JPS60163867A - N-acryloyl cyclic imine and its preparation - Google Patents

Abstract

NEW MATERIAL:The N-acryloyl cyclic imine of formula I (n is 6-10). EXAMPLE:N-Acryloylhexahydroazepine. USE:Raw material for the preparation of adhesive, paint, paper processing agent, textile processing agent, emulsion, urethane hardener, pigment dispersing agent, additive for plastics, polymer flocculant, resin for adsorptive separation, macrocyclic imine, etc. It has a structure corresponding to a cyclic imine having relatively high hydrophobic property and substituted with acryloyl group having high polymerization capability. It has high compatibility with various other substances and excellent resistance to chemicals. PREPARATION:The compound of formula I can be prepared by reacting acrylamide with the dihalogen-substituted compound of formula II (X is halogen) in an aprotic polar solvent in the presence of a strongly basic substance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an N-acryloyl cyclic imine and a method for producing the same. More specifically, the present invention relates to a polymerizable N-acryloyl cyclic imine and a method for producing the same.

The compound of the present invention is represented by the general formula (1) (where n is an integer of 6 to 10).
- It is an acryloyl cyclic imine, and is a compound that has not been described in any literature.

For the N-acryloyl cyclic imine represented by the general formula, hexahydroazepine, octahydroazoben, octahydroazonine, decahydroazecine, azacycloundecane can be applied as the heterocyclic skeleton, and their nitrogen It is a compound in which an atom is substituted with an acryloyl group.

Method 2 for producing N-acryloyl cyclic imine described above involves mixing acrylamide and a dihalogen-substituted compound represented by the following general formula (2) to → CI(2-)yX ---
−−−−−−−(2) (However, n is the same as above,
X is a halogen group. ) This is a method of manufacturing by reacting in an aprotic polar solvent in the presence of a strong basic substance.

The present invention will be explained in more detail below.

The compounds of the present invention are represented by the general formula (1), and specifically include N-acryloylhexahydroazepine, N-acryloyl octahydroazocine, N-acryloyl octahydroazonine, N-acryloyldecahydro Azecine, N-acryloyl azacycloundecane.

The method for producing N-acryloyl cyclic imine exemplified above is produced by reacting acrylamide and a dihalogen-substituted compound represented by the above general formula (2) in an aprotic polar solvent in the presence of a strong basic substance. It's a method. Acrylamide used in the present invention is usually in solid form. On the other hand, dihalogen compounds have halogen groups,
Any of chlorine, bromine, and iodine can be used, and specifically, for example, 1,6-dichlorohexane, 1,7-dichlorohebutane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10- Dichlorodecane, 1,6-dibromohexane, 1,7-dibromohebutane, 1,8-dibromooctane, 1,9-dibromononane, 1.10=dibromodecane, 1,6-short hexane, 1,7 -Short hebutane, 1,8-short octane, 1.9-
Short nonane, 1,1o-jododecane.

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, tetrahydrofuran, and tetrahydrofuran. Glymes such as hydropyran, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxycyto, N-methylpyrrolidone, hexamethylphosphoramide, sulfolane, oxepane, triglyme, tetraglyme, Tetramethylurea, tetraethylurea, 1,3-dimethyl-2-
Imidazolidinone, 1,6-dimethyl-6゜4,5.6
Also included are alkyl ureas such as -tetrahydro-2(IH)-pyrimidinone. Among the above, more preferably used solvents include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide,
Examples include dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, tetraglyme, and 1,3-dimethyl-2-imidazolidinone.

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 the reactants including the solvent. On the other hand, the strong basic substance used in the present invention is
A solid substance, a solution of the substance dissolved in a polar solvent such as water, or even a liquid substance can be used, but in order for the reaction to occur properly, one part of the strong basic substance must be small. Since it is preferable to start the reaction while stirring, it is preferable to use a solid strongly basic substance. The strength of basicity is such that when dissolved or concentrated in water, the pH of the aqueous solution is preferably 10 or higher, preferably 7 (or 11).
Anything above can be used. However, 7. 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, or among them, those that are more suitable for carrying out the method of the present invention are, for example, alkali metal hydroxides, alkali metal oxides, alkaline earth metal hydroxides, and ion exchange resins. Examples of the above substances include thorium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, lithium oxide, sodium oxide, potassium oxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, These include strontium hydroxide, barium hydroxide, OH type strongly basic ion exchange resin, and free type weakly basic ion exchange resin.

In addition, the relative usage amounts of the raw materials acrylamide, dihalogen-substituted compounds, and strong basic substances cannot be uniformly prescribed because they vary depending on factors such as the reactivity of the 6-dihalogen-substituted compound and acrylamide, but in general, the dihalogen-substituted The amount of the compound used is 0.0% relative to acrylamide.
The range is 2 to 20 times the mole, preferably 04 to 15 times the mole, and the amount of the strong basic substance used is 0 to acrylamide.
．． It is in the range of 2 to 15 times the mole, preferably 04 to 8 times the mole.

The reaction temperature depends on the reactivity of the acrylamide used and the dihalogen-substituted compound, but is usually between -20 and '100.
℃, preferably in the temperature range of -10 to 90℃. As long as it 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 appropriately set the reaction temperature to allow the reaction to occur efficiently.

The reaction time also varies depending on the acrylamide and dihalogen-substituted compound used as well as the reaction temperature, but it is at most 30 hours, 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 acrylamide, the dihalogen-substituted compound, and the 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 acrylamide and a ShibaCl-substituted compound are first added IC, and then a strong basic substance is gradually added.

However, when using a highly reactive dihalogen-substituted compound, it is preferable to add the dihalogen-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. After the reaction for a predetermined period of time, the metal halide produced as a by-product is separated from P, and the solvent and raw materials are distilled off from the f' liquid. The desired product can be obtained as a residue. . However, in general, the residue is purified by operations such as vacuum distillation or recrystallization 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, the residue can be removed by using a combination of solvents that form two layers, such as benzene-water or chloroform-water, after distilling off the solvent. 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 distillation, recrystallization, or the like.

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 of extracting and separating the target substance using a solvent that forms two layers can also be applied.

The N-acryloyl cyclic imine of the present invention is a relatively hydrophobic cyclic imine substituted with an acryloyl group that has high polymerization ability, and has a well-balanced hydrophilic group and hydrophobic group within the molecule. . Therefore, these polymers have better compatibility with various substances than those with low polarity, and also have excellent chemical resistance such as hydrolysis resistance. It has the advantage of being able to control It is also useful as a raw material for producing macrocyclic imines.

Furthermore, the method for producing N-acryloyl cyclic imine of the present invention is not based on the reaction of a carboxylic acid halide and an amine, which is the conventional method for producing N-substituted amides, but is based on the reaction between an amide and a dihalogen-substituted compound. Since it uses inexpensive industrial raw materials, N-acryloyl cyclic imine can be produced industrially and at low cost.

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

Example 1 Preparation of N-acryloylhexahydroazepine; 10-N,N-dimethylformamide 50-, acrylamide 5197 and 1,6-dipromohegisane 17.81 g
and while stirring in a water bath, add 86% of potassium hydroxide.
2v was gradually added to start the reaction. Thereafter, the reaction was carried out at 2°C for 6 hours. After the reaction, the insoluble part was separated in a furnace, and the P liquid was distilled to collect fractions 75 to bT-17.
%) was obtained. Elemental analysis of the obtained N-acryloyl hexahydroazepine revealed that it contained 6971% carbon, 968% hydrogen, and 923% nitrogen. The calculated values are 70.55% carbon, 987% hydrogen, and 914% nitrogen.

The melting point is 10-13℃, and the refractive index at 25℃ is NDi
, 5D665.

Example 2 Production of N-acryloyl octahydroazonine; 1,8-dibromooctane 19 as a dihalogen-substituted compound
．． The reaction was carried out in exactly the same manner as in Example 1 except that 8647' was used. After the reaction, the insoluble part was separated in a furnace and the solvent was distilled off,
The residue was recrystallized from benzene to obtain 9.4 g (yield: $71.0%) of N-acryloyl octahydroazonine. Elemental analysis of the obtained lyloyl octahydroazonine revealed that carbon was 7195% and hydrogen was 1%.
053% and nitrogen 786%. In addition, the calculation/direction is 7288% carbon, 1.56% hydrogen, and 773% nitrogen. Moreover, the melting point was 61-63°C.

Example 6 Preparation of N-acryloyl azacycloundecane jθ; The reaction was carried out in exactly the same manner as in Example 1 except that 1,10-dibromodecane was used as the dihalogen-substituted compound. After the reaction, the treatment was carried out in exactly the same manner as in Example 2), and N-acryloyl azacycloundecane 11.4!1I (74,6
%) was obtained. Elemental analysis of the obtained N-acryloyl azacycloundecane revealed that it contained 7381% carbon, 1097% hydrogen, and 680% 9 elements. The calculated value is
The carbon content is 74.59%, hydrogen 1108%, and nitrogen 669%. Moreover, the melting point was 45-48°C.

Example 4 Production of thermosensitive polymer: In a 1D 〇- 4-tube round bottom flask with stirring under nitrogen gas flow, 47.5 r of distilled water and 2.45 ml of N-acryloylpyrrolidine were added. i', N-acryloyl azacycloundecane 0.05F was added. Thereafter, 025v of ammonium persulfate and 011g of sodium bisulfite were added, and polymerization was carried out at 15 to 30°C for 4 hours.

When the aqueous polymer solution obtained above was heated,
It started to become slightly cloudy at 60°C, and became cloudy at 62°C.

From the above results, a temperature-sensitive polymer with a cloud point of 60°C was synthesized.

patent applicant Mitsui Toatsu Chemical Co., Ltd. 13-

Claims (2)

[Claims] (1) N represented by general formula (1) (where n is an integer from 6 to 10)
-Acryloyl cyclic imine. (2) Acrylamide and dino-
Rogen-placed compound ) in an aprotic polar solvent in the presence of a strong basic substance (wherein n is an integer from 6 to 10).
- A method for producing an acryloyl cyclic imine.