JP2500316B2 - 1,4,5,8-Tetrakis (halogenomethyl) naphthalene derivative and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound, a 1,4,5,8-tetrakis (halogenomethyl) naphthalene derivative, and a method for producing the compound.

[Conventional technology]

Conventionally, 1,8 in which the halogenomethyl group-(-CH ₂ X, X is a halogen atom) is substituted at the peri position (1,8 position) of naphthalene
-Bis (halogenomethyl) naphthalene is a well known compound.

[Problems to be Solved by the Invention]

However, 1,4,5,8-tetrakis (halogenomethyl) naphthalene, which is a bisperi-substituted product in which a halogenomethyl group is substituted at the other peri-position (4,5-position) of the naphthalene ring, is Although it is expected to have a wide range of uses, it was difficult to synthesize.

An object of the present invention is to provide a novel compound 1,4,5,8-tetrakis (halogenomethyl) naphthalene derivative and a method for producing the compound.

[Means for solving the problem]

1,4,5 of the novel compounds according to the present invention to achieve the above object
The 8-tetrakis (halogenomethyl) naphthalene derivative is represented by the following general formula (II).

However, in the formula (II), R is a halogenated isothiuronio group — [SC (NH ₂ ) ₂ ] ⁺ X ⁻ , and X is a bromine atom or a chlorine atom.

Further, the 1,4,5,8-tetrakis (halogenomethyl) naphthalene derivative represented by the general formula (II) is a 1,4,5,8-tetrakis (halogenomethyl) derivative represented by the following structural formula (I). It is produced by treating naphthalene with thiourea.

However, in the formula (I), X is a bromine atom or a chlorine atom.

The 1,4,5,8-tetrakis (halogenomethyl) naphthalene represented by the general formula (I) is converted into the 1,4,5,8-tetrakis (hydroxymethyl) naphthalene represented by the following structural formula (A). It is produced by reacting a halogenating agent.

In the general formula (I), 1,4,5,8-tetrakis (chloromethyl) naphthalene represented by the following structural formula (C) in which X is a chlorine atom is 1,4,5,8 as described above. -In addition to being produced by reacting tetrakis (hydroxymethyl) naphthalene (A) with a halogenating agent, 1,4,5,8-tetrakis (bromomethyl) naphthalene represented by the following structural formula (B) is used as a halogen exchange agent. It can also be produced by utilizing the halogen exchange reaction treated with.

According to the method for producing 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I), the reaction is carried out in an inert organic solvent such as ethers and benzene. First of all,
A suspension is prepared by adding the above inert organic solvent to 4,5,8-tetrakis (hydroxymethyl) naphthalene (A),
Next, a halogenating agent is added dropwise to this to carry out a halogenation reaction. As the halogenating agent, phosphorus halide such as phosphorus tribromide and thionyl halide such as thionyl chloride are used. Usually, the halogenating agent acts excessively in an amount of about 5 times, and this is added in several times to complete the halogenation reaction. The reaction temperature is in the range of room temperature to 50 ° C., and in order to increase the reaction yield, it is preferable to constantly and efficiently stir during the reaction.

When the reaction is carried out in this manner, the suspension of the raw material 1,4,5,8-tetrakis (hydroxymethyl) naphthalene (A) immediately disappears into a transparent solution with the progress of the halogenation reaction, and soon after. The product 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I) separates from the reaction solution as a white precipitate. After completion of the reaction, the precipitate is filtered and collected to obtain 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I).

However, in the formula (I), X is a bromine atom or a chlorine atom.

In addition, 1,4,5,8-tetrakis (hydroxymethyl) naphthalene (A), which is a raw material for the production of 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I), can be prepared as shown in the following reaction formula. , Usually commercially available naphthalene-1,4,5,
After treating 8-tetracarboxylic acid (D) with dimethyl sulfate in an alkaline solution to give naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E), it is reduced with a hydrogenating agent, It is prepared by converting the ester group (-CO ₂ Me) to a hydroxymethyl group (-CO ₂ OH).

Further, according to the present invention, in 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I), when X is a chlorine atom, the above 1,4,5,8-tetrakis (hydroxy) is used as a production method. In addition to the production method using methyl) naphthalene (A) as a raw material, a production method using a halogen exchange reaction is further provided. That is, when lithium chloride is allowed to act on 1,4,5,8-tetrakis (bromomethyl) naphthalene (B) as a halogen exchange agent, a halogen exchange reaction occurs as shown in the following reaction formula, and four of the four 1,4,5,8-Tetrakis (chloromethyl) naphthalene (C) in which the bromine atom is replaced by a chlorine atom is obtained.

The reaction is carried out using acetone, dimethylformamide or the like as a solvent, the reaction temperature is in the range of room temperature to 50 ° C., and the reaction time is 10 to 20 hours. When the reaction is carried out in this way, as the reaction proceeds, the starting bromide (B) dissolves and becomes a transparent solution, so if the product is treated with water after completion of the reaction, 1,4,5,8-tetrakis (chloro) Methyl) naphthalene (C) is obtained.

Next, the 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I) thus obtained was treated with thiourea to give 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I). 1,4,5,8-tetrakis (isothiuroniomethyl) naphthalene-tetrahalide (II), which is a thiourea derivative of the above). The reaction is carried out in a solvent such as alcohol and the reaction temperature is in the range of 50 ° C to 80 ° C. As the reaction progresses, the raw materials 1,4,5,8-
The crystals of tetrakis (halogenomethyl) naphthalene (I) and thiourea disappeared, and the new compound 1,4,5,8-tetrakis (isothiuroniomethyl) naphthalene-tetrahalide (II) was obtained as shown in the following reaction formula. The crystals of are obtained.

However, in the formula (I), X is a bromine atom or a chlorine atom, and in the formula (II), R is a halogenated isothiuronio group (-
[SC (NH ₂ ) ₂ ] ⁺ X ⁻ ).

The obtained 1,4,5,8-tetrakis (halogenomethyl) naphthalene (I) thiourea derivative 1,4,5,8-tetrakis (isothiuroniomethyl) naphthalene-tetrahalide (II) is It is a new compound.

 Hereinafter, the present invention will be described in more detail with reference to Examples.

〔Example〕

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

To a solution prepared by dissolving 16 g of sodium carbonate in 200 ml of water, 15.2 g of naphthalene-1,4,5,8-tetracarboxylic acid (D) was added little by little. Bubbles of carbon dioxide gas were generated vigorously as the carboxylic acid reacted. After the carboxylic acid was added 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. Dimethyl sulfate 19 was added to this solution.
ml was added dropwise over 5 minutes, and the mixture was reacted at 50 ° C. for 40 minutes.

Next, sodium carbonate 11 g, followed by dimethyl sulfate 19 ml
Was added and reacted for 40 minutes at the same temperature, and then 5.5 g of sodium carbonate and 10 ml of dimethyl sulfate were sequentially added, and the reaction was terminated by stirring for 1 hour. The reaction mixture was cooled to room temperature and the white precipitate that had precipitated was suction filtered, washed with water and dried. The product thus obtained was recrystallized from dioxane and purified to give naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E) as colorless crystals (1
5.0 g, 84% yield).

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) Reference example 2 1 Production of 4,4,5,8-tetrakis (hydroxymethyl) naphthalene (A).

To a stirred solution of 1000 ml of hexane containing 1 mol of diisobutylaluminium hydride, 25 g of naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E) crystals were added little by little.

The reaction flask was occasionally cooled with an ice-water bath so that the reaction solution did not exceed room temperature due to an exotherm. The ester was dissolved immediately upon addition, and a transparent reaction solution was obtained. After the addition is complete
The reaction was stirred for another 8 days at room temperature. To the reaction mixture, under cooling, methanol, water and dilute hydrochloric acid were added in that order to decompose excess hydride, water was further added and the mixture was stirred at room temperature. The resulting white solid was collected by suction filtration, washed thoroughly with water and dried,
When recrystallized from a mixed solvent of dimethyl sulfoxide-chloroform, 1,4,5,8-tetrakis (hydroxymethyl) naphthalene (A) was obtained as colorless fine crystals (1
6.2 g, 94% yield).

mp229-231 ℃ 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) Reference example 3 1 Produced to 4,4,5,8-tetrakis (bromomethyl) naphthalene (B).

180 ml of phosphorus tribromide was added dropwise to a suspension of 1.4 l of dioxane containing 42.5 g of 1,4,5,8-tetrakis (hydroxymethyl) naphthalene (A) over 10 minutes. Crystals of the starting tetraol were soon dissolved, and a new white solid was deposited. After 1 hour, 180 ml of phosphorus tribromide was added and the mixture was stirred overnight. Water was added to the reaction mixture under cooling with an ice-water bath to decompose unreacted phosphorus tribromide, and then water was further added to bring the total volume to about 3 l, and the mixture was stirred at room temperature for 30 minutes. The white solid deposited was filtered off with suction, washed with water and dried. The product thus obtained was recrystallized from dioxane and purified to give 1,4,
5,8-Tetrakis (bromomethyl) naphthalene (B) was obtained as colorless crystals (79.1 g, yield 93%).

mp> 220 ° C (decomposition) 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 ⁷⁹ ₂ ▼
▲ Br ⁸¹ ₂ ▼) Mass spectrometry; Measured value 500 Calculated value 500 (C ₁₄ H ₁₂ ▲ Br ⁷⁹ ₂ ▼ ▲ Br
⁸¹ ₂ ▼) IR (Nujol): ν = 545 cm ⁻¹ (C—Br) Reference Example 4 Production of 1,4,5,8-tetrakis (chloromethyl) naphthalene (C).

To a solution prepared by dissolving 0.3 g of lithium chloride in 15 ml of dimethylformamide, 0.3 g of 1,4,5,8-tetrakis (bromomethyl) naphthalene (B) was added and stirred at room temperature. The white solid of tetrabromide gradually dissolves as the reaction progresses,
After 1 hour, it turned into a clear solution. After stirring overnight at room temperature, water was added to bring the total volume to 500 ml, and the mixture was stirred at room temperature for 1 hour. The formed precipitate was collected, washed with water and dried to obtain 1,4,5,8-tetrakis (chloromethyl) naphthalene (C) as a colorless solid. The product thus obtained was further recrystallized from a mixed solvent of dimethyl sulfoxide-methanol-water system for purification (0.187 g, yield 97%).

mp207-209 ° C Elemental analysis: Measured value C; 52.35, H; 3.51 Calculated value C; 52.20, H; 3.76 (C ₁₄ H ₁₂ Cl ₄ ) Mass spectrometry: Measured value 322 Calculated value 322 (C ₁₄ H ₁₂ ▲ Cl ³⁵ ₃ ▼ ▲ Cl
³⁷ ₁ ▼) ¹ H-NMR (DMSO-d ₆ : δ = 7.82 (s, 4H, ArH) 5.39 (s, 8H, CH ₂ ) IR (Nujol): ν = 620 cm ^-1 (C-Cl) Example 1. To a heated and stirred solution of 200 ml of 99% ethanol containing 6.08 g of thiourea, 10 g of 1,4,5,8-tetrakis (bromomethyl) naphthalene (B) crystals were added little by little. After dissolution, a new white solid was precipitated, and the white suspension was heated and refluxed for 2 hours while stirring to terminate the reaction.
After adding 0 ml and stirring for 30 minutes under ice cooling, the product was collected by suction filtration. The thus obtained product was washed twice with benzene and then twice with pentane, and dried in vacuum to give 1,4,5,8-tetrakis (bromomethyl) naphthalene as a thiourea derivative of 1,4,5. , 8-Tetrakis (isothiuriomethyl) naphthalene-tetrabromide (II)
Was obtained as white powdery crystals (15.61 g, yield 97
%).

mp> 195 ° C (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 B
r 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 2 Thio To a heated stirring solution of 150 ml of 99% ethanol containing 4.72 g of urea, 5.0 g of 1,4,5,8-tetrakis (chloromethyl) naphthalene (C) crystals were added little by little. After dissolution, a new white solid was precipitated, and the white suspension was heated and refluxed for 2 hours with stirring to terminate the reaction, 70 ml of benzene was added to the reaction mixture, and the mixture was stirred for 30 minutes under ice cooling. The product was collected by suction filtration.
The thus obtained product was washed with benzene three times and then with pentane twice, and dried in vacuum to give 1,4,5,8-tetrakis (chloromethyl) naphthalene as a thiourea derivative of 1,4,4,4. 5,8-Tetrakis (isothiuroniomethyl)
Naphthalene-tetrachloride (II) was obtained as white powdery crystals (9.23 g, yield 95%).

mp> 180 ℃ (decomposition) Elemental analysis: Measured value C; 34.87, H; 4.35 Calculated value C; 34.50, H; 4.50 (C ₁₈ H ₂₈ N ₈ S ₄ C
l ₄ ) ¹ H-NMR (DMSO-d ₆ : δ = 9.25 (s, 16H, C (NH ₂ ) ₂ Cl) 7.81 (s, 4H, ArH) 5.14 (s, 8H, CH ₂ ) [Effect of the invention As described above, according to the present invention, as a novel compound, 1,4,5,8-tetrakis (halogenomethyl) naphthalene is a thiourea derivative of 1,4,5,8-tetrakis (isothiuroniomethyl). Naphthalene-tetrahalide is obtained.

Such a compound is useful as a monomer for polyesters and polyethers, and also as a raw material for producing a surfactant.

And such compounds are commercially available naphthalene-1,4,5,8
-Can be easily produced from tetracarboxylic acid.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References Journal of Organic Chemistry, Vol. 47 No. 6 P. 1011-1018 (1982)

Claims (2)

(57) [Claims] 1. A 1,4,5,8-tetrakis (halogenomethyl) naphthalene derivative represented by the following general formula (II). However, in the formula (II), R is a halogenated isothiuronio group-
[SC (NH ₂ ) ₂ ] ⁺ X ⁻ , and X is a bromine atom or a chlorine atom. 2. A 1,4,5,8-tetrakis (halogenomethyl) naphthalene represented by the following general formula (I) is treated with thiourea, which is represented by the following general formula (II):
Process for producing 4,5,8-tetrakis (halogenomethyl) naphthalene derivative. However, in the formula (I), X is a bromine atom or a chlorine atom, and in the formula (II), R is a halogenated isothiuronio group-
[SC (NH ₂ ) ₂ ] ⁺ X ⁻ .