JP2003055336A - Method for producing aminoester compound or its mineral acid salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aminoester compound or its mineral acid salt without causing the rise of liquid level and the overflow of the reaction liquid in the esterification reaction. SOLUTION: The aminoester compound expressed by general formula (I): H-N(R<2> )-W<2> -SO2 CH2 CH2 -OY (I) [W<2> is a (substituted) alkylene; and R<2> is H, a (substituted) alkyl, a (substituted) phenyl or the like] is produced by reacting an amino alcohol compound expressed by general formula (II): H-N(R<1> )-W<1> -SO2 CH2 CH2 -OH (II) [W<1> is a (substituted) alkylene; and R<1> is H, a (substituted) alkyl, a (substituted) phenyl or the like], etc., with a specific amount of sulfuric acid, etc., based on the theoretical value per one hydroxy group under heating and evacuation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various industrial products,
In particular, the present invention relates to a method for producing an amino ester compound or its mineral acid salt, which is useful as an intermediate for water- and oil-repellent finishing agents, silver halide photographic hardening agents, surfactants, dyes, pharmaceuticals, agricultural chemicals and the like.

[0002]

2. Description of the Related Art A method for converting an aminoalcohol compound or a mineral acid salt thereof into a sulfuric acid ester by reacting an aminoalcohol compound or a mineral acid salt thereof with a specific amount of sulfuric acid while heating and depressurizing water to remove water. A method of doing so is known (see Japanese Patent Laid-Open No. 9-176109).

[0003]

However, in the known method, it is necessary to finely adjust the degree of pressure reduction and the heating temperature in order to prevent the reaction liquid surface from rising due to the foaming during the esterification reaction and the reaction liquid from rising. However, it is not necessarily industrially advantageous.

[0004]

Means for Solving the Problems The inventors of the present invention have made earnest studies to provide a method for producing an amino ester compound or a mineral acid salt thereof which is industrially advantageous. Distill off water or water and acetic acid under heat and reduced pressure in the presence of a silicone antifoaming agent using 1.25 to 10 times the molar amount of sulfuric acid or fuming sulfuric acid with respect to the theoretical amount per hydroxy group. However, the present invention has been completed by finding that the above problems can be solved by esterification.

That is, the present invention provides (i) the general formula (II) R—N (R ¹ ) —W ¹ —SO ₂ CH ₂ CH ₂ —OH (II) [wherein R represents hydrogen or acetyl. , R ¹ represents hydrogen, optionally substituted C ₁ -C ₄ alkyl, optionally substituted phenyl or —W ¹ —SO ₂ CH ₂ CH ₂ OH. W ¹ represents a linear or branched C ₂ -C ₆ alkylene, which may be substituted, and the carbon chain of the alkylene is interrupted by —O— or —NR ³ —. May be. R ³ represents hydrogen or C ₁ -C ₄ alkyl. ] The amino alcohol compound or its mineral acid salt shown by these, and 1.25-1 with respect to the theoretical amount per hydroxy group in this amino alcohol compound or its mineral acid salt.
0-fold molar amount of is reacted with a sulfuric acid or fuming sulfuric acid, the general formula (I) H-N (R 2) -W 2 -SO 2 CH 2 CH 2 -OY (I) wherein, W ² is a straight It represents a chain or branched C ₂ -C ₆ alkylene, which may be substituted, and the carbon chain of the alkylene may be interrupted by —O— or —NR ³ —. R ³ has the same meaning as described above. R ² is hydrogen, optionally substituted C ₁ -C ₄ alkyl, optionally substituted phenyl or —W ² —SO ₂ CH ₂ CH ₂ OY
, Y represents —SO ₃ M, and M represents hydrogen, an alkali metal or an alkaline earth metal. ] In the method for producing an amino ester compound or a mineral acid salt thereof represented by
In the presence of a silicone-based defoaming agent, water or water and acetic acid are reacted while being distilled off under heating and reduced pressure conditions, and the aminoester compound of the general formula (I) or its mineral acid salt Production method, and (ii) the amino alcohol compound or the mineral acid salt thereof described in (i) above, and a 1.25 to 10-fold molar amount relative to the theoretical amount of one hydroxy group in these compounds or salts. With sulfuric acid or fuming sulfuric acid in the presence of a silicone antifoaming agent under heating and reduced pressure conditions while distilling off water or water and acetic acid, and then reacting the obtained reaction product with water or ice. The present invention provides a method for producing the aminoester compound or the mineral acid salt thereof described in (i) above, which comprises treatment. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the mineral acid salt of the aminoalcohol compound represented by the general formula (II) include hydrochloride and sulfate. These amino alcohol compounds and mineral acid salts can be used in a water-containing state or a dry state. Further, the amino alcohol compound and the mineral acid salt may contain an inorganic salt such as NaCl or Na ₂ SO ₄ . In the present invention, when a compound in which R of the amino alcohol compound (II) is acetyl is used as a starting compound, acetic acid by-produced by hydrolysis of the acetylamino group needs to be removed from the reaction system.

The concentration of sulfuric acid used in the reaction is not particularly limited, but is preferably 20 to 100%, more preferably 40 to 100%.
The concentration is adjusted to 98%. When fuming sulfuric acid is used, its concentration is not particularly limited. Further, sulfuric acid and fuming sulfuric acid may be used in combination. The amount of sulfuric acid or fuming sulfuric acid used is 100% sulfuric acid conversion, and is 1.25 to 10 times the molar amount of the amino alcohol compound represented by the general formula (II) or its theoretical amount per hydroxy group of its mineral acid salt. And preferably 1.2
It is 5 to 5 times the molar amount. Therefore, when the aminoalcohol compound represented by the general formula (II) or its mineral acid salt has two or more hydroxy groups, the amount of sulfuric acid or fuming sulfuric acid used is the above (1.25 to 10 times the molar amount). X (number of hydroxy groups). If the amount of sulfuric acid or fuming sulfuric acid used is less than 1.25 times the molar amount per hydroxy group, the fluidity of the reaction product will be poor and it will be difficult to take out the aminoester compound or its mineral acid salt. However, the extraction yield tends to decrease. On the other hand, if the amount of sulfuric acid or fuming sulfuric acid used exceeds 10 times the molar amount per hydroxy group, the reaction rate tends to be slow.

In the present invention, the order of charging the aminoalcohol compound represented by the general formula (II) or a mineral acid salt thereof, and sulfuric acid or fuming sulfuric acid is not particularly limited. From the viewpoint of reaction rate, it is generally preferable that the reaction temperature is a high temperature, but at a higher temperature than necessary, a side reaction occurs and the yield of the amino ester compound represented by the general formula (I) or its mineral acid salt is increased. Since it tends to decrease, it is preferably 80 to
200 degreeC, More preferably, it is 100-180 degreeC. The degree of reduced pressure is set so that water or water and acetic acid can be distilled out of the reaction system at the set reaction temperature.
It is preferably 1 to 200 mmHg, more preferably 5 to 50 mmHg. Water or water and acetic acid existing in the reaction system are distilled out of the reaction system under heating and reduced pressure conditions in the presence of a silicone antifoaming agent, usually by stirring. The method of the present invention can be carried out by a batch method using an ordinary reactor such as a can, a tank and a kettle.

The present invention provides amino alcohol compounds (I
I) or its mineral acid salt is heated in the presence of 1.25 to 10 times the molar amount of sulfuric acid or fuming sulfuric acid, based on the theoretical amount per hydroxy group in these compounds, and a silicone antifoaming agent. The reaction is carried out under reduced pressure while distilling off water or water and acetic acid. As the silicone antifoaming agent, for example, modified silicone emulsions and silicone emulsions are preferable, and silicone emulsions are particularly preferable. Examples of the silicone emulsion include Foam Clean S- manufactured by Hakuto Co., Ltd.
37, antifoam E-20 manufactured by Kao corporation, and the like. The preferred amount of the silicone antifoaming agent is in the range of 0.05 to 0.5 parts by weight per 100 parts by weight of the amino alcohol compound (II) or its mineral acid salt.

The substituent of the linear or branched C ₂ -C ₆ alkylene group represented by W ¹ in the general formula (II) is
For example, halogen, hydroxy, sulfate, carboxy, cyano, sulfo and the like can be mentioned. Examples of the C ₁ -C ₄ alkyl substituent represented by R ¹ in the general formula (II) include halogen, hydroxy, sulfo, sulfate, carboxy, cyano and phenyl. Examples of the phenyl substituent represented by R ¹ include halogen, hydroxy, sulfo, sulfate, carboxy and the like. W in the general formula (I)
Examples of the substituent of the linear or branched C _{2 to} C ₆ alkylene group represented by ² include, for example, a sulfate which may be present in the form of a halogen, an alkali metal or an alkaline earth metal salt, an alkali metal Alternatively, there may be mentioned carboxy, cyano which may be present in the form of an alkaline earth metal salt, and sulfo which may be present in the form of an alkali metal or alkaline earth metal salt. Examples of the C ₁ -C ₄ alkyl substituent represented by R ² in the general formula (I) include halogen, sulfo, sulfate, carboxy, cyano and phenyl. Further, examples of the substituent of phenyl represented by R ² include halogen, sulfo, sulfate, carboxy and the like.

The amino alcohol compound (II) or its mineral acid salt can be prepared by a known method, for example, by condensing the corresponding chloro or bromoalkylamines with mercaptoethanol, and then oxidizing the resulting thioether compound with hydrogen peroxide. It is manufactured by the method. When the R of the amino alcohol compound (II) is acetyl, it is produced by a method of acetylating the thioether compound obtained by condensation with acetic anhydride and then oxidizing the obtained acetylated product with hydrogen peroxide. It Examples of the amino alcohol compound (II) include the following compounds.

[0012] _{H 2 N-C 2 H 4} SO 2 C 2 H 4 -OH H 2 N-C 3 H 6 SO 2 C 2 H 4 -OH H 2 N-C 4 H 8 SO 2 C 2 H 4 - _{OH H 2 N-C 5 H} 10 SO 2 C 2 H 4 -OH H 2 N-C 6 H 12 SO 2 C 2 H 4 -OH H 2 N-C 2 H 4 OC 2 H 4 SO 2 C 2 H _{4 -OH H 2 N-C 2} H 4 OC 3 H 6 SO 2 C 2 H 4 -OH HN (C 2 H 4 SO 2 C 2 H 4 -OH) 2 HN (CH 3) -C 2 H 4 SO _{2 C 2 H 4 -OH HN (} C 2 H 5) -SO 2 C 2 H 4 -OH HN (C 2 H 5) -C 3 H 6 SO 2 C 2 H 4 -OH H 2 N-CH (C _{2 H 5) -CH 2 SO 2} C 2 H 4 -OH H 2 N-C 2 H 4 -NH-C 2 H 4 SO 2 C 2 H 4 -OH H 2 N-C 2 H 4 -NH-CH _{(CH 3) -CH 2 SO 2} C 2
_{H 4 -OH CH 3 CO-NH} -C 2 H 4 SO 2 C 2 H 4 -OH CH 3 CO-NH-C 3 H 6 SO 2 C 2 H 4 -OH CH 3 CO-NH-C 4 H 8 _{SO 2 C 2 H 4 -OH HN} (C 6 H 5) -C 2 H 4 SO 2 C 2 H 4 -OH

Removal of the aminoester compound (I) or its mineral acid salt is preferably carried out by treating the reaction product obtained after completion of the reaction with water or ice. Specifically, for example, in ice water and cold water, or in ice water or cold water to which alkali such as sodium bicarbonate, potassium hydrogen carbonate, soda ash, potassium carbonate, sodium hydroxide and potassium hydroxide is added, is preferable. Can be taken out in a liquid state by adding the reaction product kept at 80 to 150 ° C. When the reaction product is added to ice water or cold water to obtain a liquid, the alkali may be added to the obtained liquid. The aminoester compound (I) or its mineral acid salt can also be isolated from these liquids by a known method such as concentration, freeze-drying and filtration. In particular,
For use as a water and oil repellent finishing agent, a silver halide photographic curing agent, a surfactant, etc., it is preferable to use the amino ester compound (I) or its mineral acid salt after alkali neutralization.

[0014]

EXAMPLES Next, the present invention will be described more specifically by way of examples.

Example 1 45 kg of 98% sulfuric acid and 25 g of a silicone-based emulsion defoaming agent [Form Clean S-37 manufactured by Hakuto Co., Ltd.]
And 109 kg of a 25 wt% aqueous solution of [2- (2-aminoethyl) sulfonyl] ethanolsulfate were reduced to 15 mmHg with stirring, and then heated to 130 ° C.
The water was removed from the reaction system by distilling off the by-produced water, and the reaction was continued at 130 ° C. After the reaction, 120 ~
The reaction product kept at 130 ° C. was poured into 153 kg of ice water, the resulting aqueous solution was neutralized to pH 1-2 with soda ash, and the production rate of [2- (2-aminoethyl) sulfonyl] ethanol sulfuric acid ester was 98. Earned in%. The properties of the reaction liquid were good when the water was distilled off, and the liquid surface did not rise due to foaming.

Comparative Example 1 [2- (2-Aminoethyl) sulfonyl] ethanol sulfate ester was obtained in the same manner as in Example 1 except that the silicone emulsion defoaming agent was not added. When water was distilled off, the reaction solution vigorously foamed and the liquid level rose.

Comparative Example 2 The same as Example 1 except that 25 g of a higher alcohol type antifoaming agent [methylisobutylcarbinol (4-methyl-2-pentanol)] was added in place of 25 g of the silicone emulsion defoaming agent. As a result, [2- (2-aminoethyl) sulfonyl] ethanol sulfuric acid ester was obtained, but when water was distilled off, an increase in the liquid level due to foaming of the reaction liquid was observed.

[0018]

According to the method of the present invention, the aminoester compound represented by the general formula (I) or its mineral acid salt can be produced with good operability.

Continued front page    (72) Inventor Akihiro Ono             3-1,98-1 Kasugade, Konohana-ku, Osaka             Tomo Chemical Co., Ltd. F-term (reference) 4H006 AA02 AC61 BC10 BC31 BE03

Claims (6)

[Claims] 1. A compound represented by the general formula (II) R—N (R ¹ ) —W ¹ —SO ₂ CH ₂ CH ₂ —OH (II) [wherein R represents hydrogen or acetyl, R ¹ is hydrogen or a substituent]. which may C ₁ -C ₄ alkyl optionally represents phenyl which may be substituted or _{^{-W 1 -SO 2 CH 2 CH 2}} OH. W ¹ represents a linear or branched C ₂ -C ₆ alkylene, which may be substituted, and the carbon chain of the alkylene is interrupted by —O— or —NR ³ —. May be. R ³ represents hydrogen or C ₁ -C ₄ alkyl. ] The amino alcohol compound or its mineral acid salt shown by these, and 1.25-1 with respect to the theoretical amount per hydroxy group in this amino alcohol compound or its mineral acid salt.
0-fold molar amount of is reacted with a sulfuric acid or fuming sulfuric acid, the general formula (I) H-N (R 2) -W 2 -SO 2 CH 2 CH 2 -OY (I) wherein, W ² is a straight It represents a chain or branched C ₂ -C ₆ alkylene, which may be substituted, and the carbon chain of the alkylene may be interrupted by —O— or —NR ³ —. R ³ has the same meaning as described above. R ² is hydrogen, optionally substituted C ₁ -C ₄ alkyl, optionally substituted phenyl or —W ² —SO ₂ CH ₂ CH ₂ OY
, Y represents —SO ₃ M, and M represents hydrogen, an alkali metal or an alkaline earth metal. ] In the method for producing an amino ester compound or a mineral acid salt thereof represented by
In the presence of a silicone-based defoaming agent, water or water and acetic acid are reacted while being distilled off under heating and reduced pressure conditions, and the aminoester compound of the general formula (I) or its mineral acid salt Production method. 2. The aminoalcohol compound or mineral acid salt thereof according to claim 1, and 1.25 to 10-fold molar amount of sulfuric acid based on the theoretical amount of one hydroxy group of these compounds or mineral acid salts. Alternatively, fuming sulfuric acid is reacted in the presence of a silicone antifoaming agent while distilling water or water and acetic acid under heating and reduced pressure conditions, and then treating the resulting reaction product with water or ice. The method for producing an aminoester compound or a mineral acid salt thereof according to claim 1, wherein 3. A 1.25 to 5-fold molar amount of sulfuric acid or fuming sulfuric acid is used with respect to the theoretical amount per hydroxy group in the aminoalcohol compound or its mineral acid salt according to claim 1. The manufacturing method according to 1 or 2. 4. The reaction temperature of the aminoalcohol compound or its mineral acid salt according to claim 1 with sulfuric acid or fuming sulfuric acid is 1.
The manufacturing method according to any one of claims 1 to 3, which has a temperature of 00 to 180 ° C. 5. Obtained by the reaction of the aminoalcohol compound or its mineral acid salt according to claim 1 with sulfuric acid or fuming sulfuric acid,
And the manufacturing method in any one of Claims 2-4 which processes the reaction product heat-retained in the range of 80-150 degreeC with water or ice. 6. The method according to claim 1, wherein the silicone antifoaming agent is a silicone emulsion.