JPH03158489A - Production of oxathiazine derivative - Google Patents

Abstract

PURPOSE:To produce a oxathiazine deriv. in a high yield by putting a thiohydroxamic acid deriv. and an alpha,beta-dihalopropionic acid deriv. in the cathode chamber of an electrolytic cell and supplying electric current or by putting the thiohydroxamic acid deriv. in the cathode chamber, supplying electric current and allowing generated anions to react with the alpha,beta-dihalopropionic acid deriv. CONSTITUTION:A thiohydroxamic acid deriv. represented by general formula I, an alpha,beta-dihalopropionic acid deriv. represented by general formula II, an aprotic polar solvent such as DMF and a supporting electrolyte such as a quat. ammonium salt are charged into the cathode chamber of an electrolytic cell divided with a diaphragm such as a glass filler, a biscuit cylinder or an ion exchange membrane, the above-mentioned solvent and supporting electrolyte are charged into the anode chamber and electric current is supplied with electrodes of a metal such as Pt, Hg, Pb or Cu, carbon, etc. A oxathiazine deriv. represented by general formula III is produced by simple operation in >=80% yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel oxathiazine derivative represented by the general formula (m) using an electrolytic reaction. More specifically, in the cathode chamber, a thiohydroxamic acid derivative and α
, put a β-dihalopropionic acid derivative and energize it once, or
Alternatively, it relates to a method for producing an oxathiazine derivative by introducing a thiohydroxamic acid derivative, applying electricity, and reacting the generated anion species with an α,β-dihalopropionic acid derivative.

The oxathiazine derivatives of general formula (m) produced by the method of the present invention are useful as herbicides, and a patent application has previously been filed by the applicant. This compound is also useful as an intermediate for the synthesis of physiologically active substances such as agricultural chemicals and medicines. Therefore, the production method of the present invention can be used in the chemical industry, particularly in the agrochemical and pharmaceutical manufacturing fields.

Until now, some compounds having a 5,6-sihydro-1,4,2-oxathiazine structure and their conventional organic synthesis methods have been known.
No. 9-80670 discloses that 3-aryl substituted-5,6
-dihythro1゜4.2-oxathiazine derivatives and 3-aryl substituted-5 (or 6)-methyl substituted-5,
6-sihydro1.4.2-oxathiazine derivative is α
- Reaction between chloraldoximes and β-chloroethyls, or thiohydroxamic acid and α.

It is described that it was obtained by reaction with a β-dihaloethane derivative. Also Chemical Abstracts Vol. 78 1
11268y (1973) contains 4-aryl-5-
It is stated that methyl (or unsubstituted)-6-acetamino derivatives were obtained by reacting sodium 2-acetamidoalkenethiolate with α-chloraldoximes or aryl nitrile oxides. However, there is no literature description so far regarding a method for producing a compound having a carboxylic acid derivative as a substituent at the 5-position by electrolytic reaction.

(Problem B to be Solved by the Invention) The present invention is based on a novel 5,6-sihydro 1.4 which has a carboxylic acid as a substituent at the 5-position by applying an electrolytic reaction rather than using conventional organic synthesis methods. An object of the present invention is to provide a method for producing 2-oxathiazine derivatives with extremely high yield.

The present inventors tried various synthetic methods to achieve the above object. As a result, the following general formula (I
) and the compound of the general formula (■) are put together and electricity is applied, or the compound of the general formula CI) is put and electricity is applied, and the generated anion species is reacted with the compound of the general formula (II). It has been found that an oxathiazine derivative of general formula (m) useful as a herbicide can be produced industrially and advantageously. Therefore, the gist of the present invention is that in the electrolytic cell, the general formula (I) R, -CN
HOH(I) 1 (wherein R represents a lower alkyl group, a benzyl group, or a phenyl group; however, the phenyl group may be substituted with any one halogen atom or lower alkyl group).

) and the general formula (1
1) (In the formula, R2 represents a hydroxy group, a lower alkoxy group, an amino group, a benzylamino group, or a phenylamino group, and X and Y represent a halogen atom. However, up to two phenylamino groups may be present on the benzene ring. may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, or a haloalkyl group. Formula (I) R, -C-NHOH (I) 1 (wherein, R1 represents a lower alkyl group, a pencil group or a phenyl group. However, the phenyl group represents any one halogen atom or lower alkyl group) may be replaced with
) and the thiohydroxamic acid derivative represented by the general formula (I
T) CH2-CH-COR2(II) Y (wherein, R2 represents a hydroxy group, lower alkoxy group, amino group, benzylamino group or phenylamino group, and X and Y represent a halogen atom.However, phenylamino The group may be substituted with up to two halogen atoms, lower alkyl groups, lower alkoxy groups or haloalkyl groups on the benzene ring. The present invention provides a method for producing a dioxazine derivative represented by the general formula (m) (wherein Ftl and Rt are as defined above).

Table 1 shows the physical properties of the compound of formula (m) obtained by the production method of the present invention.

In the definitions of general formulas (1) to (III), lower means 1 to
Each group containing 6 carbon atoms is shown.

In addition, compound decomposition is also referred to in the following examples.

(According to this method) The present invention can be carried out roughly into the following first method and second method, but these two methods can be carried out by a combination method or a continuous method thereof. The first method is to put the compounds represented by general formulas (I) and (■), a solvent, and a supporting electrolyte in the cathode chamber of an electrolytic cell separated by a diaphragm, and put the solvent and supporting electrolyte in the anode chamber, and then A direct current is passed as an electric quantity across 2Fmof-' of the compound of formula (II).

As the solvent, aprotic polar solvents are preferred, and dimethylformamide, dimethylsulfoxide, hexamethylphosphonamide, sulfolane, acetonitrile and methanol can be used.

As the supporting electrolyte, a quaternary ammonium salt is preferable, and examples of the cation include tetramethylammonium, trimethylbenzylammonium, tetraethylammonium, triethylbenzylammonium, tetrapropylammonium, tetraethylammonium, tetrabutylammonium, and tetrahexylammonium. Examples of anions used include chloride ion, bromide ion, iodide ion, paratoluenesulfonate ion, penzelesulfonate ion, perchloride ion, sulfate ion, nitrate ion, and fluoroborate ion.
In particular, tetraethylammonium perchlorate and tetrabutylammonium perchlorate are often used.

As the diaphragm, glass filters, unglazed cylinders and ion exchange membranes can be used. As an electrode.

Metal electrodes such as platinum, mercury, lead, copper, etc., and those commonly used in electrolytic reactions, such as carbon, can be used in various shapes depending on the reaction apparatus, but particularly preferred electrodes are platinum and carbon.

The electrolytic reaction requires electrolysis at a constant potential lower than these reduction potentials in order to avoid reduction of the compound of formula (II), but since the reduction potential of the compound of formula (Z) is generally lower, an appropriate level of reduction potential is required. Even if electrolysis is carried out at a constant current, the yield will be low (in many cases the desired product will be obtained).The temperature of the electrolytic reduction reaction can be set arbitrarily within the range from room temperature to the boiling point of the solvent, but is usually between room temperature and 80°C. Perform at a temperature range of °C.

The molar ratio of the starting materials, the compound of formula (I) and the compound of formula ([I 2 ), can be set arbitrarily, or is preferably set around 1:1.

Further, it is preferable to perform stirring in order to carry out the electrolytic reaction smoothly. After the reaction is complete, the target product can also be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform to extract the target product, and then distilling off the solvent, as in a normal organic reaction. Ru.

In the second method, the compound represented by formula (I), a solvent, and a supporting electrolyte are placed in a cathode chamber separated by a diaphragm, and the solvent and supporting electrolyte are placed in an anode chamber. Then, through the electrode, a direct current of around 1 IFmo is applied as the amount of electricity necessary to convert the compound of formula (1) into an anion. (n) React the compound of formula.The solvent used here,
The supporting electrolyte, diaphragm, and electrodes are exactly the same as in the first method, and the reaction temperature and post-treatment are also in accordance with the first method. The second method can be applied to all compounds of the present invention, but is particularly advantageous when the compound of formula (H) is easily reduced.

In addition, the compounds of formulas (I) and (II), which are the raw materials, can be easily produced using known compounds or known similar synthetic methods.

Next, the method of the present invention will be specifically explained in Examples 1 to 3. However, the present invention is not limited to these examples only.

Production of No. 5)N
-benzylthiocarbonylhydroxylamine 1.6
7 g (0.0 f mol), 2.16 g (0.01 mol) of ethyl 3-bromo-2-chloropropionate and a DMF solution of tetraethylammonium perchlorate (0.0 f mol),
5 molar concentration) 60 nJj, and the anode chamber was filled with 20 m of DMF solution of tetraethylammonium perchlorate (0.75 molar concentration), and the current density at both electrodes was 1.5 Ad+.
*-2 was applied with a current of 2.0 Fmol-' for 80 minutes at 50°C with stirring, then cooled, and the liquid in the cathode chamber was poured into a mixture of toluene and water. Add organic bath to IN hydrochloric acid, then I
It was washed with N sodium hydroxide, washed with water, and then dried with anhydrous sodium sulfate. When the solvent was distilled off under reduced pressure, 2.36 g of the title compound was obtained as brown crystals (yield: 89%, current efficiency: 89%). Propionic acid amide 2.74
(0.01 mol) and 30 mJ1 of a DMF solution (0.5 molar concentration) of tetraethylammonium paratoluene sulfonate were placed in the UA electrode chamber. )lomJl, and the current density at both poles is 1.5Ad.
A current of 2-2 was applied at 1.0Fon-' and 60°C for 80 minutes with stirring. After energization, it was cooled, and the liquid in the cathode chamber was poured into a mixture of toluene and wood, and treated in the same manner as in Example 1 to obtain 3.38 g of the title compound as brown crystals (yield: 87%, current yield: 87%). , recrystallized from a hexane-ethyl acetate mixed solvent to give white crystals with a melting point of 195.
~198°C was shown.

N in the anode chamber of the reaction solvent, equipped with an unglazed cylindrical diaphragm and a platinum electrode.
-(4-chlorophenyl)thiocarbonylhydroxylamine 1.88g
3.6 g (0.02 mol) of N-phenylthiocarbonylhydroxylamine and a DMF solution of tetraethylammonium perchlorate (0.02 mol) were placed in the cathode chamber of a reaction vessel equipped with a phenyl 3-trifluoro-glazed cylindrical diaphragm and a platinum electrode. 5 molar concentration), and the anode chamber was filled with a DMF solution of tetraethylammonium perchlorate (0.7
5 molar concentration) 20rrJL, and the current density at both poles was 1.
, 9 Ads-'' was applied for 80 minutes with stirring at room temperature.
(3-)-Lifluoromethylphenyl)-2,3-dibromopropionic acid amide 3.75 g (0.0 g mol)
was added and stirred at room temperature for 1 hour. After the completion of the reaction, Example 1
When the treatment is carried out according to the method described in 3.
．． 15 g (yield: 86%, current efficiency: 86%) was obtained, and recrystallization from a hexane-acetone mixed solvent gave white crystals with a melting point of 130-132°C.

According to the method of the present invention, the compound of formula (m), which is highly useful as an intermediate for herbicides and pharmaceuticals and agricultural chemicals, can be industrially advantageously produced. That is, first, the target product can be obtained with high purity, high yield, and high electrical efficiency, and with simple operation. In particular, the method of the present invention has a yield of 8.
It is 0% or more.

Secondly, especially the second method is advantageous when the compound of formula (II) is easily reduced, and the desired product can be obtained without side reactions.

Thirdly, both the first method and the second method basically proceed at the same level of reaction mechanism, and can obtain the target product at almost the same level of high yield. Hence,
It is also possible to perform a combination of the first and second methods or a continuous reaction.

Fourth, since it uses electrical energy, it can be operated cleanly.

Claims (1)

[Claims] In the electrolytic cell, the cathode chamber contains the general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R_1 represents a lower alkyl group, benzyl group, or phenyl group.However, , the phenyl group may be substituted with any one halogen atom or lower alkyl group) and the thiohydroxamic acid derivative represented by the general formula (
II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_2 represents a hydroxy group, lower alkoxy group, amino group, benzylamino group, or phenylamino group, and X and Y represent a halogen atom. However, the phenylamino group has up to two halogen atoms on the benzene ring,
It may be substituted with a lower alkyl group, a lower alkoxy group or a haloalkyl group. ) is charged with the α,β-dihalopropionic acid derivative represented by the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ( In the formula, R_1 represents a lower alkyl group, a benzyl group, or a phenyl group.However, the phenyl group may be substituted with any one halogen atom or lower alkyl group.) After energization, the generated anion species is represented by the general formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_2 represents a hydroxy group, lower alkoxy group, amino group, benzylamino group, or phenylamino group. and X and Y represent halogen atoms.However, the phenylamino group has up to two halogen atoms on the benzene ring,
It may be substituted with a lower alkyl group, a lower alkoxy group or a haloalkyl group. ) General formula (III) characterized by reacting with an α,β-dihalopropionic acid derivative represented by ) A method for producing a dioxazine derivative represented by