JPS59504B2 - Imidocarboxylic ester Allyl ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing allyl esters containing imide groups, which are novel compounds.

The present inventor first discovered that by reacting 1 mole of tricarboxylic acid monoimide, such as trimellitimide, with 2 moles or more of allyl chloride in the presence of an acid acceptor (e.g., potassium carbonate), 4-allyloxycarbohydrate It has been found that Ni-N-allylphthalimide can be obtained.

The above reaction involves two types of reactions involving allyl chloride, namely, allyl esterification reaction and Gapriel reaction type N-
This includes the allylimide production reaction.

Therefore, if there is a large difference in the activity of the two reactions, there is a possibility that one of the allylated products, i.e., 4-allyloxycarbonylphthalimide or N-allyl trimellitimide, will be preferentially obtained. As a result of intensive research, it was discovered that the former reaction product can be selectively obtained in high yield, leading to the present invention.

That is, the present invention provides an imidocarboxylic acid represented by the general formula [] and an allyl halide represented by the general formula [] (wherein R is a hydrogen atom or a methyl group, and X is a halogen atom), The carboxyl group of the imidocarboxylic acid is converted into an allyl ester by reacting in the presence of a basic acid acceptor to obtain imidocarboxylic acid allyl esters represented by the general formula (wherein R is the same as defined above). This is a characteristic method for producing imidocarboxylic acid allyl esters.

The imidocarboxylic acid allyl esters obtained by the present invention are novel compounds, and are useful as raw materials for, for example, allyl resins.

The imidocarboxylic acid represented by the general formula [] used in the present invention can be easily produced by reacting trimellitic anhydride with an ammonia-generating compound such as ammonia or ammonia carbonate. I can do it. The allyl halide represented by the general formula [] is preferably one in which R is a hydrogen atom or a methyl group, and X is preferably chlorine, bromine, or iodine.

Preferred examples include allyl chloride, allyl furomide, 2
-Methyl allyl chloride, and especially allyl chloride is an inexpensive industrial raw material and has high reactivity and is preferably used.

The basic acid acceptors used in the present invention include hydroxides and oxides of alkali metals and alkaline earth metals such as caustic soda, caustic potash, calcium hydroxide, and calcium oxide;
Carbonates and bicarbonates of alkali metals and alkaline earth metals such as potassium carbonate, soda carbonate, sodium bicarbonate, calcium carbonate, and magnesium carbonate; triethylamine, tri-n-
Examples include tertiary amines such as butylamine and N-methylpiperidine.

The reaction in the present invention is preferably carried out in an inert organic polar medium because it can be carried out under mild conditions and the formation of by-products such as resinous substances can be suppressed.

In particular, it is preferable to use an aprotic polar solvent as the solvent since it has the effect of accelerating the reaction. Examples of such solvents include the so-called Examples include amide, sulfoxide, and sulfone solvents. In the reaction of the present invention, the imidocarboxylic acid represented by the general formula [] is treated with the general formula []
It is also possible to carry out the reaction by using the allyl halide and the basic acid acceptor represented by the formula in excess of the stoichiometrically required amount and appropriately controlling the reaction time, reaction temperature, etc. Care must be taken in setting the reaction conditions to suppress the by-product of allyl imide and allyl ester.

Therefore, for 1 mole of the imidocarboxylic acid, approximately N1 mole of the allyl halide and about an equivalent or an excess amount of the basic acid acceptor are used, or when using an excessive amount of the allyl halide, the basic acid acceptor is used. It is appropriate to use the equivalent amount. This is because allyl halides do not substantially react with either imide or carboxyl groups in a system without a basic acid acceptor, but in a system with an acid acceptor,
Since the carboxyl group has higher nucleophilicity toward allyl halides than the imide group, it reacts with the carboxyl group first, so if equivalent amounts of basic acid acceptors are used, an excess molar amount of allyl halides may be used. Allyl esters are also given preferentially.

On the other hand, when a basic acid acceptor is used in an amount of about N equivalent or more, allyl halide reacts selectively with the carboxyl group to give only an allyl ester if 1 mole of allyl halide is used, but if an excess mole is used, the basic acid Since the receptor remains in the reaction system, the allyl halide may also react with the imide group and N-allylimidocarboxylic acid allyl esters may be produced as a by-product, which is not preferable. In addition, whether the basic acid acceptor is used in an equivalent amount or more, if the allyl halide is used in an amount of 1 mole or less, unreacted carboxyl groups remain and the purity of the product decreases, which is preferable. do not have. In general, it is easier to obtain high purity imidocarboxylic acid allyl ester by using an equivalent amount of basic acid acceptor and using an excess molar amount of allyl halide, and allyl halide used in excess can be easily removed by distillation or other means. This is preferable because it can be separated and recovered.

The reaction temperature is preferably in the range of 40°C to 150°C. At a temperature lower than this, the reaction is slow, and at a temperature higher than this, side reactions tend to occur, which is not preferable. The reaction time depends on the solubility of the imidocarboxylic acid and the reaction temperature, but is usually about 0.5 to 30 hours.

Especially when imidocarboxylic acids are in a dissolved state, 0.
5 to 10 hours is sufficient.

Below the lower limit, the reaction may not proceed sufficiently, and above the upper limit, even if the time is increased, no particularly significant effect can be obtained. The reaction is generally carried out under normal pressure,
It can also be performed under pressure.

Isolation and purification of the produced imidocarboxylic acid allyl esters is carried out, for example, as follows.

That is, when the reaction product is introduced into an acidic aqueous solution, imidocarboxylic acid allyl esters are generally liberated as a solid. Separate and wash the liberated solid with water. The solid mainly contains imidopolycarboxylic acid allyl ester and unreacted allyl halide. Unreacted allyl halide can be removed by washing with steam or an organic solvent such as acetone or alcohol, and the imidocarboxylic acid allyl ester product can be isolated. If necessary, the purity can be further increased by further purifying this product by means such as recrystallization. Product purity can be determined by chromatography.

Further, the structure can be confirmed by elemental analysis, infrared absorption spectrum, etc. The present invention will be explained in detail with reference to Examples below. The examples are intended to be illustrative and not limiting. Example 1 Trimellitimide 19.17 (0.1 mol), allyl chloride 7.7y (0.1 mol), potassium carbonate 6.9
7 (0.05 mol) was added to 50 ml of N-methylpyrrolidone, and the mixture was heated to reflux at 100°C for 5 hours with stirring.

As the reaction progresses, the potassium carbonate converts to potassium chloride and the system becomes a suspension containing thin potassium chloride precipitates. After the reaction is complete, the suspension is poured into ice water to form a white precipitate. When the white precipitate was washed with water by Sawabetsu, it became 16.67 (72%).
) to obtain trimellitimide allyl ester. The melting point is 1
It was 40°C. Further recrystallization from ethanol 5 and 1
47 to 148°C crystals were obtained. The infrared absorption spectrum of this product is 2300-3 as shown in I in the attached drawing.
500? A complex absorption based on the stretching vibration of the imide NH was observed in -1, and characteristic absorption based on the carbonyl stretching vibration of the O imide bond was observed in 1765, 1745CTL-1 and 1690CTIL-1, and 1720? A characteristic absorption based on the carbonyl stretching vibration of the ester was observed in -1.
Elemental analysis values are C56.38%H2.68%N7.52%
(Theoretical value C56.55%H2.64%N7.33%). 5 Reference Example The compound obtained in Example 1 was confirmed by comparing its melting point and infrared absorption spectrum with trimellitimide allyl ester obtained by separate synthesis using the following route.

(1) Synthesis of trimellitic acid anhydride allyl ester; trimellitic acid chloride and equimolar allyl alcohol were synthesized by heating and refluxing in benzene for 3 hours.

Boiling point 16"C/0.5mmHg (4) Synthesis of trimellitic allyl ester; 23.2y (0.1 mol) of trimellitic anhydride allyl ester and 9.67 (0.1 mol) ammonium carbonate were added to 20 ml of xylene. including 7
Add 0 ml (:l) of N-methylpyrrolidone and gradually heat while stirring under a nitrogen stream to raise the temperature to 200° C. while distilling off the produced water together with xylene.

The reaction is continued at 200° C. for an additional 3 hours. After cooling to room temperature, the mixture is poured into water, and the resulting precipitate is separated, washed with water, and dried to obtain trimellitimide allyl ester having a melting point of 150°C. The infrared absorption spectrum of this product is Example 1
It was completely consistent with what was obtained.

Example 2 Trimellitimide 9.57 (0.05 mol), methallyl chloride 9.1y (0.1 mol) and potassium carbonate 3
．． 57 (0.025 mol) is added to 40 ml of N-methylpyrrolidone and heated under reflux for 6 hours with stirring.

After the reaction was completed, the resulting suspension was poured into ice water, and the precipitate was washed with Sawabetsu water, and then with methanol.
0.47 (85%) of trimellitimide methallyl ester is obtained. Melting point: 146-147°C; infrared absorption spectrum: 2500-3500CrIL as shown in the attached drawings
-1 has an absorption based on the imide NH stretching vibration, 1760 and 1690 -1 has a special absorption based on the stretching vibration of the carbonyl group of the imide bond, and 1715? Absorption based on the C=0 stretching vibration of methallyl ester 1 was observed in -1.

Elemental analysis is C58, 32% H3, 54% N6.95% (
The theoretical values were C58.54%H3.44%N6.83%). Example 3 Trimellitimide 19.17 (0.1 mol), allyl chloride 7,77 (0.1 mol), triethylamine 1
5y (0.15 mol) was dissolved in 50 ml of N-methylpyrrolidone and heated under reflux at 100'C for 4 hours.

After the reaction is complete, excess triethylamine is distilled off and the mixture is poured into ice water. The obtained precipitate is separated, washed with water, further washed with methanol, and then dried to obtain 18.27 (79%) of trimellitimide allyl ester. Melting point: 149°C (ethanol recrystallization). The infrared absorption spectrum matched that of trimellitimide obtained in Example 1. Example 4 trimellitimide 19.17 (0.1
mol), allyl bromide 12.1f (0.1 mol),
Potassium carbonate 6.9y (0.05 mol) was added to 50ml (7
) Add to N-methylpyrrolidone and heat at 100°C for 5 hours with stirring.

The reaction progresses. After the reaction was completed, the suspension was poured into ice water, and the precipitate formed was separated, washed with water, washed with methanol, and then dried.
7.6y (76%) of trimellitimide allyl ester is obtained. The melting point was 147.5°C (ethanol recrystallization) and the infrared absorption spectrum matched the spectrum of trimellitimide allyl ester obtained in Example 1.

[Brief explanation of the drawing]

The attached drawings are infrared absorption spectra of trimellitimide allyl ester and trimellitimide memaryl ester obtained in Examples 1 and 2.

Claims (1)

[Claims] 1. Imidocarboxylic acid represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R in the formula is a hydrogen atom or a methyl group. , X represents a halogen atom) in the presence of a basic acid acceptor to convert the carboxyl group of the imidocarboxylic acid into an allyl ester, forming the general formula ▲ mathematical formula, chemical formula, table, etc. A method for producing imidocarboxylic acid allyl esters, which is characterized by obtaining imidocarboxylic acid allyl esters represented by ▼ (wherein R is the same as defined above).