CN1305843C - Process for preparing 3-chloro-2-methyl thiobenzoxide - Google Patents
Process for preparing 3-chloro-2-methyl thiobenzoxide Download PDFInfo
- Publication number
- CN1305843C CN1305843C CNB2005100301635A CN200510030163A CN1305843C CN 1305843 C CN1305843 C CN 1305843C CN B2005100301635 A CNB2005100301635 A CN B2005100301635A CN 200510030163 A CN200510030163 A CN 200510030163A CN 1305843 C CN1305843 C CN 1305843C
- Authority
- CN
- China
- Prior art keywords
- chloro
- preparation
- methyl
- thiobenzoxide
- methyl thiobenzoxide
- 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 - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012954 diazonium Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 12
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 7
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- WFNLHDJJZSJARK-UHFFFAOYSA-N 2-chloro-6-methylaniline Chemical compound CC1=CC=CC(Cl)=C1N WFNLHDJJZSJARK-UHFFFAOYSA-N 0.000 claims description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 3
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- -1 nitrous acid ester Chemical class 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- 235000010289 potassium nitrite Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- AYHCZKPXGIFQQF-UHFFFAOYSA-N ClC=1C(=C(C[N+]#N)C=CC1)N Chemical class ClC=1C(=C(C[N+]#N)C=CC1)N AYHCZKPXGIFQQF-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to the technical field of a preparation method of 3-chlorine-2-methyl thiobenzoxide. In the preparation method of the 3-chlorine-2-methyl thiobenzoxide, 3-chlorine-2-methylaniline is used as a raw material; a diazotization reagent is added into an acidic solution to carry out diazoreaction and prepare a diazonium salt I, wherein X <-> is an acid ion; the diazonium salt I reacts with a water solution of an amethanethiol metal salt to obtain a product II; the product II is treated to obtain the 3-chlorine-2-methyl thiobenzoxide. The raw materials of the 3-chlorine-2-methylaniline and a water solution of sodium methyl mercaptide used by the present invention are both commercialized in large scale at home and abroad, and the price is low; any organic solvent does not need in a reaction process, so a post-treatment process can be reduced. The present invention has the advantages of simple preparation process, cheap raw material, easy raw material acquirement and high yield; the yield can reach more than 80%; the preparation method is used for large-scale commercial production.
Description
Technical field
The invention belongs to preparation method's technical field of 3-chloro-2-methyl thiobenzoxide.
Background technology
3-chloro-2-methyl thiobenzoxide is agricultural chemicals and medical useful as intermediates, its production method such as document (Synthesis 1982 such as Chianelli, 6,475) in, with 2, the 6-toluene dichloride is that the preparation method of raw material is as follows substantially: by 2,6-toluene dichloride and exsiccant sodium methyl mercaptide solid are in the solvent HMPA, reacting by heating under the anhydrous condition, yield is about 86%.But when using this method and preparing, wherein raw material 2, and the 6-toluene dichloride is on the high side: another kind of raw material, and the exsiccant sodium methyl mercaptide solid commercial prod utmost point is difficult to obtain, and at present domestic still do not have commodity; The solvent HMPA price of reacting used is also very expensive, and reclaims difficult.According to aforesaid method, raw material is difficult for obtaining with production cost too high, so the utmost point is not suitable for large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of easy, economical and be suitable for the method for preparing 3-chloro-2-methyl thiobenzoxide of large-scale commercial production.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, its reaction formula is as follows:
Concrete steps are:
(1), with 3-chloro-2-aminotoluene as raw material, in acidic solution, add diazo reagent, carry out diazotization reaction and prepare diazonium salt I, wherein X
-Be acid ion;
(2), the above-mentioned diazonium salt I that will make and the reaction of thiomethyl alcohol aqueous metal salt obtain product II, aftertreatment gets final product.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the used acid of step (1) can be sulfuric acid, hydrochloric acid or acetic acid etc., and wherein hydrochloric acid is more suitable.The consumption of acid is generally excessive slightly than the molar weight of 3-chloro-2-aminotoluene, and yield is reduced, and can be 1.5～10 times of 3-chloro-2-aminotoluene molar weight, is the best with 2～2.5 wherein; Its mass percent concentration can be 10～50%, is the best with 20～30% acidic solutions.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the used diazo reagent of step (1) can be nitrite or nitrous acid ester, as Sodium Nitrite, potassium nitrite, ethyl nitrite, nitrous acid isopropyl ester etc., is preferably Sodium Nitrite; The concentration of sodium nitrite solution is 5～50%, considers the economy of production and the generation of waste water, and wherein 40% sodium nitrite solution is best; The mol ratio of 3-chloro-2-aminotoluene and diazo reagent is 1: (0.8～1.5) is preferably (1～1.1).
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein step (1) can be carried out at-20～20 ℃, and is more suitable-5～5 ℃ of reactions.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the used thiomethyl alcohol metal-salt of step (2) alkaline aqueous solution as sodium methyl mercaptide alkaline aqueous solution, the thiomethyl alcohol potash aqueous solution etc., is preferably the sodium methyl mercaptide alkaline aqueous solution.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the mass percent concentration of the used thiomethyl alcohol saline alkali of step (2) aqueous solution is 15～25%, is preferably 20～25%.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the temperature of reaction of step (2) is-20～40 ℃, the temperature of reaction of optimization is 0～10 ℃; If reaction after diazonium salt adds, removes cryostat at low temperatures, make it nature and be warming up to room temperature, generally at 15～50 ℃, be controlled at 25～30 ℃ preferably, continuation reaction for some time makes and reacts completely.At last with the product that obtains through extraction, phase-splitting, precipitation, the rectifying aftertreatment obtains content＞99.5% of 3-chloro-2-methyl thiobenzoxide.
Beneficial effect of the present invention: the raw material 3-chloro-2-aminotoluene that the present invention is used and the sodium methyl mercaptide aqueous solution reach in the world all large-scale commercial and cheap at home, without any need for organic solvent, can reduce last handling process in the reaction process.The inventive method preparation process is simple, raw material is cheap and easy to get, productive rate is high, can reach more than 80%, and the utmost point is suitable for large-scale commercial production.
Embodiment
Embodiment 1
(1) preparation 3-chloro-2-aminotoluene diazonium salt
In the 10L four-hole bottle of thermometer, prolong is housed, drop into the hydrochloric acid of 4198g (23mol) 20%, be cooled to T
InAbout=10 ℃, stir fast down, be added dropwise to 1415g (10mol) 3-chloro-2-aminotoluene, after dropwising, stirred 0.5 hour.Reaction system is cooled to T
In=0～5 ℃, to wherein dripping 1815g 40% sodium nitrite solution, keep temperature of reaction at 0～5 ℃, dropwised in 2.5 hours, make clarifying diazonium liquid, standby in-5～5 ℃ of preservations.
(2) preparation 3-chloro-2-methyl thiobenzoxide
Have in the 20L four-hole bottle of prolong that thermometer, constant pressure funnel, top be connected with bubbler in another and to add 5000g 20% sodium methyl mercaptide alkaline aqueous solution, be cooled to T
In=5～10 ℃, in bottle, drip above-mentioned diazonium liquid, exothermic heat of reaction is kept reaction T
In=5～10 ℃, N
2Constantly emit, dropwised in 2 hours, whole system is always strong basicity.After dripping diazonium liquid, continue to keep low temperature to stir 0.5 hour, remove cryostat, be warming up to room temperature naturally, stirring reaction 2.5 hours does not have bubble substantially and emits, and reaction terminating leaves standstill, and reaction solution is divided into two-layer, lower floor's yellow oil.Add 2L toluene, stirred 2 hours, leave standstill phase-splitting, water again with the extraction of 2L toluene once, combining extraction liquid adds anhydrous magnesium sulfate drying, filters, after filtrate decompression is sloughed about 2/3rds toluene, rectifying obtains product 1466g, productive rate 85%, its b.p.117/10mmHg.
Embodiment 2
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 5635g (23mol) 20% sulfuric acid at the 10L four-hole bottle that thermometer, prolong are being housed, other operational conditions all with
Embodiment 1 step (1) is identical.
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1380g, productive rate 80%.
Embodiment 3
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 2738g (15mol) 20% hydrochloric acid, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 724.5g, productive rate 42%.
Embodiment 4
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 18250g (100mol) 20% hydrochloric acid, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1052g, productive rate 30%.
Embodiment 5
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 2798g (23mol) 30% hydrochloric acid, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1052g, productive rate 54%.
Embodiment 6
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Operational condition is all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Adding temperature except that the diazonium drop is that 35～40 ℃ of operational conditions are all identical with embodiment 1 step (2), obtains product 1069g, productive rate 62%.
Embodiment 7
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Operational condition is all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Adding temperature except that the diazonium drop is that-20～-10 ℃ of operational conditions are all identical with embodiment 1 step (2), obtains product 1362g, productive rate 79%.
Embodiment 8
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 2136g (24mol) nitrous acid isopropyl ester, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1397g, productive rate 81%.
Embodiment 9
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Removing temperature of reaction is that-20 ℃ of other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1293g, productive rate 75%.
Embodiment 10
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Removing temperature of reaction is that 20 ℃ of other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 966g, productive rate 56%.
Claims (12)
1, the preparation method of 3-chloro-2-methyl thiobenzoxide, its reaction formula is as follows:
Concrete steps are:
(1), with 3-chloro-2-aminotoluene as raw material, in acidic solution, add diazo reagent, carry out diazotization reaction and prepare diazonium salt I, wherein X-is an acid ion;
(2), the above-mentioned diazonium salt I that will make and the reaction of thiomethyl alcohol aqueous metal salt obtain product II, aftertreatment gets final product.
2, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the said acidic solution of step (1) is meant hydrochloric acid, sulfuric acid or acetic acid.
3, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 2 is characterized in that, the consumption of acid is 1.5～10 times of 3-chloro-2-aminotoluene molar weight.
4, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 3 is characterized in that, the consumption of acid is 2～2.5 times of 3-chloro-2-aminotoluene molar weight.
5, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 2 is characterized in that, the mass percent concentration of acidic solution is 10～50%.
6, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the used diazo reagent of step (1) is following nitrite or nitrous acid ester: Sodium Nitrite, potassium nitrite, ethyl nitrite, nitrous acid isopropyl ester.
7, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the mol ratio of 3-chloro-2-aminotoluene and diazo reagent is 1 in the step (1): (0.8～1.5).
8, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the temperature of reaction of step (1) is-20～20 ℃.
9, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the used thiomethyl alcohol metal-salt of step (2) alkaline aqueous solution is the sodium methyl mercaptide alkaline aqueous solution or the thiomethyl alcohol potash aqueous solution.
10, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 9 is characterized in that, the mass percent concentration of the thiomethyl alcohol saline alkali aqueous solution is 15～25%.
11, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the temperature of reaction of step (2) is-20～40 ℃.
12, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 11 is characterized in that, the temperature of reaction of step (2) is 0～10 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100301635A CN1305843C (en) | 2005-09-29 | 2005-09-29 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100301635A CN1305843C (en) | 2005-09-29 | 2005-09-29 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793118A CN1793118A (en) | 2006-06-28 |
| CN1305843C true CN1305843C (en) | 2007-03-21 |
Family
ID=36804780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100301635A Expired - Fee Related CN1305843C (en) | 2005-09-29 | 2005-09-29 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1305843C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008295B (en) * | 2016-06-03 | 2017-12-08 | 北京颖泰嘉和生物科技股份有限公司 | A kind of preparation method of the alkylthio group toluene of 2 halo 6 |
| CN106496086B (en) * | 2016-10-10 | 2018-11-06 | 沈阳药科大学 | The synthetic method of 4- methylsulfonyl butyl isothiocyanates |
| CN106631941B (en) * | 2016-12-30 | 2018-09-28 | 青岛瀚生生物科技股份有限公司 | A kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl |
| CN107162944B (en) * | 2017-04-27 | 2019-02-26 | 湖南化工研究院有限公司 | The preparation method of 2,3- dimethyl benzene methyl sulfide |
| CN110526844B (en) * | 2018-05-25 | 2021-11-12 | 江苏中旗科技股份有限公司 | Synthetic method of topramezone intermediate 2, 3-dimethyl benzylthio-ether |
| CN109053511A (en) * | 2018-08-10 | 2018-12-21 | 安徽久易农业股份有限公司 | A kind of preparation method of the chloro- 6- (methylthiomethyl) of 2- |
| CN112694427B (en) * | 2019-10-23 | 2022-11-18 | 江西天宇化工有限公司 | Method for preparing 2, 3-dimethyl sulfide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146548C (en) * | 1999-07-27 | 2004-04-21 | 阿温提斯作物科学有限公司 | Isoxazolyl- and isoxazolinyl-substituted benzoylcyclohexanediones, processes for their preparation and their use as herbicides and plant growth regulators |
-
2005
- 2005-09-29 CN CNB2005100301635A patent/CN1305843C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146548C (en) * | 1999-07-27 | 2004-04-21 | 阿温提斯作物科学有限公司 | Isoxazolyl- and isoxazolinyl-substituted benzoylcyclohexanediones, processes for their preparation and their use as herbicides and plant growth regulators |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1793118A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1305843C (en) | Process for preparing 3-chloro-2-methyl thiobenzoxide | |
| CN1173943C (en) | Process for producing 2-hydroxy-4-methylthiobutyric acid | |
| CN1634933A (en) | Process for preparing ceftriaxone sodium | |
| CN86101929A (en) | Alkyl polysulfide is degraded to the method for the horizontal polysulfide of low-sulfur | |
| CN115322102A (en) | Synthetic method for producing 2-fluoro-3-nitrobenzoic acid from 2-chloro-3-nitrotoluene | |
| CN101367940A (en) | Preparation method for small-numerator hydroxyl silicone oil | |
| CN101062887A (en) | Method for synthesizing o-phenylphenol | |
| CN1861577A (en) | Tech. of preparing 2-amino-4-acetamido methyl-phenoxide | |
| CN101066917A (en) | Process of preparing 3-trifluoromethyl benzoic acid | |
| CN1280268C (en) | Method for preparing bishalogenated phenyl disulfides | |
| CN1041175C (en) | Catalyst prepared by particular preparation method and its use in process for preparing tertiary olefins from alkyl-tert-alkylethers | |
| CN1246431C (en) | Method for preparing modified 4A zeolite for detergent auxiliary | |
| CN1164558C (en) | Method for preparing methylphenyl oxalate and diphenyl oxalate | |
| CN1362400A (en) | Synthesis of terbinafine hydrochloride | |
| CN102285997A (en) | Method for preparing chloroallyl beta-lactam antibiotic intermediate | |
| CN1317268C (en) | The preparation method of 2,6-lutidine | |
| CN101811935B (en) | Method for synthesizing chlorohydrin by using hydrochloric acid and ethylene oxide | |
| CN1053598C (en) | Zirconium oxide catalyst used in glycol series monoether acetate synthesis | |
| CN100337749C (en) | Molecular sieve catalyst and preparation method thereof | |
| CN114380713B (en) | O-methyl benzoyl cyanide synthesis method | |
| CN1156427C (en) | Preparation method of malonic acid and its ester | |
| CN1186124C (en) | Composite base catalyst and its preparing method | |
| CN100335169C (en) | Niobium catalyst for dehydropyran derivative hydrolysis and its use | |
| CN101973872B (en) | Synthetic process of 4-(4-chlorophenyl) cyclohexane-1-methanoic acid | |
| CN1473762A (en) | Process for producing aluminium hydroxide using biological fermenting waste gas CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jiangsu Weier Chemical Co., Ltd. Assignor: Shanghai Kangpeng Chemical Co., Ltd. Contract fulfillment period: 2007.12.1 to 2018.11.30 contract change Contract record no.: 2009990000590 Denomination of invention: Process for preparing 3-chloro-2-methyl thiobenzoxide Granted publication date: 20070321 License type: Exclusive license Record date: 2009.6.1 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.12.1 TO 2018.11.30; CHANGE OF CONTRACT Name of requester: JIANGSU WEIER CHEMICAL CO., LTD. Effective date: 20090601 |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Jiangsu Weier Chemical Co., Ltd. Assignor: Shanghai Kangpeng Chemical Co., Ltd. Contract record no.: 2009990000590 Date of cancellation: 20100507 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jiangsu Weier Chemical Co., Ltd. Assignor: Shanghai Kangpeng Chemical Co., Ltd. Contract record no.: 2010310000129 Denomination of invention: Process for preparing 3-chloro-2-methyl thiobenzoxide Granted publication date: 20070321 License type: Exclusive License Open date: 20060628 Record date: 20100728 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070321 Termination date: 20150929 |
|
| EXPY | Termination of patent right or utility model |