JPS6345245A - N-(substituted oxalyl)acrylamide and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is hydrocarbon group). EXAMPLE:N-(3-chloropropionyl)aminooxalyl chloride. USE:A monomer for the synthesis of polymer. An intermediate for pharmaceuticals, agricultural chemicals, chemical reagents, etc. PREPARATION:The compound of formula I can be produced by reacting acrylamide with an oxalyl monohalide monoester of formula II (X is halogen). The reaction is carried out in an inert solvent (e.g. benzene, toluene, etc.) in the presence or absence of a basic substance (e.g. potassium ethoxide) at a temperature between about 20 deg.C and the refluxing temperature. A tough and highly adhesive resin can be produced by the polymerization of the compound of formula I. Monomers having various polarity, polymerization characteristics, solubility, functional groups and reaction characteristics can be easily produced by this process.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to N-(substituted oxalyl)acrylamide and a method for producing the same, and particularly relates to N-(substituted oxalyl)acrylamide, which has excellent reactivity and is useful as a monomer for producing a polymer, and which has the formula (I): CH ,=CH-CO-NH-
The present invention relates to N-(substituted oxalyl)acrylamide represented by CO-CO-OR (wherein R represents a hydrocarbon group) and a method for producing the same.

(Conventional technology) Formula (A)・ CH,=CH-C0NH.

Acrylamide represented by is useful as a raw material for producing various functional derivatives. For example, by converting this into oxalyl civalide, acryloylisonanate represented by the formula (B): CIl, =CH-CO-NC0 can be obtained (
JP-A No. 60-115557), this compound has an ethylenic double bond and an isone-anato group, so it can participate in various reactions. The object substance of the present invention was developed in an attempt to develop a new use by deriving acrylamide (A) from acrylamide (A) with the existing ethylenic double bond intact and developing a new use for it. ) Regarding N-ethoxalyl acrylamide, which is acrylamide (I) and is R-ethyl, European Patent Application No. 0020000 describes the reaction of acrylamide and oxalyl ethyl or ethoxalyl chloride in the presence of potassium t-butoxide. There is a description that the substance can be produced together with N,N-bis(ethoxalyl acrylamide) by stirring the mixture of these reagents at room temperature for 1 to 5 days; There is nothing disclosed about detailed reaction conditions or physicochemical properties of the product.

When the present inventors reexamined the description in the above-mentioned European Application Specification, it was found that if specific reaction conditions not disclosed therein were adopted, it was possible to generate N-ethoxalyl acrylamide, but this was not the case. We confirmed that it is difficult to produce this substance, and that it is impossible to produce N,N-bis(ethoxalyl acrylamide) even if the reaction is carried out under various reaction conditions. did.

(Objective of the Invention) The present invention aims to industrially advantageously and reliably provide N-(substituted oxalyl)acrylamide (I), which can be called a substantially new substance, starting from acrylamide (A). be.

(Structure of the Invention) According to the present invention, N-(substituted oxalyl)acrylamide generally represented by the formula (I) is advantageously and reliably provided, but N-ethoxalyl in which <R=ethyl as described above is provided. Although there is some mention of acrylamide in the European Application Specification, no literature can be found that mentions other compounds. Therefore, N
-(Substituted oxalyl)acrylamide (I) is considered to be a new substance except for N-ethoxalyl acrylamide.

In N-(substituted oxalyl)acrylamide (I), the substituent R represents a hydrocarbon group. Examples of such hydrocarbon groups include alkyl groups (especially lower alkyls such as methyl, ethyl, propyl, butyl), alkenyl groups (especially lower alkenyls such as allyl and butenyl), alkynyl groups (especially lower alkenyls such as allyl and butenyl), and alkynyl groups (especially lower alkenyls such as allyl and butenyl). lower alkynyl)
, nocroalkyl groups (especially cyclolower alkyls such as pentyl and hexyl), aryl groups (especially phenyl),
Aralkyl groups (especially phenyl lower alkyls such as benol and phenethyl), unsaturated group-substituted okynealkyl groups (
In particular, lower alkenyloxy (lower alkyl) such as allyloxyethyl. Here, "lower" generally means a group having 8 or less carbon atoms, preferably 5 or less carbon atoms. Note that 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.

According to the present invention, N-(substituted oxalyl)acrylamide (
The following various methods can be employed to produce I).

Acrylamide (A) and formula (■): X-CO-CO-OR (wherein, A method via reaction with oxalyl monohalide monoester.

The above reaction is carried out in a suitable inert solvent in the presence or absence of a basic substance at a temperature of about 20 to reflux.

The molar ratio of acrylamide (A) and oxalyl monohalide monoester (II) used in the reaction is approximately 10:l-
1:10, especially 5.1 to 1.5 is preferred. 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), ether (
For example, the solvent may be selected from diethyl ether, tetrahydrofuran, dioxane, etc.

When the reaction is carried out in the presence of a basic substance, usually
N-(substituted oxalyl)acrylamide (I) is formed directly. Basic substances are inorganic or organic basic substances (
For example, it may be selected from potassium ethoxide, potassium monobutoxide, triethylamine, trimethylaniline, and pyridine, and is usually used in an amount of about 1 equivalent or more relative to acrylamide (A). When charging the reactor, it is desirable to avoid direct contact between the oxalyl monohalide monoester (II) and the basic substance.
), and finally oxalyl monohalite monoester (II
), or one of acrylamide (A) and oxalyl monohalide monoester (II), then the other, and finally the basic substance.

When the reaction is carried out in the absence of a basic substance, first the formula (III)
N- represented by OR (wherein R and X have the same meanings as above)
(Substituted oxalyl)-halopropionamide is produced. This is then treated with a basic substance, preferably in an inert solvent, to yield the N-(substituted oxalyl)acrylamide (I). In this case, the processing conditions and the types of inert substances and basic substances may be the same as described above.

When carrying out the reaction in the absence of a basic substance,
When a hydrogen chloride scavenging substance other than a basic substance is used in the reaction system, or when a means to promote the elimination of hydrogen chloride is applied to the reaction system, N-(substituted oxalyl)acrylamide (I ) is not impossible to obtain as a direct result. As hydrogen chloride scavenging substance, for example, a large excess of acrylamide can be used. Further, as means for promoting hydrogen chloride desorption, reflux and blowing of an inert gas (for example, nitrogen) can be considered.

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.

Manufacturing method 2 Acrylamide (A) and formula (■).

A method via reaction with oxalyl civalide represented by x-co-co-x (wherein X has the same meaning as above).

This method first produces formula (■) by reacting acrylamide (A) with oxalyl civalide (IV).

X CHrCHt CO NHCO CO-X
(wherein, This is carried out by producing N-(i-substituted oxalyl)-herobronpionamide (I) and then treating it with a basic substance to produce N-(i-substituted oxalyl)acrylamide (I).

The first stage reaction is generally carried out in an inert solvent at about -20 to 80
It is carried out at a temperature of 0 to 20 °C, preferably 0 to 20 °C. The molar ratio of acrylamide (A) and oxalyl civalide (IV) used in the reaction is usually about 1=1 to 3, preferably about 1.
:1-1.5. The inert solvent 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.
One selected from 2-dichloropropane, 1,4-dichlorobutane, chlorobenzene, ethylene tetrachloride, ethylene trichloride, etc. is used.

The second stage reaction is carried out at a temperature of about -30 to 40<0>C with or without an inert solvent. The molar ratio of N-(substituted oxalyl)-halopropionamide (V) and alcohol (■) used in the reaction is usually about 1.
．． 1 to 20, preferably about 1:5 to 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. In addition, alcohol (Vl), which is a reaction reagent,
Since it 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.

The third stage reaction is carried out in the presence or absence of an inert solvent, about -
Preferably, the temperature is 20 to 80°C, particularly 0 to 40°C. Basic substances include inorganic or organic bases, such as potassium etquinide, potassium t-butquine, triethylamine,
It may be appropriately selected from dimethylaniline, pyridine, etc. Since the third stage reaction is carried out subsequent to the second stage reaction, it is not necessary to add an inert solvent when carrying out the third stage reaction. If an inert solvent is added, it may be selected from hydrocarbons, halogenated hydrocarbons, ethers, and the like.

A method involving a reaction between acrylamide (A) and an oxalyl diester represented by the formula (■): RO-CO-CO-OR (wherein R has the same meaning as above).

The above reaction must be carried out in the presence of a basic substance, but except for this, the reaction of Production Method I, that is, the reaction between acrylamide (A) and oxalyl monohalide monoester (It
) may be carried out under essentially similar conditions to those employed during the reaction. The basic substance may be appropriately 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, which may be appropriately selected from hydrocarbons, halogenated hydrocarbons, ethers, alcohols, etc. Oxalyl diester (■
) may be used in excess.

The reaction results in ζN-(substituted oxalyl)acrylamide (
I) is produced as a direct product, but depending on the reaction conditions, in addition to it, the formula (~1) (Ctlz=CI-I
N-(substituted oxalyl)acrylamide represented by CONHCO )t may be produced as a by-product, and sometimes this N
-(a-substituted oxalyl)acrylamide (Xl) may be the main product.

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.

In addition, the above N-(substituted oxalyl)acrylamide (■
) is N-(substituted oxalyl)-halopropionamide (
) was reacted with acrylamide (A), and the obtained formula (
IX): (X CH=CHt CO NHC
It can also be produced by treating O 2 )2 (wherein X has the same meaning as above) with a basic substance. In addition, in this case, the first reaction involves aromatic hydrocarbons,
It is preferably carried out in an inert solvent selected from ethers and the like at temperatures of about 0 to reflux, especially 0 to 20°C. Further, it is desirable that the subsequent treatment is similarly carried out in an appropriate inert solvent selected from hydrocarbons, ethers, esters, etc. at a temperature of 0 to reflux. Basic substances are potassium ethoxide, potassium t
-butoxide, triethylamine, trimethylaniline,
It may be appropriately selected from inorganic or organic bases such as pyridine. Recovery and purification of the reaction product from the reaction mixture may be carried out by conventional methods as described above.

N-(substituted oxalyl)acrylamide (■) also has two ethylenic double bonds in its molecule, so it is useful as a monomer for polymer synthesis.

Among the various production methods disclosed above, from the viewpoint of the yield of the target compound, the preferred method is to use production method 1 to prepare acrylamide (A).
and oxalyl monohalide monoester (II) in an inert solvent in the absence of a basic substance to produce N-(substituted oxalyl)-halopropionamide (I[[), which was then converted into a basic It is a method of processing substances. In the first reaction of this method, if an inert solvent with a relatively high dielectric constant (e.g., tetrahydrofuran) is used, N-(substituted oxalyl)-halopropionamide (V) is preferentially produced; The use of an inert solvent with a low dielectric constant (for example, hexane/tetrahydrofuran (5/1 volume ratio)) increases the rate of N-(substituted oxalyl)acrylamide (In) formation. It is generally preferred that the inert solvent be selected from halogenated hydrocarbons and ethers. The basic substance used in the subsequent treatment may be appropriately selected from inorganic or organic bases such as potassium ethoxide, potassium t-butoxide, triethylamine, dimethylaniline, and pyridine. The use of relatively weak salt bridges is preferred. The use of relatively strong bases, such as potassium ethoxide and potassium ethoxide, is effective in reducing acrylamide (A) and oxalyl monohalide monoester (n
) should be done after the reaction is completed.

(Effect) The N-C1 & substituted oxalyl) acrylamide (D
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 acrylic monomers having conjugated double bonds such as styrene and alkyl (meth)acrylates. The homopolymers or copolymers obtained by polymerization can be used as paints, adhesives, and resins for plastics. The functional part has a C,N-diacylamide bond, and has a high intermolecular cohesive force and a high ability to form an intermolecular hydrogen bond. Therefore, the polymer obtained by polymerizing this compound is 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 Oxalyl chloride 1279 (I mol) was added dropwise to a solution of 71 g (I mol) of alkylamide in methylene chloride 2009 over a period of 30 minutes under water cooling. After the addition was completed, the reaction mixture was cooled to room temperature to obtain a 50% solution of N-(3-chloropropionyl)aminoxalyl chloride.

Example 2 Into a solution of 100 m of methylene chloride and 13.89 (0.3 mol) of ethanol in medium, 00 g of methylene chloride I (0.25 m
A 50% solution of N-(3-chloropropionyl)aminoxalyl chloride in mol) was added dropwise at a temperature below 25° C. for 30 minutes with stirring. After completion of the dropwise addition, the precipitated solid was filtered off, and the solvent was evaporated under reduced pressure. The obtained product was purified by silica gel column chromatography and recrystallized from benzene and hexane to obtain colorless prism-like crystals of N-ethyloxalyl-3-chloropyropionamide 41.59. Yield 80%. Melting point 79-80°C.

IRν: 3350 (NH), 1790 (C=O), +
760 (C=O), + 740 (C=O), 1500
(N-H1 variant) cr' Example 3 To 41.59 (0.2 mol) of N-ethyloxalyl-3-chloropropionamide in benzene was added 20.29 (0.2 mol) of triethylamine, and the resulting The mixture was stirred at room temperature for 30 minutes.The precipitated salt was filtered off.
The solvent was evaporated under reduced pressure. The resulting product was purified by silica gel column chromatography to obtain a white solid N.
-29.59 ml of ethyloxalylamide was obtained.

TLCRf=0.54 (mel'7t・'T-t(I4e
rck Art ) 580 B (trademark);
Developing solvent, hexane/ethyl acetate = l/l (volume) IR
ν: 3300 (N-H), l 770 (C=O), 17
40 (C=O), +700 (C=0), 1630 (C=
0), +490 (N-H, modification) cz-' Examples 4 to 7 The type and amount of alcohol and the amount of N-(3-chloropropionyl)aminoxalyl chloride solution were varied by the same method as in Example 2. The products shown in Table 1 were obtained.

Table 1 Example 1 Alcohol N-(3-11 units) Product Quantity Yield Melting point number Quantity (9, mol)
propionyl)
(9) (ren (°C) aminooxalyl chloride ff1 (y: mol) 4 7 lylufurcol too (
0,25) N-7 Lireololyl 7.2
13 5O-52 (I7,4:0.3)
3-ri no 7' n dionamide 5 7° loval 1' too (0,
25) N-7° [IA'le 4'4 5.0
9.2 85-Alcohol
ololyl 3-chloro
865 (I6,8+0.3)
7” adione amide 6
2-shido a4zoxchill too(0,2
5) 11-2-human aqno 4.0
5.4 Oily methacrylate
fjvJ9 Kurilo N No. Lil (39,0:Q,3)
3-ri τ107°a5” onamide 7 to 1 sol alcohol +00(
0,25) N-hetsuno9ru 2.7
4.0 106-(32,4:0.3)
O-A-suru 3-chloro
107 F'[l Pion 7 Mido Example 8 To a solution of 6.09 (0.25 mol) of sodium hydride in tetrahydrofuran was added phenol (
A solution of 23,59,0,25 mol) was added.

After cooling at room temperature, 50% of N-(3-chloropyropionyl)aminooxalyl chloride 1009 (0.25 mol)
% methylene chloride solution was added thereto. After 30 minutes, the reaction mixture was extracted three times with 300 mQ of deionized water. The organic layer was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the resulting brown oil was then crystallized from a mixture of hexane and benzene to yield 26 g of N-phenyloxalyl-3-chloropropionamide. . Yield 10.0%. Melting point 95-96°C.

Examples 9-13 Using a method similar to Example 3, varying the type of amide and solvent and the amount of amine and triamine, the products shown in Table 2 were obtained.

Table 2 Implementation 7mm)')llxChill Solvent Product Amount Yield Melting point example ma9: Mol)
7min amount (9:mol)
(9) (%) (”C) Number 9 N-7 Riluo 10
Henoseen N-7 Lil 1.
8 91 42-A 3- (
0, Ol)
435 black o7' a
Akukamo 7 Midohinamide (2,3:0.01) 10 Door to Exit 10 Henosen N-7180 0.8 4
4 +02-A゛LuoN call krill (0,0
1) 4' Luo A Lil
1033-Chlorobu o
7 krill 1
Midopion 7mid (2.3:0.0+) II N-(2-human u 1.0
to “7th century N-2 (2-t)”u
2.2 85 Oily A Noethylmethacrylic ([1.Ql) 4Noethylmethacrylic)oxalyl)
Oxalyl acrylic 3-g11[I7°αE°
Amidone (2.3+O.Ol) 12 N-henol 1 0
2.2
94 88-ollu3-
(0.Ql) Oxalyl
89 black 07°0 pion 7 grill 7 mid 7 mid (2.7; 0.01) 1 3 N-7r nyl 1.0
N-7X Nyl acetate No. 4 1.
7 79 99-oxalyl
(0.01) Ethyl Acrylamide 1003-Lien7''n Bionoamide (2.6:0.01) Examples 14 to 18 The type and amount of acid chloride and acrylamide were determined in the same manner as in Example 2. By varying the amount of , the products shown in Table 3 were obtained.

Table 3 Example 1 Acid/Iride Acrylic 1mide Product 9 Yield number Amount (9: mol) Mound (9; not)
(ri)(t)1 =I
N-711 Lua 41 Kamo 3.6 (0,05)
N-7 lyloroli&4.44[1 chloride
3-ri 0 lower 0 mouth E
1 on (7,4+0.05)
7 middle l 5! l-7° [
IA' + 4" le 3.6 (0,05) N
-7'l Pal A'le 54 5゜1～Risk 11 Ride 1
0ril3-rinn.

(7,3:0.05)
7° dionamide 16 2-human nhxft
v 3.6 (0,05) N-(2-human o
4) 6.27 43 Methacrylic iA Ryl Ethyloxalyl [1 Ride
Ofunesu)-3-(I1,0:0.05)
rido7"at"on7
Mid 1 7 to R'1ttNsk 3
．． 6 (0,05) N-Hen'no" 111
4.3+ 55 chloride
3-Chloro 7° at”one 7 mido (9,9:0.05) 18 F □ Niluo A1 lyl 3.6 (
I), 05)! l-7! Nilo A Lil
1.66 32ri [1 light''
3-Chlo117'ropion (
9,2;0.05)
Amide Example 19 In a reaction vessel equipped with a stirrer, thermostat, nitrogen gas inlet and dropping funnel, tetrahydrofuran 502
Q and potassium monobutoxide 5.619 (50 mmol) were charged at room temperature. 3. Add acrylamide to the mixture.
559 (50 mmol) and noethyl oxalate 7
．． 319 (50 mmol) was added dropwise thereto in 5 minutes and the reaction mixture turned into a pale yellow paste. The resulting mixture was stirred at room temperature for 30 minutes and diluted with diethyl ether 5
0xQ and 3.09 (50 mmol) of acetic acid were added thereto, the precipitate was collected by filtration, washed with water and acetone and purified with N
.

2.09 of No-bis(!-oxo-2-propenyl)ethanediamide was obtained as a white solid. Yield 4% (based on starting amide). 230-240 according to melting point measurement
It gradually became transparent (indistinct) at a temperature of °C.

"C-NMR (do-DMSO): C
I, =CII-C(=O)-N(-11)-C(=
0)-C(=0)-N(-11)-C(=O)-CII
=CI+.

(ppm) (a) 164.90 (b) 164.66 (c) 132.06 (d) 128.90 IRν: 3450.3250 (N-) [), 3200,
+764 (C=O), 1734 (C=O), 1734 (
C=O), 1618 (C=C)CI-' from the filtrate,
N-ethoxarylacrylamide 0°869 was recovered by column chromatography using a mixture of ethyl acetate and hexane as a developing solvent.

Example 20 In a reaction vessel equipped with a stirrer, thermostat, nitrogen gas inlet and dropping funnel, 50x tetrahydrofuran was added.
Q and 3.55 g (50 mmol) of acrylamide were charged. 6.589 (50 mmol) of chloroethyl oxalate was added dropwise thereto at room temperature over 10 minutes, followed by refluxing for 2 hours. The tetrahydrofuran was distilled off and the precipitated solid material was recrystallized from a mixture of benzene and hexane to give N-
Ethyloxalyl-3-chloropropionamide 6.1
I got 29. Yield 58.8%, melting point 79-80°C0 Example 21 Acrylamide in 100xij methylene chloride 14°29
(0.2 mol) was added with 50 parts of methylene chloride (in N-
(3-chloropropionyl)aminoxalyl chloride 39.69 (0.2 mol) was added dropwise at 25°C for 1 hour,
The resulting mixture was allowed to stand at room temperature for about 2 hours, then was heated overnight. The separated oily substance was shaken with 50zQ of water, and the precipitated crystals were collected and washed with acetone to obtain N,N'-
3.679 of bis(l-oxo-3-chloropropyl)ethanediamide was obtained. Yield 6.8% IRν: 3450 (N-) [), 3300 (N-H)
, 1750 (C=O), l 700 (C=O) cm
-'Example 22 N,N'-bis(I-oxo-
In a = m solution of 3.09 (II mmol) of 3-chloropropyl) ethanediamide, 2.829 (II mmol) of triethylamine was added.
28 mmol) was added and the resulting mixture was stirred at room temperature for 2 hours. The precipitated solid was collected and washed with water to give N,N'
-Bis(l-oxo-2-propenyl)ethanamide 0.19 was obtained. Yield 4.6%.

Example 23 In a reaction vessel equipped with a condenser, stirrer, thermostat and nitrogen gas inlet, 100 g of hexane, 20 x Q of tetrahydrofuran and 3.55 g of acrylamide (
50 mmol) and ethoxalyl chloride 6.83
9 (50 mmol), and the resulting mixture was refluxed for 4 hours while nitrogen gas was introduced therein. The generation of hydrogen chloride from the condenser was confirmed by using pl (test paper). After the reaction was completed, the solvent was distilled off to obtain N-ethoxalyl acrylamide and N-ethyloxalyl-3-chloropropionamide, each in a yield of 18. .7% and 27.8% (
(measured by NMR).

Reference Examples 1 to 5 1.009 of N-(substituted oxalyl)acrylamide (I) and 0.019 of azobisisobutyronitrile were added to a mixture of 1.639 of dioxane and 0.709 of butyl acetate maintained at 100°C, The resulting mixture was heated to 100
The mixture was stirred at ℃ for 3 hours. Table 4 shows the produced polymer and its physical properties.

Reference Examples 6 to 10 To a mixture of dioxane 1.639 and butyl acetate 0.709 maintained at 100°C, N-(substituted oxalyl)acrylamide (I) 0.339, styrene 0°339,
Methyl methacrylate 0339 and azobisisobutyronitrile o, o t9 were added and the resulting mixture was heated to 100
The mixture was stirred at ℃ for 3 hours. Table 4 shows the produced polymer and its physical properties.

Table 4 CIl, =C(H)-C(=0)-Nll-C(Tength 0)
-C(=0)-OR(I) Reference example N-(I conversion 74 yuan) Non-volatile content Molecular weight My/In number
Acrylamide (%)
(lin)=1 −
C, lI, 26.9
8.940 5.255
-CIl, Cl1=CIlt
24.5 4.560 3.50
9-C, II,
22.8 9.900
2.6910 -CIl, Cll=CH
120,710,5202,73 Reference Example 11 Using a bar coater, the polymers obtained in Reference Examples 1 to 5 were applied onto a tin plate, and then heated at 100°C for 3 hours to obtain a coating film with a film thickness of 20μ. Ta. The paint film was subjected to a pencil hardness test (maximum hardness without peeling) and the results are shown in Table 5.

Table 5 1, CI-1, Cm CH3HB -C1H548B -CH, CH=CH, 5HB Patent applicant Nippon Paint Co., Ltd.

Claims (1)

[Claims] 1. N-(substituted oxalyl)acrylamide represented by formula (I): CH_2=CH-CO-NH-CO-CO-OR (in the formula, R represents a hydrocarbon group) . 2. N-(substituted oxalyl)acrylamide 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 . 3. Acrylamide and formula (II): X-CO-CO-OR (In the formula, R is a hydrocarbon group and X is a halogen atom.)
oxalyl monohalide monoester represented by the formula (I): CH_2=CH-CO-NH-CO-CO-OR (wherein, R has the same meaning as above). A method for producing N-(substituted oxalyl)acrylamide. 4. Acrylamide and formula (II): X-CO-CO-OR (In the formula, R is a hydrocarbon group and X is a halogen atom.)
Oxalyl monohalide monoester represented by the formula (III) is reacted to form N represented by the formula (III): -(Substituted oxalyl)-halopropionamide is prepared and treated with a basic substance, formula (I): CH_2=CH-CO-NH-CO-CO-OR (wherein R has the same meaning as above.) A method for producing N-(substituted oxalyl)acrylamide. 5. Acrylamide and formula (IV): X-CO-CO-X (In the formula, R is a hydrocarbon group and X is a halogen atom.)
By reacting oxalyl dihalide represented by formula (V)
: X-CH_2CH_2-CO-NH-CO-CO-X (wherein, X has the same meaning as above) is prepared.
VI): R-OH (in the formula, R has the same meaning as above) to react with an alcohol represented by the formula (III): X-CH_2CH_2-CO-NH-CO-CO-OR (in the formula, R and X have the same meanings as above.) Formula (I): CH_2=CH- A method for producing N-(substituted oxalyl)acrylamide represented by CO-NH-CO-CO-OR (wherein R has the same meaning as above). 6. Formula (I): CH_2=, characterized by reacting acrylamide with oxalyl diester represented by formula (VII): RO-CO-CO-OR (wherein R has the same meaning as above) A method for producing N-(substituted oxalyl)acrylamide represented by CH-CO-NH-CO-CO-OR (wherein R has the same meaning as above). 7. Formula (III): X-CH_2CH_2-CO-NH-CO-CO-OR (In the formula, R represents a hydrocarbon group and X represents a halogen atom.)
N-(substituted oxalyl)-halopropionamide represented by: 8. Formula (VIII): N-(substituted oxalyl)acrylamide represented by (CH_2=CH-CO-NH-CO-)_2. 9. Formula (V): N-(
Substituted oxalyl)-halopropionamide. 10, Formula (IX): (X-CH_2CH_2-CO-NH-CO-)_2 (wherein, X represents a halogen atom)
Substituted oxalyl)-halopropionamide.