JP5630028B2 - Novel dithiocarbamate compounds and process for producing the same - Google Patents

Description

  The present invention relates to a novel dithiocarbamate compound which is a raw material for a polymer useful as an optical material because of its high refractive index, and a method for producing the same.

Since the dithiocarbamate compound has a bactericidal and insecticidal action as described in Patent Document 1, it is useful not only as a raw material for pharmaceuticals and agricultural chemicals but also as a polymer raw material, particularly as a polymer raw material for optical materials. is there.
Conventionally, many types of plastic lens materials have been developed and are actually used. However, what is called an ultrahigh refractive index resin material having a refractive index exceeding 1.65 is very limited.
For example, thiourethane resins represented by a refractive index of 1.67 obtained by reaction of polythiol and polyisocyanate, and resins having a refractive index exceeding 1.7 obtained by ring-opening polymerization of a polyepisulfide compound are known. However, since both of them are thermosetting, there are problems such that not only molding takes time but also molding at low temperature is difficult.
Patent Document 1 discloses light having a high refractive index by photocuring a composition containing 3,3′-thiobis (propane-1,2-dithiol), one or more ene compounds, and a photo radical polymerization initiator. Getting cured. However, the refractive indexes of these cured products were not so high as 1.598 to 1.663.
Further, the following methods are known as methods for synthesizing dithiocarbamate compounds.
Patent Document 2 describes a method for synthesizing carbamodithioic acid 2-propenyl-1,2-ethanediyl ester from ethanedithiol and allylisothiocyanate. However, it is not only a photoreaction with low productivity, but also the yield is as low as 22%, which is insufficient as an industrial production method because of the bad smell of ethanedithiol.
Patent Document 3 discloses 2-butene-1,4-dithiol bis (diallyldithiocarbamate) in which diallylamine and carbon disulfide are reacted in an aqueous sodium hydroxide solution and then reacted with 1,4-dichloro-2-butene. ) Is described.
Patent Document 4 describes a method for synthesizing dithiocarbamate by reacting bis (halomethyl) pyridine with monoallylamine and carbon disulfide. However, there was no synthesis of dithiocarbamate having an arylene group.

U.S. Pat. No. 3,884,951 US Pat. No. 2,919,182 Japanese Patent Publication No.56-35665

  It is an object of the present invention to provide a novel dithiocarbamate compound that is also useful as a polymer raw material for optical materials, and a high yield, industrially inexpensive and simple production method.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a novel dithiocarbamate compound that is also useful as a polymer raw material for optical materials, and its high yield, which is industrially inexpensive and simple. The production method was found and the present invention was completed.
That is, the subject of this invention is general formula (1).

（式中、Ｒは、アリーレン基、複数のこれらアリーレン基が直接又はヘテロ原子或いは炭素数１〜１０の炭化水素基（環式構造や分岐構造も含み、更に炭化水素基の中にヘテロ原子を含んでいてもよい。）を介してつながっていても良い。Ｚ及びＺ’は独立にＮ、ＮＨ又はＮＲ^１を表し、Ｒ^１は環構造を有していてもよい炭素数１〜１０の炭化水素基を表し、ｎ及びｍは独立に１又は２の整数を表す。）で表されるジチオカルバメート化合物によって解決される。

(Wherein, R comprises an arylene group, also hydrocarbon groups (cyclic structure or branched structure of a plurality of these arylene groups directly or heteroatom, or 1 to 10 carbon atoms, more heterozygous into charcoal hydrocarbon group atoms may contains Ndei a.) may also be connected via a .Z and Z 'represents N, NH or NR ¹ independently, R ¹ is optionally carbon atoms 1 may have a cyclic structure 10 represents a hydrocarbon group, and n and m independently represent an integer of 1 or 2).

  The present invention also provides a general formula (2)

[Chemical 2]
(CH ₂ = CH-CH ₂ ) _p Y (2)

(In the formula, Y represents NH ₂ , NH or NHR ¹ , R ¹ has the same meaning as described above, and p represents the number of 1 or 2.) After reacting carbon disulfide with allylamine represented by And general formula (3)

[Chemical formula 3]
X—CH ₂ —R—CH ₂ —X (3)

  (Wherein, R is as defined above, and X represents a halogen atom) is reacted with a dihalide represented by the general formula (1), It is also solved by the method.

  According to the present invention, a novel thiocarbamate compound that has a bactericidal and insecticidal action and is useful as a raw material for pharmaceuticals and agricultural chemicals, and particularly useful as a polymer for optical materials, can be used in one pot without using a malodorous thiol compound. It can be easily produced at a high yield, industrially inexpensively, and has high economic and industrial value.

R of the dithiocarbamate compound represented by the general formula (1) and R of the dihalide represented by the general formula (3) may be an arylene group which may have a substituent, or a plurality of these arylene groups may be directly or hydrocarbon group heteroatoms or 1 to 10 carbon atoms (cyclic structure or branched structure may comprise further heteroatoms may be free Ndei in a hydrocarbon group.) but it may also be bonded via the.
In the present invention, the cyclic structure includes an alicyclic structure, an aromatic ring structure, a heterocyclic structure, and the like.
The arylene group, a hydrocarbon group (cyclic structure or branched structure of a plurality of these arylene groups directly or heteroatom, or 1 to 10 carbon atoms include further heteroatoms may be free Ndei in a hydrocarbon group. ) Include, for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-xylylene group, 1,3-xylylene group, 1,4-xylylene group, 1, 4-naphthylene group, 4,4′-biphenylene group, 4,4′-biphenyl ether group, 4,4′-biphenylthioether group, 4,4′-biphenylsulfonyl group and the like. The substituent is not particularly limited, and for example, a linear or branched alkyl group having 1 to 10 carbon atoms (particularly 1 to 5 carbon atoms) is preferable, for example, methyl group, ethyl Group, propyl group (including isomer), butyl group (including isomer), pentyl group (including isomer), hexyl group (including isomer), heptyl group (including isomer), octyl group (including isomer) Isomers), nonyl groups (including isomers), decyl groups (including isomers), etc., preferably methyl, ethyl, propyl (including isomers), butyl groups (Including isomers), pentyl group (including isomers), hexyl group (including isomers), heptyl group (including isomers), octyl group (including isomers), particularly preferably a methyl group , Ethyl group, propyl group (isomers No), including butyl group (isomers), and pentyl (including isomers) it is.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include methylene group, ethylene group, methylmethylene group, trimethylene group, propylene group, 2-propylene group, dimethylmethylene group, tetramethylene group, and 1-methyltrimethylene group. 2-methyltrimethylene group, 3-methyltrimethylene group, 1-ethylethylene group, 2-ethylethylene group, 2,2-dimethylethylene group, 1,1-dimethylethylene group, ethylmethylmethylene group, propylmethylene Group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyltetramethylene group, 1,1-dimethyltrimethylene group, 2,2-dimethyltrimethylene group Group, 3,3-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,3-di- Tiltrimethylene group, 1,2-dimethyltrimethylene group, 1-ethyltrimethylene group, 1,1,2-trimethylethylene group, diethylmethylene group, 1-propylethylene group, 2-propylethylene group, butylmethylene group , Hexamethylene group, 1-methylpentamethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 3,3-dimethyltetramethylene group, 4,4-dimethyltetramethylene group, 1, 1,3-trimethyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,2,2-tetramethylethylene group, 1,1-dimethyl-2-ethylethylene group, 1,1-diethyl Ethylene group, 1-propyltrimethylene group, 2-propyltrimethylene group, 3-propyltrimethylene group, 1-butylethylene Group, 2-butylethylene group, 1-methyl-1-propylethylene group, 2-methyl-2-propylethylene group, 1-methyl-2-propylethylene group, 2-methyl-1-propylethylene group, pentylmethylene Group, alkylene group such as butylmethylmethylene group, ethylpropylmethylene group; hexane-1,6-diyl group, cyclohexane-1,1-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,4-diyl Alkylene groups such as 2-methylpropane-1,3-diyl group, 3-methylpentane-1,5-diyl group, dimethylmethylene group, 2,2-dimethylpropane-1,3-diyl group, etc. Alkyl having a ring structure in a carbon chain such as an alkylene group having a substituent or a cyclohexane-1,4-dimethylene group (including positional isomers) 2-thiapropane-1,3-diyl group, 3-thiapentane-1,5-diyl group, 4-thiaheptane-1,7-diyl group, 1,3-dithiapropane-1,3-diyl group, 2 , 4-dithiapentane-1,5-diyl group, 2,3-dithiabutane-1,4-diyl group, 3,4-dithiahexane-1,6-diyl group, 3,5-dithiaheptane-1,7-diyl group 2,5-dithiahexane-1,6-diyl group, 3,6-dithiaoctane-1,8-diyl group, 4,5-dithiaoctane-1,8-diyl group, 4,6-dithianonane-1,9- Diyl group, 4,7-dithiadecane-1,10-diyl group, 3,7-dithianonane-1,9-diyl group, 4,8-dithiaundecane-1,11-diyl group, 2-oxapropane-1 , 3-Diyl group, 3-oxa Ntan-1,5-diyl group, 4-oxaheptane-1,7-diyl group, 1,3-dioxapropane-1,3-diyl group, 2,4-dioxapentane-1,5-diyl group 3,5-dioxaheptane-1,7-diyl group, 2,5-dioxahexane-1,6-diyl group, 3,6-dioxaoctane-1,8-diyl group, 4,6- Dioxanonane-1,9-diyl group, 4,7-dioxadecane-1,10-diyl group, 3,7-dioxanonane-1,9-diyl group, 4,8-dioxaundecane-1,11-diyl group, Alkylene groups having a hetero atom in the carbon chain such as 1,4-dithian-2,5-diyl group and 1,4-dioxane-2,5-diyl group; 1,4-dithian-2,5-dimethyl Group (including positional isomers), 1,4-dioxane-2,5- Alkylene group having a hetero atom and the ring structure in the carbon chain such as a methyl group (position including isomers).

Z and Z ′ in the dithiocarbamate compound represented by the general formula (1) independently represent N, NH or NR ¹ , and R ¹ is a carbon atom having 1 to 10 carbon atoms which may have a ring structure. A hydrogen group, preferably a hydrocarbon group having 1 to 7 carbon atoms is represented.
Before Kisumi hydrocarbon group may be linear or branched, it may have a cyclic structure.
Moreover, n and m in the dithiocarbamate compound represented by the general formula (1) independently represent a number of 1 or 2.

The allylamine represented by the general formula (2) used in the present invention includes monoallylamine, diallylamine, allylmethylamine, allylethylamine, allyl n-propylamine, allyl n-butylamine, allylphenylamine, allylbenzylamine, allyl Examples include cyclohexylamine, preferably diallylamine, allylmethylamine, allylethylamine, allyl n-propylamine, allyl n-butylamine or allylbenzylamine, and particularly preferably diallylamine. As addition amount of this allylamine, it is 2-20 times mole with respect to 1 mol of dihalides represented by General formula (3), Preferably it is 2-10 times mole.
If the amount of allylamine added is too small, the yield may decrease, and even if the amount of allylamine added is too large, no improvement in the reaction yield is observed for the addition of a large amount of allylamine.

  The halogen atom X of the dihalide represented by the general formula (2) is a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, preferably a chlorine atom or a bromine atom.

  In this invention which concerns on the manufacturing method of a dithiocarbamate compound, after making carbon disulfide react with the allylamine represented by the said General formula (2), the dihalide represented by the said General formula (3) is made to react.

In the present invention relating to the method for producing dithiocarbamate, allylamine and carbon disulfide are first reacted.
The addition amount of carbon disulfide used in the present invention is 2 to 50 times mol, preferably 3 to 20 times mol, per 1 mol of the dihalide represented by the general formula (3). In the method for producing dithiocarbamate according to the present invention, carbon disulfide may function not only as a reaction agent with allylamine but also as a solvent, so it may be added in excess.
If the amount of carbon disulfide added to the dihalide is too small, the yield may be reduced or stirring may be difficult. If it is too large, the reaction rate may be reduced due to the reduced concentration of the reaction solution.

In the method for producing dithiocarbamate of the present invention, a base may be added when the allylamine and the carbon disulfide are reacted.
The base used at this time is not particularly limited. For example, triethylamine, pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5 Organic bases such as nonene and 1,4-diazabicyclo [2,2,2] octane; lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide Inorganic bases such as, preferably inorganic bases. The base to be used is 2 to 20 times mol, preferably 2 to 10 times mol for 1 mol of the dihalide represented by the general formula (3).
If the amount of the base added to the dihalide is too small, the yield may decrease, and if it is too large, the production efficiency may decrease.

When the amine salt of carbamate is precipitated as a solid and stirring becomes difficult, or when an inorganic base is used in combination, a solvent may be added.
The solvent is not particularly limited as long as it does not hinder the progress of the reaction. For example, water, alcohol (methanol, ethanol, etc.), aliphatic hydrocarbon (hexane, heptane, etc.), aromatic hydrocarbon (toluene, xylene, etc.), fat And aliphatic ethers (diethyl ether, diisopropyl ether, tetrahydrofuran, etc.), aliphatic amides (N, N-dimethylformamide, N-methylpyrrolidone, etc.), aliphatic sulfoxides (dimethyl sulfoxide, etc.) and the like. These solvents may be used alone or in combination of two or more. The amount of these solvents added is 0 to 50 ml, preferably 0 to 20 ml, based on 1 g of the dihalide represented by the general formula (3).
If the amount of the solvent added is too large, the production efficiency may decrease.

When the reaction solution is divided into a plurality of phases due to the addition of the solvent or the like, a phase transfer catalyst may be added to promote the reaction. As the phase transfer catalyst in the case of addition, 15-crown-5 is used. -Cyclic polyethers such as ether and 18-crown-6-ether; acyclic polyethers such as polyethylene glycol dialkyl ether; phosphonium salts such as tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, cryptand [ 2.2.1], cyclic polyetheramines such as cryptand [2.2.2]; tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethyla Moniumukurorido, as quaternary ammonium salts, such aliquot 336 and the like, preferably, quaternary ammonium salts. The phase transfer catalyst to be used is 0.001 to 0.5 times mol, preferably 0.005 to 0.1 mol, per 1 mol of the dihalide represented by the general formula (3).
When the amount of the phase transfer catalyst added to the dihalide is too small, the reaction yield may be deteriorated, and when it is too large, the quality of the dithiocarbamate may be deteriorated.

The reaction temperature in the present invention is preferably in the range of -20 ° C to 100 ° C, more preferably 0 ° C to 60 ° C. If the reaction temperature is too low, the reaction rate tends to decrease and production efficiency tends to deteriorate. If the reaction temperature is too high, the selectivity may be lowered.
After the reaction, the produced dithiocarbamate compound represented by the general formula (1) can be separated from the reaction mixture by conventional methods such as filtration, column chromatography, and recrystallization.
The obtained dithiocarbamate compound represented by the general formula (1) is mixed with a thiol such as 1,2,3-trimercaptopropane, and 2-methyl-1 [4- (methylthio) phenyl] is mixed therewith. By adding a photopolymerization initiator such as -2-morpholinopropan-1-one and carrying out photopolymerization, for example, a resin having a high refractive index exceeding 1.7 can be obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.

[Example 1]
After adding carbon disulfide (5.05 g, 66.3 mmol) to diallylamine (3.69 g, 40 mmol) at 10 ° C. or lower, and p-xylylene dichloride (1.76 g, 10 mmol) at the same temperature, Stir at 25 ° C. for 10 hours. 10 ml of water and 20 ml of ethyl acetate were added to the resulting reaction mixture, and 10 ml of 1 mol / l-hydrochloric acid was added to the separated organic layer. The separated organic layer was concentrated under reduced pressure to obtain 4.20 g of a pale yellow oil. This was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 10/1 (volume ratio)), and as a colorless powder, 1,4-bis (diallylaminothiocarbonylsulfanylmethyl) having the following structural formula Benzene (3.10 g, 6.9 mmol) was obtained (isolated yield based on p-xylylene dichloride; 69%). Further, the structure was confirmed by ¹ H-NMR.

¹ H-NMR (CDCl ₃ , δ (ppm)); 4.30 (4H, brs), 4.53 (4H, s), 4.66 (4H, brs), 5.16 to 5.28 (8H, m), 5.78 to 5.90 (4H, m), 7.32 (4H, s)

[Example 2]
Carbon disulfide (5.05 g, 66.3 mmol) was added to diallylamine (3.69 g, 40 mmol) at 10 ° C. or less, and 4,4′-bis (chloromethyl) biphenyl (2.52 g, 10 mmol) and then stirred at 25 ° C. for 2.5 hours. 10 ml of water and 20 ml of ethyl acetate were added to the resulting reaction mixture, and 10 ml of 1 mol / l-hydrochloric acid was added to the separated organic layer. The separated organic layer was concentrated under reduced pressure to obtain 4.77 g of a light yellow solid. This was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 10/1 (volume ratio)), and as a colorless powder, 1,4-bis (diallylaminothiocarbonylsulfanylmethyl) having the following structural formula Biphenyl (3.33 g, 6.4 mmol) was obtained (isolated yield based on 4,4′-bis (chloromethyl) biphenyl; 64%). Further, the structure was confirmed by ¹ H-NMR.

¹ H-NMR (CDCl ₃ , δ (ppm)); 4.32 (4H, brs), 4.60 (4H, s), 4.68 (4H, brs), 5.16 to 5.29 (8H, m), 5.80 to 5.91 (4H, m), 7.41-7.53 (8H, m)

[Example 3]
A solution obtained by diluting carbon disulfide (1.91 g, 25 mmol) with N-benzylallylamine (3.69 g, 25 mmol) with 2 ml of THF was added at 10 ° C. or lower and stirred at 25 ° C. for 1.5 hours. To this was added a solution prepared by dissolving p-xylylene dichloride (1.76 g, 10 mmol) in 8 ml of THF at the same temperature, followed by stirring at 25 ° C. for 50 hours. The obtained reaction mixture was concentrated under reduced pressure, 60 ml of ethyl acetate and 10 ml of water were added to the residue, and the separated organic layer was concentrated under reduced pressure to obtain 4.5 g of a mixture of a pale yellow liquid and colorless needles. This was purified by silica gel column chromatography (developing solvent; n-hexane / ethyl acetate = 40/1 to 20/1 (volume ratio)) to give 1,4-bis (N— Benzylallylaminothiocarbonylsulfanylmethyl) benzene (2.1 g, 3.8 mmol) was obtained (isolated yield based on p-xylylene dichloride; 38%). Further, the structure was confirmed by ¹ H-NMR.

（式中、Ｂｎはベンジル基を表す。）

(In the formula, Bn represents a benzyl group.)

¹ H-NMR (CDCl ₃ , δ (ppm)); 4.21 (2H, brs), 4.57 (4H, s), 4.66 (2H, brs), 5.15 (2H, brs), 5.16 to 5.28 (4H, m) , 5.35 (2H, brs), 5.60 ~ 6.00 (2H, m), 7.10 ~ 7.40 (14H, m)

[Reference Example 1]
1,4-bis (diallylaminothiocarbonylsulfanylmethyl) benzene (336 mg, 0.75 mmol) and 1,2,3-trimercaptopropane 0.14 mg, 1 mmol) synthesized in the same manner as in Experimental Example 1, and 2 A mixture of methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (1.1 mg) was heated at 80 ° C. for 1 minute to obtain a homogeneous solution. It inject | poured into the clearance gap of thickness 0.4mm comprised from a piece of quartz glass plate and a silicon rubber. This was irradiated from a light source of 1500 W (7000 J / cm ² ) metal halide lamp light at a distance of 10 cm for 25 seconds, and this was performed three times to be cured. The obtained light yellow film-like cured product was taken out and its refractive index was measured. The refractive index was 1.72. The refractive index was measured using a multi-wavelength Abbe refractometer (DR = M4) manufactured by ATAGO, and the refractive index at 589 (D) nm at 25 ° C. was measured.

Claims (2)

A dithiocarbamate compound represented by the following general formula (1).

(Wherein, R comprises an arylene group, also hydrocarbon groups (cyclic structure or branched structure of a plurality of these arylene groups directly or heteroatom, or 1 to 10 carbon atoms, more heterozygous into charcoal hydrocarbon group atoms may contains Ndei a.) may also be connected via a .Z and Z 'represents N, NH or NR ¹ independently, R ¹ is optionally carbon atoms 1 may have a cyclic structure 10 represents a hydrocarbon group, and n and m independently represent an integer of 1 or 2.) The dithiocarbamate compound according to claim 1, wherein allylamine represented by the following general formula (2) is reacted with carbon disulfide and then reacted with a dihalide represented by the following general formula (3). Manufacturing method.
[Chemical 2]
(CH ₂ = CH-CH ₂ ) _p Y (2)
(In the formula, Y represents NH ₂ , NH or NHR ¹ , R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a ring structure, and p represents an integer of 1 or 2. )
[Chemical formula 3]
X—CH ₂ —R—CH ₂ —X (3)
(Wherein, R comprises an arylene group, also hydrocarbon groups (cyclic structure or branched structure of a plurality of these arylene groups directly or heteroatom, or 1 to 10 carbon atoms, more heterozygous into charcoal hydrocarbon group atom may be including Ndei a.) but it may also have connected via the .X represents a halogen atom.)