JPH0463063B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides novel compounds, 1,4,5,8-
This invention relates to tetrakis(mercaptomethyl)naphthalene, derivatives thereof, and methods for producing these compounds.

[Prior art] Conventionally, 1,8 mercaptomethyl groups (-CH ₂ SH) were substituted at the peri-positions (1, 8-positions) of naphthalene.
-Bis(mercaptomethyl)naphthalene is a well-known compound (Patent Registration No. 951352, CA,
1977, Vol.86, 43448v).

However, 1,4,5,8-tetrakis(mercaptomethyl)naphthalene, which is a bisperi-substituted product in which mercaptomethyl groups are substituted at the other peri-positions (4 and 5-positions) of the naphthalene ring, has applications due to its mercapto group. Although it is expected to have a wide range of applications on surfaces, it remains an unknown compound until now due to difficulties in synthetic chemistry.

[Problems to be Solved by the Invention] As mentioned above, 1,4,5,8-tetrakis(mercaptomethyl)naphthalene and its derivatives have not been known until now.

That is, the present invention provides novel compounds 1, 4,
A method for producing 5,8-tetrakis(mercaptomethyl)naphthalene and its derivatives is provided.

[Means for Solving the Problems] The novel compound 1,4,5,8-tetrakis(mercaptomethyl)naphthalene according to the present invention is represented by the structural formula (A).

Furthermore, novel compounds 1, 4, 5, 8 according to the present invention
The -tetrakis(mercaptomethyl)naphthalene derivative is represented by the general formula ().

(In the formula (), R ¹ represents an alkyl group or an acyl group.) In addition, 1, 4, 5,
8-tetrakis[(dimethylsulfonio)methyl]
Naphthalene-tetrakis (tetrafluoroborate) is represented by structural formula (B).

(In the formula (B), R ² is a dimethylsulfonio-tetrafluoroborate group (-S (CH ₃ H) ₂ BF ₄ )
shows. ) And 1, 4, 5, shown in the above structural formula (A),
8-Tetrakis(mercaptomethyl)naphthalene is 1,4,5,8 represented by the following general formula ().
-Produced by treating tetrakis[(isothiuronio)methyl]naphthalene-tetrahalide with an alkali.

(In the formula (), R ³ represents a halogenated isothiuronio group (-[SC(NH ₂ ) ₂ ] X).) In addition, 1,4,
The 5,8-tetrakis(mercaptomethyl)naphthalene derivative is a 1,4,5,8-
Produced by treating tetrakis(mercaptomethyl)naphthalene with an alkylating or esterifying agent.

Furthermore, 1,4,5,8 represented by the above structural formula (B)
-tetrakis[(dimethylsulfonio)methyl]
Naphthalene-tetrakis (tetrafluoroborate) is 1,4,5,8 represented by the following structural formula (C).
-Produced by reacting dimethoxycarbonium tetrafluoroborate with tetrakis[(methylthio)methyl]naphthalene.

The present invention will be explained below.

According to the method for producing 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) of the present invention,
The reaction is carried out in an alkaline aqueous solution such as potassium hydroxide or sodium hydroxide.

That is, first, an alkaline aqueous solution is prepared by thoroughly aerating nitrogen to drive out dissolved oxygen, and then the raw material 1,4,5,8-tetrakis[(isothiuronio)methyl]naphthalene-tetrahalide () is added to this solution. is added and the mixture is heated to reflux under a nitrogen atmosphere. At this time, the alkali hydroxide is used in a large excess of about 20 times, and a reaction time of 2 to 5 hours is sufficient. After treating the cloudy solution produced after the reaction with an organic solvent to remove the by-product pericyclic sulfide compound, the 1,4,5,8-tetrakis(mercaptomethyl)naphthalene-tetraalkali metal salt in the aqueous solution was treated with an acid. When treated, the halogenated isothiuronio group (-[SC( _NH2 ) ₂ ]○+X○-) in the raw material molecule () is converted to a mercapto group (-SH), as shown in the reaction formula below. 4,5,8-
Tetrakis(mercaptomethyl)naphthalene (A) can be obtained.

In addition, during the acid treatment, in order to prevent the production of a pericyclic sulfide compound as a by-product, it is preferable to thoroughly cool the reaction solution while bubbling nitrogen vigorously, and to stir effectively.

(In the formula (), R ³ represents a halogenated isothiuronio group (-[SC(NH ₂ ) ₂ ] 1, which is the raw material for
4,5,8-tetrakis[(isothiuronio)methyl]naphthalene-tetrahalide () is a commercially available naphthalene-1,4,5,8-tetracarboxylic acid (D) as shown in the reaction formula below. was treated with dimethyl sulfate in an alkaline solution to give naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E), and then reduced to give 1,4,
1,4,5,8-tetrakis(halogenomethyl)naphthalene (G) obtained by converting it into 5,8-tetrakis(hydroxymethyl)naphthalene (F) and then halogenation treatment is treated with thiourea. It is manufactured by

(G) In the formula, X is a halogen atom, ()
In the formula, R ³ is a halogenated isothiuronio group (-[SC
( _NH2 ) ₂ ]X). ) Next, 1, 4, 5, 8 obtained in this way
-tetrakis(mercaptomethyl)naphthalene (A)
When treated with an alkylating agent, 1,4,5,8-
1,4,5,8-tetrakis[(alkylthio)methyl]naphthalene (Ia), which is a tetrasulfide derivative of tetrakis(mercaptomethyl)naphthalene, can be obtained.

(In formula (Ia), R ¹ is an alkyl group.) In the reaction, 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) is first treated with a base such as alkali hydroxide or sodium hydride. to form the tetramercaptide alkali metal salt of 1,4,5,8-tetrakis(mercaptomethyl)naphthalene, which is then treated with an alkalizing agent.

When the reaction is carried out in this way, a sulfide bond is formed by the reaction between the active mercaptide anion and the alkylating agent, and the mercapto group (-SH) in the raw material molecule (A) becomes an alkylthio group (-SR ¹ ; R ¹ 1,4,5,8-tetrakis(alkylthiomethyl)naphthalene (Ia), which is converted into an alkyl group), is produced.

As the reaction solvent, in addition to polar solvents such as water and alcohol, inert solvents such as benzene and ether can be used, and as the alkylating agent, alkyl halides, dialkyl sulfates, etc. can be used.

In addition, when an esterifying agent such as an acylating agent is applied to 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) to perform an esterification reaction,
1,4,5,8-tetrakis[(acylthio)methyl]naphthalene (Ib), which is a tetraester derivative of 1,4,5,8-tetrakis(mercaptomethyl)naphthalene, is obtained.

(In formula (Ib), R ¹ is an acyl group.) As the acylating agent, carboxylic acid anhydrides such as acetic anhydride and benzoic anhydride, and acyl halides such as acetyl chloride and benzoyl chloride are used. .

The reaction is carried out in a solvent such as pyridine, and the reaction temperature varies depending on the type of acylating agent.
Generally, immediately after adding the acylating agent, the temperature is between room temperature and 50℃.
The subsequent standing temperature is in the range of 0°C to room temperature.

When the reaction is carried out in this way, as shown in the reaction formula, the mercapto group (-SH) of the raw material 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) changes to the acylthio group (-SR ¹ ; ^R1 is an acyl group) 1,4,5,8-tetrakis[(acylthio)methyl]naphthalene (Ib) can be obtained.

Next, in (Ia) obtained above, R ¹ is 1,4,5,8-tetrakis[(methylthio)
When sulfonation reaction is carried out by treating methyl]naphthalene (C) with dimethoxycarbonium tetrafluoroborate, 1,4,5,8-tetrakis[(dimethylsulfonio), a tetrasulfonium salt derivative of (C), is produced. methyl]naphthalene-tetrakis(tetrafluoroborate) (B) can be obtained.

(In formula (B), R ² represents a dimethylsulfonio-tetrafluoroborate group (-S (CH ₃ ) ₂ BF ₄ )).

The reaction is carried out in a solvent such as methylene chloride or chloroform, and the reaction temperature is -20 to 5°C before and after adding the sulfonating agent dimethoxycarbonium tetrafluoroborate, and after that, the reaction temperature is 20 to 40°C. range. After the reaction is completed, when the reaction mixture is treated with an organic solvent, a white solid will precipitate, and if this is collected by filtration, 1, 4, 5,
8-tetrakis[(dimethylsulfonio)methyl]
Naphthalene-tetrakis (tetrafluoroborate) (B) is obtained.

As described above, 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) obtained in the present invention and its derivative () 1,4,5,8-tetrakis[(alkylthio)methyl]naphthalene ( a) and 1,4,5,8-tetrakis[(acylthio)methyl]naphthalene (b) and the sulfonium salt compound 1,4,5,8-tetrakis[(dimethylsulfonio)methyl]naphthalene-tetrakis(tetrafluoro borate) (B)
are all new compounds.

[Effects of the Invention] As described above, according to the present invention, 1,4,5,8-tetrakis(mercaptomethyl)naphthalene, 1,4,5,8-tetrakis[(alkylthio)methyl ] Naphthalene,
1,4,5,8-tetrakis[(acylthio)methyl]naphthalene and 1,4,5,8-tetrakis[(dimethylsulfonio)methyl]naphthalene-tetrakis(tetrafluoroborate) are obtained.

Such compounds are important as monomers for polysulfides and polythioesters, and are also useful as raw materials for producing surfactants and also as raw materials for heavy metal scavengers.

And, such a compound is naphthalene-1,4,
It can be easily produced from 5,8-tetracarboxylic acid.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 Production of naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E).

15.2 g of naphthalene-1,4,5,8-tetracarboxylic acid (D) was added little by little to a solution of 16 g of sodium carbonate dissolved in 200 ml of water. As the carboxylic acid reacted, carbon dioxide gas bubbles were generated violently. After adding the carboxylic acid over 1.5 hours, the reaction solution was heated in a water bath at about 40° C. for 30 minutes to completely dissolve the carboxylic acid crystals. Add dimethyl sulfate to this solution.
19 ml was added dropwise over 5 minutes, and the mixture was reacted at 50°C for 40 minutes.

Next, 11 g of sodium carbonate, followed by 19 ml of dimethyl sulfate were added, and the mixture was allowed to react at the same temperature for 40 minutes. After that, 5.5 g of sodium carbonate and 10 ml of dimethyl sulfate were sequentially added and stirred for 1 hour to complete the reaction. The reaction mixture was cooled to room temperature, and the precipitated white precipitate was suction filtered, washed with water, and dried. The product thus obtained was purified by recrystallization from dioxane, and naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E) was obtained as colorless crystals (15.0 g, yield: 84%). mp198−199℃.

Elemental analysis: Measured value C; 60.21, H; 4.50 Calculated value C; 60.00, H; 4.48 (C ₁₈ H ₁₆ O ₈ ) High-resolution mass spectrometry: Measured value 360.078 (Calculated value 360.085) IR (Nujol): ν = 1713 , 1726 cm ^-1 (COOCH ₃ ) ¹ H-NMR (CDCl ₃ ): δ=8.05 (s, 4H, ArH) 3.93 (s, 12H, CH ₃ ) Reference example 2 1,4,5,8-tetrakis (hydroxy Production of methyl) naphthalene (F).

Naphthalene-1,
25 g of crystals of 4,5,8-tetracarboxylic acid tetramethyl ester (E) were added little by little.

To prevent the reaction solution from exceeding room temperature due to heat generation,
From time to time the reaction flask was cooled with an ice water bath. The ester dissolved rapidly upon addition, and a transparent reaction solution was obtained. After the addition was complete, the reaction was stirred for an additional 8 days at room temperature. To the reaction mixture, methanol,
Water and dilute hydrochloric acid were added in this order to decompose the excess hydride, further water was added, and the mixture was stirred at room temperature. The resulting white solid was collected by suction filtration, thoroughly washed with water, and dried.
Recrystallization from a mixed solvent of dimethyl sulfoxide and water gave 1,4,5,8-tetrakis(hydroxymethyl)naphthalene (F) as colorless microneedle crystals (16.2 g, yield 94%). mp231−233℃.

Elemental analysis: Measured value C; 67.85, H; 6.38 Calculated value C; 67.73, H; 6.50 (C ₁₄ H ₁₆ O ₄ ) High-resolution mass spectrometry: Measured value 248.096 (Calculated value 248.105) IR (Nujol): ν = 3321 , 3224cm ^-1 (OH) ¹ H-NMR (DMSO-d ₆ ): δ = 7.56 (s, 4H, ArH) 5.19 (t, J = 5.5Hz, 4H, OH) 5.05 (d, J = 5.5Hz, 8H, CH ₂ ) Reference example 3 1,4,5,8-tetrakis (bromomethyl)
Production of naphthalene (G) 1.4 dioxane containing 42.5 g of 1,4,5,8-tetrakis(hydroxymethyl)naphthalene (F)
180 ml of phosphorus tribromide was added dropwise to the suspension over 10 minutes. The raw material tetraol crystals soon dissolved, and a new white solid precipitated. After 1 hour, 180 ml of phosphorus tribromide was further added and stirred overnight. While cooling in an ice-water bath, water was added to the reaction mixture to decompose unreacted phosphorus tribromide, and then water was further added to bring the total volume to about 3, and the mixture was stirred at room temperature for 30 minutes. The precipitated white solid was filtered off with suction, washed with water and dried. When the product thus obtained was purified by recrystallization from dioxane, 1,4,5,8-tetrakis(bromomethyl)naphthalene (G) was obtained as colorless crystals (79.1 g, yield 93%). . mp＞220℃
(Disassembly).

Elemental analysis: Measured value C; 33.80, H; 2.51 Calculated value C; 33.63, H; 2.42 (C ₁₄ H ₁₂ Br ₄ ) High-resolution mass spectrometry: Measured value 499.769 Calculated value 499.764 (C ₁₄ H ₁₂ Br ₂ ⁷⁹ Br ₂ ⁸¹ ) Mass spectrometry (m/e): 500 (M ⁺ , C ₁₄ H ₁₂ Br ₂ ⁷⁹ Br ₂ ⁸¹ ) IR (Nujol): ν = 545 cm ^-1 (C-Br) Reference example 4 1, 4, 5, Production of 8-tetrakis[(isothiuronio)methyl]naphthalene-tetrabromide () 200 ml of 99% ethanol containing 6.08 g of thiourea
10 g of crystals of 1,4,5,8-tetrakis(bromomethyl)naphthalene (G) were added little by little to the heated and stirred solution. With the generation of heat, the bromide crystals quickly melted and a new white solid precipitated. This white suspension was further heated and stirred for 2 hours.
The reaction was terminated by refluxing. After adding 100 ml of benzene to the reaction mixture and stirring for 30 minutes under ice cooling, the product was collected by suction filtration. The product thus obtained was washed twice with benzene, then twice with pentane, and then dried under vacuum to obtain 1,4,5, a thiourea derivative of 1,4,5,8-tetrakis(bromomethyl)naphthalene. , 8-tetrakis[(isothiuronio)methyl]naphthalene-tetrabromide () was obtained as white powdery crystals (15.61 g, yield 97%). mp>195℃ (decomposition).

Elemental analysis: Measured value C; 26.59, H; 3.80 Calculated value C; 26.87, H; 3.51 (C ₁₈ H ₂₈ N ₈ S ₄ Br ₄ ) ¹ H-NMR (DMSO-d ₆ ): δ = 9.22 (s, 16H, C(NH ₂ ) ₂ Br) 7.83 (s, 4H, ArH) 5.16 (s, 8H, CH ₂ ) Example 1 1. 24 g of 4,5,8-tetrakis[(isothiuronio)methyl]naphthalene-tetrabromide () was added. This mixture was heated under reflux for 3 hours while stirring under a nitrogen atmosphere. After the reaction, the resulting cloudy white solution was cooled to room temperature, benzene was added, and the mixture was separated. The benzene solution was discarded, and the aqueous layer was added dropwise to ice-diluted hydrochloric acid that was vigorously stirred through nitrogen. After stirring the resulting cloudy white solution at room temperature for 30 minutes, the precipitated white solid was collected by filtration, washed with water, and dried. When the thus obtained product was recrystallized from a benzene-hexane mixed solvent, 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) was obtained as almost colorless needle-shaped crystals. (9.0 g, yield 97%).

m.p.168−160℃.

Elemental analysis: Measured value C; 53.68, H; 5.35 Calculated value C; 53.84, H; 5.16 (C ₁₄ H ₁₆ S ₄ ) High-resolution mass spectrometry: (m/e) Measured value 312.009 Calculated value 312.013 IR (Nujol): ν=2545cm ^-1 (S-H) ¹ H-NMR (CDCl ₃ ): δ=7.44 (s, 4H, ArH) 4.40 (d, J=6.4Hz, 8H, CH ₂ ) 1.90 (t, J=6.4 Hz, 4H, SH) Example 2 0.5 g of 1,4,5,8-tetrakis(mercaptomethyl)naphthalene (A) was added to a solution of 0.5 g of sodium hydroxide dissolved in 30 ml of water while bubbling with nitrogen.
added. Stir this mixture well to completely dissolve the mercaptan crystals, then add 1ml of methyl iodide.
added. The reaction solution gradually became cloudy and a pale yellow suspension formed. After adding 10 ml of ethanol and stirring for 3 hours, a pale yellow precipitate was filtered off with suction, washed with water and dried. The crude product thus obtained was stirred at room temperature for 3 hours with 100 ml of chloroform containing a small amount of dichloromethane. Insoluble impurities were removed by suction filtration, and the filtrate portion was freed of solvent under reduced pressure. When the residual pale yellow product is purified by recrystallization from ethanol, almost colorless crystals of 1, 4,
5,8-tetrakis[(methylthio)methyl]naphthalene (C) was obtained (0.31 g, yield 53%). m.
p.118−119℃.

Elemental analysis: Measured value C; 58.40, H; 6.81 Calculated value C; 58.69, H; 6.57 (C ₁₈ H ₂₄ S ₄ ) High resolution mass spectrometry: Measured value 368.069 Calculated value 368.076 Mass spectrometry (m/e): 368 ( M ⁺ ) ¹ H-NMR (CDCl ₃ ): δ = 7.32 (s, 4H, ArH) 4.36 (s, 8H, CH ₂ ) 2.05 (s, 12H, CH ₃ ) Example 3 1, 4, 5, 8 - To a suspension of 0.21 g of tetrakis(mercaptomethyl)naphthalene (A) in 3 ml of pyridine, 2 ml of acetic anhydride is added and the mixture is brought to room temperature for 4 ml.
I left it for days. Water was added to the resulting brown solution to make a total volume of about 500 ml, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was collected by filtration, washed with water, and dried. The crude product thus obtained was purified by recrystallization from a mixed solvent of ethanol-benzene, resulting in slightly colored microcrystalline 1,4,5,8-tetrakis[(acetylthio)methyl]naphthalene (Ib ) was obtained (0.25 g, yield 78%).

m.p.153.5−155℃.

Elemental analysis: Measured value C; 54.79, H; 5.20 Calculated value C; 55.00, H; 5.04 (C ₂₂ H ₂₄ O ₄ S ₄ ) Mass spectrometry (m/e): 480 (M ⁺ ) IR (Nujol): ν = 1688 cm ^-1 (-SCOCH ₃ ) ¹ H-NMR (CDCl ₃ ): δ = 2.31 (s, 12H, SCOCH ₃ ) 4.59 (s, 8H, ArCH ₂ ) 7.44 (s, 4H, ArH) Example 4 Dimethoxy Into a stirred solution of 1.6 g of carbonium tetrafluoroborate in 2 ml of dichloromethane,
A solution of 0.2 g of 1,4,5,8-tetrakis[(methylthio)methyl]naphthalene (C) dissolved in 3 ml of dichloromethane was added at 0 DEG C. under a nitrogen atmosphere. The resulting pale yellow solution was stirred at 0° C. for 1 hour, then at room temperature for 16 hours. 10 ml of ethyl acetate was added to the reaction solution, stirred at room temperature for 15 minutes, and the pink supernatant liquid was removed. After repeating this operation two more times, 1 ml of dichloromethane and 2 ml of ethyl formate were added and stirred overnight to obtain a white powdery solid. This was filtered off with suction, thoroughly washed with ethyl formate, and then dried under vacuum. nio)methyl]naphthalene-tetrakis(tetrafluoroborate (B) was obtained (0.31 g, yield
74%).

m.p.203−208℃ (decomposition).

Elemental analysis: Measured value C; 34.23, H; 4.55 Calculated value C; 34.05, H; 4.68 (C ₂₂ H ₃₆ S ₄ B ₄ F ₁₆ ) ¹ H-NMR (DMSO-d ₆ ): δ = 7.93 (s, 4H, ArH) 5.24 (s, 8H, CH ₂ ) 2.71 (s, 12H, CH ₃ )

Claims (1)

[Claims] 1. 1,4,5,8-tetrakis(mercaptomethyl)naphthalene represented by structural formula (A). 2 A 1,4,5,8-tetrakis(mercaptomethyl)naphthalene derivative represented by the general formula (). (In the formula, R ¹ is an alkyl group or an acyl group.) 3 1,4,5,8-tetrakis[(dimethylsulfonio)methylnaphthalene-tetrakis (tetrafluoroborate) represented by structural formula (B). (In the formula, R ² is a dimethylsulfoniotetrafluoroborate group (-S (CH ₃ ) ₂ BF _4. ) 4 1,4,5,8-tetrakis[(isothiuronio)methyl] represented by the general formula () 1,4,5, represented by the following structural formula (A), characterized by alkali treatment of naphthalene-tetrahalide,
A method for producing 8-tetrakis(mercaptomethyl)naphthalene. (In the formula, ^R3 is a halogenated isothiuronio group (-[SC( _NH2 ) ₂ ]X).) 5 1,4,5,8-tetrakis(mercaptomethyl)naphthalene represented by structural formula (A) 1,4,5, represented by the following general formula (), characterized by treating with an alkylating agent or an esterifying agent,
A method for producing an 8-tetrakis(mercaptomethyl)naphthalene derivative. (In the formula, R ¹ is an alkyl group or an acyl group.) 6 Treating 1,4,5,8-tetrakis[(methylthio)methyl]naphthalene represented by structural formula (C) with dimethoxycarbonium tetrafluoroborate A method for producing 1,4,5,8-tetrakis[(dimethylsulfonio)methyl]naphthalene-tetrakis (tetrafluoroborate) represented by the following structural formula (B), characterized by: (In the formula, R ² is a dimethylsulfonio-tetrafluoroborate group (-S (CH ₃ ) ₂ BF ₄ ).