JPS6248653A - Production of n-alkyl-substituted aminophenol compound - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as an intermediate for a dye for heat-sensitive or pressure-sensitive recording paper, etc., easily at a low cost, by reacting an aminophenol with an alkyl halide in the presence of eater using ammonia as an acid acceptor in closed vessel under high temperature and pressure condition. CONSTITUTION:The objective compound of formula III can be produced by reacting the aminophenol of formula I (R1 is H or alkyl) with the alkyl halide of formula II (R2 is alkyl; X is halogen) in the presence of water using ammonia as an acid acceptor in a closed vessel at 80-120 deg.C under pressure. EFFECT:The process can be carried out without causing the problems such as the generation of large amount of waste water and sludge, formation of by- products, difficulty in separating the product, influence on the material of the reactor caused by the lowering of pH, etc. USE:Intermediate for xanthene dye, fluorescent dye, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing N-alkyl substituted aminophenols. More specifically, the present invention is as follows.

Aminophenols represented by

It is characterized in that an alkyl halide represented by the general formula (L[) R2X (11) is heated in a closed container in the presence of water, using ammonia as a deoxidizing agent, and reacted under pressure.

N-alkyl substituted aminophenol fi represented by general formula (III) R1, N/R2 ,
This is a manufacturing method of t.

N-alkyl-substituted aminophenols represented by the general formula (III) are important industrial compounds as intermediates for heat- and pressure-sensitive paper dyes, hexa/thenic dyes, fluorescent dyes, etc. Some things are flying well.

・；、r hikirai's techniquerl:j) ninj:crai, Synthesis method of the compound represented by the general formula (■) and 1
- Then, 2l-D be/ze/ is used as the starting material r.[
How to obtain LI-like products by using 3-dimensional alkaline food. An alkyl compound represented by the general formula (1) (using an alkali metal compound and/or an alkali metal compound as a deoxidizing agent, and an alkyl compound represented by the general formula (II)) A method of alkylation is known (・ruO
ll'1 person's method is (・so-called alkaline fuge fee/
Surano of law and multi: 1; glue 1 water and multi: j:. occurs, and the culm is also i As a deoxidizing agent, it is known that alkaline domain compounds, n'1 metal compounds on alkali, etc. are used as deoxidizers. Examples of hot water include sodium carbonate, sodium hydrogen carbonate, red sea bream/rum hydroxide, and calcium hydroxide.

When using carbonate, carbon dioxide gas fills the reaction vessel.

The reaction pressure becomes considerably high and the reaction is not completed.
Furthermore, since the general formula (I) has a human l-J quinyl group, it has the disadvantage that alkylation of the human V1 gy,ru group also proceeds. On the other hand, the use of alkaline earth metal hydroxides has the advantage of not generating carbon dioxide gas and causing less alkylation of hydroquine groups;
The solubility of l-type hydroxides for alkali I is low (・), which makes stirring difficult.In addition, it is also difficult to separate the chloride produced after the reaction and the N-alkyl-substituted amine phenols produced. On the other hand, as an improvement on these drawbacks, Japanese Patent Application Laid-open No. 55-55525
In Public i11. It is proposed to use inorganic phosphates as deoxidizing agents. However, in this method, the degree of reaction from N-monoalkyl-substituted aminophenol to N,N-dialkyl-substituted aminophenol is low.

The phosphoric acid frees the scorching of the scorching material Lt, and the reaction system's 1]F1 becomes 3 or less, and the material is 10. Lack 1, ′, which is a big problem. 1. It is by no means a good-looking JJ method.

(Problems to be Solved by the Invention) The present invention solves the drawbacks of these conventional techniques, that is, the problem of multiple jlls (
)1 This aims to solve problems such as the generation of water and sludge, the formation of side reactions, the difficulty of separating products, and the effect of a drop in pH on the material of the reaction vessel.

(Means for resolving the problem) The present inventors
In order to improve these shortcomings, we conducted a thorough investigation and determined that the alkylation reaction was carried out in an aqueous solvent using ammonia as a deoxidizing agent, heated and pressurized to achieve an extremely good f. It has been found that the alkyl reaction proceeds and all of the drawbacks described above can be eliminated, that is, the first feature of the present invention is in an aqueous solvent.

By using ammonia as a deoxidizing agent and deoxidizing the compound represented by the general formula (1) and the general formula (old),
It is represented by the general formula (ffI). It has the advantage that the production of N-alkyl-substituted aminophenols can be carried out on a one-liter scale at low cost. Furthermore, general formula (I) used as a raw material
, and the general formula (formula 1) is used in a wet state without drying (C1:. etc.).

The industrial value of the present invention is great. 9 This invention has a collar.

--Specifically, the compound represented by the general formula (, I) is:

For example, aminophenols, N-methylaminophenol ff1. N-ethylaminophenol lamp l.

Examples include N-propylaminophenols, N-butylaminophenol Xn, N-pentylaminophenol n'i, and N-hex/ruaminophenols. In addition, alkyl represented by the general formula '(II)
・As a ride. Examples include:

Methylchloride, ethylchloride, butylchloride, butylchloride, penothylchloride, hekynruchloride, methyl bromide.

Ethyl bromide, butyl bromide, butyl bromide, pentyl bromide, hexyl bromide, methyl iodide, ethyl iodide, iodide) 1 nobyl, butyl iodide, pentyl iodide, hexyl iodide, of these alkyl halides. use! lt is the alkyl group to be introduced 1
A molar ratio of from 1 to 2, preferably from 1 to 1.3, is sufficient. Use of ammonia, which is a feature of the present invention 1
; shi is 1 to 3 for the compound represented by general formula (1)
A molar ratio, preferably between 1.2 and 2.2, is sufficient.

In addition, in the present invention, alkali metal compounds, alkaline earth metal compounds, organic amines, etc. may be used in combination as necessary. The reaction temperature in the method of the present invention is 60-+40
°C1 Preferably 80-120°C is chosen. 60℃
If the temperature is not γ-, the reaction rate is extremely slow, whereas if the temperature exceeds 140°C, the hydrolysis of the alkyl halide and the deterioration of the N-alkyl-substituted aminophenols produced will become significant, which is not preferable.

The N-alkylation of the present invention can be applied when introducing one or two alkyl groups into the compound represented by the general formula (1), where 1 anti) = 6 is the number of alkyl groups to be introduced. Depending on the situation, it comes to be implemented in stages or in stages.

Next, the present invention will be further explained with reference to Examples (the present invention will be explained in detail, but the present invention is not limited to these).

(Example) <Example-I> 1 m-7 in a SUS 200CC autoclave with a stirrer
Minophenol 30.5gr (0.27'15mol)
, ethyl chloride 44.0 gr (0,6822 mol), water 12.3 gr.

and 28% anomonia water 21.8g (0,3590
M) L/) was charged and the reaction was carried out at 100'C for 6 hours. After the completion of the reaction, one reaction solution was immediately separated into an oil phase and an aqueous phase, and each solution was subjected to gas chromatography and
``Analysis using 3-note chromatography revealed that 9m-aminophenol conversion rate was 997%.
N,N-ethyl-m-aminofunol selectivity 8
2.0%, N-ethyl-m-aminophenol selectivity 1
2.8% 1m-diethylphenethi 9 Reaction pressure is maximum l
1. The pH of the OKq/engenG2 reaction solution was 3.8.

<Example 2> The reaction was carried out in the same manner as in Example 1 except that m-aminophenol was replaced with p-aminophenol. When similar analysis was performed on reaction d1M+, the conversion rate of p-aminophenol was 99.8%, and N,N-noethyl p
-7 minophenol selectivity 81.2%.

N-ethyl-p-aminophenol selection 4'-12,6
%.

The p-diethylph netidino selectivity was 1.0% and the dimer selectivity was 06%.

<Example-3> Ethylc “Instead of J-ride, ethyl bromide was used as JI
+(・, The other reactions were carried out at the same tp as in Example-1. When the reaction it'i-(・tell11-like analysis was performed,
m--・”Minophenol conversion fhi=<< 99.8%
, N,N-noe1-m-aminophenol selectivity 8243%, N-ethyl-m-aminotunol selectivity 1244%, 2m-noethyl-thinone selectivity 10
% 2 j, i-form selectivity was 06%.

<Comparative Example-1> In place of anomonia water number 2, 1-lium hydrogen phosphate (0
, 1795 mol) once a month, and the other conditions were the same as in Example-1.
It was low at 9, and some 'I&'4 corrosion was observed in the autoclave.
)Rarena. The oil phase and aqueous phase of the reaction solution were analyzed in the same manner as in Example 1, and m-aminophenol conversion (hi rate: 98.2) was obtained.
9σ1N, N-diethyl-m-aconof-nor selection 1
75.9%, N-ethyl-m-aminophenol selectivity 22.3%, 1m-noethylfei tidino selectivity 12%
, the dimer selectivity was 1.1%.

<Comparative Example-2> Ammonia water +: The reaction was carried out in the same manner as in Example-1 except that diammonium hydrogen phosphate (0,1795 mol) was used instead. The pH of the reaction solution was low, about 23.

Some corrosion was observed in the autoclave. The reaction result is m
-Aminophenol conversion rate 98.9%, N,N-/'ethyl-m-aminophenol selectivity 71.1'N-ethyl-m-aminophenol selectivity 25.29g.

m-noethylph neti';/selectivity 13% 2 B, j
, the body selectivity was 08%.

<Ratio 1 bite case-3> Instead of ammonia water, use sodium carbonate (0,1795
mol), and the rest was the same as in Example 1 (where this reaction was carried out, the reaction pressure was 32.6 Kq//cfl G).
Yu ascended. After the reaction was completed, the pH of one reaction solution was 3.9. The reaction AM was analyzed and the following reaction results were obtained. m-aminophenol conversion rate 98.9%, N,N-diethyl-m-aminophenol-9 selectivity 72.2%, N-ethyl-m-aminophenol S selectivity 17.4%, m-diethylphenetidine. Removal rate 47; Xi 2 i, i body selection 4
7 <・<, < 1.2% 1゜〈Ratio 1 bite case-4〉 Instead of ammonia water, hydroxide red sea bream / lamb (0,1
795 mol), and the reaction was carried out in the same manner as in Example-1 except for the following. In addition, at the beginning of the second reaction, stirring was almost impossible.

After the reaction was completed, the pH of the two reaction solutions was 3.7. Separation of the oil phase and water phase of the reaction solution is iniif.

After cooling, the outside of the oil phase was fixed and separated. Therefore.

The produced inorganic salts contained a large amount of jj'c+ fixed substance number for oil.

In addition, 1 reaction result is 9m-aminoph-nol conversion rate 99.2
%, N,N-noedyl-m-aminophenol conversion rate 77.6%, N-edyln]-aminophenol selectivity 156%, 9m-diethylfey-thousandino selectivity 13
%, dimer selectivity! ,7. ! %Met. .

<Example-4> By chemically modifying m-aminophenol, using N-ethyl-m-aminophenol (0,2795 mol) L/), ethyl chloride (0.34, 1 mol), water 12 .3g
r, 28% ammonia water (0,1795 mol) was charged and heated at 100°C for 4 +1. Reaction was performed between IJ. After reaction path f, the reaction solution 1 was analyzed in the same manner as in Example 1, and the results of the 2nd reaction were that the conversion rate of N-ethyl-m-aminophenol was 99.
3%, N,N-diethyl-m-aminopheno-9 selectivity 97.0%.

The selectivity for nl-noethylph-i-thinone was 08% and the selectivity for dimer was 0.3%.

<Comparative Example-5> Sodium carbonate (009 mol) instead of ammonia water
The rest was the same as in Example 4 (this reaction was carried out and the following results were obtained as one reaction result: N-ethyl-m-aminophenol'k conversion rate 96.2%, N,N-diethyl -m-aminopheno-9 selectivity 89.8%.

The m-noethylph netino 7 selectivity was 4.8% and the dimer selectivity was 1.0%.

<Examples 5 to 7> Table 1 (Other than what is shown here, the reaction was carried out in the same manner as in Example 1, and the results shown in Table 9 were obtained.

(Effect of the invention) By using ammonia as a deoxidizing agent in the N-alkylation reaction, the N,N-noalkylation selection method 9-1-1 improves the zero straightness after the reaction ( = The present invention uses effective and cheap ammonia (from this, N-alkyl substituted aminophenolsffi
It has an industrial advantage (it has the advantage of being able to be manufactured).

Claims (1)

[Claims] General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) Phenols and an alkyl halide represented by the general formula (II) R_2X(II) (wherein R_2 is an alkyl group having 1 to 6 carbon atoms and X represents a halogen) are used as a deoxidizing agent in the coexistence of water. General formula (III) characterized by heating ammonia in a pressurized container and reacting under pressure ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1 and R_2 have the above meanings A method for producing N-alkyl-substituted aminophenols represented by