JPS6019899B2 - Method for producing dicyanodihydroxybenzene derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a dicyanodihydroxybenzene derivative by reacting a diformyldihydroxybenzene derivative, a nitrogen-containing compound, and oxygen in the presence of a metal catalyst.

Dicyanodihydroxybenzene derivatives are compounds useful as raw materials for the synthesis of various medicines, agricultural chemicals, and dyes.

Conventionally, a method for producing penzonitrile by ammoxidizing benzaldehyde with an oxygen-containing gas and ammonia in the presence of a steel catalyst [W. Blackmane is 1, Rec.
Trav. Chim. , 82, 757 (1963); A
Misono etal, B blood. Chem. SoC. Ja
Pan. There were various difficulties in implementing it industrially as it required various operations.

Furthermore, it was found that even if this method was applied to the ammoxidation reaction of diformyldihydroxybenzene derivatives, the yield of the target product did not improve. Therefore, the present inventors conducted intensive studies with the aim of improving this method and ammoxidizing diformyldihydroxybenzene derivatives in high yield.As a result, they unexpectedly found that the reaction was inhibited in the ammoxidation of benzaldehyde. The inventors have now discovered that water can be effectively used as a reaction medium in the ammoxidation of diformyldihydroxybenzene derivatives, and have arrived at the present invention.

That is, the present invention provides general formula (1) (wherein R represents a halogen atom, a lower alkyl group, and a lower alkoxy group, and n represents 0, 1, and 2)
A diformyldihydroxybenzene derivative represented by the formula, a nitrogen-containing compound selected from the group consisting of ammonia, urea and inorganic ammonium salts, and oxygen, copper, iron, manganese, oxides of these metals, and water. General formulas (corresponding to the general formula (1)), characterized in that the reaction is carried out in a basic aqueous medium in the presence of a catalyst selected from the group consisting of oxides, chlorides, sulfates and acetates. 0) (However,
The present invention relates to a method for producing a dicyanodihydroxybenzene derivative represented by the formula (R and n have the same meanings as above).

As a typical diformyl dihydroxybenzene derivative represented by the general formula (1) used in the method of the present invention, 2,5-diformyl-4-hydroxyphenol 2
,5-diformyl-4-hydroxy-3-methylphenol 2,5-diformyl-4-hydroxy-3-methoxyphenol 2,5-diformyl-4-hydroxy-3
-chlorophenol/2,5-diformyl-4-hydroxy-3-bromophenol 2,5-diformyl-4
-Hydroxy-3,6-dimethylphenol 2,5-diformyl-4-hydroxy-3,6-dimethoxyphenol 2,5-diformyl-4-hydroxy-3,6-dichlorophenol 2,5-diformyl-4-hydroxy-3,6-dibromophenol 2,3- diformyl-4
-Hydroxyphenol/2,3-diformyl-4-hydroxy-5-methylphenol2,3-diformyl-4-hydroxy-5-methoxyphenol2,3-diformyl-4-hydroxy-5-chlorophenol/2,
3-diformyl-4-hydroxy-5-furomophenol/2,3-diformyl-4-hydroxy-5,6-dimethylphenol 2,3-diformyl-4-hydroxy-5,6-dimethoxyphenol 2,3-diformyl-
4-Hydroxy-5,6-dichlorophenol 2,3-diformyl-4-hydroxy-5,6-dibromophenol 2,4-diformyl-5-hydroxyphenol 2,4-diformyl-5-hydroxy-3-methy/lephenol 2, 4-diformyl-5-hydroxy-3-methoxyphenol 2,4-diformyl-5-hydroxy-3-chlorophenol 2,4-diformyl-5-hydroxy-3-furomophenol 2,4-diformyl-5-hydroxy-3,6-dimethylphenol 2,
4-diformyl-5-hydroxy-3,6-dimethoxyphenol 2,4-diformyl-5-hydroxy-3,
Examples include 6-dichlorophenol, 2,4-diformyl-5-hydroxy-3,6-dibromophenol, and the like.

In addition, as nitrogen-containing compounds used in the method of the present invention,
Ammonia, urea and inorganic ammonium salts may be mentioned, although various other amines may also be used.

Examples of inorganic ammonium salts include ammonium chloride,
Examples include ammonium carbonate and ammonium sulfate. When the diformyldihydroxybenzene derivative is a halogen atom in the general formula (1), it is preferable to use urea, and when R is a group other than a halogen atom in the general formula (1), it is preferable to use urea. Preferably, ammonia is used.

The amount of ammonia and ammonium chloride to be used may be stoichiometrically at least 2 times the amount of the diformyl dihydroxybenzene derivative used, preferably 4 to 100 times the amount by mole.

Further, the amount of urea, ammonium carbonate, and ammonium sulfate to be used may be stoichiometrically equal to or more than the amount of the diformyldihydroxybenzene derivative used, and is particularly preferably 2 to 10 times the amount by mole. The oxygen used in the method of the present invention includes pure oxygen, an oxygen-containing gas obtained by diluting oxygen with an inert gas such as nitrogen, and air, but it is particularly convenient and convenient to use air.

The amount of oxygen supplied is 0.01 to Z/min per reaction solution,
Particularly preferred is 0.05 to 1.0 N/min. The catalysts used in the process of the invention are copper, iron, manganese and the oxides, hydroxides, chlorides, sulfates and acetates of these metals. Among these, copper and its oxides, hydroxides, chlorides, sulfates, and acetates are preferred. The amount of catalyst used is 0.001 per mole of diformyldihydroxybenzene derivative.
It is more than a gram atom, especially 0.1 to 1 gram atom.

When the amount of the catalyst used is less than the above range, the reaction rate becomes extremely low, and even when the amount is larger than the above range, no particular effect can be expected. The basic aqueous medium used in the method of the present invention is prepared by dissolving a basic substance, ie, caustic soda, caustic potash, soda carbonate, potassium carbonate, ammonia, etc., in water.

The amount of this basic substance used is 2 to 20 times the amount of diformyldihydroxybenzene derivative used, especially 5
~10 times the mole is preferred. In addition, buffer solutions are used as the basic aqueous medium, such as an aqueous solution containing sodium carbonate and sodium bicarbonate, an aqueous solution containing monohydrogen phosphate and caustic soda, and an aqueous solution containing phosphoric acid-hydrogen soda and sodium phosphate. Examples include aqueous solutions. The concentration of the diformyldihydroxybenzene derivative in the reaction mixture is usually 0.2 to
50% by weight is suitable, particularly preferably 0.5-15% by weight.

The reaction pressure may be either normal pressure or increased pressure. The reaction temperature is 8
0 to 14,000, particularly preferably 110 to 13,000.
Moreover, the reaction time is usually about 1 to 5 hours. After completion of the reaction, the dicyanodihydroxybenzene derivative can be isolated from the resulting reaction product solution, for example, by the following operation. That is, the pH of the reaction product solution is
This is done by adding a mineral acid until the value is below 5 and then extracting the dicyanodihydroxybenzene derivative with an organic solvent such as ether, benzene or toluene. The dicyanodihydroxybenzene conductors obtained by the method of the present invention each correspond to the above general formula (1) and are represented by the above general formula (b). Typical examples include 2,5-dicyano 4-hydroxyphenol 2,5-dicyano 4-hydroxy-3-methy'lephenol 2,5-dicyano 4-hydroxy-3-methoxyphenol 2,5-dicyano 4-hydroxy-3-chlorophenol 2,5-dicyano 4-hydroxy-3-furomophenol 2,5-dicyano 4
-Hydroxy-3,6-dimethylphenol 2,5-dicyano-4-hydroxy-3,6-dimethoxyphenol 2,5-dicyano-4-hydroxy-3,6-dichlorophenol 2,5-dicyano-4-hydroxy-3,
6-dibromophenol 2,3-dicyano-4-hydroxyphenol 2,3-dicyano-4-hydroxy-5
-Methylphenol 2,3-dicyano-4-hydroxy-5-methoxyphenol 2,3-dicyano-4-
Hydroxy-5-chlorophenol/2,3-dicyano-4-hydroxy-5-bromophenol 2,3-dicyano-4-hydroxy-5,6-dimethylphenol 2,3-dicyano-4-hydroxy-5,6-dimethoxyphenol 2,3-dicyano-4-hyde.

xy-5,6-dichlorophenol 2,3-dicyano-4-hydroxy-5,6-dibromophenol 2,4-dicyano-5-hydroxyphenol 2,4-dicyano-5-hydroxy-3-methy'lephenol/shi2,4-dicyano-5-hydroxy-3 -methoxyphenol 2
,4-dicyano-5-hydroxy-3-chlorophenol 2,4-dicyano-5-hydroxy-3-fromov/1'-2,4-dicyano-5-hydroxy-3,6
-dimethylphenol 2,4-dicyano-5-hydroxy-3,6-dimethoxyphenol 2,4-dicyano-5-hydroxy-3,6-dichlorophenol 2,4-dicyano-5-hydroxy-3,6-dibromophenol and the like.

As described above, by ammoxidizing a diformyldihydroxybenzene derivative in an aqueous medium according to the method of the present invention, the corresponding dicyanodihydroxybenzene derivative can be obtained in high yield.

Examples 1-34 In an autoclave, 50 mmol of diformyldihydroxybenzene derivative, 1 part of caustic soda, 1 part of 28x% ammonium
Add 8 crabs and catalyst, and then add water to bring the total amount to 500'.
The reaction mixture was adjusted to .

2k of air was passed through the reaction mixture at 0.2 m/min.
9/Block G was reacted at 125° C. for 2 hours. After the reaction is completed, the catalyst is placed in a furnace from the reaction product to obtain a homogeneous solution.
This was adjusted to pH 2 with 1 and hydrochloric acid, extracted with ethyl ether, and the extract was analyzed by gas chromatography. The results are shown in Table 1. Table 1 Examples 35 and 36 In an autoclave, add 50 mmol of diformyldihydroxybenzene derivative, 1 part of caustic soda and catalyst,
Further water was added to adjust the total volume to 500 ml of reaction mixture.

While passing through this reaction mixture at a flow rate of 0.1 N/min of ammonia gas and 0.2 arc/min of air,
The reaction was carried out at 2500 for 2 hours. The results are shown in Table 2. Table 2 Examples 37-49 In an autoclave, 50 mmol of diformyldihydroxybenzene derivative, 1 coat of caustic soda, 1.
6g and nitrogen-containing compound aqueous solution to make a total amount of 500'
The reaction mixture was adjusted to .

The reaction mixture was heated at 125q0 at 125q0/min while passing 0.2 g/min of air through the reaction mixture. I reacted for a while.
The results are shown in Table 3. Table 3 Note that the selectivity and yield were determined using the following formula.

Claims (1)

[Claims] 1 General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ), a nitrogen-containing compound selected from the group consisting of ammonia, urea and inorganic ammonium salts, and oxygen, copper, iron, manganese, and oxides of these metals, General formulas corresponding to the above general formula (I), characterized in that the reaction is carried out in a basic aqueous medium in the presence of a catalyst selected from the group consisting of hydroxides, chlorides, sulfates and acetates. (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R and n in the formula have the same meanings as above) A method for producing a dicyanodihydroxybenzene derivative.