JPH07316111A - Production of n,n-disubstituted (meth)acrylamide derivative - Google Patents

Abstract

PURPOSE:To produce the compound useful as a modifier for fibers, etc., an adhesive, etc., in a high yield under mild condition without using special reaction apparatus from a (meth)acrylic acid ester and a sec-amine via 4 steps. CONSTITUTION:This N,N-disubstituted-(meth)acrylamide derivative of formula VII can be produced by (1) reacting a (meth)acrylic acid ester of formula I (R1 is H or methyl; R2 is an alkyl) with a sec-amine of formula II (R3 and R4 each is an alkyl or an aryl) to obtain an addition product of formula III, (2) reacting the compound of formula III with a sec-amine of formula IV (R5 and R6 each is an alkyl or an aryl), (3) reacting the resultant propionic acid amide of formula V with an alkylation agent to form a quaternary ammonium salt of formula VI (R7 is an alkyl) and finally (4) adding a basic substance and subjecting to Hofmann elimination reaction. The compound of formula VII is useful as a modifier or adhesive for fibers and plastics, secondary recovery agent for oil dilution monomer for coating material curable by UV rays or electron rays, an intermediate for organic synthesis, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing N, N-disubstituted (meth) acrylamide derivatives.

[0002]

2. Description of the Related Art N, N-disubstituted (meth) acrylamide derivatives are used as modifiers and adhesives for fibers and plastics.
Further, it is a useful compound which is expected to have a wide range of uses as a secondary recovery agent for petroleum, a diluting monomer for ultraviolet-electron beam curable coatings, and an organic synthetic intermediate.

The following methods are conventionally known as methods for synthesizing this N, N-disubstituted (meth) acrylamide derivative. When (A) (meth) acrylic acid ester is reacted with an amine, addition to a double bond is likely to occur. Therefore, when these compounds are used as raw materials, after reacting 2 moles of the amine, the generated N, A method for producing an N, N-disubstituted (meth) acrylamide derivative by thermally decomposing N-disubstituted-3-N, N-disubstituted amino- (2-methyl) propionic acid amide (J. Am. Chem. Soc., 74
Vol. 6,281, 1952 and JP-A-4-208258.
No. (B) Also, in order to suppress the addition of (meth) acrylic acid and its ester to the double bond, first, (meth) acrylic acid and its ester are added by a Diels-Alder reaction with cyclopentadiene. After forming a body to protect the double bond, it reacts with an amine in the presence of a strong basic catalyst to lead to an amide, and then cyclopentadiene is removed by thermal decomposition to give a corresponding (meth) acrylamide derivative. Manufacturing method
-66625, JP-A-63-179851, etc.).

However, since the reaction rate of thermal decomposition is slow in the above method (A), harsh reaction conditions such as high temperature and long time are required, and polymerization of N, N-dialkyl (meth) acrylamide to be produced, various kinds of reactions. A decrease in yield due to an increase in side reactions cannot be avoided. Further, the method (B) has a problem that a high temperature is required in the deprotection process and a special reaction device is required.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have an object of providing a novel method for producing an N, N-disubstituted (meth) acrylamide derivative which does not have the above-mentioned problems.

[0006]

Means for Solving the Problems In the present invention, a (meth) acrylic acid ester represented by the following general formula (1) is reacted with a secondary amine represented by the following general formula (2). An adduct represented by the formula (3) is produced, and then the adduct is reacted with a secondary amine represented by the following general formula (4) to obtain a propionic amide represented by the following general formula (5). A quaternary ammonium salt represented by the following general formula (6) is formed by adding an alkylating agent to the propionic acid amide, and then adding a basic substance to the Huffman elimination reaction. And N, N-disubstituted (meth) acrylamide derivative represented by the following general formula (7) is represented by the following general formula (7).
-A gist is a method for producing a disubstituted (meth) acrylamide derivative.

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

The process of the manufacturing method of the present invention is characterized by being roughly divided into four processes as described above.

That is, the first step is the (meth) acrylic acid ester represented by the above general formula (1) (hereinafter referred to as compound (1)
And a secondary amine represented by the general formula (2) (hereinafter abbreviated as compound (2)) are reacted, and an adduct represented by the general formula (3) (hereinafter ,
This is a step of producing an adduct (3).

In the second step, the compound (3) is reacted with another molecule of the secondary amine represented by the general formula (4) (hereinafter abbreviated as the compound (4)) to react with the general formula (5). Is a step of producing a propionic acid amide represented by (hereinafter abbreviated as compound (5)).

The third step is a step of reacting the compound (5) with an alkylating agent to form a quaternary ammonium salt represented by the general formula (6) (hereinafter abbreviated as compound (6)). .

In the fourth step, the Hoffmann elimination reaction of the compound (6) is carried out to obtain N, represented by the general formula (7).
This is a step of producing an N-disubstituted (meth) acrylamide derivative (hereinafter abbreviated as compound (7)).

Each of these four steps may be carried out by isolating the intermediate product, but it is also possible to carry out all in one pot.

In carrying out the present invention, the (meth) acrylic acid ester of the compound (1) used in the first step may be any of, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like. Can be mentioned.

The compound (2) used in the first step
Is any secondary amine, and examples thereof include dialkylamines such as dimethylamine and diethylamine, and cyclic amines such as pyrrolidine and morpholine.

In the reaction of the compound (1) with the compound (2) in the first step, the compound (2) is added to the compound (1) in the presence or absence of a solvent, or the compound (2) is added. Compound (1) may be added to 2). The addition reaction of the compound (1) with the compound (2) gives the adduct (3).

Any solvent can be used as long as it does not react with the compound (1) and the compound (2), and particularly preferable solvents are high boiling point hydrocarbons such as toluene, xylene and cumene, dioxane and methanol. And other polar solvents.

The reaction temperature in the first step is 0 to 100 ° C.
It can be set arbitrarily within the range. However, considering that the addition reaction is an exothermic reaction and that the compound (1) may polymerize in a temperature range that is too high, the reaction temperature is preferably in the range of 0 to 40 ° C. or,
The reaction time can be arbitrarily set depending on the reaction temperature, but is 0.1
It is preferable to appropriately perform the treatment within a range of from 3 hours.

The amount of the compound (2) charged during the reaction is arbitrary so as to be in the range of 0.5 to 2 times mol, preferably 1 to 1.1 times mol of the compound (1). Can be set to.

Next, in carrying out the present invention, in the second step, the compound (3) obtained in the first step is obtained.
The compound (4) is converted into the compound (5) by reacting the compound (4) with another molecule as the amine, and the compound (4) used in the second step is the same as the amine used in the first step. It may be different or different. When the same amine is used, the amine can be charged together in the first step.

The charge amount of the compound (4) in the second step is arbitrarily set to be in the range of 0.5 to 2 times mol, preferably 1 to 1.1 times mol, of the compound (1). Can be set.

The reaction of the compound (3) with the compound (4) in the second step can be carried out without a catalyst or in the presence of a basic catalyst.

When the reaction in the second step is carried out without a catalyst, the reaction temperature is lower than 100 ° C., and the reaction is slow. Therefore, it is preferable to set the temperature in the range of 100 to 200 ° C. On the other hand, when carrying out the reaction in the presence of a basic catalyst,
Since the amidation reaction occurs rapidly even at room temperature, it is preferable to carry out the reaction of the second step using a basic catalyst. The reaction temperature of the amidation reaction in the second step is in the temperature range of 0 to 100 ° C when a basic catalyst is used, but when the compound (5) produced by the reaction at a low temperature is precipitated as a solid, In order to make the reaction mixture uniform, the reaction may be performed by heating to a temperature at which the solid compound (5) is dissolved.

Preferred basic catalysts are sodium methylate and sodium ethylate.

The reaction time in the second step may be arbitrarily set within the range of 0.1 to 4 hours depending on the reaction temperature.
Three hours is the preferred reaction time.

If the first step is solvent-free, the second step can be carried out without solvent or in the presence of a solvent. As the solvent to be used, any solvent which does not react with the compound (3) or the compound (2) and the compound (4) can be used, and particularly preferred are high boiling carbonization such as toluene, xylene and cumene. Examples include polar solvents such as hydrogen, dioxane, and methanol.

Further, in carrying out the present invention, the third step can be carried out either in a solvent-free state or in a state diluted with a solvent. When a solvent is used, any solvent can be used as long as it dissolves the compound (5) and does not react with the alkylating agent. Particularly preferred solvent is toluene,
Examples thereof include high boiling point hydrocarbons such as xylene and cumene, and polar solvents such as dioxane and methanol.

In the reaction in the third step, the compound (5) is not dissolved in a solvent but an alkylating agent is directly added to the solution and stirred, or the compound (5) is dissolved in a solvent and then alkyl is added thereto. The process proceeds by adding an agent and stirring. Examples of the alkylating agent used include alkyl halides such as methyl chloride, methyl bromide and methyl iodide, and dimethyl sulfate and dimethyl carbonate.

The addition amount of the alkylating agent in the third step can be arbitrarily set in the range of 1 to 2 times by mole with respect to the compound (5), but is preferably in the range of 1.2 to 1.5 times by mole. is there.

The reaction temperature in the third step is 0 to 1
The temperature can be set in the range of 20 ° C, but preferably 60 to
It is in the range of 100 ° C.

Further, the reaction time in the third step is 1 to
Although it can be arbitrarily set within the range of 24 hours, 0.5 to 3 hours is a preferable reaction time.

In the third step, the compound (6) represented by the general formula (6) is obtained by reacting the compound (5) with the alkylating agent.
X ⁻ therein is a salt-forming anion. As the anion forming a salt of X ⁻ , a halogen ion (Cl ⁻ , B
r ⁻ , I ^−, etc.), CH ₃ OSO ₃ ⁻ , HSO ₄ ⁻ , CH ₃ CO ₂ ⁻
Etc.

Next, in the fourth step, a basic substance is added to the compound (6) obtained in the third step to carry out the Hoffmann elimination reaction to produce the compound (7). The process can be carried out in one pot without isolation of compound (6) following the process.

This Hoffmann elimination reaction can be carried out by adding a basic substance to the compound (6) obtained in the third step and aging it. Examples of the basic substance include alkali metal hydroxides such as caustic soda and caustic potash, which are preferably used as an aqueous solution.

The basic substance may be added in an amount of 1 to 1.5 times, preferably 1 to 1.1 times the mol of the compound (6).

The reaction temperature of the Hoffmann elimination reaction in the fourth step can be arbitrarily set in the range of 0 to 120 ° C., but in order to promote the elimination reaction efficiently, it is 50 to 120 ° C.
It is preferable that the temperature be within the range.

Further, the reaction time in the fourth step can be arbitrarily set within the range of 0.5 to 6 hours depending on the reaction temperature, but the reaction time of 1 to 3 hours is preferable.

The compound (7) obtained by the Hoffman elimination reaction can be isolated from the reaction solution by operations such as solvent extraction and distillation. That is, the compound (7) is extracted with a suitable extraction solvent (preferably chloroform, methylene chloride, etc.) and then isolated by distillation.
In addition, in order to prevent the polymerization of the compound (7) during distillation, hydroquinone, p-methoxyphenol, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (Ouchi Shinko Chemical Co., Ltd. Manufactured, trade name: Nocrac 6C) and the like may be added.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples. Analysis was by gas chromatography.

Example 1 Synthesis of N-acryloylmorpholine 43.05 g of methyl acrylate was placed in a glass flask equipped with a stirrer, a dropping funnel, a thermometer and a Dimroth condenser.
(0.5 mol) was charged, and morpholine 9 was added thereto at 15 ° C.
1.48 g (1.05 mol) was added dropwise over 10 minutes.

The reaction solution generated heat and the temperature of the reaction solution rose to 35 ° C. When the reaction solution was allowed to cool and aged for 50 minutes, the temperature of the reaction solution dropped to 18 ° C.
Methyl acrylate completely disappeared.

Subsequently, to this reaction solution at 18 ° C., 282% sodium methylate (methanol solution) (4.82 g) was added.
(0.025 mol) was added dropwise over 3 minutes, white crystals were precipitated, and the temperature was raised to 93 ° C. and the reaction solution was refluxed for 2 hours.

Then, the reaction solution was cooled and 1.25 g of sulfuric acid was added.
(0.0125 mol) was added to neutralize sodium methylate.

The total amount of the obtained reaction liquid was 138 g.
When 3-morpholinopropionic acid morpholide as the compound (5) in the reaction solution was analyzed by gas chromatography, the content of this compound was 75.9%, and the yield was based on the charged methyl acrylate. 91.8
%Met.

Then, when the obtained compound (5) was cooled to room temperature, it solidified, so that the solidified compound (5) 13
200 g of dioxane was added to 7.2 g, the temperature was raised to 60 ° C. to uniformly dissolve it, and then the mixture was cooled to 25 ° C. When compound (5) was precipitated again, a uniform slurry was formed.

93.72 g of methyl iodide was added to this slurry.
(0.66 mol) was added at 25 ° C., the mixture was aged at the same temperature for 2 hours, further heated to 90 ° C. and aged for 1 hour (reflux).

Then, after cooling the reaction solution to 50 ° C.,
68.97 g (0.5 mol) of 29% aqueous sodium hydroxide solution
After the addition, the temperature was raised to 88 ° C and the mixture was aged at the same temperature for 1.5 hours.

After that, when the reaction solution was cooled to room temperature, crystals were precipitated. Therefore, 89.6 g of water was added to obtain 588.2 g of a uniform reaction solution.

The compound (7) produced in this step, that is, N
-When acryloylmorpholine was quantified by gas chromatography, its content was 8.17%, and the yield was 74.7% based on the compound (5).

576.5 g of a reaction solution containing the compound (7)
Contains water and inorganic salts, so it is extracted with chloroform three times (the amount of chloroform used is 576.8 g for the first time, 2
The second time was 287.8g, and the third time was 145.3g),
The solvent was distilled off using 1000 g of the chloroform extract.

Thereafter, 1 g of Nocrac 6C as a polymerization inhibitor was added thereto, and simple distillation was carried out using a Vigreux tube. The fraction at 70 ° C was reduced to 31.6 at 5 Torr by vacuum distillation.
g was collected. This fraction was N-acryloylmorpholine, and its relative area purity in high performance liquid chromatography was 99%.

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, by adopting the method as described above, N, N-dialkyl (meth) acrylamide can be produced in a high yield under mild conditions without the need for a special reaction apparatus. It has an excellent effect such as being able to

Claims (1)

[Claims] 1. A (meth) acrylic acid ester represented by the following general formula (1) is reacted with a secondary amine represented by the following general formula (2) to be represented by the following general formula (3). An adduct is formed, and then the adduct is reacted with a secondary amine represented by the following general formula (4) to produce a propionic acid amide represented by the following general formula (5). An alkylating agent is added to the quaternary ammonium salt represented by the following general formula (6), and then a basic substance is added to the quaternary ammonium salt to carry out the Hoffman elimination reaction. A method for producing an N, N-disubstituted (meth) acrylamide derivative represented by the following general formula (7), which is an N, N-disubstituted (meth) acrylamide derivative represented. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7]