CN102516072A - Preparation method of benzoic acid herbicide dicamba - Google Patents
Preparation method of benzoic acid herbicide dicamba Download PDFInfo
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Abstract
A preparation method of a benzoic acid herbicide dicamba relates to the technical filed of pesticide production. The invention employs 2,5-dichlorophenols as a raw material and carries out esterification, Fries rearrangement, etherification and oxidation to obtain 3,6-dichloro-2-methoxybenzoic acid. The synthetic method has simple technology, easily available raw material, low cost, generates little "three wastes (waste gas, waste water and industrial residue)" and is more environment-friendly and more suitable for industrialized production.
Description
Technical field
The present invention relates to pesticide production technology field.
Background technology
Dicamba 98 (dicamba), formal name used at school 3,6-two chloro-O-Anisic Acids belong to the TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. serial herbicide, are a kind of to the weedicide of environmental facies to the close friend.Its working method adopts 2, the sylvite of 5-NSC 2879 and carbonic acid gas under condition of high voltage, carry out carboxylated, resterification, hydrolysis obtains dicamba 98.
Seldom have 3 in recent years, the compound method of 6-two chloro-O-Anisic Acids (dicamba 98) report, and 50 to the seventies its preparation method the report data more, summing up has following compound methods substantially.
1, in patent documentation Ussr345129,1973; Po1:78848,1975; Among the us4161611, be with 2-amino-3, the 6-dichlorobenzoic acid is that raw material carries out synthesizing 3,6-two chloro-O-Anisic Acids after the etherificate with methyl chloride through diazotization again.This route expensive raw materials, taller pressure still just can carry out, and is not suitable for suitability for industrialized production.Its chemical synthesis route is:
2, at patent documentation US3928432; Ger.Often2331712; In be with 2,5-two chloro-4-bromophenols are raw material, through methylolation, etherificate again through electrolysis dehydration bromine, becomes 2-methoxyl group-3 through the potassium permanganate oxygenate, the 6-dichlorobenzoic acid again.This route is longer, and it is higher that raw material also is not easy to obtain cost, and wherein, the by-product Manganse Dioxide behind the potassium permanganate oxidation can cause secondary pollution to environment.Electrolytic processes etc. all are not suitable for suitability for industrialized production.Its chemical synthesis route is:
3, at patent documentation US:3345157, US4232172, US3013054, US4670610, PO185546, GB1464320, GB1221019, Indian IN:15341; And Przam, chem, 1979,58 (10) 533-6; Deng in the document all with 2, the 5-NSC 2879 is a raw material or through 2,5 dichlorphenamide bulk powders, 1; 2, the 4-trichlorobenzene makes 2, becomes phenol sylvite behind the 5-NSC 2879 again with Pottasium Hydroxide; Obtain 3,2 hydroxyl potassium yl benzoic acid potassium and methyl-sulfate etherificate, the hydrolysis again of 6-two chloro-through the CO 2 high pressure addition is carboxylated; Obtain 2-methoxyl group-3, the 6-dichlorobenzoic acid.This route cost is low, and raw material is easy to get, and is extensively adopted, but this method need react under the highly compressed situation, production safety is brought sizable hidden danger, and will use a large amount of Pottasium Hydroxide and a large amount of acid, produces a large amount of waste water.So this route also has weak point.Its chemical synthesis route is:
4, in Japanese Patent JP4805574 document, with 2, the 5-NSC 2879 is that raw material obtains 2-methoxyl group-3 through etherificate, Claisen rearrangement, etherificate, oxidation; The 6-dichlorobenzoic acid; Its preparation method is ingenious, but its yield is lower, and has a large amount of three wastes to produce; Thereby cost is higher, is not adopted by suitability for industrialized production.Its chemical synthesis route is:
Summary of the invention
The object of the invention is to propose a kind of preparation method that can overcome the benzoic acids weedicide dicamba 98 of prior art defective.
Technical scheme of the present invention may further comprise the steps:
1) adopt 2,5-NSC 2879 or 2, an alkali metal salt of 5-NSC 2879 reacts under 0～150 ℃ of temperature environment under the condition of organic solvent and the existence of organic esterified reagent, obtains corresponding esters; Said 2, an alkali metal salt of 5-NSC 2879 is 2,5-NSC 2879 sodium or 2,5-NSC 2879 potassium; Said organic solvent is halohydrocarbon or aromatic hydrocarbons; Said organic esterified reagent is Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, diacetyl oxide, propionic anhydride or cis-butenedioic anhydride;
2) under the condition that catalyzer exists, be dissolved in the aromatic hydrocarbons, reset, obtain corresponding adjacent ketone through Fries at said ester; Said temperature of reaction is 140～180 ℃; Said catalyzer is aluminum chloride, iron trichloride, zinc chloride, tin chloride, antimony chloride or titanium tetrachloride;
3) under the catalysis of acid binding agent, said ketone is dissolved in carries out etherificate with methylating reagent behind the solvent and obtain 2-methoxyl group-3,6-dichlorobenzene ketone compounds; Said temperature of reaction is 20～50 ℃; Said methylating reagent is methyl chloride, monobromethane, methyl iodide or methyl-sulfate; The said solvent of this step is alkane, aromatic hydrocarbons, water, alcohol or ketone; Said acid binding agent is yellow soda ash, salt of wormwood, sodium hydroxide, Pottasium Hydroxide, pyridine, 4-picoline, 2-picoline or triethylamine;
4) under the condition that the supported catalyst of argentiferous, zirconium or copper exists, with said 2-methoxyl group-3,6-dichlorobenzene ketone compounds oxidation dissolution feeds oxygenant in solvent, obtain 3,6-two chloro-O-Anisic Acids; Said temperature of reaction is 70～120 ℃; The said solvent of this step is aromatic hydrocarbons, alkane, water, alcohol or sour; Oxygenant is oxygen, air, potassium permanganate, SRM 935a, ydrogen peroxide 50 or nitric acid.
The present invention adopts 2, and the 5-NSC 2879 is a raw material, obtains 3 through over-churning, Fries rearrangement, etherificate, oxidation, 6-two chloro-O-Anisic Acids, and this synthetic method craft is simple, and raw material is easy to get, and cost is low, and the three wastes are few, and more environmental protection is more suitable for suitability for industrialized production.
Described in the step 1) according to the invention 2, an alkali metal salt optimal selection of 5-NSC 2879 is 2,5-NSC 2879 potassium.
Other preferred version is:
Organic solvent described in the said step 1) is a toluene.
Organic esterified reagent described in the said step 1) is Acetyl Chloride 98Min..
Said step 2) catalyzer described in is a titanium tetrachloride.
Said step 2) aromatic hydrocarbons described in is YLENE or trimethylbenzene.
Methylating reagent described in the said step 3) is a methyl-sulfate.
Solvent described in the said step 3) is an acetone.
Acid binding agent described in the said step 3) is mixed by salt of wormwood and 4-picoline and forms.
Oxygenant described in the said step 4) is an air, and solvent is an acetate.
Embodiment
One, acetate 2, the compound method of 5-Dichlorfop:
1, in having the 1000ml four-hole bottle of mechanical stirring, TM, prolong, addition funnel, water trap, add 83.32g, 0.5mol 2; 5-NSC 2879 (purity 99%) toluene solution 500ml, 30.4g, 0.5mol Pottasium Hydroxide (purity 92%) begin to be warming up to about 5～6 hours of backflow; Divide water outlet 9 grams, having a large amount of white cotton-shaped solids to separate out in the bottle is 2,5-NSC 2879 potassium; Cool to room temperature then; And open with water-bath cooling and to drip 40.9g.0.51mol Acetyl Chloride 98Min. (purity 98%) and dripped off in about 2 hours, can the cotton-shaped solids disappeared of adularescent, the white powder solid is separated out.Sampling gas spectrum analysis filters when the 5-NSC 2879 finishes when 2, and mother liquor distills to such an extent that the deep yellow solid is 103 gram acetate 2,5-Dichlorfop, content 98%, yield 100%.Mass spectroscopy MS, (m/z, EI, 70ev); 218 (100%) M+; 220 (64%) M+2+.
2, in having the 1000ml four-hole bottle of mechanical stirring, TM, prolong, addition funnel, water trap, add 2,5-NSC 2879 (purity 99%) 83.3g (0.5mol) dichloroethane solution 500ml; Sodium hydroxide (purity 99%) 20.2g (0.5mol) begins to be warming up to about 5～6 hours of backflow; Divide water outlet 9 grams, having a large amount of white cotton-shaped solids to separate out in the bottle is 2,5-NSC 2879 sodium; Cool to room temperature then; And open dripping acetyl chloride (purity 98%) 40.9g (0.51mol) with water-bath cooling and dripped off in about 2 hours, can the cotton-shaped solids disappeared of adularescent, the white powder solid is separated out.Sampling gas spectrum analysis filters when the reaction of 5-NSC 2879 finishes when 2, and mother liquor distills to such an extent that deep yellow solid 104 grams are acetate 2,5-Dichlorfop, content 96%, yield 97.4%.
3, in having the 1000ml four-hole bottle of mechanical stirring, TM, prolong, addition funnel, water trap, add 2,5-NSC 2879 (purity 99%) 83.32g (0.5mol) dichloroethane solution 500ml; Salt of wormwood (purity 99%) 53g (0.5mol) at room temperature; And open dripping acetyl chloride (purity 98%) 40.9g (0.51mol) with water-bath cooling and dripped off in about 2 hours, sampling gas spectrum analysis filters when the reaction of 5-NSC 2879 finishes when 2; Mother liquor distills to such an extent that the deep yellow solid is 102 gram acetate 2; The 5-Dichlorfop, content 90%, yield 89.5%.
Two, 3, the compound method of 6-two chloro-2-hydroxy acetophenones
1, have mechanical stirring, TM, prolong, 1000ml glass four-hole bottle in, add last steps 102 gram acetate 2,5-Dichlorfop (content 98%; 0.5mol), trimethylbenzene 600ml, catalyzer titanium tetrachloride 2 grams, aluminum chloride 2 grams, beginning temperature rising reflux 8 hours, solution become combine red; Reaction is transferred to clear liquid in another four-hole bottle after finishing, and solvent is deviate from; Get colourless liquid 90 grams, gas spectrum analysis content 89%, yield 78.5% with steam distillation then; Mass spectroscopy M/Z (204, M+; 206, M+2+).
2, in having the 1000ml glass four-hole bottle of mechanical stirring, TM, prolong, add last steps 102 a gram acetate 2,5-Dichlorfop (content 98%; 0.5mol), YLENE 600ml, catalyzer titanium tetrachloride 2 grams, aluminum chloride 2 grams, beginning temperature rising reflux 8 hours, solution become combine red; Reaction is transferred to clear liquid in another four-hole bottle after finishing, and solvent is deviate from; Get colourless liquid 90 grams, gas spectrum analysis content 89%, yield 78.5% with steam distillation then; Mass spectroscopy MS, (M/Z, EI, 70ev), (204, M+; 206, M+2+).
Three, 3, the compound method of 6-two chloro-2-methoxyacetophenones
1, in having the 500ml glass four-hole bottle of mechanical stirring, TM, addition funnel, prolong, adds 3,6-two chloro-2-hydroxy acetophenones 21.5 (content 95%; 0.1mol), (purity 98% 0.15mol) at room temperature, drips methyl-sulfate 15.4 gram (purity 98% to acetone 200ml and salt of wormwood 21 grams; 0.12mol) dripped off in about 2～3 hours, be incubated 2 hours, filter; The mother liquor precipitation gets yellow liquid, and promptly 3,6-two chloro-2-methoxyacetophenones 23 grams; Gas spectrum analysis content 90.1%, yield 94.5%.
Mass spectroscopy MS, (M/Z, EI, 70ev), (218, M
+220, M+2
+),
1H, NMR (300MHz, CDCl
3), δ=2.485 (s, 3H, CH
3), 3.852 (s, 3H.O-CH
3), 7.014-7.224 (d, 1H, bene-H), 7.482-7.604 (d, 1H, bene-1H);
2, in having the 500ml glass four-hole bottle of mechanical stirring, TM, addition funnel, prolong, add 3,6-two chloro-2-hydroxy acetophenones 21.5 (content 95%; 0.1mol), (purity 98% 0.15mol) at room temperature, drips methyl-sulfate 15.4 gram (purity 98% to ethylene dichloride 200ml and salt of wormwood 21 grams; 0.12mol) dripped off in about 2～3 hours, be incubated 6 hours, filter; The mother liquor precipitation gets yellow liquid, and promptly 3,6-two chloro-2-methoxyacetophenones 24 grams; Gas spectrum analysis content 85.5%, yield 93.6%.
3, in having the 500ml glass four-hole bottle of mechanical stirring, TM, addition funnel, prolong, add 3,6-two chloro-2-hydroxy acetophenones 21.5 (content 95%; 0.1mol), (purity 98% 0.15mol) at room temperature, drips methyl-sulfate 15.4 gram (purity 98% to toluene 200ml and yellow soda ash 16.2 grams; 0.12mol) dripped off in about 2～3 hours, be incubated 8 hours, filter; The mother liquor precipitation gets yellow liquid, and promptly 3,6-two chloro-2-methoxyacetophenones 23.2 grams; Gas spectrum analysis content 80.4%, yield 85.1%.
4, in having the 500ml glass four-hole bottle of mechanical stirring, TM, addition funnel, prolong, add 3,6-two chloro-2-hydroxy acetophenones 21.5 (content 95%; 0.1mol), (purity 98% 0.15mol) at room temperature, drips methyl-sulfate 15.4 gram (purity 98% to methyl alcohol 200ml and yellow soda ash 16.2 grams; 0.12mol) dripped off in about 2～3 hours, be incubated 4 hours, filter; The mother liquor precipitation gets yellow liquid, and promptly 3,6-two chloro-2-methoxyacetophenones 23 grams; Gas spectrum analysis content 87.4%, yield 91.7%.
Four, 3,6-two chloro-O-Anisic Acids synthetic
1, in having the 500ml glass four-hole bottle of mechanical stirring, TM, prolong, ventpipe, add 3,6-two chloro-2-methoxyacetophenone bullions 23 grams (about 0.09mol) add catalyzer 0.5 gram and acetate 200ml again; Be warmed up to backflow, beginning bubbling air (PM 60ml) reacted about 8 hours; Cool to room temperature, filtering recovering catalyst, precipitation get yellow oil 17 grams; Get 3 with the toluene recrystallization, 6-two chloro-O-Anisic Acids 15 gram content 95%, total recovery 64%.
Mass spectroscopy MS, (m/z, EI, 70ev); 220 (100%) M
+222 (64%) M+2
+;
1H, NMR (300MHz, CDCl
3), δ=3.864 (s, 3H.O-CH
3), 7.208-7.416 (d, 1H, bene-H), 7.564-7.785 (d, 1H, bene-1H); 11.012 (s, 1H, OH)
2, in having the 500ml glass four-hole bottle of mechanical stirring, TM, prolong, ventpipe, add 3,6-two chloro-2-methoxyacetophenone bullions 23 grams add catalyzer 0.5 gram, acetate 200ml again; Be warmed up to backflow, beginning aerating oxygen PM 60ml reacted about 6 hours; Cool to room temperature, filtering recovering catalyst, precipitation get yellow oil 16.5 grams; Get 3 with the toluene recrystallization, 6-two chloro-O-Anisic Acids 14.2 gram content 95%, two step yield 61%.
The above reaction process of the present invention as shown in the formula:
Claims (10)
1. the preparation method of a benzoic acids weedicide dicamba 98 is characterized in that may further comprise the steps:
1) adopt 2,5-NSC 2879 or 2, an alkali metal salt of 5-NSC 2879 reacts under 0～150 ℃ of temperature environment under the condition of organic solvent and the existence of organic esterified reagent, obtains corresponding esters; Said 2, an alkali metal salt of 5-NSC 2879 is 2,5-NSC 2879 sodium or 2,5-NSC 2879 potassium; Said organic solvent is halohydrocarbon or aromatic hydrocarbons; Said organic esterified reagent is Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, diacetyl oxide, propionic anhydride or cis-butenedioic anhydride;
2) under the condition that catalyzer exists, be dissolved in the aromatic hydrocarbons, reset, obtain corresponding adjacent ketone through Fries at said ester; Said temperature of reaction is 140～180 ℃; Said catalyzer is aluminum chloride, iron trichloride, zinc chloride, tin chloride, antimony chloride or titanium tetrachloride;
3) under the catalysis of acid binding agent, said ketone is dissolved in carries out etherificate with methylating reagent behind the solvent and obtain 2-methoxyl group-3,6-dichlorobenzene ketone compounds; Said temperature of reaction is 20～50 ℃; Said methylating reagent is methyl chloride, monobromethane, methyl iodide or methyl-sulfate; The said solvent of this step is alkane, aromatic hydrocarbons, water, alcohol or ketone; Said acid binding agent is yellow soda ash, salt of wormwood, sodium hydroxide, Pottasium Hydroxide, pyridine, 4-picoline, 2-picoline or triethylamine;
4) under the condition that the supported catalyst of argentiferous, zirconium or copper exists, with said 2-methoxyl group-3,6-dichlorobenzene ketone compounds oxidation dissolution feeds oxygenant in solvent, obtain 3,6-two chloro-O-Anisic Acids; Said temperature of reaction is 70～120 ℃; The said solvent of this step is aromatic hydrocarbons, alkane, water, alcohol or sour; Oxygenant is oxygen, air, potassium permanganate, SRM 935a, ydrogen peroxide 50 or nitric acid.
2. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that described in the said step 1) 2, an alkali metal salt of 5-NSC 2879 is 2,5-NSC 2879 potassium.
3. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that organic solvent described in the said step 1) is a toluene.
4. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that organic esterified reagent described in the said step 1) is Acetyl Chloride 98Min..
5. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that said step 2) described in catalyzer be titanium tetrachloride.
6. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that said step 2) described in aromatic hydrocarbons be YLENE or trimethylbenzene.
7. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that methylating reagent described in the said step 3) is a methyl-sulfate.
8. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that solvent described in the said step 3) is an acetone.
9. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that acid binding agent described in the said step 3) is mixed by salt of wormwood and 4-picoline to form.
10. according to the preparation method of the said benzoic acids weedicide of claim 1 dicamba 98, it is characterized in that oxygenant described in the said step 4) is an air, solvent is an acetate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102263A (en) * | 2013-02-18 | 2013-05-15 | 青岛农业大学 | 3-bromine-4-methoxybenzoic acid preparation method and agricultural biological activity |
| CN103819327A (en) * | 2014-03-21 | 2014-05-28 | 浙江升华拜克生物股份有限公司 | Method for synthesizing 3,6-dichloro-2-methoxy benzoic acid |
| CN104086431A (en) * | 2014-07-21 | 2014-10-08 | 天津药物研究院药业有限责任公司 | Method for synthesizing intermediate of reboxetine mesylate |
| WO2015086698A1 (en) * | 2013-12-11 | 2015-06-18 | Basf Se | Process for providing dihalogen substituted salicylic acid derivatives |
| CN105061200A (en) * | 2015-09-10 | 2015-11-18 | 江苏长青农化股份有限公司 | Method for synthetizing herbicide-dicamba (2-methoxy-3,6-dichloro-salicylic acid) through catalytic oxidation |
| CN106029618A (en) * | 2014-02-21 | 2016-10-12 | 巴斯夫欧洲公司 | Process for producing 2,5-dihalophenol ethers |
| CN107501089A (en) * | 2017-10-20 | 2017-12-22 | 河南红东方化工股份有限公司 | A kind of synthetic method of Mediben active compound |
| US9988333B2 (en) | 2014-05-19 | 2018-06-05 | Basf Se | Process for making 2,5-dihalogenated phenol |
| CN108484387A (en) * | 2018-03-20 | 2018-09-04 | 盐城工学院 | A kind of preparation method of Mediben |
| US10093607B2 (en) | 2013-10-04 | 2018-10-09 | Basf Se | Selective hydrolysis and alcoholysis of chlorinated benzenes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345157A (en) * | 1966-09-12 | 1967-10-03 | Velsicol Chemical Corp | Herbicidal composition and method |
| US4161611A (en) * | 1976-02-23 | 1979-07-17 | Veesicol Chemical Corporation | Process for the production of 2-methoxy-3,6-dichlorobenzoic acid |
| CN86107445A (en) * | 1986-11-01 | 1987-04-22 | 常州化工研究所 | Secondary octanol and/or methyln-hexyl ketone are produced the caproic acid novel process |
| CN101417947A (en) * | 2008-12-08 | 2009-04-29 | 温州医学院 | Method for preparing alkoxyl benzoic acids compounds |
-
2011
- 2011-12-13 CN CN2011104145788A patent/CN102516072A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345157A (en) * | 1966-09-12 | 1967-10-03 | Velsicol Chemical Corp | Herbicidal composition and method |
| US4161611A (en) * | 1976-02-23 | 1979-07-17 | Veesicol Chemical Corporation | Process for the production of 2-methoxy-3,6-dichlorobenzoic acid |
| CN86107445A (en) * | 1986-11-01 | 1987-04-22 | 常州化工研究所 | Secondary octanol and/or methyln-hexyl ketone are produced the caproic acid novel process |
| CN101417947A (en) * | 2008-12-08 | 2009-04-29 | 温州医学院 | Method for preparing alkoxyl benzoic acids compounds |
Non-Patent Citations (1)
| Title |
|---|
| 章小波等: "安息香酸系除草剂-麦草畏的合成", 《农药》, vol. 41, no. 11, 25 November 2002 (2002-11-25) * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102263A (en) * | 2013-02-18 | 2013-05-15 | 青岛农业大学 | 3-bromine-4-methoxybenzoic acid preparation method and agricultural biological activity |
| US10093607B2 (en) | 2013-10-04 | 2018-10-09 | Basf Se | Selective hydrolysis and alcoholysis of chlorinated benzenes |
| CN105939989A (en) * | 2013-12-11 | 2016-09-14 | 巴斯夫欧洲公司 | Process for providing dihalogen substituted salicylic acid derivatives |
| WO2015086698A1 (en) * | 2013-12-11 | 2015-06-18 | Basf Se | Process for providing dihalogen substituted salicylic acid derivatives |
| US10087133B2 (en) | 2013-12-11 | 2018-10-02 | Basf Se | Process for providing dihalogen substituted salicylic acid derivatives |
| CN106029618A (en) * | 2014-02-21 | 2016-10-12 | 巴斯夫欧洲公司 | Process for producing 2,5-dihalophenol ethers |
| CN106029618B (en) * | 2014-02-21 | 2019-01-18 | 巴斯夫欧洲公司 | The method for producing 2,5- dihalo phenolic ether |
| CN103819327B (en) * | 2014-03-21 | 2016-04-27 | 浙江升华拜克生物股份有限公司 | The synthetic method of the chloro-O-Anisic Acid of a kind of 3,6-bis- |
| CN103819327A (en) * | 2014-03-21 | 2014-05-28 | 浙江升华拜克生物股份有限公司 | Method for synthesizing 3,6-dichloro-2-methoxy benzoic acid |
| US9988333B2 (en) | 2014-05-19 | 2018-06-05 | Basf Se | Process for making 2,5-dihalogenated phenol |
| CN104086431A (en) * | 2014-07-21 | 2014-10-08 | 天津药物研究院药业有限责任公司 | Method for synthesizing intermediate of reboxetine mesylate |
| CN105061200A (en) * | 2015-09-10 | 2015-11-18 | 江苏长青农化股份有限公司 | Method for synthetizing herbicide-dicamba (2-methoxy-3,6-dichloro-salicylic acid) through catalytic oxidation |
| CN105061200B (en) * | 2015-09-10 | 2019-10-18 | 江苏长青农化股份有限公司 | A kind of method of catalysis oxidation synthesis herbicide dicamba 2- methoxyl group -3,6- dichlorosalicylic acid |
| CN107501089A (en) * | 2017-10-20 | 2017-12-22 | 河南红东方化工股份有限公司 | A kind of synthetic method of Mediben active compound |
| CN108484387A (en) * | 2018-03-20 | 2018-09-04 | 盐城工学院 | A kind of preparation method of Mediben |
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Application publication date: 20120627 |