JP3356316B2 - Method for producing unsaturated carbamic acid derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for obtaining an unsaturated carbamic acid derivative from an unsaturated carbamic acid ester by a substitution reaction.

[0002]

BACKGROUND OF THE INVENTION The present inventors have already obtained the general formula:

Embedded image Developed unsaturated carbamates represented by
Its applications have also been developed (JP-A-61-275259, JP-A-61-275260 and JP-A-6-275260).
1-275270).

As an improvement of the method for producing unsaturated carbamates, Japanese Patent Application Laid-Open No. 4-66563 proposed a one-step synthesis method in which methacrylamide and chloroformate are reacted. However, chloroformates are unstable and the types of esters that can be used are limited.

Japanese Patent Application Laid-Open No. 61-275259 discloses a formula.

Embedded image It is shown that the compound can be produced by reacting a compound having an isocyanate group represented by the formula (1) with an alcohol or the like.
However, the isocyanate compound used here has a high activity and is extremely difficult to handle.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for easily deriving various unsaturated carbamic acid derivatives from an unsaturated carbamic acid ester once formed.

[0006]

Means for Solving the Problems The present inventors have found that a variety of unsaturated carbamic acid derivatives can be obtained by using an unsaturated carbamic ester once formed by a substitution reaction, and have accomplished the present invention. .

That is, the present invention provides a compound represented by the general formula:

Embedded image Reacting an unsaturated carbamic acid ester represented by the formula with an alcohol or an oxime at 40 to 150 ° C. to produce an unsaturated carbamic acid derivative in which the —OR ¹ group in the unsaturated carbamic acid ester (A) is substituted. An alkyl alcohol in which the alcohol may be substituted with a halogen atom having 1 to 30 carbon atoms, an alkenyl alcohol having 3 to 20 carbon atoms, an aralkyl alcohol having 7 to 16 carbon atoms, and an aralkenyl alcohol having 9 to 18 carbon atoms Having a molecular weight of at least one heteroatom in the molecule of 6
Is selected from the group consisting of alcohols and polyhydric alcohols 0-1000, the oxime is ^R 5 ^R 6 -C = N-
OH (wherein R ⁵ and R ⁶ are the same or different and are an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms) Alternatively, R ⁵ and R ⁶ are bonded to each other to represent an alkyl group having 4 to 8 carbon atoms), and the alcohol or oxime is added in an amount of 0.5 to 5 to 1 equivalent of the unsaturated carbamic acid ester. Provided is a method for producing an unsaturated carbamic acid derivative, wherein the reaction is carried out in an equivalent amount.

[0008] Heretofore, no synthesis example utilizing the substitution reaction of acyl carbamates has been known. A transesterification reaction is similar to this substitution reaction.
Generally known transesterification reactions require high temperatures (around 180 ° C.) or require the addition of catalysts.
However, the present inventors do not require a very high temperature for the substitution reaction using the acylcarbamic acid ester, specifically, the reaction can be carried out at a temperature of 40 to 150 ° C., and the addition of a catalyst is not particularly necessary ( Of course, it may be added).

The unsaturated carbamic acid ester (A) as the starting material of the present invention may be obtained by any method. Therefore, the above-mentioned JP-A-61-275259 has been disclosed.
Or the method disclosed in Japanese Patent Application Laid-Open No. 4-66563, or may be obtained using the method of the present invention.

The unsaturated carbamate (A) has the above-mentioned chemical structural formula. In the chemical structural formula, R is hydrogen or an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. R ¹ is a residue obtained by removing an OH group from a monohydric alcohol, and specifically includes an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a residue having 6 to 15 carbon atoms. And aralkyl groups.
The reaction of the production method of the present invention shifts the equilibrium of the reaction,
The desired compound is obtained. Therefore, in order to shift the equilibrium of the reaction, the ester portion of the unsaturated carbamic acid ester used as a raw material preferably has a small number of carbon atoms, that is, R ¹ is an alkyl group having 1 to 6 carbon atoms. In this case, the alcohol represented by R ¹ OH is distilled off to shift the equilibrium of the reaction to obtain the desired compound.

The compound which reacts with the unsaturated carbamate (A) is an alcohol or an oxime.
Alcohol is methanol, ethanol, propanol,
Isopropanol, butanol, lauryl alcohol,
Alkyl alcohols which may be substituted by halogen atoms having 1 to 30 carbon atoms such as stearyl alcohol and triacontanol; alkenyl alcohols having 3 to 20 carbon atoms such as allyl alcohol, crotyl alcohol and phytol; benzyl alcohol, phenethyl alcohol, 8 Aralkyl alcohols having 7 to 16 carbon atoms such as phenylmenthol; aralkenyl alcohols having 9 to 18 carbon atoms such as cinnamyl alcohol; and alcohols having a molecular weight of 60 to 1000 having at least one or more heteroatoms in the molecule, for example, Methoxyethanol,
Butoxyethanol, hexyloxy ethanol, methoxybutanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, an ether bond-containing alcohols such as polyethylene glycol (R ^a -O-R ^b -O
H; R ^a = C ₁ -C ₁₂ and R ^b = C ₁ -C ₁₂ );
Ester bond-containing alcohols such as ethylene glycol monoacetyl ester and 2-hydroxyethyl methacrylate; tertiary nitrogen-containing alcohols such as N, N-dimethylaminoethanol and 2-pyridylcarbinol;
Thioether-containing alcohols such as 3-methylthio-1-hexanol, methylthiopropanol and 2- (2-thienyl) ethanol; 2-fluoroethanol;
2,2,3,3,3-pentafluoro-1-propanol,
2-chloroethanol, 2,2-dichloroethanol,
2,2,2-trichloroethanol, 1,3-dichloro-
2-propanol, 3-bromo-1-propanol, 1
Halogen-containing alcohols such as -bromo-2-propanol, 2-iodoethanol; ethylene glycol;
Examples include polyhydric alcohols such as diethylene glycol, hexanediol, and trimethylolpropane. If the monovalent alcohol in this alcohol is represented as R ² —OH, R ² may be the same as R ¹ in the unsaturated carbamate ester (A) described above, From the viewpoint of displacing R ¹ , R ¹ preferably has a small number of carbon atoms and a low boiling point, and R ² has a carbon number of 3 to 3.
Those having a high boiling point of 30 are preferred.

The oxime used in the present invention is specifically R ⁵
A compound represented by R ⁶ —C ＝ N—OH wherein R ⁵ and R ⁶ are the same or different and are an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkynyl having 2 to 8 carbon atoms; Group, an aryl group having 6 to 12 carbon atoms or R
⁵ and R ⁶ are connected to each other, and examples thereof include an alkyl group having 4 to 8 carbon atoms. Specific examples of such oximes include alkanaldehyde oximes such as acetaldehyde oxime; dialkyl ketone oximes such as alkenaldehyde oxime, phenyl aldehyde oxime, acetone oxime, methyl ethyl ketone oxime and methyl isobutyl ketone oxime; dialkenyl ketone oxime; alkyl alkenyl ketone oxime; Phenylalkylketone oxime such as methyl ketone oxime; lower alkanoylacetone oxime such as acetylacetone oxime; and cycloalkanone oxime such as cyclopentanone oxime and cyclohexanone oxime.

The reaction reagent such as alcohol can be used in a ratio of 0.5 to 5 equivalents of the alcohol or oxime with respect to 1 equivalent of the unsaturated carbamic acid ester (A).
Of course, the present invention is not limited thereto, and the equilibrium of the reaction can be shifted by the presence of a large excess of any of the reaction reagents.

The reaction may be carried out in an inert solvent, if necessary. The inert solvent used in the reaction is not particularly limited as long as it does not affect the reaction, and various solvents can be used.For example, pentane, hexane, aliphatic hydrocarbons such as heptane, benzene, toluene, xylene and the like can be used. Aliphatic hydrocarbons such as aromatic hydrocarbons, cyclohexane, methylcyclohexane, and decalin; hydrocarbon solvents such as petroleum ether and petroleum benzine; halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, and 1,2-dichloroethane , Ethyl ether, isopropyl ether,
Anisole, dioxane, tetrahydrofuran (TH
F) or the like; ether solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate and butyl acetate; acetonitrile, dimethylformamide (DMF), and dimethyl sulfoxide. Just choose. These may be used alone or in a mixture.

The reaction temperature is 40 to 150 ° C., preferably 6
0-140 ° C is preferred. When the reaction temperature is low, the reaction does not proceed, while when it is too high, a side reaction is generated.

The reaction time is not particularly limited, but is usually about 0.1 to 10 hours. Of course, the reaction temperature can vary greatly depending on the reactivity of the reagent, the reaction temperature, and the like.

In order to inhibit the polymerization of the unsaturated double bond during the reaction, a polymerization inhibitor may be present in the reaction system.
Specific examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4-t-butylcatechol, bisdihydroxybenzylbenzene, and 2,2′-methylenebis ( 6
-T-butyl-3-methylphenol), 4,4-butylidenebis (6-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), p- Nitrosophenol, diisopropylxanthogen sulfide, N-nitrosophenylhydroxyamine ammonium salt, 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl, 2,6-di-t-butyl -Α- (3,5-di-butyl-4-oxo-2,5-cyclohexadiene-
1-ylidene) -p-trioxy, 2,2,6,6-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, p, p'-ditolyl trisulfide, p, p'-ditolyl tetrasulfide , Dibenzyltetrasulfide, tetraethylthiuram disulfide, phenothiazine and the like.

A catalyst may be added to the reaction if necessary. Examples of catalysts include tertiary amine catalysts such as triethylamine, tributylamine and pyridine; sulfuric acid, nitric acid,
Acidic catalysts such as hydrochloric acid, phosphoric acid, and acetic acid; lead acetate, cobalt acetate, nickel acetylacetonate, copper naphthenate,
Metal catalysts such as manganese acetylacetonate are exemplified. The amount of the catalyst to be added is not particularly limited, but is preferably 0.001 to 0.1 equivalent to the reaction reagent.

The product obtained by the reaction may be isolated or separated by a conventional purification method. The generated unsaturated carbamic acid derivative is represented by the following chemical structural formula.

[0020]

Embedded image

[0021]

According to the present invention, a wide range of carbamic acid derivatives can be easily obtained by transesterification from unsaturated carbamic acid esters. This reaction does not require a particularly high temperature, does not require a catalyst, and is advantageous over other reactions in that the reaction proceeds.

[0022]

EXAMPLES The present invention will be described in more detail with reference to Examples. The present invention should not be construed as being limited to these embodiments.

Example 1 15.7 g of ethyl N-methacryloylcarbamate and 2
-52 g of ethylhexyl alcohol was mixed, 0.1 g of hydroquinone was added, and the mixture was heated at an internal temperature of 120 ° C for 1 hour.
After the obtained mixture was concentrated under reduced pressure, it was isolated by column chromatography, and N-methacryloylcarbamic acid 2
-17.4 g of ethylhexyl were obtained (viscosity 800 cp).

EXAMPLE 2 14.3 g of methyl N-methacryloylcarbamate and 1
-27 g of octadecanol, 0.02 g of hydroquinone
And toluene were mixed and reacted at an internal temperature of 117 ° C. for 2 hours while distilling a toluene / methanol solution. After cooling, the mixture was concentrated under reduced pressure and isolated by column chromatography.
32.8 g of a white solid having a mp of 38-41 ° C. were obtained.

Example 3 15.7 g of ethyl N-methacryloylcarbamate and 2
-17.7 g of butoxyethanol and 25 g of toluene were mixed and heated. The reaction was carried out at an internal temperature of 118 ° C. for 1 hour while distilling a toluene / ethanol solution. After cooling, the mixture was concentrated under reduced pressure, isolated by column chromatography, and mp27-
16.1 g of a white solid at 28 ° C. was obtained.

Examples 4 to 6 Synthesis was performed in the same manner as in Example 3 using the reaction conditions shown in Table 1.

[0027]

[Table 1]

Example 7 7.8 g of ethyl N-methacryloylcarbamate, 20 g of acetone oxime and 20 g of ethyl acetate were mixed and heated at an internal temperature of 82 ° C. for 10 minutes. After cooling, column purification was performed to obtain 1.3 g of N-methacryloylcarbamic acid 2-propylene imino ester (mp: 31-32 ° C.).

Examples 8 to 31 Reaction products were obtained in the same manner as in Example 7 except that the conditions and reaction reagents described in Table 2 were used. Table 2 shows the chemical formula, yield and melting point of the product.

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masamichi Furukawa 19-17 Ikedananakacho, Neyagawa City, Osaka Japan Paint Co., Ltd. (56) References JP-A-61-275259 (JP, A) JP-A-61-275260 (JP, A) JP-A-2-1452 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 269/06 C07C 271/64 C07D 307/12 C07D 307/42 CASREACT (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula: In the represented unsaturated carbamic acid ester is reacted with an alcohol or oxime and 40 to 150 ° C., a process for the preparation of unsaturated carbamic acid derivatives obtained by substituting the -OR ¹ group in the unsaturated carbamate (A) ,
Is substituted with a halogen atom having 1 to 30 carbon atoms
Alkyl alcohol that may be present
Kenyl alcohol, aralkyl alcohol having 7 to 16 carbon atoms
Alkenyl alcohol having 9 to 18 carbon atoms,
A molecular weight of at least one heteroatom in the molecule of 6
0 to 1000 alcohols and polyhydric alcohols
Wherein the oxime is R ⁵ R ⁶ -C = N-
OH (wherein R ⁵ and R ⁶ are the same or different
Alkyl group having 1 to 12 primes, alkenyl having 2 to 8 carbon atoms
Group, an alkynyl group having 2 to 8 carbon atoms, an alkynyl group having 6 to 12 carbon atoms,
The reel group or R ⁵ and R ⁶ are bonded to form a C 4-8
Shows an alkyl group. ) And the compound
1 equivalent of saturated carbamic acid ester
Alternatively, a method for producing an unsaturated carbamic acid derivative , comprising reacting an oxime in an amount of 0.5 to 5 equivalents .