JPH09143151A - New bisnorbornyl sulfide and production of bisnorbornyl sulfide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new compound useful as a plasticizer, etc., and further a cocross-linking agent, etc., for an optical resin material, a rubber material, etc. SOLUTION: This bis(5-vinyl-norbornyl) sulfide represented by the formula. A bisnorbornyl sulfide compound including the compound represented by the formula is obtained by reacting (B) norbornene or an unsaturated compound having a norbornene skeleton (preferably any of norbornadiene, vinylidenenorbornene, ethylidenenorbornene and dicyclopentadiene) with (C) hydrogen sulfide in (A) an amino compound and/or a polar solvent having >=3 debye (D) dipole moment and >=30 relative permittivity. One kind selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc., is preferred as the polar solvent of the component (A). Furthermore, the compound represented by the formula is obtained by using 5-vinyl-2-norbornene as the component (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel bisnorbornyl sulfide and a process for producing a bisnorbornyl sulfide compound, and more particularly to a novel bisnorbornyl sulfide compound and an unsaturated compound having norbornene or a norbornene skeleton. The present invention relates to a method for producing a bisnorbornyl sulfide compound, which comprises reacting bisphenol with hydrogen sulfide. The bisnorbornyl sulfide compound obtained by the method of the present invention, in particular, the bisnorbornyl sulfide compound having an unsaturated group containing the novel sulfide of the present invention is
Besides plasticizers, it is useful as an optical resin material and a co-crosslinking agent for rubber materials.

[0002]

2. Description of the Related Art Usually, when an olefin is reacted with hydrogen sulfide, a sulfide as a 2: 1 addition product of an olefin and hydrogen sulfide and a monothiol which is a 1: 1 addition product are also produced. A method of generating efficiently is required.

In German Patent No. 1,259,880,
Bis (dicyclopentadienyl) sulfide is synthesized by reacting dicyclopentadiene with hydrogen sulfide in the absence of a solvent in the presence of a radical generator such as azoisobutyronitrile. However, in the case of a radically polymerizable reaction substrate, the use of a radical generator is not preferred because the polymerization of the substrate is likely to occur.

Further, Zh. Org. Khim. 1985
21: 1910-1915, chloroform [dipole model] in the presence of alkylaluminum halides.
Ment about 1.0 debye (D)], norbornadiene, ethylidene norbornene and the like are reacted with hydrogen sulfide. However, since the above-mentioned monothiol is by-produced and norbornadiene, ethylidene norbornene and the like may easily form a tricyclene compound, the selectivity of the target bisnorbornyl sulfide compound is not necessarily high.

[0005]

The first problem of the present invention
Another object is to provide a novel bisnorbornyl sulfide compound, and another object thereof is to react norbornene or an unsaturated compound having a norbornene skeleton with hydrogen sulfide to obtain norbornene monothiol or dithiol compound and tricyclene compound. The present invention provides a method for synthesizing a bisnorbornyl sulfide compound with high selectivity while suppressing the formation of such compounds.

[0006]

That is, the first aspect of the present invention
Relates to bis (5-vinyl-norbornyl) sulfide represented by the following formula (1).

[0007]

Embedded image

The second aspect of the present invention is to provide an amino compound and / or an unsaturated compound having norbornene or a norbornene skeleton in a polar solvent having a dipole moment of 3 Divide (D) or more and a relative dielectric constant of 30 or more. The present invention relates to a method for producing a bisnorbornyl sulfide compound, which comprises reacting with hydrogen sulfide.

A third aspect of the present invention is the second aspect of the present invention.
The present invention relates to a method for producing a bisnorbornyl sulfide compound in which the unsaturated compound having a norbornene skeleton is norbornadiene, vinylidene norbornene, ethylidene norbornene or dicyclopentadiene.

A fourth aspect of the present invention is the second or third aspect of the present invention.
In the method of producing a bisnorbornyl sulfide compound, wherein the polar solvent is any one polar solvent selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and a mixture thereof. Hereinafter, the present invention will be described in more detail.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated compound having a norbornene skeleton referred to in the present invention has at least one carbon-carbon double bond, preferably one or two carbon-carbon double bonds, on the norbornane ring. Compounds such as norbornene and norbornadiene, norbornene or norbornadiene substituted with an alkyl group such as methyl, propyl, or isopropyl, or an alkyl derivative of norbornadiene, such as methylnorbornene or norbornadiene, ethylmethylnorbornene or norbornadiene; norbornene Alkenyl derivatives of norbornene substituted with one or more alkenyl groups such as vinyl, propenyl and isopropenyl, eg 5-vinyl-2-norbornene, 5-propenyl 2-norbornene, 5-isopropenyl-2-norbornene and the like; methylene norbornene, ethylidene norbornene derivatives alkylidene group is substituted one or more such isopropylidene,
For example, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-methylene-2
Norbornene, etc .; norbornene derivatives in which one or more saturated or unsaturated 5-membered or 6-membered rings are fused to norbornene and alkyl or alkylidene-substituted derivatives thereof, for example, dicyclopentadiene, methyldicyclopentadiene, methylcyclo A dimer of pentadiene, octahydro-dimethanonaphthalene, ethylidene-octahydro-dimethanonaphthalene, etc .; norbornene or norbornadiene derivatives in which a cyano group is substituted on norbornene or norbornadiene, for example 5-
Cyano-2-norbornene or the like; norbornene or norbornadiene derivative in which norbornene or norbornadiene is substituted with a hydroxyethyl group, for example, 5-norbornene-2-methanol or the like; norbornene or norbornadiene derivative having a structure in which dicarboxylic acid anhydride group is condensed with norbornene or norbornadiene, For example, 5-norbornene-2,3-dicarboxylic acid anhydride and the like. These can be used alone or in combination of two or more.

A compound which exhibits particularly preferable effects as a starting material by applying the method of the present invention has an unsaturated group in addition to the carbon-carbon double bond on the norbornane ring, and is therefore easily radically polymerized or a tricyclene compound. It is an unsaturated compound having a norbornene skeleton that easily becomes Specifically, norbornadiene, vinylidene norbornene,
It is either ethylidene norbornene or dicyclopentadiene.

In the method of the present invention, an amino compound,
Alternatively, an unsaturated compound having norbornene or a norbornene skeleton is reacted with hydrogen sulfide in a polar solvent having a dipole moment of 3 Divi (D) or more and a dielectric constant of 30 or more, or a mixture thereof. .

The polar solvent has a dipole moment of 3 debye (D) or more, preferably 3 debye (D) or more and 10 debye (D) or less, and a relative dielectric constant of 30 or more, preferably 30 or more and 300 or less. It must be a solvent. The polar solvent and the amino compound are solvents that do not directly participate in the reaction in the present invention, but by using them, the remarkable effect of the present invention that bisnorbornyl sulfide can be selectively obtained. It plays. Note that 1 device (D) is 3.3564 ×
It is 10 ^-30 (Cm).

Specific physical properties of the polar solvent are described in, for example, "Solvent Handbook" (edited by Shozo Asahara et al., Published by Kodansha Co., Ltd. on March 10, 1976), such as Handbook of Solvents. Specific solvents include, for example, dimethylformamide, N-methylformamide, formamide, dimethylacetamide, N-methylacetamide,
Amide polar solvents such as acetamide; pyrrolidone polar solvents such as N-methylpyrrolidone and pyrrolidone; sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane; and mixed solvents thereof. Particularly preferred are dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and mixed solvents thereof.

In the present invention, an amino compound can also be used as a reaction solvent like the polar solvent. here,
The amino compound of the present invention means any one of a primary amine, a secondary amine and a tertiary amine, and is preferably liquid at room temperature and has a low boiling point. For example, an amino compound such as trimethylamine, triethylamine, tributylamine, diethylamine, dibutylamine and the like, which is liquid at room temperature and has a low boiling point, such as a secondary or tertiary amine, is particularly preferable. These amino compounds are different from the above-mentioned polar solvents, and particularly dipole
Ment 3 Divide (D) or more and the relative dielectric constant of 30 or more are not required. The above-mentioned amino compound and the above dipole moment 3 Divi (D) or more and a relative dielectric constant of 30
The polar solvents described above can be mixed and used.

In the production method of the present invention, the theoretical reaction equivalent ratio of norbornene or an unsaturated compound having a norbornene skeleton to hydrogen sulfide is 2: 1 in molar ratio. Therefore, the reaction is usually carried out at such a molar ratio, but it is not particularly limited to this theoretical reaction equivalent ratio, and the supply ratio of norbornene or an unsaturated compound having a norbornene skeleton and hydrogen sulfide should be appropriately determined. You can
Even if an excess of norbornene or an unsaturated compound having a norbornene skeleton or hydrogen sulfide is supplied in excess of this theoretical reaction equivalent, the excess reaction substrate only remains unreacted and This is because the selectivity of a certain bisnorbornyl sulfide compound does not substantially change.

The amount of the polar solvent or amino compound is not particularly limited, and the amount can be appropriately selected according to the reaction conditions. However, the weight ratio is preferably 0.5 to 10 times that of norbornene or an unsaturated compound having a norbornene skeleton. If the amount of the polar solvent or the amino compound is within this range, the reaction time can be shortened, and the yield per batch can be increased. .

In the method of the present invention, an unsaturated compound having a norbornene or norbornene skeleton is contained in an amino compound and / or a polar solvent amino compound having a dipole moment of 3 Divide (D) or more and a relative dielectric constant of 30 or more. The compound is reacted with hydrogen sulfide. Usually, the reaction is carried out by introducing hydrogen sulfide into a mixture of norbornene or an unsaturated compound having a norbornene skeleton and a polar solvent or an amino compound.

The reaction pressure is not particularly limited.
Since hydrogen sulfide is gaseous at room temperature and toxic, it is preferable to use a closed reactor, but the reaction pressure is not particularly limited in this case either, and it may be atmospheric pressure or pressurized.
The reaction temperature is not particularly limited as long as the reaction phase is a liquid phase. However, it is usually preferable to carry out the reaction within the range of 50 to 150 ° C. Although the reaction time is not particularly limited, it can be appropriately selected usually in the range of 1 to 20 hours.

The reaction proceeds sufficiently without using any catalyst. However, a catalyst can be appropriately used as long as the effect in the method of the present invention is not impaired. For example, when a cation exchange resin (Amberlyst 15E (trade name), etc.) is used, the selectivity of the bisnorbornyl sulfide compound as the target substance does not substantially change as compared with the non-catalyst, but an increase in the reaction rate is recognized. The reaction is completed in a short time. In addition, similarly, a radical generator such as azoisobutyronitrile as described above and an alkylaluminum halide, an acidic catalyst such as aluminum chloride or trifluoromethanesulfonic acid are also appropriately used unless they inhibit the effect of the method of the present invention. be able to.

Thus, the sulfide produced by the method of the present invention has the following formula (1):
It is a 2: 1 adduct of norbornene or an unsaturated compound having a norbornene skeleton and hydrogen sulfide. As its structure, the carbon-carbon double bond on the norbornane ring is saturated,
It is a bisnorbornyl sulfide having a structure in which two carbons of an unsaturated compound having two norbornenes or norbornene skeletons are bonded via a sulfur atom. Even if an unsaturated bond, for example, a carbon-carbon bond, exists at a position other than one carbon-carbon double bond on the norbornene ring, it is stored as it is without any particular reaction. For example, 5-vinyl-norbornene, 5-ethylidene-norbornene, dicyclopentadiene and norbornadiene are reacted with hydrogen sulfide to give bis (5-vinyl-
Norbornyl) sulfide, bis (5-ethylidene-norbornyl) sulfide, bis (dicyclopentadienyl) sulfide and bis (norbornyl) sulfide are each selectively prepared. Therefore, the reaction formula of the present invention is exemplified by the following formula (2) using a partial structure of norbornene or an unsaturated compound having a norbornene skeleton. Here, the broken line indicates a partial structure such as norbornene.

[0023]

Embedded image

The bis (5-) represented by the above formula (1)
Vinyl-norbornyl) sulfide can be produced, for example, by reacting 5-vinyl-2-norbornene with hydrogen sulfide by the method described above. The reaction formula of this 5-vinyl-2-norbornene and hydrogen sulfide is shown in the following formula (3).

[0025]

Embedded image

[0026]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. The analytical instruments used in Examples and Comparative Examples are as follows.

Infrared absorption (IR) analysis: FT / IR-7000 manufactured by JASCO Corporation Nuclear magnetic resonance (NMR) analysis: JSX GSX270J gas chromatograph (GC) analysis: Shimadzu GC-14A column ULBON HR-1 25m

Example 1 5-Vinyl-norbornene 6
0 g (0.5 mol) and 200 g of dimethylformamide were put into a 500 ml stainless steel autoclave, then 68 g (2.0 mol) of hydrogen sulfide was injected under pressure, and the mixture was heated at 80 to 90 ° C for 5
Allowed to react for hours. After the reaction, the mixture was cooled to room temperature, and excess hydrogen sulfide in the system was removed with nitrogen gas. As a result of analyzing the reaction product by gas chromatography, the reaction rate of 5-vinyl-norbornene was 100%, and bis (5-vinyl-norbornyl) was obtained.
The selectivity of sulfide was 98%. Dimethylformamide was removed from the reaction product under reduced pressure and then distilled under reduced pressure to obtain 61 g of bis (5-vinyl-norbornyl) sulfide at a boiling point of 128 to 132 ° C./0.15 mmHg. A gas chromatograph of the reaction product is shown in FIG. 1, an infrared spectrum of bis (5-vinyl-norbornyl) sulfide after distillation is shown in FIG. 2, and an NMR spectrum of the bis (5-vinyl-norbornyl) sulfide is shown in FIG. The production ratios of the raw materials and the reaction products calculated from the gas chromatograph of each reaction product in Example 1 are shown in Table 3. The reaction product after distillation [bis (5-vinyl - norbornyl) sulfide, C ₁₈ H ₂₆ S] shown below the results of elemental analysis of the. C: 78.80 (%) H: 9.56 (%) S: 11.64 (%)

(Examples 2 to 9) Under the synthetic conditions shown in Tables 2 and 3, the norbornene compound and the reaction solvent were changed in the same manner as in Example 1 to react with hydrogen sulfide. The synthesis results are also shown in Table 1 and Table 2. Infrared spectra after distillation of the reactants in Example 2, Example 3 and Example 4 are shown in FIGS. 4, 6 and 8, respectively, and NMR spectra are shown in FIGS. 5, 7 and 9, respectively.

Comparative Examples 1 and 2 Under the synthetic conditions shown in Tables 2 and 3, the norbornene compound and the reaction solvent were changed in the same manner as in Example 1 to react with hydrogen sulfide. The synthesis results are also shown in Table 1 and Table 2. Gas chromatographs of the reaction products in Comparative Example 1 and Comparative Example 2 are shown in FIGS. 10 and 11, respectively. The production ratios of the raw materials and the reaction products calculated from the gas chromatographs of the respective reaction products in Comparative Examples 1 and 2 are shown in Table 3.

The symbols in the table are shown below. VBH: 5-vinyl-2-norbornene EBH: 5-ethylidene-2-norbornene DCPD: dicyclopentadiene ND: norbornadiene DMF: dimethylformamide DMA: dimethylacetamide DMSO: dimethylsulfoxide TEA: triethylamine THF: tetrahydrofuran

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

From the results of Tables 1 to 3, according to the method of the present invention (Examples 1 to 9), the bisnorbornyl sulfide compound can be synthesized with good selectivity, while the solvent is toluene. It can be seen that in (Comparative Example 1) and THF (tetrahydrofuran) (Comparative Example 2), the selectivity of the target sulfide is extremely reduced.

[0036]

INDUSTRIAL APPLICABILITY The present invention provides a novel bis (5-vinyl-norbornyl) sulfide represented by the above formula (1), which is useful as a plasticizer and the like, a co-crosslinking agent for optical resin materials and rubber materials. To do. Further, according to the method of the present invention, in the reaction of norbornene or an unsaturated compound having a norbornene skeleton with hydrogen sulfide, generation of norbornene monothiol or dithiol compound is suppressed, and a bisnorbornyl sulfide compound is synthesized with high selectivity. You can

[Brief description of the drawings]

1 is a gas chromatograph of the reaction product of Example 1. FIG.

FIG. 2 is an infrared spectrum of bis (5-vinyl-norbornyl) sulfide after distillation in Example 1.

FIG. 3 is an NMR spectrum of bis (5-vinyl-norbornyl) sulfide after distillation in Example 1.

FIG. 4 is an infrared spectrum of the sulfide of Example 2.

5 is an NMR spectrum of the sulfide of Example 2. FIG.

FIG. 6 is an infrared spectrum of the sulfide of Example 3.

FIG. 7 is an NMR spectrum of the sulfide of Example 3.

FIG. 8 is an infrared spectrum of the sulfide of Example 4.

9 is an NMR spectrum of the sulfide of Example 4. FIG.

10 is a gas chromatograph of the reaction product of Comparative Example 1. FIG.

11 is a gas chromatograph of the reaction product of Comparative Example 2. FIG.

Claims (4)

[Claims] 1. A bis (5-vinyl-norbornyl) sulfide represented by the following formula (1). Embedded image 2. An amino compound and / or a dipole mode
A method for producing a bisnorbornyl sulfide compound, which comprises reacting norbornene or an unsaturated compound having a norbornene skeleton with hydrogen sulfide in a polar solvent having a Divide (D) of 3 or more and a relative dielectric constant of 30 or more. . 3. The method for producing a bisnorbornyl sulfide compound according to claim 2, wherein the unsaturated compound having a norbornene skeleton is any of norbornadiene, vinylidene norbornene, ethylidene norbornene and dicyclopentadiene. 4. The bis solvent according to claim 2, wherein the polar solvent is any one polar solvent selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and a mixture thereof. Process for producing norbornyl sulfide compound.