CN105294419A - Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate - Google Patents
Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate Download PDFInfo
- Publication number
- CN105294419A CN105294419A CN201510799471.8A CN201510799471A CN105294419A CN 105294419 A CN105294419 A CN 105294419A CN 201510799471 A CN201510799471 A CN 201510799471A CN 105294419 A CN105294419 A CN 105294419A
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- acid
- acids
- solvent
- trichlorobenzoic
- 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.)
- Pending
Links
- 0 Cc1ccc(*)cc1 Chemical compound Cc1ccc(*)cc1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/305—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with sulfur or sulfur-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Abstract
The invention discloses synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate. The invention provides the synthesis method of 2, 3, 6-trichlorobenzoic acid. The synthesis method comprises that in the presence of a catalyst, 2, 3, 6-benzotrichloride and an oxidation reagent undergo an oxidation reaction to produce 2, 3, 6-trichlorobenzoic acid. The synthesis methods have simple processes, a high conversion rate, a high yield, high product purity, a low production cost and environmental friendliness and are suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic method of the chloro-O-Anisic Acid of 3,6-bis-and intermediate thereof.
Background technology
Dicamba 98 (Dicamba) has another name called Dicamba, the chloro-O-Anisic Acid of chemical name 3,6-bis-.Belong to benzoic acids weedicide, have the features such as efficient, wide spectrum, low toxicity, by force herbicidal, consumption is few, and cost is low.Be mainly used in the annual or perennial broadleaf weed in grass field such as control wheat etc., as Tender Catchweed Bedstraw Herb, corn-bind, Herba Viviae Sativae, lamb's-quarters, ox chickweed, Siberian cocklebur, shepherd's purse, Herba seu Flos Convolvuli arvensis meadow pine etc. hundreds of.Dicamba 98 has Uptake and translocation effect, and for spraying after seedling, in usual dispenser 24 hours, lopsided curling symptom appears in weeds, dead in 15-20 days.The gramineous crop such as wheat, corn, paddy rice, millet absorbs after medicament can very fast metabolic breakdown, and show stronger resistance, medicament is safer to this type of gramineous crop.Dicamba 98 can decompose rapidly through microbial process in soil, can not cause the pollution to soil and water source, relative environmental protection.
The synthetic method of dicamba 98 mainly contains following several: (1) patent US3013054 is with 1,2,4-trichlorobenzene is raw material, through alkaline hydrolysis, Kolbe-Schmidt reaction is carboxylated obtains 3,6-dichlorosalicylic acid, then obtains dicamba 98 through methylation reaction, wherein the first step alkaline hydrolysis can form the phenol isomer being difficult to be separated, and can have influence on the finished product content.(2) patent US4161611 is with 2,5-dichlorphenamide bulk powder for raw material, and through diazotization, hydrolysis, Kolbe-Schmidt reaction is carboxylated, methylate obtained dicamba 98, and the method former medicine content is high, but wastewater flow rate is large, and cost is relatively high.(3) patent US3928432 is with the chloro-4-bromophenol of 2,5-bis-for raw material, and be that carboxyl obtains dicamba 98 through methylolation, phenolic hydroxyl group etherificate, debrominate, oxidation methylol, the method raw material is not easy to obtain, and cost is higher, and route is not suitable for industrialization.(4) patent JP485574 is with 2,5-chlorophenesic acid for raw material, and reset through allylation, Claisen, methylate, be oxidized obtained dicamba 98, this method yield is lower, and three wastes discharge amount is large, and cost is higher, is not suitable for suitability for industrialized production.(5) patent CN102516072 is with 2,5-chlorophenesic acid for raw material, obtains dicamba 98 through acetylize, Fries rearrangement, etherificate, oxidation, and this method three wastes discharge amount is large, and cost is higher.(6) patent CN103819327 is with 2,5-Banair for raw material, reacts prior to dichlormetbylether, again through hydrolysis, the obtained dicamba 98 of oxidation, this method yield is higher, but intermediate 1,1-dichlormetbylether and 2,5-Banair are all without industrialization product, and cost is higher.(7) patent CN102838483 is with 2,5-chlorophenesic acid for raw material, and through sulfonation, bromo, grignard reaction, carboxylated, the de-sulfo group of carbonic acid gas, methylate obtained dicamba 98, and the method route is long, and spent acid amount is large, is not suitable for industrial production.Therefore, find that good product purity, production cost that reactions steps simply obtains are low, environmental friendliness, the preparation method that is suitable for the dicamba 98 of suitability for industrialized production be the technical problem being badly in need of at present solving.
Summary of the invention
Technical problem to be solved by this invention is that the preparation method's reactions steps in order to overcome dicamba 98 in prior art is loaded down with trivial details, low conversion rate, yield are low, production cost is high, environmental pollution is serious, be not suitable for the defects such as suitability for industrialized production and provide the synthetic method of a kind of 3,6-bis-chloro-O-Anisic Acids and intermediate thereof.Synthetic method reactions steps of the present invention is simple, transformation efficiency is high, yield is high, obtained good product purity, production cost are low, environmental friendliness, be suitable for suitability for industrialized production.
The invention provides a kind of synthetic method of 2,3,6-trichlorobenzoic acid, it comprises the following steps: under catalyzer existent condition, 2,3,6-trichlorotoluene zotrichloride and oxidising agent is carried out oxidizing reaction, obtains 2,3,6-trichlorobenzoic acid;
The synthetic method of 2,3,6-described trichlorobenzoic acids can adopt the ordinary method of such oxidizing reaction in this area, particularly preferably following reaction method and condition in the present invention:
Described 2,3, in the synthetic method of 6-trichlorobenzoic acid, one or more in the preferred oxygen of described oxygenant, air, hydrogen peroxide, ozone, potassium permanganate, potassium bichromate, Peracetic Acid, peroxy tert-butyl alcohol, chromic acid, nitric acid, Potassium Persulphate, potassium perchlorate and Potcrate; One or more further preferably in potassium permanganate, nitric acid, oxygen.Described nitric acid can be conventional commercial nitron, and the mass concentration of described nitric acid preferably 10% ~ 30%, described mass concentration refers to that the quality of nitric acid accounts for the per-cent of salpeter solution total mass.When described oxygenant is gas, such as, when oxygen, air or ozone, the pressure of described reaction system preferably >=0.7Mpa.
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described oxygenant and 2,3,6-described trichlorotoluene zotrichlorides preferably 1 ~ 10, further preferably 2 ~ 5.
In the synthetic method of 2,3,6-described trichlorobenzoic acids, one or more in the preferred Vanadium Pentoxide in FLAKES of described catalyzer, ammonium vanadate, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, cobalt salt and manganese salt.Described cobalt salt refers to the material that cobalt ion and acid group are formed, such as four acetate hydrate cobalt or cobaltous acetates.Described manganese salt refers to the material that mn ion and acid group are formed, such as manganous acetate.When oxygenant is potassium permanganate, one or more in the preferred tetrabutylammonium chloride of described catalyzer, Tetrabutyl amonium bromide and tetrabutylammonium iodide; When oxygenant is nitric acid, the preferred Vanadium Pentoxide in FLAKES of described catalyzer; When described oxygenant be oxygen or air time, one or more preferably in four acetate hydrate cobalts, cobaltous acetate and manganous acetate of described catalyzer.When described catalyzer is manganese salt (such as manganous acetate), described oxidizing reaction is preferably carried out under promotor existent condition, the preferred Potassium Bromide of described promotor.The molar ratio of described promotor and described catalyzer preferably 1 ~ 3, further preferably 1 ~ 1.5.
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described catalyzer and 2,3,6-described trichlorotoluene zotrichlorides preferably 0.001 ~ 0.1, further preferably 0.005 ~ 0.05, more further preferably 0.007 ~ 0.01.
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the temperature of described oxidizing reaction preferably 50 DEG C ~ 190 DEG C, preferably 50 DEG C ~ 150 DEG C further, such as 120 DEG C ~ 140 DEG C.
Described 2,3, in the synthetic method of 6-trichlorobenzoic acid, the process of described oxidizing reaction can adopt routine monitoring method (such as TLC, HPLC, NMR or GC) in this area to monitor, generally with 2,3,6-trichlorotoluene zotrichloride is reaction end when disappearing, preferably 1 hour ~ 20 hours time of oxidizing reaction, preferably 2 hours ~ 18 hours further, further preferably 2 hours ~ 7 hours again, such as 4 hours ~ 5 hours.
The synthetic method of 2,3,6-described trichlorobenzoic acids can be carried out in a solvent or under solvent-free condition.When react carry out in a solvent time, one or more in described solvent preferably water, mineral acid, organic acid and sulfone kind solvent.Described mineral acid preferably sulfuric acid.Described sulfuric acid can be conventional commercial sulphate reagent, and the mass concentration of described sulfuric acid preferably 50% ~ 70%, described mass concentration refers to that the quality of sulfuric acid accounts for the per-cent of sulphuric acid soln total mass.One or more in the preferred acetic acid of described organic acid, propionic acid and butyric acid.The described preferred tetramethylene sulfone of sulfone kind solvent.The mass values of described solvent and 2,3,6-described trichlorotoluene zotrichlorides preferably 1 ~ 100, further preferably 1 ~ 10, such as 2 ~ 3.
The synthetic method of 2,3,6-described trichlorobenzoic acids, preferably carries out under promotor existent condition, the preferred Potassium Bromide of described promotor.The molar ratio of described promotor and described catalyzer preferably 1 ~ 3, further preferably 1 ~ 1.5.
When oxygenant is potassium permanganate, the preferably following post-processing step of employing: reaction end after heat filter, filtrate regulate about pH3, and filtration, washing, oven dry obtain 2,3,6-trichlorobenzoic acid.Described washing preferably adopts water.Described adjustment pH preferably adopts hydrochloric acid, the mass concentration of described hydrochloric acid preferably 1% ~ 10%, and further preferably 5% ~ 10%.Described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass.
When oxygenant is nitric acid, preferably adopt following post-processing step: after reaction terminates, filter and obtain 2,3,6-trichlorobenzoic acid.
When oxygenant be oxygen or air time, preferably adopt following post-processing step: except desolventizing, washing, oven dry obtain 2,3,6-trichlorobenzoic acid after reaction terminates.Described washing preferably adopts water.Described can adopt the ordinary method of this generic operation in this area except desolventizing, washing, oven dry.
The synthetic method of 2,3,6-described trichlorobenzoic acids is preferably further comprising the steps: 2,3,5-trichlorine p-methylbenzoic acid is carried out decarboxylic reaction under decarboxylation reagent and/or catalyst action, obtains 2,3,6-described trichlorotoluene zotrichlorides;
The synthetic method of 2,3,6-trichlorotoluene zotrichloride can be the ordinary method of such decarboxylic reaction in this area, and electrolysis or Hunsdiecker reaction also can be adopted to realize decarboxylation, particularly preferably following reaction method and condition in the present invention:
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the described preferred mineral alkali of decarboxylation reagent, organic bases, mineral acid or organic acid.Described inorganic basis is as one or more in soda-lime, sodium hydroxide and potassium hydroxide.The main component of soda-lime is: calcium oxide (CaO, about 75%), sodium hydroxide (NaOH, about 3%), potassium hydroxide (KOH, about 1%) and water (H
2o, about 20%), per-cent wherein refers to mass percent, refers to that the quality of each component accounts for the per-cent of soda-lime total mass.Described organic bases is as one or more in DMA, triethylamine, tri-n-butylamine, diisopropylethylamine and quinoline.Described mineral acid such as sulfuric acid.Described organic acids is as methylsulphonic acid, trifluoroacetic acid or trifluoromethanesulfonic acid.
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the molar ratio of described decarboxylation reagent and 2,3,5-described trichlorine p-methylbenzoic acids preferably 1 ~ 10, further preferably 3 ~ 5, such as 4.
In the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides, one or more in the preferred mantoquita of described catalyzer, copper, Red copper oxide, silver carbonate, sodium-chlor, lithium chloride and magnesium chloride; Further preferential oxidation is cuprous.Described mantoquita refers to the compound that cupric ion or cuprous ion and acid group are formed, such as cuprous chloride or cuprous iodide.
In the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides, the molar ratio of described catalyzer and 2,3,5-described trichlorine p-methylbenzoic acids preferably 0.005 ~ 0.1, further preferably 0.009 ~ 0.02, such as 0.01.
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the temperature of described decarboxylic reaction preferably 100 DEG C ~ 180 DEG C, such as 120 DEG C ~ 140 DEG C.
2,3, in the synthetic method of 6-trichlorotoluene zotrichloride, the process of described decarboxylic reaction can adopt routine monitoring method (such as TLC, HPLC, NMR or GC) in this area to monitor, generally with 2, and 3,5-trichlorine p-methylbenzoic acid is reaction end when disappearing, preferably 1 hour ~ 20 hours time of decarboxylic reaction, preferably 2 hours ~ 12 hours further, such as 2 hours ~ 6 hours.
The synthetic method of 2,3,6-described trichlorotoluene zotrichlorides is preferably carried out under containing n-donor ligand existent condition, described containing n-donor ligand preferred tertiary amine compounds; One or more in the preferred Tetramethyl Ethylene Diamine of described tertiary amine compounds, DMA, triethylamine, tri-n-butylamine, diisopropyl ethyl amine, quinoline and 1,10-phenanthroline, further preferably Tetramethyl Ethylene Diamine and/or 1,10-phenanthroline.The molar ratio of described containing n-donor ligand and 2,3,5-described trichlorine p-methylbenzoic acids preferably 0.005 ~ 2, further preferably 0.005 ~ 0.007.
The synthetic method of 2,3,6-described trichlorotoluene zotrichlorides can be carried out in a solvent or under condition of no solvent, preferably carries out in the absence of a solvent.When described decarboxylation reagent is liquid, the synthesis of 2,3,6-described trichlorotoluene zotrichlorides can be carried out under the condition of not other solubilizing agent.When described 2,3, when the synthesis of 6-trichlorotoluene zotrichloride is carried out in a solvent, the preferred boiling point of described solvent is higher than the polar solvent of 130 DEG C, and described boiling point is higher than polar solvent preferred amide kind solvent, ketones solvent, sulphonic acids solvent, one or more in sulfone kind solvent and sulfoxide type solvents of 130 DEG C.One or more in the preferred DMF of described amide solvent (DMF), N,N-dimethylacetamide and N-Methyl pyrrolidone (NMP).The preferred dimethyl sulfoxide (DMSO) of described sulfoxide type solvents (DMSO).Described sulphonic acids solvent preferable methyl sulfonic acid.One or more in the described preferred tetramethylene sulfone of sulfone kind solvent.The mass values of described solvent and 2,3,5-described trichlorine p-methylbenzoic acids preferably 5 ~ 10, such as 3.When the synthesis of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent, described decarboxylic reaction preferably carries out under catalyzer and/or containing n-donor ligand existent condition.
The synthetic method of 2,3,6-trichlorotoluene zotrichloride preferably adopts following post-processing step: after reaction terminates, underpressure distillation, rectifying separation obtain 2,3,6-trichlorotoluene zotrichloride.When decarboxylation reagent is DMA, triethylamine, tri-n-butylamine, diisopropylethylamine, quinoline, methylsulphonic acid or trifluoromethanesulfonic acid, decarboxylation reagent can be reclaimed in the process of underpressure distillation and apply mechanically again.
The synthetic method of 2,3,6-described trichlorobenzoic acids is preferably further comprising the steps again: in solvent, under catalyzer existent condition, p-methylbenzoic acid and chlorination reagent are carried out chlorination reaction, obtain 2,3,5-described trichlorine p-methylbenzoic acids;
The synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids can be the ordinary method of such chlorination reaction in this area, particularly preferably following reaction method and condition in the present invention:
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the preferred chlorine of described chlorination reagent.The chlorine that described chlorine directly can use chlorine or adopt hydrogenchloride and oxidant reaction to obtain.When the chlorine adopting hydrogenchloride and oxidising agent to prepare is as chlorination reagent, the preferred hydrogen peroxide of described oxygenant, ozone, oxygen or air.The molar ratio of described oxygenant and described hydrogenchloride preferably 0.5 ~ 5.
Described 2, in the synthetic method of 3,5-trichlorine p-methylbenzoic acid, the preferred inert solvent of described solvent, the preferred chlorinated hydrocarbon solvent of described inert solvent, ether solvent, sulfide solvent, amide solvent, mineral acid solvent or organic acid solvent, further preferred organic acid solvent.One or more in the preferred methylene dichloride of described chlorinated hydrocarbon solvent, ethylene dichloride, chloroform and tetracol phenixin.The preferred ether of described ether solvent and/or dioxane.The preferred DMF of described amide solvent (DMF).One or more in the described preferred acetic acid of organic acid solvent, propionic acid, butyric acid, trimethylacetic acid and methylsulphonic acid, further preferable methyl sulfonic acid and/or acetic acid.Described mineral acid solvent preferably sulfuric acid.The described preferred dithiocarbonic anhydride of sulfide solvent.
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the mass values of described solvent and described p-methylbenzoic acid preferably 1 ~ 100, further preferably 2 ~ 10, such as 3.
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described chlorination reagent and described p-methylbenzoic acid preferably 1 ~ 10, further preferably 2 ~ 6, more further preferably 3 ~ 4.
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described catalyzer preferably sulfuric acid, iodine, hypochlorous acid, methylsulfonic acid or metal chloride.Described metal chloride refers to the material that metal and chlorion are formed, such as iron(ic) chloride, zinc chloride, aluminum chloride, zirconium chloride or iron protochloride.
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described catalyzer and described p-methylbenzoic acid preferably 0.001 ~ 0.1, further preferably 0.005 ~ 0.01.
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the temperature of described chlorination reaction preferably 50 DEG C ~ 120 DEG C, such as 50 DEG C ~ 80 DEG C.
Described 2,3, in the synthetic method of 5-trichlorine p-methylbenzoic acid, the process of described chlorination reaction can adopt routine monitoring method (such as TLC, HPLC, NMR or GC) in this area to monitor, general with 2,3,5-trichlorine p-methylbenzoic acid HPLC content (area fraction) is the terminal of reaction when reaching 45% ~ 55% (preferably 50% ~ 55%), preferably 6 hours ~ 24 hours time of chlorination reaction, such as 8 hours ~ 12 hours, more such as 10 hours.
Described 2,3, in the synthetic method of 5-trichlorine p-methylbenzoic acid, when described chlorination reagent is chlorine, and when described chlorine adopts hydrogenchloride and hydrogen peroxide to be obtained by reacting, preferably adopt following steps: the mixture that p-methylbenzoic acid and solvent and hydrochloric acid are formed is warming up to 50 DEG C ~ 80 DEG C, drip hydrogen peroxide and carry out chlorination reaction, obtain 2,3,5-described trichlorine p-methylbenzoic acids.The speed dripped preferably keeps system temperature 50 C ~ 80 DEG C.
The synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids preferably adopts following post-processing step: after reaction terminates, suction filtration, washing, recrystallization obtain 2,3,5-trichlorine p-methylbenzoic acids after purifying.Described suction filtration, washing, recrystallization can adopt the ordinary method of this generic operation in this area.The preferred acetic acid of solvent that recrystallization adopts.
In the present invention, the synthetic method of 2,3,6-described trichlorobenzoic acids preferably adopts following synthetic route:
Present invention also offers a kind of synthetic method of 2,3,6-trichlorobenzoic acid salt, it comprises the following steps: according to the method described above after obtained 2,3,6-trichlorobenzoic acid, carry out neutralization reaction in organic solvent, obtain 2,3,6-trichlorobenzoic acid salt with alkali;
Wherein, M is sodium or potassium.
The synthetic method of 2,3,6-described trichlorobenzoic acid salt can be particularly preferably following reaction method and condition in the ordinary method of such neutralization reaction in this area and condition the present invention:
In the synthetic method of 2,3,6-described trichlorobenzoic acid salt, described organic solvent preferred alcohols kind solvent, described alcoholic solvent particular methanol.
In the synthetic method of 2,3,6-described trichlorobenzoic acid salt, the mass values of described organic solvent and 2,3,6-described trichlorobenzoic acids preferably 1 ~ 10, further preferably 2 ~ 6.
In the synthetic method of 2,3,6-described trichlorobenzoic acid salt, the preferred sodium hydroxide of described alkali and/or potassium hydroxide.
In the synthetic method of 2,3,6-described trichlorobenzoic acid salt, the molar ratio of described alkali and 2,3,6-described trichlorobenzoic acids preferably 1 ~ 5.
In the synthetic method of 2,3,6-described trichlorobenzoic acid salt, the temperature of described neutralization reaction preferably 25 DEG C ~ 65 DEG C, preferably 50 DEG C ~ 60 DEG C further.
Described 2,3, in the synthetic method of 6-trichlorobenzoic acid salt, the process of described neutralization reaction can adopt routine monitoring method (such as TLC, HPLC, NMR or GC) in this area to monitor, for reaction end when generally disappearing with 2,3,6-trichlorobenzoic acid, preferably 1 hour ~ 10 hours time of neutralization reaction, preferably 2 hours ~ 3 hours further.
The synthetic method of 2,3,6-described trichlorobenzoic acid salt preferably adopts following post-processing step: after reaction terminates, except desolventizing, dry, obtains 2,3,6-trichlorobenzoic acid salt.The preferred recovery of solvent of removing.
In the present invention, preferably after obtained 2,3,6-trichlorobenzoic acid salt drying treatment, without being further purified the synthesis being directly used in 2-methoxyl group-3,6-dichlorobenzoic acid.
The synthetic method of 2,3,6-described trichlorobenzoic acid salt preferably adopts following route:
Wherein, described in the definition ditto of M.
Present invention also offers a kind of 2-methoxyl group-3, the synthetic method of 6-dichlorobenzoic acid, it comprises the following steps: according to the method described above after obtained 2,3,6-trichlorobenzoic acid salt, again in organic solvent, 2,3,6-described trichlorobenzoic acid salt are carried out nucleophilic substitution reaction under highly basic effect, obtain 2-methoxyl group-3,6-dichlorobenzoic acid;
Wherein, described in the definition ditto of M.
The synthetic method of 3,6-bis-described chloro-O-Anisic Acids can adopt the ordinary method of such nucleophilic substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
In the synthetic method of 3,6-bis-described chloro-O-Anisic Acids, one or more in described organic solvent preferred alcohols kind solvent, sulfoxide type solvents and sulfone kind solvent, further preferred sulfoxide type solvents.Described alcoholic solvent particular methanol; The preferred methyl-sulphoxide of described sulfoxide type solvents; The described preferred tetramethylene sulfone of sulfone kind solvent.
In the synthetic method of 3,6-bis-described chloro-O-Anisic Acids, the mass values of described organic solvent and 2,3,6-described trichlorobenzoic acid salt preferably 1 ~ 100, further preferably 2 ~ 10.
In the synthetic method of 3,6-bis-described chloro-O-Anisic Acids, described highly basic particular methanol sodium and/or potassium methylate.
In the synthetic method of 3,6-bis-described chloro-O-Anisic Acids, the molar ratio of described highly basic and 2,3,6-described trichlorobenzoic acid salt preferably 1 ~ 3, further preferably 1 ~ 2.
In the synthetic method of 3,6-bis-described chloro-O-Anisic Acids, the temperature of described nucleophilic substitution reaction preferably 70 DEG C ~ 150 DEG C, preferably 70 DEG C ~ 100 DEG C further.
Described 3, in the synthetic method of the chloro-O-Anisic Acid of 6-bis-, the process of described nucleophilic substitution reaction can adopt routine monitoring method (such as TLC, HPLC, NMR or GC) in this area to monitor, general with 2,3,6-trichlorobenzoic acid salt is reaction end when disappearing, preferably 2 hours ~ 9 hours time of nucleophilic substitution reaction, such as 3 hours ~ 6 hours, more such as 5 hours.
The synthetic method of 3,6-bis-described chloro-O-Anisic Acids preferably includes following post-processing step: after reaction terminates, except desolventizing, be acidified to about pH3, filtration, recrystallization obtain the chloro-O-Anisic Acid of 3,6-bis-.Described can adopt the ordinary method of this generic operation in this area except desolventizing, acidifying, filtration, recrystallization.Described acidifying preferably adopts hydrochloric acid, and the mass concentration of described hydrochloric acid preferably 1% ~ 10%, the mass concentration further preferably described in 5% ~ 10% refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass.The solvent of described recrystallization preferably adopts alcoholic solvent, described alcoholic solvent particular methanol.
The synthetic method of 3,6-bis-described chloro-O-Anisic Acids preferably adopts following route:
In the present invention, according to the method described above after obtained 2,3,6-trichlorobenzoic acid, also can again according to method synthesis 2-methoxyl group-3, the 6-dichlorobenzoic acid that document US3444192 reports.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
In the present invention, described room temperature refers to envrionment temperature, is 10 DEG C ~ 35 DEG C.
In the present invention, described normal pressure refers to a normal atmosphere, is 101325Pa.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: the present invention take p-methylbenzoic acid as raw material, obtains dicamba 98, compare traditional method through chlorination, decarboxylation, oxidation, etherificate, this method raw material sources are wide, and technique is simple, and three waste discharge is few, production cost is low, environmental benefit is large, is conducive to industrialization.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
The preparation of embodiment 12,3,5-trichlorine p-methylbenzoic acid
68g p-methylbenzoic acid (HPLC purity 99%) joins in 200g methylsulphonic acid, add 0.81g iron trichloride, be heated to 80 DEG C of stirrings, under normal pressure, (101325Pa) slowly passes into 106.5g chlorine, logical chlorine reaction 10 hours, liquid phase (HPLC) detects 2, 3, room temperature is down to after 5-trichlorine p-methylbenzoic acid area fraction about 50%, the white crystals that suction filtration is separated out, wash with a small amount of methylsulfonic acid, add 50g Recrystallisation from acetic acid, cooled and filtered, mainly a chlorine product and dichloro product in mother liquor, apply mechanically to next batch chlorination reaction, filter cake is 2, 3, 5-trichlorine p-methylbenzoic acid 64.7g, HPLC purity is 93%, yield 54%, apply mechanically rear yield 85%.
The preparation of embodiment 22,3,5-trichlorine p-methylbenzoic acid
68g p-methylbenzoic acid (HPLC purity 99%) joins in 200g methylsulphonic acid, add 0.81g iron trichloride, be heated to 120 DEG C of stirrings, under normal pressure, (101325Pa) slowly passes into 106.5g chlorine, logical chlorine reaction 6 hours, liquid phase (HPLC) detects 2, 3, room temperature is down to after 5-trichlorine p-methylbenzoic acid area fraction about 50%, the white crystals that suction filtration is separated out, wash with a small amount of methylsulfonic acid, add 50g Recrystallisation from acetic acid, cooled and filtered, mainly a chlorine product and dichloro product in mother liquor, apply mechanically to next batch chlorination reaction, filter cake is 2, 3, 5-trichlorine p-methylbenzoic acid 57.5g, HPLC purity is 91%, yield 48%, apply mechanically rear yield 80%.
The preparation of embodiment 32,3,5-trichlorine p-methylbenzoic acid
68g p-methylbenzoic acid (HPLC purity 99%) joins in 200g methylsulphonic acid, add 0.81g iron trichloride, be heated to 50 DEG C of stirrings, under normal pressure, (101325Pa) slowly passes into 106.5g chlorine, logical chlorine reaction 24h, liquid phase (HPLC) detects 2, 3, room temperature is down to after 5-trichlorine p-methylbenzoic acid area fraction about 50%, the white crystals that suction filtration is separated out, wash with a small amount of methylsulfonic acid, add 50g Recrystallisation from acetic acid, cooled and filtered, mainly a chlorine product and dichloro product in mother liquor, apply mechanically to next batch chlorination reaction, filter cake is 2, 3, 5-trichlorine p-methylbenzoic acid 69.4g, HPLC purity is 94%, yield 58%, apply mechanically rear yield 87%.
The preparation of embodiment 42,3,5-trichlorine p-methylbenzoic acid
68g p-methylbenzoic acid (HPLC purity 99%) joins in 200g acetic acid, add 0.81g iron trichloride, be heated to 80 DEG C of stirrings, under normal pressure, (101325Pa) slowly passes into 106.5g chlorine, logical chlorine reaction 12 hours, liquid phase (HPLC) detects 2, 3, room temperature is down to after 5-trichlorine p-methylbenzoic acid area fraction about 50%, the white crystals that suction filtration is separated out, wash with a small amount of acetic acid, in mother liquor, mainly a chlorine product and dichloro product are applied mechanically to next batch chlorination reaction, obtain 2, 3, 5-trichlorine p-methylbenzoic acid 62.3g, HPLC purity is 91%, yield 52%, apply mechanically rear yield 81%.
The preparation of embodiment 52,3,5-trichlorine p-methylbenzoic acid
68g p-methylbenzoic acid (HPLC purity 99%) joins in 200g acetic acid, adding 200g mass concentration is (described mass concentration refers to that the quality of HCl accounts for the per-cent of hydrochloric acid soln total mass) in 36% hydrochloric acid, be warming up to 50 DEG C, dripping 113g mass concentration is that (described mass concentration refers to H to 30% hydrogen peroxide
2o
2quality account for the per-cent of hydrogen peroxide solution total mass), dropwise reaction 12 hours, liquid phase (HPLC) detects 2, room temperature is down to, the white crystals that suction filtration is separated out after 3,5-trichlorine p-methylbenzoic acid area fraction about 50%, add 50g Recrystallisation from acetic acid, cooled and filtered, mainly a chlorine product and dichloro product in mother liquor, apply mechanically to next batch chlorination reaction, filter cake is 2,3,5-trichlorine p-methylbenzoic acid 64.4g, HPLC purity is 94%, yield 53%, applies mechanically rear yield 82%.
The preparation of embodiment 62,3,5-trichlorine p-methylbenzoic acid
68g p-methylbenzoic acid (HPLC purity 99%) joins in 200g methylsulphonic acid, add 0.81g iron trichloride, be heated to 150 DEG C of stirrings, under normal pressure, (101325Pa) slowly passes into 106.5g chlorine, logical chlorine reaction 8 hours, liquid phase (HPLC) detects 2, 3, room temperature is down to after 5-trichlorine p-methylbenzoic acid area fraction about 50%, the white crystals that suction filtration is separated out, wash with a small amount of methylsulfonic acid, add 50g Recrystallisation from acetic acid, cooled and filtered, mainly a chlorine product and dichloro product in mother liquor, apply mechanically to next batch chlorination reaction, filter cake is 2, 3, 5-trichlorine p-methylbenzoic acid and 2, 3, 5, the mixture 79g of 6-tetrachloro p-methylbenzoic acid, 2, 3, the HPLC purity of 5-trichlorine p-methylbenzoic acid is 74%.
The preparation of embodiment 72,3,5-trichlorine p-methylbenzoic acid
6.8kg p-methylbenzoic acid (HPLC purity 99%) joins in 20kg methylsulfonic acid, add 81g iron trichloride, be heated to 80 DEG C of stirrings, under normal pressure, (101325Pa) slowly passes into 10.6kg chlorine, logical chlorine reaction 12 hours, liquid phase (HPLC) detects 2, 3, room temperature is down to after 5-trichlorine p-methylbenzoic acid content about 50%, the white crystals that suction filtration suction filtration is separated out, wash with a small amount of methylsulfonic acid, add 5kg Recrystallisation from acetic acid, cooled and filtered, mainly a chlorine product and dichloro product in mother liquor, apply mechanically to next batch chlorination reaction, filter cake is 2, 3, 5-trichlorine p-methylbenzoic acid 6.94kg, HPLC purity is 94%, yield 58%, apply mechanically rear yield 89%.
The preparation of embodiment 82,3,6-trichlorotoluene zotrichloride
By embodiment 1 obtains 2,3,5-trichlorine p-methylbenzoic acid 60g joins in 180g tri-n-butylamine, adds 0.35g Red copper oxide, be heated to 100 DEG C, react 12 hours, reaction terminates rear underpressure distillation and reclaims tri-n-butylamine, and rectifying separation obtains 2,3,6-trichlorotoluene zotrichloride 45g, GC purity 98%, yield 92%.
The preparation of embodiment 92,3,6-trichlorotoluene zotrichloride
By embodiment 1 obtains 2,3,5-trichlorine p-methylbenzoic acid 60g joins in 180g tri-n-butylamine, adds 0.35g Red copper oxide, be heated to 180 DEG C, react 2 hours, reaction terminates rear underpressure distillation and reclaims tri-n-butylamine, and rectifying separation obtains 2,3,6-trichlorotoluene zotrichloride 46.4g, GC purity 98%, yield 95%.
The preparation of embodiment 102,3,6-trichlorotoluene zotrichloride
2,3,5-trichlorine p-methylbenzoic acid 60g embodiment 1 obtained join in 180g methyl-sulphoxide (DMSO), add 0.35g Red copper oxide, 0.2g Tetramethyl Ethylene Diamine, is heated to 140 DEG C, reacts 5 hours, reaction terminates rear vacuum distillation recovered solvent DMSO, rectifying separation obtains 2,3,6-trichlorotoluene zotrichloride 45g, GC purity 98%, yield 92%.
The preparation of embodiment 112,3,6-trichlorotoluene zotrichloride
By embodiment 1 obtains 2,3,5-trichlorine p-methylbenzoic acid 60g joins in 180g diisopropylethylamine, adds 0.35g Red copper oxide, be heated to 120 DEG C, react 2 hours, reaction terminates rear underpressure distillation and reclaims diisopropylethylamine, and rectifying separation obtains 2,3,6-trichlorotoluene zotrichloride 46.5g, GC purity 98%, yield 95%.
The preparation of embodiment 122,3,6-trichlorotoluene zotrichloride
2,3,5-trichlorine p-methylbenzoic acid 6kg is joined in 18kg tri-n-butylamine, adds 35g Red copper oxide, be heated to 180 DEG C, reaction 3h, reaction terminates rear underpressure distillation and reclaims tri-n-butylamine, and rectifying separation obtains 2,3,6-trichlorotoluene zotrichloride 4.7kg, GC purity 98%, yield 95%.
The preparation of embodiment 132,3,6-trichlorobenzoic acid
By embodiment 8 obtains 2,3,6-trichlorotoluene zotrichloride 39g joins in 100g water, add 0.4g tetrabutylammonium chloride as phase-transfer catalyst, add 63g potassium permanganate, be heated to 50 DEG C, after 6h reaction terminates, filtered while hot, filtrate regulates pH to 3 with the hydrochloric acid (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass) of mass concentration 5%, has a large amount of white solid to separate out, the solid that suction filtration is separated out, use a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 43.3g, HPLC purity 95%, yield 96%.
The preparation of embodiment 142,3,6-trichlorobenzoic acid
It is 70%H that 2,3,6-trichlorotoluene zotrichloride 39g embodiment 8 obtained join 100g mass concentration
2sO
4in (described mass concentration refers to that the quality of sulfuric acid accounts for the per-cent of sulphuric acid soln total mass), add 0.36g Vanadium Pentoxide in FLAKES, be heated to 120 DEG C, dripping 210g mass concentration is 30% nitric acid (described mass concentration refers to that the quality of nitric acid accounts for the per-cent of salpeter solution total mass), reaction in 4 hours terminates rear near room temperature (25 DEG C), the white crystals that suction filtration is separated out, use a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 41.0g, HPLC purity is 95%, yield 91%.
The preparation of embodiment 152,3,6-trichlorobenzoic acid
It is 70%H that 2,3,6-trichlorotoluene zotrichloride 39g embodiment 8 obtained join 100g mass concentration
2sO
4in (described per-cent refers to that the quality of sulfuric acid accounts for the per-cent of sulphuric acid soln total mass), add 0.36g Vanadium Pentoxide in FLAKES, be heated to 140 DEG C, dripping 210g mass concentration is 30% nitric acid (described per-cent refers to that the quality of nitric acid accounts for the per-cent of salpeter solution total mass), reaction in 2 hours terminates rear near room temperature (25 DEG C), the white crystals that suction filtration is separated out, use a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 41.5g, HPLC purity is 95%, yield 92%.
The preparation of embodiment 162,3,6-trichlorobenzoic acid
2,3,6-trichlorotoluene zotrichloride 39g embodiment 8 obtained join in reactor, add 100g acetic acid, 0.5g tetra-acetate hydrate cobalt, 0.35g manganous acetate, 0.24g Potassium Bromide, pass into oxygen, be warming up to 150 DEG C, pressurize >=0.7MPa in still, be cooled to room temperature (25 DEG C) after reaction in 5 hours terminates, acetic acid is reclaimed in underpressure distillation, uses a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 42.4g, HPLC purity is 95%, yield 94%.
The preparation of embodiment 172,3,6-trichlorobenzoic acid
2,3,6-trichlorotoluene zotrichloride 39g embodiment 8 obtained join in 100g butyric acid, 0.5g tetra-acetate hydrate cobalt, 0.35g manganous acetate, 0.24g Potassium Bromide, be warming up to 150 DEG C, pass into oxygen, pressurize >=0.7Mpa in still, be cooled to room temperature (25 DEG C) after reaction in 18 hours terminates, butyric acid is reclaimed in underpressure distillation, uses a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 42.8g, HPLC purity is 95%, yield 95%.
The preparation of embodiment 182,3,6-trichlorobenzoic acid
2,3,6-trichlorotoluene zotrichloride 3.9kg is joined in reactor, adds 10kg acetic acid, 50g tetra-acetate hydrate cobalt, 35g manganous acetate, 24g Potassium Bromide, pass into oxygen, be warming up to 150 DEG C, pressurize >=0.7MPa in still, be cooled to room temperature (25 DEG C) after reaction in 7 hours terminates, acetic acid is reclaimed in underpressure distillation, uses a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 4.3kg, HPLC purity is 95%, yield 95%.
The preparation of the chloro-O-Anisic Acid of embodiment 193,6-bis-
By embodiment 13 obtains 2, 3, 6-trichlorobenzoic acid 22.5g joins in 50g methyl alcohol, add 4.0g sodium hydroxide, be heated to 50 DEG C, room temperature (25 DEG C) is cooled to after reaction in 2 hours terminates, Distillation recovery methyl alcohol, dry 2, 3, 6-trichlorobenzoic acid sodium, by 2, 3, 6-trichlorobenzoic acid sodium joins in 50gDMSO, add 5.4g sodium methylate, be warming up to 70 DEG C, room temperature (25 DEG C) is cooled to after reaction in 9 hours terminates, DMSO is reclaimed in underpressure distillation, mass concentration be 5% dilute hydrochloric acid be acidified to about pH3 (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass), suction filtration, add 5g recrystallizing methanol, cooled and filtered obtains 3, the chloro-O-Anisic Acid 17.2g of 6-bis-, HPLC purity is 98%, yield 78%.
The preparation of the chloro-O-Anisic Acid of embodiment 203,6-bis-
By embodiment 13 obtains 2, 3, 6-trichlorobenzoic acid 22.5g joins in 50g methyl alcohol, add 4.0g sodium hydroxide, be heated to 50 DEG C, room temperature (25 DEG C) is cooled to after reaction in 2 hours terminates, Distillation recovery methyl alcohol, dry 2, 3, 6-trichlorobenzoic acid sodium, by 2, 3, 6-trichlorobenzoic acid sodium joins in 50gDMSO, add 5.4g sodium methylate, be warming up to 150 DEG C, room temperature (25 DEG C) is cooled to after reaction in 2 hours terminates, DMSO is reclaimed in underpressure distillation, mass concentration be 5% dilute hydrochloric acid be acidified to about pH3 (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass), suction filtration, add 5g recrystallizing methanol, cooled and filtered obtains 3, the chloro-O-Anisic Acid 16.1g of 6-bis-, HPLC purity is 98%, yield 73%.
The preparation of the chloro-O-Anisic Acid of embodiment 213,6-bis-
By embodiment 13 obtains 2, 3, 6-trichlorobenzoic acid 22.5g joins in 50g methyl alcohol, add 4.0g sodium hydroxide, be heated to 50 DEG C, room temperature (25 DEG C) is cooled to after reaction in 2 hours terminates, Distillation recovery methyl alcohol, dry 2, 3, 6-trichlorobenzoic acid sodium, by 2, 3, 6-trichlorobenzoic acid sodium joins in 50gDMSO, add 5.4g sodium methylate, be warming up to 100 DEG C, room temperature (25 DEG C) is cooled to after reaction in 5 hours terminates, DMSO is reclaimed in underpressure distillation, mass concentration be 5% dilute hydrochloric acid be acidified to about pH3 (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass), suction filtration, add 5g recrystallizing methanol, cooled and filtered obtains 3, the chloro-O-Anisic Acid 17.4g of 6-bis-, HPLC purity is 98%, yield 79%.
The preparation of the chloro-O-Anisic Acid of embodiment 223,6-bis-
By embodiment 13 obtains 2, 3, 6-trichlorobenzoic acid 22.5g joins in 50g methyl alcohol, add 4.0g sodium hydroxide, be heated to 50 DEG C, room temperature (25 DEG C) is cooled to after reaction in 2 hours terminates, Distillation recovery methyl alcohol, dry 2, 3, 6-trichlorobenzoic acid sodium, by 2, 3, 6-trichlorobenzoic acid sodium joins in 50gDMSO, add 20g sodium methylate, be warming up to 100 DEG C, room temperature (25 DEG C) is cooled to after reaction in 3 hours terminates, DMSO is reclaimed in underpressure distillation, mass concentration be 5% dilute hydrochloric acid be acidified to about pH3 (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass), suction filtration, add 5g recrystallizing methanol, cooled and filtered obtains 3, the chloro-O-Anisic Acid of 6-bis-and 3, the mixture 16g of the chloro-2 hydroxybenzoic acid of 6-bis-, 3, 6-bis-chloro-O-Anisic Acid HPLC purity is 48%.
The preparation of the chloro-O-Anisic Acid of embodiment 233,6-bis-
By 2, 3, 6-trichlorobenzoic acid 2.25kg joins in 5kg methyl alcohol, add 0.4kg sodium hydroxide, be heated to 50 DEG C, room temperature (25 DEG C) is cooled to after reaction in 3 hours terminates, Distillation recovery methyl alcohol, dry 2, 3, 6-trichlorobenzoic acid sodium, by 2, 3, 6-trichlorobenzoic acid sodium joins in 5kgDMSO, add 0.54kg sodium methylate, be warming up to 100 DEG C, room temperature (25 DEG C) is cooled to after reaction in 6 hours terminates, DMSO is reclaimed in underpressure distillation, mass concentration be 5% dilute hydrochloric acid be acidified to about pH3 (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass), suction filtration, add 0.5kg recrystallizing methanol, cooled and filtered obtains 3, the chloro-O-Anisic Acid 1.8kg of 6-bis-, HPLC purity is 98%, yield 82%.
Claims (15)
1. the synthetic method of a trichlorobenzoic acid, is characterized in that it comprises the following steps: under catalyzer existent condition, 2,3,6-trichlorotoluene zotrichloride and oxidising agent is carried out oxidizing reaction, obtains 2,3,6-trichlorobenzoic acid;
2. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 1, is characterized in that:
Described 2,3, in the synthetic method of 6-trichlorobenzoic acid, described oxygenant is one or more in oxygen, air, hydrogen peroxide, ozone, potassium permanganate, potassium bichromate, Peracetic Acid, peroxy tert-butyl alcohol, chromic acid, nitric acid, Potassium Persulphate, potassium perchlorate and Potcrate;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described oxygenant and 2,3,6-described trichlorotoluene zotrichlorides is 1 ~ 10;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, described catalyzer is one or more in Vanadium Pentoxide in FLAKES, ammonium vanadate, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, cobalt salt and manganese salt;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described catalyzer and 2,3,6-described trichlorotoluene zotrichlorides is 0.001 ~ 0.1;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the temperature of described oxidizing reaction is 50 DEG C ~ 190 DEG C;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the time of described oxidizing reaction is 1 hour ~ 20 hours;
And/or,
The synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent or under solvent-free condition;
And/or,
The synthetic method of 2,3,6-described trichlorobenzoic acids, carries out under promotor existent condition;
And/or,
When oxygenant is potassium permanganate, adopt following post-processing step: reaction end after heat filter, filtrate regulate about pH3, and filtration, washing, oven dry obtain 2,3,6-trichlorobenzoic acid;
And/or,
When oxygenant is nitric acid, adopt following post-processing step: after reaction terminates, filter and obtain 2,3,6-trichlorobenzoic acid;
And/or,
When oxygenant be oxygen or air time, adopt following post-processing step: except desolventizing, washing, oven dry obtain 2,3,6-trichlorobenzoic acid after reaction terminates.
3. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 2, is characterized in that:
In the synthetic method of 2,3,6-described trichlorobenzoic acids, when described oxygenant is nitric acid, the mass concentration of described nitric acid is 10% ~ 30%, and described mass concentration refers to that the quality of nitric acid accounts for the per-cent of salpeter solution total mass;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, when described oxygenant is oxygen, air or ozone, the pressure >=0.7Mpa of described reaction system;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described oxygenant and 2,3,6-described trichlorotoluene zotrichlorides is 2 ~ 5;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, described cobalt salt is four acetate hydrate cobalt or cobaltous acetates;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, described manganese salt is manganous acetate;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, when oxygenant is potassium permanganate, described catalyzer is one or more in tetrabutylammonium chloride, Tetrabutyl amonium bromide and tetrabutylammonium iodide;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, when oxygenant is nitric acid, described catalyzer is Vanadium Pentoxide in FLAKES;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, when described oxygenant be oxygen or air time, described catalyzer is one or more in four acetate hydrate cobalts, cobaltous acetate and manganous acetate;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described catalyzer and 2,3,6-described trichlorotoluene zotrichlorides is 0.005 ~ 0.05;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the temperature of described oxidizing reaction is 50 DEG C ~ 150 DEG C;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent, described solvent is one or more in water, mineral acid, organic acid and sulfone kind solvent;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent, the mass values of described solvent and 2,3,6-described trichlorotoluene zotrichlorides is 1 ~ 100;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out under promotor existent condition, described promotor is Potassium Bromide;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out under promotor existent condition, the molar ratio of described promotor and described catalyzer is 1 ~ 3.
4. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 3, is characterized in that:
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the molar ratio of described catalyzer and 2,3,6-described trichlorotoluene zotrichlorides is 0.007 ~ 0.01;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the temperature of described oxidizing reaction is 120 DEG C ~ 140 DEG C;
And/or,
In the synthetic method of 2,3,6-described trichlorobenzoic acids, the time of described oxidizing reaction is 2 hours ~ 7 hours;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent, described mineral acid is sulfuric acid;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent, described organic acid is one or more in acetic acid, propionic acid and butyric acid;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent, described sulfone kind solvent is tetramethylene sulfone;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out in a solvent, the mass values of described solvent and 2,3,6-described trichlorotoluene zotrichlorides is 1 ~ 10;
And/or,
When the synthetic method of 2,3,6-described trichlorobenzoic acids is carried out under promotor existent condition, the molar ratio of described promotor and described catalyzer is 1 ~ 1.5.
5. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 1, is characterized in that: the synthetic method of 2,3,6-described trichlorobenzoic acids is further comprising the steps; 2,3,5-trichlorine p-methylbenzoic acid is carried out decarboxylic reaction under decarboxylation reagent and/or catalyst action, obtains 2,3,6-described trichlorotoluene zotrichlorides;
6. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 5, is characterized in that:
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, described decarboxylation reagent is mineral alkali, organic bases, mineral acid or organic acid;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the molar ratio of described decarboxylation reagent and 2,3,5-described trichlorine p-methylbenzoic acids is 1 ~ 10;
And/or,
In the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides, described catalyzer is one or more in mantoquita, copper, Red copper oxide, silver carbonate, sodium-chlor, lithium chloride and magnesium chloride;
And/or,
In the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides, the molar ratio of described catalyzer and 2,3,5-described trichlorine p-methylbenzoic acids is 0.005 ~ 0.1;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the temperature of described decarboxylic reaction is 100 DEG C ~ 180 DEG C;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the time of described decarboxylic reaction is 1 hour ~ 20 hours;
And/or,
The synthetic method of 2,3,6-described trichlorotoluene zotrichlorides is carried out under containing n-donor ligand existent condition;
And/or,
The synthetic method of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent or under condition of no solvent;
And/or,
The synthetic method of 2,3,6-trichlorotoluene zotrichloride adopts following post-processing step: after reaction terminates, underpressure distillation, rectifying separation obtain 2,3,6-trichlorotoluene zotrichloride.
7. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 6, is characterized in that:
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, described mineral alkali is one or more in soda-lime, sodium hydroxide and potassium hydroxide;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, described organic bases is one or more in DMA, triethylamine, tri-n-butylamine, diisopropylethylamine and quinoline;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, described mineral acid is sulfuric acid;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, described organic acid is methylsulphonic acid, trifluoroacetic acid or trifluoromethanesulfonic acid;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the molar ratio of described decarboxylation reagent and 2,3,5-described trichlorine p-methylbenzoic acids is 3 ~ 5;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the temperature of described decarboxylic reaction is 120 DEG C ~ 140 DEG C;
And/or,
In the synthetic method of 2,3,6-trichlorotoluene zotrichloride, the time of described decarboxylic reaction is 2 hours ~ 12 hours;
And/or,
When the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides is carried out under containing n-donor ligand existent condition, described containing n-donor ligand is tertiary amine compounds;
And/or,
When the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides is carried out under containing n-donor ligand existent condition, the molar ratio of described containing n-donor ligand and 2,3,5-described trichlorine p-methylbenzoic acids is 0.005 ~ 2;
And/or,
When described 2,3, when the synthesis of 6-trichlorotoluene zotrichloride is carried out in a solvent, described solvent is boiling point higher than the polar solvent of 130 DEG C, and described boiling point is one or more in amide solvent, ketones solvent, sulphonic acids solvent, sulfone kind solvent and sulfoxide type solvents higher than the polar solvent of 130 DEG C;
And/or,
When the synthesis of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent, the mass values of described solvent and 2,3,5-described trichlorine p-methylbenzoic acids is 5 ~ 10;
And/or,
2, in the post-processing step of the synthetic method employing of 3,6-trichlorotoluene zotrichloride, when decarboxylation reagent is N, when accelerine, triethylamine, tri-n-butylamine, diisopropylethylamine, quinoline, methylsulphonic acid or trifluoromethanesulfonic acid, in the process of underpressure distillation, reclaim decarboxylation reagent apply mechanically again.
8. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 7, is characterized in that:
When the synthetic method of 2,3,6-described trichlorotoluene zotrichlorides is preferably carried out under catalyzer and/or containing n-donor ligand existent condition, described mantoquita is cuprous chloride or cuprous iodide;
And/or,
The molar ratio of described catalyzer and 2,3,5-described trichlorine p-methylbenzoic acids is 0.009 ~ 0.02;
And/or,
Described tertiary amine compounds is one or more in Tetramethyl Ethylene Diamine, DMA, triethylamine, tri-n-butylamine, diisopropyl ethyl amine, quinoline and 1,10-phenanthroline;
And/or,
The molar ratio of described containing n-donor ligand and 2,3,5-described trichlorine p-methylbenzoic acids is 0.005 ~ 0.007;
And/or,
When the synthesis of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent, described amide solvent is one or more in DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone;
And/or,
When the synthesis of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent, described sulfoxide type solvents is dimethyl sulfoxide (DMSO);
And/or,
When the synthesis of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent, described sulphonic acids solvent is methylsulphonic acid;
And/or,
When the synthesis of 2,3,6-described trichlorotoluene zotrichlorides is carried out in a solvent, described sulfone kind solvent is one or more in tetramethylene sulfone.
9. as claimed in claim 52,3, the synthetic method of 6-trichlorobenzoic acid, is characterized in that: described 2,3, the synthetic method of 6-trichlorobenzoic acid is further comprising the steps again: in solvent, under catalyzer existent condition, p-methylbenzoic acid and chlorination reagent are carried out chlorination reaction, obtains described 2,3,5-trichlorine p-methylbenzoic acid;
10. the synthetic method of 2,3,6-trichlorobenzoic acids as claimed in claim 9, is characterized in that:
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described chlorination reagent is chlorine;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described solvent is inert solvent;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the mass values of described solvent and described p-methylbenzoic acid is 1 ~ 100;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described chlorination reagent and described p-methylbenzoic acid is 1 ~ 10;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described catalyzer is sulfuric acid, iodine, hypochlorous acid, methylsulfonic acid or metal chloride;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described catalyzer and described p-methylbenzoic acid is 0.001 ~ 0.1;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the temperature of described chlorination reaction is 50 DEG C ~ 120 DEG C;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the time of described chlorination reaction is 6 hours ~ 24 hours;
And/or,
The synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids adopts following post-processing step: after reaction terminates, suction filtration, washing, recrystallization obtain 2,3,5-trichlorine p-methylbenzoic acids after purifying.
The synthetic method of 11. 2,3,6-trichlorobenzoic acids as claimed in claim 10, is characterized in that:
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the chlorine that described chlorine directly uses chlorine or adopts hydrogenchloride and oxidant reaction to obtain;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described inert solvent is chlorinated hydrocarbon solvent, ether solvent, sulfide solvent, amide solvent, mineral acid solvent or organic acid solvent;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the mass values of described solvent and described p-methylbenzoic acid is 2 ~ 10;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described chlorination reagent and described p-methylbenzoic acid is 2 ~ 6;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described metal chloride is iron(ic) chloride, zinc chloride, aluminum chloride, zirconium chloride or iron protochloride;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described catalyzer and described p-methylbenzoic acid is 0.005 ~ 0.01;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the temperature of described chlorination reaction is 50 DEG C ~ 80 DEG C;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the time of described chlorination reaction is 8 hours ~ 12 hours;
And/or,
In the post-processing step that the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids adopts, the solvent that described recrystallization adopts is acetic acid.
The synthetic method of 12. 2,3,6-trichlorobenzoic acids as claimed in claim 11, is characterized in that:
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, when the chlorine adopting hydrogenchloride and oxidising agent to prepare is as chlorination reagent, described oxygenant is hydrogen peroxide, ozone, oxygen or air;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, when the chlorine adopting hydrogenchloride and oxidising agent to prepare is as chlorination reagent, the molar ratio of described oxygenant and described hydrogenchloride is 0.5 ~ 5;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, the molar ratio of described chlorination reagent and described p-methylbenzoic acid is 3 ~ 4;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described chlorinated hydrocarbon solvent is one or more in methylene dichloride, ethylene dichloride, chloroform and tetracol phenixin;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described ether solvent is ether and/or dioxane;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described amide solvent is DMF;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described organic acid solvent is one or more in acetic acid, propionic acid, butyric acid, trimethylacetic acid and methylsulfonic acid;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described mineral acid solvent is sulfuric acid;
And/or,
In the synthetic method of 2,3,5-described trichlorine p-methylbenzoic acids, described sulfide solvent is dithiocarbonic anhydride.
The synthetic method of 13. a kind of 2,3,6-trichlorobenzoic acid salt, is characterized in that it comprises the following steps: according to the method described in any one of claim 1 ~ 12 obtained 2, after 3,6-trichlorobenzoic acid, the more ongoing reaction with alkali in organic solvent, obtain 2,3,6-trichlorobenzoic acid salt;
Wherein, M is sodium or potassium.
14. a kind 3, the synthetic method of the chloro-O-Anisic Acid of 6-bis-, it is characterized in that it comprises the following steps: after obtained 2,3, the 6-trichlorobenzoic acid salt of the method described in any one of claim 1 ~ 13, again in organic solvent, 2,3,6-described trichlorobenzoic acid salt are carried out nucleophilic substitution reaction under highly basic effect, obtain 2-methoxyl group-3,6-dichlorobenzoic acid;
The synthetic method of 15. 2,3,6-trichlorobenzoic acids as claimed in claim 14, is characterized in that:
In the synthetic method of described 3,6-bis-chloro-2-methoxy-benzoic acid, described organic solvent is one or more in alcoholic solvent, sulfoxide type solvents and sulfone kind solvent;
And/or,
In the synthetic method of described 3,6-bis-chloro-2-methoxy-benzoic acid, the mass values of described organic solvent and 2,3,6-described trichlorobenzoic acid salt is 1 ~ 100;
And/or,
In the synthetic method of described 3,6-bis-chloro-2-methoxy-benzoic acid, described highly basic is sodium methylate and/or potassium methylate;
And/or,
In the synthetic method of described 3,6-bis-chloro-2-methoxy-benzoic acid, the molar ratio of described highly basic and 2,3,6-described trichlorobenzoic acid salt is 1 ~ 3;
And/or,
In the synthetic method of described 3,6-bis-chloro-2-methoxy-benzoic acid, the temperature of described nucleophilic substitution reaction is 70 DEG C ~ 150 DEG C;
And/or,
In the synthetic method of described 3,6-bis-chloro-2-methoxy-benzoic acid, the time of described nucleophilic substitution reaction is 2 hours ~ 9 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510799471.8A CN105294419A (en) | 2015-11-18 | 2015-11-18 | Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510799471.8A CN105294419A (en) | 2015-11-18 | 2015-11-18 | Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105294419A true CN105294419A (en) | 2016-02-03 |
Family
ID=55192350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510799471.8A Pending CN105294419A (en) | 2015-11-18 | 2015-11-18 | Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105294419A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946685A (en) * | 2016-01-07 | 2017-07-14 | 江苏联化科技有限公司 | The preparation method of 2- methyl -3- methoxy benzoic acids and its intermediate |
| CN107324993A (en) * | 2017-06-20 | 2017-11-07 | 蚌埠学院 | A kind of preparation method of the fluobenzoic acid of 4 bromine 3 |
| CN107827735A (en) * | 2017-11-23 | 2018-03-23 | 江苏联化科技有限公司 | A kind of synthetic method of the dichlorobenzoic acid of 2 hydroxyl 3,6 |
| CN107903165A (en) * | 2017-10-25 | 2018-04-13 | 常州大学 | A kind of method that m-methyl benzoic acid is continuously prepared using tubular reactor |
| CN108530297A (en) * | 2017-03-03 | 2018-09-14 | 联化科技股份有限公司 | The preparation method of the chloro- 3- methyl benzoic acids of 2- and its intermediate |
| CN110003106A (en) * | 2019-04-24 | 2019-07-12 | 郑州原理生物科技有限公司 | A kind of preparation method of acridine |
| CN113402378A (en) * | 2021-07-28 | 2021-09-17 | 浙江解氏新材料股份有限公司 | Efficient and environment-friendly method for synthesizing 2-chloro-4-fluorobenzoic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3444192A (en) * | 1961-04-17 | 1969-05-13 | Hooker Chemical Corp | Process for preparing alkoxychlorinated benzoic acids |
| CN1251833A (en) * | 1999-10-22 | 2000-05-03 | 首都师范大学 | Process for preparing substituted benzoic acid |
| CN101633601A (en) * | 2008-07-25 | 2010-01-27 | 浙江省东阳市兴华化工有限公司 | Industrial production method for 2, 6-dichlorotoluene |
| WO2015086698A1 (en) * | 2013-12-11 | 2015-06-18 | Basf Se | Process for providing dihalogen substituted salicylic acid derivatives |
| CN104844412A (en) * | 2015-04-07 | 2015-08-19 | 浙江林江化工股份有限公司 | Preparation method of 1,2,4-trifluorobenzene |
-
2015
- 2015-11-18 CN CN201510799471.8A patent/CN105294419A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3444192A (en) * | 1961-04-17 | 1969-05-13 | Hooker Chemical Corp | Process for preparing alkoxychlorinated benzoic acids |
| CN1251833A (en) * | 1999-10-22 | 2000-05-03 | 首都师范大学 | Process for preparing substituted benzoic acid |
| CN101633601A (en) * | 2008-07-25 | 2010-01-27 | 浙江省东阳市兴华化工有限公司 | Industrial production method for 2, 6-dichlorotoluene |
| WO2015086698A1 (en) * | 2013-12-11 | 2015-06-18 | Basf Se | Process for providing dihalogen substituted salicylic acid derivatives |
| CN104844412A (en) * | 2015-04-07 | 2015-08-19 | 浙江林江化工股份有限公司 | Preparation method of 1,2,4-trifluorobenzene |
Non-Patent Citations (2)
| Title |
|---|
| J. B. COHEN ET AL.: "The Chlorination of the Dichlorotoluenes in Presence of the Aluminium-Mercury Couple. The Constitution of the Trichlorotoluenes", 《 JOURNAL OF THE CHEMICAL SOCIETY, TRANSACTIONS》 * |
| 田琳等: "麦草畏及其中间体的合成评述", 《现代农药》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946685A (en) * | 2016-01-07 | 2017-07-14 | 江苏联化科技有限公司 | The preparation method of 2- methyl -3- methoxy benzoic acids and its intermediate |
| CN106946685B (en) * | 2016-01-07 | 2020-06-23 | 江苏联化科技有限公司 | Preparation method of 2-methyl-3-methoxybenzoic acid and intermediate thereof |
| CN108530297A (en) * | 2017-03-03 | 2018-09-14 | 联化科技股份有限公司 | The preparation method of the chloro- 3- methyl benzoic acids of 2- and its intermediate |
| CN108530297B (en) * | 2017-03-03 | 2021-09-24 | 联化科技股份有限公司 | Preparation method of 2-chloro-3-methylbenzoic acid and intermediate thereof |
| CN107324993A (en) * | 2017-06-20 | 2017-11-07 | 蚌埠学院 | A kind of preparation method of the fluobenzoic acid of 4 bromine 3 |
| CN107903165A (en) * | 2017-10-25 | 2018-04-13 | 常州大学 | A kind of method that m-methyl benzoic acid is continuously prepared using tubular reactor |
| CN107827735A (en) * | 2017-11-23 | 2018-03-23 | 江苏联化科技有限公司 | A kind of synthetic method of the dichlorobenzoic acid of 2 hydroxyl 3,6 |
| CN107827735B (en) * | 2017-11-23 | 2021-07-30 | 江苏联化科技有限公司 | Synthetic method of 2-hydroxy-3, 6-dichlorobenzoic acid |
| CN110003106A (en) * | 2019-04-24 | 2019-07-12 | 郑州原理生物科技有限公司 | A kind of preparation method of acridine |
| CN110003106B (en) * | 2019-04-24 | 2020-11-06 | 郑州原理生物科技有限公司 | Preparation method of acridine |
| CN113402378A (en) * | 2021-07-28 | 2021-09-17 | 浙江解氏新材料股份有限公司 | Efficient and environment-friendly method for synthesizing 2-chloro-4-fluorobenzoic acid |
| CN113402378B (en) * | 2021-07-28 | 2022-03-25 | 浙江解氏新材料股份有限公司 | Method for synthesizing 2-chloro-4-fluorobenzoic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105294419A (en) | Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate | |
| CN105237330B (en) | A kind of synthetic method of 2,3,6 trichlorobenzoic acid and its intermediate | |
| CN112707799B (en) | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer | |
| CN103224451B (en) | Method for synthesizing 3,5-dichlorobenzoic acid | |
| CN102584724B (en) | A kind of preparation method of Quizalotop-ethyl | |
| CN106748716B (en) | A kind of new method for preparing 2,4,5 trifluoro benzene acetic acids | |
| CN108467343A (en) | The preparation method of 2,4- dichlorphenoxyacetic acids | |
| CN108530326A (en) | A kind of preparation method of 2- nitryl-4-thiamphenicol benzoic acids | |
| CN105837432A (en) | Novel preparation method of 3,5-dichlorobenzoyl chloride | |
| CN105601529B (en) | The synthetic method of pretilachlor | |
| CN105175317B (en) | A kind of method for preparing picosulfate sodium | |
| CN103058984A (en) | Synthesis method of watermelon ketone | |
| WO2019179287A2 (en) | Preparation method for 2,4-dichlorophenoxyacetic acid or salt thereof | |
| CN105906502A (en) | Preparation method of 3,5-dichlorobenzoyl chloride | |
| CN106866406B (en) | A kind of preparation method of 2,4,5- trifluoro benzene acetic acid | |
| CN105399703B (en) | A kind of preparation method of methylene blue | |
| CN108503544A (en) | The preparation method of 2,4- dichlorphenoxyacetic acids | |
| CN112010793B (en) | Synthetic method of 2-methylsulfonyl-4-trifluoromethylbenzoic acid | |
| CN103570521A (en) | Preparation method of atovaquone | |
| CN104529924B (en) | The preparation method of 5-cyclopropyl-4-[2-methylthio group-4-(trifluoromethyl) benzoyl] isoxzzole | |
| CN107739343B (en) | Environment-friendly process for producing quizalofop-p-ethyl | |
| CN104628559B (en) | Ozone oxidation method used for preparing halogenated acetic acid and esters of halogenated acetic acid | |
| CN106883147B (en) | A kind of preparation method of phenyl-pentafluoride formonitrile HCN | |
| CN110615734B (en) | Industrialized synthesis method of o-aldehyde phenyl fatty acid | |
| CN108424360A (en) | The preparation method of one kind 2,4- dichlorphenoxyacetic acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160203 |