CN103224451A - Method for synthesizing 3,5-dichlorobenzoic acid - Google Patents
Method for synthesizing 3,5-dichlorobenzoic acid Download PDFInfo
- Publication number
- CN103224451A CN103224451A CN2013101844686A CN201310184468A CN103224451A CN 103224451 A CN103224451 A CN 103224451A CN 2013101844686 A CN2013101844686 A CN 2013101844686A CN 201310184468 A CN201310184468 A CN 201310184468A CN 103224451 A CN103224451 A CN 103224451A
- Authority
- CN
- China
- Prior art keywords
- acid
- dichlorobenzonitrile
- during
- dichlorobenzoic
- benzene nitrile
- 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.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 3,5-dichlorobenzoic acid, which comprises the following steps: chlorinating benzonitrile used as a raw material to generate 3,5-dichlorobenzonitrile; and then, performing hydrolysis and acidification reaction to obtain 3,5-dichlorobenzoic acid. According to the invention, the benzonitrile is used as the raw material; sodium hypochlorite or a mixture of oxydol and hydrochloric acid is used in the chlorination process; the traditional chlorine gas chlorination process is omitted; the obtained 3,5-dichlorobenzonitrile is high in purity; no diazotization procedure is required; and the process safety is enhanced. The process has the advantages of accessible and cheap raw material, low production cost of the product, high process safety coefficient and short process flow, is simple to operate, is more beneficial to industrial production, is a new process for synthesizing 3,5-dichlorobenzoic acid, and provides a new idea for synthesizing propyzamide.
Description
Technical field
The present invention relates to a kind of synthetic 3, the method for 5-dichlorobenzoic acid, being specifically related to a kind of is 3 of starting raw material with the benzene nitrile, the synthetic method of 5-dichlorobenzoic acid.
Background technology
Halo formic acid and derivative thereof are a class important chemical and medicine intermediates, be used as the raw material of producing sterilant, sterilant, dyestuff and medicine in a large number, 3, the 5-dichlorobenzoic acid is exactly wherein a kind of, can be used for multiple Chemicals such as preparation medicine, agricultural chemicals, dyestuff, sterilant.In recent years, the demand of this product is the trend that rises year by year, R and D have progressively caused people's attention.
3 of present report, the synthetic method of 5-dichlorobenzoic acid has following two kinds by the raw material classification:
The one,, with 3, the 5-diaminotoluene is a raw material, and first diazotization generates 3, and the 5-toluene dichloride is solvent again with acetate, and acetate bores and is catalyzer, and oxidation produces 3, the 5-dichlorobenzoic acid;
The 2nd,, with the anthranilic acid is raw material, with the anthranilic acid is raw material synthetic 3, the 5-dichlorobenzoic acid has following several operational path: (1) is raw material with the anthranilic acid, is solvent with ethylene dichloride, DMF, uses the SULPHURYL CHLORIDE chlorination, obtain 2-amino-3, the 5-dichlorobenzoic acid, diazotization and getting again, yield is 60%.(2) with the anthranilic acid be raw material, hydrochloric acid is solvent, and iron trichloride is a catalyzer, about 10 ℃, directly logical chlorine obtains 2-amino-3, the 5-dichlorobenzoic acid, carry out diazotization reaction again, adding copper sulfate, isopropanol reaction get crude product, get product with the toluene recrystallization again.(3) with the anthranilic acid be raw material, acetic acid and aqueous solution liquid directly lead to Cl down as solvent about 40 ℃
2, obtaining 3,5-two chloro-o-amino benzoic acids carry out diazotization reaction again, add Virahol, hydrochloric acid and Catalysts Cu SO
4Reaction obtains crude product, and the toluene recrystallization gets product.(4) anthranilic acid has been to expect, and 10% hydrochloric acid is solvent, and logical chlorine is 4 hours under 28-30 ℃, adds Virahol under above-mentioned reaction conditions, drips NaNO down at 80-85 ℃
2The aqueous solution dripped off in 2 hours, reacted half an hour again under this temperature, and reaction solution carries out simple distillation again, collected 80-90 ℃ of Virahol and water, and the distillation residuum is cooled to 20-25 ℃ and placed 2 hours, carries out suction filtration.Filter cake is 3, the 5-dichlorobenzoic acid, and drying gets 3,5-dichlorobenzoic acid dry product.(5) anthranilic acid is a raw material, and hydrochloric acid is solvent, adds hydrogen peroxide and carries out chlorination, sulfuric acid system dropping NaNO
2Solution, ethanol is made reductive agent, carries out diazotization reaction and obtains target product.
Above-mentioned synthetic 3, in the method for 5-dichlorobenzoic acid, have the following disadvantages: with 3, the 5-diaminotoluene is a raw material, this method raw materials cost height, and yield is low, pollutes greatlyyer, and production environment is abominable; With anthranilic acid has been the comparatively economy of expecting, but this method ubiquity, long reaction time is operated loaded down with trivial details shortcoming, and especially the diazotization operation is dangerous high.Therefore be 3, it is problem demanding prompt solution that the 5-dichlorobenzoic acid is sought new synthetic route, adopts other technologies to synthesize 3 at present, and the technology of 5-dichlorobenzoic acid is not appeared in the newspapers as yet.
Summary of the invention
The present invention is directed to above-mentioned deficiency, provide a kind of and synthesized 3, the method for 5-dichlorobenzoic acid, this method flow is brief, safety coefficient is high, and product purity and yield height overcome the shortcoming that exists in the prior art.
The concrete technical scheme of the present invention is as follows:
A kind of synthetic 3, the method for 5-dichlorobenzoic acid is characterized in that, step comprises: with the benzene nitrile is raw material, in the presence of solvent and chlorizating agent, and chlorination generation 3 in sour environment, 5-dichlorobenzonitrile; 3, the 5-dichlorobenzonitrile earlier is hydrolyzed to 3 under alkaline environment, 5-dichlorobenzoic acid salt, acidifying gets 3 again, the 5-dichlorobenzoic acid, perhaps 3, the 5-dichlorobenzonitrile is hydrolysis under sour environment directly, 3, the 5-dichlorobenzoic acid.Reaction equation is:
In the aforesaid method, step comprises: with the benzene nitrile is raw material, and the benzene nitrile is dissolved in solvent and the acidic medium, drips chlorizating agent at a certain temperature, and the suitable pH value of control, and reaction obtains 3, the 5-dichlorobenzonitrile; Under normal pressure,, add alkaline matter in the 5-dichlorobenzonitrile then, pH value of reaction system is kept within the specific limits to 3, insulation reaction, hydrolysis gets 3,5-dichlorobenzoic acid salt, 3,5-dichlorobenzoic acid salt filters, dries through acidifying, promptly gets 3, the 5-dichlorobenzoic acid; Or, directly add acid in the 5-dichlorobenzonitrile to 3, and pH value of reaction system is kept within the specific limits, insulation reaction directly obtains 3, the 5-dichlorobenzoic acid.
In the aforesaid method, described solvent be methyl alcohol, Virahol, second cyanogen, ethyl acetate, chloroform, methylene dichloride, ether, toluene, trichloromethane and alcoholic acid one or more.Be preferably trichloromethane and alcoholic acid mixture, most preferably trichloromethane and ethanol mass ratio are 3: 1.
In the aforesaid method, described solvent and benzene nitrile mass ratio are 1-80: 1.
In the aforesaid method, described chlorizating agent is a clorox, or the mixture of hydrogen peroxide and hydrochloric acid.Benzene nitrile and clorox mol ratio are 1: 2.0-2.4; Benzene nitrile, HCl and hydrogen peroxide (refer to H
2O
2) mol ratio be 1: 2.0-2.5: 2.1-2.6, HCl provides with the form of aqueous hydrochloric acid, concentration of hydrochloric acid solution has no special requirements.
In the aforesaid method, during the chlorination of benzene nitrile, keeping the pH value is 0-6.0, and temperature of reaction is 50-70 ℃, and used acid is monobasic or polybasic mineral acid, and described acid includes but not limited to hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; Wherein concentration of hydrochloric acid is more than 25%, and sulfuric acid concentration is more than 30%, and phosphoric acid concentration is more than 85%, concentration of nitric acid is more than 65%, consider the operating equipment utilization ratio and simplify last handling process, the concentrated acid that preferred water content is less, for example concentrated hydrochloric acid, the vitriol oil, strong phosphoric acid or concentrated nitric acid.
In the aforesaid method, 3, during 5-dichlorobenzonitrile alkaline hydrolysis (i.e. hydrolysis under alkaline environment), keeping the pH value is 11-14, and temperature of reaction is 50-90 ℃, and preferred 80-90 ℃, the general reaction times is 2-3h.3, when being hydrolyzed under the 5-dichlorobenzonitrile normal pressure alkaline environment, keep alkaline environment with sodium hydroxide, potassium hydroxide or their aqueous solution, used sodium hydroxide solution or potassium hydroxide solution concentration generally between 10wt%-30wt%, are preferably sheet alkali.
In the aforesaid method, 3, during the acidifying of 5-dichlorobenzoic acid salt, maintenance pH is 0-3, and keeping temperature is 50-90 ℃, preferred 50-60 ℃, the general reaction times is 0.5-1h, and used acid is monobasic or polybasic mineral acid, and described acid includes but not limited to hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; Wherein concentration of hydrochloric acid is more than 25%, and sulfuric acid concentration is more than 30%, and phosphoric acid concentration is more than 85%, concentration of nitric acid is more than 65%, consider the operating equipment utilization ratio and simplify last handling process, the concentrated acid that preferred water content is less, for example concentrated hydrochloric acid, the vitriol oil, strong phosphoric acid or concentrated nitric acid.
In the aforesaid method, 3, during the direct acidic hydrolysis of 5-dichlorobenzonitrile (i.e. directly hydrolysis under sour environment), keeping the pH value is 1-4, and temperature is 50-90 ℃, and preferred 80-90 ℃, the general reaction times is 2-3h.Used acid is monobasic or polybasic mineral acid, and described acid includes but not limited to hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; Wherein concentration of hydrochloric acid is more than 25%, and sulfuric acid concentration is more than 30%, and phosphoric acid concentration is more than 85%, concentration of nitric acid is more than 65%, consider the operating equipment utilization ratio and simplify last handling process, the concentrated acid that preferred water content is less, for example concentrated hydrochloric acid, the vitriol oil, strong phosphoric acid or concentrated nitric acid.
The invention has the beneficial effects as follows:
1, proposing with the benzene nitrile first is raw material, and first chlorination generates 3, the 5-dichlorobenzonitrile, and hydrolysis reaction gets 3 then, 5-dichlorobenzoic acid, chlorination have been abandoned traditional chlorinated with chlorine, make chlorination safe, gained 3,5-dichlorobenzonitrile purity height need not the diazotization operation, has improved process safety.
2, this raw materials technology be easy to get, cheapness, the products production cost is low, process safety coefficient height, simple to operate, technical process is brief, more helps suitability for industrialized production, is synthetic 3, the novel process of 5-dichlorobenzoic acid provides new approaches for synthetic pentyne grass amine again.
Description of drawings
Fig. 1 is made 3 for the present invention, 5-dichlorobenzoic acid liquid phase spectrogram.
Embodiment
The invention will be further described below in conjunction with specific embodiment, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
100.0g in the benzene nitrile (content 99%), add the 300g trichloromethane respectively, 100g ethanol, drop into 1209.4g clorox (content 13%) again, it is 3.0-4.0 that hydrochloric acid with 37% keeps system pH, and under 55-60 ℃, reaction is to 3, control content is 99.5% in the 5-dichlorobenzonitrile, under normal pressure, add 30% sodium hydroxide then, make pH value of reaction system remain on 12-13, behind the 80-90 ℃ of insulation reaction 2.5h, be 1.0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 1.0h, refilter, 90-110 ℃ of down oven dry, promptly get 182.5g content and be 99.0% 3, the 5-dichlorobenzoic acid.
Embodiment 2
100.0g in the benzene nitrile (content 99%), add the 1500g trichloromethane respectively, 500g ethanol, drop into 1209.4g clorox (content 13%) again, it is 5.0-6.0 that sulfuric acid with 98% keeps system pH, and under 60-70 ℃, reaction is to 3, control content is 99.4% in the 5-dichlorobenzonitrile, under normal pressure, add 20% sodium hydroxide then, make pH value of reaction system remain on 11-12, behind the 80-90 ℃ of insulation reaction 3.0h, be 0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.5h, refilter, 90-110 ℃ of down oven dry, promptly get 182.5g content and be 99.0% 3, the 5-dichlorobenzoic acid.
Embodiment 3
100.0g in the benzene nitrile (content 99%), add the 75g trichloromethane respectively, 25g ethanol, drop into 1209.4g clorox (content 13%) again, it is 0-1.0 that hydrochloric acid with 25% keeps system pH, and under 55-70 ℃, reaction is to 3, control content is 99.5% in the 5-dichlorobenzonitrile, under normal pressure, add 10% sodium hydroxide then, make pH value of reaction system remain on 13-14, behind the 80-90 ℃ of insulation reaction 2.7h, be 1.5 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.6h, refilter, 90-110 ℃ of down oven dry, promptly get 182.3g content and be 99.0% 3, the 5-dichlorobenzoic acid.
Embodiment 4
100.0g in the benzene nitrile (content 99%), add 75g trichloromethane, 25g ethanol respectively, drop into 1209.4g clorox (content 13%) again, it is 0-1.0 that hydrochloric acid with 25% keeps system pH, and under 55-70 ℃, reaction is to 3, control content is 99.5% in the 5-dichlorobenzonitrile, under normal pressure, adds 25% hydrochloric acid then, make pH value of reaction system remain on 1.0-2.5, behind the 80-90 ℃ of insulation reaction 2.7h, refilter 90-110 ℃ of oven dry down, promptly get 182.3g content and be 99.0% 3, the 5-dichlorobenzoic acid.
Embodiment 5
100.0g in the benzene nitrile (content 99%), add 75g trichloromethane 25g ethanol respectively, drop into 1209.4g clorox (content 13%) again, it is 0-1.0 that hydrochloric acid with 25% keeps system pH, and under 55-70 ℃, reaction is to 3, control content is 99.5% in the 5-dichlorobenzonitrile, under normal pressure, adds 37% hydrochloric acid then, make pH value of reaction system remain on 2.0-4.0, behind the 80-90 ℃ of insulation reaction 2.7h, refilter 90-110 ℃ of oven dry down, promptly get 182.3g content and be 99.0% 3, the 5-dichlorobenzoic acid.
Embodiment 6
100.0g in the benzene nitrile (content 99%), add 3000g methyl alcohol respectively, 5000g ethanol, drop into 1099.5g clorox (content 13%) again, it is 2.0-3.2 that phosphoric acid with 85% keeps system pH, and under 55-65 ℃, reaction is to 3, control content is 99.4% in the 5-dichlorobenzonitrile, under normal pressure, add 30% potassium hydroxide then, make pH value of reaction system remain on 11-13, behind the 80-90 ℃ of insulation reaction 2.6h, be 3.0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.8h, refilter, 90-110 ℃ of down oven dry, promptly get 181.3g content and be 98.1% 3, the 5-dichlorobenzoic acid.
Embodiment 7
100.0g in the benzene nitrile (content 99%), add the 6000g Virahol respectively, drop into 1154.4g clorox (content 13%) again, it is 4.0-5.0 that nitric acid with 65% keeps system pH, and under 50-65 ℃, reaction is to 3, control content is 99.1% in the 5-dichlorobenzonitrile, under normal pressure, add sheet alkali then, make pH value of reaction system remain on 12-14, behind the 80-90 ℃ of insulation reaction 2.0h, be 2.0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.9h, refilter, 90-110 ℃ of down oven dry, promptly get 181.5g content and be 98.0% 3, the 5-dichlorobenzoic acid.
Embodiment 8
100.0g in the benzene nitrile (content 99%), add 4000g second cyanogen respectively, drop into 1264.4g clorox (content 13%) again, it is 5.0-6.0 that sulfuric acid with 30% keeps system pH, and under 50-68 ℃, reaction is to 3, control content is 99.3% in the 5-dichlorobenzonitrile, under normal pressure, add sheet alkali then, make pH value of reaction system remain on 12-13, behind the 80-90 ℃ of insulation reaction 2.2h, be 2.5 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.7h, refilter, 90-110 ℃ of down oven dry, promptly get 181.2g content and be 98.4% 3, the 5-dichlorobenzoic acid.
Embodiment 9
100.0g in the benzene nitrile (content 99%), add 3000g toluene respectively, drop into 1319.4g clorox (content 13%) again, it is 1.0-3.0 that sulfuric acid with 80% keeps system pH, and under 53-65 ℃, reaction is to 3, control content is 99.0% in the 5-dichlorobenzonitrile, under normal pressure, add sheet alkali then, make pH value of reaction system remain on 12-13, behind the 80-90 ℃ of insulation reaction 3.0h, be 1.5 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.5h, refilter, 90-110 ℃ of down oven dry, promptly get 181.0g content and be 98.4% 3, the 5-dichlorobenzoic acid.
Embodiment 10
100.0g in the benzene nitrile (content 99%), add the 6000g ethyl acetate respectively, the 1000g chloroform, drop into 266.0g hydrogen peroxide (content 27%) again, 227.3g hydrochloric acid (content 37%), keeping system pH with 65% nitric acid again is 1.0-4.0, under 60-70 ℃, reaction to 3, control content is 99.0% in the 5-dichlorobenzonitrile, then under normal pressure, add sheet alkali, making pH value of reaction system remain on 12-13, behind the 80-90 ℃ of insulation reaction 2.5h, is 1.0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 1.0h refilters, 90-110 ℃ of oven dry down, promptly get 181.9g content and be 98.3% 3, the 5-dichlorobenzoic acid.
Embodiment 11
100.0g in the benzene nitrile (content 99%), add the 1000g methylene dichloride respectively, drop into 241.9g hydrogen peroxide (content 27%) again, 294.4g hydrochloric acid (content 25%), keeping system pH with 80% sulfuric acid again is 1.0-4.0, under 60-65 ℃, reaction to 3, control content is 99.0% in the 5-dichlorobenzonitrile, then under normal pressure, add sheet alkali, making pH value of reaction system remain on 12-13, behind the 80-90 ℃ of insulation reaction 2.5h, is 2.0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 0.9h refilters, 90-110 ℃ of oven dry down, promptly get 181.3g content and be 98.4% 3, the 5-dichlorobenzoic acid.
Embodiment 12
100.0g in the benzene nitrile (content 99%), add the 500g ether respectively, drop into 302.3g hydrogen peroxide (content 27%) again, 246.2g hydrochloric acid (content 37%), keeping system pH with 30% sulfuric acid again is 1.0-4.0, under 60-65 ℃, reaction to 3, control content is 99.0% in the 5-dichlorobenzonitrile, then under normal pressure, add sheet alkali, making pH value of reaction system remain on 12-13, behind the 80-90 ℃ of insulation reaction 2.5h, is 1.0 with 37% hcl acidifying to system pH again, under 50-60 ℃, reaction 1.0h refilters, 90-110 ℃ of oven dry down, promptly get 181.2g content and be 98.3% 3, the 5-dichlorobenzoic acid.
Claims (10)
1. one kind is synthesized 3, and the method for 5-dichlorobenzoic acid is characterized in that, step comprises: with the benzene nitrile is raw material, and in the presence of solvent and chlorizating agent, chlorination generates 3, the 5-dichlorobenzonitrile in sour environment; 3, the 5-dichlorobenzonitrile earlier is hydrolyzed to 3 under alkaline environment, 5-dichlorobenzoic acid salt, acidifying gets 3 again, the 5-dichlorobenzoic acid, perhaps 3, the 5-dichlorobenzonitrile is hydrolysis under sour environment directly, 3, the 5-dichlorobenzoic acid.
2. method according to claim 1 is characterized in that: described solvent be methyl alcohol, Virahol, second cyanogen, ethyl acetate, chloroform, methylene dichloride, ether, toluene, trichloromethane and alcoholic acid one or more.
3. method according to claim 2 is characterized in that: described solvent is trichloromethane and alcoholic acid mixture, and trichloromethane and ethanol mass ratio are 3: 1.
4. according to claim 1,2 or 3 described methods, it is characterized in that: the mass ratio of described solvent and benzene nitrile is 1-80: 1.
5. method according to claim 1 is characterized in that: described chlorizating agent is a clorox, or the mixture of hydrogen peroxide and hydrochloric acid.
6. method according to claim 5 is characterized in that: during the chlorination of benzene nitrile, the mol ratio of benzene nitrile and clorox is 1: 2.0-2.4; The mol ratio of benzene nitrile, HCl and hydrogen peroxide is 1: 2.0-2.5: 2.1-2.6.
7. method according to claim 1 is characterized in that: during the chlorination of benzene nitrile, keeping the pH value is 0-6.0, and temperature of reaction is 50-70 ℃; 3, during the alkaline hydrolysis of 5-dichlorobenzonitrile, keeping temperature is 50-90 ℃, and the pH value is 11-14; 3, during the acidifying of 5-dichlorobenzoic acid salt, maintenance pH is 0-3, and souring temperature is 50-90 ℃; 3, during 5-dichlorobenzonitrile acidic hydrolysis, keeping temperature is 50-90 ℃, and the pH value is 1-4.
8. method according to claim 7 is characterized in that: 3, and when 5-dichlorobenzonitrile alkalescence or acidic hydrolysis, temperature is 80-90 ℃, the time is 2-3h; 3, during the acidifying of 5-dichlorobenzoic acid salt, temperature is 50-60 ℃, and the time is 0.5-1h.
9. method according to claim 1 is characterized in that: during the chlorination of benzene nitrile, keep sour environment with monobasic or polybasic mineral acid; 3, during the alkaline hydrolysis of 5-dichlorobenzonitrile, keep alkaline environment with sodium hydroxide, potassium hydroxide or their aqueous solution, 3, during the acidifying of 5-dichlorobenzoic acid salt, carry out acidifying with monobasic or polybasic mineral acid; 3, during 5-dichlorobenzonitrile acidic hydrolysis, keep sour environment with monobasic or polybasic mineral acid.
10. method according to claim 9 is characterized in that: during the chlorination of benzene nitrile, keep sour environment with hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; 3, during the alkaline hydrolysis of 5-dichlorobenzonitrile, keep alkaline environment with sheet alkali, 3, during the acidifying of 5-dichlorobenzoic acid salt, carry out acidifying with hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; 3, during 5-dichlorobenzonitrile acidic hydrolysis, keep sour environment with hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310184468.6A CN103224451B (en) | 2013-05-20 | 2013-05-20 | Method for synthesizing 3,5-dichlorobenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310184468.6A CN103224451B (en) | 2013-05-20 | 2013-05-20 | Method for synthesizing 3,5-dichlorobenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103224451A true CN103224451A (en) | 2013-07-31 |
| CN103224451B CN103224451B (en) | 2015-03-25 |
Family
ID=48835125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310184468.6A Active CN103224451B (en) | 2013-05-20 | 2013-05-20 | Method for synthesizing 3,5-dichlorobenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103224451B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262087A (en) * | 2014-08-29 | 2015-01-07 | 新岸诺亚（北京）化工科技有限公司 | Preparation method of 3,5-dichloro-4-methylbenzoic acid |
| CN105669483A (en) * | 2016-03-01 | 2016-06-15 | 滨海新东方医化有限公司 | Preparation method of propyzamide |
| CN107540566A (en) * | 2017-08-28 | 2018-01-05 | 江苏绿叶农化有限公司 | A kind of preparation method of propyzamide |
| CN108341776A (en) * | 2018-04-13 | 2018-07-31 | 北京朗依制药有限公司沧州分公司 | The technique for synthesizing Chlorquinaldol |
| CN114181139A (en) * | 2021-12-27 | 2022-03-15 | 四川仁安药业有限责任公司 | Synthetic method of 5-halogenated nicotinic acid |
| CN114805051A (en) * | 2021-08-03 | 2022-07-29 | 浙江宇龙生物科技股份有限公司 | Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320960A (en) * | 2011-08-02 | 2012-01-18 | 安徽东健化工科技有限公司 | Preparation method of 6-fluoro salicylic acid |
| CN102838481A (en) * | 2011-06-23 | 2012-12-26 | 徐州师范大学 | Synthesis of 3,5-dichlorobenzoyl chloride |
-
2013
- 2013-05-20 CN CN201310184468.6A patent/CN103224451B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838481A (en) * | 2011-06-23 | 2012-12-26 | 徐州师范大学 | Synthesis of 3,5-dichlorobenzoyl chloride |
| CN102320960A (en) * | 2011-08-02 | 2012-01-18 | 安徽东健化工科技有限公司 | Preparation method of 6-fluoro salicylic acid |
Non-Patent Citations (3)
| Title |
|---|
| ACS: "Halogenation of benzene derivatives with electron-acceptor substituents under conditions generating electrophilic chlorine and bromine", 《CASREACT》 * |
| 孙旭军等: "2,4- 二氯苯甲酸的合成研究", 《应用化工》 * |
| 赵明华: "6-甲基3-硝基-2-氯苯酚的合成及其副产物分析", 《中国药业》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262087A (en) * | 2014-08-29 | 2015-01-07 | 新岸诺亚（北京）化工科技有限公司 | Preparation method of 3,5-dichloro-4-methylbenzoic acid |
| CN104262087B (en) * | 2014-08-29 | 2015-12-30 | 新岸诺亚（北京）化工科技有限公司 | The preparation method of the chloro-4-tolyl acid of a kind of 3,5-bis- |
| CN105669483A (en) * | 2016-03-01 | 2016-06-15 | 滨海新东方医化有限公司 | Preparation method of propyzamide |
| CN105669483B (en) * | 2016-03-01 | 2018-02-23 | 滨海新东方医化有限公司 | A kind of preparation method of pentyl xanthate |
| CN107540566A (en) * | 2017-08-28 | 2018-01-05 | 江苏绿叶农化有限公司 | A kind of preparation method of propyzamide |
| CN108341776A (en) * | 2018-04-13 | 2018-07-31 | 北京朗依制药有限公司沧州分公司 | The technique for synthesizing Chlorquinaldol |
| CN108341776B (en) * | 2018-04-13 | 2021-04-09 | 北京金城泰尔制药有限公司沧州分公司 | Process for synthesizing chloroquinate |
| CN114805051A (en) * | 2021-08-03 | 2022-07-29 | 浙江宇龙生物科技股份有限公司 | Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer |
| CN114805051B (en) * | 2021-08-03 | 2023-08-15 | 浙江宇龙生物科技股份有限公司 | Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer |
| CN114181139A (en) * | 2021-12-27 | 2022-03-15 | 四川仁安药业有限责任公司 | Synthetic method of 5-halogenated nicotinic acid |
| CN114181139B (en) * | 2021-12-27 | 2023-12-08 | 四川仁安药业有限责任公司 | Synthesis method of 5-halogenated nicotinic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103224451B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103224451B (en) | Method for synthesizing 3,5-dichlorobenzoic acid | |
| CN103242190B (en) | Synthetic method of propyzamide | |
| CN103254058B (en) | Process for synthesizing 2, 3, 3, 3-tetrafluoropropionic acid | |
| CN106748716B (en) | A kind of new method for preparing 2,4,5 trifluoro benzene acetic acids | |
| CN103086959A (en) | Novel process for producing 3,5,6-sodium trichloropyrindinol | |
| CN102757312A (en) | High-selectivity and low-energy-consumption preparation method for benzyl alcohol | |
| CN104086480A (en) | Preparation method of 2-chloro-5-chloromethylpyridine | |
| CN103058984B (en) | Synthesis method of watermelon ketone | |
| CN105198710B (en) | The synthetic method of one inter-species tert-butyl phenol | |
| CN104072384A (en) | Synthesis method of mesalazine | |
| CN102898328A (en) | Synthesis method of diethyl azodicarboxylate and intermediate of diethyl azodicarboxylate | |
| CN104892371A (en) | Method for producing glycol dimethyl ether | |
| CN108530301A (en) | A kind of synthetic method of tri- fluorin benzyl amines of 2,4,6- | |
| CN110283067B (en) | Synthetic method of 2, 4-dihydroxy-3, 3-dimethylbutyric acid | |
| CN102603571A (en) | Preparation method of 2,4-dichloro-3-cyano-5-fluobenzoic acid | |
| CN103408418B (en) | Preparation and purification method of solid malonic acid | |
| CN101575301A (en) | Preparation method of 2-amino-5-chlorobenzamide | |
| CN103992241A (en) | Preparation method of N-substituted phenyl glycine | |
| CN102311362A (en) | Method for preparing ethyl hydrazinoacetate hydrochloride | |
| CN104230747B (en) | A kind of preparation method of asymmetry aromatic azo-compound | |
| CN104262087B (en) | The preparation method of the chloro-4-tolyl acid of a kind of 3,5-bis- | |
| CN102030616A (en) | Preparation method for 2,3,5,6-tetrafluorohydroquinone | |
| CN101805277A (en) | Preparation method of 2,2'-dithio-salicylic acid | |
| CN102173993A (en) | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) | |
| CN107879944B (en) | Method for preparing butyl betaine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Applicant after: Shandong Weifang Rainbow Chemical Co., Ltd. Address before: Haiyuan Binhai Economic and Technological Development Zone in Shandong province Weifang City 600 street 262737 No. 1 ranked No. 1 Applicant before: Shandong Weifang Rainbow Chemical Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: No. 03001, chlor alkali Road, Weifang Coastal Economic Development Zone, Shandong, Shandong Patentee after: Shandong Weifang Rainbow Chemical Co.,Ltd. Address before: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Patentee before: Shandong Weifang Rainbow Chemical Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder |