JPH07258203A - Production of sulfoxide compound - Google Patents

Abstract

PURPOSE:To provide a production method capable of efficiently producing a sulfoxide compound from a corresponding thioether compound by using chlorophyll capable of self regeneration as a photooxidation assistant. CONSTITUTION:This is a method for producing a sulfoxide compound such as dimethyl sulfoxide by applying light to a thioether compound such as methyl sulfide in the presence of chlorophyll and oxidizing it.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for efficiently photooxidizing a thioether compound to produce a sulfoxide compound.

[0002]

2. Description of the Related Art Although thioether compounds are relatively stable to heat, it is known that they are oxidized to form sulfoxide compounds when irradiated with ordinary visible light.
Since the oxidation reaction at this time proceeds very slowly, a photooxidation aid such as methylene blue, rose bengal, humic acid, or anthraquinone is usually added to accelerate the reaction.

However, the action of these photooxidation aids decreases as they participate in the reaction in the reaction system.
Since it is necessary to continuously assist, it is inevitable that the operation becomes complicated. Also known is a method of using a photosynthetic bacterium as a photooxidation auxiliary agent that does not cause such a decrease in action, but since this method requires maintaining anaerobic conditions, it is necessary to manage the reaction system. It has the drawback of being difficult.

[0004]

DISCLOSURE OF THE INVENTION The present invention uses a photo-oxidation aid which can self-regenerate upon photo-oxidation of a thioether compound, and which, once added, can continuously promote the oxidation reaction without replenishing it thereafter. The present invention has been made for the purpose of providing a method capable of efficiently producing a sulfoxide compound.

[0005]

Means for Solving the Problems The present inventor has conducted various studies on photooxidation aids for thioether compounds,
It was found that chlorophyll has an excellent accelerating effect on the photooxidation of thioether compounds, and that its ability is continuously exhibited, and that the heat-treated one further improves the accelerating effect. The present invention has been completed based on the findings.

That is, the present invention provides a method for producing a sulfoxide compound, which comprises irradiating a thioether compound with light in the presence of a heat-treated product of chlorophyll.

The thioether compound used as a raw material in the method of the present invention is a compound having a chemical structure in which two hydrocarbon groups are bonded via one sulfur atom, and examples thereof include dimethylthioether, diethylthioether and dipropyl. Dialkyl thioethers such as thioether, methylethyl thioether, methylbutyl thioether, cyclic thioethers such as tetrahydrothiophene, tetrahydrothiapyran, aromatic thioethers such as methylphenyl sulfide, ethylphenyl sulfide, diphenyl sulfide, dibenzyl sulfide, etc. To be

These are preferably dissolved in water and used as an aqueous solution, but if desired, they can be used by dissolving them in a mixture of water and a water-miscible organic solvent such as alcohols. At this time, the concentration of the thioether compound is 1
A range of ~ 50 mmol, preferably 2-10 mmol is used.

Next, chlorophyll contains a, b, c and d.
Although five kinds of e and e are known, any of them can be used in the present invention. In the present invention, in addition to the isolated chlorophyll, chlorophyll-containing plants such as Chlorell (Chlorell)
a), Dunaliella sp.,
Thalassiosa Weiss Frosii
ira weissflogii), Chattonella antiqua,
It is possible to use algae such as Honda straw (Sargassum sp.) And Ulva perlusa, and tissue of higher plants such as spinach (Spinacia oleracea) and nettle (Urticales) and extracts thereof.

When these tissues are used, the plant tissues such as leaves and stems are ground in an aqueous liquid, or in the case of unicellular algae in the culture liquid thereof, they are ground with a homogenizer or the like, or ultrasonic waves are applied. It is preferable to use the one that has been treated and crushed. Further, a ground product or a crushed product of these plant tissues or a lyophilized product thereof extracted with an appropriate solvent may be used.

As the extraction solvent at this time, for example, water,
Alcohol, acetone, chloroform, dimethylformamide, ether, ethyl acetate and the like are used, but hydrous acetone and a mixed solvent of chloroform and alcohol are particularly preferable.

In the method of the present invention, chlorophyll may be used as it is, but it is advantageous to use it after further heat treatment. This heat treatment operation is usually 70 ° C to 130 ° C,
It is preferably carried out by heating at 80 ° C to 120 ° C for 1 minute to 1 hour. At this time, chlorophyll is preferably provided as an aqueous liquid, and the liquid is acidic or neutral,
Particularly preferably, it is preferably adjusted to weak acidity. Such acidic or neutral aqueous liquids include, for example, phosphoric acid,
An aqueous solution of boric acid, acetic acid, citric acid, succinic acid or a mixture of these acids, to which an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate is added within an acidic or neutral range. And phosphate buffer.

[0013]

According to the method of the present invention, upon photooxidation of a thioether compound, chlorophyll used as a photooxidation aid or its heat-treated product can self-regenerate, and once added, it can be continuously supplied without replenishment. Since the oxidation reaction can be promoted, the remarkable effect that the sulfoxide compound can be efficiently produced is obtained.

[0014]

The present invention will be described in more detail with reference to Examples.

Example 1 800 ml of seawater, 57.6 mg of KNO ₃ and KH ₂ PO ₄
7.2 mg, FeEDTA 4 mg, vitamin B ₁₂
The marine unicellular alga Dunaliella (Dunalie) using 1.6 μg, Tris 400 mg, pH 8.1 medium.
lla sp. ) For 12 days while irradiating with fluorescent light at 4000 lux at 24 ° C., and then culturing each in 20 ml of 100 ml aluminum sealed vials.
It was dispensed by ml, and one was heat-treated at 90 ° C. for 10 minutes. Next, add 1 μl of methyl sulfide to each bottle and seal with a septum. Then, leave it at 24 ° C for 5 days while irradiating with a fluorescent lamp at 4000 lux, and quantify the produced dimethyl sulfoxide by gas chromatography. The results obtained are shown in Table 1.

Example 2 In place of Donariella, Tarasio Sila Weissfrosii (T
halassiosira weissflogii)
The same operation as in Example 1 was performed except that was used. The results of quantifying the produced dimethyl sulfoxide by gas chromatography are shown in Table 1.

Example 3 Instead of Donariella, Shatonella Antica (Cha
The same operation as in Example 1 was carried out except that ttonella antiqua) was used. The results of quantifying the produced dimethyl sulfoxide by gas chromatography are shown in Table 1.

Comparative Example 1 1 μl of methyl sulfide was placed in a 100 ml aluminum sealed vial and sealed with a septum.
While irradiating at 00 lux, leave at 24 ℃ for 5 days,
The results of quantifying the produced dimethyl sulfoxide by gas chromatography are shown in Table 1.

[0019]

[Table 1]

Example 4 In the same manner as in Example 1, Donariella was cultivated, only the algae were collected by centrifugation, and 7 mg each was suspended in 2 ml of distilled water with a wet weight to make a 100 ml aluminum sealed vial bottle 4. I put it in a book. Acetic acid, phosphoric acid and boric acid 0.04M each
14.5 ml of this mixed solution is prepared.
PH = 4 liquid added with 3.5 ml of 2M sodium hydroxide, pH = 6 liquid added with 5.3 ml of 0.2M sodium hydroxide to 12.7 ml of the above mixed liquid, 11.
A pH = 8 solution obtained by adding 6.8 ml of 0.2 M sodium hydroxide to 2 ml and a solution of pH = 10 obtained by adding 7.9 ml of 0.2 M sodium hydroxide to 10.1 ml of the above mixed solution were prepared, Dispense into each vial bottle,
Heat treatment was performed at 105 ° C. for 5 minutes. To the treated product thus obtained, dimethyl sulfide was added so as to be 1.77 mM and the container was tightly sealed, and the mixture was allowed to stand for 3 days under the same conditions as in Example 1 to produce dimethyl sulfoxide by gas chromatography. Table 2 shows the results of quantification by.

[0021]

[Table 2]

Example 5 Spinach (Spincia oleracea)
a), Ulva perlusa, and Sargassum sp. are freeze-dried,
After crushing in a mortar, 1.5 mg each was placed in a 100 ml aluminum sealed vial bottle, and 0.1 M phosphate buffer (pH =
20 ml of 7.0) was added and heat treatment was performed at 105 ° C. for 5 minutes.

With respect to the processed product thus obtained,
After adding dimethyl sulfide to 2 mM and sealing the container, the mixture was allowed to stand for 3 days under the same conditions as in Example 1. The dimethyl sulfoxide produced was 30% in the case of spinach in a molar ratio with respect to dimethyl sulfide. 16% in the case of and 20% in the case of Honda Walla.

Example 6 Algae of Donariella collected in the same manner as in Example 2 were freeze-dried, and from each 1.5 mg thereof, a volume ratio of acetone containing 10% water and chloroform / methanol was 2%.
Extraction is performed using a solvent of 1: 1 and each extraction solvent is 100 m
After putting in a 1-liter aluminum sealed vial and removing the solvent by evaporation and freeze-drying, 20 ml of 0.1 M phosphate buffer (pH = 7.0) was added, and the mixture was heated at 105 ° C. for 5
Heat treated for minutes.

Each treated product thus obtained was added with dimethyl sulfide to a concentration of 2 mM and sealed, and the mixture was allowed to stand for 3 days under the same conditions as in Example 1. The dimethyl sulfoxide produced was sulfurized. The molar ratio to dimethyl was 51% in both cases.

Example 7 0.066 mM, 0.2 mM, 0.66 mM or 2 mM
Concentrations of chlorophyll a in acetone were used,
To obtain the concentrations shown in Table 3, 100 ml each was added to a 100 ml aluminum-sealed vial containing 20 ml of 0.1 M phosphate buffer (pH = 7.0). One was prepared, one was heat-treated at 105 ° C. for 5 minutes, and the other was used as it was as a sample. After adding dimethyl sulfide to each sample to 2 mM and sealing it,
Table 3 shows the ratio of dimethyl sulfoxide to dimethyl sulfide, which was formed by standing for 3 days under the same conditions as in Example 1.

[0027]

[Table 3]

Example 8 Donariella cultivated in the same manner as in Example 1 was added to the 100 ml volume aluminum-sealed vial as the culture solution, and 1
Heat treatment was performed at 05 ° C. for 5 minutes. To the treated product thus obtained, tetrahydrothiophene was added to a concentration of 2 mM and the container was sealed.
The tetramethylene sulfoxide produced by leaving it for one day was quantified by gas chromatography, and as a result, it was found to be 8.2% in molar ratio with respect to tetrahydrothiophene.

Example 9 The Donariella culture broth obtained in the same manner as in Example 1 and the one in which the cells were disrupted by ultrasonic treatment were used as samples, and each sample was placed in a 100 ml aluminum-sealed vial. Dimethyl sulfide was added to this to a concentration of 2 mM and the container was sealed, and the mixture was allowed to stand for 6 days under the same conditions as in Example 1. The produced dimethyl sulfoxide remained in the Donariella culture solution in a molar ratio to dimethyl sulfide. Case 1.1
%, And the case of destruction was 4.1%.

Claims (4)

[Claims] 1. A method for producing a sulfoxide compound, which comprises irradiating a thioether compound with light in the presence of chlorophyll. 2. The method according to claim 1, wherein chlorophyll is present as a chlorophyll-containing plant tissue or an extract thereof. 3. A method for producing a sulfoxide compound, which comprises irradiating a thioether compound with light in the presence of a heat-treated substance of chlorophyll. 4. The method according to claim 3, wherein the heat-treated product of chlorophyll is present as a heat-treated product of a ground product of a chlorophyll-containing plant or an extract thereof.