JPH0797366A - Production of imino compound - Google Patents

Abstract

PURPOSE:To obtain an imino compound useful as an intermediate for pigments and heat-sensitive coloring materials a simple process, by reacting an acid anhydride with ammonium and urea in the presence of a specific catalyst. CONSTITUTION:A compound of formula I (A<2> is O or NH; Z is an aromatic ring or a heterocycle capable of forming a conjugate system with >C=NH) is made to react with ammonia or urea using a heteropolyacid whose polyacid atom is molybdenum as a catalyst in a solvent (e.g. nitrobenzene) at 100-200 deg.C to provide the objective imino compound of formula II (A' is O or NH). An amount of the catalyst used for producing 1mol compound of formula II is 0.00001-10 equivalent based on molybdenum atom. As the compound of formula II, when A' is oxygen, 3-iminoisoindolin-1-one is exemplified and when A' is NH, 1,3-diiminoisoindoline is exemplified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an imino compound which is useful as an intermediate for pigments and as a thermosensitive coloring material.

[0002]

2. Description of the Related Art General formula (1)

[Chemical 3] (In the formula, A ¹ represents O or NH, and Z represents an aromatic ring group or a heterocyclic group capable of forming a conjugated system with a> C═NH group.), A compound represented by the general formula (2)

[Chemical 4] (In the formula, A ² represents O or NH. Z is as defined above.) A method for producing a compound represented by the formula as a raw material has long been known.

Japanese Patent Publication No. 29-3324 discloses a method for producing 1,3-diiminoisoindoline by reacting phthalic anhydride with urea in the presence of a catalyst such as ammonium molybdate. This method can obtain the target product in a relatively high yield when using unsubstituted phthalic anhydride as a raw material. Chem.
/ 68. Jahrg. 1956 / Nr. As described in No. 4, when phthalic anhydride is substituted with an electron-withdrawing group, it is not a preferable method and is not always a general method. Even when using unsubstituted phthalic anhydride as a raw material, at least 5 by-products different from the target product are obtained.
%, A method of synthesizing in a higher yield has been required. Above, Angew. Chem. / 6
8. Jahrg. 1956 / Nr. For 4, after adding chlorine to phosphorus trichloride and phosphorus oxychloride to make phosphorus pentachloride,
Reaction with tetrachlorophthalimide 1, 3, 3,
A method for obtaining 4,5,6,7-heptachloro-isoindolenine and further reacting it with ammonia to synthesize 1,3-diimino4,5,6,7-tetrachloroisoindoline is shown. This method can obtain the target product even when phthalic anhydride having a substituent is used as a raw material, but on the other hand, it requires a reaction agent such as phosphorus pentachloride that is fuming and difficult to handle, and has a long reaction process. There was a point.

[0004]

An object of the present invention is to use a compound represented by the general formula (2) as a raw material and to obtain the general formula (1).
It is an object of the present invention to provide a method for producing an imino compound represented by the above-mentioned without using a reactant such as phosphorus pentachloride by a simple process and a high yield.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the object can be achieved by reacting with a specific catalyst, and It came to completion. That is, the present invention has the general formula (1)

[Chemical 5] (In the formula, A ¹ represents O or NH, and Z represents an aromatic ring group or a heterocyclic group capable of forming a conjugated system with a> C═NH group.), An imino compound represented by the general formula (2 )

[Chemical 6] (In the formula, A ² represents O or NH. Z is as defined above.) In the method for producing by reacting the compound represented by the formula (A) with ammonia or urea, the catalyst is The present invention provides a method for producing an imino compound, which is a heteropolyacid having an acid atom of molybdenum.

The present invention will be described in detail below. The imide compound represented by the general formula (1) of the present invention is a compound having at least one or more> C═NH group in its structure, and examples of the aromatic ring group represented by Z are: Benzene ring, naphthalene ring, biphenyl ring, anthracene ring, indene ring, fluorene ring, phenanthrene ring, acenaphthene ring and their derivatives, and examples of heterocyclic groups include furan ring, pyrrole ring, thiophene ring, benzofuran ring, indole ring. Ring, indazole ring, coumarone ring, benzimidazolone ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, pyridine ring, quinoline ring, isoquinoline ring,
Examples thereof include a quinazoline ring, acridine ring, phenazine ring, pyrazine ring, oxazine ring, xanthene ring, purine ring, dibenzofuran ring, dibenzopyrrole ring, anthraquinone ring and the like, and derivatives thereof. Examples of the substituent forming the derivative include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group,
Examples thereof include amide group, nitro group, sulfo group, carboxyl group, hydroxyl group, amino group, mercapto group and alkylmercapto group.

A ¹ in the general formula (1) is O or N.
H. When the compound of the general formula (1) is produced from the compound of the general formula (2) by the method of the present invention, first, a compound in which A ¹ is O is obtained, and then a compound in which A ¹ is NH is obtained at ^once. To be All of these are useful compounds, and A ¹
It is within the scope of the present invention whether A is O, NH, or a mixture of O and NH. As such an imide compound, many compounds are known as a raw material for synthesizing an azomethine pigment, especially an isoindolinone pigment, or a compound having a partial structure of the pigment structure, for example, JP-A-48-4601. , JP-A-48
-83116, JP-A-49-128933, JP-A-54-83026, JP-A-56-10
9255, etc.

As a specific example, for example, when A ¹ is O, 3-iminoisoindoline-1-one, 3-imino4,5,6,7-tetrachloroisoindoline-1-one, 3-imino4,5,5. 6,7-Tetrabromoisoindoline-1-one, 3-imino4,5,6,7-tetrafluoroisoindoline-1-one, 3-imino-5,6-dichloroisoindoline-1-one, 3-imino4,5,7 -Trichloro-6-methoxy-isoindoline-1-one, 3-imino4,5,7-trichloro-6-methylmercapto-isoindoline-1-one, 3-imino-8-nitroisoindoline-1-one, etc., and when A ¹ is NH 1,3-diiminoisoindoline, 1,3-diimino4,5,6,7-tetrachloroisoindo Phosphorus, 1,3-diimino 6-methoxyisoindoline, 1,3-diimino 6-cyanoisoindoline, 7-amino-2,3-dimethyl-5-oxopyrrolo [3,4b] pyrazine, 7-amino-2,
Examples thereof include 3-diphenyl-5-oxopyrrolo [3,4b] pyrazine.

The compound represented by the general formula (1) has the following formula depending on the conditions.

[Chemical 7] It is said to have an isomeric structure like [P. F. C
lark et, al. Chem. Soc. 359
3 (1953)]. Therefore, although the compound names described above may be represented by different names depending on the case, they are all included in the general formula (1). In the compound of the general formula (2) used in the present invention, Z which is an aromatic ring group or a heterocyclic group is exactly the same as described above. A ² represents O or NH. A compound in which A ² is NH is an intermediate product when the present invention is carried out using a compound in which A ² is O as a raw material.

In the present invention, the compound of the general formula (1) can be obtained by reacting the compound of the general formula (2) with ammonia or urea in the presence of a heteropoly acid having molybdenum as a polyacid. it can. As ammonia, either liquid ammonia or ammonia gas can be used. It is also possible to use ammonia and urea in combination for the reaction. Ammonia or urea is usually used in excess of the stoichiometric amount for producing the desired imide compound. Usually, it is in the range of 1.01 to 1000 times, preferably 1.1 to 300 times the stoichiometric amount.

The heteropolyacid used as a catalyst in the present invention is a condensed acid composed of two or more kinds of oxygen acids. The polyacid atom is molybdenum, and the hetero atom is P,
AS, Si, Ge, Ti, Ce, Th, Mn, Ni, T
e, I, Co, Cr, Fe, Ga, etc. may be mentioned. Specific examples of the heteropoly acid of molybdic acid include H ₃ (PM
o ₁₂ O ₄₀ ), H ₃ (AsMo ₁₂ O ₄₀ ), H ₄ (SiMo ₁₂
O ₄₀ ), H ₄ (GeMo ₁₂ O ₄₀ ), H ₄ (TiMo
₁₂ O ₄₀ ), H ₈ (CeMo ₁₂ O ₄₂ ), H ₈ (ThMo ₁₂ O
_{42), H 7 (PMo 11} O 39), H 7 (AsMo 11 O 39),
H ₈ (GeMo ₁₁ O ₃₉ ), H ₆ (MnMo ₉ O ₃₂ ), H
₆ (NiMo ₉ O ₃₂ ), H ₆ (TeMo ₆ O ₂₄ ), H ₅ (I
Mo ₆ O ₂₄ ), H ₃ (CoMo ₆ O ₂₄ H ₆ ), H ₃ (CrM
o ₆ O ₂₄ H ₆ ), H ₃ (FeMo ₆ O ₂₄ H ₆ ), H ₃ (GaM
o ₆ O ₂₄ H ₆ ), H ₄ (NiMo ₆ O ₂₄ H ₆ ), H ₆ (P ₂ M
o ₁₈ O ₆₂ ), H ₆ (As ₂ Mo ₁₈ O ₆₂ ), and the like.

Further, a mixed coordination heteropolyacid in which two or more kinds of atoms are coordinated, such as H ₄ PMoW ₁₁ O ₄₀ and H ₄ PR.
eW ₁₁ O ₄₀ , H ₄ PVMo ₁₁ O ₄₀ , H ₅ PV ₂ Mo
₁₀ O ₄₀ , H ₃ PMo ₆ W ₆ O _{40 and the} like are also used. These heteropolyacids may be hydrates. All of these heteropolyacids are known. From the viewpoint of ease of synthesis or availability, a heteropoly acid containing P or Si as a hetero atom is preferable, and 12-molybdophosphoric acid and 12-molybdo silicic acid are particularly preferable. These catalysts may be used alone or in combination of two or more.

There are no particular restrictions on the amount of these catalysts used in the present invention, but they are usually used in the range of 0.00001 to 10 equivalents, preferably 0, on a molybdenum atom basis to produce 1 mol of the desired product. It is used in the range of 0.0001 to 3 equivalents. When the amount of the catalyst is less than this range, the reaction rate becomes slow, and when the amount of the catalyst is large, the effect of increasing the yield becomes small. In the present invention,
The reaction temperature is preferably 100 to 200 ° C, more preferably 130 to 180 ° C. The yield decreases both above and below this temperature range. The reaction pressure is not particularly limited and is usually carried out under normal pressure, but it is also a preferable method to carry out the reaction under pressure in order to increase the concentration of ammonia in the reaction solution and accelerate the reaction rate. The reaction time varies depending on the reaction temperature, the amount of catalyst, the type of the desired imide compound, and the like, and is not particularly limited, but is usually selected in the range of 10 minutes to 30 hours.

The reaction of the present invention can be carried out without a solvent, but if necessary, a solvent is used. The solvent used is not particularly limited, but normally, a chlorinated hydrocarbon solvent, alcohol solvent, ether solvent, ketone solvent, ester solvent, nitrogen compound solvent, etc. are used. Specific examples thereof include monochlorobenzene, dichlorobenzene, trichlorobenzene, ethyl benzoate, ethylene glycol, methyl cellosolve, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, nitrobenzene and the like. When carrying out the reaction in the present invention, a stabilizer may be present in the reaction system, if necessary. Examples of stabilizers include nitric acid, phosphoric acid, hydrochloric acid,
Examples thereof include inorganic acids and organic acids such as methanesulfonic acid, methionic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid, or ammonium salts thereof. These stabilizers are often effective in improving the yield of the desired product.

[0015]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. The quantitative analysis of the reaction product was carried out using a high performance liquid chromatograph after the reaction product was dissolved in dimethylacetamide. (Example 1) 1.48 g of phthalic anhydride and 7.5 of urea were placed in a 100 ml glass four-necked flask equipped with a stirrer.
g, 12-molybdosilicic acid 30 hydrate 0.018 g (molybdenum 0.09 mg equivalent), nitrobenzene 20.0
g and 1.62 g of ammonium nitrate were charged, and the mixture was heated to 170 ° C. in an oil bath and reacted. After 2 hours of reaction, the conversion rate of phthalic anhydride was 100%, and the yield of each reaction product was 1.9% phthalimide, 41.5% 3-iminoisoindoline-1-one, 1,3-diyne. The iminoisoindoline was 55.6%, the other unknown components were 1.0%, and the total reaction yield of the target product was 97.1%.

(Comparative Example 1) 0.016 g of ammonium molybdate tetrahydrate instead of 12-molybdosilicic acid
The reaction was carried out in exactly the same manner as in Example 1 except that (molybdenum 0.09 mg equivalent) was used as the catalyst. The conversion rate of phthalic anhydride was 100%, and the yield of each reaction product was 3.1% of phthalimide, 42.1% of 3-iminoisoindoline-1-one and 5% of 1,3-diiminoisoindoline.
The reaction yield was 0.8%, the other unknown components were 4.0%, and the total reaction yield of the target product was 92.9%, which was lower than that in Example 1.

Example 2 A reaction was carried out in exactly the same manner as in Example 1 except that 2.85 g of tetrachlorophthalic anhydride was used instead of phthalic anhydride and the reaction time was 3 hours. The conversion rate of tetrachlorophthalic anhydride was 100%, and the yield of each reaction product was 10.8% of tetrachlorophthalimide, 3-imino4,5,6,7-tetrachloroisoindoline-1-one 37.3. %, 1,3-diimino 4,5,6,7-tetrachloroisoindoline 4
The total reaction yield of the target product was 78.6% with 1.3% and other unknown components 10.6%.

COMPARATIVE EXAMPLE 2 Except for using 0.016 g of ammonium molybdate tetrahydrate (0.09 mg equivalent of molybdenum) as a catalyst instead of 12-molybdosilicic acid 30 hydrate, exactly the same as in Example 2. The reaction was carried out.
The conversion rate of tetrachlorophthalic anhydride is 100%,
The yield of each reaction product is tetrachlorophthalimide 2
3.6% 3-Imino 4,5,6,7-tetrachloroisoindoline-1-one 24.3% 1,3-Diimino 4,5,6,7-tetrachloroisoindoline 1
It was 8.5% and other unknown components were 33.6%, and the total reaction yield of the target product was 42.8%, which was lower than that in Example 2.

(Example 3) 100 m equipped with a stirrer
A 4-liter glass four-neck flask was charged with 0.57 g of tetrachlorophthalic anhydride, 15.0 g of urea, 0.36 g of 12-molybdosilicic acid (1.81 mg of molybdenum), 10.0 g of nitrobenzene, and 3.24 g of ammonium nitrate, and an oil bath. Was heated to 140 ° C. and reacted. After 30 minutes of reaction, the conversion of tetrachlorophthalic anhydride was 100%, and the yield of each reaction product was tetrachlorophthalimide 5.5%, 3-imino 4,5,6,7.
-Tetrachlorisoindoline-1-on 45.2%,
1,3-Diimino 4,5,6,7-tetrachloroisoindoline was 45.6%, other unknown components were 3.7%, and the total reaction yield of the target product was 90.8%.

Example 4 Instead of phthalic anhydride, 4
-A reaction was performed in exactly the same manner as in Example 1 except that 2.04 g of sulfophthalimide was used. After 2 hours of reaction, the conversion rate of 4-sulfophthalimide was 92%, and the yield of each reaction product was 3-imino 4-sulfoisoindoline-1.
-On 42.5%, 1,3-diimino 4-sulfoisoindoline 45.3%, and other unknown components 4.2%, and the total reaction yield of the target product was 87.8%.

(Example 5) 0.375 g of 12-molybdophosphoric acid 30 hydrate instead of 12-molybdosilicic acid
The reaction was carried out in exactly the same manner as in Example 3 except that (molybdenum 1.81 mg equivalent) was used as the catalyst. The conversion rate of tetrachlorophthalic anhydride was 100%, and the yield of each reaction product was tetrachlorophthalimide 5.9%, 3-imino4,5,6,7-tetrachloroisoindoline-1-one 45.9. %, 1,3-diimino 4, 5, 6,
7-Tetrachloroisoindoline 44.2%, other unknown components 4.0%, the total reaction yield of the target compound is 9
It was 0.1%.

[0022]

INDUSTRIAL APPLICABILITY According to the present invention, an imino compound useful as a pigment intermediate or a heat-sensitive color-forming material can be produced in a high yield by a simple process without using a difficult-to-handle reactant.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 209/62 8217-4C 209/68 8217-4C 471/04 104 H Z 487/04 140 7019- 4C 495/04 103 498/04 103 513/04 325 // C07B 61/00 300 (C07D 487/04 207: 00 241: 00)

Claims (1)

[Claims] 1. A general formula (1): (In the formula, A ¹ represents O or NH, and Z represents an aromatic ring group or a heterocyclic group capable of forming a conjugated system with a> C═NH group.), An imino compound represented by the general formula (2 ) [Chemical 2] (In the formula, A ² represents O or NH. Z is as defined above.) In the method for producing by reacting the compound represented by the formula (A) with ammonia or urea, the catalyst is A method for producing an imino compound, which is a heteropolyacid having an acid atom of molybdenum.