JPS62149653A - Production of n-substituted acrylamide or methacrylamide - Google Patents

Abstract

PURPOSE:To obtain a compound useful as a high polymer material, etc., readily, in high purity and in high yield, by dissolving an amine and an alkali metallic hydroxide or an alkali metallic salt in a mixed solvent and then reacting the solution with a (meth)acrylic acid halide. CONSTITUTION:A primary or secondary amine or its salt and an alkali metallic hydroxide or an alkali salt are predissolved or dispersed into a mixed solvent of two phase system of water and an organic solvent and reacted with an acrylic acid halide shown by the formula (R is H or methyl; X is Cl or Br) at -10-60 deg.C, preferably 0-40 deg.C to give the aimed substance.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to N-substituted acrylamides or methacrylamides [hereinafter referred to as N-substituted (meth)acrylamides]. ] Concerning the manufacturing method. More specifically, the present invention includes:
A primary or secondary amine or a salt thereof and an alkali metal hydroxide or alkali metal salt are dissolved or dispersed in advance in a two-phase mixed solvent of water and an organic solvent that is substantially insoluble in water, and then into the mixture general formula (I)C
H2=CC0X (in the formula, R represents a hydrogen atom or a methyl group, and X represents a chlorine atom or a bromine atom) is added intermittently or continuously to This is a method for producing N-substituted acrylamide or methacrylamide, which is characterized in that it does not react with primary or secondary amines or their salts.

The N-substituted (meth)acrylamides provided by the present invention can be polymerized by themselves or copolymerized with other polymerizable vinyl monomers to produce thermoresponsive polymer materials, moisture-controlling and moisture-permeable polymers. It is expected to be used as a variety of functional polymer materials, such as biocompatible polymer materials, polymerizable polymer deterioration inhibitors, etc., and has wide application fields. In addition, (meth)acrylamides with substituted amino groups become cationic monomers by quaternization, and their polymers can be used as polymer flocculants, adhesives, papermaking agents, ion exchange resins, etc. Monomers having two or more (meth)acrylamide groups therein can be used as crosslinking agents, curing agents, etc.

<Prior art> Conventionally known methods for synthesizing N-substituted (meth)acrylamides include, for example, using an aqueous sodium hydroxide solution as a reaction aid in the reaction of (meth)acrylic acid chloride with alkylamines. Dropwise reaction method (U.S. Pat. No. 2,311,548) N-(3-dimethylaminopropyl ) Method of Synthesizing Acrylamide (U.S. Pat. No. 2,595,
No. 907); A method in which a trialkylamine or the amine itself as a reaction substrate is used as a reaction aid in the reaction of (meth)acrylic acid chloride and amines [US Pat. No. 3,285,886.

J, Org, Chem, 46.2182 (1981
), 2 hours, ObshcheiKhim,, 272
239 (1957)]: A method of reacting (meth)acrylic acid and amines in the gas phase (U.S. Patent No. 2.7)
19.177, US Pat. No. 2.719.178); method of synthesis by reaction of alkyl (meth)acrylate with amines (US Pat. No. 2.451.436, US Pat. No. 3.
No. 878.247, No. 4.251.461, No. 4
．． No. 267.372, No. 4.287.363, JP-A No. 54-138.513, No. 56-100.749 of the same town
No. 56-131.555, No. 57-42.6 of the same town
No. 61, 58-949@), etc. However, in the method described in the above literature using (meth)acrylic acid chloride, it is difficult to adjust the dropping rate of the sodium hydroxide aqueous solution and (meth)acrylic acid chloride and control the reaction temperature, and it is difficult to quickly remove the generated hydrogen chloride. However, hydrochloric acid adducts and Michael adducts are produced, resulting in lower yields and purity, and the types of amines that can be used are also limited. Particularly in reactions with dialkylamines and dialkylaminoalkylamines, there is the problem of by-product Michael adducts, and when water-soluble products are subjected to IRF, it is difficult to isolate and purify the products from the reaction products. This is not easy and usually has to be purified by distillation, which has the disadvantage that polymerization of the product is particularly likely to occur during this process, resulting in an unavoidable reduction in yield. On the other hand, there have been no reports on the reaction of amines with salts. Furthermore, in the method described in the above-mentioned literature in which trialkylamine or the amine itself as a reaction substrate is used as a reaction aid, not only does the problem of DJ production of the Michael adduct arise, but also the hydrochloride of the amine produced from the reaction product is There is a drawback that the operation becomes complicated due to the removal.

In the method described in the above literature, in which (meth)acrylic acid and amine are reacted in the gas phase, not only the reaction takes place in two stages, but also the problems of formation and polymerization of Michael adducts are unavoidable, as well as high boiling point or solid state. The disadvantage is that it is difficult to react with amines.

The method described in the above-mentioned literature, which involves the reaction of an alkyl (meth)acrylate with an amine, has the disadvantage that a low yield of F due to by-products of Michael adducts and polymerization is unavoidable.

Problems to be Solved by the Present Invention The present invention avoids the above-mentioned Michael adducts, reaction J5, and yield reduction due to polymerization during purification, and produces N-substituted (
The object of the present invention is to provide an industrially advantageous manufacturing method for obtaining meth)acrylamides.

<Means and effects for solving the problems> In order to solve the above-mentioned problems, the present inventors have intensively studied methods for producing N-substituted (meth)acrylamides.

By the reaction of (meth)acrylic acid halide with amine, N
When producing -substituted <meth)acrylamides, it is known to use an aqueous solution of an alkali metal hydroxide or a V1 solvent that is substantially insoluble in water. However, the yield and
We found that the purity varies considerably, and after detailed study, we found that the primary or secondary amine or its salt and the alkali metal hydroxide or alkali metal salt were mixed in water and in an organic solvent substantially immiscible with water. Preliminarily dissolved or dispersed in a phase-based mixed solvent, and then added to the mixture by general formula (I)
H2=CC0X (in the formula, R represents a hydrogen atom or a methyl group, and X represents a chlorine atom or a bromine atom) is added intermittently or continuously to The present invention was completed by discovering that N-substituted (meth)acrylamides can be easily produced in high yield and purity by reacting with primary or secondary amines or their salts.

Examples of the (meth)acrylic acid halide represented by the general formula (1) used in the present invention include acrylic acid a-ride, acrylic acid bromide, methacrylic acid chloride, and methacrylic acid bromide. Regarding the use M of the above (meth)acrylic acid halide, -NH in the amine compound
2JJ or >0.25 to 2.0 for the sum of the number of NH groups
The value is preferably in the range of 0.5 to 1.5. 0
．． When the temperature is less than 25 degrees, the conversion rate decreases and a large amount of unreacted amine compounds remain in the reaction system. If the amount is more than 2.0, it is not only economically disadvantageous, but also the treatment after the reaction becomes complicated.

The primary or secondary amines or salts thereof used in the present invention include aliphatic primary amines such as methylamine, butylamine, octadecylamine, and 2-methylthioethylamine, amines such as cysteamine salt Mffi, and cystamine ram salt. salts of dimethylamine, diethylamine, aliphatic secondary amines such as ethyleneimine, alkylene diamines such as ethylenediamine and trimethylenediamine, 2,2-dimethylthiazolidine, 4-amino-2,2,6,6 Cyclic amines such as -teI-ramethylpiperidine, piperidine, piperazine, morpholine, 2-dimethylaminoethylamine, 2-
diethylaminoethylamine, 3-dimethylamino-n
- dialkylaminoalkylamines such as propylamine, 3-diethylamino-n-propylamine, 2
- [(2-dimethylaminoethyl)aminocoethylamine, 3-[(3-dimethylamino]-n-propyl)
triamines such as amino-n-propylamine or their homologues, tetraamines, aniline,
Examples include aromatic amines such as N-methylaniline, α-naphthylamine, p-phenylenediamine, 1)-N,N-dimethylphenylenediamine, 2-aminobenzophenone, and 2-aminoacetophenone.

Examples of the alkali metal hydroxide or alkali metal salt used in the present invention include sodium oxide, potassium hydroxide, sodium carbonate, #1 potassium, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.

The amount of the alkali metal hydroxide or alkali metal salt to be used can be selected from the range of 0.25 to 3.0 equivalents based on the sum of the numbers of -NH2 groups and >NH groups of the amine compound, and is preferably It is 0.55-1.6 equivalent. 0.2
If the yield is less than 5, the yield of the product decreases, and the yield is lower than 3.0.
If the river has more than the equivalent amount, it will be economically disadvantageous.

When an amine salt is used, in addition to the above-mentioned W, an alkali metal hydroxide or an alkali metal salt is used to neutralize the salt.

The organic solvent used in the present invention is preferably one that is stable under the reaction conditions, does not substantially dissolve in water, and dissolves the reaction product well. For example, pentane, hexane,
Aliphatic hydrocarbons such as heptane; benzene, toluene,
Examples include aromatic hydrocarbons such as xylene; halogen compounds such as carbon tetrachloride, chloroform, and dichloromethane. The above organic solvents may be used alone or in a mixture of two or more. The organic solvent/water volume ratio is preferably 0.25 or more, more preferably 1 or more.

When the above-mentioned volume ratio is smaller than 0.25, the amount of the product eluted into the aqueous layer increases and the isolation yield decreases.

When the above-mentioned volume ratio is 1 or more, less product is eluted into the aqueous layer, and the decrease in isolation yield is small. The use of mixed solvents is particularly advantageous when the reaction product is not or cannot be purified by distillation.

The reaction temperature is -10 to 60°C, preferably 0 to 40°C. The reaction is slow at temperatures lower than -10℃, and 60℃
At higher temperatures, side reactions such as Michael addition reactions and polymerization reactions tend to occur, which is undesirable. Although it is not necessarily essential to have a polymerization inhibitor present in the reaction system, p-methoxyphenol, hydroquinone, phenothiazine, cuprous chloride, talolanil, p-nitroben-if M, 2.
It is preferable to add 5-dichloro-p-benzoquinone or the like to the reaction system.

Embodiments of the separation and purification of the N-substituted (meth)acrylamides obtained by the present invention will be described below, but these embodiments are not intended to limit the present invention. Generally, after the reaction, salts are removed as an aqueous solution by separating the reaction mixture, then the organic solvent is removed by distillation, and if necessary, N-
A-substituted (meth)acrylamides can be separated and produced by M.

<Effects of the Invention> According to the method of the present invention, by using an inexpensive alkali metal hydroxide or alkali metal salt in a mixed solvent of water and an organic solvent, the reaction quickly proceeds and is completed, and the desired product is produced after the reaction. N-substituted (meth)acrylamides can be obtained in high yield and purity by a simple operation of liquid separation.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 A 50% aqueous solution of dimethylamine was added to a 21 volume flask equipped with a stirrer, addition funnel, reflux condenser and thermometer.
(J (2,218 mol), sodium hydroxide 88.
7c+ (2,218 mol), 524 d of water, 288 d of dichloromethane, and 35 fn9 of D-methoxyphenol were added, and the internal temperature was cooled to 10° C. or lower.

Add methacrylic acid Oride 220.3 to this while stirring.
g (2,107 El) was added dropwise over 4 hours. During the reaction, internal wetting was maintained at 10°C or less. After the reaction, stirring was continued for an additional 1.5 hours to complete the reaction. After the reaction is completed, separate the reaction solution,
The aiso layer of the reaction solution was dried with anhydrous sodium sulfate, and the sodium sulfate was removed by filtration. Next, dichloromethane was distilled off under reduced pressure, followed by vacuum distillation (64°C/10 t
orr) for N,N-dimethylmethacrylamide 22
7.2(+(2,008 mol)) was obtained. The yield was 95.3% based on the starting methacrylic acid chloride.

Example 2 Diethylamine 73.1 (1 (
1,OO0 mol), sodium hydroxide 40.0o(1,
000 mol), water 280 d, dichloromethane 250 d,
Prepared 15 Ing of phenothiazine, and added 86 Oa of acrylic acid chloride instead of methacrylic acid chloride.
The same operation as in Example 1 was carried out except that (0,950 mol) was used. N,N-diethylacrylamide 102.7(] (
The yield was 84.9% based on the starting acrylic acid chloride.

Comparative Example 1 Volume ff 1500 m equipped with stirrer, dropping funnel, reflux condenser and thermometer! ! diethylamine 73 in the flask of
．． 1 (](1,○OO mol), diethyl needle 20
0ml1. Hydroquinone O and ioog were charged, and the internal temperature was cooled to 10°C or less. Add 90% acrylic acid chloride to this while stirring. ! M (1,000 mol) and
A solution of 40.0 (1,000 mol) of sodium hydroxide dissolved in 100 rR1 of water was simultaneously added dropwise over a period of 2 hours. During the dropping, internal wetting was maintained at 15° C. or lower.

After the dropwise addition was completed, stirring was continued for an additional hour. After the reaction was completed, the reaction solution was separated, the organic layer was washed twice with 100ml of 0.2% aqueous sodium hydroxide solution, and then washed with 25ml of water, and the aqueous layer was extracted with 40ml of diethyl ether.

The washed organic layer and extracted ether layer were combined and dried over magnesium sulfate, and then the ether was distilled off under reduced pressure. Then, it was distilled under reduced pressure to obtain N,N-diethylacrylamide (boiling point 7).
9℃/10torr) 63.5 (1 (yield 49.9
%) was obtained.

Examples 3 to 8 In the same manner as in Example 1, N-substituted amides of acrylic acid or methacrylic acid were synthesized by reacting acrylic acid chloride or methacrylic acid chloride with amine compounds. The results are shown in Table-1.

Example 9 In a 1300 d flask equipped with a stirrer, addition funnel, reflux condenser and thermometer were added 17.60 (0,200 mol) of 2-dimethylamine ethylamine, 8.80 (1 (0,220 mol)) of sodium hydroxide. mol), p-nitrobenzoin M/1.7 IIrg, water 13.2 m (!) and dichloromethane 132 d, and the internal temperature was cooled to 10°C. While stirring, methacrylic acid chloride 22.0 a (0 , 210 mol) was added dropwise over 120 minutes.The internal temperature was kept below 20°C during the reaction.After the reaction was completed, the reaction solution was separated.Anhydrous sodium sulfate was added to the dichloromethane layer obtained by the separation and dried. After that, sodium sulfate was removed by filtration. Dichloromethane was then distilled off under reduced pressure to obtain N=(2-dimethylaminoethyl)methacrylamide 2.
8.5 g (0,182 mol: yield 91.2%) was obtained.

Example 10 In an apparatus similar to Example 9, 17.6 (1 (0,200 mol)) of 2-dimethylaminoethylamine, 8.40 g (0,210 mol) of sodium hydroxide, and 7,8 mg of p-methoxyphenol were added. , 160 d of water and 160 yf of dichloromethane were charged, and the internal temperature was cooled to 10°C. 22.0 g of methacrylic acid chloride was added to this while stirring.
(0,210 mol) was added dropwise over 120 minutes. The internal temperature was kept below 20°C during the reaction. After the reaction was completed, the reaction solution was separated. Anhydrous sodium sulfate was added to the dichloromethane layer obtained by liquid separation, and after drying, sodium sulfate was removed by filtration. Next, dichloromethane was distilled off under reduced pressure to give N-(2-dimethylamineethyl)methacrylamide 24.2a(
0,155 mol (yield 77.3%) was obtained.

Examples 11 to 16 Into the same apparatus as in Example 9, the prescribed amounts of amine compound, alkali metal hydroxide, polymerization inhibitor, water, and organic solvent shown in Table 2 were charged, and the internal temperature was brought to 10°C while stirring. Cooled. A predetermined amount of (meth)acrylic acid halide was added dropwise to the mixture over 120 minutes while stirring. The internal temperature was maintained at 20°C during the reaction. After the reaction was completed, the reaction mixture was treated in the same manner as in Example 9,
An N-substituted (meth)acrylamide compound was obtained. The results are shown in Table-2.

Example 17 Aniline 279.9% was added to a 3-capacity glass flask equipped with a stirrer, thermometer, Dimroth condenser, and addition funnel.
4 a (3,000 mol), dichloromethane 540
d, 120.0 g (3,000 mol) of sodium hydroxide
,Wed 1080#11! and p-methoxyphenol 2
8η was prepared in advance. While stirring vigorously, keep the inside of the system below 20°C. Methacrylic acid chloride 313.5
g (3,000 mol) was added over 100 minutes. After the dropwise addition was completed, stirring was continued for an additional 30 minutes, and the mixture was separated into two phases. The obtained organic layer was washed with dilute hydrochloric acid, water, and a 5% aqueous sodium carbonate solution, and then washed repeatedly with water until the aqueous layer became neutral. After drying the organic layer obtained by 1q with anhydrous sodium sulfate, t[i? Dichloromethane inside was distilled off, and N
-Phenyl methacrylamide 465.5 (1 (yield 96
．． 2%).

Examples 18-21 In the same manner as in Example 17, N-substituted amides of acrylic acid or methacrylic acid were synthesized by reacting acrylic acid or methacrylic acid chloride with an amine compound. The results are shown in Table-3.

Example 22 In a 300 d flask equipped with a stirrer, thermometer and addition funnel, 120 m of chloroform, 10.0 a (50,7 mmol) of 2-aminobenzophenone, 15 m of water and 5.54 m (1 (66, 0 mmol) was charged, and 6.72 g (64.3 mmol) of methacrylic acid chloride was added dropwise over 75 minutes while maintaining the temperature in the reaction system at 2 to 4°C. After the dropwise addition, the temperature in the reaction system was lowered to 4°C. After stirring for 3 hours while maintaining the temperature at ~7°C, the reaction was completed.

After the reaction is complete, add 3 water to the reaction system! M! was added, stirred, and then separated. The organic layer of the reaction solution was washed twice with 50 d of 1.6% aqueous sodium carbonate solution and then twice with 100 d of water. After the solvent of this organic layer was distilled off under reduced pressure, it was dried under reduced pressure and N-methacryloyl-2-amino-benzophenone 12.5!
J (47.1 mmol) was obtained. The yield was 92.9% based on the 2-aminobenzophenone used. The purity was determined to be 99.6% by high performance liquid chromatography (using a 003 column).

Examples 23 to 25 In the same manner as in Example 22, the N-
Substituted amides were synthesized. The results are shown in Table-4.

Claims (1)

[Claims] (1) A primary or secondary amine or a salt thereof and an alkali metal hydroxide or alkali metal salt are dissolved or dispersed in advance in a two-phase mixed solvent of water and an organic solvent that is substantially immiscible with water. , then into the mixture is acrylic acid represented by the general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a hydrogen atom or a methyl group, and X represents a chlorine atom or a bromine atom.) A method for producing an N-substituted acrylamide or methacrylamide, which comprises adding a halide or a methacrylic acid halide intermittently or continuously to react with the primary or secondary amine or a salt thereof.