JPH10204053A - Production of dicyanobenzenesulfonic acids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing dicyanobenzenesulfonic acids, capable of surely and readily substituting sulfonate group at the o-position with respect to the nitrile groups of phthalonitrile and available in good yield. SOLUTION: Nitrophthaloniriles are reacted with at least one of sulfites and hydrogensulfites to produce dicyanobenzenesulfonic acids having sulfonate group or its salt at the 3- or the 4-position.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing dicyanobenzenesulfonic acids such as 2,3-dicyanobenzenesulfonic acid.

[0002]

2. Description of the Related Art As dicyanobenzenesulfonic acids, for example, 2,3-dicyanobenzenesulfonic acid, 4,4
5-dicyanobenzenesulfonic acid and salts thereof. 2,3-dicyanobenzenesulfonic acid and the like are important compounds as a raw material for synthesizing a dye, for example, a phthalocyanine dye, and the dye is used in a compact disk or the like. It is used for the recording layer of an optical information recording medium. Of these, 2,3-dicyanobenzenesulfonic acid can be produced by directly sulfonating phthalonitrile with fuming sulfuric acid, but it is not possible to sulfonate phthalonitrile in this way. It's not easy. That is, since the benzene ring having a nitrile group as a substituent is meta-oriented, the sulfonic acid group is easily substituted at the meta position with respect to the nitrile group, but the sulfone group is substituted at the ortho position with respect to the nitrile group. Because it is difficult.
As an alternative to this direct sulphonation of phthalonitrile, ortho-dibromobenzene is sulphonated (Journal fur praktishChem).
IE 138 (1933), p. 90), and then a method of substituting bromide with a nitrile group (JOC 44 vol.)
(1979) 1359).

[0003]

However, in the sulfonation of ortho-dibromobenzene, the sulfonic acid group is substituted not only at the ortho position but also at the meta position with respect to the bromide, and a disulfonated product is formed. is there. The separation of the ortho-substituted mono-sulfonated product from the meta-substituted product or di-substituted product (disulfonated product) is extremely difficult and cannot be completely performed. In addition, there is also a problem that the nitrilation in which bromine is substituted with a nitrile group has a remarkably low yield.

[0004] A first object of the present invention is to provide a process for producing dicyanobenzenesulfonic acid which can surely substitute a sulfonic acid group at an ortho position to a nitrile group of phthalonitrile. A second object of the present invention is to provide a process for producing dicyanobenzenesulfonic acids which can easily carry out a reaction of introducing a sulfonic acid group at an ortho position to a nitrile group of phthalonitrile. A third object of the present invention is to provide a process for producing dicyanobenzenesulfonic acids having a good yield.

[0005]

In order to solve the above-mentioned problems, the present invention provides (1) a method of reacting nitrophthalonitriles with at least one of sulfites and bisulfites at the 3- or 4-position. To provide dicyanobenzenesulfonic acids having a sulfonic acid group or a salt thereof. Also,
In the present invention, the nitrophthalonitrile is 3-nitrophthalonitrile, and the dicyanobenzenesulfonic acid is 2,2.
3. A method for producing dicyanobenzenesulfonic acid according to claim 1, which is 3-dicyanobenzenesulfonic acid.

The dicyanobenzenesulfonic acids include the above-mentioned compounds. However, in the production method of the present invention, as described above, it is difficult to introduce a sulfonic acid group ortho to the phthalonitrile (position 3). Therefore, it can be said that the production of 2,3-dicyanobenzenesulfonic acid having a sulfonic acid group at the ortho position and salts thereof is particularly significant. However, the present invention is not limited to this. 4,5 from nitrophthalonitrile
-Dicyanobenzenesulfonic acid and salts thereof can be produced in a similar manner. In the production method of the present invention, 2,3-
Dicyanobenzenesulfonic acid is obtained by a reaction formula represented by at least one of the following [Formula 1] and [Formula 2].

[0007]

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[0008]

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The reaction formula of the chemical formula (1) is based on the reaction of (a) 3-nitrophthalonitrile with (b) sulfites represented by the general formula M ₂ SO ₃ (M represents a monovalent alkali metal). , (C) a salt of 2,3-dicyanobenzenesulfonic acid and (d) a nitrite of a monovalent alkali metal, and the reaction formula of [Formula 2] is represented by (a) 3-nitrophthalonitrile And (e) a reaction of bisulfites represented by the general formula MHSO ₃ (M represents a monovalent alkali metal) to form (c) a salt of 2,3-dicyanobenzenesulfonic acid; This shows that 3-dicyanobenzenesulfonic acid, (g) nitrous acid, and (d) salts of the monovalent alkali metal are formed. In the salts of (c), a sulfonic acid group can be easily converted to a sulfonic acid group by reaction with an acid. As a result of such reactions of [Chemical Formula 1] and [Chemical Formula 2], a sulfonic acid group or the like is surely introduced at an ortho position with respect to a nitrile group of phthalonitrile. The mechanism by which the nitro group at the ortho-position is replaced with the sulfonic acid group is that the nitro group at the 3-position becomes active due to the electron-withdrawing property of the nitrile group of 3-nitrophthalonitrile, and a nucleophilic substitution reaction is easily caused. it is conceivable that. As another similar reaction of the nucleophilic substitution reaction on 3-nitrophthalonitrile, a reaction in which a nitro group is substituted with an alkoxyl by a reaction formula shown in the following [Chemical Formula 3] is known.

[0010]

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The reaction formula of the chemical formula (3) is that (a) 3-nitrophthalonitrile and (i) an alcohol represented by the general formula ROH (R represents an alkyl group) are sodium hydride in a dimethylformaldehyde solvent. The reaction is carried out using (NaH) as a catalyst to obtain (j) 2,3-dicyanobenzene alcoholate (Nouveau Journal)
al Dechemie 6 Volume 653-658 (1
982).

In the present invention, the above [formula 1] and [formula 2]
In order to make the reaction proceed, at least one of the inorganic sulfites of the component (b) and the bisulfite of the component (e) is reacted with the organic 3-nitrophthalonitrile of the component (a). It is necessary to make good contact to make it easy. To this end, on the one hand, water is used as a solvent to dissolve at least one of the components (b) and (e) so that an aqueous solution thereof is obtained, and on the other hand, an organic solvent that dissolves the component (a) is used. In order to satisfy both of these, it is preferable to use the above-mentioned organic solvent which is mixed with water. In this case, it is preferable to mix an aqueous solution in which at least one of the components (b) and (e) is well dissolved and an organic solvent solution in which the component (a) is well dissolved. ) And at least one of the components (e) and one of the components (a) may be dissolved, and then the other components may be dissolved, or both may be dissolved at the same time.
Examples of such an organic solvent mixed with water include acetone, diacetone alcohol, dioxane, N, N-dimethylformamide, formamide, sulfolane, and a mixed solvent of two or more kinds of ethylene glycol, Not limited to this, any other solvent that is mixed with water and dissolves 3-nitrophthalonitrile can be used. Further, as a catalyst, a metal sulfate such as iron (II) sulfate, iron (III) sulfate, copper sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, magnesium sulfate,
Any of palladium sulfate, silver sulfate, mercury sulfate and the like can be used. The amount used is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight on a 0.1 molar scale.

The components (b) and (e) need only be present so that they can be brought into contact with the component (a) in a solvent. For this purpose, they may be produced from a raw material in a solvent. Is added to an organic solvent dissolving the component (a) or a mixed solvent of an organic solvent and water, and an aqueous solution dissolving the other raw material or a mixed solvent of water and an organic solvent is added thereto. Component (b) and component (e) may be generated. Specifically, one raw material is an alkali agent such as a carbonate or hydroxide of a monovalent alkali metal such as sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide, and the other raw material is Examples include, but are not limited to, sulfurous acid and bisulfite.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The details will be described with reference to the following examples, but using 3-nitrophthalonitrile as a raw material and a sulfite or a sulfite obtained from an alkali agent of a monovalent metal and sulfurous acid to obtain 2,3 In synthesizing dicyanobenzenesulfonic acid and a salt thereof, N, N-dimethylformamide, acetone and dioxane are used as organic solvents for dissolving the former 3-nitrophthalonitrile, and the latter sulfite is dissolved in water; The latter solution is added dropwise to the former solution, and further reacted at 50 ° C. to 120 ° C. for 5 to 10 hours or at room temperature for 10 to 24 hours. Although the obtained 2,3-dicyanobenzenesulfonic acid and its salt are dissolved in the above-mentioned mixed solvent of organic solvent and water, the solution contains residual raw materials and by-products. For removal, 2,3-dicyanobenzenesulfonic acid and its salt are precipitated in an organic solvent mixed with water, or the solution is concentrated by filtration at room temperature or hot, and the precipitate or residue is further washed with water. The remaining raw material, such as 3-nitrophthalonitrile and the like, is removed as an insoluble material by treatment, and optionally treated with activated carbon, and 2,3-dicyanobenzenesulfonic acid and a salt thereof are obtained from the dissolved matter. In this way, 2,3-dicyanobenzenesulfonic acid and its salt can be obtained in a yield of 50 to 90%, but the reaction conditions can be relaxed and each processing step can be simplified. Using a 3-nitrophthalonitrile in which a nitro group is introduced at the 3-position as a raw material, and replacing the activated nitro group with a sulfonic acid group using a nucleophilic substitution reaction. And how to use it.

[0015]

Next, embodiments of the present invention will be described. Example 1 17.3 g (1/10 mol) of 3-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd .; the same applies hereinafter) was dissolved in 75 g of N, N-dimethylformamide, and the solution was cooled (15 ° C.). Temperature), an aqueous solution of 15.8 g of potassium sulfite dissolved in 40 g of water in a nitrogen stream.
Add dropwise over ~ 20 minutes. Thereafter, the reaction was carried out with stirring overnight at room temperature, and the reaction solution was
Pour into 1 liter of acetone to form a precipitate. The precipitate is filtered off by suction filtration, washed well with acetone and dried on a desiccator. In this way, a solid content of 30 g was obtained. This solid was dispersed in 100 g of ice water to precipitate the remaining raw material, 3-nitrophthalonitrile, and further added amidosulfuric acid or urea to remove by-product potassium nitrite contained in the solid, The treated product was further filtered off, and the filtrate was evaporated to dryness to obtain 12 g.
Was obtained. On the other hand, the solvent was removed from the acetone solution of the filtrate filtered off from the precipitate by evaporation, and the concentrated liquid was poured into water at room temperature, and the filtrate was collected by filtration to obtain a filtrate which was dissolved in water, and the water was evaporated. After drying, 5.2 g of powder was obtained. The powder obtained from the precipitate and the filtrate was 1 in total.
7.2 g, and the yield was 82.7% (100% when all the 3-nitrophthalonitrile as the raw material was 2,3-dicyanobenzenesulfonic acid; the same applies hereinafter). This powder is hygroscopic and turns black and sticky when left in the air. Therefore, drying and storage are suitably performed in a desiccator containing silica gel and concentrated sulfuric acid. When the infrared absorption spectrum of this powder was measured by the KBr tablet method, the result shown in FIG. 1 was obtained. In the figure,
3450 cm ^-1 absorption of stretching vibration by OH sulfonic acid was observed at, also, 1210Cm from 1060 cm ^{-1 -1}
Shows absorption of stretching vibration of S = O, and 2240c
At m ^-1 , absorption due to stretching vibration due to -CN is observed.
The powder was subjected to elemental analysis. The results of the elemental analysis (by weight) were as follows. C: 46.10, H: 1.91, N: 13.51 On the other hand, 2,3-dicyanobenzenesulfonic acid is C ₈ H ₄
The theoretical value of the elemental analysis value (weight ratio) is represented by O ₃ N ₂ S ₁ as follows. C: 46.15, H: 1.92, N: 13.46 From the results of these analyses, no absorption of NO ₂ was observed from the results of the infrared absorption spectrum analysis, and instead, the absorption of the sulfonic acid group was reduced. The obtained powder can be identified as 2,3-dicyanobenzenesulfonic acid from the fact that it is observed and the molecular formula obtained from the elemental analysis value.

Example 2 17.3 g (1/10 mol) of 3-nitrophthalonitrile was dissolved in 120 g of acetone at room temperature.
An aqueous solution in which 2.6 g of sodium sulfite is dissolved in 120 g of water is added dropwise over 5 minutes. Thereafter, the reaction is carried out for 10 hours while boiling (refluxing) acetone in a flask equipped with a cooling tube, followed by filtration. Water and acetone are removed by distillation from the acetone-water layer of the filtrate, and the residue is treated with water to remove remaining insolubles such as 3-nitrophthalonitrile and the like. And evaporated to dryness to give a solid. The yield of this solid was 28.8 g. Sodium nitrite was removed from this solid in the same manner as in Example 1,
13.5 g of a powder were obtained. FIG. 2 shows the results of infrared absorption spectrum analysis of this powder measured in the same manner as in Example 1.
Shown in From this result and the analogy of the result of Example 1, the obtained powder can be identified as 2,3-dicyanobenzenesulfonic acid.

Example 3 17.3 g (1/10 mol) of 3-nitrophthalonitrile was dissolved in 120 g of acetone at room temperature, and 5.
0 g (1/20 mol) of sodium carbonate is added and dissolved, and 60 ml of an aqueous solution in which 10.4 g (1/10 mol) of sodium bisulfite is dissolved in water is added dropwise with stirring over 5 minutes. Thereafter, the mixture is reacted for 20 hours while refluxing acetone in a flask equipped with a cooling tube, and then filtered while hot. Water and acetone were removed from the acetone-water layer of the filtrate by distillation, and the residue was washed with 200 ml of water.
And the remaining insolubles, such as 3-nitrophthalonitrile, are precipitated. The treated product is filtered, and the aqueous solution of the filtrate is evaporated to dryness. Thus, 11.6 g of a powder was obtained. FIG. 3 shows the result of infrared absorption spectrum analysis of this powder measured in the same manner as in Example 1. Results and Example 1
Can be identified as 2,3-dicyanobenzenesulfonic acid. In this embodiment, sodium sulfite was produced using sodium carbonate and sodium hydrogen sulfite as raw materials, and this was used. However, the above-mentioned alkali agent may be used instead of sodium carbonate.

Example 4 In Example 1, instead of stirring overnight at room temperature, 1
A powder of the final stage was obtained in the same manner except that stirring was performed at 00 ° C. for 12 hours. The yield was 15 g. Example 1
FIG. 4 shows the results of infrared absorption spectrum analysis of this powder measured in the same manner as in FIG. From this result and the analogy of the result of Example 1, the obtained powder can be identified as 2,3-dicyanobenzenesulfonic acid.

Example 5 A final stage powder was obtained in the same manner as in Example 4, except that the reaction was carried out with the addition of 5.0 g of iron (III) sulfate n-hydrate. The yield was 16 g. FIG. 5 shows the results of infrared absorption spectrum analysis of this powder measured in the same manner as in Example 1.
Shown in

Comparative Example 1 3-chloro-1,2-dicyanobenzene 0.81 g
(0.005 mol) and 0.80 g (0.006 mol)
0.1 g of sodium sulfite and 0.1 g of copper sulfate were dispersed in 30 ml of a 50% aqueous solution of dioxane, boiled for 3 hours, cooled, and the deposited precipitate was separated by filtration. The solvent was distilled off from the filtrate, and 10 ml of water was added to the residue to dissolve it.
of ethanol, the precipitated inorganic insolubles were separated by filtration, and the ethanol-water layer was evaporated to dryness.
%) Of 2,3-dicyanobenzenesulfonic acid.
(VM DERKACHEVA et al., Phosphor.
us, sulfer and Silicon and
the Related Elements No.
104, pp 161-167 (1995). ).

[0021]

According to the present invention, the sulfonic acid group can be reliably substituted at the ortho position to the nitrile group of phthalonitrile, and the reaction of introducing the sulfonic acid group at the ortho position to the nitrile group of phthalonitrile can be facilitated. The present invention can provide a process for producing dicyanobenzenesulfonic acids having a good yield.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a final product obtained according to a first embodiment of the present invention.

FIG. 2 is an infrared absorption spectrum diagram of a final product obtained according to a second embodiment of the present invention.

FIG. 3 is an infrared absorption spectrum diagram of a final product obtained according to a third embodiment of the present invention.

FIG. 4 is an infrared absorption spectrum of a final product obtained according to a fourth embodiment of the present invention.

FIG. 5 is an infrared absorption spectrum of a final product obtained according to a fifth embodiment of the present invention.

Claims (2)

[Claims] 1. The reaction of nitrophthalonitriles with at least one of sulfites and bisulfites to produce 3
A method for producing dicyanobenzenesulfonic acids having a sulfonic acid group or a salt thereof at the 4- or 4-position. 2. The nitrophthalonitrile is 3-nitrophthalonitrile, and the dicyanobenzenesulfonic acid is 2,3-dicyanobenzenesulfonic acid.
A method for producing the dicyanobenzenesulfonic acid described in the above.