JPS6345246A - N-(substituted oxalyl)alkylacrylamide and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is lower alkyl; R' is hydrocarbon group). EXAMPLE:N-ethoxyl methacrylamide. USE:A monomer for production of polymer. Useful also as an intermediate for pharmaceuticals, agricultural chemicals, chemical reagents, etc. PREPARATION:The compound of formula I can be produced by reacting an alpha-lower alkyl acrylamide with an oxalyl monohalide monoester of formula II (R' is hydrocarbon group; X is halogen). The reaction is carried out in a proper inert solvent in the presence or absence of a basic substance at about 20-200 deg.C. The compound of formula I has a functional region of e.g. formula III, the functional region (b) contains C,N-diacylamide bond and the compound has high intermolecular cohesivity and high capability to form intermolecular hydrogen bond. Accordingly, the compound has advantages of e.g. giving a tough and highly adhesive resin by polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to N-(substituted oxalyl)alkyl acrylamides and processes for their preparation, particularly to N-(substituted oxalyl)alkylacrylamides of formula (I) which are highly reactive and useful as monomers for the production of polymers.

CHy=CRCO NHCO CO OR' (in the formula, R represents a lower alkyl group and Ro represents a hydrocarbon group)
The present invention relates to an N-(substituted oxalyl)alkylacrylamide represented by and a method for producing the same.

(Conventional technology) Formula (A).

α-Alkylacrylamide represented by CI (t = CRCON Ht (in the formula, R has the same meaning as Q as above) is useful as a raw material when producing various functional derivatives. For example, this By converting into oxalyl civalide, an α-alkyl acryloyl isocyanate represented by the formula (B): CH,=CR-CO-NCO (wherein R has the same meaning as above) can be obtained (as disclosed in JP-A-Sho). 60
115557), and since it has an ethylenic double bond and an isocyanato group, it can participate in various reactions. The present invention was also carried out in an attempt to develop new uses by converting α-alkylacrylamide (A) into a derivative thereof while leaving the ethylenic double bond present therein.

The target substance of the present invention is N-(substituted oxalyl)alkylacrylamide (I), and regarding N-ethoxalyl acrylamide where R=hydrogen and R°=ethyl, acrylamide The material is converted to N,N-bis(ethoxalyl acrylamide) by reacting with oxalyl diethyl or ethoxalyl chloride in the presence of potassium t-butoxide, i.e. by stirring the mixture of these reagents at room temperature for 1 to 5 days. ), but there is no disclosure of more detailed reaction conditions or physicochemical properties of the product.

When the present inventors conducted a follow-up study of the description in the above-mentioned European Application Specification, it was found that if specific reaction conditions not disclosed therein were adopted, N-ethoxalyl acrylamide could be produced. Otherwise, it is difficult to produce the substance, and furthermore, it is impossible to produce N,N-bis(ethoxalyl acrylamide) even if the reaction is carried out under various reaction conditions. It was confirmed.

(Object of the invention) The present invention starts from α-alkylacrylamide (A) and aims to industrially advantageously and reliably provide a new substance, N-(substituted oxalyl)alkylacrylamide (+). .

(Structure of the Invention) According to the present invention, N-(substituted oxalyl)alkylacrylamides generally represented by the formula (I) are advantageously and reliably provided. Although there is some mention of N-ethoxarylacrylamide in the European Application Specification, no literature can be found that mentions other compounds.

Therefore, it can be said that N-(@substituted oxalyl)alkylacrylamide (I) is a new substance.

N-(substituted oxalyl)alkylacrylamide (+)
, the substituent R represents a lower alkyl group, and the substituent R
゛ represents a hydrocarbon group. Examples of hydrocarbon groups include alkyl groups (especially lower alkyls such as methyl, ethyl, propyl, butyl), alkenyl groups (especially lower alkenyls such as allyl, butenyl), alkynyl groups (especially lower alkenyls such as propynyl, butynyl), lower alkynyl), cycloalkyl groups (especially cyclo-lower alkyl such as pentyl and hexyl), aryl groups (especially phenyl), aralkyl groups (especially phenyl-lower alkyl such as benzyl and phenethyl), unsaturated group-substituted oxyalkyl groups ( In particular, lower alkenyloxy (lower alkyl) such as allyloxyethyl. In addition, in this specification, "lower" generally means a group having 8 or less carbon atoms, preferably 5 or less carbon atoms. However, the hydrocarbon group is not necessarily limited to the above-mentioned lower groups, but may also be a relatively higher alkyl group such as stearyl.

In order to produce N (iZ-substituted oxalyl alkyl acrylamide (I)) according to the present invention, the following various methods can be employed.

Manufacturing method l α-Alkylacrylamide (A) and formula (■).

A method via reaction with oxalyl monohalide monoester represented by X-CO-CO-OR' (wherein, X represents a halogen atom (for example, chlorine, bromine); Ro has the same meaning as above).

The above reaction is carried out in a suitable inert solvent in the presence or absence of a basic substance at about 20-200°C. The molar ratio of α-alkylacrylamide (A) and oxalyl monohalide monoester (TI) used in the reaction is preferably about 10-1 to 1;10, particularly 5:1-1:5. Inert solvents are generally hydrocarbons (e.g. benzene, toluene, xylene, hexane), halogenated hydrocarbons (e.g. chloroform, methylene chloride, carbon tetrachloride, chlorobenzene, dichlorobenzene), esters (e.g. cellosolve acetate, ethyl acetate, acetic acid). butyl), ethers (eg diethyl ether, tetrahydrofuran, dioxane), etc.

Hydrogen chloride is produced as a by-product during the reaction, but this may add to the once formed N-(substituted oxalyl)alkylacrylamide (I) and reduce its yield. Therefore, in order to avoid such a decrease in yield and to facilitate the progress of the reaction, it is necessary to include a hydrogen chloride-trapping substance in the reaction system or apply means to promote the removal of hydrogen chloride from the reaction system. It is desirable to do so. Basic substances, in particular inorganic or organic basic substances (e.g. potassium ethoxide,
Potassium monobutoxide, triethylamine, dimethylaniline, pyridine) are added to the reaction system. Alternatively, α-alkylacrylamide (A) may be used in large excess to also serve as a hydrogen chloride scavenger. Further, hydrogen chloride may be quickly removed from the reaction system by carrying out the reaction under a stream or while blowing an inert gas (for example, nitrogen gas).

In order to collect and purify the reaction product from the reaction mixture, a conventional and appropriate separation and purification means such as extraction, column chromatography, recrystallization, vacuum distillation, etc. may be applied.

Production method 2 α-alkylacrylamide (A) and formula (■): x-c
A method via reaction with oxalyl civalide represented by o-co-x (wherein X has the same meaning as above).

In this method, the formula (I
An oxazolinedione hydrohalide represented by the formula (V): Ro -0l-1 (wherein, Ro is It is carried out by reacting with an alcohol represented by (same meaning as above) to produce N-(substituted oxalyl)alkylacrylamide (I).

The first stage reaction is generally carried out in an inert solvent at a temperature from about -50°C to the decomposition temperature of the oxazolinedione hydrohalide (■), preferably from 0 to 80°C. The molar ratio of α-alkylacrylamide (A) and oxalyl civalide (III) used in the reaction is usually 1:1 to 3.
, preferably about 1:l-1°5. The inert solvent is
It may be selected from hydrocarbons, halogenated hydrocarbons, ethers, esters, etc., but preferably halogenated hydrocarbons, such as carbon tetrachloride, chloroform, dichloromethane, 1.1-dichloroethane, 1,2-dichloroethane, 1.1 .1-Trichloroethane, 1,1,2-trichloroethane, 1,2-nochloropropane, 1,4-dichlorobutane, chlorobenzene, ethylene tetrachloride, ethylene trichloride, etc. are used.

The second stage reaction is carried out at about -30 to 40°C, preferably at -10 to 3°C, with or without an inert solvent.
It is carried out at a temperature of 0°C. Oxazolinedione hydrohalide (IV) and alcohol (V) used in the reaction
The molar ratio of is usually 1:1 to 20, preferably about 1=5 to
It is 15. Since the second stage reaction is usually carried out subsequent to the first stage reaction, it is not necessary to add an inert solvent especially during the second stage reaction. Moreover, since alcohol (V), which is a reaction reagent, is often a liquid, it may itself serve as a reaction medium. If an inert solvent is used, it may be selected from hydrocarbons, halogenated hydrocarbons, ethers, and the like.

In addition, in this second stage reaction, since hydrogen halide is produced as a by-product, it is desirable to use a hydrogen halide scavenger as in the case of Production Method 1. The reaction is usually carried out by adding the oxazolinedione hydrohalide (IV) to a mixture of the alcohol (V), a hydrogen chloride scavenger, and optionally an inert solvent.

In order to collect and purify the reaction product from the reaction mixture, a conventional and appropriate separation and purification means such as extraction, column chromatography, recrystallization, vacuum distillation, etc. may be applied.

As a result of recent research using N x IR, some doubts have arisen regarding the formula (IV) given to the oxazolinedione hydrohalide, and rather the formula (
IV'): It is possible that the following is more or less correct. However, when chemical behavior is considered, formula (IV) seems to be more appropriate than formula (■゛). Therefore, in this specification, formula (■) is used uniformly.

Furthermore, oxazolinedione hydrohalide (■)
, in an inert solvent (e.g. noethyl ether, dioxane, tetrahydrofuran, benzene, acetone) in the presence of a base (e.g. sodium hydride) from about O to 40
When reacted with α-alkylacrylamide (A) at ℃ (preferably around room temperature), the formula (■): (CHt=CR-CO-N)I-CO-)=(in the formula, R
has the same meaning as above. ) is obtained. This compound is also useful as a monomer component for producing polymers because of the ethylenic double bond present in the molecule.

Production method 3 α-acrylamide A method via the reaction of acrylamide (A) with an oxalyl diester represented by the formula (■) rt'o-co-co-oR' (wherein Ro has the same meaning as above) .

The above reaction must be carried out in the presence of a basic substance, but other than this, it is not adopted in the reaction of Production Method 1, that is, the reaction of α-acrylamide acrylamide (A) and oxalyl monohalide monoester (I[). The method may be carried out under conditions essentially similar to those described above. The hydrogen chloride scavenger may be suitably selected from inorganic or organic bases, but
Generally, strong bases are preferred, and it is desirable to use inorganic bases such as potassium ethoxide and potassium t-butoxide. The reaction is usually carried out in an inert solvent,
It may be appropriately selected from hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and the like. Instead of the inert solvent, oxalyl diester (Vl) may be used in excess.

As a result of the reaction, N-(substituted oxalyl) acrylamide acrylamide (D) is produced as a direct product, but depending on the reaction conditions, a bis(α-alkylacrylamide) form (■) may also be produced as a by-product, and sometimes This bis(α-alkylacrylamide) form (■) may be the main resultant.

In order to recover and purify the reaction product from the reaction mixture, any suitable separation and purification means commonly used may be applied, such as extraction, column chromatography, recrystallization, and vacuum distillation.

(Effects) The N-(substituted oxalyl)alkylacrylamide (I) of the present invention has a functional moiety represented by the formula. The functional part a has a conjugated double bond and is a part that can be homopolymerized or copolymerized.

Therefore, it can be copolymerized with an acrylic monomer having a conjugated double bond such as styrene, alkyl acrylate, or alkyl methacrylate. The homopolymers or copolymers obtained by polymerization can be used as paints, adhesives, and resins for plastics. Functional parts are C, N
-It has diacylamide bonds, and has high intermolecular cohesive force and high ability to form intermolecular hydrogen bonds. Therefore, the polymer obtained by polymerizing this compound becomes a tough and highly adhesive resin. Functional moiety C has a ketoester bond, and R can be easily changed to another substituent.

Therefore, monomers having different polarities, polymerization properties, solubility, functional groups, reaction properties, etc. can be easily obtained.

The compounds of the present invention serve as starting materials for various polymers as described above, but they can also be used as intermediates for various medicines, agricultural chemicals, chemical reagents, and the like.

(Example) Hereinafter, specific embodiments of the present invention will be described with reference to Examples.

Example 1 Benzene 288.5zQ and methacrylamide 49.19<0.577 mol) were charged into a reaction vessel equipped with a stirrer, a cooler, a nitrogen gas inlet and a dropping funnel,
The resulting mixture was heated to reflux.

Reflux and nitrogen bubbling were continued while 78.59 (0,577 mmol) of ethoxyl chloride was added dropwise thereto for 2.5 hours. After the addition was completed, reflux was continued for 5 hours. Benzene was distilled off, hydroquinone was added thereto, and vacuum distillation was performed to obtain N-ethoxydylmethacrylamide 485.
I got a 9. Yield 43%1. Far East 110-115°C1
0.3 shoulder strike tg, refractive index 1.473 Inν 3300 (NH), l 760 (C=C),
1720 (C=C), +690 (C=C), l640
(C=C), l l 90 (C-0), l I 60 (
C-0), 1120 (C-0), l l 00 (C-
0) cx-' Example 2 In the same reaction vessel as in Example 1, ethoxyl chloride 1
2.31? (0.09 mol) and the reaction vessel was cooled in a water bath. A solution of methacrylamide (7.79C0.09 mol) in 32.4zQ chloroform was added dropwise thereto over a period of 10 minutes. After the addition is complete, a mixture of 7.29 (0.09 mol) of pyridine and 10RQ of chloroform is added dropwise to the bottom.
The resulting mixture was stirred at room temperature for 1 hour. The reaction mixture was shaken with chloroform 5002Q and water 500z (the chloroform layer was separated and dried over anhydrous magnesium sulfate, then the chloroform was removed. 0.01 g of hydroquinone was added thereto and vacuum distillation was performed to obtain N-
5.39% of ethoxyl methacrylamide was obtained.

Yield 32%.

Example 3 In the same reaction vessel as in Example 1, ethoxyl chloride 1
2.3 g (0.09 mol) was charged and the reaction vessel was cooled in a water bath. Chloroform90. A solution of 20.39 (0.24 mol) methacrylamide in OxC was added dropwise thereto over a period of 30 minutes. The mixture was then stirred at room temperature for 3 days. The reaction mixture was shaken with 500 ml of chloroform and 500 ml of water, the chloroform layer was separated and dried over anhydrous magnesium sulfate, then the chloroform was removed. 0.019 of hydroquinone was added thereto and vacuum distillation was performed to obtain 4.89 of N-ethoxyl methacrylamide.

Yield 29%.

Example 4 In the same reaction vessel as in Example 1, toluene 20:n(I and methacrylamide 2,1y (0,025 mol)) were charged and the resulting reaction mixture was heated to 90°C. Benzyloxalyl chloride After completing the 10 minute dropwise addition of 509, the resulting mixture was bubbled vigorously with nitrogen gas and then
The mixture was stirred at 0°C for 4 hours. The reaction mixture was diluted with chloroform
The organic phase was separated and dried over anhydrous magnesium sulfate, then the toluene and chloroform were removed under reduced pressure. The obtained product was purified by gel chromatography to obtain 2.9 g of N-penzyloxalyl methacrylamide as a colorless, transparent viscous liquid.

IRν: 3350 (NH), 1750 (C=C), +
730 (C=C), + 690 (C=C), 1630
(C=C), 1500 (N-H1 modification), 695 (C-
H1 variant) C shoulder-1 Example 5 In the same reaction vessel as in Example 1, ethanol 230°49 (
5,0 mol) and pyridine 39.6 g (0°5 mol)
was charged and the reaction vessel was cooled to 00C in a water bath. 2-isopropenyloxazoline-4,5-noone hydrochloride 87
．． 89 (0.5 mol) was added dropwise thereto for 30 minutes while stirring and maintaining the reaction temperature at 0-10°C. After the addition was complete, excess ethanol was removed under reduced pressure. The reaction mixture was shaken with ethyl acetate 1000, wC and plenty of water, the ethyl acetate layer was separated and dried over anhydrous magnesium sulfate, then the ethyl acetate was removed. 0, Qlg of hydroquinone was added thereto, and vacuum distillation was performed to obtain 30.59 of N-ethoxyl methacrylamide.

Yield 33%.

Example 6 In the same reaction vessel as in Example 1, benzyl alcohol 27
．． 09 (0,25 mol) and pyridine 409 (0,0
5 mol) and the reaction vessel was cooled to 0°C in a water bath. 2-isopropenyloxazoline-! 8.8 g (0.05 mol) of 1,5-dione hydrochloride was added dropwise thereto for 30 minutes while stirring and maintaining the reaction temperature at 0-10°C. After the addition was complete, excess benzyl alcohol was removed under reduced pressure. The reaction mixture was diluted with 300% chloroform. x12 and water 1000. The chloroform layer was separated and dried over anhydrous magnesium sulfate, then the chloroform was removed. The residue was purified by silica gel chromatography to obtain 3.99% of N-benzyloxalyl methacrylamide as a colorless, transparent viscous liquid.

Yield 32%.

Example 7 In the same reaction vessel as in Example 1, phenol 23°59 (
0.25 mol), 4.0 y (0.05 mol) of pyridine and 25.09 y of ethyl acetate and the reaction vessel was cooled to 10° C. in a water bath. 2-isopropenyloxazoline-
8.89 (0.05 mol) of 4,5-dione hydrochloride was added thereto for 30 minutes while maintaining the reaction temperature at 10-20°C with stirring. After the addition was complete, ethyl acetate and phenol were removed by vacuum distillation. The reaction mixture was shaken with 300 m of benzene (and 1000 x Q of water, the benzene layer was separated and dried over anhydrous magnesium sulfate, then the benzene was removed. The residue was purified by silica gel chromatography to give N-phenyloxalyl methacrylamide 2 .59 was obtained as a white powder.

Yield 21%, melting point 83-85°C.

IRν・3250(NH), 3180(C-1(),
+ 785 (C-0), 1725 (C-0), 1690
(C=O), 1650(C=C), I48'O(C
-1-(.

Variation), 690 (C-)t, Variation) O "1 Example 8 In a reaction vessel similar to that used in Example 1, !, 32.59 (0° 25 mol) of 2-hydroxyethyl methacrylate.
, pyridine 4.09 (0.05 mol) and chloroform 3009 and the reaction vessel was cooled to 10° C. in a water bath. 8.8 g (0.05 mol) of 2-isopropenyloxazoline-4,5-dione hydrochloride was added thereto for 30 minutes with stirring while maintaining the reaction temperature at 10-20°C. After the addition was complete, the resulting mixture was stirred at room temperature for 2 hours.

The reaction mixture was diluted with 500R of chloroform & 1000R of water.
After shaking for 5 minutes with sake, the chloroform layer was separated and dried over anhydrous magnesium sulfate, and then the chloroform was removed. The residue was purified by silica gel chromatography to obtain 3.49% of N-[(2-methacryloyloxyethyl)oxalyl]methacrylamide as a colorless, transparent viscous liquid.

Yield 25%, refractive index 1.490°IRν: 3370 (NH), 1170 (C=C), 1
760 (C=C), l 730 (C=C), 1700 (
C=C), 1640 (C=C), l 500 (C-H.

Variation), 1160 (C-0, variation) c+y-' Example 9 In a reaction vessel similar to that used in Example 1, 13.59 C0.05 mol of stearyl alcohol, 4.09 mol of pyridine were added.
(0.05 mol) and ethyl acetate 13o,o9 and the reaction vessel was maintained at 20°C in a water bath. 2-isopropenyloxazoline-4゜5-dione hydrochloride 8.89 (
0.05 mol) was added thereto for 30 minutes with stirring while maintaining the reaction temperature at 20-30°C. After the addition is complete,
The resulting mixture was diluted with 300 ml of chloroform and 1 ml of water.
After shaking with 000x & for 5 minutes, the chloroform layer was separated and dried over anhydrous magnesium sulfate, then the chloroform was removed. The residue was purified by silica gel chromatography to obtain 08 g of N-stearyloxalyl methacrylamide as a white solid.

Yield 4%, melting point 67-70°C IRν: 3300 (NH), 2950 (C-) 1),
1820 (C=C), 1765 (C=C), 1720 (
C=O), 1470 (C-H, deformed), 1170 (C
-〇, variant) cx-1 Example IO In a reaction vessel similar to that used in Example 1, methanol 16
09 (5 mol) and pyridine 39.69 (0.5 mol) and the reaction vessel was cooled to 0°C in a water bath. 2-
Isopropenyloxazoline-4,5-dione hydrochloride 8
7.89 (0.5 mol) was added dropwise thereto for 30 minutes while stirring and maintaining the reaction temperature at 0-10°C. After the addition was complete, excess methanol was removed by vacuum distillation. reaction,
The mixture was shaken with 30 d of ethyl acetate (I/j) and 1000 d of water, the organic layer was separated and dried over anhydrous magnesium sulfate, then the ethyl acetate was removed. The residue was purified by Norica gel chromatography, r- N-methoxalyl methacrylamide 16.19 was obtained as white crystals.

Yield 19%, melting point 48.0-49.5℃ IRν 330
0(N-1(), l 760(C=C), 1740(
C-0), 1695 (C=C), 1640 (C=C
), 1500 (N-H, modified) C "1 Example 11 By the same method as in Example IO, n-butanol 148
．． 29 (2 mol), pyridine 15.89 (02 mol) and 2-isopropenyloxazoline-4,5-dione hydrochloride 35.19 (0.2 mol), , 3 g as a colorless liquid. Yield 3%, reflectance 1.4693 IRν・3300 (NH), 1760 (C=C), 1
730 (C=C), l 695 (C=C), 1635 (
C=C), 1500 (N-H, deformation) ci-' Example 12 Allyl alcohol 87
．． 19 (I, 5 mol), pyrinone 11.99 (0,15
mole) and 2-isopropenyloxazoline-4,5
- using 26.39 (0.15 mol) of dione hydrochloride, N
- 46 g of allyloxalyl methacrylamide was produced as a colorless liquid. Yield 16%, reflectance 1.4931 1Rν: 3300 (NH), l 760 (cmo),
1730 (C=0), 1695 (C=C), 1650 (
C=C), 1 6 3 5(C=C), 1
500 (Sai-H.

Variation) C11-1 Example 13 By the same method as in Example 10, propargyl alcohol 84.19 (I, 5 mol), pyridine 11.99 (0
, 15 mol) and 2-isopropenyloxazoline-
Using 26.39 (0°15 mol) of 4,5-dione hydrochloride, 4.0 of N-propargyloxalyl methacrylamide
9 was produced as white needle-like crystals. Yield 14%, melting point 3
6.5-38.0°C.

IRν: 3450 (C=CH), 3300 (N-1-1
), 2150 (C=C), 1770 (C=C), 174
0 (C=C), 1695 (C=C), 1640 (C=C
), 1500 (N-H1 variant) CI-'Example 14 In a reaction vessel similar to that used in Example 1, 2-propatol+89 (0.3 mol) and dioxane 200tC
and the reaction vessel was heated to 75°C in an oil bath. Metallic sodium (3.49 CO, 15 mol) was added dropwise thereto with stirring. After the consumption of metallic sodium was completed, the reaction system was cooled to 10° C. in a water bath. 2-isopropenyloxazoline-4゜5-dione hydrochloride 26.39 (0,1
5 mol) therein for 30 minutes, with stirring at a temperature of 0-10
The mixture was added while maintaining the temperature at °C. After the addition was complete, the reaction mixture was shaken with 301)+ g of ethyl acetate and 1000++2 g of water, the organic layer was separated and dried over anhydrous magnesium sulfate, then the ethyl acetate was removed. The residue was purified by silica gel chromatography to obtain 1.59% of N-isoproboxalyl methacrylamide as a colorless, transparent liquid. Yield 5%, reflectance 1467.1 1 Itton: 3300 (N-)-1), 1760 (C=
C), 1740 (C=C), 1695 (C=C), 16
40 (C=C), l 500 (NH, deformation) cm
-'Example 15 In a reaction vessel similar to that used in Example 1, tetrahydrofuran lOOλQ and potassium t-butoxide l 1
．． 29 (0.1 mol) was charged at room temperature.

To the mixture, 8.59 (0.1 mol) of methacrylamide were added at room temperature, followed by 14.69 mol of diethyl oxalate.
(0.1 mol) was added dropwise. The reaction mixture turned into a white paste with a slight exotherm. The mixture was stirred at room temperature for 3 hours, then 100x ethanol (and 6.09x acetic acid) was added.
(0.1 mol) was added.

The precipitate was filtered and 200i17 of water was added thereto.

The separated organic phase was concentrated under reduced pressure to give N,N'-
Bis(l-oxo-2-butenyl)ethanediamide 5.49 was obtained. Yield 48.3%, melting point 159-160°C I nν: 3250 (NH), I 720 (C=C)
, 1690 (C=C), l 670 (C=C), 162
5(C=C)cx-' Example 16 Sodium hydride 2.09<60% in oil, 50 mmol) was washed with diethyl ether and diluted with diethyl ether 20
1e. To the resulting suspension, 4.35 g (50 mmol) of methacrylamide was added to the resulting suspension, followed by stirring for 30 minutes. 8.759 (50 mmol) of 2-isopropenyloxazoline-4,5-dione hydrochloride were added thereto and the resulting mixture was stirred for 1 hour and then carefully poured into water. The precipitate was collected by filtration and washed with acetone to obtain 50% N,N'-bis(l-oxo-2-butenyl)ethanediamide. Yield 0.4% Example 17 Into a reaction vessel similar to that used in Example 1, 50xQ of tetrahydrofuran, 4.269 (50 mmol) of methacramide, and 6°83 g (50 mmol) of ethoxalyl chloride were charged. The mixture was heated to reflux for an hour. The organic solvent was distilled off under reduced pressure to obtain 6.59 g of N-ethoxalyl methacrylamide. Yield 70.6%.

Reference example 1 Cellosolve acetate 1509 and butyl acetate 25.09
A mixture of N-ethoxalyl methacrylamide 8, 89 and methyl methacrylate 8 was added to the mixture held at 100°C.
．． 89, styrene t2. U, 2-hydroxyethyl methacrylate 11.89, r+-butyl acrylate 8.
A mixture of 29 and 1.09 of azobisisobutyronitrile was added dropwise over 2 hours. After finishing dropping, add azobisisobutyronitrile 059 and cellosolve acetate 100g
The mixture was added dropwise over 30 minutes and aged for 3 hours to obtain a pale yellow reaction mixture containing a polymer. Non-volatile content 50%. Molecular weight (measured by gel permeation chromatography (GPC)) 7,700° Reference example 2 Cellosolve acetate 15.09 and butyl acetate 25,0
A mixture of 8.g of N-ethoxalyl methacrylamide and 8.g of methyl methacrylate was maintained at 100°C.
8g, styrene 6.99, methacrylic acid 11.89, n
A mixture of 13.79 g of -butyl acrylate and 1.09 g of azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, a mixture of 0.59% of azobisisobutyronitrile and 10.09% of cellosolve acetate was added dropwise over 30 minutes, and aging was performed for 3 hours to obtain a pale yellow reaction mixture containing a polymer. Non-volatile content 50%. Molecule 1k (
Measured by GPC) 3.900° Reference Example 3 A mixture of cellosolve acetate 5.09 and butyl acetate 3.89 was kept at 100°C, and N-ethoxalyl methacrylamide 7.59 and cellosolve acetate 7.5
A mixture of g and 0.159 g of azobisisobutyronitrile was added dropwise over 2 hours.

After completion of the dropwise addition, a mixture of 0.079% of azobisisobutyronitrile and 6.29% of cellosolve acetate was added dropwise over 30 minutes, and aging was performed for 3 hours to obtain a pale yellow reaction mixture containing a polymer. Non-volatile content 19%. Molecular weight (G
Measured by PC) 3.500° Reference Examples 4 to 12 A mixture of 1.639% dioxane and 0.709% butyl acetate was maintained at 100°C, and N-(substituted othuryl)alkylacrylamide (I) 1 .009 and azobisisobutyronitrile 0.019 were added and stirred at the same temperature for 3 hours. Table 1 shows the obtained polymer and its physical properties.

Reference Examples 13-21 A mixture of dioxane 1.639 and butyl acetate 0.709 was held at 100°C, and N-(substituted oxalyl) was added to it.
Alkylacrylamide (I) 0.339, methyl methacrylate 0.339 and azobisisobutyronitrile 0019 were added and stirred at the same temperature for 3 hours. Table 1 shows the obtained polymer and its physical properties.

Table 1 CIll・C(C11,)-C(=O)-Nil-C(
=O)-C(・0)-OR' (lR=cH,)Reference example N-(substitution j 4! 11l) Non-volatile content
Molecular weight My/Mn number Full N-ruacryl 7mide (%) (Mn
) (I:R=CI+3)(R”) Honanabon0sv-4-C1ls
20. Q 3.540
3.285 -(CIl, ), CIl3
16.8 3.970
13.136 -CIl, Cl1=CI
+, 22.4 4°93
0 4.207 -CIl, CmiCI
+ 20.1 6.350 28
08/C11・16・92・5501・9
7-CIl\. H3 12-CIl, C1l□oc-c=co,
(Cellification generation) 0 C1+.

(continued) Reference example N- (substituted 01 duck) Non-volatile content Molecular weight
Mv/Mn number Alkylacrylamide (2) (N) (I:
R=CH3XR') Komoto Rimer 13 ~ CI1.
Ht, 4
5.790 2.8514
-(CIll)ICI+3 18.0
6.190 2.5415
-C1l, CH: (Jlt
15.3 g, 370 2.9
216 -C1l, C=CII
15.1 7.580
2.9121 -CIl,CII,QC-C=C
11, (Cellification generation)ll OC1+.

Reference Example 22 Using a percoater, the polymers obtained in Reference Examples 3.6.7, 1O and 11 were applied onto a tin plate, and then 10
It was heated at 0° C. for 3 hours to obtain a coating film with a thickness of 20 μm. A pencil hardness test was conducted on the paint film (maximum hardness without peeling).
, the results are shown in Table 2.

Table 2 -CHIC2CH7tlB -C, l-1, 3! (B -CH2CH=CH,6HB Patent applicant Nippon Paint Co., Ltd.

Claims (1)

[Claims] 1. Formula (I): CH_2=CR-CO-NH-CO-CO-OR' (in the formula, R represents a lower alkyl group and R' represents a hydrocarbon group)
N-(substituted oxalyl)alkylacrylamide represented by: 2. N-(substituted oxalyl)alkyl according to claim 1, wherein the hydrocarbon group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an unsaturated group-substituted oxyalkyl group Acrylamide. 3. α-Lower alkyl acrylamide and formula (II) X-C
Formula (I): CH_2=, which is characterized by reacting an oxalyl monohalide monoester represented by O-CO-OR' (in the formula, R' is a hydrocarbon group and X is a halogen atom). C
N represented by R-CO-NH-CO-CO-OR' (in the formula, R represents a lower alkyl group. R' has the same meaning as above)
- A method for producing (substituted oxalyl)alkyl acrylamide. 4. The production method according to claim 3, wherein the reaction is carried out in the presence of a hydrogen halide scavenger. 5, α-lower alkyl acrylamide and formula (III)
Oxalyl dihalide represented by CO-CO-X (in the formula, X represents a halogen atom) is reacted with the formula (IV): An oxazolinedione hydrohalide represented by the formula (V): R'-OH (wherein R' represents a hydrocarbon group) is prepared. ): CH
_2=CR-CO-NH-CO-CO-OR' (in the formula,
R and R' have the same meanings as above. ) A method for producing N-(substituted oxalyl)alkylacrylamide. 6. The production method according to claim 5, wherein the second stage reaction is carried out in the presence of a hydrogen halide scavenger. 7. α-Lower alkyl acrylamide and formula (IV) R′O
-CO-CO-OR' (wherein, R' represents a hydrocarbon group) is reacted with an oxalyl diester of the formula (
I): N-(substituted oxalyl)alkylacrylamide represented by CH_2=CR-CO-NH-CO-CO-OR' (in the formula, R represents a lower alkyl group. R' has the same meaning as above) manufacturing method. 8. The production method according to claim 7, wherein the reaction is carried out in the presence of a hydrogen halide scavenger. 9. Formula (VII): (CH_2=CR-CO-NH-CO-)_2 (in the formula,
R represents a lower alkyl group. ) N-(substituted oxalyl)alkylacrylamide represented by: