too short, the reaction does not proceed sufficiently, and if it is too long, production efficiency may decrease due to the formation of by-products.
In addition, the sulfur-containing bicyclic compound of the present invention produced in the reaction solution may leave the active hydrogen in the presence of a base for a long time, thereby leading to the elimination of active hydrogen and the subsequent rearrangement reaction of the cyclic structure. Along with this, a large number of decomposition products and isomers are produced, and thus it is necessary to quickly purify and isolate them after the completion of the reaction.

The TMHTA derivative bromide as a starting material can be produced by brominating a compound represented by the following formula (6 ′) by a radical reaction as described in, for example, JP-A 2010-222346.
(Wherein R ₁ is the same as in formula (1).)

Examples of the radical reaction include a reaction using a radical reaction initiator and a brominating agent.
In this reaction, radical species are thermally generated by using a radical reaction initiator and further brominated by reaction with a brominating agent to obtain a bromide of tetrahexathiaadamantane. The reaction can be suppressed, and a bromide of hexathiaadamantane can be synthesized with high selectivity.

The radical reaction initiator is not particularly limited. For example, AIBN [2,2′-azobis (isobutyronitrile)], 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′- And azobis (1-cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (isobutyric acid), dimethyl 1,1′-azobis (1-cyclohexanecarboxylic acid), benzoyl peroxide, and the like. 2'-azobis (isobutyronitrile)) is preferred.
Although there is no restriction | limiting in particular as a brominating agent, NBS (N-bromosuccinimide) and a bromine are mentioned, N-bromosuccinimide is preferable.

As reaction conditions, the radical reaction initiator is usually used in an amount of 0.05 to 2.0 equivalents based on the hexathiaadamantane compound represented by the formula (6 ′), and the brominating agent is represented by the formula (6 ′). 1.0-5.0 equivalent is used with respect to the hexathiaadamantane compound represented by these.
About a brominating agent, Preferably 2.0-4.0 equivalent is used with respect to the hexathiaadamantane compound represented by Formula (6 ').
In addition, for example, when synthesizing a disubstituted product, a trisubstituted product, and a tetrasubstituted product such as the compound represented by the formula (9), the reaction may be performed using a large amount of a brominating agent and a radical reaction initiator.

The radical reaction can be carried out in the presence or absence of an organic solvent, but when an organic solvent is used, the concentration of the hexathiaadamantane compound is adjusted to be about 0.1 to 10 mol / L. It is preferable. When the concentration is 0.1 mol / L or more, a sufficient amount is generated even in a normal reactor, which is economically preferable. When the concentration is 10 mol / L or less, the temperature of the reaction solution can be easily controlled. It is preferable.
Usable organic solvents include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene; ethers such as diethyl ether, dibutyl ether, THF (tetrahydrofuran), dioxane, DME (dimethoxyethane), etc. Solvents: Halogen solvents such as carbon tetrachloride, chloroform, dichloromethane; DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), NMP (N-methyl-2-pyrrolidone), HMPA (hexamethyl phosphate triamide) ), HMPT (hexamethyl phosphite triamide), aprotic polar solvents such as carbon disulfide, etc., and these may be used alone or in combination.

In the above radical reaction, the reaction temperature is not particularly limited because the appropriate temperature is determined by the half-life of the radical reaction initiator, but is usually −200 ° C. to 200 ° C., preferably room temperature to 100 ° C. When the reaction temperature is within this range, the reaction time can be moderated and side reactions can be suppressed, so that production efficiency can be improved.
The reaction pressure is usually 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. If the pressure is too high, special equipment is required and it is not economical.
The reaction time is usually 1 minute to 5 days, preferably 2 to 10 hours. When the reaction time is within the range, the reaction smoothly proceeds and the production efficiency can be improved. That is, if the reaction time is too short, the reaction does not proceed sufficiently, and if it is too long, production efficiency may decrease due to the formation of by-products.

[Optical materials containing sulfur-containing polycyclic compounds]
The sulfur-containing polycyclic compound of the present invention is excellent in transparency and can exhibit a high refractive index and Abbe number, and can be suitably used as a high refractive index material or a high refractive index material precursor. Here, the high refractive index material refers to a material in which a molded body composed of the material has a high refractive index, and the refraction of a molded body composed of the composition by adding it to another material, for example, a base resin. It means both materials that can improve the rate. Below, the latter may be described as a refractive index improving material.
For example, unlike an optical material in which inorganic oxide fine particles are dispersed in a base resin, the optical material containing the sulfur-containing polycyclic compound of the present invention does not need to contain fine particles, and has long-term storage stability and dispersion stability of inorganic fine particles. There is no need to consider balance. In addition, TMHTA, which is a basic skeleton, is an inexpensive compound and thus has excellent industrial properties.

The composition of the present invention suitable as an optical material contains the sulfur-containing bicyclic compound of the present invention. The sulfur-containing polycyclic compound contained in the composition of the present invention may be a single type or a mixture of two or more types.
Although content of the sulfur containing bicyclic compound in a composition can be suitably adjusted with the target refractive index, it is preferable to set it as 1 to 50 weight% or less with respect to transparent resin. If it is less than 1% by weight, the effect is not sufficient from the viewpoint of increasing the refractive index. If it exceeds 50% by weight, the mechanical strength and stability derived from the transparent resin are reduced, or the sulfur-containing bicyclic compound is contained in the transparent resin. In such a case, it becomes difficult to disperse sufficiently.

The composition of the present invention can further contain a transparent resin.
Examples of the transparent resin include polycarbonate, polymethyl methacrylate, polyethersulfone, polysulfone, poly (1,4-phenylenesulfide), polyetheretherketone, poly (1,4-butylene terephthalate), polycaprolactam ( Nylon 6), polyethylene, polypropylene, polystyrene, polyhydroxystyrene, poly (α-methylstyrene), polyorganosiloxane and the like.

  In addition to the sulfur-containing polycyclic compound and the transparent resin, the composition of the present invention is a third material within a range that does not impair the transparency and the high refractive index for the purpose of the present invention, or the stability and heat resistance of the composition. Ingredients can be used as additives. Specifically, conventionally known resin additives such as ultraviolet absorbers and softening agents can be mentioned.

Hereinafter, the present invention will be described using examples.
The TMHTA used in the following examples is 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane produced by the method described in JP2010-209005A. It is. In addition, a method for producing a bromo compound in which a part of hydrogen atoms of TMHTA is substituted with a bromine atom is produced by the method described in JP2010-222346A.

[Preparation of sulfur-containing polycyclic compounds]
Example 1
A mixture comprising a sulfide compound, a disulfide compound and a tristolide compound was produced from the monobromo compound by the following method.

In a 100 ml three-necked flask, 0.43 g (1.14 mmol) of 1-bromomethyl-3,5,7-trimethyl-2,4,6,8,9,10-hexathiaadamantane as a monobromo compound and sodium hydrosulfide (Anhydrous) 0.32 g (5.7 mmol) was charged, and 10 ml of N, N-dimethylformamide was added as a solvent and stirred, followed by reaction at room temperature for 5 hours.
After confirming the disappearance of the raw materials by thin layer chromatography (TLC), ethyl acetate was added to the reaction mixture and the mixture was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure, and 0.7 g of the resulting residue is purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 10: 1), and the fraction containing the main components is collected to remove the solvent. Gave 177 mg of white solid.

When the obtained white solid was analyzed by ¹ H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane), a singlet peak was observed at 2.17 ppm. Furthermore, singlet peaks were observed at 3.77 ppm, 3.91 ppm and 3.99 ppm, respectively, at an integration ratio of 7: 4: 1. The ratio of the integrated value of the peak at 2.17 ppm and the integrated value of the three peaks at 3.77 ppm, 3.91 ppm and 3.99 ppm was 9: 2.

As a result of performing LC-MS analysis on the obtained white solid, components having m / z, 630, 662, and 694 as parent ion peaks were detected, respectively. From the analysis results of H-NMR and LC-MS, the obtained compound was a mixture of a sulfide compound, a disulfide compound, and a trisulfide compound shown in the above reaction formula, and the sulfide compound was a main component, It was found that the disulfide compound and the trisulfide compound were obtained in this order.
Furthermore, H-NMR peaks of sulfide compounds are 2.17 ppm and 3.77 ppm, H-NMR peaks of disulfide compounds are 2.17 ppm and 3.91 ppm, and NMR peaks of trisulfide compounds are 2.17 ppm and 3.77 ppm. It was found to be 99 ppm. The obtained LC-MS chart (LC-UV (254 nm) chromatogram) is shown in FIG.

Example 2
A mixture 1 comprising a sulfide compound, a disulfide compound and a tristolide compound was produced from the monobromo compound by the following method.

In a 100 ml three-necked flask, 1-bromomethyl-3,5,7-trimethyl-2,4,6,8,9,10-hexathiaadamantane, 1.80 g (4.75 mmol) and sodium hydrosulfide (anhydrous) 0.53 g (9.5 mmol) was charged, 20 ml of N, N-dimethylformamide was added as a solvent, dissolved by stirring, and reacted at room temperature for 5 hours.
When the progress of the reaction was confirmed by TLC, the raw material had disappeared, so ethyl acetate was added to the reaction mixture, the organic layer was taken out, washed with water and then saturated brine, dried over anhydrous sodium sulfate. I let you. The solvent was removed under reduced pressure, and 3.8 g of the resulting residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 20: 3). The fractions containing the main component were collected and the solvent was removed. 0.70 g of a white solid was obtained.

  The obtained white solid was analyzed by H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane). As in Example 1, a singlet peak was observed at 2.17 ppm, and 3.77 ppm, Singlet peaks were observed at 3.91 ppm and 3.99 ppm at an integration ratio of 2: 7: 1, respectively. The ratio of the integrated value of the peak at 2.17 ppm and the integrated value of the three peaks at 3.77 ppm, 3.91 ppm, and 3.99 ppm was 9: 2.

As a result of performing LC-MS analysis on the obtained white solid, components having m / z, 630, 662, and 694 as parent ion peaks were detected. From the analysis results of H-NMR and LC-MS, the obtained mixture 1 is a mixture of a sulfide compound, a disulfide compound and a trisulfide compound, as in Example 1, but the main component is a disulfide compound, It was found that the compounds were obtained in the order of sulfide compound and trisulfide compound.
The obtained LC-MS chart (LC-UV (254 nm) chromatogram) is shown in FIG.

Example 3
Compound 1 which is a thiobisphenyl sulfide compound was produced from the monobromo compound by the following method.

A 100 ml three-necked flask was charged with 1.66 g (12 mmol) of potassium carbonate and 1.0 g (4.0 mmol) of 4,4′-thiobisbenzenethiol, and nitrogen was introduced to form a nitrogen atmosphere. As a solvent, 25 ml of N, N-dimethylformamide was added and stirred, and 3.79 g (10-hexathiaadamantane, 1-bromomethyl-3,5,7-trimethyl-2,4,6,8,9,10) as a raw material. Mmol) was added as a solid. After heating in a 90 ° C. oil bath and reacting for 7 hours, it was confirmed by TLC that the raw material had disappeared.
The reaction mixture was diluted by pouring into 200 ml of water and extracted three times with ethyl acetate. The organic layers were combined, washed twice with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained crude product (5.1 g) was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 6: 1), the main component fractions were collected, the solvent was removed, and a white solid (yield: 0.00) was collected. 89 g, yield: 26%).

When the obtained white solid was analyzed by H-NMR, it was confirmed to be the desired thiobisphenyl sulfide compound.
H-NMR (ppm: solvent: deuterated chloroform, internal standard: tetramethylsilane) 2.165 (s, 18H), 3.923 (s, 4H), 7.263 (dd, 4H), 7.431 (dd , 4H)

Example 4
A benzyl sulfide compound was produced from a monobromo compound by the following method.

A 100 ml three-necked flask was charged with 0.29 g (2.1 mmol) of potassium carbonate and 0.25 ml (2.1 mmol) of benzyl mercaptan, and nitrogen was introduced to form a nitrogen atmosphere. 25 ml of N, N-dimethylformamide as a solvent was added and stirred, and 0.64 g (1) of 1-bromomethyl-3,5,7-trimethyl-2,4,6,8,9,10-hexathiaadamantane as a raw material. 0.7 mmol) was added as a solid. After stirring for 7 hours at room temperature, it was confirmed by TLC that the raw material had disappeared.
The reaction mixture was diluted by pouring into about 100 ml of water and extracted three times with ethyl acetate. The organic layers were combined, washed twice with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. 1.0 g of the obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 20: 1), and the main component fractions were collected and the solvent was removed to obtain 0.20 g of a white solid. (Yield: 0.20 g, Yield: 28%).

When the obtained white solid was analyzed by H-NMR, it was confirmed to be the target benzyl sulfide compound.
H-NMR (ppm: solvent: deuterated chloroform, internal standard: tetramethylsilane) 2.165 (s, 9H), 3.393 (s, 2H), 3.914 (s, 2H), 7.259-7 .356 (m, 5H)

Example 5
An alcohol compound was produced from the monobromo compound by the following method.

In a 100 ml three-necked flask, 1.90 g (5.0 mmol) of potassium carbonate, 1.90 g (5.0 mmol) of raw material 1-bromomethyl-3,5,7-tetratrimethyl-2,4,6,8,9,10-hexathiadamantane. 70 g (5.1 mmol) was charged, and nitrogen was introduced to form a nitrogen atmosphere. As a solvent, 25 ml of N, N-dimethylformamide and 0.45 ml (0.50 g, 6.4 mmol) of 2-mercaptoethanol were added and stirred. After stirring at room temperature for 1 hour, the reaction was conducted by heating in an oil bath at 80 ° C. for 5 hours, and it was confirmed by TLC that the raw material had disappeared.
The reaction mixture was diluted by pouring into 200 ml of water and extracted three times with ethyl acetate. The extracts were combined, washed three times with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and 2.5 g of the resulting residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3: 2). (Yield: 1.19 g, yield: 64%) was obtained.

When the obtained transparent oily substance was analyzed by H-NMR, it was confirmed to be the target alcohol compound.
H-NMR (ppm: solvent: deuterated chloroform, internal standard: tetramethylsilane) 2.173 (s, 9H), 2.954 (t, 2H), 3.608 (s, 2H), 3.832 (q , 2H)

Example 6
An acrylate compound was produced from the alcohol compound by the following method.

A 100 ml three-necked flask was charged with 0.44 g (1.17 mmol) of the alcohol compound prepared in Example 5, and nitrogen was introduced to form a nitrogen atmosphere. As a solvent, 25 ml of tetrahydrofuran and further 0.33 ml (2.38 mmol) of triethylamine were added and stirred, cooled in an ice salt bath, and cooled to 0 ° C. in the reaction vessel. 0.20 ml (2.47 mmol) of acryloyl chloride was diluted with 5 ml of tetrahydrofuran and added slowly so that the temperature did not exceed 5 ° C. With cooling, the mixture was further stirred for 1 hour to react, and the disappearance of the starting alcohol compound was confirmed by TLC.
The reaction mixture was diluted with 100 ml of water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a transparent oil (yield: 0.16 g, yield 31%).

When the obtained transparent oily substance was analyzed by H-NMR, it was confirmed to be the target acrylate compound.
H-NMR (ppm: solvent: deuterated chloroform, internal standard: tetramethylsilane) 2.171 (s, 9H), 3.021 (t, 2H), 3.629 (s, 2H), 4.384 (t , 2H), 5.864 (dd, 1H), 6.128 (dd, 1H), 6.432 (dd, 1H)

Example 7
A bisphenol compound was produced from the dibromo compound by the following method.

In a 100 ml three-necked flask, 0.36 g (0.79 mmol) of raw material 1,3-bis (bromomethyl) -5,7-dimethyl-2,4,6,8,9,10-hexathiaadamantane (dibromo compound) ), 4-hydroxybenzenethiol 0.36 g (2.9 mmol) and potassium carbonate 0.40 g (2.9 mmol) were charged, and nitrogen was introduced to form a nitrogen atmosphere. 30 ml of N, N-dimethylformamide was added as a solvent, and the mixture was stirred and reacted by heating in an oil bath at 60 ° C. for 3 hours. The disappearance of the starting dibromo compound was confirmed by TLC.
The reaction mixture was diluted by pouring into about 300 ml of water and extracted three times with ethyl acetate. The extracts were combined, washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. 1.0 g of oil was obtained. The obtained oil was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 5: 3). The main component fractions were collected and the solvent was removed to obtain a white solid (yield 204 mg, 47%). Obtained.

When the obtained white solid was analyzed by H-NMR, it was confirmed to be the objective bisphenol compound.
H-NMR (ppm: solvent: deuterated chloroform, internal standard: tetramethylsilane) 2.16 (s, 6H), 3.83 (s, 4H), 5.08 (broad, 2H), 6.78 (d , 4H), 7.44 (d, 4H)

[Evaluation of Sulfur-Containing Bicyclic Compound Composition]
Examples 8-25 and Comparative Examples 1-4
Using 1,1,2,2-tetrachloroethane as a coating solvent, a coating solution having a sulfur-containing polycyclic compound and a base polymer in the composition shown in Table 1 was prepared. A silicon substrate was fixed to a spin coater, and the coating solution prepared on the substrate was dropped and rotated at 2000 rpm for 60 seconds to uniformly coat the substrate. The substrate having the coating solution coating was placed on a hot plate set at 100 ° C. in advance, and the solvent was removed by heating and drying for the time shown in Table 1 to form a thin film having the composition shown in Table 1 on the silicon substrate.
The refractive index of each wavelength in the wavelength range of 200 to 1700 nm of the obtained thin film was determined by measuring with a spectroscopic ellipsometer and analyzing with a general dispersion formula model. The refractive indexes in the wavelength range of 200 to 1700 nm obtained by analysis using the general dispersion formula models of Example 8-25 and Comparative Example 1-4 are shown in FIG. 3-24, respectively. Table 2 shows the refractive index n _D and the Abbe number obtained by analyzing the general dispersion formula.
The Abbe number is a numerical value representing the wavelength dispersion of the refractive index, calculated from (n _D −1) / (n _F −n _C ) n _D : refractive index of D line (589.3 nm) n _F : F line Refractive index of (486.1 nm) n _C : Refractive index of C line (656.3 nm)

  From the results of Tables 1 and 2, it can be seen that the thin film formed of the composition containing the sulfur-containing polycyclic compound of the present invention has a high refractive index and a high Abbe number.

  The composition containing the sulfur-containing polycyclic compound of the present invention is suitable for optical materials such as transparent plates, optical lenses, optical fibers, optical waveguides, and photonic crystals that require optical properties (high refractive index and high Abbe number). Can be used.

Claims (12)

A sulfur-containing polycyclic compound represented by the following formula (1).
(In the formula, each R ₁ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —R′—R _a . , At least one R ₁ is a group represented by —R′—R _a .
R _a is a hydrogen atom, a carboxyl group, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, two substituted or unsubstituted fats Or a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group. However, when R _a is a substituted or unsubstituted 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantyl group, R ′ is 1,3,5 , 7-Tetramethyl-2,4,6,8,9,10-bonds to the carbon atom constituting the methyl group of the hexathiaadamantyl group.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents two or more groups selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group, and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group. ) The sulfur-containing polycyclic compound of Claim 1 represented by following formula (2).
(R ₂ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _c , respectively. R ₂ is a group represented by —S—R _c .
R _c represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. It is. ) Of the twelve _{R 2,} 1 to 3 one of _{R 2} is a sulfur-containing-cyclic compound according to claim 2 respectively is a group represented by _{-S-R c.} The sulfur-containing bicyclic compound of Claim 1 represented by following formula (3).
(Wherein R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _e , respectively.
R _e is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. is there.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group. ) The sulfur-containing bicyclic compound of Claim 1 represented by following formula (4).
(In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _d , respectively. At least one R ₃ is a group represented by —S—R _d .
R _d represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. It is. ) The sulfur-containing bicyclic compound of Claim 1 represented by following formula (5).
(Wherein R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, or a group represented by —S—R _e , respectively.
R _e is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group in which two substituted or unsubstituted aliphatic hydrocarbon groups are bonded by an ester bond. is there.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats A group hydrocarbon group is bonded by an ester bond. ) The manufacturing method of the sulfur containing bicyclic compound which makes the compound represented by following formula (6) and the thiol compound represented by following formula (7) react on basic conditions.
(Wherein R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic carbon groups. A hydrogen group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats Group hydrocarbon group bonded by an ester bond.
n is an integer of 1 or 2. ) The manufacturing method of the sulfur containing bicyclic compound which makes the compound represented by following formula (6), and the thiol compound represented by following formula (8) react on basic conditions.
(Wherein R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic carbon groups. A hydrogen group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
R ″ represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a divalent group represented by —S—, or —S—. And a divalent group obtained by combining two or three groups selected from a substituted or unsubstituted divalent aliphatic hydrocarbon and a substituted or unsubstituted divalent aromatic hydrocarbon group. ) The manufacturing method of the sulfur containing bicyclic compound which makes the compound represented by following formula (9) and the thiol compound represented by following formula (7) react on basic conditions.
(Wherein R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a group represented by —R′—R _A , respectively.
R _A is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, or two substituted or unsubstituted aliphatic groups A hydrocarbon group is a group bonded by an ester bond.
R ′ is a divalent group represented by —S—, —S—S—, —S—S—S—, or —S—R _b —S—.
R _b represents a linking group selected from a divalent group represented by —S—, a substituted or unsubstituted divalent aliphatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group. A combined divalent group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic hydrocarbon group.
A represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a carboxyl group, or two substituted or unsubstituted fats Group hydrocarbon group bonded by an ester bond.
n is an integer of 1 or 2. )   The high refractive index material which is the sulfur-containing polycyclic compound according to any one of claims 1 to 6 or 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane .   Abbe number improving material which is the sulfur-containing polycyclic compound according to claim 1 or 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane . It consists of a composition containing the sulfur-containing polycyclic compound according to any one of claims 1 to 6 or 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiaadamantane. Optical member.