JPH0789921A - Novel acid halide compound and production thereof - Google Patents

Abstract

PURPOSE:To provide a novel acid halide compound useful for producing a 2-alkyl-2-propenoyl isocyanate useful as an intermediate for organic syhtheses, medicines and agrochemicals, and as a starting raw material for reactive polymer materials. CONSTITUTION:An acid halide compound of formula I (R<1> is 1-10C alcohol residue; R<2> is H, 1-5C lower alkyl; X is halogen), e.g a compound of formula II. The compound of formula I is obtained by reacting a compound of formula III with a hydrogen halide of formula: HX 111 the presence of a compound of formula: R<1> OH and subsequently reacting the reaction product with an oxalyl halide of formula: (COX)2. The compound of formula I is subjected to a thermal hydrogen halide-removing reaction in a highly concentrated homogeneous system to obtain a 2-alkyl-2-propenoyl isocyanate of formula IV. The novel acid halide compound of formula I has high solubility in general organic solvents.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an acid halide compound, a process for producing the same, and a process for producing an unsaturated acyl isocyanate compound using the compound, particularly to the formula

[0002]

[Chemical 8]

(Wherein R ¹ is an alcohol residue having 1 to 10 carbon atoms, R ² is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and X is a halogen atom). The present invention relates to an acid halide compound, a method for producing the same, and a method for producing 2-alkyl-2-propenoyl isocyanate (2) using the compound.

[0004]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 62-238254 discloses a method of reacting an alkyl acrylamide with an oxalyl halide.

[0005]

[Chemical 9]

A heterocyclic compound (3) represented by the formula (wherein R ² and X have the same meanings as described above) is obtained, and the heterocyclic compound (3) is subjected to a thermal decomposition reaction to give a compound of the formula

[0007]

[Chemical 10]

2-alkyl-2-propenoyl isocyanate (2) represented by the formula: wherein R ² has the same meaning as defined above.
And a synthetic method for obtaining the hydrogen chloride adduct thereof. The heterocyclic compound (3) has a property of low solubility in a general organic solvent, and it is necessary to lower the system concentration in order to carry out the reaction in a homogeneous system. Further, when the reaction must be carried out in a heterogeneous system, particularly in the case of industrialization, there is a problem that productivity is low, for example, it is necessary to enhance equipment such as increasing the capacity of a stirring device.

In addition, Zh. Org. Khimi. vo
l. 6, No. 1, pp. 85-88 January,
1970. As a method for synthesizing an acyl isocyanate compound, an acid chloride compound is synthesized by reacting an imino ester or its hydrochloride with oxalyl chloride,
A method of thermally decomposing this is disclosed. This document does not consider a compound containing an unsaturated group.

[0010]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a new compound for obtaining 2-alkyl-2-propenoyl isocyanate (2) which does not have the above problems.

[0011]

The present inventors have found that the novel acid halide compound (1) is highly soluble in general organic solvents, and use the novel acid halide compound (1). As a result, it was discovered that 2-alkyl-2-propenoyl isocyanate (2) can be obtained by heating in a homogeneous system having a higher concentration than in the past and performing a dehydrohalogenation reaction. That is, the present invention is a formula,

[0012]

[Chemical 11]

(Wherein R ¹ is an alcohol residue having 1 to 10 carbon atoms, R ² is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and X is a halogen atom). Provided are acid halide compounds. Further, the present invention has the formula

[0014]

[Chemical 12]

(Wherein R ² is as defined above) and R ¹ OH
(Wherein R ¹ has the same meaning as defined above), the compound is reacted with hydrogen halide, and then oxalyl halide (COX) ₂
(Wherein X has the same meaning as defined above) to provide a method for producing the acid halide compound (1).

Furthermore, the present invention provides an acid halide compound (1)
Obtained by heating or by heating 2-
Provided is a method for producing a 2-alkyl-2-propenoyl isocyanate (2) by performing dehydrohalogenation of a hydrogen halide adduct of the alkyl-2-propenoyl isocyanate (2).

The acid halide compound of the present invention comprises a nitrile compound and an alcohol R ¹ OH having 1 to 10 carbon atoms (in the formula, R ¹
Is the same as defined above, and is reacted with hydrogen halide in the presence of oxalyl halide (COX) ₂ (wherein X is
Is obtained by reacting with the same meaning as above.

As a reaction method, a method of mixing a nitrile compound and alcohol and blowing a hydrogen halide gas thereto is desirable. At that time, it is not necessary to use a solvent, but a solvent may be used if necessary.

As the nitrile compound which can be used, methacrylonitrile, acrylonitrile, 2-cyano-1-
Propene, 2-cyano-1-butene, 2-cyano-3-
Methyl-1-butene, 2-cyano-1-pentene, 2-
Cyano-1-hexene, 2-cyano-1-heptene and the like can be mentioned. Examples of preferred nitrile compounds include:
Examples thereof include methacrylonitrile and acrylonitrile.

As the alcohol having 1 to 10 carbon atoms,
Primary to tertiary alcohols can be used, for example, methanol,
Ethanol, n-propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, isopropyl alcohol, isobutyl alcohol and the like include t-butyl alcohol, but preferably methanol, ethanol, n-propyl alcohol, isopropyl alcohol. , Butanol.

Any solvent may be used as long as it is inert to the reaction and can be selected from compounds having no active hydrogen. For example, an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent, an ether-based solvent, an ester-based solvent, or the like can be used.

Examples of the aliphatic hydrocarbon type are hexane, heptane, cyclohexane and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene, methoxybenzene and the like. Examples of the halogenated hydrocarbon system include carbon tetrachloride, chloroform, 1,2-dichloroethane, dichloromethane, chlorobenzene and dichlorobenzene. Examples of ethers include diethyl ether, dibutyl ether, diethylene glycol dimethyl ether, dioxane and the like. Examples of the ester type include ethyl acetate and butyl acetate.

When carrying out the reaction, the respective amount ratios are such that the alcohol is 0.5 to 1.5 mol, preferably 1.0 to 1.05 mol, and the hydrogen halide is 1 to 1 mol of the nitrile.
It is 10 mol, preferably 1 to 2 mol. If the ratio exceeds these amounts, it will remain in the system as it is. On the contrary, if it is too small, the reaction may not be completed sufficiently.

The reaction temperature is 0 to 50 ° C, preferably 20 to 30 ° C. Outside of these ranges, the polymerization of unsaturated groups may proceed at high temperatures, and the reaction rate may decrease at low temperatures. By the above reaction, once the formula

[0025]

[Chemical 13]

An iminoester compound represented by the formula (wherein R ¹ and R ² are as defined above) and a hydrochloride thereof are obtained. This iminoester compound can be isolated if necessary.

With respect to the obtained iminoester compound,
The desired acid halide compound can be obtained by reacting oxalyl halide.

When the iminoester compound is synthesized in a solvent-free system or is isolated, the above-mentioned solvent is added. Then, the reaction is carried out by adding oxalyl halide without solvent or by dissolving it in the above solvent and dropping it. The amount of oxalyl halide is the imino ester compound 1
1 to 5 mol, preferably 1 to 1.
2 mol. If the amount of oxalyl halide is too high,
It simply remains in the system as it is. On the contrary, if it is too small, the reaction may not be fully completed.

The reaction temperature in the second step is 0 to 60.
C., preferably 20 to 50.degree. If it exceeds 60 ° C, it may decompose, and if it is 0 ° C or less, the reaction rate may decrease.

The acid halide compound (1) obtained by the above reaction has a yellowish brown liquid state. This acid halide formation can be confirmed by a general analytical method such as an NMR spectrum and an IR spectrum. Since this acid halide compound has an acid halide group, it is highly reactive and can be used for intermediates such as organic synthesis and pharmaceuticals and agricultural chemicals, but it is generally found to be a very useful compound. 2
The use of -alkyl-2-propenoyl isocyanate (2) and its hydrogen halide adduct as a synthetic intermediate has important meaning.

This novel acid halide compound (1) was heated to give 1000
It is possible to obtain 2-alkyl-2-propenoyl isocyanate (2) having an acyl isocyanate group known to have 0 times the activity and a hydrogen halide adduct thereof.

The heating temperature is 50 to 200 ° C., preferably 70 to 200 ° C. If it is lower than this range, the decomposition reaction does not proceed sufficiently, and if it is higher than this range, the decomposition products may be further decomposed.

It is not particularly necessary to use a solvent, but when used, the above-mentioned inert solvent can be used.
Among them, halogenated hydrocarbons are preferable, and chloroform, carbon tetrachloride and dichloroethane are more preferable.

The reaction time varies depending on the presence or absence of a solvent and the heating temperature, but it is 2 to 20 hours, preferably 3 to 10 hours. If the reaction time is shorter than this, the thermal decomposition may not proceed sufficiently, and conversely, if the reaction time is longer, the decomposition product may further decompose.

The hydrogen halide adduct of 2-alkyl-2-propenoyl isocyanate can be easily used as a starting material for intermediates of organic synthesis, pharmaceuticals and agricultural chemicals, and reactive polymer materials by carrying out dehydrohalogenation reaction. It can be easily converted to 2-alkyl-2-propenoyl isocyanate (2).

The dehydrohalogenation reaction is performed using 2-alkyl-2
It is carried out by treating a hydrogen halide adduct of propenoyl isocyanate with an organic base such as triethylamine. Organic base does not contain active hydrogen 3
Primary amines are preferred. Examples of aliphatic amines include triethylamine, tributylamine, and methyldicyclohexylamine, and examples of aromatic compounds include dimethylaniline.

The temperature of the dehalogenated hydrocarbon reaction is 0 to 5
The temperature is 0 ° C, preferably 10 to 30 ° C. If it is lower than this range, the dehalogenated hydrocarbon reaction may not proceed sufficiently, and if it is higher than this range, the polymerization reaction may proceed as a side reaction.

It is not necessary to use a solvent, but when used, the above-mentioned inert solvent can be used.
Of these, halogenated hydrocarbons are preferable, and dichloromethane, dichloroethane and dichlorobenzene are more preferable.

By using the novel acid halide compound (1), the reaction system proceeds in a uniform system, so that the reaction concentration can be increased. As a result, the conventional 2-alkyl-2-propenoyl isocyanate production method of thermally decomposing a compound obtained by reacting an alkyl acrylamide and an oxalyl halide has a heterogeneous system, and thus the concentration cannot be increased. It solves the problem of low production efficiency.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 20.1 g (0.3 mol) of methacrylonitrile and 14.1 g (0.3 mol) of ethanol were mixed, and 38.9 g of hydrogen chloride gas was blown into the mixture under ice cooling for 5 hours. This was concentrated and the unreacted raw materials were removed to obtain a pale yellow liquid. The viscosity of this liquid is 77 cps / 24 ° C (EM
Type viscometer), and 1650 from IR spectrum
Imino ether-based absorption was confirmed at cm ^-1 .

60 g of carbon tetrachloride was added thereto, and 40 g (0.36 mol) of oxalyl chloride was added dropwise over 30 minutes under ice cooling. Then, the reaction temperature was raised to 50 ° C. and the mixture was stirred for 45 minutes. At this time, from the IR spectrum of the reaction solution, 176
5 cm ^-1, the absorption based on the carbonyl group in 1740 cm ^-1, also the absorption based on an imino group 1650 cm ^-1 were observed.

After the reaction was completed, the solution was concentrated to obtain a yellowish brown liquid. When the viscosity of this liquid was measured, it was 118 cp
It was s / 24 ° C. (measured with an EM type viscometer). Also NM
From the R spectrum, the target formula

[0043]

[Chemical 14]

It was found that was obtained.

Example 2 The compound obtained in Example 1 was dissolved in carbon tetrachloride to obtain 60
Upon heating at 70 ° C. for 1 hour at 70 ° C. for 4 hours, absorption based on an acyl isocyanate group was confirmed at 2250 cm ⁻¹ in the IR spectrum. Further, from the NMR spectrum, δ =
3.6ppm (doublet), δ = 3.0ppm (multiplet), δ = 1.38ppm (doublet),
It was found that 2- (1-chloromethyl) propionyl isocyanate, which is a hydrogen chloride adduct of methacryloyl isocyanate, was produced. Furthermore, at δ = 5.9 and 6.3 ppm, a signal based on the methylene group at the terminal of the methacryl group was confirmed, and it was confirmed that methacryloyl isocyanate was produced.

Example 3 1.28 g of 2- (1-chloromethyl) propionyl isocyanate synthesized and isolated based on Example 2 was dissolved in 5 ml of chloroform, and 0.75 g of triethylamine was added dropwise thereto at room temperature. Then, the reaction mixture was directly distilled under reduced pressure to obtain 0.68 g of the target product, methacryloyl isocyanate.

Reference Example 1 139.6 g of oxalyl chloride and 400 g of o-dichlorobenzene were mixed and cooled to 0 to 10 ° C. there,
85.1 g of methacrylamide was added as a solid little by little over 40 minutes, and then seed crystals were added to precipitate crystals, and 600 g of hexane was added. (The thermal decomposition reaction concentration at this time is 15
%) This was pyrolyzed to give methacryloyl isocyanate in a yield of 88.4%.

Claims (4)

[Claims] 1. The formula: (In the formula, R ¹ is a residue of an alcohol having 1 to 10 carbon atoms,
R ² represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and X represents a halogen atom. ) A novel acid halide compound (1). 2. The formula: (Wherein R ² is as defined above) and R ¹ OH (wherein R ¹ is as defined above), hydrogen halide HX (wherein
X is as defined above, and then reacted with oxalyl halide (COX) ₂ (wherein X is as defined above), and Acid halide compound (1) characterized by obtaining
Manufacturing method. 3. The formula: (Wherein R ¹ and R ² have the same meanings as defined above) (In the formula, R ² has the same meaning as defined above) A process for producing an unsaturated acyl isocyanate compound (2). 4. The formula: (Wherein R ¹ and R ² have the same meanings as described above), and then a dehydrohalogenation reaction is carried out. (In the formula, R ² has the same meaning as defined above) A process for producing an unsaturated acyl isocyanate compound (2).