JP2688760B2 - Method for producing imides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic compound having at least two adjacent halogen atoms, which may be the same or different, on an aromatic hydrocarbon or heterocyclic hydrocarbon ring which may have a substituent. An amine in the amount of equimolar to less than twice the amount of a halogenide in the presence of a base using a palladium compound and a phosphine compound as a catalyst, with respect to a pair of adjacent halogen atoms on the ring of carbon monoxide and an organic halide The present invention relates to a method for producing imides, which is characterized by reacting with, and more specifically, general formula (IV): R ¹ (Y) m (IV) (wherein R ¹ has a substituent). An aromatic hydrocarbon or a heterocyclic hydrocarbon group, Y is a halogen atom which may be the same or different, and m is an integer of 2 or more. And phosphine The compound as a catalyst in the presence of a base, an equimolar to 2-fold molar amount less than the general expression for the adjacent pair of the halogen atom on a ring carbon monoxide and organic halide (V): R ² NH ₂ (V) (in the formula, R ² may have a hydrogen atom or a substituent and represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic hydrocarbon group). General formula (VI) characterized by reacting with a class: (In the formula, R ¹ and R ² are the same as described above.) The present invention relates to a method for producing imides.

The imides obtained by the production method of the present invention are themselves useful compounds as agricultural chemicals, pharmaceuticals, other chemicals and intermediates thereof, and the present invention provides a novel production method of these compounds. .

Conventionally, as a method for producing imides, a method by a dehydration condensation reaction between an acid anhydride or a dibasic acid and amines is generally used. However, although there are some that can be inexpensively obtained as industrial raw materials such as phthalic acid and phthalic anhydride, which are raw material compounds of imides, the types of acid anhydrides or dibasic acids generally available as industrial raw materials are There is a limitation, and a novel method for producing imides from a raw material compound that does not use an acid anhydride or a dibasic acid as a raw material compound and can be inexpensively obtained as an industrial raw material is desired.

In order to solve the above problems, the present inventors have conducted extensive studies on the reaction between organic halides and amines, and as a result, have established a novel production method not described in the literature and completed the present invention. is there.

The production method of the present invention can be inexpensively obtained as an industrial raw material as a raw material compound, and various imides can be easily produced by using a wide variety of organic halides. It is also possible to produce imides that cannot be produced by.

The reaction of the present invention can be represented schematically as follows, for example.

(In the formula, R ¹ , R ² , Y, and m are the same as above.) That is, the organic halide represented by the general formula (IV) is
Using a palladium compound and one phosphine compound as a catalyst, in the presence of a base, in the presence or absence of an inert solvent, with respect to carbon monoxide and a pair of adjacent halogen atoms on the ring of an organic halide. The desired imides represented by the general formula (VI) can be produced by reacting with the amines represented by the general formula (V) in an equimolar to less than 2-fold molar amount.

In the production method of the present invention, preferably, one phosphine selected from trialkylphosphine, triarylphosphine, and a compound represented by the following general formula (I), (II) or (III) is used as the phosphine compound. Done.

General formula (I): (R) ₂ -P-XP- (R) ₂ (I) [In formula, R shows an alkyl group or a phenyl group which may have a substituent, X is a carbon atom. An alkylene group of the numbers 1 to 6, (1 represents an integer of 2 to 4) or a binaphthyl group. ] General formula (II): (In the formula, R is the same as above) General formula (III): (In the formula, n represents an integer of 1 to 5.) Further, in the production method of the present invention, particularly when the palladium compound is a palladium metal, a 0-valent, 2-valent or 4-valent complex supported on a solid, Palladium compound is palladium-
It is preferably carried out when it is carbon, palladium chloride or palladium acetate.

The organic halide represented by the general formula (IV) used in the present invention is at least two on the ring of an alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic hydrocarbon which may have a substituent. Of organic halides having adjacent halogen atoms, and also includes condensed ring hydrocarbons and condensed heterocyclic hydrocarbons, and representative examples thereof include dichlorobenzene, trichlorobenzene, tetrachlorobenzene, and pentachlorobenzene. Chlorobenzene, hexachlorobenzene, dichlorofluorobenzene, dichlorodifluorobenzene, dichlorotrifluorobenzene, dichlorotetrafluorobenzene, trichlorofluorobenzene, trichlorodifluorobenzene, trichlorotrifluorobenzene, tetrachlorofluorobenzene, tetrachlorodifluorobenzene Zen, dichlorotrifluoromethylbenzene, dichloroditrifluoromethylbenzene, dichlorotoluene, trichlorotoluene, tetrachlorotoluene, pentachlorotoluene, ethyldichlorobenzene, dichlorocumene, dichlorotrimethylbenzene, dichloroxylene, trichloroxylene, tetrachloroxylene, Dichlorophenol, trichlorophenol, dichloroanisole, trichloroanisole, dichlorodimethoxybenzene, dichlorotrimethoxybenzene, dichloromethylenedioxybenzene, dichlorophenoxyphenol, dichlorobenzoylphenol, dichlorobenzenesulfonylphenol, dichloronitrobenzene, dichloronitrobenzene, dichlorocyanobenzene, Dichlorophenyl acetic acid ester, N -Acetyldichloroaniline, dichlorophenoxyaniline, dichlorobenzoylaniline, dichlorobenzenesulfonylaniline, dichloroacetophenone, dichlorobenzophenone, dichloromethylthiobenzene, dichlorobenzoic acid ester, dichlorodiphenyl ether, benzyloxydichlorobenzene, dichlorophenylbutoxybenzene, dichlorodiphenyl ether, dichlorobenzophenone , Dichlorodiphenylmethane, dichlorodiphenyldifluoromethane, dichlorodiphenylhexafluoropropane, dichlorodiphenyl sulfide, dichlorodiphenyl sulfoxide, dichlorodiphenyl sulfone, dichlorobiphenyl, tetrachlorodiphenyl ether, tetrachlorobenzophenone, tetrachlorodipheniphenyl Methane, tetrachloromethane diphenyl difluoromethane, tetrachloromethane diphenyl hexafluoropropane, tetrachloro diphenyl sulfide, tetrachloro diphenyl sulfoxide, tetrachloro diphenyl sulfone, tetrachlorobiphenyl, dichloronaphthalene, trichloronaphthalene, tetrachloronaphthalene,
Aromatic organic halides such as dichloromethylnaphthalene and dichloroanthraquinone, dichlorothiophene, dichlorofuran, dichloroindole, dichloropyridine,
Heterocyclic organic halides such as dichlorotrifluoromethylpyridine, dichloropicoline, dichloroquinoline, trichloroquinoline and dichloroquinoxaline, as well as dipromobenzene, jodobenzene, chloropromobenzene and chloroiodobenzene can be used.

The organic halide may be used in a predetermined amount, or may be used in excess and used as a solvent.

Examples of the amines represented by the general formula (V) used in the present invention include aliphatic amines such as ammonia, methylamine and ethylamine, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane and diamino. Aliphatic diamines such as octane and diaminodecane, aliphatic amine alcohols such as ethanolamine, aminopropanol, aminobutanol, aminopentanol and aminohexanol, aniline, alkylaniline (toluidine,
Diethylaniline, diisopropylaniline), haloaniline (chloroaniline, fluoroaniline, dichloroaniline), haloalkylaniline (trifluoromethylaniline, chlorotrifluoromethylaniline), alkoxyaniline (anisidine, ethoxyaniline, isopropoxyaniline, trifluoromethoxyaniline) ), Benzylamine (chlorobenzilamine, fluorobenzylamine), diaminodiphenyl ether,
Diaminobenzophenone, diaminodiphenylmethane,
Aromatic amines such as diaminodiphenyl sulfide, diaminodiphenyl sulfone, aminophenoxyphenol, aminohydroxybenzophenone, aminohydroxydiphenylmethane, aminohydroxydiphenylsulfide, aminohydroxydiphenylsulfone, aminopyridine, aminotriazole, aminoimidazole, aminothiophene, aminothiazole And heterocyclic amines such as aminofuran, aminobenzimidazole, aminobenzthiazole, aminobenzoxazole, and aminoquinoline.

The reaction amount of the amines may be present in the reaction system in an amount in the range of equimolar to less than 2 times the molar amount of a pair of adjacent halogen atoms on the ring of the organic halide, such as one pair such as ortho-dichlorobenzene. An organic halide having adjacent halogen atoms on the ring may be used in an amount of equimolar to less than twice the molar amount of ortho-dichlorobenzene, but two pairs of rings such as 1,2,4,5-tetrachlorobenzene. The above-mentioned organic halide having adjacent halogen atoms requires an amount of 2 to less than 4 times the molar amount of 1,2,4,5-tetrachlorobenzene.

The palladium compound used as a catalyst in the present invention may be used in combination with a phosphine compound, and examples of the palladium compound include metal palladium, palladium carbon, palladium alumina, palladium chloride, palladium bromide, palladium acetate, dichlorobiscyanophenyl. Examples thereof include palladium, dichlorobistriphenylphosphine palladium, tetrakistriphenylphosphine palladium and the like.

Examples of the trialkylphosphine or triarylphosphine that can be used in combination with the palladium compound in the present invention include trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine,
Tributylphosphine, triphenylphosphine, triparafluorophenylphosphine, tri-pentafluorophenylphosphine, triparatolylphosphine, triorthotolylphosphine, triorthodimethylaminophenylphosphine, triphenoxyphosphine, dimethylphenylphosphine, methyldiphenylphosphine, dipentafluoro Examples of phenylphosphine and the like and the phosphine compound represented by the general formula (I) include 1,1-bis (dimethylphosphino) methane, 1,1-bis (diethylphosphino) methane, and 1,2-bis (dimethyl). Phosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, 1,4-bis (dimethylphosphino) butane, and other bis (dialkylphosphino) alkanols Kinds; 1,1-bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane,
1,6-bis (diphenylphosphino) hexane, 2,3-0
-Isopropylidene-2,3-dihydroxy-1,4-bisdiphenylphosphinobutane, bisdiphenylphosphinoferrocene, bisdiphenylphosphinobinaphthyl, 1,
2-bis (diphenylphosphite) benzene, α, α '
-Bis (diphenylphosphino) xylene, [1,2-cyclopentanediyl (methylene)] bis (diphenylphosphine), [1,2-cyclohexanediyl (methylene)] bis (diphenylphosphine), and the general formula (II Examples of the phosphine compound represented by) include methyldibenzophosphole, ethyldibenzophosphole, propyldibenzophosphole, butylbenzophosphole, pentylbenzophosphole, phenyldibenzophosphole, tolyldibenzophosphole, anisyldibenzophosphole. And the phosphine compound represented by the general formula (III), for example, 1,1-bis (dibenzophosphoryl) methane, 1,2-bis (dibenzophosphoryl)
Ethane, 1,3-bis (dibenzophosphoryl) propane,
1,4-bis (dibenzophosphoryl) butane, 1,5-bis (dibenzophosphoryl) pentane and the like can be mentioned.

The addition amount of the phosphine compound may be 0.01 to 10,000 times the molar amount of the palladium compound, preferably 0.1.
It may be used up to 100 times mol.

The catalyst that can be used in the present invention may be used in combination with the palladium compound and the phosphine compound, and may be added individually to the reaction system, or may be prepared in the form of a complex in advance and added. The amount of the catalyst added is not particularly limited, but it may be used in the range of 0.0001 times to 0.5 times mol, preferably 0.001 times, the mol of the organic halide represented by the general formula (IV). It may be selected from the range of mol to 0.1 times mol.

The base that can be used in the present invention may be selected from an inorganic base or an organic base, for example, an inorganic base such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, tributylamine, diisopropylethylamine, triisooctylamine. , Pyridine, N-methylpyrrolidine, N-methylmorpholine, N
Examples thereof include organic bases such as ethylmorpholine.

The amount of the inorganic base or the organic base used is preferably the amount necessary for neutralizing the hydrogen chloride produced, but it may be smaller or larger than this.

The reaction in the present invention may be carried out in the presence or absence of an inert solvent, as an inert solvent that can be used, as long as it does not significantly inhibit the present reaction, for example, hexane, benzene, ether, tetrahydrofuran, Inert solvents such as acetonitrile, dimethylformamide, hexamethylphosphorotramide, acetone and the like can be mentioned.

The reaction of the present invention is carried out under normal pressure to elevated pressure, and the pressure of carbon monoxide is selected from the range of 1 to 200 atm, preferably 1 to 50 atm.

The reaction temperature of the present invention is usually in the range of 100 ° C to 300 ° C, preferably 150 ° C to 250 ° C.

The reaction vessel used in the present invention may be a commonly used reaction vessel, and in the case of a pressurized reaction, any reaction vessel that can withstand the reaction pressure may be used, and a metal or glass reaction vessel is usually used.

The reaction time is not constant depending on the amount of the reactants, the reaction temperature, etc., but may be selected from the range of several minutes to 48 hours as long as the reaction is completed.

After the completion of the reaction, the desired imides can be obtained by treating in a conventional manner.

Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 Production of N-phenylphthalimide Add ortho-dichlorobenzene (5.
84g), aniline (1.86g), palladium chloride (17.7m)
g), 1,4-bisdiphenylphosphinobutane (426m
g), sodium carbonate (2.33 g) and benzene (25 ml) were added and the mixture was replaced with carbon monoxide several times, and then charged with 30 kg / cm ² and the reaction was carried out for 3 hours while stirring at an internal temperature of 200 ° C. in a salt bath.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. 1.52 g of the target product, N-phenylphthalimide was obtained.

Melting point 206-207 ° C Example 2 Production of N- (3-isopropoxyphenyl) phthalimide Add ortho-dichlorobenzene (1.
47g), meta-isopropoxyaniline (1.5g), palladium chloride (17.6mg), 1,4-bisdiphenylphosphinobutane (106mg), sodium carbonate (4.2g), benzene (15ml) and add carbon monoxide. After substituting twice, the mixture was filled with 30 kg / cm ² , and the reaction was carried out for 5 hours while stirring at an internal temperature of 200 ° C. in a salt bath.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water and the precipitated crystals were washed with excess water and dried. Phthalimide (m /
e281) was obtained in a gas chromatogram area percentage of 25%. Melting point 103-4 ° C Similarly, from 1,2,4,5-tetrachlorobenzene (1.08g) and metaisopropoxyaniline (1.5g) to 4,5-dichloro-N- (3-isopropoxyphenyl) phthalimide (m / e349) with a gas chromatograph area percentage yield of 1.3
%Obtained.

Example 3 Preparation of 3-methyl-N-phenylphthalimide In a metal autoclave 3-methyl-1,2-dichlorobenzene (6.44g), aniline (1.86g), palladium chloride (17.7mg), 1,4-bisdiphenylphosphinobutane (426mg), sodium carbonate (4.2g ), Benzene (25m
l) was added and the mixture was replaced with carbon monoxide several times, and then filled with 30 kg / cm ² , and the reaction was carried out for 3 hours while stirring with a salt bath having an internal temperature of 200 ° C.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. Zero the target phthalimide.
I got 71g.

Melting point 132-134 ° C. Similarly, 4-methyl-1,2-dichlorobenzene (1.6 g) and aniline (0.93 g) gave 4-methyl-N-phenylphthalimide (m / e237).

Example 4 Preparation of 3-methoxy-N-phenylphthalimide 3-methoxy-1,2-dichlorobenzene (3.54g), aniline (0.93g), palladium chloride (8.8mg), 1,4-bisdiphenylphosphinobutane (213mg), sodium carbonate (2.1g) in a metal autoclave. ), Benzene (15m
l) was added and the mixture was replaced with carbon monoxide several times, and then filled with 30 kg / cm ² , and the reaction was carried out for 3 hours while stirring with a salt bath having an internal temperature of 200 ° C.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. Zero the target phthalimide.
I got 50g.

Melting point 185-188 ° C Example 5 Preparation of N-phenyl-4-trifluoromethylphthalimide 4-trifluoromethyl-1, in a metal autoclave,
2-dichlorobenzene (8.6g), aniline (1.86g), palladium chloride (17.7mg), 1,4-bisdiphenylphosphinobutane (426mg), sodium carbonate (2.33g), benzene (25ml) and monoxide 30 kg / c after several replacements with carbon
It was filled with m ² and the reaction was carried out for 3 hours while stirring with a salt bath having an internal temperature of 200 ° C.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. Target phthalimide 3.
86 g was obtained.

Melting point 153-14.5 ° C Example 6 Preparation of N-2-pyridylphthalimide Add ortho-dibromobenzene (4.
72g), 2-aminopyridine (0.94g), palladium chloride (8.8mg), 1,4-bisdiphenylphosphinobutane (21
3 mg), sodium carbonate (2.33 g) and benzene (30 ml) were added and the mixture was replaced with carbon monoxide several times, and then filled with 20 kg / cm ² and the reaction was carried out for 3 hours while stirring at an internal temperature of 180 ° C. in a salt bath.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. The target product, N-2-pyridylphthalimide (m / e224), was obtained in a gas chromatogram area percentage yield of 14.6%. Melting point 227-228 ° C Example 7 Preparation of N-n-hexylphthalimide Add ortho-dibromobenzene (4.
72g), hexylamine (1.01g), palladium chloride (8.
8mg), 1,4-bisdiphenylphosphinobutane (213m
g), sodium carbonate (2.33 g), and benzene (30 ml) were added, the mixture was replaced with carbon monoxide several times, and the mixture was filled with 20 kg / cm ² and the reaction was carried out for 3 hours while stirring at an internal temperature of 180 ° C. in a salt bath.

After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. 2.35 g of the target product, Nn-hexylphthalimide (m / e242), was obtained.

Similarly, 0.59 g of n-propylamine to 0.63 g of N-n-propylphthalimide (m / e189) and 0.7 of n-butylamine.
3g to N-n-butylphthalimide (m / e203) 1.12g,
1.57 g of n-octylamine to N-n-octylphthalimide (melting point 54 to 55 ° C) 1.
I got 24g.

Example 8 Preparation of N, N'-di- (n-hexyl) pyromellitimide In a metal autoclave 1,2,4,5-tetrachlorobenzene (4.3g), hexylamine (2.02g), palladium chloride (17.7mg), 1,4-bisdiphenylphosphinobutane (426mg), sodium carbonate (4.66g). g), benzene (30
ml) and substituted several times with carbon monoxide and then filled with 40 kg / cm ² , and the reaction was carried out for 3 hours while stirring at 220 ° C. in a salt bath. After the reaction, the mixture was cooled to room temperature, the reaction solution was poured into water, and the precipitated crystals were washed with excess water and dried. The target imide (m / e384) was 1.46.
g obtained.

Melting point 197-199 ° C Example 9 Preparation of 6-phenyl-pyrrolo [3,4-b] pyridine-5,7-dione 2,3-dichloropyridine 1.14 in metal autoclave
g, aniline 0.72 g, palladium chloride 1.4 mg, 1,4-bisdiphenylphosphinobutane 33 mg, sodium carbonate 1.95 g
Then, 10 ml of benzene and 10 ml of carbon monoxide were substituted, and the mixture was filled with 20 kg / cm ² and the inside temperature was 180 ° C. in a salt bath, and the reaction was carried out for 3 hours with stirring. After completion of the reaction, the reaction solution was cooled to room temperature, then poured into water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.52 g of the desired product.

Melting point 185.0-187.0 ° C Yield 63% (gas chromatogram area percentage)

Claims (5)

(57) [Claims] 1. A palladium compound is used as an organic halide having at least two adjacent halogen atoms, which may be the same or different, on an aromatic hydrocarbon or heterocyclic hydrocarbon ring which may have a substituent. And a phosphine compound as a catalyst, in the presence of a base, carbon monoxide and a pair of adjacent halogen atoms on the ring of the organic halide are reacted with an equimolar amount to an amount of less than 2 times the molar amount of amines. And a method for producing imides. 2. The phosphine compound is a trialkylphosphine, a triarylphosphine, the following general formulas (I) and (I
The method for producing imides according to claim 1, which is one kind of phosphine selected from the compounds represented by I) or (III). General formula (I): (R) ₂ -P-XP- (R) ₂ (I) [In formula, R shows an alkyl group or a phenyl group which may have a substituent, X is a carbon atom. An alkylene group of the numbers 1 to 6, (1 represents an integer of 2 to 4) or a binaphthyl group. ] General formula (II): (In the formula, R is the same as above.) General formula (III): (In the formula, n represents an integer of 1 to 5.) 3. The method for producing imides according to claim 1, wherein the palladium compound is a palladium metal, a 0-valent, 2-valent or 4-valent complex supported on a solid. 4. The method for producing imides according to claim 3, wherein the palladium compound is palladium-carbon, palladium chloride or palladium acetate. 5. The method for producing imides according to claim 1, wherein the reaction temperature is 100 to 300 ° C.