JPH05140079A - New sulfonate and its production - Google Patents

Abstract

PURPOSE:To provide the subject compound having excellent bleaching power and useful as a precursor of organic peracid for oxygen-based bleaching agent. CONSTITUTION:The compound of formula I [R<1> is 1-5C alkyl or alkenyl; R<2> and R<3> are (1-8C alkylene or 1-5C alkyl-substituted)phenylene; A is 2-4C alkylene; M is alkali metal atom, alkaline-earth metal atom, etc.; (n) is 0-100], e.g. 2- ethoxyethoxyacetonyl oxyethylsulfonic acid sodium salt. The compound of formula I can be produced e.g. by reacting 1mol of a compound of formula HO-R<3>-SO3M with preferably 0.8-2mol of a compound of formula II (Y is hydroxy, halogen, etc.) in an inert organic solvent preferably at 80-220 deg.C optionally in the presence of an esterification catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sulfonate useful as an organic peracid precursor in a household bleaching agent such as a fungicide, a kitchen bleaching agent and a clothing bleaching agent, and a process for producing the sulfonate.

[0002]

2. Description of the Related Art Conventionally, chlorine-based bleaching agents and oxygen-based bleaching agents have been known as bleaching agents, but the former has a strong chlorine-based odor, strong irritation to eyes, skin, etc. There is a problem that toxic gas is generated when used in combination with the detergent.

Therefore, in recent years, oxygen-based bleaching agents which do not have such a danger have been widely used.
Then, in order to enhance the bleaching activity, a first agent containing hydrogen peroxide or a peroxide that generates a peracid in an aqueous solution and a second agent containing an organic peracid precursor are used in combination. ing. As the organic peracid precursor to be blended in the second agent, for example, tetraacetylethylenediamine, tetraacetylglycoluril, pentaerythritol tetraacetate, etc. are used (Japanese Patent Laid-Open Publication No. 6-58242).
No. 2-4794).

[0004]

However, the conventional organic peracid precursors have the drawback that they have a strong pungent odor and are difficult to put into practical use because they generate peracetic acid as a bleaching active species.

[0005]

Under these circumstances, the inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, the novel sulfonate represented by the following general formula (1) has no irritating odor and is excellent. The present invention has been completed by discovering that it exhibits a bleaching power and is useful as an organic peracid precursor of an oxygen-based bleaching agent.

That is, the present invention has the following general formula (1):

[0007]

[Chemical 3]

[In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 1 to 5 carbon atoms, and R ² and R ^2
3 are the same or different and each represents a linear or branched alkylene group having 1 to 8 carbon atoms or a phenylene group which may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, and A is The same or different, each represents an alkylene group having 2 to 4 carbon atoms, M represents an alkali metal atom, an alkaline earth metal atom, ammonium, an alkylammonium or an alkanolammonium, and n represents a number from 0 to 100]. And a method for producing the same.

In the sulfonate represented by the formula (1) of the present invention, the linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms represented by R ¹ is methyl,
Ethyl, propyl, butyl, pentyl, isopropyl,
Examples thereof include isobutyl and isopentyl groups. Also, R
² and R ³ represent a straight-chain or branched alkylene group having 1 to 8 carbon atoms, or a phenylene group which may be substituted with a straight-chain or branched alkyl group having 1 to 5 carbon atoms, methylene, Ethylene, propylene, ethylethylene, trimethylene, tetraethylene, hexamethylene,
Heptamethylene, octamethylene, 1,2-phenylene, 1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2- Butyl-1,4-phenylene, 2-heptyl-1,4-phenylene, 2- (1-methylethyl) -1,4-phenylene, 2- (1-methylpropyl) -1,4-phenylene, 2- (2-methylbutyl) -1,4-phenylene group and the like can be mentioned. Examples of the alkylene group having 2 to 4 carbon atoms represented by A include ethylene, propylene, trimethylene, and tetramethylene. Examples of the alkali metal atom represented by M include a sodium atom and a potassium atom, examples of the alkaline earth metal atom include a magnesium atom and calcium atom, and examples of the alkylammonium include methylammonium and diethylammonium. Examples of the alkanol ammonium include monoethanol ammonium and triethanol ammonium.

In the general formula (1) representing the sulfonate of the present invention, n oxyalkylene groups (AO) are used.
May be one kind of oxyalkylene group or a combination of different oxyalkylene groups. Specifically, a polyoxyethylene group, a polypropylene group, a polyoxyethylene-polyoxypropylene group and the like can be mentioned.

The sulfonate (1) of the present invention is obtained by reacting an ethercarbonyl compound represented by the general formula (2) with a hydroxyalkanesulfonic acid represented by the general formula (3), for example, according to the following reaction formula. Can be manufactured by.

[0012]

[Chemical 4]

[Wherein R ¹ , R ² , R ³ , A, M and n
Have the same meaning as described above, and Y represents a hydroxy group, a halogen atom or an alkoxy group having 1 to 3 carbon atoms] In the above formula, the halogen atom represented by Y is a chlorine atom, a fluorine atom, a bromine atom, Examples thereof include an iodine atom, and examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy,
A propoxy group etc. are mentioned.

Examples of the ether carbonyl compound represented by the general formula (2) used in the production method of the present invention include methoxyacetic acid, 2-methoxypropionic acid,
p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid,
2-propoxypropionic acid, p-propoxybenzoic acid, butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid, 2-methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid, 2-methoxy-2-methyl Ethoxyacetic acid, 2-ethoxyethoxyacetic acid, 2-
(2-Ethoxyethoxy) propionic acid, p- (2-ethoxyethoxy) benzoic acid, 2-ethoxy-1-methylethoxyacetic acid, 2-ethoxy-2-methylethoxyacetic acid, 2-propoxyethoxyacetic acid, 2-propoxy- 1
-Methylethoxyacetic acid, 2-propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid, 2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid, 2- (2-methoxyethoxy) ethoxy Acetic acid, 2- (2-methoxy-1-methylethoxy) ethoxyacetic acid, 2- (2-methoxy-2-methylethoxy)
Organic acids such as ethoxyacetic acid and 2- (2-ethoxyethoxy) ethoxyacetic acid or mixed acids thereof, acid halides of the above organic acids or mixtures thereof, lower alcohol esters of the above organic acids or mixtures thereof are used. Be done.

These ether carbonyl compounds (2)
Can be obtained by any method, but in the case of the organic acid (2-a) in which Y is a hydroxy group in the formula (2), the corresponding glycol ether salt ( It can be obtained by reacting 4) with a halogen compound (5).

[0016]

[Chemical 5]

[In the formula, R ¹ , R ² , A, M and n have the same meanings as described above, and X represents a halogen atom]

In the formula (2), the organic acid (2-b) in which Y is a hydroxy group is prepared by reacting the (poly) oxyethylene ether (6) with oxygen or air in the presence of a platinum or palladium catalyst according to the following reaction formula. It can also be obtained by using and oxidizing.

[0019]

[Chemical 6]

[Wherein R ¹ , A and n have the same meanings as described above] Furthermore, in the formula (2), an acid halide (2-c) in which Y is a halogen atom and Y has 1 to 3 carbon atoms. The lower alcohol ester (2-d) which is an alkoxy group can be produced from the organic acid (2-a) or organic acid (2-b) obtained above by a known method.

Examples of the hydroxyalkanesulfonic acid represented by the general formula (3) used in the production method of the present invention include 2-hydroxyethanesulfonic acid (isethionic acid), 2-hydroxypropane-1-sulfonic acid, 1 -Hydroxypropane-2-sulfonic acid, 1-hydroxybutane-2-sulfonic acid, 2-hydroxypentane-1-sulfonic acid, 4-hydroxyphenylsulfonic acid, 2-methyl-4-hydroxyphenylsulfonic acid, 2-ethyl -4-hydroxyphenyl sulfonic acid,
2-propyl-4-hydroxyphenyl sulfonic acid, 2
-Butyl-4-hydroxyphenylsulfonic acid, 2-
Hydroxyalkanesulfonic acids such as (1-methylethyl) -4-hydroxyphenylsulfonic acid, 2- (2-methylpropyl) -4-hydroxyphenylsulfonic acid, and 2- (2-methylbutyl) -4-hydroxyphenylsulfonic acid. Sodium salt, potassium salt, calcium salt,
Examples thereof include ammonium salt, methylammonium salt, diethylammonium salt and triethanolammonium salt.

In the production method of the present invention, the ether carbonyl compound (2) is used in an amount of 0.5 to 3 mol, particularly 0.8 mol, based on 1 mol of the hydroxyalkanesulfonate (3).
It is preferable to react 2 to 2 mol. A solvent is not always necessary for this reaction, but it can be used. As the solvent used here, any solvent may be used so long as it is inert to the raw materials and the reaction product, and particularly in the reaction with an organic acid, an azeotropic mixture is formed with water to perform a dehydrating action. An inert organic solvent that facilitates the process is preferable.
Examples of such an inert organic solvent include inert solvents such as benzene, cyclohexane, toluene, xylene, ethylbenzene and monochlorobenzene, and these can be used alone or in combination.

The reaction temperature is 70 to 250.
C., especially 80 to 220.degree. C. are preferred.

The reaction in the production method of the present invention proceeds satisfactorily without using a catalyst, but the reaction can be carried out more efficiently by using an esterification reaction catalyst usually used in the esterification reaction. Of such esterification reaction catalysts, examples of acidic catalysts include sulfuric acid, hydrochloric acid,
Examples of the basic catalyst include paratoluenesulfonic acid and the like, and examples of the basic catalyst include alkali metal hydroxides and alkali metal alcoholates. The amount of the esterification reaction catalyst used is 0.1 to 5% by weight based on the whole reaction system.
A degree is preferable.

Further, the progress of the reaction in the production method of the present invention can be confirmed by measuring the amount of water or alcohol distilled out of the system. In addition to the desired sulfonate of the present invention represented by the formula (1), the obtained reaction mixture may contain unreacted ether carbonyl compound (2) and hydroxyalkanesulfonic acid (3) depending on the reaction molar ratio.
Alternatively, the solvent or catalyst used is included. The reaction product thus obtained can be used as it is depending on the purpose of use, but can be further purified to obtain a highly pure product.

Examples of the purification method include filtration or distillation under reduced pressure for removal of the reaction solvent, and crystallization, reprecipitation, dialysis, etc. for removal of unreacted raw materials and catalyst. For example, sodium 2-ethoxyethoxyacetonyloxyethyl sulfonate [in the compound of formula (1), R ¹ = C ₂ H ₅ , R ² = CH ₂ , R ³ = C ₂ H ₄ , A = C
₂ H ₄ , M = Na], 2-ethoxyethoxyacetic acid and sodium 2-hydroxyethylsulfonate (sodium isethionate) are reacted without solvent and without a catalyst, and then acetone is added to wash the product. High-purity sodium 2-ethoxyethoxyacetonyloxyethyl sulfonate can be obtained by filtration.

[0027]

INDUSTRIAL APPLICABILITY The novel sulfonate (1) of the present invention reacts with hydrogen peroxide or a peroxide which forms hydrogen peroxide in an aqueous solution to form an organic peracid, and has no irritating odor and is excellent in bleaching. Since it exhibits power, it is excellent as an organic peracid precursor of an oxygen-based bleaching agent, and a bleaching agent composition containing this is a household bleaching agent such as a mold remover, a kitchen bleaching agent, and a clothing bleaching agent. Is particularly useful as

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 222 g (1.5 mol) of 2-ethoxyethoxyacetic acid and 148 g of sodium isethionate were placed in a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen condenser and a reflux condenser equipped with a water separator. (1.0 mol) was charged and heated from the outside while stirring under a nitrogen atmosphere. Distillation of water produced by the reaction was observed during the temperature rise, and the temperature was further raised to 180 ° C. After 5 hours at this temperature, the amount of distilled water became 17 ml, and the distillation was stopped, so the reaction was terminated and the reaction mixture was cooled. As a result, 353 g of a pale yellow paste was obtained. Next, 200 ml of acetone is added to the reaction product, and the mixture is stirred and solid-liquid separated by filtration. After repeating this washing operation three times, the acetone was distilled off under reduced pressure, and the residue was further purified by column chromatography to obtain 261 g of sodium 2-ethoxyethoxyacetonyloxyethylsulfonate as a pale yellow solid (based on sodium isethionate). The yield was 93.9%). ¹ H-NMR: δ (ppm) 1.20 (t, 3H, C H ₃ CH ₂ O-) 3.50 (broad, 2H, CH ₃ C H ₂ O-) 3.56 (broad, 4H, -OC H ₂ C H ₂ O-) 3.70 (s, 2H, -OC H ₂ COO-) 4.58 (t, 2H, -OC H ₂ CH ₂ SO ₃ Na) 3.24 (t, 2H, -OCH ₂ C H ₂ SO ₃ Na) ¹³ C -NMR:

[0030]

[Chemical 7]

Δ (ppm): a; 15.0, h; 49.8, g; 61.0, b; 61.4, c; 67.6, e; 69.9, d;
73.7, f; 170.5 Elemental analysis:

[0032]

[Table 1]

Example 2 In a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen blow-in tube and a reflux condenser equipped with a water separator, 198 g (1.5 mol) butoxyacetic acid and ammonium 2-hydroxypropanesulfonate were added. 157 g (1.0 mol), p-toluenesulfonic acid 17.2 g (0.1 mol) and xylene 200 ml were charged and heated from the outside with stirring under a nitrogen atmosphere to 140 ° C. It was observed that the water produced by the reaction distilled out as an azeotrope with xylene and separated in a water separator. After 6 hours at this temperature, the distilled water amounted to 17 ml, and the distillation was stopped, so the reaction was terminated and the mixture was cooled. Then, the reaction product was subjected to suction filtration for solid-liquid separation, and further washed with 200 ml of acetone three times.
Thereafter, acetone was distilled off under reduced pressure, and the residue was further purified by column chromatography to give 255 g of a pale yellow solid ammonium butoxyacetonyloxypropyl sulfonate (yield 94.1% based on ammonium 2-hydroxypropane sulfonate). was gotten. Elemental analysis:

[0034]

[Table 2]

Example 3 222 g (1.5 mol) of 2-ethoxyethoxyacetic acid and p-phenolsulfone were placed in a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a reflux condenser equipped with a water separator. 196 g (1.0 mol) of sodium acidate and 200 ml of xylene were charged and heated from the outside with stirring under a nitrogen atmosphere to 140 ° C. It was observed that the water produced by the reaction distilled out as an azeotrope with xylene and separated in a water separator. After 8 hours at this temperature, the distilled water amounted to 16 ml, and since the distillation stopped, the reaction was terminated and the mixture was cooled. Then, the reaction product was subjected to suction filtration for solid-liquid separation, and further washed with 200 ml of acetone three times. After that, acetone was distilled off under reduced pressure, and the residue was further purified by column chromatography to give 290 g of sodium 2-ethoxyethoxyacetonyloxyphenylsulfonate as a pale yellow solid (yield 89.0 based on sodium p-phenolsulfonate). %)was gotten. Elemental analysis:

[0036]

[Table 3]

Example 4 243 g (1.5 mol) methyl 2-ethoxyethoxyacetate and sodium isethionate were placed in a 1 liter flask equipped with a stirrer, thermometer, nitrogen blowing tube and reflux condenser with water separator. 148 g (1.0 mol) was charged and heated from the outside with stirring under a nitrogen atmosphere. Distillation of methanol produced by the reaction was observed during the temperature rise, and the temperature was further raised to 180 ° C. After 5 hours at this temperature, the amount of distilled methanol reached 30 g, and the distillation stopped, so the reaction was terminated and the reaction mixture was cooled.
was gotten. Next, 200 ml of acetone is added to the reaction product, and the mixture is stirred and solid-liquid separated by filtration. After repeating this washing operation three times, acetone was distilled off by vacuum drying and further purified by column chromatography. As a result, 256 g of sodium 2-ethoxyethoxyacetonyloxyethylsulfonate as a pale yellow solid (based on sodium isethionate) was obtained. The yield was 92.1%). Elemental analysis:

[0038]

[Table 4]

Example 5 In a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a reflux condenser equipped with a water separator, 75.3 g (0.5 mol) of butoxyacetic acid and 2-hydroxypropanesulfone were added. 157 g (1.0 mol) of ammonium acidate and 200 ml of xylene were charged, and the mixture was heated from the outside with stirring under a nitrogen atmosphere to 90 ° C. At this temperature, 150.5 g (1.0 mol) of butoxyacetic acid chloride was added dropwise.
At this time, a slight exotherm was observed. After that, 140 ° C
The temperature was raised to 0 ° C., and stirring was continued for 5 hours at this temperature, then the reaction was terminated and the mixture was cooled. Then, the reaction product was subjected to suction filtration for solid-liquid separation, and further washed with 200 ml of acetone three times. Then, acetone was distilled off under reduced pressure, and the residue was further purified by column chromatography to give a pale yellow solid ammonium butoxyacetonyloxypropyl sulfonate 2
45 g (yield 90.4% based on ammonium 2-hydroxypropanesulfonate) was obtained. Elemental analysis:

[0040]

[Table 5]

Test Example 1 A bleaching agent aqueous solution containing 10% by weight of tetraacetylethylenediamine and 3% by weight of hydrogen peroxide, which are conventionally used as the sulfonates or organic peracid precursors of the present invention obtained in Examples 1 to 3. (Available oxygen concentration of about 1.41%) was prepared and subjected to the mold bleaching power test and odor test by the following methods. The results are shown in Table 6.

Mold bleaching power: A plastic plate (A) inoculated with Cladosporium herbarum and cultured at 30 ° C. for 14 days (A
(Made of BS resin) is used as a model mold plate, which is placed horizontally, 40 μl of a bleaching agent composition aqueous solution is dropped, left for 30 minutes, washed with water and air-dried, and then using a colorimeter 1001DP manufactured by Nippon Electric Industry Co., Ltd. The lightness (L value) was measured. still,
The L value of the plastic plate was 92.4, and the L value of the model mold plate was 65 to 75. The higher the number, the better the mold bleaching power. Odor: The odor of the aqueous solution of the bleaching composition was sensory evaluated by 10 panelists. ◯: No irritating odor or offensive odor ×: Irritating or offensive odor

[0043]

[Table 6]

Test Example 2 Each sulfonate of the present invention obtained in Examples 1 to 3 or 10% by weight of tetraacetylethylenediamine conventionally used as an organic peracid precursor, 10% by weight of sodium percarbonate and 2 of sodium dodecylsulfate. An aqueous bleaching agent solution containing about 1% by weight (effective oxygen concentration: about 1.22%) was prepared and subjected to the bleaching power test of black tea-contaminated cloth by the following method and the odor test by the same method as in Test Example 1. The results are shown in Table 7.
Shown in.

Bleaching power of black tea-contaminated cloth: The black tea-contaminated cloth was dipped in an aqueous solution of a bleaching agent, and after 10 minutes, the bleaching power was measured, and the bleaching rate was calculated by the following formula. The higher this value, the better the bleaching power of the black tea-contaminated cloth.

[0046]

[Equation 1]

[0047]

[Table 7]

Front Page Continuation (72) Inventor Yumoto Politics 4954 Hanawa-cho, Haga-gun, Tochigi Kao-jomi Dormitory D-311

Claims (2)

[Claims] 1. The following general formula (1): [In the formula, R ¹ represents a straight-chain or branched-chain alkyl group or alkenyl group having 1 to 5 carbon atoms, R ² and R ³ are the same or different and each represents a straight-chain or branched-chain group having 1 to 8 carbon atoms. An alkylene group or a phenylene group which may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, A is the same or different and represents an alkylene group having 2 to 4 carbon atoms, and M is an alkali A metal atom, an alkaline earth metal atom, ammonium, an alkylammonium or an alkanolammonium, and n represents a number of 0 to 100]. 2. The following general formula (2): [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 1 to 5 carbon atoms, and R ² represents a linear or branched alkylene group having 1 to 8 carbon atoms or 1 to 5 carbon atoms. Represents a phenylene group which may be substituted with a linear or branched alkyl group, wherein A is the same or different and has 2 carbon atoms.
To 4 alkylene groups, Y represents a hydroxy group, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and n is 0.
To the ether carbonyl compound represented by the following general formula (3) HO-R ³ -SO ₃ M (3) [wherein R ³ is a straight chain or branched chain having 1 to 8 carbon atoms] Shows an alkylene group of a chain or a phenylene group which may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms,
M represents an alkali metal atom, an alkaline earth metal atom, ammonium, an alkylammonium or an alkanolammonium]. The method according to claim 1, wherein the hydroxyalkanesulfonic acid is reacted.