JPS5943457B2 - Method for producing phthalamide derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (I)Q■I■■, which is important as an intermediate for isoisotrinon pigments, which are high-grade yellow pigments. and m is 0 or 1 to 4
The integer R represents a divalent aromatic diacine residue or a divalent heterocyclic diamine residue.

) relates to a method for producing a phthalamide derivative represented by
Conventionally, one of the methods for producing isoisotrinon pigments is
By heating the phthalamide derivative represented by the above general formula (I) with phosphorus pentahalide in an inert organic solvent, an isoisotrinon pigment which is a higher organic pigment (in the formula, X, R, n and m are the above-mentioned general It represents the same content as in the case of formula (I).

) is known (Japanese Patent Publication No. 51-42610). However, the general formula (
As described in the patent publication, the method for producing the phthalamide derivative represented by I) involves extremely complicated steps. That is, after reacting halogenated phthalic anhydride and aromatic diamine or heterocyclic diamine at a temperature of 30°C or lower in a dimethylformamide solvent, phosphorus oxychloride, phosphorus trichloride, and phosphorus pentachloride are reacted at a temperature of 30°C or lower. This method involves condensing with an acid condensing agent such as, and then adding aqueous ammonia to the condensation agent. However, this method requires the use of acid condensing agents such as phosphorus monooxychloride, phosphorus trichloride, and phosphorus pentachloride, which are extremely expensive, highly corrosive, and hazardous substances, and which are difficult to treat in waste water. The phthalamide derivative of general formula (I) formed into very fine crystals caused many industrial problems, such as the fact that it was extremely difficult to separate or wash the crystals from the reactants.

As a result of continuing research to solve these drawbacks, the present inventors have discovered that phthalimide represented by the general formula () can be easily obtained from unsubstituted or halogen-substituted phthalic anhydride and aromatic diamine or hexerocyclic diamine. When the derivative was reacted with ammonia in the absence or presence of an organic solvent such as benzene or alcohol, it was discovered that the phthalamide derivative of general formula (1) could be obtained in high yield, and the present invention was completed.

The method of the present invention is characterized by reacting a phthalimide derivative represented by the general formula (1) with ammonia, and further carrying out the reaction in the presence of an inert medium. It consists in a method for producing phthalamide derivatives.

The phthalimide derivative represented by the general formula (), which is a raw material used in the method of the present invention, can be easily obtained, for example, by the following method.

That is, unsubstituted or halogen-substituted phthalic anhydride (
Hereinafter, it will be abbreviated as phthalic anhydride. ) and aromatic diamine or hexerocyclic diamine (hereinafter abbreviated as diamines) at 30°C or lower.
It can be obtained with high purity and high yield by heating above 50°C or by heating the above-mentioned phthalic anhydride and diamine above 50°C from the beginning. Therefore, even if the obtained phthalimide derivative of the general formula (H) is a phthalimide derivative of the general formula () with respect to the type of halogen substituted to the benzene nucleus of phthalic anhydride, the number of substitutions of the halogen, and the dia shift, the present invention It can be used as a raw material in the method of usually,
The phthalic anhydrides used include mono-, di-, tri-, or tetrachloro-mono-phthalic anhydride; mono-, di-, tri-, or tetrabromo-mono-phthalic anhydride, especially tetrachlorophthalic anhydride. are common, and examples of diamines include diamines conventionally used as raw materials for isointrinon, such as O-, m-, P-phenylenediamine, O-dianisidine, benzidine,
-,m-tolidine, 3,3″-dichlorobenzidine, 0
, m-tolidine, 3,3'-dichlorobenzidine, 4,
4'-diaminodiphenylmethane, 3,3'-dichloro-4,41-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-diaminodiphenyl, Examples include 2,6-diamino, pyridine, 2,6-diaminobentthiazole, and the like. In the method of the present invention, first, the phthalimide derivative of the general formula () and ammonia are stirred, preferably under pressure of ammonia, at a temperature of usually 6°C or less, preferably 0 to 30°C, so that the imide ring opens. General formula (
A phthalamide derivative of 1) is obtained.

The yield is higher when the temperature is 60°C or lower.

This reaction can be carried out even in the presence of an inert medium, and is advantageous in that the resulting amide crystals can be separated with high purity.

Naturally, the inert medium is selected from compounds that are liquid at least during the reaction and are inert to the raw materials and products. Of course, a solvent that dissolves the phthalimide derivative of general formula () and/or ammonia is preferable, but a so-called dispersion medium in which the raw material or product is only slightly dissolved may also be used. As the inert medium, commonly used organic solvents are usually used.
For example, aromatic, aliphatic or cycloaliphatic hydrocarbons such as benzene, toluene, xylene, heptane, octane, cyclohexane; nitrobenzene, monochlorobenzene,
Aromatic hydrocarbon derivatives such as dichlorobenzene and trichlorobenzene; halogenated aliphatic hydrocarbons such as dichloroethane, trichloroethane, trichloroethylene, and dichloropropylene; monohydric hydrocarbons such as methanol, ethanol, propyl alcohol, ethylene glycol, and propylene glycol or polyhydric alcohols; amines such as diethylamine, triethylamine, dipropylamine; polyhydric alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether: diethyl ether, dipropyl ether, etc. Examples include bulk ethers such as ethers and dioxane; ketones such as dimethyl ketone and methyl ethyl ketone. In the method of the present invention, when the reaction is carried out in the presence of an inert medium, the reaction conditions are preferably selected appropriately depending on the type of the medium, and the reaction temperature is usually -10 to 60°C, preferably is preferably 0 to 30°C.

The reaction pressure may be either normal pressure or elevated pressure, but in general, in the presence of a nonpolar solvent such as benzene or xylene, it is advantageously carried out under ammonia pressure. The reaction time is not particularly limited, but it is preferable to select a time suitable for the reaction conditions. For example, when dispersing in benzene and conducting the reaction at a reaction temperature of 5° C. and an ammonia pressure of 2 to 3 kg/Cril, the reaction is completed in about 4 hours. To specifically carry out the method of the present invention, the raw material phthalimide derivative of general formula () and/or an inert medium is placed in a container such as an autoclave, and excess liquid ammonia or ammonia gas is added to the raw material. In addition, the mixture is reacted at a predetermined temperature and pressure with stirring.

After the reaction, the formed crystals are separated from the reaction mixture by a normal post-treatment method such as filtration, and washed well with methanol etc. to obtain a highly purified phthalamide derivative of general formula (1) in high yield. . The product can be used as is as an intermediate in the production of pigments. Moreover, the product obtained by the present invention has good filterability and is easy to handle, and furthermore, the method of the present invention generates less waste water and is easy to work up. Hereinafter, the method of the present invention will be explained in detail using Examples, but the contents thereof do not directly limit the contents and conditions of the present invention.

Example 1 30.0 parts of the compound (hereinafter abbreviated as compound ^) and 350 parts of benzene were placed in an autoclave, and heated at 5°C with stirring.
160 parts of ammonia was added thereto, and the mixture was stirred at the same temperature for 4 hours.

After the reaction is complete, ammonia is released and the white crystals formed are filtered off.
000 parts was used for dispersion cleaning. It was dried at a temperature of 60°C to obtain 28.5 parts of white crystals. Yield 90.2%. Infrared absorption spectral analysis revealed that the crystals (hereinafter referred to as compound (B)
) has been identified.

Example 2 30.0 parts of compound (A) and 350 parts of ethyl alcohol were placed in a flask, and ammonia gas was passed through the flask at 20° C. for 9 hours while stirring.

After separating the produced white crystals with P, the obtained crystals are treated with 1,
Dispersion cleaning was performed using 1,000 parts of methyl alcohol.
It was dried at a temperature of 60°C to obtain 27.3 parts of white crystals. Yield 86.4%. The crystals were identified as compound (B) by infrared absorption spectroscopy. Example 3 30.0 parts of the compound (total) and 350 parts of triethylamine were placed in an autoclave, and 16 parts of ammonia was charged with stirring at 5°C, followed by stirring at the same temperature for 4 hours.

After releasing the ammonia, the white crystals formed were filtered off and washed in a dispersed manner using 1,000 parts of methyl alcohol. After drying, 29.3 parts of the crystals were obtained. Yield 92.7
%o infrared absorption spectroscopy revealed that the crystal was a compound (B
) was identified. Example 4 Compound (A) 30
．． 0 parts were taken into an autoclave, and while cooling to 0°C, 350 parts of ammonia were added.

The temperature is then raised to 5° C. and this temperature is then *maintained with stirring for 4 hours. After the reaction is complete, ammonia is distilled off,
The resulting residue is dispersed in 1,000 parts of methyl alcohol and stirred for 30 minutes at 20°C. After washing, the crystals were dried separately to obtain 27.8 parts of the crystals. As a result of infrared absorption spectrum analysis, the crystal was identified as compound (B).
Example 5 30.0 parts of the compound and 350 parts of benzene were placed in an autoclave, and while stirring and keeping the liquid temperature at 5°C, 1 part of ammonia was added.
Add 6 parts and stir at the same temperature for 4 hours.

After releasing the ammonia pressure, collect P1= crystals from the reaction product,
The crystals are dispersed and washed using 1,000 parts of methyl alcohol. The crystals were separated and dried to obtain 28.5 parts of white crystals. The crystal was identified by infrared absorption spectrum.

Claims (1)

[Scope of Claims] 1 Phthalamide represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ characterized by reacting a phthalimide derivative represented by the following with ammonia ▲ There are mathematical formulas, chemical formulas, tables, etc. Method for producing derivatives. (In the formula, X is a halogen atom, n and m are 0 or 1 to 4
The integer R represents a divalent aromatic diamine residue or a divalent heterocyclic diamine residue. )2 The method according to claim 1, wherein the reaction is carried out in the presence of an inert medium. 3. The method according to claim 1 or 2, which comprises reacting under pressure with ammonia.