CA1168246A - Process for the manufacture of 2,6- dichlorobenzoxazole and 2,6-dichlorobenzthiazole - Google Patents
Process for the manufacture of 2,6- dichlorobenzoxazole and 2,6-dichlorobenzthiazoleInfo
- Publication number
- CA1168246A CA1168246A CA000381302A CA381302A CA1168246A CA 1168246 A CA1168246 A CA 1168246A CA 000381302 A CA000381302 A CA 000381302A CA 381302 A CA381302 A CA 381302A CA 1168246 A CA1168246 A CA 1168246A
- Authority
- CA
- Canada
- Prior art keywords
- chloro
- chlorination
- potassium
- chlorine
- dichlorobenzthiazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
Abstract A process for the manufacture of 2,6-dichloro-benzoxazole and 2,6-dichlorobenzthiazole by chlorinating K+ or Na+ salts of 6-chloro-2-mercaptobenzoxazole or of 6-chloro-2-mercaptobenzthiazole in halogenated hydro-carbons as suspending agents.
Description
~ 168246 It is kncwn that 2-chlorobenzthiazoles and 2-chlorokenzoxa-zoles can be prepared from the corresponding 2-mercaptobenzazoles by direct chlorination (German Offenlegungsschrift 1,670,453, and J.
Org. Chem. 23, 1,500 (1958)). In this pro oe ss, the reaction is car-ried out, in the case of the thiazole, at elevated bemperatures and in the presen oe of catalytically active quantities of N-substituted carboxylic acid amides, such as, for example, dimethylformamide, and
Org. Chem. 23, 1,500 (1958)). In this pro oe ss, the reaction is car-ried out, in the case of the thiazole, at elevated bemperatures and in the presen oe of catalytically active quantities of N-substituted carboxylic acid amides, such as, for example, dimethylformamide, and
2-chlorobenzthiazole is obtained in a yield of pu,re m~terial of 87%
of theory.
The oxazole is also prepared by carrying out the reaction in an inert solvent, but at a 1GW temFeratu~e and without the addi-tion of a catalyst; the yield of 2-chlorobenzoxazole is 82% of theory. If it is ncw desired to synthesize 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole, which are valuable intermediate pro-duct~, for example for the manufact~re of active oowpcurds for plant prokection (German Offenlegungsschrift 2,640,730), in the same man-ner, but using 6-chloro-2-mercaptobenzthiazole and 6-chloro-2--mercaptobenzoxazole as the starting materials, it has to be stated that, in this case, it is only possible to achieve oonsiderably lcwer yields and that a large quantity of 1 ~68~4 mdistillable residues is formed.
The present invention is therefore based on the object of improving the yields in the preparation of 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole and of reducing the formation of by-products which cannot be utilized further.
It has been found that this is possible if the potassium or sodium salts of 6-chloro-2-mercaptobenzthi-azole are chlorinated instead of the free compound and if these salts are suspended, for this reaction, in special ine~t solvents.
m e invention relates, therefore, to a process for the manufacture of 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole of the formula Cl ~ X ~ ~l - which comprises subjecting the potassium or sodium salts of 6-chloro-2-mercaptobenzoxazole or 6-chloro-2-~ercapto-benzthiazole to chlorination in the presence of a halo-genated aliphatic or aromatic hydrocarbon, as a suspend-ing agent.
Yields of 90% or more of the desired process pro-ducts are obtained by the procedure according to the invention The quantities of residue are correspond-ingly low.
From many points of view it could not be foreseen that the reaction would proceed smoothly. Thus, it is surprising that the reaction takes place at all, since the al~ali metal salts of the free mercapto compounds are virtually insoluble in the halogenated hydrocarbons used.
Secondly, it was known that only the disulfides are formed if benzthiazole and benzoxazole mercaptides are ch~orinated in solution (German Offenlegungsschrift 2,800,462).
m e process according to the invention also makes it possible to use, as starting materials, without having to accept an appreciable reduction in yield there-by, crude alkali metal 2-mercaptides of 6-chlorobenzthi-azole or 6-chlorobenzoxazole, which are available as intermediate products.
~he chlorination is carried out in the tempera-ture range betwe~n -20 and ~150C. Somewhat higher temperatures are required for the chlorination of the thiazole (~ 20C, preferably 80 - 100) than for the - chlorination of the oxazole, which is carried out at the temperature which is set up spontaneously, namely between -lO and 100C, preferably between 20 and 60C. In the chlorination of the thiazole it is advantageous to fol-low a procedure in which part of the quantity of chlorine required is passed in at temperatures from 20 to 8~C, until the sulfenyl chloride has been formed, after which the temperatures are increased and chlorination is con-tinued. It is also possible to pass in all the chlorine at the higher temperature. ~n the case of the oxazole, the chlorination of the sulfenyl chloride which is formed as an intermediate does not require l 1~8246 elevated temperatures.
~ he quantity of chlorine required is approx.
2.3 to 3 moles per mole of alkali metal mercaptide emp-loyed, if the chlorine is passed into the reaction 5 mixture at atmospheric pressure. If the reaction is carried out in a closed system, that is to say excluding chlorine losses as far as possible, it is possible to reduce the quantity of chlorine to 2 to approx. 2.3 moles.
The solven-ts used àre halogenated hydrocarbons, such as, for example, carbon tetrachloride, tetrachloro-e*hane or chlorinated benzenes, but chiefly chlorobenzene and o-dichlorobenzene and particularly the last of these.
In general, the quantities of solvent are such that the suspension formed can still be stirred. However, it is also possible to use less solvent and then to pass chlorine into the suspension under pressure in a closed system.
If desired, catalytic quantities of an N-substituted carboxylic acid amide, for example dimethyl-formamide, can be added in order to accelerate thereaction.
When the reaction is complete, the sulfur dichloride formed in the reaction is removed by distil-lation, if appropriate also as a mixture with the solvent, it being possible to re-use the latter.
m e alkali metal chloride produced in the chlor-ination can be removed by filtration or, in the case of the chlorination of thiazole, extracted with water after previously removing the sulfur dichloride.
1 16~2~
The alkali metal mercaptides of 6-chloro-2-mercapto-benzoxazole and 6-chloro-2-mercaptobenzthiazole required as starting materials are accessible, for example, by reacting 5-chloro-2-aminophenol with alkali metal xanthates.
The process according to the invention is carried out, for example, by suspending the mercaptide (particularly the potassium salt, in the case of 6-chloro-2-mercaptobenzoxazole) in the solvent and passing in l.0 to 1.05 moles of chlorine per mole of mercaptide, initially at room temperature, if appropriate with cooling and, if appropriate, in the presence of catalytically active quantities of dimethylformamide (0.1 to 5~ by weight, relative to the mercaptide). The mixture is then heated, in the case of the thiazole, to 80 to 100C and a further 1.3 to 2.0 moles of chlorine are passed in at this temperature; in the case of the oxazole, the further chlorine iB also added at room temperature.
The sulfur dichloride which has been formed is then distilled off, the alkali metal chlorides are removed by filtration or by extraction with water and, finally, the volatile constituents (solvents) are removed by distillation under normal pressure. The 2,6-dichlorobenzazoles are then obtained in a very pure condition by distillation in vacuo. It is possible to dispense with further purification of the reaction products.
The following examples are intended to illustrate the invention in greater detail.
~ ~82~
Example 1 240 g (1 mole) of potassium 2-~ercapto-6-chlorokenzthia-zole are suspended in 800 ml of tetrachloroethane and 3.5 g of dimethylformamide are added. 1.0 mole of chlorine is passed in at room temperature and 1.4 moles of chlorine are passed in at 85 to 90 C. The sulfur dichloride is then distilled off, together with a little tetrachlor oe thane, and the potassium chloride is filtered off and rinsed with 200 ml of tetrachloroethane. ~fter the tetrachloro-ethane has been removed by distillation under normal pressure, 192.1 g of 2,6~dichlorobenzthiazole (99.6~ pure according to gas chromatography), corresponding to a yield of pure material of 93.8%
of theory, are obtained by vacuum distillation (under 1.3 mbars).
Melting point 96C.
Example 2 The reaction is carried out as described in Example 1.
Hcwever, 3.0 moles of chlorine are passed in. The solvent 1l~Pd is chlorobenzene.
Yield: 191.1 g of 2,6-dichlorcbenzthiazole (99.9% pure according to gas chrcmatography), corresponding to a yield of pure material of 93.7~ of theory. ~elting point 96 & .
Example 3 240 g (1 mole) of 98% strength potassium 2-mercapto-6--chlorobenzthiazole are suspended in 800 ml of chlorobenzene. 3.5 g of d~methylformamide are added and 1 mole of chlorine is passed in initially at room temperature, follcwed by a further 2 moles of chlorine ~r~
.
1 1~824~
at 85 to 90C. m e sulfur dichloride which has been formcd is tllen clistilled off, together with some chloro-benzene (150.9 g), and 200 ml of water are added at approx. 60C. The aqueous phase is drained off, after which the solvent is distilled off from the organic phase under normal pressure. The residue is distilled in vacuo, under 1.3 mbars, 187.4 g of 2,6-dichlorobenz-thiazole (9~% pure according to gas chromatography) being produced, corresponding to a yield of pure material of 92.0% of theory. Melting point 95C.
Example 4 The reaction is carried out as in Example 1, but without the addition of dimethylformamide, and 190.6 g (93 4~ of theory) of 2,6-dichlorobenzthiazole are obtained.
Example 5 223 5 g (1 mole) of potassium 6~chloro-2-mer-captobenzoxazole are suspended in 500 ml of chlorobenz-ene and 180 g (2.5 moles) of chlorine gas are added in the course of 3 hours at a temperature of approx. 25C.
Stirring is con~inued for 12 hours at room temperature and excess chlorine is blown out of the mixture by means of nitrogen. The precipitated potassium chloride is filtered off and rinsed with approx. 200 ml of chloro-benzene. The filtrate is then distilled. Whenthe sulfur dichloride and chlorobenzene have been dis-tilled off, 171 g (91% of theory) oX 2,6-dichlorobenz-oxazole are obtained, having a melting point of 49 - 51C and a boiling point of 124 - 12~.5C under 116824~
_ g _ approA. 25 mbars.
EXam~le 6 (_onlpaIison) 202 g (1 mole)of 6-chloro-2-mercaptobenzthiazole and 3 5 g of dimethylformamide are suspended in 1,000 ml of tetrachloroethane, and 1.05 moles of chlorine are i.nitially passed in at room temperature, followed by 1.4 moles of chlorine at 85C. m e sulfur dichloride and the tetrachloroethane are distilled off under normal pressure and 167.6 g of 2,6-dichlorobenzthiazole, cor-responding to 82.1,' of theory, are then obtained by ~acuum distillation under a pressure of 1.3 mbars at a delivery temperature of approx. 123C.
of theory.
The oxazole is also prepared by carrying out the reaction in an inert solvent, but at a 1GW temFeratu~e and without the addi-tion of a catalyst; the yield of 2-chlorobenzoxazole is 82% of theory. If it is ncw desired to synthesize 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole, which are valuable intermediate pro-duct~, for example for the manufact~re of active oowpcurds for plant prokection (German Offenlegungsschrift 2,640,730), in the same man-ner, but using 6-chloro-2-mercaptobenzthiazole and 6-chloro-2--mercaptobenzoxazole as the starting materials, it has to be stated that, in this case, it is only possible to achieve oonsiderably lcwer yields and that a large quantity of 1 ~68~4 mdistillable residues is formed.
The present invention is therefore based on the object of improving the yields in the preparation of 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole and of reducing the formation of by-products which cannot be utilized further.
It has been found that this is possible if the potassium or sodium salts of 6-chloro-2-mercaptobenzthi-azole are chlorinated instead of the free compound and if these salts are suspended, for this reaction, in special ine~t solvents.
m e invention relates, therefore, to a process for the manufacture of 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole of the formula Cl ~ X ~ ~l - which comprises subjecting the potassium or sodium salts of 6-chloro-2-mercaptobenzoxazole or 6-chloro-2-~ercapto-benzthiazole to chlorination in the presence of a halo-genated aliphatic or aromatic hydrocarbon, as a suspend-ing agent.
Yields of 90% or more of the desired process pro-ducts are obtained by the procedure according to the invention The quantities of residue are correspond-ingly low.
From many points of view it could not be foreseen that the reaction would proceed smoothly. Thus, it is surprising that the reaction takes place at all, since the al~ali metal salts of the free mercapto compounds are virtually insoluble in the halogenated hydrocarbons used.
Secondly, it was known that only the disulfides are formed if benzthiazole and benzoxazole mercaptides are ch~orinated in solution (German Offenlegungsschrift 2,800,462).
m e process according to the invention also makes it possible to use, as starting materials, without having to accept an appreciable reduction in yield there-by, crude alkali metal 2-mercaptides of 6-chlorobenzthi-azole or 6-chlorobenzoxazole, which are available as intermediate products.
~he chlorination is carried out in the tempera-ture range betwe~n -20 and ~150C. Somewhat higher temperatures are required for the chlorination of the thiazole (~ 20C, preferably 80 - 100) than for the - chlorination of the oxazole, which is carried out at the temperature which is set up spontaneously, namely between -lO and 100C, preferably between 20 and 60C. In the chlorination of the thiazole it is advantageous to fol-low a procedure in which part of the quantity of chlorine required is passed in at temperatures from 20 to 8~C, until the sulfenyl chloride has been formed, after which the temperatures are increased and chlorination is con-tinued. It is also possible to pass in all the chlorine at the higher temperature. ~n the case of the oxazole, the chlorination of the sulfenyl chloride which is formed as an intermediate does not require l 1~8246 elevated temperatures.
~ he quantity of chlorine required is approx.
2.3 to 3 moles per mole of alkali metal mercaptide emp-loyed, if the chlorine is passed into the reaction 5 mixture at atmospheric pressure. If the reaction is carried out in a closed system, that is to say excluding chlorine losses as far as possible, it is possible to reduce the quantity of chlorine to 2 to approx. 2.3 moles.
The solven-ts used àre halogenated hydrocarbons, such as, for example, carbon tetrachloride, tetrachloro-e*hane or chlorinated benzenes, but chiefly chlorobenzene and o-dichlorobenzene and particularly the last of these.
In general, the quantities of solvent are such that the suspension formed can still be stirred. However, it is also possible to use less solvent and then to pass chlorine into the suspension under pressure in a closed system.
If desired, catalytic quantities of an N-substituted carboxylic acid amide, for example dimethyl-formamide, can be added in order to accelerate thereaction.
When the reaction is complete, the sulfur dichloride formed in the reaction is removed by distil-lation, if appropriate also as a mixture with the solvent, it being possible to re-use the latter.
m e alkali metal chloride produced in the chlor-ination can be removed by filtration or, in the case of the chlorination of thiazole, extracted with water after previously removing the sulfur dichloride.
1 16~2~
The alkali metal mercaptides of 6-chloro-2-mercapto-benzoxazole and 6-chloro-2-mercaptobenzthiazole required as starting materials are accessible, for example, by reacting 5-chloro-2-aminophenol with alkali metal xanthates.
The process according to the invention is carried out, for example, by suspending the mercaptide (particularly the potassium salt, in the case of 6-chloro-2-mercaptobenzoxazole) in the solvent and passing in l.0 to 1.05 moles of chlorine per mole of mercaptide, initially at room temperature, if appropriate with cooling and, if appropriate, in the presence of catalytically active quantities of dimethylformamide (0.1 to 5~ by weight, relative to the mercaptide). The mixture is then heated, in the case of the thiazole, to 80 to 100C and a further 1.3 to 2.0 moles of chlorine are passed in at this temperature; in the case of the oxazole, the further chlorine iB also added at room temperature.
The sulfur dichloride which has been formed is then distilled off, the alkali metal chlorides are removed by filtration or by extraction with water and, finally, the volatile constituents (solvents) are removed by distillation under normal pressure. The 2,6-dichlorobenzazoles are then obtained in a very pure condition by distillation in vacuo. It is possible to dispense with further purification of the reaction products.
The following examples are intended to illustrate the invention in greater detail.
~ ~82~
Example 1 240 g (1 mole) of potassium 2-~ercapto-6-chlorokenzthia-zole are suspended in 800 ml of tetrachloroethane and 3.5 g of dimethylformamide are added. 1.0 mole of chlorine is passed in at room temperature and 1.4 moles of chlorine are passed in at 85 to 90 C. The sulfur dichloride is then distilled off, together with a little tetrachlor oe thane, and the potassium chloride is filtered off and rinsed with 200 ml of tetrachloroethane. ~fter the tetrachloro-ethane has been removed by distillation under normal pressure, 192.1 g of 2,6~dichlorobenzthiazole (99.6~ pure according to gas chromatography), corresponding to a yield of pure material of 93.8%
of theory, are obtained by vacuum distillation (under 1.3 mbars).
Melting point 96C.
Example 2 The reaction is carried out as described in Example 1.
Hcwever, 3.0 moles of chlorine are passed in. The solvent 1l~Pd is chlorobenzene.
Yield: 191.1 g of 2,6-dichlorcbenzthiazole (99.9% pure according to gas chrcmatography), corresponding to a yield of pure material of 93.7~ of theory. ~elting point 96 & .
Example 3 240 g (1 mole) of 98% strength potassium 2-mercapto-6--chlorobenzthiazole are suspended in 800 ml of chlorobenzene. 3.5 g of d~methylformamide are added and 1 mole of chlorine is passed in initially at room temperature, follcwed by a further 2 moles of chlorine ~r~
.
1 1~824~
at 85 to 90C. m e sulfur dichloride which has been formcd is tllen clistilled off, together with some chloro-benzene (150.9 g), and 200 ml of water are added at approx. 60C. The aqueous phase is drained off, after which the solvent is distilled off from the organic phase under normal pressure. The residue is distilled in vacuo, under 1.3 mbars, 187.4 g of 2,6-dichlorobenz-thiazole (9~% pure according to gas chromatography) being produced, corresponding to a yield of pure material of 92.0% of theory. Melting point 95C.
Example 4 The reaction is carried out as in Example 1, but without the addition of dimethylformamide, and 190.6 g (93 4~ of theory) of 2,6-dichlorobenzthiazole are obtained.
Example 5 223 5 g (1 mole) of potassium 6~chloro-2-mer-captobenzoxazole are suspended in 500 ml of chlorobenz-ene and 180 g (2.5 moles) of chlorine gas are added in the course of 3 hours at a temperature of approx. 25C.
Stirring is con~inued for 12 hours at room temperature and excess chlorine is blown out of the mixture by means of nitrogen. The precipitated potassium chloride is filtered off and rinsed with approx. 200 ml of chloro-benzene. The filtrate is then distilled. Whenthe sulfur dichloride and chlorobenzene have been dis-tilled off, 171 g (91% of theory) oX 2,6-dichlorobenz-oxazole are obtained, having a melting point of 49 - 51C and a boiling point of 124 - 12~.5C under 116824~
_ g _ approA. 25 mbars.
EXam~le 6 (_onlpaIison) 202 g (1 mole)of 6-chloro-2-mercaptobenzthiazole and 3 5 g of dimethylformamide are suspended in 1,000 ml of tetrachloroethane, and 1.05 moles of chlorine are i.nitially passed in at room temperature, followed by 1.4 moles of chlorine at 85C. m e sulfur dichloride and the tetrachloroethane are distilled off under normal pressure and 167.6 g of 2,6-dichlorobenzthiazole, cor-responding to 82.1,' of theory, are then obtained by ~acuum distillation under a pressure of 1.3 mbars at a delivery temperature of approx. 123C.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of 2,6-dichlorobenzthiazole and 2,6-dichlorobenzoxazole of the formula (X = O or S) which comprises subjecting the potassium or sodium salts of 6-chloro-2-mercaptobenzoxazole or of 6-chloro-2-mercaptobenzthiazole to chlorination in the presence of a halogenated aliphatic or aromatic hydrocarbon as a suspending agent.
2. A process as claimed in claim 1, wherein the solvent used is chlorobenzene or o-dichlorobenzene.
3. A process as claimed in claim 1, wherein the chlorination is carried out in the presence of catalytic quantities of an N-substituted carboxylic acid amide.
4. A process as claimed in claim 1, 2 or 3 wherein the potassium or sodium salt of 6-chloro-2-mercaptobenzoxazole is subjected to chlorination at a temperature in the range of 20° to 60°C.
5. A process as claimed in claim 1, 2 or 3, wherein the potassium salt is employed in the case of the oxazole.
6. A process as claimed in claim 1, 2 or 3, wherein the potassium or sodium salt of 6-chloro-2-mercaptobenzthiazole is subjected to chlorination at a temperature in the range of 80° to 100°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3025910.0 | 1980-07-09 | ||
| DE19803025910 DE3025910A1 (en) | 1980-07-09 | 1980-07-09 | METHOD FOR PRODUCING 2,6-DICHLORBENZTHIAZOL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168246A true CA1168246A (en) | 1984-05-29 |
Family
ID=6106732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381302A Expired CA1168246A (en) | 1980-07-09 | 1981-07-08 | Process for the manufacture of 2,6- dichlorobenzoxazole and 2,6-dichlorobenzthiazole |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0043573B1 (en) |
| CA (1) | CA1168246A (en) |
| DE (2) | DE3025910A1 (en) |
| IL (1) | IL63247A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3221938A1 (en) * | 1982-06-11 | 1983-12-22 | Cassella Ag, 6000 Frankfurt | METHOD FOR PRODUCING CRYSTALLINE 2,6-DICHLORBENZOTHIAZOL |
| DE3334417A1 (en) * | 1983-09-23 | 1985-04-04 | Cassella Ag, 6000 Frankfurt | METHOD FOR PRODUCING 2-CHLORBENZOXAZOLES |
| DE3405241A1 (en) * | 1984-02-15 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | 1- / 4- (BENZOTHIA- OR -OXAZOL-2-YLTHIO- OR -2-YLOXY) PHENYL / -1,3,5-TRIAZINE-2,4,6- (1H, 3H, 5H) -TRIONE, METHOD FOR THEIR PRODUCTION AND USE AS A MEDICINAL PRODUCT |
| DE3406909A1 (en) * | 1984-02-25 | 1985-09-05 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 2,6-DICHLORBENZOXAZOLE |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1164413B (en) * | 1960-07-06 | 1964-03-05 | Basf Ag | Process for the preparation of 2-chlorobenzothiazole or 2-chlorobenzoxazole, which are optionally substituted by alkyl or alkoxy groups or by further chlorine atoms |
| DE2758002A1 (en) * | 1976-09-10 | 1979-07-05 | Hoechst Ag | Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemate |
| DE2830066A1 (en) * | 1978-07-08 | 1980-01-17 | Hoechst Ag | Benzoxazole, benzothiazole and benzimidazole derivs. - useful as selective herbicides |
-
1980
- 1980-07-09 DE DE19803025910 patent/DE3025910A1/en not_active Withdrawn
-
1981
- 1981-07-04 DE DE8181105184T patent/DE3160815D1/en not_active Expired
- 1981-07-04 EP EP81105184A patent/EP0043573B1/en not_active Expired
- 1981-07-07 IL IL63247A patent/IL63247A/en unknown
- 1981-07-08 CA CA000381302A patent/CA1168246A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IL63247A0 (en) | 1981-10-30 |
| EP0043573B1 (en) | 1983-08-31 |
| IL63247A (en) | 1984-09-30 |
| DE3160815D1 (en) | 1983-10-06 |
| EP0043573A1 (en) | 1982-01-13 |
| DE3025910A1 (en) | 1982-02-04 |
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