JPH048419B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to N-substituted alkoxycarboxylic acid amide compounds and methods for producing the same. More specifically, N substituted with an allyl group or a β-methallyl group
- Substituted alkoxycarboxylic acid amide compound and method for producing the same. The compounds of the present invention have the general formula (R ₁ is hydrogen or a methyl group, and R ₂ is a phenylene group or an ethylene group.) This is an N-substituted alkoxycarboxylic acid amide compound represented by the following formula, and is a new compound that has not been described in any literature. There are two types of N-substituted alkoxycarboxylic acid amide compounds represented by the above general formula: those having a benzene ring skeleton and those having an ethylene group skeleton.
There are several species, each with isomers having different substitution sites for the alkoxy group and amide group. The method for producing the above-mentioned N-substituted alkoxycarboxylic acid amide compound includes a hydroxyl-substituted amide compound represented by the following general formula and a halogen-substituted compound represented by the following general formula: HO-R ₂ -CONH ₂ (R ₂ is the same as above) and (R ₁ is the same as above, and X is a halogen group.) This is a method of producing by reacting in an aprotic polar solvent in the presence of a strong basic substance, and more specifically, the above-mentioned hydroxyl group It consists of reacting a substituted amide compound and an excess amount of a halogen-substituted compound in an aprotic polar solvent in the presence of a strongly basic substance. The present invention will be explained in more detail below. The compound of the present invention is represented by the following general formula (1), (R ₁ and R ₂ are the same as above.) There are two types, one with a benzene ring as the skeleton and the other with an ethylene group as the skeleton.If they are expressed as a general formula, those with a benzene ring as the skeleton are general. formula (R ₁ is the same as above.) There are three types of substituents: ortho, meta, and para. In addition, for those with an ethylene group as the skeleton, the general formula is (R ₁ is the same as above.) and general formula (R ₁ is the same as above.) There is a compound represented by the following. Representative examples of the compounds of the present invention are illustrated below. For those with a benzene ring as the skeleton, for example o
-allyloxy-N,N-diallylbenzamide,
m-allyloxy-N,N-diallylbenzamide, p-allyloxy-N,N-diallylbenzamide, o-methallyloxy-N,N-dimethallylbenzamide, m-methallyloxy-N,N-dimethallylbenzamide, p-methallyloxy- N, N-
Examples include dimethallylbenzamide, and those with an ethylene group as the skeleton include α-allyloxy-N,
N-diallylpropioamide, β-allyloxy-
N,N-diallylpropioamide, α-methallyloxy-N,N-dimethallylpropioamide, β-
Examples include methallyloxy-N,N-dimethallylpropioamide. The method for producing the above-mentioned N-substituted alkoxycarboxylic acid amide compound includes a hydroxyl-substituted amide compound represented by the following general formula and a halogen-substituted amide compound represented by the following general formula HO-R ₂ -CONH ₂ (R ₂ is the same as above). compound and (R ₁ is the same as above, and X is a halogen group.) This is a method for producing by reacting in an aprotic polar solvent in the presence of a strong basic substance. Hydroxyl group-substituted amide compounds that can be applied to the present invention are broadly classified into hydroxyl group-substituted aromatic carboxylic acid amides and hydroxyl group-substituted saturated fatty acid amides, and specific examples of these compounds include salicylamide, m-hydroxybenzamide, Examples include p-hydroxybenzamide, lactic acid amide, and β-hydroxypropionamide. On the other hand, halogen-substituted compounds are broadly classified into allyl halide and methallyl halide, and specifically include allyl chloride, allyl bromide, allyl iodide,
Examples include methallyl chloride, methallyl bromide, and methallyl iodide. The reaction solvent used in the present invention is not particularly limited as long as it is an aprotic polar solvent, but suitable ones for carrying out the reaction include, for example, acetonitrile, dioxane, pyridine, dimethoxyethane, and tetrahydrofuran. , tetrahydropyran, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, sulfolane, oxepane, triglyme, glymes such as tetraglyme, tetra methylurea, tetraethylurea,
1,3-dimethyl-2-imidazolidinone, 1,
3-dimethyl-3,4,5,6-tetrahydro-
Also included are alkyl ureas such as 2(IH)-pyrimidinone. Among the above, more preferably used solvents include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, sulfolane, tetraglyme, 1,3-dimethyl-2- Examples include imidazolidinone. The amount of solvent used is not particularly limited, but it is 5 to 95% by weight, preferably 10 to 90% by weight based on the total amount of reactants including the solvent.
% by weight. On the other hand, the strong basic substance used in the present invention can be a solid substance, a solution prepared by dissolving it in a polar solvent such as water, or even a liquid substance, but it is possible to use a solid substance or a liquid substance. In order to carry out the reaction, it is preferable to start the reaction in a state where at least a part of the strong basic substance is suspended, so it is preferable to use a solid strong basic substance. The strength of basicity is such that when dissolved or suspended in water, the pH of the aqueous solution is preferably 10 or more.
It can be used if it is 11 or above. However, ion exchange resins and other ion exchangers are not subject to this condition and will be exemplified later. There are many types of strong basic substances that meet such conditions, and any of them can be applied, but among them, those that are more suitable for carrying out the method of the present invention are, for example, alkali metal hydroxides and alkali metal hydroxides. metal oxides, alkaline earth metal hydroxides, and ion exchange resins. Examples of the above substances include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, lithium oxide, sodium oxide, potassium oxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, water Strontium oxide, barium hydroxide,
These include OH type strongly basic ion exchange resins and free type weakly basic ion exchange resins. In addition, the relative usage amounts of the hydroxyl-substituted amide compound, halogen-substituted compound, and strong basic substance, which are raw materials, cannot be uniformly prescribed because they vary depending on the reactivity of the halogen-substituted compound and the hydroxyl-substituted amide compound, but in general The amount of the halogen-substituted compound to be used is preferably 1.0 to 30 times the mole of the amide compound.
The amount of the strong basic substance used is 1.5 to 20 times, preferably 2.0 to 15 times, the amount of the amide compound. The reaction temperature depends on the reactivity of the hydroxyl-substituted amide compound and halogen-substituted compound used, but is usually in the range of -20 to 100°C, preferably -10 to 90°C. As long as it is within this range, it is not necessarily necessary to keep the temperature 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. Further, the reaction time also varies depending on the amide compound and halogen-substituted compound used as well as the reaction temperature, but it is 30 hours at the longest, and usually within 20 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. Next, embodiments of the method of the present invention will be described. First, the order and method of adding the hydroxyl-substituted amide compound, halogen-substituted compound, and strong basic substance may be any method. For example, the three raw materials may be added at the same time, or the third raw material may be added gradually. Usually, a method is adopted in which a hydroxyl-substituted amide compound and a halogen-substituted compound are added first, and then a strong basic substance is gradually added. However, when using a highly reactive halogen-substituted compound, it is preferable to add the halogen-substituted compound last. Furthermore, the reaction temperature does not need to be kept constant during the reaction, and may be changed depending on the progress of the reaction. Usually, a method is adopted in which the reaction is started at a relatively low temperature and then the temperature is raised. Next, the desired product is separated, and by separating the metal halide produced as a by-product after the reaction for a predetermined period of time, and distilling off the solvent and raw materials from the liquid, the desired product can be obtained as a residue. However, the residue is generally purified by operations such as vacuum distillation to separate the desired product. In addition, when by-product metal halides are dissolved in the reaction solution, or in the case of non-volatile amide compounds, a combination of solvents that forms two layers, such as benzene-water or chloroform-water, is used after the solvent is distilled off. The residue may be washed with water, and the metal halide and unreacted amide compound may be dissolved in the aqueous solution layer, and the target product may be dissolved in the organic layer and separated. Furthermore, if necessary, the target product separated from the organic layer is purified by operations such as distillation. Furthermore, when using a solvent with high affinity for water such as dimethyl sulfoxide as a reaction solvent, there is a method of adding water to the reaction solution and separating the target product as an oil layer, or a method of adding water to the reaction solution and separating the target product as an oil layer, or a method of adding water to the reaction solution and separating the target product as an oil layer. A method in which the target substance is extracted and separated using a solvent that forms two layers can also be applied. The N-substituted alkoxycarboxylic acid amide compound of the present invention has an allyl group or methallyl group bonded to an aromatic or saturated aliphatic skeleton via an ether group and an amide group, and is typically represented by conventional diallylphthalate. Its structure is different from that of the carboxylic acid allyl ester type, and its applied products have improved properties such as acid resistance, alkali resistance, chemical resistance, moisture resistance, and heat resistance. Specific uses include water-absorbing resins, crosslinking agents for various resins such as polyester resins, modifiers for epoxy resins, plasticizers for vinyl and fiber resins, and the like, since the molecule has three allyl or methallyl groups. additives to rubber,
It can be used as a raw material for various molded products, as a raw material for decorative laminates, as a resin raw material for coating or dipping industrial laminates, and as a raw material for optical materials such as plastic lenses due to its high refractive index. Next, the present invention will be further explained by examples. Example 1 Production of α-allyloxy-N,N-diallylpropionamide; 7.13 g of lactic acid amide and 43.55 g of allyl bromide were added to 50 ml of N,N-dimethylformamide,
While stirring in an ice bath, 42.75 g of potassium hydroxide was gradually added to start the reaction. Then 6 at 2℃
A time reaction was performed. After the reaction, the insoluble part was separated and the liquid was distilled to collect a 64-66°C/0.1 mmHg fraction to obtain 15.0 g (yield 89.6%) of α'-allyloxy-N,N-diallylpropionamide. Ta. The obtained α
Elemental analysis of -aryloxy-N,N-diallylpropionamide revealed that 68.23% carbon, hydrogen
9.21% and nitrogen 6.65%. In addition, the calculated value is
It is 68.87% carbon, 9.15% hydrogen, and 6.69% nitrogen. Furthermore, when the refractive index at 25° C. was measured, a measurement result of n ²⁵ _D of 1.47280 was obtained. Examples 2 to 7 Reactions were carried out in the same manner as in Example 1 using the combinations of raw materials, strong basic substances, and solvents listed in Table 1 under the conditions listed in Table 1. After the reaction, treatment was carried out in exactly the same manner as in Example 1, and the results shown in Table 2 were obtained.

【table】

【table】

[Table] Reference example Production of water-absorbing resin: 1% tert-butylperoxy-2-ethylhexanoate was added to N-n-propylacrylamide containing 0.2% β-allyloxy-N,N-diallylpropionamide. The mixture was left at 40°C for 50 hours to carry out solvent-free polymerization, and then heat-treated at 90°C for 5 hours to obtain a block-like polymer. The polymer was ground to obtain a powder. 1.0g of this sample powder
The water absorption capacity of the resin was measured at 25℃ by pouring it into a measuring cylinder containing 50ml of distilled water.
It was 19ml.

Claims (1)

[Claims] 1 General formula (1) (However, R ₁ is hydrogen or a methyl group, and R ₂
represents a phenylene group or an ethylene group. ) An N-substituted alkoxycarboxylic acid amide compound represented by: 2 A hydroxyl _- substituted amide compound _represented by the following general formula and a halogen-substituted compound represented by _the following general formula (However, R ₁ is hydrogen or a methyl group, and
represents a halogen group. ) The general formula (1) is characterized by being reacted in the presence of a strong basic substance in an aprotic polar solvent. (R ₁ and R ₂ are the same as above.) A method for producing an N-substituted alkoxycarboxylic acid amide compound.