JPS6049181B2 - Method for producing N-alkylamine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for making N-alkylamines.

More specifically, the present invention is based on the general formula [■]) N The benzene ring A may be further substituted with a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, a hydroxy group or an acylamino group.

) and the general formula [■]Hal
-R2[■]F (In the formula, Hal represents a chlorine atom, a bromine atom or an iodine atom, and R2 represents an alkyl group having 4 to 10 carbon atoms.

) in the presence of an acid binder in an aqueous solvent or an aqueous solvent to which a small amount of an organic solvent has been added.
General formula [characterized by the reaction being carried out at 0 to 120°C]
1] (wherein R3 represents the same meaning as R1 or R2, and R2 and ring A represent the same meaning as above.

) is the method for producing the amine shown in Conventionally, general formula [
The reaction between the compound represented by [■] and the C4 or higher alkylating agent represented by the general formula [■] requires a reaction temperature of 100'C or higher, and the alkyl halide tends to decompose in high-temperature water. However, this method requires an expensive organic solvent, and its handling and post-reaction treatment are complicated. A certain general formula [■]
The compounds of [■] and [■] must be dried and used in a substantially water-free state, which is not a preferable method in terms of operation.

As a result of intensive research in order to improve these drawbacks, the present inventors conducted the alkylation reaction in an aqueous medium or in an aqueous medium to which a small amount of an organic solvent was added, using an alkali metal compound or alkaline earth metal compound as an acid binder. , a compound or, if necessary, an organic weakly basic compound, at 60°C to 120°C, the alkylation reaction can surprisingly be carried out extremely well. ■] to R
1 and the water-insoluble group that can be substituted with the alkyl group represented by R3 in the general formula [1], specifically, a cyano group, an alkoxy group, an alkoxyalkoxy group, a phenyl group, a phenoxy group, a hydroxyl group, an alkyl group. There are carbonyloxy groups, alkoxycarbonyloxy groups, benzoyloxy groups, and halogen atoms.

It has also been found that, as a substituted alkyl group, the hydrogen of the hydroxyl group at the β or γ position is transferred to an alkyl group, an acyl group, and the like. In particular, when the alkyl halide used and the alkyl group of the amine produced have 4 or more carbon atoms, both the alkyl halide and the amine become poorly soluble in water. Although it was expected that the reaction would be difficult to proceed, it is surprising that the reaction proceeds much better when water is used as a solvent as in the method of the present invention than when an organic solvent is used. Ta.

That is, the feature of the method of the present invention is that the compound represented by the general formula [■] and the general formula [■] are mixed in an aqueous solvent.
This is a method of reacting with an alkylating agent of C4 or higher shown in It has the advantage of being an extremely good production method in terms of countermeasures, and furthermore, it can be used as a wet cake or as a wet cake without drying the compound represented by the general formula [previously shown] and the alkylating agent represented by the general formula [■], which are used as raw materials. The present invention has great industrial value as it can be used as a raw material without completely requiring dehydration.

As another method for obtaining the object of the present invention, a method using p-toluenesulfonic acid ester is known, but this ester is relatively easily decomposed in the presence of an acid binding agent, and it is difficult to carry out this reaction. , has the disadvantage of consuming large amounts of ester.

The industrial advantages of the method of the invention are summarized in the table below.

β-hydroxy-γ optionally substituted with rubamoyl group
-Alkoxypropyl group, β-hydroxy-γ-phenoxypropyl group, β-hydroxy-γ-hydroxypropyl group, β-hydroxy-γ-aryloxypropyl group, β-hydroxy-γ-aralkyloxypropyl group, β-hydroxy-γ-phenoxyalkyl group Examples include oxypropyl group and β-hydroxy-γ-halogenopropyl group. Specific examples of compounds represented by the general formula [formula] include the following.

Aniline, m-toluidine, m-chloroaniline, m-
Acetylaminoaniline, 2-methoxy5-acetylaminoaniline, o-nitroaniline, m-nitroaniline, 3,5-dichloroaniline, 2-methyl-5-
Methoxyaniline, m-benzoylaminoaniline, m
-propionylaminoaniline, 2-ethoxy 5-acetylaminoaniline, 2,5-dimethynoleaniline,
2,55-dimethoxyaniline, N-ethylaniline,
N-cyanoethylaniline, N-(β-methoxyethyl)aniline, N-methyl-m-toluidine, N-cyanoethyl-m-toluidine, N-(β-methoxyethyl)
-m-acetylaniline, N-(β-acetoxyethyl)-aniline, N-(β-hydroxyethyl)-m-
Acetylaminoaniline, N-butyl-m-cyanoaniline, N-(β-methoxyethoxyethyl)-aniline, N-phenethyl-m-toluidine, N-(β-phenoxyethyl)-m-benzoylaminoaniline, N-(
β-methoxycarbonyloxyethyl)-m-methoxyaniline, N-(β-benzoyloxyethyl)-m-
Chloraniline, N-(β-hydroxy-γ-alkoxypropyl)aniline, N-(β-hydroxy-γ-phenoxypropyl)-m-toluidine, N-butyl m
-acetylaminoaniline, N-amylaminoaniline, 3-(N-amylamino)-4-methoxyacetanilide, N-cyanoethylm-acetylaminoaniline.

Examples of the alkyl halide represented by the general formula [■] include the following. Butyl bromide, isobutyl bromide, butyl chloride, isobutyl chloride, butyl iodide, isobutyl iodide, amyl bromide, isoamyl bromide, amyl chloride, isoamyl chloride, isoamyl iodide, hexyl chloride, hexyl bromide, heptyl bromide, heptane iodide, chloro heptane, octyl bromide, Se
c-octyl bromide, Sec-octene iodide, 2
-Ethylhexyl bromide, promononane, promodegan, chlorodecane, cyclohexyl bromide, cyclopentyl bromide, benzyl bromide, benzyl chloride.

The amount of these alkyl halides to be used is 1 to 2 molar ratio, preferably 1 to 1.3 molar ratio per one alkyl group to be introduced.

In the present invention, examples of organic vehicles added as necessary include alcohol, ethylene glycol monoalkyl ether, benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, nitrobenzene, etc. It is preferably 20% or less.

Examples of the acid binder include alkali metal compounds, alkaline earth metal compounds, and organic weakly basic compounds used as necessary.

The acid binders of the former include, for example, sodium or potassium bicarbonates, sodium, potassium, magnesium or calcium carbonates, hydroxides or oxides;
There are sodium and potassium salts of organic acids, and specific examples include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, calcium carbonate, magnesium oxide, magnesium hydroxide, calcium hydroxide, and sodium acetate.

Examples of the weakly basic organic compound include tertiary amines such as pyridine, picoline, dimethylaniline, and diethylaniline, either alone or in mixtures.

If desired, a catalyst such as potassium iodide or natronium iodide or a phase transfer catalyst such as benzyltrimethylammonium chloride or tetra-n-butylammonium bromide may be used alone or in combination.

The reaction of the invention is carried out at a temperature of 60-120°C, preferably 56°C.
The temperature is 0°C or higher and lower than the azeotropic point of the solvent and the alkyl halide.

If the temperature is below 60°C, the reaction will be extremely slow, which is not preferable.

The alkylation of the present invention is applicable when one or two alkyl groups are introduced into a benzene-based amine.

The reaction can be carried out temporarily or stepwise depending on the number and type of alkyl groups to be introduced. According to the method of the present invention, the target product can be obtained in high yield and purity, and the obtained compound [1] can be used, for example, as a coupling component in dye synthesis, and can be obtained by this method. In terms of yield and quality, the resulting dye is comparable to conventional methods in organic solvents, and may even produce more favorable results, such as less formation of diazo decomposition products.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these. In the example,
Parts refer to parts by weight.

Example 1 m-17.6 parts of acetylaminoaniline wet cake (purity 85%), 4.8 parts of magnesium oxide, and (a) parts of water were charged, heated to 90°C, and 362 parts of amyl bromide was added at the same temperature. Drop 3 drops of powder and add 90~9
Stir at 5°C for 4 hours.

After the reaction was completed, the water in which the inorganic salt was dissolved was removed at 80 to 90°C by liquid separation to obtain four parts of N,N-diamylum-m-acetaminoaniline. This product is used, for example, as a coupling component during dye synthesis.

Example 2 N-cyanoethyl-m-acetylaminoaniline 20.
3 parts of potassium carbonate, 8.3 parts of potassium iodide, 2.6 parts of a 50% aqueous solution of benzyltrimethylammonium chloride, and a portion of water were added and the temperature was raised to 95-105°C.

At the same temperature, 18.5 parts of aluminum bromide was added dropwise over 1 hour, and after further stirring at 105-110°C for 6 hours,
Separate the liquid at 70°C. 22.0 parts of N-cyanoethyl-N-amy-m-acetylaminoaniline was obtained. This product is used, for example, as a coupling component during dye synthesis.

Example 3 Wet cake of m-acetylaminoaniline 17.6
(purity 85%), 5 parts of sodium carbonate, 20j parts of water and 3 parts of ethanol, and the temperature was raised to 70°C.

At the same temperature, 13.7 parts of butyl bromide was added dropwise in three powders.
The temperature is raised to 80-90°C and stirred at the same temperature for 5 hours. 6 parts of sodium carbonate and 1.1 parts of cupotassium iodide are added to the obtained reaction solution of N-butyl-m-acetylaminoaniline, and the temperature is raised to 90 to 95°C. At the same temperature, 12.8 parts of amyl chloride was added dropwise, and after stirring at 90-95°C for 6 hours, the mixture was separated at 70-80°C. 251 parts of N-butyl-N-amylacetylaminoaniline were obtained. This product is used, for example, as a coupling component during dye synthesis.

Example 4 10.7 parts of m-toluidine, 6 parts of sodium carbonate, 1.6 parts of potassium iodide and 1C8 of water were charged and heated to 90°C.
After raising the temperature to , 232 parts of octyl bromide was added dropwise in three parts.

After further stirring at 100-115°C for 6 hours, the mixture was separated at 90'C. N-octyl-m-toluidine part O was obtained. Furthermore, 6 parts of sodium carbonate, 2 parts of potassium iodide, and 5 parts of tetra-n-butylammonium bromide were added to the above reaction solution.
Add 4 parts of 0% aqueous solution and 232 parts of octyl bromide, stir at 105 to 120°C for 3 hours, and then separate the mixture at 590°C.

32.7 parts of N,N-dioctyl-m-toluidine were obtained. Example 5 9.3 parts of aniline, 7.3 parts of sodium carbonate. After adding ヅ$ and water mark part and raising the temperature to 80℃, bromodecane 33.2 parts)
It takes 3 drops to drip.

Then, the temperature is raised to 100-110°C, and after stirring at the same temperature for 6 hours, the mixture is separated at 70-80°C. N-decylaniline 2
0. A tank was obtained. This product is used, for example, as a coupling component during dye synthesis. Example 6 14.6 parts of N-cyanoethylaniline, 8 parts of potassium carbonate
．． 3 parts, 1.8 parts of potassium iodide and (very) parts of water were heated to 80°C, and 24.8 parts of hexyl bromide was added.
1 hour.

Then, the temperature is raised to 100-115°C, and after stirring at the same temperature for 6 hours, the mixture is separated at 80°C. 21.9 parts of N-cyanoethyl-N-hexylaniline were obtained. This product is used, for example, as a coupling component during dye synthesis.

Example 7 Wet cake of m-acetylaminoaniline 17.6
(purity 85%) 5 parts of sodium carbonate, 12 parts of potassium iodide and 2 parts of water were charged, and the temperature was raised to 80°C.

Claims (1)

[Claims] 1 General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (In the formula, R_
1 represents a hydrogen atom or an alkyl group having 2 to 6 carbon atoms which may be substituted with a water-insoluble substituent, and the benzene ring A
may be further substituted with a lower alkyl group, lower alkoxy group, halogen atom, nitro group, hydroxy group or acylamino group);
General formula [III] Hal-R_2 [III] (in the formula, Hal represents a chlorine atom, a bromine atom or an iodine atom, and R_2
represents an alkyl group having 4 to 10 carbon atoms. ) in the presence of an acid binder in an aqueous solvent or an aqueous solvent to which a small amount of an organic solvent has been added.
General formula [characterized by the reaction being carried out at 0 to 120°C]
I 〕▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕(In the formula, R_3 represents the same meaning as R_1 or R_2, and R
_2 and benzene ring A have the same meanings as above. ) A method for producing N-alkylamine shown by