CN105237330A - Synthesizing method for 2,3,6-trichlorobenzoic acid and intermediate of 2,3,6-trichlorobenzoic acid - Google Patents

Synthesizing method for 2,3,6-trichlorobenzoic acid and intermediate of 2,3,6-trichlorobenzoic acid Download PDF

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CN105237330A
CN105237330A CN201510800636.9A CN201510800636A CN105237330A CN 105237330 A CN105237330 A CN 105237330A CN 201510800636 A CN201510800636 A CN 201510800636A CN 105237330 A CN105237330 A CN 105237330A
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preparation
mixture
trichlorotoluene
toluene dichloride
dichloride
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CN105237330B (en
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樊小彬
林行军
陈冬辉
周述勇
陈国彬
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Jiangsu Lianhua Technology Co ltd
Lianhua Angjian Zhejiang Pharmaceutical Co ltd
Lianhe Chemical Technology Co Ltd
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LIANHUA TECHNOLOGY (YANCHENG) Co Ltd
JIANGSU LIANHUA TECHNOLOGY Co Ltd
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Abstract

The invention discloses a synthesizing method for 2,3,6-trichlorobenzoic acid and intermediate of the 2,3,6-trichlorobenzoic acid, and provides a preparation method for 2,3,6-trichlorotoluene. The preparation method for the 2,3,6-trichlorotoluene comprises the following steps that on the condition that a catalyst exists, a chlorination reaction is performed on a mixture of dichlorotoluene and a chlorination agent to obtain the 2,3,6-trichlorotoluene; metal and/or metal halide are/is adopted as the catalyst, and a mixture of 2,6-dichlorotoluene and 2,3-dichlorotoluene or a mixture of 2,6-dichlorotoluene, 2,3-dichlorotoluene and 2,5-dichlorotoluene is adopted as the mixture of the 2,6-dichlorotoluene. The synthesizing method is high in reaction yield, selectivity and purity of the prepared product, low in production cost, easy to operate, mild in reaction condition and suitable for industrialize production.

Description

The synthetic method of a kind of 2,3,6-trichlorobenzoic acid and intermediate thereof
Technical field
The present invention relates to the synthetic method of a kind of 2,3,6-trichlorobenzoic acid and intermediate thereof.
Background technology
2,3,6-trichlorobenzoic acid, trade(brand)name tribac is benzoic acid herbicide, can be used for preventing and kill off some annual and perennial dark root broadleaf weeds and some shrub.It can be used as an important intermediate (US3444192) of synthesis dicamba 98 through just obtaining dicamba 98 (Dicamba) with sodium methylate single step reaction.Along with the approval of anti-dicamba 98 genetically modified crops is gone on the market, the market outlook of dicamba 98 are very good, and 2,3,6-trichlorobenzoic acid correspondingly also will have the increasing market requirement.
The method of current synthesis 2,3,6-trichlorobenzoic acid mainly contains following several:
Patent US3086991A, patent 20030216577A1 and document (JournaloftheChemicalSociety, 1951,1208-1212) report with 2,3,6-trichlorotoluene zotrichloride is raw material, with oxygen, obtained 2,3, the 6-trichlorobenzoic acid of method of ozone or nitric acid oxidation.These three kinds of methods all need to do raw material with 2,3,6-trichlorotoluene zotrichloride, and price is all higher, and market is not easily buied on a large scale, and raw material ratio is more limited, causes the economic feasibility of suitability for industrialized production poor.
Patent CN102947000A reports with 1,2,4-trichlorobenzene for raw material, with CO under the complex catalysis of azepine Cabbeen with gold 2reaction is obtained 2,3,6-trichlorobenzoic acid directly.Shortcoming needs to make catalyzer with azepine Cabbeen and the complex compound of gold, and catalyzer is more expensive, and production cost is high, also should not use in suitability for industrialized production.
Therefore the technical problem that raw material is simple and easy to get, preparation method is simple, the low preparation method being suitable for 2,3,6-trichlorobenzoic acids of suitability for industrialized production of production cost is urgent need solution is at present found.
Summary of the invention
Technical problem to be solved by this invention is to overcome in prior art 2,3, preparation method's cost of material of 6-trichlorobenzoic acid is high to be not easy to obtain, preparation method is complicated, reaction preference is poor, obtained product purity is poor, yield is low, production cost is high, be not suitable for the defects such as suitability for industrialized production and provide one 2, the synthetic method of 3,6-trichlorobenzoic acid and intermediate thereof.Synthetic method reaction yield of the present invention is high, selectivity is high, obtained product purity is high, production cost is low, simple to operate, reaction conditions is gentle, be suitable for suitability for industrialized production.
The invention provides a kind of preparation method of 2,3,6-trichlorotoluene zotrichloride, it comprises the following steps: catalyzer by the mixture of toluene dichloride, carries out chlorination reaction with chlorination reagent and obtains 2 under existing, 3,6-trichlorotoluene zotrichloride, described catalyzer is metal and/or metal halide, the mixture of described toluene dichloride is 2, the mixture of 6-toluene dichloride and 2,3-toluene dichloride or 2,6-DCT, 2, the mixture of 3-toluene dichloride and 2,5-toluene dichloride;
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described metal can for the element with the metal general character conventional in this area, one or more in the present invention particularly preferably in iron powder, zinc powder, manganese powder, nickel powder and aluminium powder; Preferred iron powder further.Described metal halide is the preferred dichloride copper of binary compound that halogen that the metal of this area routine and halogen are formed shows negative valency, zinc dichloride, cobalt dichloride, Nickel Chloride, manganous chloride, lanthanum trichloride, Indium-111 chloride, iron trichloride, aluminum chloride, butter of antimony, titanium tetrachloride, zirconium tetrachloride, tin tetrachloride, germanium tetrachloride, antimony pentachloride, molybdenum pentachloride, tungsten hexachloride, dibrominated copper, dibrominated zinc, cobalt dihromide, Nickel Bromide, manganese dibromide, tribromide lanthanum, indium tribromide, ferric bromide, alchlor, antimony tribro-, titanium tetrabromide, tetrabormated zirconium, tin tetrabromide, germanium tetrabromide, five bromize antimonies, six tungsten bromides, diiodinating copper, diiodinating zinc, one or more in cobalt diiodide and diiodinating nickel, one or more further preferably in aluminum chloride, butter of antimony, titanium tetrachloride and Nickel Chloride, further preferably butter of antimony and/or titanium tetrachloride again.
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the mass values of the mixture of described catalyzer and described toluene dichloride preferably 0.001 ~ 0.05, further preferably 0.003 ~ 0.01, such as 0.005.
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described chlorination reagent can be the conventional chlorinating agents of such chlorination reaction in this area as chlorine or SULPHURYL CHLORIDE etc., particularly preferably chlorine in the present invention.
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the molar ratio of the mixture of described chlorination reagent and described toluene dichloride preferably 1 ~ 5, further preferably 1.1 ~ 2.0, such as 1.2,1.3,1.4 or 1.9.
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, in the mixture of described toluene dichloride, described 2,6-DCT and described 2, quality shared by 3-toluene dichloride is preferably greater than or equal to 65% than sum and is less than 100%, is preferably greater than or equal to 80% further and is less than 100%; Described mass ratio refers to that the total mass of described 2,6-DCT and 2,3-described toluene dichloride accounts for the per-cent of the mixture total mass of described toluene dichloride.
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the temperature of described chlorination reaction can be the ordinary temperature of such chlorination reaction in this area, in the present invention particularly preferably 10 DEG C ~ 50 DEG C, preferably 25 DEG C ~ 40 DEG C further.
Described 2,3, in the preparation method of 6-trichlorotoluene zotrichloride, the process of described chlorination reaction can adopt the routine monitoring method (such as TLC, HPLC, GC or NMR) in this area to monitor, it is the terminal of reaction when generally disappearing with the mixture of described toluene dichloride, preferably 5 hours ~ 8 hours time of described chlorination reaction, such as 5.5 hours or 6 hours.
The preparation method of 2,3,6-described trichlorotoluene zotrichlorides can carry out in a solvent or under condition of no solvent, when the preparation method of 2,3,6-described trichlorotoluene zotrichlorides carries out in a solvent, and the preferred chlorinated hydrocarbon solvent of selected solvent; One or more in the preferred methylene dichloride of described chlorinated hydrocarbon solvent, chloroform, 1,2-ethylene dichloride and glyceryl trichloride, further preferred 1,2-ethylene dichloride.The mass values of the mixture of described solvent and described toluene dichloride preferably 0.5 ~ 5, further preferably 1 ~ 2.
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, when described chlorination reagent is chlorine, preferably adopt following steps: in the system that mixture and the catalyzer of toluene dichloride is formed, pass into chlorine, carry out chlorination reaction, obtain 2,3,6-trichlorotoluene zotrichloride.Preferred 1bar ~ the 1.5bar of pressure of described logical chlorine, the preferred 5g/h ~ 15g/h of speed of described logical chlorine, such as 10g/h.
The preparation method of 2,3,6-described trichlorotoluene zotrichlorides preferably includes following post-processing step: after reaction terminates, rectifying obtains 2,3,6-trichlorotoluene zotrichloride.Described rectifying can adopt the ordinary method of this generic operation in this area.
The preparation method of 2,3,6-described trichlorotoluene zotrichlorides, preferably further comprising the steps: under condition of no solvent, under catalyzer exists, 2-toluene(mono)chloride and chlorination reagent are carried out the mixture that chlorination reaction obtains described toluene dichloride, and described catalyzer is M-ZSM-12, the mixture of described toluene dichloride is 2, the mixture of 6-toluene dichloride and 2,3-toluene dichloride or 2,6-DCT, 2, the mixture of 3-toluene dichloride and 2,5-toluene dichloride;
Wherein, M-ZSM-12 represents the mixture of molecular sieve and metal chloride, and M represents metal chloride, and ZSM-12 represents that particle diameter be 400 order ~ 500 object models is the molecular sieve of ZSM-12.
In the preparation method of the mixture of described toluene dichloride, the chlorine element that described metal chloride can be formed for the metal of this area routine and chlorine element shows the binary compound of negative valency, one or more in the present invention particularly preferably in zinc dichloride, Nickel Chloride, manganous chloride, iron trichloride, aluminum chloride, butter of antimony, lanthanum trichloride, titanium tetrachloride, zirconium tetrachloride and tin tetrachloride, one or more further preferably in zinc dichloride, iron trichloride, butter of antimony and titanium tetrachloride.
In the preparation method of the mixture of described toluene dichloride, the mass values of described catalyzer and the chloro-toluene of described 2-preferably 0.005 ~ 0.05, further preferably 0.01 ~ 0.02.
In the preparation method of the mixture of described toluene dichloride, described chlorination reagent can be the conventional chlorinating agents of such chlorination reaction in this area as chlorine or SULPHURYL CHLORIDE etc., particularly preferably chlorine in the present invention.
In the preparation method of the mixture of described toluene dichloride, the molar ratio of described chlorination reagent and described 2-toluene(mono)chloride preferably 0.7 ~ 1.5, further preferably 0.80 ~ 1.00, such as 0.89,0.86,1.23 or 0.94.
In the preparation method of the mixture of described toluene dichloride, the temperature of described chlorination reaction can be the ordinary temperature of such chlorination reaction in this area, in the present invention particularly preferably 0 DEG C ~ 60 DEG C, preferably 25 DEG C ~ 40 DEG C further.
In the preparation method of the mixture of described toluene dichloride, the process of described chlorination reaction can adopt the routine monitoring method (such as TLC, HPLC, GC or NMR) in this area to monitor, it is the terminal of reaction when generally reaching 80% ~ 90% with reaction conversion ratio, preferably 5 hours ~ 10 hours time of described chlorination reaction, such as 5.5 hours or 7 hours.
In the preparation method of the mixture of described toluene dichloride, when described chlorination reagent is chlorine, preferred employing following steps: pass into chlorine in the mixture system that the chloro-toluene of 2-and catalyzer are formed, carry out chlorination reaction, (mixture of described toluene dichloride is 2,6-DCT and 2 to obtain the mixture of described toluene dichloride, the mixture of 3-toluene dichloride or 2, the mixture of 6-toluene dichloride, 2,3-toluene dichloride and 2,5-toluene dichloride).Preferred 1bar ~ the 1.5bar of pressure of described logical chlorine, the preferred 5g/h ~ 15g/h of speed of described logical chlorine, such as 10g/h.
The preparation method of the mixture of described toluene dichloride preferably includes following post-processing step: after reaction terminates, rectifying obtains the mixture of described toluene dichloride, and (mixture of described toluene dichloride is 2,6-toluene dichloride and 2, the mixture of 3-toluene dichloride, or 2, the mixture of 6-toluene dichloride, 2,3-toluene dichloride and 2,5-toluene dichloride).Described rectifying can adopt the ordinary method of this generic operation in this area.
(mixture of described toluene dichloride is 2 to the mixture of the preferred obtained described toluene dichloride of the preparation method of the mixture of described toluene dichloride, 6-toluene dichloride and 2, the mixture of 3-toluene dichloride, or 2,6-DCT, 2,3-toluene dichloride and 2, the mixture of 5-toluene dichloride) after, without further separation and purification, be directly used in preparation 2, the reaction of 3,6-trichlorotoluene zotrichloride.
In the present invention, in the mixture of the toluene dichloride that the preparation method of the mixture of described toluene dichloride obtains, described 2,6-toluene dichloride and described 2, quality shared by 3-toluene dichloride is greater than 65% than sum and is less than or equal to 100%, preferably described 2,6-DCT and described 2, quality shared by 3-toluene dichloride is greater than 80% than sum and is less than or equal to 100%, and such as 81%, 93%, 95% or 99%.
In the preparation method of the mixture of described toluene dichloride, described M-ZSM-12 can adopt following method to prepare: under the action of an acid, ZSM-12 molecular sieve and metal chloride is reacted, and obtains described M-ZSM-12.
In the preparation method of described M-ZSM-12, the preferred mineral acid of described acid, the preferred hydrochloric acid of described mineral acid.Described hydrochloric acid can be commercially available hydrochloric acid reagent conventional in this area, and the mass concentration of described hydrochloric acid preferably 5% ~ 50%, described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass.
In the preparation method of described M-ZSM-12, the mass values of described acid and described ZSM-12 molecular sieve preferably 5 ~ 10.
In the preparation method of described M-ZSM-12, the mass values of described metal chloride and described ZSM-12 molecular sieve preferably 0.1 ~ 1, such as 0.3.
In the preparation method of described M-ZSM-12, the temperature of described reaction preferably 80 DEG C ~ 100 DEG C.
In the preparation method of described M-ZSM-12, preferably 20 hours ~ 30 hours time of described reaction.
The preparation method of described M-ZSM-12 preferably includes following post-processing step: after reaction terminates, and is washed to neutrality, drying, activation obtain described M-ZSM-12.Described washing, drying, activation can adopt the ordinary method of this generic operation in this area, the temperature of described drying preferably 100 DEG C ~ 150 DEG C, preferably 24 hours ~ 30 hours time of such as, drying described in 120 DEG C.The temperature of described activation preferably 400 DEG C ~ 600 DEG C, preferably 5 hours ~ 10 hours time of described activation.
The preparation method of 2,3,6-described trichlorotoluene zotrichlorides preferably adopts following synthetic route:
Present invention also offers a kind of preparation method of 2,3,6-trichlorobenzoic acid, it comprises the following steps: obtain 2 according to the method described above, after 3,6-trichlorotoluene zotrichloride, then under catalyzer existent condition, by 2,3,6-trichlorotoluene zotrichloride and oxidising agent carry out oxidizing reaction, obtain 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 preferred 0.7Mpa ~ 2Mpa of pressure of described reaction system, further preferred 0.7Mpa ~ 1Mpa.
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, such as 4.
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 ~ 200 DEG C, preferably 50 DEG C ~ 170 DEG C further, such as 120 DEG C, 140 DEG C, 150 DEG C or 160 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% ~ 90%, 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 ~ 20, 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, filtration, washing, recrystallization obtain 2,3,6-trichlorobenzoic acid.Described filtration, washing, recrystallization can adopt the ordinary method of this generic operation in this area, recrystallization solvent preferably water.
When oxygenant be oxygen or air time, preferably adopt following post-processing step: except desolventizing, washing, recrystallization, 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, recrystallization solvent preferably water except desolventizing, washing, recrystallization, oven dry.
In the present invention, the preparation method of 2,3,6-described trichlorobenzoic acids preferably adopts following synthetic route:
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.
Agents useful for same of the present invention and raw material are all commercially.
In the present invention, described room temperature refers to that envrionment temperature is 20 DEG C ~ 30 DEG C.
In the present invention, described normal pressure refers to 1 normal atmosphere, is 101325Pa.
Positive progressive effect of the present invention is: synthetic method reaction yield of the present invention is high, selectivity is high, obtained product purity is high, production cost is low, simple to operate, reaction conditions is gentle, be suitable for suitability for industrialized production.
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 method of embodiment 1M-ZSM-12
The preparation method of M-ZSM-12 is: take a certain amount of ZSM-12 molecular sieve and be placed in round-bottomed flask, the mass concentration adding 5 times of mass equivalents is the metal chloride of the hydrochloric acid of 5% (described mass concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass) and 1/3rd mass equivalents, 100 DEG C of return stirrings 20 hours, be washed with water to neutrality, at 120 DEG C, carry out drying 24 hours again, at the temperature of 400 DEG C, activate 5 hours.Metal chloride is zinc dichloride, iron trichloride, and when butter of antimony or titanium tetrachloride, gained mixture is designated as Zn-ZSM-12 respectively, Fe-ZSM-12, Sb-ZSM-12, Ti-ZSM-12.
The preparation of embodiment 2 dichlorobenzene mixture
In four mouthfuls of round-bottomed flasks, add 100g ortho-chlorotolu'ene, 1gFe-ZSM-12,25 DEG C are stirred normal pressure after 30 minutes and pass into 49.8g chlorine, and logical chlorine speed 10g/h, reacts after about 5 hours, vapor detection transformation efficiency 87%, stops logical chlorine.Obtain reaction solution 124.2g, consist of ortho-chlorotolu'ene 13%, 2,6-DCT 42%, 2,3-toluene dichloride 27%, 2,5-toluene dichloride 16%, trichlorotoluene zotrichloride and other impurity 2.0%.Rectifying, steams ortho-chlorotolu'ene recovery, the dichlorobenzene mixture 112.3g steamed, yield 88.3% (applying mechanically rear yield 95.7%), can be directly used in next step reaction.
The preparation of embodiment 3 dichlorobenzene mixture
In four mouthfuls of round-bottomed flasks, add 100g ortho-chlorotolu'ene, 1gSb-ZSM-12,25 DEG C are stirred normal pressure after 30 minutes and pass into 48.2g chlorine, and logical chlorine speed 10g/h, reacts after about 5 hours, vapor detection transformation efficiency 85%, stops logical chlorine.Obtain reaction solution 123.4g, consist of ortho-chlorotolu'ene 15%, 2,6-DCT 55%, 2,3-toluene dichloride 23%, 2,5-toluene dichloride 6%, trichlorotoluene zotrichloride and other impurity 1.0%.Rectifying steams ortho-chlorotolu'ene recovery, the dichlorobenzene mixture 109.5g steamed, yield 86.1% (applying mechanically rear yield 96.8%), can be directly used in next step reaction.
The preparation of embodiment 4 dichlorobenzene mixture
In four mouthfuls of round-bottomed flasks, add 100g ortho-chlorotolu'ene, 1gZn-ZSM-12,25 DEG C are stirred normal pressure after 30 minutes and pass into 68.9g chlorine, and logical chlorine speed 10g/h, reacts after about 7 hours, vapor detection transformation efficiency 80%, stops logical chlorine.Obtain reaction solution 122.3g, consist of ortho-chlorotolu'ene 20%, 2,6-DCT 36%, 2,3-toluene dichloride 38%, 2,5-toluene dichloride 4%, trichlorotoluene zotrichloride and other impurity 2.0%.Rectifying steams ortho-chlorotolu'ene recovery, the dichlorobenzene mixture 103.3g steamed, yield 81.2% (applying mechanically rear yield 95.6%), can be directly used in next step reaction.
The preparation of embodiment 5 dichlorobenzene mixture
In four mouthfuls of round-bottomed flasks, add 100g ortho-chlorotolu'ene, 1gTi-ZSM-12,25 DEG C are stirred normal pressure after 30 minutes and pass into 52.9g chlorine, and logical chlorine speed 10g/h, reacted after about 5.5 hours, after vapor detection transformation efficiency 85%, stop logical chlorine.Obtain reaction solution 123.4g, consist of ortho-chlorotolu'ene 15%, 2,6-DCT 62%, 2,3-toluene dichloride 21%, 2,5-toluene dichloride 1%, trichlorotoluene zotrichloride and other impurity 1%.Rectifying steams ortho-chlorotolu'ene recovery, the dichlorobenzene mixture 109.5g steamed, yield 86.1% (applying mechanically rear yield 96.8%), can be directly used in next step reaction.
The preparation of embodiment 62,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 5 gained toluene dichloride mixture 100g, 1g iron powder, 25 DEG C of normal pressures pass into 53.9g chlorine, and logical chlorine speed 10g/h, reacted after about 5.5 hours, and the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 120.9g, consist of 2,3,6-trichlorotoluene zotrichloride 62%, 2,3,4-trichlorotoluene zotrichloride 6%, 2,4,6-trichlorotoluene zotrichloride 24%, 2,4,5-trichlorotoluene zotrichloride 5%, other four chloro-product and impurity about 3%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 80.5g, yield 66.3%, purity 93% (GC).
The preparation of embodiment 72,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 5 gained toluene dichloride mixture 100g, 1g aluminum chloride, 25 DEG C of normal pressures pass into 59.5g chlorine, and logical chlorine speed 10g/h, reacted after about 6 hours, and the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 121.3g, consist of 2,3,6-trichlorotoluene zotrichloride 51%, 2,3,4-trichlorotoluene zotrichloride 6%, 2,4,6-trichlorotoluene zotrichloride 30%, 2,4,5-trichlorotoluene zotrichloride 8%, other four chloro-product and impurity about 5%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 70.9g, yield 58.4%, purity 86% (GC).
The preparation of embodiment 82,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 5 gained toluene dichloride mixture 100g, 0.5g butter of antimony, 25 DEG C of normal pressures pass into 57.0g chlorine, and logical chlorine speed 10g/h, reacted after about 6 hours, and the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 120.3g, consist of 2,3,6-trichlorotoluene zotrichloride 91%, 2,3,4-trichlorotoluene zotrichloride 5%, 2,4,6-trichlorotoluene zotrichloride 0.5%, 2,4,5-trichlorotoluene zotrichloride 3%, other four chloro-product and impurity about 0.5%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 113.0g, yield 93.1%, purity 97% (GC).
The preparation of embodiment 92,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 5 gained toluene dichloride mixture 100g, 0.5g titanium tetrachloride, 25 DEG C of normal pressures pass into 61.7g chlorine, and logical chlorine speed 10g/h, reacted after about 6 hours, and the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 120.4g, consist of 2,3,6-trichlorotoluene zotrichloride 86%, 2,3,4-trichlorotoluene zotrichloride 7%, 2,4,6-trichlorotoluene zotrichloride 2%, 2,4,5-trichlorotoluene zotrichloride 4%, other four chloro-product and impurity about 1%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 108.2g, yield 89.1%, purity 96% (GC).
The preparation of embodiment 102,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 5 gained toluene dichloride mixture 100g, 1g Nickel Chloride, 25 DEG C of normal pressures pass into 81.6g chlorine, and logical chlorine speed 10g/h, reacted after about 8 hours, and the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 122.3g, consist of 2,3,6-trichlorotoluene zotrichloride 47%, 2,3,4-trichlorotoluene zotrichloride 10%, 2,4,6-trichlorotoluene zotrichloride 25%, 2,4,5-trichlorotoluene zotrichloride 8%, other four chloro-product and impurity about 10%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 66.1g, yield 54.4%, purity 85% (GC).
The preparation of embodiment 112,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 2 gained toluene dichloride mixture 100g, 0.5g butter of antimony, 25 DEG C of normal pressures pass into 57.0g chlorine, and logical chlorine speed 10g/h, reacted after about 6 hours, and the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 120.4g, consist of 2,3,6-trichlorotoluene zotrichloride 75%, 2,3,4-trichlorotoluene zotrichloride 12%, 2,4,6-trichlorotoluene zotrichloride 1%, 2,4,5-trichlorotoluene zotrichloride 11%, other four chloro-product and impurity about 1%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 103.4g, yield 85.2%, purity 87% (GC).
The preparation of embodiment 122,3,6-trichlorotoluene zotrichloride
In four mouthfuls of round-bottomed flasks, add embodiment 3 gained toluene dichloride mixture 100g, 0.5g butter of antimony, 25 DEG C of normal pressures pass into 57.0g chlorine, logical chlorine speed 10g/h, and after reacting about 6h, the reaction of vapor detection toluene dichloride is complete, stop logical chlorine.Obtain reaction solution 120.5g, consist of 2,3,6-trichlorotoluene zotrichloride 87%, 2,3,4-trichlorotoluene zotrichloride 6%, 2,4,6-trichlorotoluene zotrichloride 0.5%, 2,4,5-trichlorotoluene zotrichloride 5%, other four chloro-product and impurity about 1.5%.Rectifying can obtain 2,3,6-trichlorotoluene zotrichloride 110.6g, yield 91.1%, purity 95% (GC).
The preparation of embodiment 132,3,6-trichlorobenzoic acid
It is 98%H that 2,3,6-trichlorotoluene zotrichloride 50g of embodiment 8 gained are joined 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 0.5g Vanadium Pentoxide in FLAKES, be heated to 140 DEG C, dripping 215g 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), and reaction in 4 hours terminates rear near room temperature (25 DEG C), thin up suction filtration, use a small amount of water washing, obtain 2,3,6-trichlorobenzoic acid crude product.Rear reusable heat water recrystallization, suction filtration, dry, namely obtain 2,3,6-trichlorobenzoic acid sterling 52.9g, HPLC purity is 99%, yield 93.6%.
The preparation of embodiment 142,3,6-trichlorobenzoic acid
It is 98%H that 2,3,6-trichlorotoluene zotrichloride 50g of embodiment 8 gained are joined 150g 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 0.5g Vanadium Pentoxide in FLAKES, be heated to 160 DEG C, dripping 215g 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), and reaction in 4 hours terminates rear near room temperature (25 DEG C), thin up suction filtration, use a small amount of water washing, obtain 2,3,6-trichlorobenzoic acid crude product.Rear reusable heat water recrystallization, suction filtration, dry, namely obtain 2,3,6-trichlorobenzoic acid sterling 50.7g, HPLC purity is 98%, yield 88.8%.
The preparation of embodiment 152,3,6-trichlorobenzoic acid
By embodiment 8 obtains 2, 3, 6-trichlorotoluene zotrichloride 50g joins in reactor, add 150g acetic acid, 0.5g tetra-acetate hydrate cobalt, 0.35g manganous acetate, 0.25g Potassium Bromide, pass into oxygen, be warming up to 150 DEG C, pressurize >=0.7MPa in still, room temperature (25 DEG C) is cooled to after reaction in 5 hours terminates, acetic acid is reclaimed in underpressure distillation, the residual 20g of the adding mass concentration of still is 5% dilute hydrochloric acid suction filtration, use a small amount of water washing, obtain 2, 3, 6-trichlorobenzoic acid crude product hot water recrystallization, suction filtration, dry, namely 2 are obtained, 3, 6-trichlorobenzoic acid sterling 51.9g, HPLC purity is 97%, yield 90%.
The preparation of embodiment 162,3,6-trichlorobenzoic acid
2,3,6-trichlorotoluene zotrichloride 50g embodiment 8 obtained join in 150g butyric acid, 0.5g tetra-acetate hydrate cobalt, 0.35g manganous acetate, 0.25g Potassium Bromide, is warming up to 170 DEG C, pass into oxygen, pressurize >=0.7Mpa in still, after reaction in 18 hours terminates, be cooled to room temperature (25 DEG C), butyric acid is reclaimed in underpressure distillation, and the residual 20g of the adding mass concentration of still is 5% dilute hydrochloric acid suction filtration, uses a small amount of water washing, dry, obtain 2,3,6-trichlorobenzoic acid 52g, HPLC purity is 98%, yield 91.1%.
The preparation of embodiment 172,3,6-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 182,3,6-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 192,3,6-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 202,3,6-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 212,3,6-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 222,3,6-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%.

Claims (10)

1. the preparation method of a trichlorotoluene zotrichloride, it is characterized in that it comprises the following steps: catalyzer by the mixture of toluene dichloride, carries out chlorination reaction with chlorination reagent and obtains 2 under existing, 3,6-trichlorotoluene zotrichloride, described catalyzer is metal and/or metal halide, the mixture of described toluene dichloride is 2, the mixture of 6-toluene dichloride and 2,3-toluene dichloride or 2,6-DCT, 2, the mixture of 3-toluene dichloride and 2,5-toluene dichloride;
2. the preparation method of 2,3,6-trichlorotoluene zotrichlorides as claimed in claim 1, is characterized in that:
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described metal is one or more in iron powder, zinc powder, manganese powder, nickel powder and aluminium powder;
And/or,
Described 2, 3, in the preparation method of 6-trichlorotoluene zotrichloride, described metal halide is dichloride copper, zinc dichloride, cobalt dichloride, Nickel Chloride, manganous chloride, lanthanum trichloride, Indium-111 chloride, iron trichloride, aluminum chloride, butter of antimony, titanium tetrachloride, zirconium tetrachloride, tin tetrachloride, germanium tetrachloride, antimony pentachloride, molybdenum pentachloride, tungsten hexachloride, dibrominated copper, dibrominated zinc, cobalt dihromide, Nickel Bromide, manganese dibromide, tribromide lanthanum, indium tribromide, ferric bromide, alchlor, antimony tribro-, titanium tetrabromide, tetrabormated zirconium, tin tetrabromide, germanium tetrabromide, five bromize antimonies, six tungsten bromides, diiodinating copper, diiodinating zinc, one or more in cobalt diiodide and diiodinating nickel,
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the mass values of the mixture of described catalyzer and described toluene dichloride is 0.001 ~ 0.05;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described chlorination reagent is chlorine or SULPHURYL CHLORIDE;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the molar ratio of the mixture of described chlorination reagent and described toluene dichloride is 1 ~ 5;
And/or,
Described 2,3, in the preparation method of 6-trichlorotoluene zotrichloride, in the mixture of described toluene dichloride, described 2,6-DCT and described 2, quality shared by 3-toluene dichloride is more than or equal to 65% than sum and is less than 100%, described mass ratio refers to that the total mass of described 2,6-DCT and 2,3-described toluene dichloride accounts for the per-cent of the mixture total mass of described toluene dichloride;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the temperature of described chlorination reaction is 10 DEG C ~ 50 DEG C;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the time of described chlorination reaction is 5 hours ~ 8 hours;
And/or,
The preparation method of 2,3,6-described trichlorotoluene zotrichlorides carries out in a solvent or under condition of no solvent;
And/or,
The preparation method of 2,3,6-described trichlorotoluene zotrichlorides comprises following post-processing step: after reaction terminates, rectifying obtains 2,3,6-trichlorotoluene zotrichloride.
3. the preparation method of 2,3,6-trichlorotoluene zotrichlorides as claimed in claim 2, is characterized in that:
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described metal is iron powder;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described metal halide is one or more in aluminum chloride, butter of antimony, titanium tetrachloride and Nickel Chloride;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the mass values of the mixture of described catalyzer and described toluene dichloride is 0.003 ~ 0.01;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, described chlorination reagent is chlorine;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the molar ratio of the mixture of described chlorination reagent and described toluene dichloride is 1.1 ~ 2.0;
And/or,
Described 2,3, in the preparation method of 6-trichlorotoluene zotrichloride, in the mixture of described toluene dichloride, described 2,6-DCT and described 2, quality shared by 3-toluene dichloride is more than or equal to 80% than sum and is less than 100%, described mass ratio refers to that the total mass of described 2,6-DCT and 2,3-described toluene dichloride accounts for the per-cent of the mixture total mass of described toluene dichloride;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the temperature of described chlorination reaction is 25 DEG C ~ 40 DEG C;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the time of described chlorination reaction is 5.5 hours or 6 hours;
And/or,
When the preparation method of 2,3,6-described trichlorotoluene zotrichlorides carries out in a solvent, selected solvent is chlorinated hydrocarbon solvent;
And/or,
When the preparation method of 2,3,6-described trichlorotoluene zotrichlorides carries out in a solvent, the mass values of the mixture of described solvent and described toluene dichloride is 0.5 ~ 5;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, when described chlorination reagent is chlorine, adopt following steps: in the system that mixture and the catalyzer of toluene dichloride is formed, pass into chlorine, carry out chlorination reaction, obtain 2,3,6-trichlorotoluene zotrichloride.
4. the preparation method of 2,3,6-trichlorotoluene zotrichlorides as claimed in claim 3, is characterized in that:
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the molar ratio of the mixture of described chlorination reagent and described toluene dichloride is 1.2,1.3,1.4 or 1.9;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, the mass values of the mixture of described catalyzer and described toluene dichloride is 0.005;
And/or,
When the preparation method of 2,3,6-described trichlorotoluene zotrichlorides carries out in a solvent, the mass values of the mixture of described solvent and described toluene dichloride is 1 ~ 2;
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, when described chlorination reagent is chlorine, in the step of employing, the pressure of described logical chlorine is 1bar ~ 1.5bar;
And/or,
In the preparation method of 2,3,6-described trichlorotoluene zotrichlorides, when described chlorination reagent is chlorine, in the step of employing, the speed of described logical chlorine is 5g/h ~ 15g/h.
5. as claimed in claim 12,3, the preparation method of 6-trichlorotoluene zotrichloride, it is characterized in that: described 2,3, the preparation method of 6-trichlorotoluene zotrichloride, further comprising the steps: under condition of no solvent, under catalyzer exists, 2-toluene(mono)chloride and chlorination reagent are carried out the mixture that chlorination reaction obtains described toluene dichloride, described catalyzer is M-ZSM-12, and the mixture of described toluene dichloride is 2,6-DCT and 2, the mixture of 3-toluene dichloride or 2, the mixture of 6-toluene dichloride, 2,3-toluene dichloride and 2,5-toluene dichloride;
Wherein, M-ZSM-12 represents the mixture of molecular sieve and metal chloride, and M represents metal chloride, and ZSM-12 represents that particle diameter be 400 order ~ 500 object models is the molecular sieve of ZSM-12.
6. the preparation method of 2,3,6-trichlorotoluene zotrichlorides as claimed in claim 5, is characterized in that:
In the preparation method of the mixture of described toluene dichloride, described metal chloride is zinc dichloride, Nickel Chloride, manganous chloride, iron trichloride, aluminum chloride, butter of antimony, lanthanum trichloride, titanium tetrachloride, zirconium tetrachloride or tin tetrachloride;
And/or,
In the preparation method of the mixture of described toluene dichloride, the mass values of described catalyzer and the chloro-toluene of described 2-is 0.005 ~ 0.05;
And/or,
In the preparation method of the mixture of described toluene dichloride, described chlorination reagent is chlorine or SULPHURYL CHLORIDE;
And/or,
In the preparation method of the mixture of described toluene dichloride, the molar ratio of described chlorination reagent and described 2-toluene(mono)chloride is 0.7 ~ 1.5;
And/or,
In the preparation method of the mixture of described toluene dichloride, the temperature of described chlorination reaction is 0 DEG C ~ 60 DEG C;
And/or,
In the preparation method of the mixture of described toluene dichloride, the time of described chlorination reaction is 5 hours ~ 10 hours;
And/or,
In the preparation method of the mixture of described toluene dichloride, when described chlorination reagent is chlorine, adopt following steps: in the mixture system that the chloro-toluene of 2-and catalyzer are formed, pass into chlorine, carry out chlorination reaction, obtain the mixture of described toluene dichloride;
And/or,
The preparation method of the mixture of described toluene dichloride comprises following post-processing step: after reaction terminates, rectifying obtains the mixture of described toluene dichloride;
And/or,
After the preparation method of the mixture of described toluene dichloride obtains the mixture of described toluene dichloride, without further separation and purification, be directly used in the reaction of preparation 2,3,6-trichlorotoluene zotrichloride.
7. the preparation method of 2,3,6-trichlorotoluene zotrichlorides as claimed in claim 6, is characterized in that:
In the preparation method of the mixture of described toluene dichloride, described metal chloride is one or more in zinc dichloride, iron trichloride, butter of antimony and titanium tetrachloride;
And/or,
In the preparation method of the mixture of described toluene dichloride, the mass values of described catalyzer and the chloro-toluene of described 2-is 0.01 ~ 0.02;
And/or,
In the preparation method of the mixture of described toluene dichloride, described chlorination reagent is chlorine;
And/or,
In the preparation method of the mixture of described toluene dichloride, the molar ratio of described chlorination reagent and described 2-toluene(mono)chloride is 0.80 ~ 1.00;
And/or,
In the preparation method of the mixture of described toluene dichloride, the time of described chlorination reaction is 5.5 hours or 7 hours;
And/or,
In the preparation method of the mixture of described toluene dichloride, the temperature of described chlorination reaction is 25 DEG C ~ 40 DEG C;
And/or,
In the preparation method of the mixture of described toluene dichloride, when described chlorination reagent is chlorine, in the step of employing, the pressure of described logical chlorine is 1bar ~ 1.5bar;
And/or,
In the preparation method of the mixture of described toluene dichloride, when described chlorination reagent is chlorine, in the step of employing, the speed of described logical chlorine is 5g/h ~ 15g/h.
8. as claimed in claim 12,3, the preparation method of 6-trichlorotoluene zotrichloride, it is characterized in that: in the preparation method of the mixture of described toluene dichloride, described M-ZSM-12 adopts following method to prepare: under the action of an acid, ZSM-12 molecular sieve and metal chloride are reacted, obtains described M-ZSM-12.
9. the preparation method of 2,3,6-trichlorotoluene zotrichlorides as claimed in claim 8, is characterized in that:
In the preparation method of described M-ZSM-12, described acid is mineral acid;
And/or,
In the preparation method of described M-ZSM-12, the mass values of described acid and described ZSM-12 molecular sieve is 5 ~ 10;
And/or,
In the preparation method of described M-ZSM-12, the mass values of described metal chloride and described ZSM-12 molecular sieve is 0.1 ~ 1;
And/or,
In the preparation method of described M-ZSM-12, the temperature of described reaction is 80 DEG C ~ 100 DEG C;
And/or,
In the preparation method of described M-ZSM-12, the time of described reaction is 20 hours ~ 30 hours;
And/or,
The preparation method of described M-ZSM-12 preferably includes following post-processing step: after reaction terminates, and is washed to neutrality, drying, activation obtain described M-ZSM-12.
10. the preparation method of a trichlorobenzoic acid, it is characterized in that it comprises the following steps: according to the preparation method described in any one of claim 1 ~ 9 obtained 2, after 3,6-trichlorotoluene zotrichloride, then under catalyzer existent condition, by 2,3,6-trichlorotoluene zotrichloride and oxidising agent carry out oxidizing reaction, obtain 2,3,6-trichlorobenzoic acid;
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