JPS58219158A - Hydroxyalkanesulfonic acid, its derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula (R is 1-10C alkyl) and its derivative. EXAMPLE:2-Phenyl-2-hydroxypropanesulfonic acid and its salt. USE:Useful as a raw material of an amidoalkanesulfonic acid derivative which is useful as a lime soap dispersing agent, a modifier of fiber made of water-soluble polymer, etc. PROCESS:The compound of formula can be prepared by reacting an alpha-alkylstyrene (e.g. alpha-methylstyrene, alpha-ethylstyrene, etc.) with bisulfite ion in a solvent such as water, alcohol, tetrahydrofuran, etc. in the presence of oxygen at -20- +70 deg.C, preferably -10-+60 deg.C for 20min-10hr. Addition of a phase transfer catalyst (e.g. tetramethylammonium chloride) to the reaction system promotes the reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel hydroxyalkanesulfonic acids and derivatives thereof and methods for their production. More specifically, the present invention relates to a hydroxyalkanesulfonic acid i-conductor useful as a raw material for producing amidoalkanesulfonic acid derivatives and a method for producing the same.

The compound of the present invention has the general formula (where R represents a lower alkyl group having 1 to 10 carbon atoms).
It is a hydroxyalkanesulfonic acid and its derivatives represented by, and is a new compound that has not been described in any literature.

In the above general formula, R is a lower alkyl group having 1 to 10 carbon atoms, and its structure may be linear or branched.

In addition, the sulfonic acid derivative represented by the above general formula is
It refers to ammonium salts, alkali metal salts and alkaline earth metal salts of the sulfonic acid, and the alkali metal salts include lithium salts, sodium salts and potassium salts, and the alkaline earth metal salts include magnesium salts, calcium salts and barium salts. are mentioned as common ones.

The compounds of the present invention include 2-phenyl-2-hydroxypropanesulfonic acid and its ammonium salt, Na+ salt, K+ salt, Mg2+ salt, Ca2+ salt, Ba2+ salt, 2-
Phenyl-2-hydroxy-butanesulfonic acid and its ammonium salt v Na+ salt, K+ salt, Mg2+ salt,
Ca 2+ salt, Ba 2+ salt, 2-phenyl-2-hydroxy-3-methyl-butanesulfonic acid and its ammonium salt, Na tate salt, K teshio, Mg 2+ salt, Ca 2+ salt,
Examples include Ba 2+ salt, 2-phenyl-2-hydroxy-pentanesulfonic acid and its amphium salt, N 3+ salt, K salt, Mg 2+ salt, Ca 2+ salt, and Ba 2+ salt.

The compounds of the present invention can be easily produced by reacting α-alkylstyrene with bisulfite ions in an aqueous medium in the presence of oxygen.

As the α-alkylstyrene, styrene derivatives substituted with a lower alkyl group having 1 to 10 carbon atoms at the α position of the double bond of styrene can be used, such as α-methylstyrene, α
-ethylstyrene, α-n-furobylstyrene, α-isopropylstyrene, and the like.

Further, as the oxygen to be supplied to the reaction system, pure oxygen gas may be supplied, or an oxygen-containing gas such as air may be supplied. However, it is advantageous for the reaction to proceed more quickly if the oxygen concentration in the supplied gas is higher.

Various types of water can be used as the aqueous medium, such as well water, tap water, industrial water, and ion exchange water. The brush can also use a mixture of water and a water-miscible organic solvent as the reaction solvent. As the organic solvent to be mixed with water, either a protic solvent such as alcohol or an aprotic solvent such as acetonitrile, tetrahydrofuran, didimethylacetamide, or dimethyl sulfokide can be used. However,
Since α-alkylstyrene has low solubility in water, α
- In order to increase the amount of alkylstyrene dissolved in the reaction solution, a mixed solvent of an organic solvent and water is convenient; However, it is not necessarily economically advantageous.

Moreover, various surfactants or phase transfer catalysts can be added to speed up the reaction.

As the surfactant, various types of cationic, nonionic, and anionic surfactants can be used, and among them, cationic and nonionic surfactants are preferably used. Such phase transfer catalysts include tetramethylammonium chloride, tetraethylammonium bromide,
Quaternary ammonium salts such as tetrabutylammonium bromide, benzyltriethylammonium chloride, and trioctylmethylammonium chloride can be used. The sulfite ice ion supply material can be obtained by dissolving alkali metal bisulfite or alkaline earth metal sulfite such as sulfite, ammonium hydrogen sulfite, sodium sulfite water ice, potassium hydrogen sulfite, and ice lithium sulfite in sulfite water. Hydrogen sulfites of alkaline earth metals such as magnesium hydrogen sulfite, calcium hydrogen sulfite, and barium hydrogen sulfite can also be used.
Fes+, which forms a redox system with hydrogen sulfite ions;
The reaction can also be carried out by adding transition metal ions such as Cu2+. Regarding the pH of the reaction solution, pH 0.2 to 7.
, preferably adjusted to 05 to 6 to carry out the reaction. If the pH is lower than 0.5, the concentration of hydrogen sulfite ions in the reaction solution decreases, the concentration of undissociated sulfite becomes relatively high, and the progress of the reaction tends to be delayed. on the other hand,
When the pH is 6 or more, the depth of sulfite ions becomes relatively high, the production of by-products takes priority, and the yield of the target product tends to decrease.

Normally, the pH decreases as the reaction progresses, but if the pH drops below 0.5, an alkaline substance such as an alkali metal or alkaline earth metal hydroxide or carbonate may be added. Just adjust the pH.

The reaction temperature is -20~70℃, preferably -10~60℃
The reaction time varies depending on the reaction temperature, but is usually in the range of 20 minutes to 10 hours.

The quantitative relationship between hydrogen sulfite ion and α-alkylstyrene is such that the former is usually present in excess for the reaction, and their molar ratio is in the range of 10 to 20.0, preferably 1.5 to 15. The relative proportions of α-alkylstyrene and aqueous medium are:
The volume ratio is usually in the range of 5/95 to 60/4°.

To suitably carry out the method of the present invention, a hydrogen sulfite ion supplying substance and an α-alkylstyrene are added to an aqueous medium, and an oxygen-containing gas such as oxygen gas or air is present in the aqueous medium.
The reaction may be carried out under stirring.

The hydrogen sulfite ion supply substance may be added in solid form or may be added in dissolved form. On the other hand, since α-alkylstyrene has low solubility in water, the reaction solution usually forms two transparent layers, but the reaction may be carried out by suspending the α-alkylstyrene by stirring.

On the other hand, oxygen may be supplied by blowing oxygen or an oxygen-containing gas under flow, or may be supplied under pressure in a closed system. The latter reaction in a closed system is more convenient in that the reaction can be carried out more quickly. Furthermore, in order to carry out the reaction quickly, the stirring speed should be increased so that oxygen gas can be easily absorbed into the reaction solution and α-alkylstyrene p
What is necessary is to make the dispersion in the reaction liquid more fine. After carrying out the reaction for a predetermined period of time while monitoring the reaction, the desired 2-phenyl-2-hydroxyalkanesulfonate salt can be separated according to a conventional method.

As a method for monitoring the reaction, supply of oxygen, disappearance of 2-alkylstyrene, production of the target product, etc. may be comprehensively monitored using a gas flowmeter, gas chromatograph, high performance liquid chromatograph, or the like. Conventional methods for separating the target product include, for example, leaving the reaction solution to cool and separating it by crystallization, and distilling off the aqueous medium from the reaction solution.
The remaining part can be separated by recrystallization with a polar solvent such as water or hydrous alcohol, or the liquid can be passed through an ion exchange resin such as H-type strongly acidic cation exchange resin and the effluent can be mixed with alkaline earth metal water. Adding oxides or carbonates,
There is a method of obtaining the target product as an aqueous solution by removing unreacted average acid groups and by-produced sulfate groups.

In addition, the type of cation that is the counter ion of the sulfonate of the compound of the present invention can be determined by the counter cation of the hydrogen sulfite ion to be reacted, or it can be determined by passing the solution through an H-type strongly acidic cation exchange resin. It can also be determined by neutralizing the effluent with a predetermined alkali. Furthermore, ° can also be determined by replacing the cation exchange resin with the desired cation and passing the solution through the cation exchange resin.

The hydroxyalkanesulfonate produced according to the above method may contain 2-phenyl-2-sulfate-alkane-1-sulfonate as a by-product. However, this compound can be exchanged to the desired compound by hydrolysis with acid or alkali, and when used as a raw material for producing amidoalkanesulfonic acid derivatives, compounds containing the above-mentioned by-products can be used. Even when used, the desired amidoalkanesulfonic acid derivative can be produced without any problem.

The sulfonic acid and its derivatives of the present invention are useful as raw materials for amidoalkanesulfonic acid derivatives, which have uses as limestone dispersants, water-soluble polymer raw material fiber modifiers, etc. In particular, diamidoalkanesulfonic acid derivatives can be produced very easily.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 674 f of hydrogen sulfite and 1.2 t of water were added to a 2 t round bottom flask, and the mixture was poured with stirring.

After replacing the atmosphere in the Scotch with oxygen, α-methylstyrene 1922 was added, and the stirring speed was increased to 1. The reaction was carried out at 50° C. for 10 hours at ooo rpn. □The reaction was carried out in a closed system, and the pressure inside the flask was increased to 10 mmHg.
Oxygen was supplied.

During this time, the pH of the reaction solution was 0. When the pH decreased to below 0.5, an aqueous solution of caustic soda was added to maintain the pH above 0.5. This operation was repeated 10 times until the reaction was completed. The reaction solution was left overnight in a water bath to crystallize.

522f crystals were obtained, which contained 32% sodium sulfate. When this was further recrystallized with water, white crystals with a sodium sulfate content of 9 - 610? (
Yield: 73%).

1 This substance was subjected to infrared absorption spectrum, nuclear magnetic resonance spectrum, and structural determination as a benzylamine salt derivative.

The infrared absorption spectrum is shown in FIG. 1, and the nuclear magnetic resonance spectrum is shown in FIG. 2. The analytical values when converted into benzylamine salt are shown below.

Elemental analysis value (4) Analysis at a melting point of 139-140°C or higher shows the structure of the compound obtained in the above reaction as 2-phenyl-2-hydroxypro6-1-
It was determined to be sodium sulfonate.

H3 Example 2 and Example 1 The pH of the reaction solution was adjusted to 0.4 with sulfuric acid, and the reaction was carried out in exactly the same manner as in Example 1, except that 252 of the target compound was obtained (yield: 6%).

Example 6 When the reaction was carried out in the same manner as in Example 1 except that the pH was adjusted to 7 with caustic soda, a white substance of 260% was obtained.
I got t. The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product showed absorption peaks other than those of the target compound, and the presence of some by-products was recognized.

Example 4 The reaction was carried out in exactly the same manner as in Example 1 except that one drop of 10 copper thiosulfate aqueous solution was added, and the target compound was reduced to 3.
0J f (yield: 72 cm) was obtained.

Example 5 Sodium 2-phenyl-2-hydroxy-propanesulfonate 281 was dissolved in 300-m water, and this aqueous solution was added to 300 ml of H-type strong acid cation exchange resin at sv (space velocity) 3 H,-1. A solution was passed through the tube to perform ion exchange.

Divide the effluent into two equal parts, and remove the water from one half by distilling off the water.
Phenyl-2-hydroxy-propanesulfonic acid 112
I got it.

Calcium carbonate 152 was added to half of the residue, and after thorough stirring, the insoluble portion was separated and 2-phenyl-2-hydroxy-
Calcium propanesulfonate was obtained in an aqueous solution. This aqueous solution was evaporated to dryness to obtain calcium 2-phenyl-2-hydroxypropanesulfonate 111.

[Brief explanation of the drawing]

FIGS. 1 and 2 are examples of R and NMR spectra of products obtained according to the invention. Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) General formula (where R represents a lower alkyl group having 1 to 10 carbon atoms)
Hydroxyalkanesulfonic acid and its derivatives represented by: (2) The hydroxyalkanesulfonic acid and its derivatives according to claim 1, which are 2-phenyl-2-hydroxy-propanesulfonic acid and its salts. (6) Hydroxy alkane represented by the general formula (R represents a lower alkyl group having 1 to 10 carbon atoms) by reacting α-alkylstyrene with hydrogen sulfite ion in an aqueous medium in the presence of oxygen. A method for producing sulfonic acid and its derivatives. (4) The method according to claim 3, wherein the α-alkylstyrene is α-methylstyrene.