JP2002255960A - Dibenzothiophene compound, intermediate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new dibenzothiophene compound useful as an optically functional material, and having reactive two substituents on the 3- and 7- positions, to provide an intermediate for the new compound, and to provide a method for highly selectively producing the intermediate. SOLUTION: This dibenzothiophene compound is expressed by formula (1) or (2). The second objective benzothiophene oxide as an intermediate for the above compounds is expressed by formula (3) or (4). The other objective method for producing the above intermediates is also provided. In the above formulas, A<1> to A<6> are each H, F or the like; X is a halogen atom; and Y is a halogen atom or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dibenzothiophene compound, an intermediate and a method for producing the same.

[0002]

2. Description of the Related Art As a method for introducing a substituent into a dibenzothiophene compound, a method described in J. Am. Chem. Soc., 1948, 70 , 1748 and a method described in Heterocyclic Chem., 1985, 22 , 215 are known. It is. However, these methods have made it difficult to selectively introduce two highly reactive substituents into the 3,7-position of the dibenzothiophene compound.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound having a high reactivity at the 3,7-position which is useful as an optically functional material.
An object of the present invention is to provide a novel dibenzothiophene compound having a substituent, an intermediate thereof, and a highly selective production method thereof.

[0004]

According to the present invention, the expression (1)
(Hereinafter, referred to as dibenzothiophene compound (1)).

Embedded image (In the formula, A ^{1 to} A ⁶ each independently represent a hydrogen atom, a fluorine atom, or a carbon atom which may be substituted with a fluorine atom.
X represents an alkyl group or an alkoxy group, X represents a halogen atom, and Y represents a halogen atom or a hydroxyl group. According to the present invention, there is also provided a dibenzothiophene compound represented by the formula (2) (hereinafter referred to as dibenzothiophene compound (2)).

Embedded image (In the formula, A ^{1 to} A ⁶ and X have the same meanings as those in the formula (1).) Further, according to the present invention, dibenzothiophene oxides represented by the formula (3) (hereinafter referred to as dibenzothiophene) Oxides
(Referred to as (3)).

Embedded image (In the formula, A ^{1 to} A ⁶ and X have the same meanings as those in the formula (1).) Further, according to the present invention, dibenzothiophene oxides represented by the formula (4) (hereinafter, dibenzothiophene oxides) Thiophene oxides (referred to as (4)) are provided.

Embedded image (In the formula, A ^{1 to} A ⁶ and X have the same meanings as those in the formula (1).)

According to the present invention, the dibenzothiophene compound (2) is diazotized to decompose a diazonium salt in the presence of an anion corresponding to Y in the formula (1) (hereinafter referred to as an anion Y). The method for producing the dibenzothiophene compound (1) is provided. Further, according to the present invention, there is provided a method for producing the dibenzothiophene compound (2), wherein the dibenzothiophene oxides (3) are reduced. Furthermore, according to the present invention, there is provided a method for producing the above dibenzothiophene oxides (3), which comprises nitrating the dibenzothiophene oxides (4). Further, according to the present invention, a dibenzothiophene compound represented by the formula (5) (hereinafter, referred to as a dibenzothiophene compound (5)) (where A ^{1 to} A ⁶ and X represent the same meaning as described above). And a method for producing the above-mentioned dibenzothiophene oxides (4), characterized by oxidizing.

Embedded image

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The dibenzothiophene compound (1) of the present invention has the above formula (1)
Indicated by In formula (1), A ^{1 to} A ⁶ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, and X represents a halogen atom. And Y represents a halogen atom or a hydroxyl group.

Specific examples of A ^{1 to} A ⁶ include, independently of each other, for example, a hydrogen atom; a fluorine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group , A nonyl group, a decyl group, an undecyl group, an alkyl group such as a dodecyl group, and a fluoroalkyl group in which these are substituted with a fluorine atom (for example, a trifluoromethyl group, a pentafluoroethyl group, etc.); , Butoxy, pentyloxy, hexyloxy, octyloxy,
Nonyloxy group, decyloxy group, undecyloxy group, alkoxy groups such as dodecyloxy group and a fluoroalkoxy group substituted with a fluorine atom (for example,
A methoxy group substituted with 1 to 3 fluorine atoms, 1 to 5
Ethoxy group substituted with a single fluorine atom).

The dibenzothiophene compound (1) of the present invention includes, for example, 7-chlorodibenzothiophen-3-ol, 7-bromodibenzothiophen-3-ol, 7-iododibenzothiophen-3-ol, 3,7 -Dichlorodibenzothiophene, 3-bromo-7-chlorodibenzothiophene, 3
-Chloro-7-iododibenzothiophene, 3,7-dibromodibenzothiophene, 3-bromo-7-iododibenzothiophene, 3,7-diiododibenzothiophene,

7-chloro-2-methyldibenzothiophen-3-
All, 7-bromo-2-methyldibenzothiophen-3-ol, 7-iodo-2-methyldibenzothiophen-3-ol,
3,7-dichloro-2-methyldibenzothiophene, 3-bromo-
7-chloro-2-methyldibenzothiophene, 3-chloro-7-iodo-2-methyldibenzothiophene, 3,7-dibromo-2-methyldibenzothiophene, 3-bromo-7-iodo-2-methyldibenzothiophene, 3,7-diiodo-2-methyldibenzothiophene, 7-chloro-8-methyldibenzothiophene-3-
All, 7-bromo-8-methyldibenzothiophen-3-ol, 7-iodo-8-methyldibenzothiophen-3-ol,
3,7-dichloro-8-methyldibenzothiophene, 3-bromo-
7-chloro-8-methyldibenzothiophene, 3-chloro-7-iodo-8-methyldibenzothiophene, 3,7-dibromo-8-methyldibenzothiophene, 3-bromo-7-iodo-8-methyldibenzothiophene, 3,7-diiodo-8-methyldibenzothiophene, 7-chloro-2,8-dimethyldibenzothiophen-3-ol, 7-bromo-2,8-dimethyldibenzothiophen-3-ol, 7-iodo-2, 8-dimethyldibenzothiophen-3-ol, 3,7-dichloro-2,8-dimethyldibenzothiophene, 3-bromo-7-chloro-2,8-dimethyldibenzothiophene, 3-chloro-7-iodo-2, 8-dimethyldibenzothiophene, 3,7-dibromo-2,8-dimethyldibenzothiophene, 3-bromo-7-iodo-2,8-dimethyldibenzothiophene, 3,7-diiodo-2,8-dimethyldibenzothiophene, 7
-Chloro-4-methyldibenzothiophen-3-ol, 7-bromo-4-methyldibenzothiophen-3-ol, 7-iodo
-4-methyldibenzothiophen-3-ol, 3,7-dichloro
-4-methyldibenzothiophene, 3-bromo-7-chloro-4-
Methyldibenzothiophene, 3-chloro-7-iodo-4-methyldibenzothiophene, 3,7-dibromo-4-methyldibenzothiophene, 3-bromo-7-iodo-4-methyldibenzothiophene, 3,7-diiodo- 4-methyldibenzothiophene, 7-chloro-6-methyldibenzothiophen-3-ol,
7-bromo-6-methyldibenzothiophen-3-ol, 7-iodo-6-methyldibenzothiophen-3-ol, 3,7-dichloro-6-methyldibenzothiophene, 3-bromo-7-chloro
-6-methyldibenzothiophene, 3-chloro-7-iodo-6-
Methyldibenzothiophene, 3,7-dibromo-6-methyldibenzothiophene, 3-bromo-7-iodo-6-methyldibenzothiophene, 3,7-diiodo-6-methyldibenzothiophene, 7-chloro-4,6- Dimethyldibenzothiophen-3-ol, 7-bromo-4,6-dimethyldibenzothiophen-3-ol, 7-iodo-4,6-dimethyldibenzothiophen-3-ol, 3,7-dichloro-4,6- Dimethyldibenzothiophene, 3-bromo-7-chloro-4,6-dimethyldibenzothiophene, 3-chloro-7-iodo-4,6-dimethyldibenzothiophene, 3,7-dibromo-4,6-dimethyldibenzothiophene, Three
-Bromo-7-iodo-4,6-dimethyldibenzothiophene,
3,7-diiodo-4,6-dimethyldibenzothiophene, 7-chloro-2,4-dimethyldibenzothiophen-3-ol, 7-bromo-2,4-dimethyldibenzothiophen-3-ol, 7-iodo- 2,4-dimethyldibenzothiophen-3-ol, 3,7-
Dichloro-2,4-dimethyldibenzothiophene, 3-bromo-
7-chloro-2,4-dimethyldibenzothiophene, 3-chloro-
7-iodo-2,4-dimethyldibenzothiophene, 3,7-dibromo-2,4-dimethyldibenzothiophene, 7-chloro-2,6-
Dimethyldibenzothiophen-3-ol, 7-bromo-2,6-
Dimethyldibenzothiophen-3-ol, 7-iodo-2,6-
Dimethyldibenzothiophen-3-ol, 3,7-dichloro-
2,6-dimethyldibenzothiophene, 3-bromo-7-chloro-
2,6-dimethyldibenzothiophene, 3-chloro-7-iodo-
2,6-dimethyldibenzothiophene, 3,7-dibromo-2,6-
Dimethyldibenzothiophene, 7-chloro-6,8-dimethyldibenzothiophen-3-ol, 7-bromo-6,8-dimethyldibenzothiophen-3-ol, 7-iodo-6,8-dimethyldibenzothiophen-3- All, 3,7-dichloro-6,8-dimethyldibenzothiophene, 3-bromo-7-chloro-6,8-dimethyldibenzothiophene, 3-chloro-7-iodo-6,8-dimethyldibenzothiophene, 3, 7-dibromo-6,8-dimethyldibenzothiophene, 7-chloro-4,8-dimethyldibenzothiophen-3-ol, 7-bromo-4,8-dimethyldibenzothiophen-3-ol, 7-iodo-4, 8-dimethyldibenzothiophen-3-ol, 3,7-dichloro-4,8-dimethyldibenzothiophene, 3-bromo-7-chloro-4,8-dimethyldibenzothiophene, 3-chloro-7-iodo-4, 8-dimethyldibenzothiophene, 3,7-dibromo-4,8-dimethyldibenzothiophene, 7- B-2,4,6-trimethyldibenzothiophen-3-ol, 7-bromo-2,4,6-trimethyldibenzothiophen-3-ol, 7-iodo-2,4,6-trimethyldibenzothiophen-3- All, 3,7-dichloro-2,4,6-trimethyldibenzothiophene, 3-bromo-7-chloro-2,4,6-trimethyldibenzothiophene, 3-chloro-7-iodo-2,4,
6-trimethyldibenzothiophene, 3,7-dibromo-2,4,6
-Trimethyldibenzothiophene, 7-chloro-2,4,8-trimethyldibenzothiophen-3-ol, 7-bromo-2,4,8-
Trimethyldibenzothiophen-3-ol, 7-iodo-2,
4,8-trimethyldibenzothiophen-3-ol, 3,7-dichloro-2,4,8-trimethyldibenzothiophene, 3-bromo-7-chloro-2,4,8-trimethyldibenzothiophene, 3-
Chloro-7-iodo-2,4,8-trimethyldibenzothiophene, 3,7-dibromo-2,4,8-trimethyldibenzothiophene, 7-chloro-2,6,8-trimethyldibenzothiophene-3-
All, 7-bromo-2,6,8-trimethyldibenzothiophen-3-ol, 7-iodo-2,6,8-trimethyldibenzothiophen-3-ol, 3,7-dichloro-2,6,8- Trimethyldibenzothiophene, 3-bromo-7-chloro-2,6,8-trimethyldibenzothiophene, 3-chloro-7-iodo-2,6,8-trimethyldibenzothiophene, 3,7-dibromo-2,6, 8-trimethyldibenzothiophene, 7-chloro-4,6,8-trimethyldibenzothiophen-3-ol, 7-bromo-4,6,8-trimethyldibenzothiophen-3-ol, 7-iodo-4,6, 8-trimethyldibenzothiophen-3-ol, 3,7-dichloro-
4,6,8-trimethyldibenzothiophene, 3-bromo-7-chloro-4,6,8-trimethyldibenzothiophene, 3-chloro-
7-iodo-4,6,8-trimethyldibenzothiophene, 3,7-
Dibromo-4,6,8-trimethyldibenzothiophene, 7-chloro-2,4,6,8-tetramethyldibenzothiophen-3-ol, 7-bromo-2,4,6,8-tetramethyldibenzothiophene- 3-ol, 7-iodo-2,4,6,8-tetramethyldibenzothiophen-3-ol, 3,7-dichloro-2,4,6,8-tetramethyldibenzothiophene, 3-bromo-7- Chloro-2,4,6,8-
Tetramethyldibenzothiophene, 3-chloro-7-iodo-
2,4,6,8-tetramethyldibenzothiophene, 3,7-dibromo-2,4,6,8-tetramethyldibenzothiophene,

7-chloro-2-ethyldibenzothiophen-3-
All, 7-bromo-2-ethyldibenzothiophen-3-ol, 7-iodo-2-ethyldibenzothiophen-3-ol,
3,7-dichloro-2-ethyldibenzothiophene, 3-bromo-
7-chloro-2-ethyldibenzothiophene, 3-chloro-7-iodo-2-ethyldibenzothiophene, 3,7-dibromo-2-ethyldibenzothiophene, 3-bromo-7-iodo-2-ethyldibenzothiophene, 3,7-diiodo-2-ethyldibenzothiophene, 7-chloro-8-ethyldibenzothiophen-3-
All, 7-bromo-8-ethyldibenzothiophen-3-ol, 7-iodo-8-ethyldibenzothiophen-3-ol,
3,7-dichloro-8-ethyldibenzothiophene, 3-bromo-
7-chloro-8-ethyldibenzothiophene, 3-chloro-7-iodo-8-ethyldibenzothiophene, 3,7-dibromo-8-ethyldibenzothiophene, 3-bromo-7-iodo-8-ethyldibenzothiophene, 3,7-diiodo-8-ethyldibenzothiophene, 7-chloro-2,8-diethyldibenzothiophen-3-ol, 7-bromo-2,8-diethyldibenzothiophen-3-ol, 7-iodo-2, 8-diethyldibenzothiophen-3-ol, 3,7-dichloro-2,8-diethyldibenzothiophene, 3-bromo-7-chloro-2,8-diethyldibenzothiophene, 3-chloro-7-iodo-2, 8-diethyldibenzothiophene, 3,7-dibromo-2,8-diethyldibenzothiophene, 3-bromo-7-iodo-2,8-diethyldibenzothiophene, 3,7-diiodo-2,8-diethyldibenzothiophene, 7
-Chloro-4-ethyldibenzothiophen-3-ol, 7-bromo-4-ethyldibenzothiophen-3-ol, 7-iodo
-4-ethyldibenzothiophen-3-ol, 3,7-dichloro
-4-ethyldibenzothiophene, 3-bromo-7-chloro-4-
Ethyl dibenzothiophene, 3-chloro-7-iodo-4-ethyldibenzothiophene, 3,7-dibromo-4-ethyldibenzothiophene, 3-bromo-7-iodo-4-ethyldibenzothiophene, 3,7-diiodo- 4-ethyldibenzothiophene, 7-chloro-6-ethyldibenzothiophen-3-ol,
7-bromo-6-ethyldibenzothiophen-3-ol, 7-iodo-6-ethyldibenzothiophen-3-ol, 3,7-dichloro-6-ethyldibenzothiophene, 3-bromo-7-chloro
-6-ethyldibenzothiophene, 3-chloro-7-iodo-6-
Ethyl dibenzothiophene, 3,7-dibromo-6-ethyldibenzothiophene, 3-bromo-7-iodo-6-ethyldibenzothiophene, 3,7-diiodo-6-ethyldibenzothiophene, 7-chloro-4,6- Diethyldibenzothiophen-3-ol, 7-bromo-4,6-diethyldibenzothiophen-3-ol, 7-iodo-4,6-diethyldibenzothiophen-3-ol, 3,7-dichloro-4,6- Diethyldibenzothiophene, 3-bromo-7-chloro-4,6-diethyldibenzothiophene, 3-chloro-7-iodo-4,6-diethyldibenzothiophene, 3,7-dibromo-4,6-diethyldibenzothiophene, Three
-Bromo-7-iodo-4,6-diethyldibenzothiophene,
3,7-diiodo-4,6-diethyldibenzothiophene, 7-chloro-2,4-diethyldibenzothiophen-3-ol, 7-bromo-2,4-diethyldibenzothiophen-3-ol, 7-iodo- 2,4-diethyldibenzothiophen-3-ol, 3,7-
Dichloro-2,4-diethyldibenzothiophene, 3-bromo-
7-chloro-2,4-diethyldibenzothiophene, 3-chloro-
7-iodo-2,4-diethyldibenzothiophene, 3,7-dibromo-2,4-diethyldibenzothiophene, 7-chloro-2,6-
Diethyldibenzothiophen-3-ol, 7-bromo-2,6-
Diethyldibenzothiophen-3-ol, 7-iodo-2,6-
Diethyldibenzothiophen-3-ol, 3,7-dichloro-
2,6-diethyldibenzothiophene, 3-bromo-7-chloro-
2,6-diethyldibenzothiophene, 3-chloro-7-iodo-
2,6-diethyldibenzothiophene, 3,7-dibromo-2,6-
Diethyldibenzothiophene, 7-chloro-6,8-diethyldibenzothiophen-3-ol, 7-bromo-6,8-diethyldibenzothiophen-3-ol, 7-iodo-6,8-diethyldibenzothiophen-3- All, 3,7-dichloro-6,8-diethyldibenzothiophene, 3-bromo-7-chloro-6,8-diethyldibenzothiophene, 3-chloro-7-iodo-6,8-diethyldibenzothiophene, 3, 7-dibromo-6,8-diethyldibenzothiophene, 7-chloro-4,8-diethyldibenzothiophen-3-ol, 7-bromo-4,8-diethyldibenzothiophen-3-ol, 7-iodo-4, 8-diethyldibenzothiophen-3-ol, 3,7-dichloro-4,8-diethyldibenzothiophene, 3-bromo-7-chloro-4,8-diethyldibenzothiophene, 3-chloro-7-iodo-4, 8-diethyldibenzothiophene, 3,7-dibromo-4,8-diethyldibenzothiophene, 7- B-2,4,6-triethyldibenzothiophen-3-ol, 7-bromo-2,4,6-triethyldibenzothiophen-3-ol, 7-iodo-2,4,6-triethyldibenzothiophen-3- All, 3,7-dichloro-2,4,6-triethyldibenzothiophene, 3-bromo-7-chloro-2,4,6-triethyldibenzothiophene, 3-chloro-7-iodo-2,4,
6-triethyldibenzothiophene, 3,7-dibromo-2,4,6
-Triethyldibenzothiophene, 7-chloro-2,4,8-triethyldibenzothiophen-3-ol, 7-bromo-2,4,8-
Triethyldibenzothiophen-3-ol, 7-iodo-2,
4,8-triethyldibenzothiophen-3-ol, 3,7-dichloro-2,4,8-triethyldibenzothiophene, 3-bromo-7-chloro-2,4,8-triethyldibenzothiophene, 3-
Chloro-7-iodo-2,4,8-triethyldibenzothiophene, 3,7-dibromo-2,4,8-triethyldibenzothiophene, 7-chloro-2,6,8-triethyldibenzothiophene-3-
All, 7-bromo-2,6,8-triethyldibenzothiophen-3-ol, 7-iodo-2,6,8-triethyldibenzothiophen-3-ol, 3,7-dichloro-2,6,8- Triethyldibenzothiophene, 3-bromo-7-chloro-2,6,8-triethyldibenzothiophene, 3-chloro-7-iodo-2,6,8-triethyldibenzothiophene, 3,7-dibromo-2,6, 8-triethyldibenzothiophene, 7-chloro-4,6,8-triethyldibenzothiophen-3-ol, 7-bromo-4,6,8-triethyldibenzothiophen-3-ol, 7-iodo-4,6, 8-triethyldibenzothiophen-3-ol, 3,7-dichloro-
4,6,8-triethyldibenzothiophene, 3-bromo-7-chloro-4,6,8-triethyldibenzothiophene, 3-chloro-
7-iodo-4,6,8-triethyldibenzothiophene, 3,7-
Dibromo-4,6,8-triethyldibenzothiophene, 7-chloro-2,4,6,8-tetraethyldibenzothiophen-3-ol, 7-bromo-2,4,6,8-tetraethyldibenzothiophen-3- All, 7-iodo-2,4,6,8-tetraethyldibenzothiophen-3-ol, 3,7-dichloro-2,4,6,8-tetraethyldibenzothiophene, 3-bromo-7-chloro-2, 4,6,8-
Tetraethyldibenzothiophene, 3-chloro-7-iodo-
2,4,6,8-tetraethyldibenzothiophene, 3,7-dibromo-2,4,6,8-tetraethyldibenzothiophene,

7-chloro-2-trifluoromethyldibenzothiophen-3-ol, 7-bromo-2-trifluoromethyldibenzothiophen-3-ol, 7-iodo-2-trifluoromethyldibenzothiophen-3-ol , 3,7-dichloro-
2-trifluoromethyldibenzothiophene, 3-bromo-7
-Chloro-2-trifluoromethyldibenzothiophene, 3-
Chloro-7-iodo-2-trifluoromethyldibenzothiophene, 3,7-dibromo-2-trifluoromethyldibenzothiophene, 3-bromo-7-iodo-2-trifluoromethyldibenzothiophene, 3,7-diiodo- 2-trifluoromethyldibenzothiophene, 7-chloro-8-trifluoromethyldibenzothiophen-3-ol, 7-bromo-8-trifluoromethyldibenzothiophen-3-ol, 7-iodo-8-
Trifluoromethyldibenzothiophen-3-ol, 3,7
-Dichloro-8-trifluoromethyldibenzothiophene,
3-bromo-7-chloro-8-trifluoromethyldibenzothiophene, 3-chloro-7-iodo-8-trifluoromethyldibenzothiophene, 3,7-dibromo-8-trifluoromethyldibenzothiophene, 3-bromo- 7-iodo-8-trifluoromethyldibenzothiophene, 3,7-diiodo-8-trifluoromethyldibenzothiophene, 7-chloro-2,8-bis
(Trifluoromethyl) dibenzothiophen-3-ol, 7
-Bromo-2,8-bis (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-2,8-bis (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-2,8 -
Bis (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-2,8-bis (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,8-bis (trifluoromethyl) dibenzothiophene , 3,7-dibromo-2,8-bis
(Trifluoromethyl) dibenzothiophene, 3-bromo-7
-Iodo-2,8-bis (trifluoromethyl) dibenzothiophene, 3,7-diiodo-2,8-bis (trifluoromethyl) dibenzothiophene, 7-chloro-4-trifluoromethyldibenzothiophen-3-ol , 7-bromo-4-trifluoromethyldibenzothiophen-3-ol, 7-iodo-4-trifluoromethyldibenzothiophen-3-ol, 3,7-dichloro-4-trifluoromethyldibenzothiophene, 3-
Bromo-7-chloro-4-trifluoromethyldibenzothiophene, 3-chloro-7-iodo-4-trifluoromethyldibenzothiophene, 3,7-dibromo-4-trifluoromethyldibenzothiophene, 3-bromo-7- Iodo-4-trifluoromethyldibenzothiophene, 3,7-diiodo-4-trifluoromethyldibenzothiophene, 7-chloro-6-trifluoromethyldibenzothiophen-3-ol, 7-bromo-6-
Trifluoromethyldibenzothiophen-3-ol, 7-
Iodo-6-trifluoromethyldibenzothiophen-3-ol, 3,7-dichloro-6-trifluoromethyldibenzothiophene, 3-bromo-7-chloro-6-trifluoromethyldibenzothiophene, 3-chloro-7- Iodo-6-trifluoromethyldibenzothiophene, 3,7-dibromo-6-trifluoromethyldibenzothiophene, 3-bromo-7-iodo-6-
Trifluoromethyldibenzothiophene, 3,7-diiodo
-6-trifluoromethyldibenzothiophene, 7-chloro-
4,6-bis (trifluoromethyl) dibenzothiophen-3-
All, 7-bromo-4,6-bis (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-4,6-bis (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro- 4,6-bis (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-4,6-bis (trifluoromethyl)
Dibenzothiophene, 3-chloro-7-iodo-4,6-bis (trifluoromethyl) dibenzothiophene, 3,7-dibromo-
4,6-bis (trifluoromethyl) dibenzothiophene, 3-
Bromo-7-iodo-4,6-bis (trifluoromethyl) dibenzothiophene, 3,7-diiodo-4,6-bis (trifluoromethyl) dibenzothiophene, 7-chloro-2,4-bis (trifluoro Methyl) dibenzothiophen-3-ol, 7-bromo
-2,4-bis (trifluoromethyl) dibenzothiophene-3-
All, 7-iodo-2,4-bistrifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-2,4-bis (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-2, 4-bis (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,4-bis (trifluoromethyl)
Dibenzothiophene, 3,7-dibromo-2,4-bis (trifluoromethyl) dibenzothiophene, 7-chloro-2,6-bis
(Trifluoromethyl) dibenzothiophen-3-ol, 7
-Bromo-2,6-bis (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-2,6-bis (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-2,6 -
Bis (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-2,6-bis (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,6-bis (trifluoromethyl) dibenzothiophene , 3,7-dibromo-2,6-bis
(Trifluoromethyl) dibenzothiophene, 7-chloro-
6,8-bis (trifluoromethyl) dibenzothiophene-3-
All, 7-bromo-6,8-bis (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-6,8-bis (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro- 6,8-bis (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-6,8-bis (trifluoromethyl)
Dibenzothiophene, 3-chloro-7-iodo-6,8-bis (trifluoromethyl) dibenzothiophene, 3,7-dibromo-
6,8-bis (trifluoromethyl) dibenzothiophene, 7-
Chloro-4,8-bis (trifluoromethyl) dibenzothiophen-3-ol, 7-bromo-4,8-bis (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-4,8-bis
(Trifluoromethyl) dibenzothiophen-3-ol,
3,7-dichloro-4,8-bis (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-4,8-bis (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-4, 8
-Bis (trifluoromethyl) dibenzothiophene, 3,7-
Dibromo-4,8-bis (trifluoromethyl) dibenzothiophene, 7-chloro-2,4,6-tris (trifluoromethyl)
Dibenzothiophen-3-ol, 7-bromo-2,4,6-tris
(Trifluoromethyl) dibenzothiophen-3-ol, 7
-Iodo-2,4,6-tris (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-2,4,6-tris (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro -2,4,6-tris (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,4,6-tris (trifluoromethyl) dibenzothiophene, 3,7-dibromo-2,4,6 -Tris (trifluoromethyl) dibenzothiophene, 7-chloro
-2,4,8-tris (trifluoromethyl) dibenzothiophen-3-ol, 7-bromo-2,4,8-tris (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-2,4 , 8-
Tris (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-2,4,8-tris (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-2,4,8-tris ( (Trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,4,8-tris (trifluoromethyl) dibenzothiophene, 3,7-dibromo-2,4,8-tris (trifluoromethyl) dibenzothiophene , 7-chloro-2,6,8-tris
(Trifluoromethyl) dibenzothiophen-3-ol, 7
-Bromo-2,6,8-tris (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-2,6,8-tris (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro -2,6,8-tris (trifluoromethyl) dibenzothiophene, 3-bromo-7-chloro-2,6,8-tris (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,6 , 8
-Tris (trifluoromethyl) dibenzothiophene, 3,7
-Dibromo-2,6,8-tris (trifluoromethyl) dibenzothiophene, 7-chloro-4,6,8-tris (trifluoromethyl) dibenzothiophen-3-ol, 7-bromo-4,6,8 -Tris (trifluoromethyl) dibenzothiophen-3-ol, 7-iodo-4,6,8-tris (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-4,6,8-tris
(Trifluoromethyl) dibenzothiophene, 3-bromo-7
-Chloro-4,6,8-tris (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-4,6,8-tris (trifluoromethyl) dibenzothiophene, 3,7-dibromo-4,6 , 8-
Tris (trifluoromethyl) dibenzothiophene, 7-chloro-2,4,6,8-tetrakis (trifluoromethyl) dibenzothiophen-3-ol, 7-bromo-2,4,6,8-tetrakis
(Trifluoromethyl) dibenzothiophen-3-ol, 7
-Iodo-2,4,6,8-tetrakis (trifluoromethyl) dibenzothiophen-3-ol, 3,7-dichloro-2,4,6,8-tetrakis (trifluoromethyl) dibenzothiophene, 3-bromo -7-chloro-2,4,6,8-tetrakis (trifluoromethyl) dibenzothiophene, 3-chloro-7-iodo-2,4,6,8-
Tetrakis (trifluoromethyl) dibenzothiophene,
3,7-dibromo-2,4,6,8-tetrakis (trifluoromethyl) dibenzothiophene and the like.

The dibenzothiophene compound (1) of the present invention
Can be produced by diazotizing a dibenzothiophene compound (2) and decomposing a diazonium salt in the presence of an anion Y. As a method for diazotizing the above dibenzothiophene and decomposing the diazonium salt in the presence of the anion Y, for example, Org.Synth.CV1,404, Org.Synt
hCV3,130, Chem. Ber. 1951, 84, 557 and the like can be used to carry out the method.

Examples of the diazotizing agent used in the above-mentioned production method include nitric acid, nitrosylsulfuric acid, sodium nitrite and the like. Although the amount of the diazotizing agent is not particularly limited, it is usually 1 to 1 with respect to the dibenzothiophene compound (2).
It is about 100 mole times, preferably about 1 to 10 mole times.

The diazotization of the dibenzothiophene compound (2) is usually carried out in an atmosphere of an inert gas such as argon or nitrogen. The reaction can be carried out without a solvent or in a solvent. As the solvent used, for example,
Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; aliphatic hydrocarbons such as hexane, heptane, octane and nonane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; diethyl ether; Ether solvents such as tetrahydrofuran; organic acids such as acetic acid and methanesulfonic acid; mineral acids such as nitric acid and sulfuric acid; water or mixtures thereof. The reaction temperature during the diazotization is not particularly limited, but is usually in the range of about -50 to 100C, preferably about -30 to 50C.

The diazonium salt formed by the above diazotization reaction is generally poor in stability, and is used as it is in the reaction mixture in the next diazo decomposition step.
By performing ordinary operations such as recrystallization and column chromatography, it can be easily separated from the reaction mixture.

After the above diazonium salt is formed, the donor of the anion Y coexisting when decomposing it is water,
Examples thereof include copper (I) chloride, copper (I) bromide, hydrogen chloride, and hydrogen bromide. The amount of the donor of the anion Y is not particularly limited, but is usually 1 to 1 with respect to the dibenzothiophene compound (2).
It is about 100 mole times, preferably about 1 to 10 mole times.

The decomposition of the diazonium salt in the presence of the anion Y is usually carried out in an atmosphere of an inert gas such as argon or nitrogen. The reaction can be carried out without a solvent or in a solvent. Examples of the solvent used include halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; aliphatic hydrocarbons such as hexane, heptane, octane and nonane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene. Hydrogen; ether solvents such as diethyl ether and tetrahydrofuran; organic acids such as acetic acid and methanesulfonic acid; mineral acids such as nitric acid and sulfuric acid; water and mixtures thereof. The temperature of the decomposition reaction is not particularly limited, but is usually-
The temperature is in the range of 50 to 200C, preferably about -30 to 150C. The dibenzothiophene compound (1) produced by the above decomposition reaction is extracted and extracted with an organic solvent as necessary.
By performing ordinary operations such as washing with water, distillation, recrystallization, and column chromatography, the compound can be easily separated from the reaction mixture.

The dibenzothiophene compound of the present invention used in the method for producing the dibenzothiophene compound (1) and the like
(2) is represented by the above equation (2). In equation (2), A ¹
-A ⁶ and X have the same meanings as in formula (1). Further, specific examples of the dibenzothiophene compound (2) include:
A ¹ to A ¹ corresponding to the above-mentioned dibenzothiophene compound (1)
Compounds having A ⁶ and X can be exemplified.

The dibenzothiophene compound (2) of the present invention
Can be produced by reducing dibenzothiophene oxides (3). The reduction at this time reduces two functional groups of a sulfoxide group and a nitro group, but it is possible to sequentially reduce one functional group at a time or to reduce two functional groups at the same time. The above dibenzothiophene oxides (3)
Can be carried out using a known technique described in, for example, J. Am. Chem. Soc. 1952, 74, 1165. As the reducing agent used in the production method, for example, tin (II) chloride,
Iron and the like. Although the amount of the reducing agent is not particularly limited, it is usually 1 to 1 relative to dibenzothiophene oxides (3).
The molar ratio is about 100 to 100 times, and preferably about 1 to 10 times.

The reduction of the dibenzothiophene oxides (3) is usually carried out in an atmosphere of an inert gas such as argon or nitrogen. The reaction can be carried out without a solvent or in a solvent. Examples of the solvent used include halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; aliphatic hydrocarbons such as hexane, heptane, octane and nonane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene. Hydrogen; ether solvents such as diethyl ether and tetrahydrofuran; organic acids such as acetic acid and methanesulfonic acid; mineral acids such as nitric acid and sulfuric acid; water; and mixtures thereof.

The temperature of the reduction reaction is not particularly limited, but is usually -50 to 200 ° C, preferably -30 to 150 ° C.
It is in the range of about ° C. The dibenzothiophene compound (2) generated by the above reduction reaction is easily separated from the reaction mixture by performing ordinary operations such as extraction and washing with an organic solvent, water washing, distillation, recrystallization, and column chromatography, if necessary. be able to.

The dibenzothiophene oxides (3) of the present invention used in the method for producing the dibenzothiophene compound (2) and the like are represented by the above formula (3). In equation (3),
A ^{1 to} A ⁶ and X have the same meanings as those in formula (1).
Further, specific examples of the dibenzothiophene oxides (3) include compounds having A ^{1 to} A ⁶ and X corresponding to the above-mentioned dibenzothiophene compound (1).

The dibenzothiophene oxides of the present invention
(3) can be produced by nitrating dibenzothiophene oxides (4). The nitration of dibenzothiophene oxides (4) is described, for example, in J. Am. Chem.
Soc. 1952, 74, 1165 can be used for the implementation. Examples of the nitrating agent used in the production method include nitrates or nitrites such as sodium, potassium and silver; alkyl nitrates such as butyl nitrate and amyl nitrate; and nitric acid. The amount of the nitrating agent used is not particularly limited, but usually, dibenzothiophene oxides
It is about 1 to 100 mole times with respect to (4), preferably 1 to 100 times.
It is in the range of about 10 to 10 times.

The nitration of the dibenzothiophene oxides (4) is usually performed in an atmosphere of an inert gas such as argon or nitrogen. The reaction can be carried out without a solvent or in a solvent. Examples of the solvent used include halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; aliphatic hydrocarbons such as hexane, heptane, octane and nonane; ether solvents such as diethyl ether and tetrahydrofuran; acetic acid and methane Organic acids such as sulfonic acid; mineral acids such as nitric acid and sulfuric acid; water or a mixture thereof.

The reaction temperature of the nitration is not particularly limited, but is usually -50 to 200 ° C, preferably -30 to 15 ° C.
The range is about 0 ° C. The dibenzothiophene oxides (3) produced in the above nitration reaction can be easily converted from the reaction mixture by performing ordinary operations such as extraction with an organic solvent, washing with water, distillation, recrystallization, and column chromatography, if necessary. Can be separated.

The dibenzothiophene oxides (4) of the present invention used in the method for producing the dibenzothiophene compound (3) and the like are represented by the above formula (4). In equation (4),
A ^{1 to} A ⁶ and X have the same meanings as those in formula (1).
Specific examples of the dibenzothiophene oxides (4) include compounds having A ^{1 to} A ⁶ and X corresponding to the above-mentioned dibenzothiophene compound (1).

The dibenzothiophene oxides of the present invention
(4) can be produced by oxidizing the dibenzothiophene compound (5). Oxidation of the dibenzothiophene compound (5) can be performed, for example, by the method described in J. Am. Chem. Soc.
It can be implemented using the known technique described. Examples of the oxidizing agent used in the production method include organic peroxides such as m-chloroperbenzoic acid; perhalates such as sodium periodate; chlorine / water; and hydrogen peroxide. Although the amount of the oxidizing agent is not particularly limited, it is usually about 1 to 100 mol times, preferably about 1 to 10 mol times with respect to the dibenzothiophene compound (5).

The oxidation of the dibenzothiophene compound (5) is usually carried out in an atmosphere of an inert gas such as argon or nitrogen. The reaction can be carried out without a solvent or in a solvent. Examples of the solvent used include halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; aliphatic hydrocarbons such as hexane, heptane, octane and nonane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene. Hydrogens;
Organic acids such as acetic acid and methanesulfonic acid; mineral acids such as nitric acid and sulfuric acid; water and mixtures thereof.

The temperature of the oxidation reaction is not particularly limited, but is usually -50 to 200 ° C, preferably -30 to 150 ° C.
It is in the range of about ° C. The dibenzothiophene oxides (4) formed by the above oxidation reaction can be easily separated from the reaction mixture by performing ordinary operations such as extraction with an organic solvent, washing with water, distillation, recrystallization, and column chromatography, if necessary. can do.

[0030]

The dibenzothiophene compound of the present invention
(2), dibenzothiophene oxides (3) and (4)
The dibenzothiophene compound (1), which is useful as a raw material for producing an optical functional material and is a conjugated compound produced using these compounds, is particularly useful as a composition material of a liquid crystal material.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In addition, a series of reaction formulas of Examples 1 to 4 shown below are shown below.

Embedded image

Example 1 3-Bromodibenzothiophene was synthesized by the method described in J. Am. Chem. Soc., 1951, 73 , 5887. Under a nitrogen atmosphere, 44.1 g of 3-bromodibenzothiophene synthesized above and 441 g of carbon tetrachloride were charged into a flask equipped with a stirrer and a thermometer, and cooled to -5 ° C. This was bubbled at -7 ° C to -12 ° C for 5 hours while stirring chlorine gas. Thereafter, the reaction mass was poured into 1000 g of ice water and stirred at 5 ° C. or lower for 40 minutes. The resulting reaction was filtered and washed with carbon tetrachloride. The obtained crystals were dried to obtain 27.91 g of 3-bromodibenzothiophene-5-oxide. The results of elemental analysis of the obtained product were as follows. Elemental analysis: C ₁₂ H ₇ BrOS (theoretical value (%): C = 51.6)
3, H = 2.53, analysis value (%): C = 51.59, H = 2.58)

Example 2 In a flask equipped with a stirrer and a thermometer, 69.8 g of glacial acetic acid and 3
27.9 g of bromodibenzothiophene-5-oxide was charged and cooled to 10 ° C. 239.8 g of concentrated sulfuric acid was added dropwise thereto. Then, it was cooled to -2 ° C,
72.0 g of nitric acid was added dropwise at -2 to 8 ° C, and the mixture was stirred at 5 ° C or lower for 2 hours. This was poured into 1200 g of ice water to stop the reaction, and the mixture was further stirred. The obtained reaction product was filtered, washed with water and dried. The obtained dry cake is washed with ethanol, and 3-bromo-7-nitrodibenzothiophene-5 is obtained.
-31.9 g of oxide were obtained. The results of elemental analysis of the obtained product were as follows. Elemental analysis: C ₁₂ H ₆ BrNO ₃ S (theoretical value (%): C = 44.
46, H = 1.87, analysis value (%): C = 44.42, H = 1.84)

Example 3 In a flask equipped with a stirrer and a thermometer, 26.98 g of the intermediate 3-bromo-7-nitrodibenzothiophene-5-oxide prepared in Example 2 and 269 g of glacial acetic acid under a nitrogen atmosphere. 0.8 g was charged. Add SnCl ₂・ 2H
₂ and the O 112.7 g was dissolved in concentrated hydrochloric acid 158g solution 1
The mixture was added dropwise at 4 to 18 ° C over 1 hour and stirred at room temperature overnight. The obtained reaction product was filtered, and glacial acetic acid / concentrated hydrochloric acid = 1/1.
And washed. Next, 1100 g of a 7% by mass aqueous sodium hydroxide solution was added for neutralization, and the reaction product was extracted with ethyl acetate. After washing with water, the mixture was concentrated and purified by silica gel chromatography using 0.1% by mass of hexane / chloroform and 0.1% by mass of triethylamine as a mobile phase to obtain the desired 7-bromodibenzothiophene-3.
17.31 g of -ylamine were obtained. The results of elemental analysis of the obtained product were as follows. Elemental analysis: C ₁₂ H ₈ BrNS (theoretical value (%): C = 51.8)
1, H = 2.90, analysis value (%): C = 51.77, H = 2.92)

Example 4 A flask equipped with a stirrer and a thermometer was charged with 209.3 g of concentrated sulfuric acid and 8.93 g of NaNO ₂ under a nitrogen atmosphere and cooled to 2 ° C. Then, the intermediate 7-bromodibenzothiophen-3-ylamine 2 prepared in Example 3
4.0 g was added, and the mixture was stirred at 2 to 4 ° C for 3 hours. This was mixed with 99.8 g of water and heated to 80 ° C. in 65% by mass sulfuric acid 34.
The mixture was co-injected into 8.7 g, and stirred at 80 to 85 ° C for 5 hours.
Then, the mixture was cooled to room temperature, and the obtained reaction product was filtered, extracted with 300 ml of ethyl acetate six times, and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography using chloroform as a mobile phase to obtain 7.11 g of the objective 7-bromodibenzothiophen-3-ol. The results of ¹ H-NMR spectrum analysis and elemental analysis of the purified product obtained are shown below. ¹ H-NMR (CDCl ₃ , δ): 4.98 (s, 1H), 6.95-7.00 (m, 1H), 7.25
-7.27 (m, 1H), 7.50-7.54 (m, 1H), 7.84-7.88 (m, 1H), 7.91-
7.93 (m, 1H), 7.93-7.97 (m, 1H) Elemental analysis: C ₁₂ H ₇ BrOS (theoretical value (%): C = 51.6)
3, H = 2.53, analysis value (%): C = 51.58, H = 2.55)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayoshi Minami 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Industries Co., Ltd. (72) Inventor Koichi Fujisawa 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd. Inside

Claims (8)

[Claims] 1. A dibenzothiophene compound represented by the formula (1). Embedded image (In the formula, A ^{1 to} A ⁶ each independently represent a hydrogen atom, a fluorine atom, or a carbon atom which may be substituted with a fluorine atom.
X represents an alkyl group or an alkoxy group, X represents a halogen atom, and Y represents a halogen atom or a hydroxyl group. ) 2. A dibenzothiophene compound represented by the formula (2). Embedded image (In the formula, A ^{1 to} A ⁶ and X have the same meanings as those in the formula (1).) 3. Dibenzothiophene oxides represented by the formula (3). Embedded image (In the formula, A ^{1 to} A ⁶ and X have the same meanings as those in the formula (1).) 4. Dibenzothiophene oxides represented by the formula (4). Embedded image (In the formula, A ^{1 to} A ⁶ and X have the same meanings as those in the formula (1).) 5. The method according to claim 1, wherein the dibenzothiophene compound represented by the formula (2) is diazotized and the diazonium salt is decomposed in the presence of an anion corresponding to Y in the formula (1). A method for producing a dibenzothiophene compound represented by the formula (1). 6. The compound according to claim 2, wherein the dibenzothiophene oxide represented by the formula (3) is reduced.
A method for producing the dibenzothiophene compound represented by (2). 7. The method for producing a dibenzothiophene oxide represented by the formula (3) according to claim 3, wherein the dibenzothiophene oxide represented by the formula (4) is nitrated. 8. Dibenzothiophenation represented by the formula (5)
Compound (wherein, A¹~ A ⁶And X have the same meanings as described above.
You. ) Is oxidized.
Method for producing dibenzothiophene oxides shown in (4)
Law. Embedded image