CN104672127B - 3,5,6-trichlopyr and the preparation method of salt thereof - Google Patents

3,5,6-trichlopyr and the preparation method of salt thereof Download PDF

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CN104672127B
CN104672127B CN201510068461.7A CN201510068461A CN104672127B CN 104672127 B CN104672127 B CN 104672127B CN 201510068461 A CN201510068461 A CN 201510068461A CN 104672127 B CN104672127 B CN 104672127B
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trichlopyr
salt
preparation
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trichloropyridine
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CN104672127A (en
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王宇
李华轩
龙婉晓
吴婳婳
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Hunan Peter biochemical Polytron Technologies Inc
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Hunan Bhide Biochemical Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention discloses 3,5,6 trichlopyrs and the preparation method of salt thereof, the method is with trichloropyridine alkoxide as raw material, alkalescence with catalysts conditions under, with monoxone alkali salt synthetic reaction, isolate degree by solvent concentration, crystallisation by cooling further > 99.0% 3,5,6 trichlopyr salt, more oxidized decolouring, mineral acid acidified after, filter wash i.e. obtain degree > 99.0% 3,5,6 trichlopyr white crystals.Compared with prior art, the present invention passes through one-step synthesis method, and technique is simple, and solvent recycles, and unit production capacity wastewater discharge is greatly reduced, it is provided that a kind of high-quality, low energy consumption, preparation 3,5,6 trichlopyr of ecological, environmental protective and the production technology of salt thereof.

Description

3,5,6-trichlopyr and the preparation method of salt thereof
Technical field
The invention belongs to the preparation field of pesticide original medicine, be specifically related to herbicide 3,5,6-trichlorine pyrroles Fluoroacetic acid and the preparation method of salt thereof.
Background technology
Trichlopyr is a kind of efficient, Uptake and translocation herbicide of low toxicity, is mainly used in making Before woods weeding go out filling, safeguard fire line, hold up educate pinaster and forest farm transformation.As far back as 1979 Promote the use of through Successful commercial, there is good market prospect.At present, existing document and patent The synthetic method of report mainly has the trichlopyr alkyl with trichloro pyridyl sodium alcoholate as raw material Ester Hydrolyze method and 4 chloro pyridine method.
Trichlopyr Arrcostab Hydrolyze method technique: US3969360A discloses a kind of 3,5,6- The method that three Chloro-2-Pyridyle sodium alkoxide generate trichlopyr methyl ester with methyl chloroacetate etherificate, Yield is 90%；WO2010/023679 discloses a kind of trichlopyr Arrcostab hydrolysis The method obtaining trichlopyr after acidifying, yield is 79～94%.This technique etherification reaction During the trichlopyr Arrcostab crude product purity that obtains relatively low, need to be by washing, decompression Distilation, operating process is complicated, and energy consumption is big, and cost is high.Trichlopyr Arrcostab water Producing a large amount of waste water Han alcohols in solution preocess, in this waste water, alcohol concentration is low, it is difficult to reclaim, right Environmental effect is big.
4 chloro pyridine method technique: US3862952A discloses a kind of 4 chloro pyridine, paraformaldehyde React in water solublity aprotic solvent with alkali-metal cyanide, then through extraction, washing, steam Evaporating solvent, obtain tetrachloro pyrrole epoxide acetonitrile, tetrachloro pyrrole epoxide acetonitrile obtains after hydrolyzing in sulphuric acid Trichlopyr.The yield of this technique is only 84.2%, produces a large amount of containing severe toxicity cyaniding simultaneously In the waste water of thing, environmental pollution is serious.
Summary of the invention
, waste water difficult recovery low for prior art yield or waste water there is hypertoxic by-product, right The problems such as environmental pollution is serious, it is contemplated that following two purpose: an object of the present invention It is: find out a new synthetic route and prepare 3,5,6-trichlopyrs and salt thereof, this conjunction Route is simple, energy consumption is low, three wastes quantum of output is few and disposable for one-tenth.The two of the purpose of the present invention Be: on the basis of synthetic route, further research various process parameters etc., obtain high-quality, The product of high yield, and the problem solving raw material and recycled solvent.
For realizing above goal of the invention, the technical solution adopted in the present invention is:
One of technical scheme:
The preparation method of 3,5,6-trichlopyr salt, with chloracetate and trichloropyridine alkoxide For raw material, add solvent, react under conditions of alkalescence and phase transfer catalyst and prepare, Described solvent is water or polar organic solvent；
The synthetic route of 3,5,6-trichlopyr salt is:
Described chloracetate is ClCH2COOR1, wherein R1Selected from alkali metal ion, ammonium root Any one in ion, triethylamine radical ion, pyridine cation.
Described trichloropyridine alkoxide isWherein R2Selected from alkali metal from Son.
Preferably concrete technology step includes: chloracetate, trichloropyridine alkoxide and solvent are added Entering in reactor, controlling reactant liquor is alkalescence, and reacts under the effect of phase transfer catalyst, Reaction is 0.05%～0.2%, 3,5,6-through high performance liquid chromatography detection trichloropyridine alkoxide content Trichlopyr salt content is 95%～99.5%, stopped reaction, must contain 3,5,6-trichlorine pyrrole oxygen The feed liquid of acetate；If solvent is polar organic solvent, then above-mentioned mixed liquor is steamed through decompression Evaporate, crystallisation by cooling, filtration separate after 3,5,6-trichlopyr salt；Described decompression distillation After solvent and filter separate after filtrate be all recycled to reactions steps.
Control reaction temperature between 50 DEG C～150 DEG C, preferably 80 DEG C～120 DEG C.
Described trichloropyridine alkoxide is preferably 1:(1～2 with the mol ratio of chloracetate).
Described alkalescence preferably control ph is 9～10.
The quality consumption of described solvent is preferably 2～20 times of raw materials quality.
Described organic solvent be preferably selected from N,N-dimethylformamide, N-Methyl pyrrolidone, One or more in dimethyl sulfoxide, acetonitrile, more preferably N, N-dimethyl formyl Amine or dimethyl sulfoxide.
Described phase transfer catalyst is selected from benzyltriethylammoinium chloride, tetrabutyl ammonium bromide or four fourths One or more in the phase transfer catalysts such as ammonium chloride.Described phase transfer catalyst consumption is The 0.1%-1% of trichloro pyridyl sodium alcoholate consumption.
Described chloracetate uses after the most directly preparing: by monoxone with molten Agent is placed in reactor, and controlling feed temperature is-10 DEG C～50 DEG C, is slowly added to rub with monoxone You than be 1:(1～1.5) alkali, after dripping continue stirring 30～60 minutes, obtain monoxone Salt suspensioning liquid.
Chloracetate synthetic route is:
R1 and R2 is defined as above described.
Described feed temperature is preferably-5 DEG C～5 DEG C, more preferably 0 DEG C.
Described alkali be preferably selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, Any one in ammonia, pyridine.
If using after preparing chloracetate by the method for the present invention, need main 2 points: 1 is material The control of liquid temp and the selection of alkali, the two condition is to ensure that in chloracetate, chlorine is not by water The key solved.
The two of technical scheme:
The preparation method of 3,5,6-trichlopyrs,
At above-mentioned prepared 3,5,6-trichlopyr salt or the trichlopyr Han 3,5,6- On the basis of the feed liquid of salt, it is acidified with acid to obtain 3,5,6-trichlopyrs.
The synthetic route of 3,5,6-trichlopyr is:
R1 and R2 is defined as above described.
The temperature of described acidifying is preferably 50 DEG C～150 DEG C.
Further preferably before being acidified with acid, use alkaline oxidiser oxidative decoloration.
Described alkaline oxidiser is preferably selected from any one in sodium hypochlorite, SODIUM PERCARBONATE；Institute State that alkaline oxidiser consumption is 3,5,6-trichlopyr salt quality consumption 0.1～0.7 times.
Compared with prior art, present invention have an advantage that
1, in the present invention, trichloropyridine alkoxide and chloracetate one-step synthesis trichlopyr, Degree is isolated by solvent concentration, crystallisation by cooling > the 3,5,6-trichlorine pyrrole oxygen of 99.0% Acetate, further use oxidative decoloration, mineral acid acidified after, filter and i.e. obtain percentage ratio and contain Amount > 99.0% 3,5,6-trichlopyr.Compared with prior art, the present invention passes through a step Method synthesizes, and is substantially reduced the consumption of solvent, and product purity is high.Meanwhile, unreacted is completely The lower batch that can directly proceed to trichloropyridine alkoxide continues to recycle as reaction raw materials, it is provided that A kind of high-quality, low energy consumption, ecological, environmental protective prepare 3,5,6-trichlopyr and salt thereof Production technology.
2, the technique of the present invention is simple, the white crystal of constant product quality, purity high (99% Above), product yield is high, and yield is generally higher than 90%, can reach more than 96%.
Accompanying drawing explanation
Fig. 1 is the preparation technology stream preparing 3,5,6-trichlopyr with organic solvent for solvent Cheng Tu.
Fig. 2 is the process chart preparing 3,5,6-trichlopyr with water for solvent.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Except special instruction Outward, described in embodiment, percentage composition is weight/mass percentage composition.
The preparation of trichlopyr
Embodiment 1
(1) 71.0g (98.5%, 0.75mol) monoxone and 100gN, N-dimethyl methyl are taken Amide puts in 500ml four-hole bottle, opens cryogenic thermostat bath, is cooled to 0 DEG C, by 30g (0.75 Mol) sodium hydrate solid slowly puts in four-hole bottle, and keeping temperature is 0～5 DEG C, has put into Quan Hou, continues stirring 0.5h, obtains mixture；
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g tetrabutyl phosphonium bromide are taken Ammonium, 500gN, dinethylformamide puts in 1000ml four-hole bottle, opens stirring, heats up To 100 DEG C, at the uniform velocity add step (1) mixture, control reaction temperature 100 DEG C, reaction 5h, distillation and concentration reaction feed liquid, to bottom feed liquid weight 500g, is cooled to 0～5 DEG C, filters, filter Cake weight 304g, filtrate weight 196g.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, opens Open stirring, be warming up to 70 DEG C, be slowly added dropwise into 70g saturated liquor natrii hypochloritis (effective chlorine Content > 10.0%), continue stirring 0.5h after completion of dropwise addition, be then slowly added dropwise 70g 30% salt Acid, is cooled to room temperature, filters washing, and filtration cakes torrefaction i.e. obtains trichlopyr 142.9g, Appearance white crystal, purity is 99.70%, and yield is 92.7%.
Embodiment 2
(1) 71.0g (98.5%, 0.75mol) monoxone and 100gN, N-dimethyl methyl are taken Amide puts in 500ml four-hole bottle, opens cryogenic thermostat bath, is cooled to 0 DEG C, by 39.7g (0.38mol) sodium carbonate liquor slowly puts into four-hole bottle, and keeping temperature is 0～5 DEG C, After dropping completely, continue stirring 0.5h, obtain mixture；
(2) 155.6g (86.1%, 0.56mol) trichloropyridine potassium alcoholate, 2g tetrabutyl chlorine are taken Changing ammonium, 500gN, dinethylformamide puts in 1000ml four-hole bottle, opens stirring, rises Temperature, to 100 DEG C, at the uniform velocity adds step (1) mixture, controls reaction temperature 100 DEG C, reaction 5h, distillation and concentration reaction feed liquid, to bottom feed liquid weight 500g, is cooled to 0～5 DEG C, filters, filter Cake weight 310g, filtrate weight 190g.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, opens Open stirring, be warming up to 70 DEG C, be slowly added dropwise into 70g saturated liquor natrii hypochloritis (effective chlorine Content > 10.0%), continue stirring 0.5h after completion of dropwise addition, be then slowly added dropwise 70g 30% salt Acid, is cooled to room temperature, filters washing, and filtration cakes torrefaction i.e. obtains trichlopyr 137.6g, Appearance white crystal, purity is 99.1%, and yield is 94.6%%.
Embodiment 3
(1) 71.0g (98.5%, 0.75mol) monoxone and 100gN, N-dimethyl methyl are taken Amide puts in 500ml four-hole bottle, opens cryogenic thermostat bath, is cooled to 2 DEG C, by 50.3g Potash solid slowly puts into four-hole bottle, and keeping temperature is 0～5 DEG C, after dropping completely, Continue stirring 0.5h, obtain mixture；
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium are taken Ammonium chloride, 500gN, dinethylformamide puts in 1000ml four-hole bottle, opens stirring, It is warming up to 80 DEG C, at the uniform velocity adds step (1) mixture, control reaction temperature 80 DEG C, reaction 6h, distillation and concentration reaction feed liquid, to bottom feed liquid weight 500g, is cooled to room temperature, filters, filter Cake weight 314g, filtrate weight 186g.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, opens Open stirring, be warming up to 45 DEG C, be slowly added to 30.0g SODIUM PERCARBONATE, stir 0.5h, then delay Slow dropping 70g 30% hydrochloric acid, is cooled to room temperature, filters washing, and filtration cakes torrefaction i.e. obtains trichlorine Pyrrole fluoroacetic acid 144.7g, appearance white puffy powder, purity is 99.3%, and yield is 94.0%.
Embodiment 4
(1) 71.0g (98.5%, 0.75mol) monoxone and 100gN, N-dimethyl methyl are taken Amide puts in 500ml four-hole bottle, opens cryogenic thermostat bath, is cooled to 0～5 DEG C, slowly leads to Entering 12.8g ammonia in four-hole bottle, keeping temperature is 0～5 DEG C, after being passed through completely, continues to stir Mix 0.5h, obtain mixture；
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium are taken Ammonium chloride, 500gN, dinethylformamide puts in 1000ml four-hole bottle, opens stirring, It is warming up to 100 DEG C, at the uniform velocity adds step (1) mixture, control reaction temperature 120 DEG C, instead 4h, distillation and concentration reaction feed liquid is answered to bottom feed liquid weight 500g, to be cooled to room temperature, filter, Filter cake weight 316g, filtrate weight 184g.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, opens Open stirring, be warming up to 100 DEG C, be slowly added dropwise into 70g saturated liquor natrii hypochloritis (effective chlorine Content > 10.0%), continue stirring 0.5h after completion of dropwise addition, be then slowly added dropwise 70g 30% salt Acid, is cooled to room temperature, filters washing, and filtration cakes torrefaction i.e. obtains trichlopyr 146.9g, Appearance white puffy powder, purity is 99.2%, and yield is 95.3%.
Embodiment 5
(1) 71.0g (98.5%, 0.75mol) monoxone and 100gN, N-dimethyl methyl are taken Amide puts in 500ml four-hole bottle, opens cryogenic thermostat bath, is cooled to 0～5 DEG C, by 75.8g Triethylamine is slowly added dropwise to four-hole bottle, and keeping temperature is 0～5 DEG C, after dropping completely, continues Stirring 0.5h, obtains mixture；
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium are taken Ammonium chloride, 500gN, dinethylformamide puts in 1000ml four-hole bottle, opens stirring, It is warming up to 100 DEG C, at the uniform velocity adds step (1) mixture, control reaction temperature 100 DEG C, instead 5h, distillation and concentration reaction feed liquid is answered to bottom feed liquid weight 500g, to be cooled to room temperature, filter, Filter cake weight 396g, filtrate weight 104g.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, opens Open stirring, be warming up to 80 DEG C, be slowly added dropwise into 70g saturated liquor natrii hypochloritis (effective chlorine Content > 10.0%), continue stirring 0.5h after completion of dropwise addition, be then slowly added dropwise 70g 30% salt Acid, is cooled to room temperature, filters washing, and filtration cakes torrefaction i.e. obtains trichlopyr 147.6g, Appearance white crystal, purity is 99.2%, and yield is 95.1%.
Embodiment 6
(1) 71.0g (98.5%, 0.75mol) monoxone and 100gN, N-dimethyl methyl are taken Amide puts in 500ml four-hole bottle, opens cryogenic thermostat bath, is cooled to 0 DEG C, by 59.3g Pyridine is slowly added dropwise to four-hole bottle, and keeping temperature is 0～5 DEG C, after dropping completely, continues to stir Mix 0.5h, obtain mixture；
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium are taken Ammonium chloride, 500gN, dinethylformamide puts in 1000ml four-hole bottle, opens stirring, It is warming up to 100 DEG C, at the uniform velocity adds step (1) mixture, control reaction temperature 100 DEG C, instead 5h, distillation and concentration reaction feed liquid is answered to bottom feed liquid weight 500g, to be cooled to room temperature, filter, Filter cake weighs 346, filtrate weight 154g.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, opens Open stirring, be warming up to 80 DEG C, be slowly added dropwise into 70g saturated liquor natrii hypochloritis (effective chlorine Content > 10.0%), continue stirring 0.5h after completion of dropwise addition, be then slowly added dropwise 70g 30% salt Acid, is cooled to room temperature, filters washing, and filtration cakes torrefaction i.e. obtains trichlopyr 146.0g, Appearance white crystal, purity is 99.3%, and yield is 94.8%.
Embodiment 7
(1) take 71.0g (98.5%, 0.75mol) monoxone and 100g solvent puts into 500ml tetra- In mouthful bottle, open cryogenic thermostat bath, be cooled to 0 DEG C, 75.8g triethylamine is slowly added dropwise to In four-hole bottle, keeping temperature is 0～5 DEG C, after dropping completely, continues stirring 0.5h, obtains mixing Thing；
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium chlorination are taken Ammonium, 500g solvent put in 1000ml four-hole bottle, open stirring, are warming up to 100 DEG C, even Speed adds step (1) mixture, controls reaction temperature 100 DEG C, reacts 5h, distillation and concentration Reaction feed liquid, to bottom feed liquid weight 500g, is cooled to room temperature, filters.
(3) proceeding in 1000ml four-hole bottle by filter cake in step (2), add water 500g, and unlatching is stirred Mix, be warming up to 80 DEG C, be slowly added dropwise into the saturated liquor natrii hypochloritis of 70g that (effective chlorine contains Amount > 10.0%), continue stirring 0.5h after completion of dropwise addition, be then slowly added dropwise 70g 30% hydrochloric acid, Being cooled to room temperature, filter washing, filtration cakes torrefaction i.e. obtains trichlopyr.
Reacting under the conditions of different solvents, yield and the content of trichlopyr are shown in Table 1.
Table 1 reacts under the conditions of different solvents, the yield of trichlopyr and content
Solvent Yield/% Content/%
Embodiment 7 Acetonitrile 65.1 83.1
Embodiment 8 Water 93.5 99.2
Embodiment 9 Dimethyl sulfoxide 95.2 99.0
Embodiment 10 N-Methyl pyrrolidone 84.1 97.9
The preparation of trichlopyr triethylamine salt water preparation
Embodiment 1
(1) take 71.0g (98.5%, 0.75mol) monoxone and 100g water puts into 500ml In four-hole bottle, open cryogenic thermostat bath, be cooled to 0 DEG C, 75.8g triethylamine is slowly added dropwise To four-hole bottle, keeping temperature is 0～5 DEG C, after dropping completely, continues stirring 0.5h.
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium are taken Ammonium chloride, 500g water put in 1000ml four-hole bottle, open stirring, are warming up to 100 DEG C, At the uniform velocity add step (1) mixture, control reaction temperature 100 DEG C, react 5h, reaction knot Shu Hou, is cooled to 75 DEG C, is slowly added dropwise into the saturated liquor natrii hypochloritis of 70g that (effective chlorine contains Amount > 10.0%), continue stirring 0.5h after completion of dropwise addition, then distillation and concentration reaction feed liquid is to still Bed material liquid weight 420g, is cooled to room temperature, is filtered to remove a small amount of insoluble impurity and salt, and filtrate is i.e. Trichlopyr triethylamine salt water preparation, weight is 310.8g, outward appearance weak yellow liquid, HPLC Analyzing effective ingredient trichlopyr content is 45.9%, and yield is 92.7%.
Embodiment 2
(1) take 71.0g (98.5%, 0.75mol) monoxone and 100g water puts into 500ml In four-hole bottle, open cryogenic thermostat bath, be cooled to 0 DEG C, 75.8g triethylamine is slowly added dropwise To four-hole bottle, keeping temperature is 0～5 DEG C, after dropping completely, continues stirring 0.5h.
(2) 155.6g (85.2%, 0.6mol) trichloro pyridyl sodium alcoholate, 2g benzyl triethyl ammonium are taken Ammonium chloride, 500g water put in 1000ml four-hole bottle, open stirring, are warming up to 100 DEG C, At the uniform velocity add step (1) mixture, control reaction temperature 100 DEG C, react 5h, reaction knot Shu Hou, is cooled to 75 DEG C, is slowly added dropwise into the saturated liquor natrii hypochloritis of 70g that (effective chlorine contains Amount > 10.0%), continue stirring 0.5h after completion of dropwise addition, then distillation and concentration reaction feed liquid is to still Bed material liquid weight 500g, is cooled to room temperature, is filtered to remove a small amount of insoluble impurity and salt, and filtrate is i.e. Trichlopyr triethylamine salt water preparation, weight is 461.2g, outward appearance weak yellow liquid, HPLC Analyzing effective ingredient trichlopyr content is 30.8%, and yield is 92.1%.

Claims (16)

  1. The preparation method of 1.3,5,6-trichlopyr salt, is characterized in that, with chloracetate and Trichloropyridine alkoxide is raw material, adds solvent, anti-under conditions of alkalescence and phase transfer catalyst Should prepare, described solvent is water or polar organic solvent；Described organic solvent is selected from One or more in N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide；
    Described chloracetate is ClCH2COOR1, wherein R1Selected from alkali metal ion, ammonium root Any one in ion, triethylamine radical ion, pyridine cation；
    Described trichloropyridine alkoxide isWherein R2Selected from alkali metal from Son.
  2. The most according to claim 1, the preparation method of 3,5,6-trichlopyr salt, it is special Levying and be, concrete technology step includes: chloracetate, trichloropyridine alkoxide and solvent are added anti- Answering in still, controlling reactant liquor is alkalescence, and reacts under the effect of phase transfer catalyst, reaction It is 0.05%～0.2% through high performance liquid chromatography detection trichloropyridine alkoxide content, 3,5,6-trichlorines Pyrrole fluoroacetate content is 95%～99.5%, stopped reaction, must contain 3,5,6-trichlopyrs The feed liquid of salt；If solvent is polar organic solvent, then above-mentioned mixed liquor is distilled through decompression, Crystallisation by cooling, filtration obtain 3,5,6-trichlopyr salt after separating；After described decompression distillation Filtrate after solvent and filtration separate all is recycled to reactions steps.
  3. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, control reaction temperature 50 DEG C～150 DEG C.
  4. The most according to claim 3, the preparation method of 3,5,6-trichlopyr salt, it is special Levying and be, controlling reaction temperature is 80 DEG C～120 DEG C.
  5. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, described trichloropyridine alkoxide is 1:(1～2 with the mol ratio of chloracetate).
  6. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, described alkalescence be control ph be 9～10.
  7. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, quality consumption is raw materials quality 2～20 times of described solvent.
  8. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, described organic solvent is DMF or dimethyl sulfoxide.
  9. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, described phase transfer catalyst is selected from benzyltriethylammoinium chloride, tetrabutyl ammonium bromide Or one or more in tetrabutylammonium chloride；Described phase transfer catalyst consumption is trichloropyridine The 0.1%-1% of sodium alkoxide consumption.
  10. The preparation method of 3,5,6-trichlopyr salt the most according to claim 1 or claim 2, It is characterized in that, the preparation method of described chloracetate is: monoxone and solvent are placed in reactor In, controlling feed temperature is-10 DEG C～50 DEG C, and being slowly added dropwise with monoxone mol ratio is 1: The alkali of (1～1.5), continues stirring 30～60 minutes, obtains chloracetate after dripping.
  11. The preparation method of 11. 3,5,6-trichlopyr salt according to claim 10, its Feature is, described feed temperature is preferably-5 DEG C～5 DEG C.
  12. The preparation method of 12. 3,5,6-trichlopyr salt according to claim 10, it is special Levying and be, described alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia three second Any one in amine, pyridine.
  13. The preparation method of 13.3,5,6-trichlopyrs, is characterized in that, in claim 1-12 3,5,6-trichlopyr salt prepared by one of or the material containing 3,5,6-trichlopyr salt On the basis of liquid, it is acidified with acid to obtain 3,5,6-trichlopyrs.
  14. 14. according to described in claim 13 3, the preparation method of 5,6-trichlopyrs, and it is special Levying and be, the temperature of described acidifying is 50 DEG C～150 DEG C.
  15. 15. according to described in claim 13 3, the preparation method of 5,6-trichlopyrs, and it is special Levy and be, before being acidified with acid, use alkaline oxidiser oxidative decoloration.
  16. 16. according to described in claim 15 3, the preparation method of 5,6-trichlopyrs, and it is special Levying and be, described alkaline oxidiser is selected from any one in sodium hypochlorite, SODIUM PERCARBONATE.
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