JPH11302255A - New compound containing sulfur and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as lubricating oil, an additive for the same, grease, an antioxidant, or the like, which are excellent in oxidation stability and thermal stability, and capable of being synthesized from an easily available raw material, by reacting easily available 2,6-dihalopyridine with benzenethiol. SOLUTION: This compound is expressed by formula I [wherein, R<1> and R<2> are each a halogen or a 1-24C hydrocarbon; (m) and (n) are each 0-5], e.g. 2,6-diphenylthiopyridine. The compound of formula I is obtained by reacting 2,6-dihalopyridine of formula II with benzenethiols of formula III and formula IV pref. in the presence of a base. The compound of formula II is easily obtained by the halogenation of pyridine. It is preferable that the compound of formula II is 2,6-dichloropyridine or the like, a sort of benzenethiols is benzenethiol or the like, a base is sodium methylate or the like and the reaction temperature is 100-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel sulfur-containing compound and a method for producing the same. More specifically, the present invention relates to a novel sulfur-containing compound suitable as a lubricating oil, a lubricating oil additive, a grease, an antioxidant and the like having excellent oxidation stability and heat stability, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, synthetic hydrocarbon oils such as petroleum hydrocarbon oils, silicone oils, polyphenylthioether oils and ester oils have been used as lubricating oils. Of these,
Petroleum hydrocarbon oils have the drawback of low heat resistance and oxidation resistance, and ester oils and silicone oils have the drawback of being susceptible to hydrolysis.

On the other hand, polyphenylthioether compounds are disclosed in JP-A-8-259520 as an excellent lubricating oil which is excellent in heat resistance and oxidation resistance and is not easily hydrolyzed. It has been shown that the polyphenylthioether compound is obtained from a thiophenol metal salt and m-dihalobenzene, but the raw material m-
Dihalobenzene is difficult to obtain industrially,
Furthermore, the reactivity of m-dihalobenzene is low, so that there is a problem in practicality such as a need to react at a high temperature for a long time.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a sulfur-containing polyphenylthioether oil which retains heat resistance and oxidation resistance, which are characteristics of polyphenylthioether oil, and which can be easily synthesized using easily available raw materials. An object is to provide a compound and a method for producing the compound.

[0005]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above-mentioned problems, and as a result, they can be obtained by reacting easily available 2,6-dihalopyridine with benzenethiols. The present inventors have found that the novel sulfur-containing compounds are useful as lubricating oils, lubricating oil additives, greases, antioxidants and the like having excellent oxidation stability and heat stability, and completed the present invention.

That is, the gist of the present invention is as follows: (1) Equation (1):

Embedded image Wherein R ¹ and R ² may be the same or different and each represents a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and m represents 0 to 5
And n represents an integer of 0 to 5. (2) Formula (2) in which m and n are each 0 in formula (1):

Embedded image (3) In the formula (1), R ¹ and R ² are both linear alkyl groups having 1 to 20 carbon atoms, and m is an integer of 1 to 5 So,
(1) The novel sulfur-containing compound according to (1), wherein n is an integer of 1 to 5, (4) In the formula (1), R ¹ and R ² are both methyl groups, and m and n are each 1 3):

Embedded image 2,6-di (4-methylbenzenethio) pyridine represented by the following formula (5):

Embedded image And a 2,6-dihalopyridine represented by the formula (5):

Embedded image And equation (6):

Embedded image A process for producing a novel sulfur-containing compound represented by the formula (1), wherein R ¹ and R ² may be the same or different from each other. Represents a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms, m represents an integer of 0 to 5, n represents 0 to 5
Represents an integer. (6) The method according to (5), wherein the reaction is performed in the presence of a base.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The novel sulfur-containing compound of the present invention is represented by the formula (1). Where R ¹
And R ² may be the same or different,
Represents a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms. m represents an integer of 0 to 5, and n represents an integer of 0 to 5.

[0008] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The C 1-24 hydrocarbon group includes a C 1-24 linear alkyl group, a C 3-24 branched alkyl group, a C 3-24 linear alkenyl group, A branched alkenyl group having 3 to 24 carbon atoms, a carbon number of 6 to
24 cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and the like. Among these, preferred hydrocarbon groups are linear alkyl groups having 1 to 20 carbon atoms.

Specific examples of the novel sulfur-containing compound represented by the formula (1) include, for example, 2,6-diphenylthiopyridine, 2,6-di (2-chlorobenzenethio) pyridine,
2,6-di (3-chlorobenzenethio) pyridine, 2,
6-di (4-chlorobenzenethio) pyridine, 2,6-
Di (2-bromobenzenethio) pyridine, 2,6-di (3-bromobenzenethio) pyridine, 2,6-di (4
-Bromobenzenethio) pyridine, 2,6-di (2-iodobenzenethio) pyridine, 2,6-di (3-iodobenzenethio) pyridine, 2,6-di (4-iodobenzenethio) pyridine, 2,6-di (2-fluorobenzenethio) pyridine, 2,6-di (3-fluorobenzenethio) pyridine, 2,6-di (4-fluorobenzenethio) pyridine, 2,6-di (2,5 -Dichlorobenzenethio) pyridine, 2,6-di (2,6-dichlorobenzenethio) pyridine, 2,6-di (3,4-dichlorobenzenethio) pyridine, 2,6-di (2,5-dibromo Benzenethio) pyridine, 2,6-di (2,6-dibromobenzenethio) pyridine, 2,6-di (3,4-dibromobenzenethio) pyridine, 2,6-di (2,5-diiodobenzene) Thio Pyridine, 2,6-di (2,6-di-iodobenzene thio) pyridine, 2,6-di (3,4
Diiodobenzenethio) pyridine, 2,6-di (2.5
-Difluorobenzenethio) pyridine, 2,6-di (2,6-difluorobenzenethio) pyridine, 2,6
-Di (3,4-difluorobenzenethio) pyridine,
2,6-di (2,4,5-trichlorobenzenethio) pyridine, 2,6-di (2,4,5-tribromobenzenethio) pyridine, 2,6-di (2,4,5-tri Iodobenzenethio) pyridine, 2,6-di (2,4,5-trifluorobenzenethio) pyridine, 2,6-di (2,
3,5,6-tetrachlorobenzenethio) pyridine,
2,6-di (2,3,5,6-tetrabromobenzenethio) pyridine, 2,6-di (2,3,5,6-tetraiodobenzenethio) pyridine, 2,6-di (2 3,
5,6-tetrafluorobenzenethio) pyridine, 2,
6-di (2,3,4,5,6-pentachlorobenzenethio) pyridine, 2,6-di (2,3,4,5,6-pentabromobenzenethio) pyridine, 2,6-di (2 ,
3,4,5,6-pentaiodobenzenethio) pyridine, 2,6-di (2,3,4,5,6-pentafluorobenzenethio) pyridine, 2,6-di (2-chloro-4)
-Bromobenzenethio) pyridine, 2,6-di (2-bromo-4-chlorobenzenethio) pyridine, 2,6-di (2,4-dichloro-5-bromobenzenethio) pyridine, 2,6-di ( 2,4-dibromo-5-chlorobenzenethio) pyridine, 2,6-di (2-methylbenzenethio) pyridine, 2,6-di (3-methylbenzenethio)
Pyridine, 2,6-di (4-methylbenzenethio) pyridine, 2,6-di (2-ethylbenzenethio) pyridine, 2,6-di (3-ethylbenzenethio) pyridine,
2,6-di (4-ethylbenzenethio) pyridine, 2,
6-di (2-propylbenzenethio) pyridine, 2,6
-Di (3-propylbenzenethio) pyridine, 2,6-
Di (4-propylbenzenethio) pyridine, 2,6-di (2-butylbenzenethio) pyridine, 2,6-di (3
-Butylbenzenethio) pyridine, 2,6-di (4-butylbenzenethio) pyridine, 2,6-di (4-pentylbenzenethio) pyridine, 2,6-di (4-hexylbenzenethio) pyridine, 2,6-di (4-cyclohexylbenzenethio) pyridine, 2,6-di (4-heptylbenzenethio) pyridine, 2,6-di (4-octylbenzenethio) pyridine, 2,6-di (4-nonyl) Benzenethio) pyridine, 2,6-di (4-decylbenzenethio) pyridine, 2,6-di (4-undecylbenzenethio) pyridine, 2,6-di (4-dodecylbenzenethio) pyridine, 2, 6-di (4-tridecylbenzenethio) pyridine, 2,6-di (4-tetradecylbenzenethio) pyridine, 2,6-di (4-pentadecylbenzenethio) pyridine 2,6-di (4-hexadecylbenzenethio) pyridine, 2,6-di (4-heptadecylbenzenethio) pyridine, 2,6-di (4-octadecylbenzenethio) pyridine, 2,6-di ( 4-nonadecylbenzenethio) pyridine, 2,6-di (4-icosylbenzenethio) pyridine, 2,6-di (4-henicosylbenzenethio) pyridine, 2,6-di (4-docosyl) Benzenethio) pyridine, 2,6-di (4-tricosylbenzenethio) pyridine, 2,6-di (4-tetracosylbenzenethio) pyridine, 6-di (4-chloro-2-methylbenzenethio) Pyridine, 2,6-di (2-chloro-3-methylbenzenethio) pyridine, 2,6-di (2
-Chloro-4-methylbenzenethio) pyridine, 2,6
-Di (4-chloro-2-ethylbenzenethio) pyridine, 2,6-di (2-chloro-4-ethylbenzenethio) pyridine, 2,6-di (2-chloro-4-ethylbenzenethio) pyridine, 2, 6-di (2-chloro-4-
Propylbenzenethio) pyridine, 2,6-di (2-chloro-4-butylbenzenethio) pyridine, 2,6-di (2-chloro-4-hexylbenzenethio) pyridine,
2,6-di [2-chloro-4- (cyclohexyl) benzenethio] pyridine, 2,6-di (2-chloro-4-dodecylbenzenethio) pyridine, 2,6-di (2-chloro-4-tetra Kosylbenzenethio) pyridine, 2,6
-Di (4-fluoro-2-methylbenzenethio) pyridine, 2,6-di (2-fluoro-3-methylbenzenethio) pyridine, 2,6-di (2-fluoro-4-methylbenzenethio) pyridine , 2,6-di (2-ethyl-4
-Fluorobenzenethio) pyridine, 2,6-di (4-
Ethyl-2-fluorobenzenethio) pyridine, 2,6
-Di (2-fluoro-4-propylbenzenethio) pyridine, 2,6-di (2-fluoro-4-butylbenzenethio) pyridine, 2,6-di (2-fluoro-4-hexylbenzenethio) pyridine 2,6-di [2-fluoro-4- (cyclohexyl) benzenethio] pyridine,
2,6-di (2-fluoro-4-dodecylbenzenethio) pyridine, 2,6-di (2-fluoro-4-tetracosylbenzenethio) pyridine, 2,6-di (3,4-
Dichloro-2-methylbenzenethio) pyridine, 2,6
-Di (2,3-dichloro-4-methylbenzenethio) pyridine, 2,6-di (2,5-dichloro-4-methylbenzenethio) pyridine, 2,6-di (2,4-dichloro-3) -Methylbenzenethio) pyridine, 2,6-di (2,5-dichloro-3-methylbenzenethio) pyridine, 2,6-di (3,4-dichloro-2-ethylbenzenethio) pyridine, 2,6- Di (2,5-dichloro-4
-Ethylbenzenethio) pyridine, 2,6-di (2.5
-Dichloro-4-propylbenzenethio) pyridine,
2,6-di (2,5-dichloro-4-butylbenzenethio) pyridine, 2,6-di (2,5-dichloro-4-hexylbenzenethio) pyridine, 2,6-di [2,5-
Dichloro-4- (cyclohexyl) benzenethio] pyridine, 2,6-di (2,5-dichloro-4-dodecylbenzenethio) pyridine, 2,6-di (2,5-dichloro-4-tetracosylbenzenethio) ) Pyridine, 2,6-
Di (3,4-dichloro-2-methylbenzenethio) pyridine, 2,6-di (2,3-difluoro-4-methylbenzenethio) pyridine, 2,6-di (2,5-difluoro-4-) Methylbenzenethio) pyridine, 2,6-di (2,4-difluoro-3-methylbenzenethio) pyridine, 2,6-di (2,5-difluoro-3-methylbenzenethio) pyridine, 2,6- Di (3,4-difluoro-2-ethylbenzenethio) pyridine, 2,6-di (2,5-difluoro-4-ethylbenzenethio) pyridine, 2,6-di (2,5-difluoro-4-propylbenzene) Thio) pyridine, 2,6-di [2,5-difluoro-4- (cyclohexyl) benzenethio] pyridine, 2,6-di (2,5-difluoro-4-butylbenzenethio) pyridine, 6-di (2,5-difluoro-4-hexylbenzenethio) pyridine, 2,6-di (2,5-difluoro-4-dodecylbenzenethio) pyridine, 2,6-di (2,5-difluoro- 4-tetracosylbenzenethio) pyridine, 2,6-di (2,3,
5,6-tetrachloro-4-methylbenzenethio) pyridine, 2,6-di (2,5-dichloro-4-ethylbenzenethio) pyridine, 2,6-di (2,3,5,6-tetrachloro) -4-propylbenzenethio) pyridine,
2,6-di (2,3,5,6-tetrachloro-4-butylbenzenethio) pyridine, 2,6-di (2,3,5
6-tetrachloro-4-hexylbenzenethio) pyridine, 2,6-di [2,3,5,6-tetrachloro-4-
(Cyclohexyl) benzenethio] pyridine, 2,6-
Di (2,3,5,6-tetrachloro-4-dodecylbenzenethio) pyridine, 2,6-di (2,3,5,6-tetrachloro-4-tetracosylbenzenethio) pyridine, 2, 6-di (2,3,5,6-tetrafluoro-4-
Methylbenzenethio) pyridine, 2,6-di (2,5-
Difluoro-4-ethylbenzenethio) pyridine, 2,
6-di (2,3,5,6-tetrafluoro-4-propylbenzenethio) pyridine, 2,6-di (2,3,5
6-tetrafluoro-4-butylbenzenethio) pyridine, 2,6-di (2,3,5,6-tetrafluoro-4)
-Hexylbenzenethio) pyridine, 2,6-di [2,
3,5,6-tetrafluoro-4- (cyclohexyl)
Benzenethio] pyridine, 2,6-di (2,3,5,6
-Tetrafluoro-4-dodecylbenzenethio) pyridine, 2,6-di (2,3,5,6-tetrafluoro-4)
-Tetracosylbenzenethio) pyridine, 2,6-di (2,3-dimethylbenzenethio) pyridine, 2,6-
Di (2,4-dimethylbenzenethio) pyridine, 2,6
-Di (2,5-dimethylbenzenethio) pyridine, 2,
6-di (2,6-dimethylbenzenethio) pyridine,
2,6-di (3,4-dimethylbenzenethio) pyridine, 2,6-di (3,5-dimethylbenzenethio) pyridine, 2,6-di (2,5-diethylbenzenethio) pyridine, 2,6 -Di (2-methyl-4-butylbenzenethio) pyridine, 2,6-di (2-methyl-4-hexylbenzenethio) pyridine, 2,6-di [2-methyl-
4- (cyclohexyl) benzenethio] pyridine, 2,
6-di (2-methyl-4-dodecylbenzenethio) pyridine, 2,6-di (2-methyl-4-tetracosylbenzenethio) pyridine, 2,6-di (2-ethyl-4-butylbenzene) Thio) pyridine, 2,6-di (2-ethyl-4-hexylbenzenethio) pyridine, 2,6-di (2-ethyl-4-dodecylbenzenethio) pyridine,
2,6-di (2-ethyl-4-tetracosylbenzenethio) pyridine, 2,6-di (2,4,6-trimethylbenzenethio) pyridine, 2,6-di (2,3,4, 5-
Tetramethylbenzenethio) pyridine, 2,6-di (2,3,4,5,6-pentamethylbenzenethio) pyridine, 2,6-di (2-ethyl-4,6-dimethylbenzenethio) pyridine, 2,6-di (4,6-dimethyl-2-propylbenzenethio) pyridine, 2,6-di (4,6-dimethyl-2-butylbenzenethio) pyridine, 2,6-di (4,6- Dimethyl-2-pentylbenzenethio) pyridine, 2,6-di (4,6-dimethyl-
2-hexylbenzenethio) pyridine, 2,6-di (2
-Cyclohexyl-4,6-dimethylbenzenethio) pyridine, 2,6-di (2-octyl-4,6-dimethylbenzenethio) pyridine, 2,6-di (2-octadecyl-4,6-dimethylbenzenethio) ) Pyridine, 2,6
-Di (4,6-dimethyl-2-tetracosylbenzenethio) pyridine, 2,6-di (2-octyl-4-methylbenzenethio) pyridine, 2,6-di (2,6-dioctyl-4) -Methylbenzenethio) pyridine, 2,6-di (2-ethyl-6-octyl-4-methylbenzenethio) pyridine, 2-phenylthio-6- (4-methylbenzenethio) pyridine, 2-phenylthio-6- (4-
Chlorobenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-chlorobenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-octylbenzenethio) pyridine, 2,6- Di (4-octylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-nonylbenzenethio) pyridine,
2,6-di (4-nonylbenzenethio) pyridine, 2-
(4-methylbenzenethio) -6- (4-decylbenzenethio) pyridine, 2,6-di (4-decylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6
(4-undecylbenzenethio) pyridine, 2,6-di (4-undecylbenzenethio) pyridine, 2- (4-
Methylbenzenethio) -6- (4-dodecylbenzenethio) pyridine, 2,6-di (4-dodecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6
(4-tridecylbenzenethio) pyridine, 2,6-di (4-tridecylbenzenethio) pyridine, 2- (4-
Methylbenzenethio) -6- (4-tetradecylbenzenethio) pyridine, 2,6-di (4-tetradecylbenzenethio) pyridine, 2- (4-methylbenzenethio)
-6- (4-pentadecylbenzenethio) pyridine,
2,6-di (4-pentadecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-hexadecylbenzenethio) pyridine, 2,6-di (4-hexadecylbenzenethio) Pyridine, 2- (4-methylbenzenethio) -6- (4-heptadecylbenzenethio) pyridine, 2,6-di (4-heptadecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6
-(4-octadecylbenzenethio) pyridine, 2,6
-Di (4-octadecylbenzenethio) pyridine and the like.

Preferably, 2,6-diphenylthiopyridine, 2,6-di (4-methylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-octylbenzenethio) pyridine, , 6-di (4-octylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-nonylbenzenethio) pyridine,
2,6-di (4-nonylbenzenethio) pyridine, 2-
(4-methylbenzenethio) -6- (4-decylbenzenethio) pyridine, 2,6-di (4-decylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6
(4-undecylbenzenethio) pyridine, 2,6-di (4-undecylbenzenethio) pyridine, 2- (4-
Methylbenzenethio) -6- (4-dodecylbenzenethio) pyridine, 2,6-di (4-dodecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6
(4-dodecylbenzenethio) pyridine, 2,6-di (4-dodecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-tetradecylbenzenethio) pyridine, 2,6-di (4-tetradecylbenzenethio) pyridine, 2- (4-methylbenzenethio)-
6- (4-pentadecylbenzenethio) pyridine, 2,
6-di (4-pentadecylbenzenethio) pyridine, 2
-(4-methylbenzenethio) -6- (4-hexadecylbenzenethio) pyridine, 2,6-di (4-hexadecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4 -Heptadecylbenzenethio) pyridine, 2,6-di (4-heptadecylbenzenethio) pyridine, 2- (4-methylbenzenethio) -6- (4-
Octadecylbenzenethio) pyridine, 2,6-di (4
-Octadecylbenzenethio) pyridine and the like.

Particularly preferably, in the formula (1), 2,6-diphenylthiopyridine wherein m and n are each 0, R ¹ is a dodecyl group, m = 1, R ² is a methyl group, and n = 2- (4-methylbenzenethio) -6 which is 1
-(4-dodecylbenzenethio) pyridine, 2,6-di (4-dodecylbenzenethio) pyridine wherein R ¹ and R ² are dodecyl groups and m and n are each 1;
2,6-di (4-methylbenzenethio) pyridine wherein ¹ and R ² are methyl groups and m and n are each 1;

Next, the method for producing the novel sulfur-containing compound of the present invention will be described in detail. That is, the novel sulfur-containing compound of the present invention can be obtained by reacting 2,6-dihalopyridine with benzenethiols in the presence of a base, as shown in the following reaction formula.

Embedded image (Wherein, X represents a halogen atom, R ¹ and R ² may be the same or different, each represents a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms, m represents an integer of 0 to 5, n represents an integer of 0 to 5.)

The 2,6-dihalopyridine used in the reaction can be easily obtained by halogenating pyridine. In particular, as the dichloro compound, a commercially available product produced industrially can be used. Specific examples of 2,6-dihalopyridine include 2,6-dichloropyridine and 2,6-dichloropyridine.
Dibromopyridine, 2,6-difluoropyridine, 2,
6-diiodopyridine and the like.
6-dichloropyridine and 2,6-dibromopyridine are exemplified.

The benzenethiols used in the reaction are:
For example, Can. J. Chem. , 53, 1480 (1
975) and the like, and can be easily obtained by a nucleophilic substitution reaction between a diazonium salt and a sulfide anion.

Specific examples of benzenethiols include, in addition to benzenethiol, substituted benzenethiols such as 2-chlorobenzenethiol, 3-chlorobenzenethiol, 4-chlorobenzenethiol, 2-bromobenzenethiol, 4-bromobenzenethiol. , 4-iodobenzenethiol, 2-fluorobenzenethiol, 3-fluorobenzenethiol, 4-fluorobenzenethiol, 2,5-dichlorobenzenethiol,
2,6-dichlorobenzenethiol, 3,4-dichlorobenzenethiol, 2,5-dibromobenzenethiol, 2,6-dibromobenzenethiol, 3,4-dibromobenzenethiol, 2,5-diiodobenzenethiol, , 5-difluorobenzenethiol, 2,6-
Difluorobenzenethiol, 3,4-difluorobenzenethiol, 2,4,5-trichlorobenzenethiol, 2,4,5-tribromobenzenethiol, 2,
4,5-trifluorobenzenethiol, 2,3,5
6-tetrachlorobenzenethiol, 2,3,5,6-
Tetrafluorobenzenethiol, 2,3,4,5,6
-Pentachlorobenzenethiol, 2,3,4,5,6
-Pentafluorobenzenethiol, 2-methylbenzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, 2-ethylbenzenethiol, 4-
Ethylbenzenethiol, 4-propylbenzenethiol, 4-butylbenzenethiol, 4-pentylbenzenethiol, 4-hexylbenzenethiol, 4-cyclohexylbenzenethiol, 4-heptylbenzenethiol, 4-octylbenzenethiol, 4-nonylbenzenethiol 4-decylbenzenethiol, 4-undecylbenzenethiol, 4-dodecylbenzenethiol, 4-tridecylbenzenethiol, 4-tetradecylbenzenethiol, 4-pentadecylbenzenethiol, 4-hexadecylbenzenethiol, Heptadecylbenzenethiol, 4-octadecylbenzenethiol, 4-nonadecylbenzenethiol, 4-icosylbenzenethiol, 4-henicosylbenzenethiol, 4-docosyl Nzenchioru, 4- Trichoderma sill benzenethiol, 4-tetracosyl benzenethiol,
4-chloro-2-methylbenzenethiol, 2-chloro-3-methylbenzenethiol, 2-chloro-4-methylbenzenethiol, 4-chloro-2-ethylbenzenethiol, 2-chloro-4-ethylbenzenethiol,
2-chloro-4-propylbenzenethiol, 2-chloro-4-butylbenzenethiol, 2-chloro-4-hexylbenzenethiol, 2-chloro-4- (cyclohexyl) benzenethiol, 2-chloro-4-dodecylbenzene Thiol, 2-chloro-4-tetracosylbenzenethiol, 4-fluoro-2-methylbenzenethiol, 2-fluoro-3-methylbenzenethiol,
-Fluoro-4-methylbenzenethiol, 2-ethyl-4-fluorobenzenethiol, 4-ethyl-2-fluorobenzenethiol, 2-fluoro-4-propylbenzenethiol, 2-fluoro-4-butylbenzenethiol, -Fluoro-4-hexylbenzenethiol, 2-fluoro-4- (cyclohexyl) benzenethiol, 2-fluoro-4-dodecylbenzenethiol, 2-fluoro-4-tetracosylbenzenethiol, 3,4-dichloro-2 -Methylbenzenethiol,
2,3-dichloro-4-methylbenzenethiol, 2,
5-dichloro-4-methylbenzenethiol, 2,4-
Dichloro-3-methylbenzenethiol, 2,5-dichloro-3-methylbenzenethiol, 3,4-dichloro-2-ethylbenzenethiol, 2,5-dichloro-4
-Ethylbenzenethiol, 2,5-dichloro-4-propylbenzenethiol, 2,5-dichloro-4-butylbenzenethiol, 2,5-dichloro-4-hexylbenzenethiol, 2,5-dichloro-4- (cyclohexyl ) Benzenethiol, 2,5-dichloro-4-dodecylbenzenethiol, 2,5-dichloro-4-tetracosylbenzenethiol, 3,4-difluoro-2-
Methylbenzenethiol, 2,3-difluoro-4-methylbenzenethiol, 2,5-difluoro-4-methylbenzenethiol, 2,4-difluoro-3-methylbenzenethiol, 2,5-difluoro-3-methylbenzene Thiol, 3,4-difluoro-2-ethylbenzenethiol, 2,5-difluoro-4-ethylbenzenethiol, 2,5-difluoro-4-propylbenzenethiol, 2,5-difluoro-4-butylbenzenethiol, 2, 5-difluoro-4-hexylbenzenethiol, 2,5-difluoro-4- (cyclohexyl) benzenethiol, 2,5-difluoro-4-dodecylbenzenethiol, 2,5-difluoro-4-tetracosylbenzenethiol, 2,3,5,6-tetrachloro-4-methylbe Zenchioru, 2,5-dichloro-4-ethylbenzene-thiol, 2,3,5,6-tetrachloro-4-propylbenzene-thiol, 2,3,
5,6-tetrachloro-4-butylbenzenethiol,
2,3,5,6-tetrachloro-4-hexylbenzenethiol, 2,3,5,6-tetrachloro-4- (cyclohexyl) benzenethiol, 2,3,5,6-tetrachloro-4-dodecyl Benzenethiol, 2,3
5,6-tetrachloro-4-tetracosylbenzenethiol, 2,3,5,6-tetrafluoro-4-methylbenzenethiol, 2,5-difluoro-4-ethylbenzenethiol, 2,3,5,6- Tetrafluoro-4-propylbenzenethiol, 2,3,5,6-tetrafluoro-4-butylbenzenethiol, 2,3,5,6-
Tetrafluoro-4-hexylbenzenethiol, 2,
3,5,6-tetrafluoro-4- (cyclohexyl)
Benzenethiol, 2,3,5,6-tetrafluoro-
4-dodecylbenzenethiol, 2,3,5,6-tetrafluoro-4-tetracosylbenzenethiol, 2,
3-dimethylbenzenethiol, 2,4-dimethylbenzenethiol, 2,5-dimethylmethylbenzenethiol, 2,6-dimethylbenzenethiol, 3,4-dimethylbenzenethiol, 3,5-dimethylbenzenethiol, 2,5 -Diethylbenzenethiol, 2-methyl-4-butylbenzenethiol, 2-methyl-4-hexylbenzenethiol, 2-methyl-4-dodecylbenzenethiol, 2-methyl-4-tetracosylbenzenethiol, 2-ethyl- 4-butylbenzenethiol,
2-ethyl-4-hexylbenzenethiol, 2-ethyl-4-dodecylbenzenethiol, 2-ethyl-4-
Examples include tetracosylbenzenethiol, 2,4,6-trimethylbenzenethiol, 2,3,4,5-tetramethylbenzenethiol, and 2,3,4,5,6-pentamethylbenzenethiol.

Preferably, 4-methylbenzenethiol, 4-ethylbenzenethiol, 4-propylbenzenethiol, 4-butylbenzenethiol, 4-pentylbenzenethiol, 4-hexylbenzenethiol,
4-cyclohexylbenzenethiol, 4-heptylbenzenethiol, 4-octylbenzenethiol, 4-
Nonylbenzenethiol, 4-decylbenzenethiol, 4-undecylbenzenethiol, 4-dodecylbenzenethiol, 4-tridecylbenzenethiol,
-Tetradecylbenzenethiol, 4-pentadecylbenzenethiol, 4-hexadecylbenzenethiol,
4-heptadecylbenzenethiol, 4-octadecylbenzenethiol, 4-nonadecylbenzenethiol,
4-icosylbenzenethiol, 4-henicosylbenzenethiol, 4-docosylbenzenethiol, 4-tricosylbenzenethiol, 4-tetracosylbenzenethiol, benzenethiol and the like.

Particularly preferred is benzenethiol,
Methylbenzenethiol, 4-octylbenzenethiol, 4-nonylbenzenethiol, 4-decylbenzenethiol, 4-undecylbenzenethiol, 4-dodecylbenzenethiol, 4-tridecylbenzenethiol, 4-tetradecylbenzenethiol, -Pentadecylbenzenethiol, 4-hexadecylbenzenethiol, 4-heptadecylbenzenethiol, 4-octadecylbenzenethiol and the like.

The total amount of benzenethiols used is 2,
It is 2 to 5 moles, preferably 2 to 3 moles relative to 6-dihalopyridine. 2 benzenethiols used
If the molar ratio is less than twice, the yield of the target sulfur-containing compound decreases,
Use of more than 5 moles is not preferable because no effect corresponding to the use is obtained and it is not economical.

Examples of the base used in the present invention include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, trimethylamine, triethylamine, tripropylamine, tributylamine, and the like. Examples include tertiary amines such as N, N-dimethylaniline, and metal alcoholates such as sodium methylate, sodium ethylate, and potassium tert-butylate. Preferred are metal alcoholates such as sodium methylate, sodium ethylate, potassium tert-butylate and the like, and more preferred are sodium methylate and potassium tert-butylate.

The amount of the base to be used is generally 2 to 5 moles, preferably 2 to 3 moles, relative to 2,6-dihalopyridine. If the amount of the base used is less than 2 moles, the yield of the target sulfur-containing compound decreases, and if it is used in excess of 5 moles, the effect corresponding thereto cannot be obtained and it is not economical.

The reaction temperature is 0 to 250 ° C., preferably 1 to 250 ° C.
00 to 200 ° C. When the reaction temperature exceeds 250 ° C., by-products increase, and the yield of the target sulfur-containing compound decreases. On the other hand, if the reaction temperature is lower than 0 ° C., the reaction rate is low, which is not practical.

The reaction proceeds without solvent, but a polar organic solvent can also be used. As the polar organic solvent, for example, N-methyl-2-pyrrolidone, N-propyl-2-
Examples include pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like.

The reaction can be carried out in a two-phase system of water and an organic solvent. Examples of the organic solvent include hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as monochlorobenzene and o-dichlorobenzene. In this case, when a quaternary ammonium salt such as tetra-n-butylammonium bromide or tetra-n-butylammonium chloride is used as a phase transfer catalyst,
The reaction proceeds smoothly.

The reaction can be carried out at normal pressure, that is, at atmospheric pressure, but can also be carried out under pressure.
When the reaction is performed under pressure, the pressure range is 1 to 15 kg / c.
It is preferably set to m ^2, and more preferably set to ¹ to 10 Kg / cm ² .

The reaction time varies depending on the reaction temperature, but is usually about 1 to 15 hours. The progress of the reaction can be confirmed by liquid chromatography. After completion of the reaction, the product can be isolated and purified by a method such as recrystallization.

[0027]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to only these.

Example 1 2,6-dichloropyridine 29 was placed in a 5-liter four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser.
6.2 g (2.0 mol) and benzenethiol 44
0.7 g (4.0 mol) and 1200 g of N, N-dimethylformamide were charged and 848.9 g of a 28% sodium methylate solution at a reaction temperature of 20 to 70 ° C.
(4.4 mol) was added dropwise over 2 hours. After dropping,
After methanol was distilled off, stirring was continued at 120 ° C for 2 hours, and then cooled to 20 ° C. 1500 g of methylene chloride was added to the reaction solution, and the mixture was stirred for 30 minutes.
After adding 0 g and stirring for 30 minutes, the reaction solution was separated. The organic layer was further washed twice with 1000 g of water, dried over anhydrous sodium sulfate, and methylene chloride was distilled off to obtain a pale yellow solid. The solid was recrystallized and purified to obtain white needle crystals.

An analysis was performed to determine the structure of the new sulfur-containing compound. The results are shown below. Melting point: 101.0-101.4 ° C Elemental analysis value Theoretical value (%) C: 69.11 H: 4.44 S: 2
1.71 N: 4.74 Analytical value (%) C: 69.23 H: 4.29 S: 2
1.59 N: 4.89 Infrared absorption spectrum (KBr, cm ^-1 ) 1473, 1438, 1413, 1371, 1307,
1162, 1139, 777, 756, 690, 68
8,509 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, based on tetramethylsilane) δ (ppm) 6.54 (d, J = 7.7 Hz, 2H, pyridine ring 3,
Hydrogen at position 5) 7.0 to 7.6 (m, 10H, benzene ring hydrogen and
(1H, pyridine ring 4-position hydrogen) Mass spectrometry (M + H) ⁺ = 296 From the results of the above analysis, the white needle-like crystal was identified as 2,6-diphenylthiopyridine. Yield 502.2 g
The yield was 8 based on the starting material 2,6-dichloropyridine.
It was 5.0%.

Example 2 A 5-liter four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 2,6-dichloropyridine 14
8.1 g (1.0 mol), 24-8.4 g (2.0 mol) of 4-methylbenzenethiol and 1200 g of N, N-dimethylformamide were charged, and the reaction temperature was 20 to
848. 28% sodium methylate solution between 70 ° C.
9 g (4.4 mol) was added dropwise over 2 hours. After completion of the dropwise addition, methanol was distilled off, and stirring was continued at 120 ° C. for 5 hours, followed by cooling to 20 ° C. To this reaction solution, 500 g of methylene chloride was added, and the mixture was stirred for 30 minutes.
0 g was added and stirred for 30 minutes. Crystals were precipitated, and the reaction solution in a slurry state was filtered to obtain a pale yellow solid. The solid was recrystallized and purified to obtain white needle crystals.

An analysis was performed to determine the structure of the new sulfur-containing compound. The results are shown below. Melting point: 193.6-194.4 ° C Elemental analysis value Theoretical value (%) C: 70.55 H: 5.30 S: 1
9.82 N: 4.33 Analysis value (%) C: 70.64 H: 5.25 S: 1
9.69 N: 4.42 infrared absorption spectrum (KBr, cm ^-1 ) 2360, 2337, 1595, 1552, 1547,
1490, 1411, 1209, 1178, 1157,
1147,1094,943,835,810,78
9,775,706,667,513,444 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, based on tetramethylsilane) δ (ppm) 7.39 (d, J = 7.7 Hz, 1H, pyridine ring 4th position) Hydrogen) 7.39 (d, J = 7.9 Hz, 4H, benzene ring 3,
Hydrogen (5th position) 7.11 (d, J = 7.9 Hz, 4H, benzene ring 2,
6.39 (d, J = 7.7 Hz, 2H, pyridine ring 3,
5-position hydrogen) 2.31 (S, 6H, -S -C 6 H 4 -C H 3) Mass spectrometry (M ⁺ H) ⁺ = 324 white needles from the results of the above analysis crystal, 2,6-di ( 4
-Methylbenzenethio) pyridine. The yield was 307.3 g, and the yield was 95.0% based on the starting material, 2,6-dichloropyridine.

[0032]

According to the present invention, a novel sulfur-containing compound suitable as a lubricating oil, a lubricating oil additive, a grease, an antioxidant, etc. having excellent oxidation stability and heat stability can be easily obtained. And can be easily produced.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Hata 346-1 Miyanishi, Harima-cho, Kako-gun, Hyogo Pref.

Claims (6)

[Claims] (1) Formula (1): A sulfur-containing compound represented by the formula: (Wherein, R ¹ and R ² may be the same or different, each represents a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms, m represents an integer of 0 to 5, and n represents 0 to 5; Represents an integer.) 2. Formula (2) wherein m and n are each 0 in formula (1): The sulfur-containing compound according to claim 1, which is 2,6-diphenylthiopyridine represented by the formula: 3. In the formula (1), R ¹ and R ² are both linear alkyl groups having 1 to 20 carbon atoms, and m is 1 to 5;
The sulfur-containing compound according to claim 1, wherein n is an integer of 1 to 5. 4. A compound of the formula (1) wherein R ¹ and R ² are both methyl groups and m and n are each 1. The sulfur-containing compound according to claim 1, which is 2,6-di (4-methylbenzenethio) pyridine represented by the formula: (5) Formula (4): And a 2,6-dihalopyridine represented by the formula (5): And formula (6): A method for producing a sulfur-containing compound represented by the formula (1), characterized by reacting with a benzenethiol represented by the formula:
(Wherein, R ¹ and R ² may be the same or different, each represents a halogen atom or a hydrocarbon group having 1 to 24 carbon atoms, m represents an integer of 0 to 5, and n represents 0 to 5; Represents an integer.) 6. The method according to claim 5, wherein the reaction is carried out in the presence of a base.