JP4857678B2 - Method for producing sulfur-containing hydroxycarboxylic acid - Google Patents

Description

  The present invention relates to a method for producing a sulfur-containing hydroxycarboxylic acid.

  Conventionally, in order to produce a sulfur-containing hydroxycarboxylic acid, a method of hydrolyzing cyanohydrin has been used. Industrially, a method using sulfuric acid as a catalyst is known. Also known are methods for hydrolyzing hydroxynitrile compounds by the action of microorganisms to convert them into the corresponding hydroxycarboxylic acids (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3).

Japanese Patent Publication No.58-15120 Japanese Patent Laid-Open No. 2-84198 Japanese Patent Laid-Open No. 4-40898

  However, in the method using sulfuric acid as a catalyst, as a result of the reaction between the hydroxynitrile compound and sulfuric acid, the target product, hydroxycarboxylic acid, and an equimolar amount of ammonium sulfate are by-produced. This necessitates complicated processes and increased manufacturing costs.

  In addition, in the method for producing a corresponding hydroxycarboxylic acid compound from a hydroxynitrile compound using a microorganism, the enzyme activity retained by the microorganism is inhibited by cyanide or the like, which is a decomposition product from the hydroxynitrile compound, or the ammonium salt to be purified is purified. A desalting treatment or the like is required, resulting in an increase in manufacturing cost.

  As a result of intensive investigations to find a method for producing a sulfur-containing hydroxycarboxylic acid that does not use a hydroxynitrile compound as a raw material, the present inventors have found that the compound represented by the general formula (1)

(In the formula, R ¹ represents hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
It is possible to preferentially oxidize the primary hydroxyl group of the dihydroxy compound by using a microbial cell or a treated product of a microorganism having the ability to convert the sulfur-containing dihydroxy compound represented by the formula into a corresponding α-hydroxycarboxylic acid compound. The headline, the present invention has been reached.

That is, the present invention
1. General formula (1)

(In the formula, R ¹ represents hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
Or a treated product of a microorganism having the ability to convert the sulfur-containing dihydroxy compound into a corresponding α-hydroxycarboxylic acid compound (hereinafter sometimes referred to as the present microorganism). General formula (2), characterized in that

(Wherein R ¹ represents the same meaning as described above.)
A process for producing a sulfur-containing α-hydroxycarboxylic acid compound represented by the formula (hereinafter sometimes referred to as the process of the present invention);
2. 2. The microorganism according to item 1 above, wherein the microorganism is one or more microorganisms selected from the group consisting of Alcaligenes, Bacillus, Pseudomonas, Rhodobacter and Rhodococcus. Manufacturing method;
3. The production method according to the above item 1 or 2, wherein R ¹ in the sulfur-containing dihydroxy compound represented by the general formula (1) is a C 1-8 alkyl group;

  According to the present invention, a sulfur-containing hydroxycarboxylic acid compound can be produced effectively.

The production method of the sulfur-containing α-hydroxycarboxylic acid compound of the present invention (hereinafter sometimes referred to as the production method of the present invention) is obtained by adding the sulfur-containing dihydroxy compound to the sulfur-containing dihydroxy compound represented by the general formula (1). It has the process of making the microbial cell or the microbial cell processed material of the microorganisms (henceforth abbreviated as this microorganism) which have the capability to convert into a corresponding alpha-hydroxy carboxylic acid compound act.

In the sulfur-containing dihydroxy compound represented by the general formula (1) and the sulfur-containing hydroxycarboxylic acid compound represented by the general formula (2), examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ include methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group. The aryl group having a carbon number of 6-20 represented by R ^1, for example, a phenyl group, a tolyl group, a naphthyl group.

R ₁ in the sulfur-containing dihydroxy compound represented by the general formula (1) is preferably an alkyl group having 1 to 8 carbon atoms.

  The sulfur-containing hydroxycarboxylic acid compound represented by the general formula (2) corresponding to the sulfur-containing dihydroxy compound represented by the general formula (1), which is produced by the production method of the present invention and recovered from the reaction solution, is in the form of a salt. It may be.

  The microbial cell or treated microbial product as a catalyst used in the production method of the present invention is a microbial cell or treated microbial product having an ability to convert a sulfur-containing hydroxycarboxylic acid compound into a corresponding α-hydroxycarboxylic acid. For example, Alcaligenes faecalis, Alcaligenes denitrificans, Alcaligenes eutrophus, Alcaligenes sp., Alcaligenes sp. Microorganisms belonging to the genus Alkigenes such as Alcaligenes xylosoxydans, Bacillus alvei, Bacillus badius, Bacillus brevis, Bacillus cereus, Bacillus cereus Circulation (Bacillus circulans), Bacillus coagulans, Bacillus firmus, Bacillus lentus, Bacillus licheniformis, Bacillus macerans, Bacillus megaterium, Bacillus megaterium Bacillus moritai, Bacillus mycoides, Bacillus polymyxa, Bacillus pumilus, Bacillus sphaericus, Bacillus subtilis, Bacillus subtilis, Bacillus subtilis, Bacillus subtilis (Bacillus thuringenesis), microorganisms belonging to the genus Bacillus such as Bacillus validus, Pseudomonas auricularis, Pseudomonas azotoformans (Pseudomona) s azotoformans, Pseudomonas caryophylli, Pseudomonas chlororaphis, Pseudomonas denitrificans, Pseudomonas diminuta, Pseudomonas diminuta Pseudomonas fragi), Pseudomonas fulva, Pseudomonas mendocina, Pseudomonas mutabilis, Pseudomonas nitroreducens, Pseudomonas olere smono (Pseudomonas ovalis), Pseudomonas oxalaticus, Pseudomonas planta Pseudomonas plantarii, Pseudomonas pseudoalcaligenes, Pseudomonas putida, Pseudomonas putrefaciens, Pseudomonas riboflavona, Pseudomonas sp. ), Pseudomonas straminea, Pseudomonas synxantha, Pseudomonas syringae, Pseudomonas tabaci, Pseudomonas icularis trolis Microorganisms belonging to the genus Pseudomonas such as Rhodobacter sphaeroides Rhodococcus erythropolis, Rhodococcus groberulus, Rhodococcus rhodochrous, Rhodococcus sp. And other Rhodococcus sp. A body treatment product can be mentioned.

  More specifically, for example, Alcaligenes faecalis IFO13111t, Alcaligenes denitrificans JCM5490, Alcaligenes eutrophus ATCC43123, Alcaligenes sp.IFO14130 , Alcaligenes xylosoxydans IFO15125t, Bacillus alvei IFO3343t, Bacillus badius ATCC14574t, Bacillus brevis IFO12334, Bacillus cereus (250) Bacillus cereus (Bacillus cereus)・ Circulance (Bacillus circulans) ATCC13403, Bacillus coagulans (Bacillus coagulans) JCM2257t, Bacillus firmus (Bacillus firmus) JCM2512t, Bacillus lentus (Bacillus lentus) JCM2511t, Bacillus licheniformis (Bacillu s licheniformis IFO12195, Bacillus macerans JCM2500t, Bacillus megaterium IFO12108, Bacillus moritai ATCC21282, Bacillus mycoides IFO3039, poly20 Bacillus pumilus IFO12092t, Bacillus sphaericus (Bacillus sphaericus) IFO3341, Bacillus subtilis JCM1465t, Bacillus thuringenesis (Bacillus thuringenesis) ATCC13366, Bacillus validus (Bacillus thalisius) Pseudomonas auricularis) IFO13334t, Pseudomonas azotoformans JCM2777t, Pseudomonas caryophylli IFO13591, Pseudomonas chlorolafis Pseudomonas chlororaphis) IFO3121t, Pseudomonas denitrificans IAM1923, Pseudomonas diminuta JCM2788t, Pseudomonas fluorescens IFO14160t, Pseudomonas fluorescens IFO14160t , Pseudomonas mendocina IFO14162, Pseudomonas mutabilis ATCC31014, Pseudomonas nitroreducens JCM2782t, Pseudomonas oleovorans (Pseudomonas oleovorans)・ Pseudomonas oxalaticus IFO13593t, Pseudomonas plantarii JCM5492t Pseudomonas pseudoalcaligenes JCM5968t, Pseudomonas putida IFO3738, Pseudomonas putida IAM1002, Pseudomonas putida IAM1090, Pseudomonas putida P236 (Pseudomonas putida) ATCC39213, Pseudomonas putrefaciens IFO3910, Pseudomonas riboflavina IFO13584t, Pseudomonas sp. ATCC53617, Pseudomonas stramon (Pseudomonas synxantha) IFO3913t, Pseudomonas syringae IFO14055, Pseudomonas tabaci IFO3508, Shu Pseudomonas taetrolens IFO3460, Pseudomonas vesicularis JCM1477t, Rhodobacter sphaeroides ATCC17023, Rhodococcus erythropolis (123) Examples thereof include Rhodococcus rhodochrous JCM3202t, Rhodococcus rhodochrous ATCC15610, and Rhodococcus sp. ATCC19148.

  The microorganism is preferably at least one microorganism selected from the group consisting of Alcaligenes genus, Bacillus genus, Pseudomonas genus, Rhodobacter genus, and Rhodococcus genus. . The microorganism is preferably at least one microorganism selected from the group consisting of the genus Bacillus, the genus Pseudomonas, and the genus Rhodococcus, and the genus Pseudomonas, and Rhodococcus More preferably, it is at least one microorganism selected from the group consisting of the genus (Rhodococcus), particularly preferably a microorganism of the genus Rhodococcus.

  The primary hydroxyl group of the sulfur-containing dihydroxy compound represented by the general formula (1) can be preferentially oxidized by reacting such a microbial cell or a treated product thereof. Here, “preferentially oxidizable” means that oxidation of the primary hydroxyl group proceeds (position) selectively over oxidation of the secondary hydroxyl group or sulfide oxidation of the sulfur-containing dihydroxy compound.

Next, the preparation method of this microorganism is demonstrated.
What is necessary is just to culture | cultivate this microorganism using the culture medium for culture | cultivating the various microorganisms containing a carbon source, a nitrogen source, an organic salt, an inorganic salt, etc. suitably.

  Examples of the carbon source contained in the medium include glucose, sucrose, glycerol, starch, organic acid, and molasses, and examples of the nitrogen source include yeast extract, meat extract, peptone, casamino acid, malt extract, Examples include soybean flour, corn steep liquor, cottonseed flour, dry yeast, ammonium sulfate, and sodium nitrate. Examples of organic and inorganic salts include sodium chloride, potassium chloride, sodium carbonate, and phosphoric acid 1 Examples include potassium, dipotassium phosphate, calcium carbonate, ammonium acetate, magnesium sulfate, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride.

  Examples of the culture method include solid culture and liquid culture (test tube culture, flask culture, jar fermenter culture, etc.).

  The culture temperature and the pH of the culture solution are not particularly limited as long as the microorganism grows. For example, the culture temperature is in the range of about 15 to 45 ° C., and the pH of the culture solution is about 4 to 8. A range can be mentioned. The culture time can be appropriately selected depending on the culture conditions, but is usually about 1 to 7 days.

  The cells of this microorganism can be used in the production method of the present invention as they are. As a method of using the cells of this microorganism as they are, (1) a method of using the culture solution as it is, (2) collecting the cells by centrifugation of the culture solution, and collecting the collected cells (if necessary, a buffer solution Or a method using a wet cell after washing with water.

  In the production method of the present invention, a treated product of the microorganism can also be used. Examples of the treated cells include cells obtained by culturing cells treated with an organic solvent (acetone, ethanol, etc.), freeze-dried or alkali-treated, or cells physically or Enzymatically crushed or crude enzyme separated and extracted from these can be mentioned. Furthermore, what was fixed by the well-known method is included in a microbial cell processed material after giving the said process.

  The production method of the present invention is usually performed in the presence of water. The water in this case may be in the form of a buffer solution. Examples of the buffer used in the buffer include alkali metal salts of phosphoric acid such as sodium phosphate and potassium phosphate, and alkali metal salts of acetic acid such as sodium acetate and potassium acetate.

  In addition, the production method of the present invention can be carried out using a hydrophobic organic solvent in the presence of water and a hydrophobic organic solvent. Examples of the hydrophobic organic solvent used in this case include esters such as ethyl formate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate and butyl propionate, n-butyl alcohol, n-amyl alcohol, n- Alcohols such as octyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether and methyl-t-butyl ether, and halogenated hydrocarbons such as chloroform and 1,2-dichloroethane And mixtures thereof.

  Moreover, this invention manufacturing method can also be performed in presence of water and an aqueous medium using a hydrophilic organic solvent. Examples of the hydrophilic organic solvent used in this case include ketones such as acetone, ethers such as dimethoxyethane, tetrahydrofuran and dioxane, and mixtures thereof.

  The production method of the present invention is usually carried out within a pH range of 3 to 10 in the aqueous layer, but may be appropriately changed within the range in which the reaction proceeds.

  The production method of the present invention is usually performed within a range of about 0 to 60 ° C., but may be appropriately changed within a range in which the reaction proceeds.

  The production method of the present invention is usually performed within a range of about 0.5 hours to about 10 days. The end point of the reaction can be confirmed by measuring the amount of the sulfur-containing dihydroxy compound in the reaction solution, for example, by liquid chromatography, gas chromatography or the like after the addition of the sulfur-containing dihydroxy compound as the raw material compound. it can.

  The concentration of the sulfur-containing dihydroxy compound that is the raw material compound in the production method of the present invention is usually 50% (w / v) or less, and in order to keep the concentration of the sulfur-containing dihydroxy compound in the reaction system substantially constant, The sulfur-containing dihydroxy compound may be continuously or sequentially added to the reaction system.

  In the production method of the present invention, a sugar such as glucose, sucrose, or fructose, or a surfactant such as Triton X-100 or Tween 60 can be added to the reaction system as necessary.

  After completion of the reaction, the reaction solution may be subjected to usual post-treatment such as organic solvent extraction and concentration to recover the sulfur-containing hydroxycarboxylic acid compound corresponding to the sulfur-containing dihydroxy compound from the reaction solution. The recovered sulfur-containing hydroxycarboxylic acid compound can be further purified by column chromatography, distillation or the like, if necessary.

EXAMPLES Hereinafter, although the Example manufacturing method is demonstrated in detail by an Example, this invention manufacturing method is not limited to these examples.

Reference Example 1 (Synthesis of raw material 4- (methylthio) butane-1,2-diol)
To a 100 mL flask equipped with a magnetic rotor, 880 mg of 3-butene-1,2-diol and 10 mg of azobisisobutyronitrile were added. Methanethiol was bubbled through the mixture for 1 hour while stirring the mixture at 25 ° C. Further, the mixture was stirred at the same temperature for 1 hour, and then nitrogen was bubbled through the mixture for 0.5 hour to remove the remaining methanethiol, and finally 1245 mg of colorless oil was obtained. When this oil was analyzed by a gas chromatography area percentage method, the yield of 4- (methylthio) butane-1,2-diol was 72.5%. The amount of 3-butene-1,2-diol remaining unreacted was 26.6% of the charged amount.

  Next, water was added to the obtained colorless oil so that the concentration of 4- (methylthio) butane-1,2-diol was 10% (w / v), and then insoluble matter (that is, azo By removing (bisisobutyronitrile) by filtration, the raw material (10% (w / v) 4- (methylthio) butane-1,2-diol aqueous solution) used in Example 2 was obtained.

Example 2 (Production example of sulfur-containing hydroxycarboxylic acid compound from sulfur-containing dihydroxy compound by the production method of the present invention)
Sterilized medium (glucose 20 g, polypeptone 5 g, yeast extract 3 g, meat extract 3 g, ammonium sulfate 0.2 g, potassium dihydrogen phosphate 1 g and magnesium sulfate heptahydrate 0.5 g was added to a test tube. Thereafter, 5 ml of a solution adjusted to pH 7.0) was added, and various cells shown in Table 1 were inoculated therein. This was cultured with shaking at 30 ° C. under aerobic conditions. After culturing, the cells were separated by centrifugation to obtain viable cells. 2 ml of 0.1 M potassium phosphate buffer (pH 7) was placed in a screw-mouth test tube, and the above viable cells were added thereto, followed by suspension. To the suspension, 0.2 ml (that is, 4- (methylthio) butane of 10% (w / v) 4- (methylthio) butane-1,2-diol aqueous solution) obtained in Reference Example 1 was added. After adding -1,2-diol to a final concentration of 1% (w / v), the resulting mixture was shaken at 30 ° C. for 2-3 days.

After completion of the reaction, 1 ml of the reaction solution was sampled. After removing the cells from the sampling solution, the amount of 2-hydroxy-4-methylthiobutyric acid produced was analyzed by liquid chromatography. The obtained results are shown in Tables 1 to 4.
(Content analysis conditions)
Column: Cadenza CD-C18 (4.6 mmφ × 15 cm, 3 μm) (manufactured by Imtakt)
Mobile phase: A liquid 0.1% trifluoroacetic acid aqueous solution, B liquid Methanol time (min) A liquid (%): B liquid (%)
0 80:20
10 80:20
20 50:50
30 50:50
30.1 80:20
Flow rate: 0.5 ml / min Column temperature: 40 ° C
Detection: 220nm

According to the present invention, a sulfur-containing hydroxycarboxylic acid compound can be produced efficiently.

Claims (3)

General formula (1)

(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.)
The sulfur-containing dihydroxy compound represented by the formula is allowed to act on one or more microorganisms selected from the group P having the ability to oxidize the sulfur-containing dihydroxy compound to the corresponding α-hydroxycarboxylic acid compound or a treated product thereof. The general formula (2)

(Wherein R ¹ represents the same meaning as described above.)
A process for producing a sulfur-containing α-hydroxycarboxylic acid compound represented by the formula:
P group: Alcaligenes faecalis, Alcaligenes denitrificans, Alcaligenes eutrophus, Alcaligenes sp., Alkaline genes xylosoxy dance ( Alcaligenes xylosoxydans), Bacillus alvei, Bacillus badius, Bacillus brevis, Bacillus cereus, Bacillus circulans, Bacillus coagulans coagulans), Bacillus firmus, Bacillus lentus, Bacillus licheniformis, Bacillus macerans, Bacillus megaterium, Bacillus moritai, Bacillus mycoides, Bacillus polymyxa, Bacillus pumilus, Bacillus sphaericus, Bacillus subtilis (Bacillus subtilis) Thuringenesis (Bacillus thuringenesis), Bacillus validus (Pseudomonas auricularis), Pseudomonas azotoformans (Pseudomonas phytomonas), Pseudomonas phytomonas (Pseudomonas caryophylous) , Pseudomonas denitrificans, Pseudomonas diminuta, Pseudomonas fluorescen s), Pseudomonas fragi, Pseudomonas fulva, Pseudomonas mendocina, Pseudomonas mutabilis, Pseudomonas nitroresence, Pseudomonas nitroreus Pseudomonas oleovorans), Pseudomonas ovalis, Pseudomonas oxalaticus, Pseudomonas plantarii, Pseudomonas pseudoalcalous, Pseudomonas pseudoalcalous, Pseudomonas pseudoalcalous Pteudomonas putrefaciens, Pseudomonas riboflavina, Pseumonas sp domonas sp.), Pseudomonas straminea, Pseudomonas synxantha, Pseudomonas syringae, Pseudomonas tabaci, Pseudomonas taboci, Pseudomonas tadoli Pseudomonas vesicularis), Rhodobacter sphaeroides, Rhodococcus erythropolis, Rhodococcus groberulus, Rhodococcus rhodoccus rhodoccus General formula (1)

(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.)
The sulfur-containing dihydroxy compound represented by the formula is allowed to act on one or more microorganisms selected from group Q having the ability to oxidize the sulfur-containing dihydroxy compound to the corresponding α-hydroxycarboxylic acid compound or a treated product thereof. The general formula (2)

(Wherein R ¹ represents the same meaning as described above.)
A process for producing a sulfur-containing α-hydroxycarboxylic acid compound represented by the formula:
Q group: Alcaligenes faecalis IFO13111t, Alcaligenes denitrificans JCM5490, Alcaligenes eutrophus ATCC43123, Alcaligenes sp. IFO14130, Alkigenes sp. IFO14130 Alcaligenes xylosoxydans IFO15125t, Bacillus alvei IFO3343t, Bacillus badius ATCC14574t, Bacillus brevis IFO12334, Bacillus cereus (CM) Bacillus circulans ATCC13403, Bacillus coagulans JCM2257t, Bacillus firmus JCM2512t, Bacillus lentus JCM2511t, Bacillus licheniformis IFO12195 Bacillus macerans JCM2500t, Bacillus megaterium IFO12108, Bacillus moritai ATCC21282, Bacillus mycoides IFO3039, Bacillus poly30x, Bacillus poly30x pumilus) IFO12092t, Bacillus sphaericus (Bacillus sphaericus) IFO3341, Bacillus subtilis JCM1465t, Bacillus thuringenesis (ATCC13366), Bacillus validus (I) 33413 Pseudomonas azotoformans JCM2777t, Pseudomonas caryophylli IFO13591, Pseudomonas chlororaphis IFO3521t, Pseudomonas denitrificans IAM1923, Pseudomonas diminuta JCM2788t, Pseudomonas fluorescens IFO14160t, Pseudomonas fulum Pseudomonas mendocina IFO14162, Pseudomonas mutabilis ATCC31014, Pseudomonas nitroreducens JCM2782t, Pseudomonas oleovorans Pioudomonas oleovos Pseudomonas oxalaticus IFO13593t, Pseudomonas plantarii JCM5492t, Pseudomonas Pseudomonas pseudoalcaligenes JCM5968t, Pseudomonas putida IFO3738, Pseudomonas putida IAM1002, Pseudomonas putida IAM1090, Pseudomonas putida 236, Pseudomonas putida Pida (Pseudomonas putida) ATCC39213, Pseudomonas putrefaciens IFO3910, Pseudomonas riboflavina IFO13584t, Pseudomonas sp. ATCC53617, Pseudomonas stramon (Pseudomonas synxantha) IFO3913t, Pseudomonas syringae IFO14055, Pseudomonas tabaci IFO3508, Pseudomonas taet Rse (Pseudomonas taetrolens) IFO3460, Pseudomonas vesicularis (JCM1477t), Rhodobacter sphaeroides ATCC17023, Rhodococcus erythropolis (Rhodococcus rosthoculo Rhodococcus rhodochrous) JCM3202t, Rhodococcus rhodochrous ATCC15610, Rhodococcus sp. ATCC19148, Alcaligenes faecalis IFO 12669, Alkaline genes IFalis faecalis (Alcaligenes faecalis) JCM 5485t, Alcaligenes xylosoxydans IFO15126t, Bacillus cereus JCM 2152t, Bacillus cereus ATCC 21281, Bacillus cereus IFO 3039, Bacillus circulans IFO3329, Bacillus circulans JCM2504t, Bacillus circuniformi 278 , Bacillus licheniformis IFO12197, Bacillus licheniformis IFO12200t, Bacillus megaterium JCM2506t, Bacillus polymyxa JCM2507t, phas Bacillus sphaericus) IFO3526, Bacillus sphaericus (Bacillus sphaericus) IFO3527, Bacillus sphaericus (Bacillus sphaericus) IFO3528, Bacillus subtilis (Bacillus subtilis) IFO3037, Bacillus Subtilis (Bacillus subtilis) IFO3108, Bacillus subtilis (Bacillus subtilis) IFO3134, Bacillus subtilis (Bacillus subtilis) IFO3026, Bacillus subtilis (Bacillus subtilis) ATCC14593, Bacillus subtilis (Bacillus subtilis) ATCC15841, Bacillus subtilis (Bacillus subtilis) IFO03026, Bacillus subtilis IFO03108, Bacillus subtilis IFO03134, Pseudomonas chlororaphis IFO3904t, Pseudomonas fluorescens fr 402, Pseudomonas fluorescens・ Pseudomonas putida ATCC17428, Pseudomonas putida ATCC17484, Pseudomonas putida IAM1094, Pseudomonas putida IFO12996, pseudo Pseudomonas putida IFO13696, Pseudomonas putida IFO14164t, Pseudomonas putida IFO14671, Pseudomonas putida IFO14796, Pseudomonas putida PudoIFas38 putida) IFO12653, Pseudomonas putida IFO6156, Pseudomonas putida IFO6157, Pseudomonas putida IFO6158, Rhodococcus rhodochrous ATCC190ho, ATCC190ho Rhodococcus rhodochrous ATCC19150, Rhodococcus rhodochrous ATCC21197, Rhodococcus rhodochrous ATCC21199, Rhodococcus rhodochrous ATCC21199, Rhodococcus rhodochrous ATCC21199, Rhodococcus rhodochrous ATCC21199, Rhodococcus rhodochrous Rhodococcus sp. ATCC19070, Rhodococcus sp. ATCC19071 The process according to claim 1 or 2, wherein R ¹ in the sulfur-containing dihydroxy compound represented by the general formula (1) is an alkyl group having ¹ to 8 carbon atoms .