JPH01287078A - Production of n-acyl cyclic imine compound - Google Patents

Abstract

PURPOSE:To readily obtain the subject compound useful in a wide field in high yield, by starting reaction in suspending a strong basic substance in simultaneously bringing the strong basic substance into contact with an amide compound and dihalogen-substituted compound as raw materials in a solvent. CONSTITUTION:A strong basic substance, an amide compound and a dihalogen- substituted compound are used as raw materials and reacted by a method for simultaneously feeding and mixing the above-mentioned three raw materials with an aprotic polar solvent (preferably acetonitrile, N,N-dimethylformamide, etc., provided care should be taken for contamination of water) to suspend the strong basic substance or suspending the strong basic substance in the above- mentioned solvent, then simultaneously feeding the afore-mentioned other raw materials, etc., to afford the aimed compound. The amount of water in the reaction system in starting the reaction is preferably <=5wt.%. The amounts of the raw materials based on the amide compound are as follows. The halogen- substituted compound is used in a molar amount of 1.5-15 times and the strong basic substance is used in a molar amount of 2.0-1.5 times.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing N-acyl cyclic imine compounds.

In general, N-substituted amide compounds have a good balance between the parent group and the hydrophobic group in the molecule, so they have good compatibility with various substances.
They have strong resistance to hydrolysis, and unsaturated amide compounds have other advantages such as excellent monopolymerization or copolymerizability, so they can be used in adhesives, paints, paper processing agents, fiber processing agents, emulsions, urethane curing agents, and pigment dispersions. It is known for its application in a wide range of fields such as additives, plastic additives, polymer flocculants, and ion exchange resins. It is also a useful compound as a raw material, intermediate, and product for compounds with complex structures such as pharmaceuticals, agricultural chemicals, amino acids, and natural products, and also as a raw material for amine production. However, since an inexpensive industrial production method for N-substituted amide compounds has not been established, they have not been used in large quantities.

Conventionally, industrially used methods for producing N-substituted amide compounds include the reaction of a carboxylic acid chloride with an amine and the Ritter reaction, but these methods are expensive. Alternatively, the types of compounds that can be produced are limited, and their applications are currently limited to specific fields.

In addition, as a general method for producing N-substituted amide compounds,
A method for producing an N-substituted amide compound by converting an amide compound into an alkali metal-substituted amide compound by the action of a strong basic substance such as an alkali metal alkoxide, and then reacting with a halogen-substituted compound such as an alkyl halide, For example, W, J, H4ckinbomujin 0III chopsticks Rea
tions of Organic Compou
nds 3rd edition, Longmans, Green and
Go.

(1957) p. 344 and U.S. Pat. No. 3,084.
, No. 191, etc. However, these methods require the production process to consist of two steps, the use of protic solvents such as liquid ammonia or alcohol that are highly reactive with halogen-substituted compounds under basic catalysts, and the use of alkali metal amides. There are various disadvantages such as the use of highly basic substances such as hydrogen compounds, alkoxides, etc., which are difficult to handle. Therefore, the yield of the desired product is low, the halogen-substituted compound to be reacted lacks versatility, and all the desired products are N-monosubstituted amide compounds, and N
, when producing N-disubstituted amide compounds, problems arise such as having to repeat the same production process, and this method cannot be widely adopted industrially as a general method for producing N-substituted amide compounds. Not yet reached.

Furthermore, in recent years G, L, l5ele, Hachi, Luttrin
ghous.

5ynthesis 1971 (5), p. 266, an amide compound and a strong basic substance are reacted in advance in an aprotic polar solvent to form an alkali metal-substituted amide compound, and then an alkali metal-substituted amide compound such as an alkyl halide is prepared. A two-step process for producing N-alkyl-substituted amide compounds by reaction with halogen-substituted compounds is also known. However, even if such a method is adopted, satisfactory results have not been obtained.

Furthermore, in USSR Inventor's Certificate No. 667547, a basic substance such as caustic soda is added as an aqueous solution in a method for producing an N-alkylated organic compound in a polar solvent, and the basic substance starts the reaction in a liquid state. A method is disclosed in which the presence of water in the reaction mixture is said to be highly advantageous for the progress of the reaction. However, according to the research conducted by the present inventors, this method produces a significant amount of side reactants, and the target N
- Low selectivity to substituted amide compounds, target N-
It has been found that the yield decreases significantly depending on the substituted amide compound.

In view of the actual situation regarding the production of the above-mentioned N-substituted amide compounds, the present inventors conducted extensive studies on the relationship between the total presence of water in the reaction system and reactivity with the aim of improving the production method. Substituted amide compound, in other words N
-We have discovered that the effect on selectivity to acyl cyclic imine compounds is extremely large and have arrived at the present invention. In other words, the presence of water in the reaction system, which was previously thought to be advantageous,
Contrary to this assumption, in order to inhibit the formation of the target N-acyl cyclic imine compound by causing side reactions, and to perform the N-substitution reaction favorably, it is necessary to use conventional amide compounds and strong basic substances. Instead of reacting with a strong basic substance, and then reacting with a halogen-substituted compound,
The present invention was achieved by discovering that it is necessary to carry out a catalytic reaction of an amide compound and a halogen-substituted compound simultaneously.

The present invention provides a method for producing an N-acyl cyclic imine by simultaneously contacting a strong basic substance, an amide compound, and a halogen-substituted compound in an aprotic polar solvent, in which the reaction is carried out while the basic substance is suspended. Characterized by starting.

In the present invention, a specific method for starting the reaction while suspending a strong basic substance is a method of simultaneously supplying and mixing the three substances in an aprotic polar solvent to suspend the strong basic substance and causing the reaction. , a method in which a strong basic substance is suspended in an aprotic polar solvent, and then an amide compound and a halogen-substituted compound are simultaneously supplied and reacted, and a method in which an amide compound and a halogen-substituted compound are dissolved or An appropriate method may be employed, such as suspending and then adding and suspending a strong basic substance.

The amide compounds that are the object of the present invention are broadly classified into monoamide compounds and polyamide compounds that are higher than diamide compounds.

Examples of the monoamide compound include aliphatic saturated carboxylic acid amide, aliphatic unsaturated carboxylic acid amide, aromatic carboxylic acid amide, alicyclic carboxylic acid amide, urea and its derivatives.

The aliphatic saturated carboxylic acid amide has the formula -CnJn-+(
:0NH2, where n is an integer of 0 to 20. Furthermore, those into which one or more substituents such as a nitro group, a cyano group, an amino group, a carboxylic acid group, a sulfonic acid group, an alkoxy group, and a carboxylic acid ester group are introduced are also targeted.

Aliphatic unsaturated carboxylic acid amide has the formula: CnH2□l
-2-(:0NH2 compound (where n is 2 to
20, m is an integer of 1 to 5), and contains one or more carbon-carbon double bonds and/or triple bonds in the molecule. Furthermore, those in which one or more substituents such as a nitro group, cyano group, amino group, carboxylic acid group, sulfonic acid group, alkoxy group, or carboxylic acid ester group are introduced are also targeted.

Aromatic carboxylic acid amide contains an aromatic ring in its molecule, and examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like. Furthermore, one or more substituents such as a nitro group, cyano group, alkoxy group, amino group, carboxylic acid group, sulfonic acid group, carboxylic acid ester group, alkyl group, alkenyl group, or aryl group are introduced into the aromatic ring. It also includes compounds whose substituents or aromatic rings are bonded to aromatic rings such as ether groups, sulfone groups, and sulfide groups. Alicyclic carboxylic acid amide is a compound having an alicyclic structure in the molecule, and also includes a heterocyclic compound composed of different elements. In addition, urea and its derivatives include N-C0-N and N-
It is a compound having a GO-N-N atomic group.

Examples of the monoamide compounds mentioned above include formamide, acetamide, propionamide, butyramide, pareramide, isovaleramide, pivalamide, lauramide, myristamide, valmitamide, stearamide, methoxyacetamide, ethoxyacetamide, methoxypropionamide, etc. Examples include mido, ethoxypropionamide, cyanobutinamide, nitropropionamide, aminopropionamide, carbamoylpropanesulfonic acid, carbamoylpropanoic acid, and methyl carbamoylpropanoate.

Aliphatic unsaturated carboxylic acid amides include, for example, acrylamide, methacrylamide, vinylacetamide, crotonamide, decenamide, nonadecenamide, proviolamide, butynamide, hexadienecarboxamide, bentinamide, hebutinamide, ethoxyacrylamide, ethoxymethacrylamide, cyanobutinamide, nitrobutinamide, aminobutinamide. Carbamoyl Examples include propenesulfonic acid, carbamoylcrotonic acid, and methyl carbamoylcrotonate.

Examples of aromatic carboxylic acid amides include benzamide, natutamide, anthracenecarboxamide, anthraquinone carboxamide, biphenylcarboxamide, phenylacetamide, phenylpropionamide, phenyldecanamide, nitrocinnamamide, nitronatutamide, nitrocinnamamide, cyanobenzamide, methoxybenzamide , ethoxybenzamide, methoxynatutamide, N,N-dimethylaminobenzamide, N,N-dimethylamitunaphthamide, carbamoylbenzenesulfonic acid, carbamoylnaphthalenesulfonic acid, toluamide,
propylbenzamide, decylbenzamide, carbamoylnaphthoic acid, vinylbenzamide, decylbenzamide, butenylbenzamide, phenyl rubamoyl phenyl ether, vinylcarbamoyl phenyl ether,
These include phenylcarbamoylphenylsulfone, phenylcarbamoylphenylsulfy F, and the like.

In the greasy ring amide, for example, Calphonate includes, for example, cyclooctankarboxamide, cyclob tankarboxamide, cyclopenten kalboxamide, cyclohexan kalboxamide, cyclo to sicro -tankarboxamide, cycloocarboxamide, cyclo. Cyclroocarboxamide, Vyrol Calboxamide, Francarboxamide, Tioofenkarboxamide, Cyclo These include hexylacetamide, cyclohexylbionamide, pyridine carboxamide, virolidine carboxamide, morpholine carboxamide, imidazole carboxamide, and quinoline carboxamide. Examples of urea and its rust conductors include urea, biuret, thiobiuret, triuret, semicarbazide, carbohydrazide, and carbazone.

Among these amide compounds exemplified, unsubstituted amide compounds are preferred in that they allow the reaction to occur efficiently.

More preferred are conjugated amide compounds in which the amide group of the amide compound is conjugated to a double bond, such as aliphatic unsaturated amide compounds such as acrylamide, methacrylamide, crotonamide, benzamide, tolylamide, isopropylbenzamide, natutamide, etc. There are aromatic amide compounds such as.

On the other hand, the polyamide compounds include aliphatic saturated polycarboxylic acid amide, aliphatic unsaturated polycarboxylic acid amide, aromatic polycarboxylic acid amide, and alicyclic polycarboxylic acid amide.

The aliphatic saturated polycarboxylic acid amide has the formula CoHzn
−+t (CONIIz), where n and m are integers, n is 0 to 20, and m is 2 to 4. Also,
1 such as nitro group, cyano group, amino group, carboxylic acid group, sulfonic acid group, alkoxy group, carboxylic acid ester group, etc.
Those in which one or more species or more have been introduced are also eligible.

The aliphatic unsaturated polycarboxylic acid amide is an integer, n is 2 to 20, m is 2 to 4, and r is 1
~4. Furthermore, those into which one or more of a nitro group, a cyano group, an amino group, a carboxylic acid group, a sulfonic acid group, an alkoxy group, a carboxylic acid ester group, etc. are introduced are also targeted.

Aromatic polyvalent carboxylic acid amide contains an aromatic ring in the molecule, and examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and the number of substitutions in the carboxylic acid amide is 2 to 6. Furthermore, one or more of a nitro group, a cyano group, an amino group, a carboxylic acid group, a sulfonic acid group, an alkoxy group, a carboxylic acid ester group, an alkyl group, an alkenyl group, an aryl group, etc. are introduced into the aromatic ring. Also included are compounds in which these substituents or aromatic rings are bonded to the aromatic ring via an ether group, sulfone group, sulfite group, etc. Alicyclic polyvalent carboxylic acid amide is a compound having an alicyclic structure in the molecule, and also includes a heterocyclic compound composed of different elements, and the number of substitutions in the carboxylic acid amide is 2 to 5.

Next, examples of polyamide compounds include aliphatic saturated carboxylic acid amides such as oxamide, malonamide, sufcinamide, geltalamide, adipamide, pimeramide,
Suberamide, azeramide, sebaamide, carbamoylmethylmethylgeltalamide, butenetetracarboxamide, tetradecanedicarboxamide, octadecanedicarboxamide, methoxyadipamide, cyanoadipamide,
These include nitroadipamide, aminoadipamide, dicarbamoylbutanesulfonic acid, dicarbamoylbutanoic acid, dicarbamoylbutyl acetate, and the like.

Among the aliphatic unsaturated polycarboxylic acid amides, for example, maleamide, fumaramide, citraconamide, mesaconamide, decenedilypoxamide, tetradecendiylypoxamide, octadecendiylypoxamide, butenetetracarboxamide, hexadiene dilypoxamide, pentyne dicarboxamide, methoxybutene dilypoxamide , cyanobutene dilupoxamide, nitrobutene dicarboxamide, aminobutene dicarboxamide, dicarbamoylbutenesulfonic acid, dicarbamoylbutenoic acid, methyl dicarbamoylbutenoate, and the like. Examples of aromatic polyalboxylic acid azides include phthalamide, isophthalamide,
Terephthalamide, Natsutalene dilupoxamide, Anthracene dilupoxamide, Anthraquinone dicarboxamide, Biphenyl dilupoxamide, Phenylcitraconamide, Naphthalene tricarboxamide, Pyromelitamide, Nitroadipamide, Cyanoadipamide, Aminoadipamide, Methoxyadipamide, N,N-dimethylaminophthalamide , dicarbamoylbenzene sulfonic acid, dicarbamoyl benzoic acid, dicarbamoyl benzyl acetate, methyl phthalamide, probyl phthalamide, allyl phthalamide, phenyl dicarbamoylphenyl ether, vinyl dicarbamoyl phenyl ether, fue, dicarbamoylphenyl sulfone, phenyl dicarbamoylphenyl sulfide and the like.

Examples of the alicyclic polycarboxylic acid amides include cyclobrobanedicarboxamide, cyclopentanedilupoxamide, canforamide, cyclohexane dilupoxamide, cyclohexenedilupoxamide, pyronidilupoxamide, pyridine dilupoxamide, and pyridinetricarboxamide.

Among these amide compounds exemplified, unsubstituted amide compounds are preferred in that they allow the reaction to occur efficiently.

More preferred are conjugated amide compounds conjugated to the double bond of the amide group of the amide compound, such as aliphatic unsaturated polyamide compounds such as fumaramide, maleamide, citraconamide, phthalamide, isophthalamide, terephthalamide, and benzene. Examples include aromatic polyamide compounds such as dolcarboxamide.

Further, examples of the dihalogen-substituted compound to be reacted with the amide compound include dihaloalkane compounds, bishaloalkyl ether compounds, and bishaloalkyl sulfide compounds. The dihaloalkane compound has the general formula X +
It is represented by C112+nX (X: halogen atom), where n is an integer of 2 to 5. Specifically, 1,2-dichloropropane, 1.4-dichlorobutane, 1.5-dichloropentane, 1.2-dibromoethane, 1.3-dibromopropane, 1.4-dibromobutane, 1,5 -dibromopentane, 1.2-short ethane, 1.3-short propane, 1.4-short butane, 1.5-short pentane, etc. The bishaloalkyl ether compound has the general formula x +CH2+no 10lh +nx
(x: halogen atom), where n is an integer of 1
~3.

Specifically, bischloroethyl ether, bischloroethyl ether, bischloroethyl ether, bisbromomethyl ether, bisbromoethyl ether, bisbromopropyl ether, bisiodomethyl ether, bisiodoethyl ether, bisiodopropyl ether, etc. There is. The bishaloalkyl sulfide compound is represented by the general formula (%), where n is an integer and is 1 to 3. Specifically, bischloroethyl sulfide, bischloroethyl sulfide, bischloropropylsulfide, bisbromomethylsulfide, bisbromoethylsulfide, bisbromopropylsulfide, bisiodomethylsulfide, bisiodoethylsulfide, bisiodopropylsulfide. etc.

By reaction with the above-described halogen-substituted compound, dihaloalkane compounds can produce N-acyl-substituted imine compounds, such as N-acylethyleneimine, N-acylazetidine, N-acylpyrrolidine, and N-acylpiperidine. N-acylmorpholine and the like can be produced using a bishaloalkyl ether compound, and N-acylthiomorpholine and the like can be produced using a bishaloalkyl sulfide compound.

The reaction solvent used in the present invention may be any aprotic polar solvent, such as acetonitrile, dioxane, nitromethane, nitroethane, nitrobenzene, pyridine, dimethoxyethane, tetrahydrofuran, tetrahydrobyran, 2-methyl-tetra hydrofuran,
Benzonitrile, N, N-dimethylformamide, N,
N-dimethylacetamide, N,N-diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone,
Glymes such as hexamethylphosphoramide, sulfolane, oxepane, monoglyme, diglyme, triglyme, tetraglyme, tetramethylurea, tetraethylurea, ■, 3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3, Alkylureas such as 4,5,6-tetrahydro-2(II+)-pyrimidinone, etc. can be used. Among the above-mentioned solvents, more suitable solvents include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, sulfolane, tetraglyme, 1,3-dimethyl-2-imidashiwadinone, and the like. Since these solvents generally have a strong affinity for water, care must be taken as water may be mixed in due to water absorption or water may be mixed in during circulation and reuse.

In the reaction system of the method of the present invention, it is necessary to start the reaction in a state where at least a part of the strong basic substance is suspended, and in such a state, the amount of water in the reaction system is Usually, it is around 6%.

If the amount of water in this case exceeds this, side reactions such as hydrolysis of the halogen-substituted compound or amide compound are likely to occur, resulting in a significant decrease in yield. In order to carry out the reaction efficiently and increase the yield of the target product, the water content of the reaction system is preferably 5% by weight or less, more preferably 2.5% by weight.
Below, it is particularly preferably carried out at 10,000 ppm or less.

The amount of the solvent to be used is not particularly limited, but is in the range of 5 to 95% by weight, preferably 10 to 90% by weight, based on the total amount of reactants including the solvent.

Next, the strong basic substance used in the present invention is a solid substance, and when dissolved or suspended in water, the pH of the aqueous solution is 1.
It can be used as long as it is 0 or more, preferably 11 or more.

However, when using ion exchange resins and other ion exchangers, this condition does not apply, and this will be described later. Examples of such strong basic substances include alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydrides, and alkaline earth metal oxides. These include metal hydrides, alkali metal amides, alkali metal alkoxides, ion exchange resins, and other ion exchangers.

To illustrate the above substances, examples of the alkali metal oxide include sodium oxide, potassium oxide, lithium oxide, rubidium oxide, and cesium oxide. Examples of alkaline earth metal oxides include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. Alkali metal hydroxides are, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. Examples of alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide,
It is barium hydroxide.

Alkali metal carbonates are, for example, sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of the alkali metal hydroxide include sodium hydride, potassium hydride, and lithium hydride.

Examples of alkaline earth metal hydrides include beryllium hydride, magnesium hydride, and calcium hydride.

Alkali metal amides are alkali metal amide compounds of ammonia, such as sodium amide, potassium amide,
Lithium amide, etc. Alkali metal alkoxides are compounds in which the protons of the hydroxyl groups of alcohols are replaced with alkali metals, such as sodium methoxide, sodium ethoxide, sodium monobutoxide, potassium methoxide, potassium ethoxide, and potassium L-butoxide.

For ion exchange resins, either the leaf type of strongly basic resin or the free type of strongly basic resin can be used, preferably resin-containing moisture or 1
It has a F content of 5% or more. Other ion exchangers may be substances that exhibit an anion exchange phenomenon, such as anion exchange cellulose, anion exchange Sephadex, anion exchange liquid, salt dolomite, hydrated iron oxide, hydrated zirconium oxide, etc. It is sufficient if it is of a type that can perform a neutralization reaction.

Among the above-mentioned basic substances, those suitable for carrying out the method of the present invention are, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal Carbonates, ion exchange resins, and other ion exchange resin bodies, and more suitable ones include, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, Alkali metal carbonates, ion exchange resins, and other ion exchangers.

These strong basic substances are usually used in the reaction in solid form, and the reaction is initiated while at least a portion of them is suspended in the reaction solution.

In carrying out the present invention, the relative usage amounts of the raw materials, amide compound, halogen-substituted compound, and strong basic substance, vary depending on the reactivity of the halogen-substituted compound and amide compound, etc. The amount of the halogen-substituted compound used is 1.0 to 20 times the mole of the amide compound, preferably 1.5 to 15 times the mole, and the amount of the strong basic substance used is 1.5 times the mole of the amide compound. ~20 moles, preferably 2.0 to 1.5 times the mole.

When using an unsaturated amide compound, it is preferable to add a polymerization inhibitor to prevent polymerization of raw materials and products during the reaction and purification steps. The polymerization inhibitor in this case is not particularly limited, but generally phenolic inhibitors,
Examples include amine inhibitors, mercaptan inhibitors, and copper powder.

For the reaction method, a normal reaction vessel may be used, or if a strongly basic substance with low solubility is used, it is packed in a column and a mixed solution of an amide compound and a halogen-substituted compound is prepared. A flow type method in which the liquid is passed and circulated may also be used. However, a reaction vessel is more convenient for equipment maintenance and management.

When producing in a reaction vessel, there is no restriction on the order in which raw materials are added, but when using a highly reactive halogen-substituted compound, it is better to add the halogen-substituted compound last and react to suppress side reactions. It is convenient in this respect.

The reaction temperature depends on the reactivity of the amide compound and halogen-substituted compound used, but if the reaction temperature is low, the reaction progresses slowly, while if the temperature is high, side reactions such as hydrolysis of the amide compound may occur and the product may deteriorate. Yield decreases. Therefore, the reaction is usually carried out at a temperature range of -20 to 100°C, preferably -10 to 70°C, and particularly preferably at a temperature of 0 to 50°C, except for specific halogen-substituted compounds. As long as the temperature is within this range, it is not necessarily necessary to keep the humidity constant during the reaction, but it is sufficient to monitor the progress of the reaction and set the reaction temperature appropriately to carry out the reaction efficiently.

The reaction time also varies depending on the amide compound and halogen-substituted compound used, as does the reaction temperature, or is at most 30 hours, but usually within 10 hours. The progress of the reaction can be understood by observing changes in the properties of the reaction system and the concentrations of raw materials and target products in the reaction solution by gas chromatography or high performance liquid chromatography.

After the reaction, by-produced metal chlorides are filtered off and distilled under reduced pressure using a conventional method to obtain a highly pure target product. However, if a metal chloride is dissolved in the reaction solution or if a sublimable raw material amide compound remains, after distilling off the solvent, use a solvent that forms two layers such as benzene-water or chloroform-water. After removing the substances listed in E in combination, the target product with high purity can be obtained by distillation under reduced pressure. Furthermore, when the desired product has a high boiling point or is thermally decomposable, the desired product can be purified by methods such as solvent extraction and crystallization.

When the reaction solvent has a high affinity for water, such as dimethyl sulfoxide, and the desired product is highly lipophilic, such as an N-alkyl-substituted amide compound, water is added to the reaction solution after the reaction to obtain the desired product. A method in which the target product is separated as an oil layer, or a method in which the target product is extracted and separated using a solvent that forms two layers with water, such as benzene, toluene, or chloroform, can also be applied.

According to the present invention, N
- Substituted amide compounds can be produced in one step at low cost. In addition, it becomes possible to supply N-substituted amide compounds to a variety of uses that could not be applied conventionally.

Furthermore, since the present invention employs the same reaction pattern, it is possible to produce a wide variety of N-substituted amide compounds in the same reactor, which has the advantage of being suitable for producing a wide variety of products in small quantities.

Next, the present invention will be further explained by examples.

Example I Preparation of N-acryloylpyrrolidine 150 ml of dimethyl sulfoxide, g of acrylamide, potassium hydroxide and 38 g of 1,4-dichlorobutane
The mixture was added, stirred, and reacted at 40"C for 4 hours.

After the reaction, insoluble matter was filtered off, and the filtrate was distilled to obtain 101i-108.
℃/10ma+t1g fraction was collected, and 19g of N-acryloylpyrrolidine was collected.

Example 2 Production of N-methacryloylpyrrolidine 17 g of methacrylamide, 65 g of 1,4-dibromobutane and 0.5 g of phenothiazine α were added to 150 mJl of N,N-dimethylformamide, and 25 g of potassium hydroxide was gradually added while stirring in a water bath. Added. The reaction temperature was maintained at 10°C and the reaction was carried out for 6 hours.

After the reaction, the insoluble part is filtered off, the filtrate is distilled, and the
A 1g fraction at 11°C/15mmt was collected to obtain 23g (yield: 82%) of N-methacryloylpyrrolidine.

Examples 3 to 7 Combinations of raw materials, strong basic substances, and solvents listed in Table 1 were prepared.
The reaction was carried out under the conditions described in 1. In addition, Examples 3 and 6~
In No. 7, 0.05 g of phenothiazine was added to carry out the reaction.

After the reaction, treatment was carried out in exactly the same manner as in Example 2, and the results shown in Table-
The products listed in Table 2 were separated under the distillation conditions listed in Table 2.

Example 8 Preparation of N,N''-Carponyl dipyrrolidine N,N-dimethylformamide + 50mR, urea 13g, l, 4
-9 figs of dibromobutane and 50 g of potassium hydroxide were added, and the reaction was carried out at 20° C. for 4 hours.

After the reaction, the insoluble portion was filtered off, the filtrate was distilled and heated to 38-40°C.
A 10.6 mmHg fraction was collected to obtain 29 g of N,N'-carponyl dipyrrolidine (yield 78%).

Example 9 Production of N,N'-carponyl dibiberidine 1.3-dimethyl-2-imidazolidinone 150 mft and urea 13
g, 150 g of 1,5-dibromopentane and 50 g of potassium hydroxide were added, and the reaction was carried out at 20° C. for 4 hours.

After the reaction, the insoluble portion is filtered off, the solvent and raw materials are distilled off from the filtrate, and the remainder is recrystallized to obtain N, N' with a melting point of 45-46°C.
-33 g (yield 77%) of carbonyl dipiveridine was obtained.

Claims (1)

[Claims] 1. A method for producing an N-acyl cyclic imine compound by simultaneously contacting and reacting a strongly basic substance, an amide compound, and a dihalogen-substituted compound in an aprotic polar solvent, wherein the base 1. A method for producing an N-acyl cyclic imine compound, characterized in that the reaction is initiated in the presence of a suspension of a cyclic imine compound. 2. The method according to claim 1, wherein the amount of water in the reaction system at the start of the reaction is 5% by weight or less.