CN105566211A - Triclopyr production method - Google Patents
Triclopyr production method Download PDFInfo
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- CN105566211A CN105566211A CN201610089990.XA CN201610089990A CN105566211A CN 105566211 A CN105566211 A CN 105566211A CN 201610089990 A CN201610089990 A CN 201610089990A CN 105566211 A CN105566211 A CN 105566211A
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- Prior art keywords
- acid
- triclopyr
- production method
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- trichloropyridine
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- 0 CC(C*C(C(Cl)=C1)=NCC(Cl)=C1Cl)=O Chemical compound CC(C*C(C(Cl)=C1)=NCC(Cl)=C1Cl)=O 0.000 description 1
- MNYBZEHWPRTNJY-UHFFFAOYSA-N COC(COc(nc(c(Cl)c1)Cl)c1Cl)=O Chemical compound COC(COc(nc(c(Cl)c1)Cl)c1Cl)=O MNYBZEHWPRTNJY-UHFFFAOYSA-N 0.000 description 1
- WCYYAQFQZQEUEN-UHFFFAOYSA-O [OH2+]c(c(Cl)c1)nc(Cl)c1Cl Chemical compound [OH2+]c(c(Cl)c1)nc(Cl)c1Cl WCYYAQFQZQEUEN-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- 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
Abstract
The invention provides a triclopyr production method. Firstly, sodium trichloropyrindinol and methyl chloroacetate have etherification reaction in a polar solvent to generate a midbody trichloropyridine peroxyacetic acid methyl ester, and trichloropyridine peroxyacetic acid methyl ester is subjected to alkaline hydrolysis and acidification in an aqueous phase to obtain triclopyr. When etherification reaction is conducted, reaction temperature is low, conditions are mild, reaction time is shortened, post-processing is simple, and the yield is high. A dispersing agent and a phase transfer catalyst are used during alkaline hydrolysis and acidification, alkaline hydrolysis and acidification are conducted in the aqueous phase, the amount of three wastes is reduced, reaction conditions are mild, the yield is high, production cost is low, industrial production is facilitated, and the yield of two-step reaction can reach 94% or above.
Description
Technical field
The present invention relates to weedicide field, relate to a kind of production method of TRICLOPYR ACID particularly.
Background technology
TRICLOPYR ACID, English popular name: Triclopyr, chemical name: 3,5,6-trichloro-2-pyridyl fluoroacetic acid, English name (3,5,6-trichloro-2-pyridibyloxy) aceticacid, be the forest weedicide of LG-DOW agricultural sciences company exploitation, structural formula is:
Physico-chemical property: former medicine outward appearance is white solid, decomposition temperature is 290 DEG C, fusing point 148-150 DEG C, and when 24.5 DEG C, in water, solubleness is 438-440mg/L, be dissolved in the organic solvents such as ethanol, 989g/kg in acetone, 307g/kg in n-Octanol, be insoluble in other ordinary organic solvents, stable under usual holding conditions, to hydrolysis-stable, but easily by photolysis, 12h internal loss 50%.Greenweed is decided to be low toxicity herbicide.
China has been the big producing country of pesticide original medicine in the world at present, and variety protection is complete, and the weedicide in farmland, sterilant, sterilant have all had respective key variety, but also lacks very much as the weedicide kind in forestry.Along with the harm of China forest weeds is more and more serious, will be day by day urgent to the demand of weedicide.The weedicide TRICLOPYR ACID of Dow Chemical company exploitation, be mainly used in forest, rubber forest, palm grove and motorway, railway both sides prevent and kill off xylophyta and broadleaf weeds, but also rice terrace or wheat paddock weeding can be mixed for other weedicides, this weedicide is widely used, and therefore develops TRICLOPYR ACID and will have very large development prospect.
About the synthetic method of TRICLOPYR ACID, from current report both domestic and external, mainly contain following several:
4 chloro pyridine and oxyacetic acid is utilized to be obtained by reacting TRICLOPYR ACID, raw material 4 chloro pyridine and oxyacetic acid expensive, and DMSO need be used to dissolve oxyacetic acid sodium salt to promote reaction, temperature of reaction 100 DEG C, raw material 4 chloro pyridine synthetic route is long, product cost high (synthesising process research of TRICLOPYR ACID, Zhang Yongzhong master thesis, China Agricultural University) during suitability for industrialized production.
Chinese patent CN201210235682 discloses by trichloro pyridyl sodium alcoholate and ethyl chloroacetate in DMF, with potassiumiodide and Tetrabutyl amonium bromide for catalyzer, generates intermediate trichloropyridine fluoroacetic acid ethyl ester; In the mixing solutions of first alcohol and water, trichloropyridine fluoroacetic acid is prepared in alkaline hydrolysis acidifying again, and according to said method, the first step need use two kinds of catalyzer, and these two kinds of catalyzer prices are all higher, and product cost is high; Second step with an organic solvent carries out alkaline hydrolysis acidifying with the mixed solvent of water, and organic solvent usage quantity is large, and solvent cost is high, and it is difficult that reaction terminates rear waste water COD height, is unfavorable for environmental protection.
According to another bibliographical information, adopt trichloro pyridyl sodium alcoholate and methyl chloroacetate to react and prepare TRICLOPYR ACID, methyl chloroacetate is that reaction solvent is again as reaction substrate, with trichloro pyridyl sodium alcoholate 90 DEG C of back flow reaction, generate intermediate trichloropyridine fluoroacetic acid methyl esters, cooling, filter, washing gained crude product, be added to the water, add potassium hydroxide, 76 DEG C of hydrolysis reaction 1h, hydrochloric acid adjusts pH=3 ~ 4, separate out solid, cold filtration obtains the acid of product TRICLOPYR ACID, and methyl chloroacetate pungency is stronger, in this method, methyl chloroacetate consumption is large, reaction system viscosity is high, aftertreatment is not easy to operation, total recovery is no more than 78%, industrial production cost aspect is without advantage (" Hangzhou chemical industry " 2006, 36 volumes, 2nd phase).
Summary of the invention
The object of the present invention is to provide a kind of production method of TRICLOPYR ACID, the etherification reaction raw materials cost of the method reduces, and reaction conditions is gentle, and aftertreatment is simple, and technological operation is simple and direct, and yield is high; In aqueous phase, carry out alkaline hydrolysis and acidifying, reaction conditions is gentle, and yield is high, and quantity of three wastes is little, and product cost is low, is beneficial to suitability for industrialized production, and two-step reaction total recovery can reach more than 94%.
In order to achieve the above object, technical scheme of the present invention is as follows:
A production method for TRICLOPYR ACID, comprises the following steps:
1) etherification reaction
Stir in polar organic solvent and add trichloro pyridyl sodium alcoholate and methyl chloroacetate, be heated to 50 ~ 100 DEG C, insulation reaction 2 ~ 4h, after reaction terminates, steam neat solvent, add water and stir 30min, be cooled to 20 ~ 35 DEG C, filter, obtain intermediate trichloropyridine fluoroacetic acid methyl esters;
2) alkaline hydrolysis, acidifying
To step 1) add water in the intermediate trichloropyridine fluoroacetic acid methyl esters that obtains, dispersion agent and phase-transfer catalyst, be heated to 60 ~ 100 DEG C, add alkali again, insulation reaction 0.5 ~ 3h after reinforced, after reaction terminates, acidifying, regulate pH to 2 ~ 4, be cooled to 20 ~ 45 DEG C, crystallization, filter, obtain TRICLOPYR ACID; Wherein, the water added is 2 ~ 10: 1, ml/g with the volume mass ratio of trichloropyridine fluoroacetic acid methyl esters;
Reaction formula is:
Preferably, step 2) consumption of dispersion agent is 0.1 ~ 1wt.% of trichloropyridine fluoroacetic acid methyl esters, described dispersion agent is selected from least one in polyoxyethylene glycol series, sodium lauryl sulphate, trisodium phosphate, many sodium-metaphosphates and linolic acid sodium.
Preferably, step 2) described in the consumption of phase-transfer catalyst be 0.2 ~ 2wt.% of trichloropyridine fluoroacetic acid methyl esters, described phase-transfer catalyst is that crown ether-like is or/and quaternary ammonium salt-type phase transfer catalyst, described crown ether-like phase transfer catalysts is selected from least one in 18 hats 6 and 15 hats 5, and described quaternary ammonium salt-type phase transfer catalyst is selected from least one in benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
Further, step 1) described in polar organic solvent and the volume ratio of trichloro pyridyl sodium alcoholate be 1 ~ 10: 1, described polar organic solvent is selected from N, dinethylformamide, N, the at least one of N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, N-Methyl pyrrolidone and DMI.
Preferably, step 1) described in trichloro pyridyl sodium alcoholate and the mol ratio of methyl chloroacetate be 1: 1.0 ~ 1.3.
Further, step 2) in alkali be mineral alkali, be selected from least one in sodium-acetate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood and cesium carbonate, the mol ratio of itself and trichloropyridine fluoroacetic acid methyl esters is 1.0 ~ 2.0: 1.
Preferably, step 2) in utilize mineral acid to carry out acidifying, described mineral acid is selected from least one in hydrochloric acid, sulfuric acid, phosphoric acid, chloric acid, sulfurous acid, phosphorous acid, chlorous acid, nitrous acid, hydroiodic acid HI and Hydrogen bromide.
The present invention is through two step synthesis TRICLOPYR ACID, the first step is that trichloro pyridyl sodium alcoholate and methyl chloroacetate carry out etherification reaction in suitable solvent, system dispersion better, do not use catalyzer, temperature of reaction is low, and under relatively mild condition, raw material just can transform completely, and, raw material is easy to get cheap, and aftertreatment is easy, obtains trichloropyridine fluoroacetic acid methyl ester intermediate.
In the present invention, the trichloropyridine fluoroacetic acid methyl ester intermediate crude product obtained by etherification reaction does not need to do further purification, be directly used in second step alkaline hydrolysis acidification reaction, this alkaline hydrolysis acidification reaction is avoided with an organic solvent, carries out in aqueous phase, solvent is made with water, add dispersion agent and phase-transfer catalyst simultaneously, trichloropyridine fluoroacetic acid methyl ester intermediate is fully contacted with alkali, and product double team phenomenon can not be produced, guarantee that raw material can fully react, therefore yield is higher; Because alkaline hydrolysis of the present invention, acidification reaction carry out in aqueous phase, avoid with an organic solvent, wastewater flow rate reduces, and the wastewater flow rate of output is only the half not using dispersion agent and phase-transfer catalyst scheme, simplifies postprocessing working procedures, reduces industrial production cost.
Compared with prior art, beneficial effect of the present invention is embodied in:
1) the present invention carries out alkaline hydrolysis and acidifying in aqueous phase, with water as solvent, not with an organic solvent, adds dispersion agent and phase-transfer catalyst simultaneously, decreases quantity of three wastes, and reaction conditions is gentle, and yield is high, and product cost is low, is beneficial to suitability for industrialized production.
2) expensive reagent is not used in raw material of the present invention, reaction conditions is gentle, and reaction yield is high, raw material consumption is low, aftertreatment is simple, and quantity of three wastes is little, and the two-step reaction total recovery obtaining TRICLOPYR ACID product can reach more than 94%, product purity > 99%, synthesise various cost reduces by 20% ~ 30%.
Accompanying drawing explanation
Fig. 1 is the HPLC spectrogram of the trichloropyridine fluoroacetic acid methyl esters that the embodiment of the present invention 1 obtains.
Fig. 2 is the HPLC spectrogram of the TRICLOPYR ACID product that the embodiment of the present invention 1 obtains.
Fig. 3 is the HPLC spectrogram of the trichloropyridine fluoroacetic acid methyl esters that the embodiment of the present invention 2 obtains.
Fig. 4 is the HPLC spectrogram of the TRICLOPYR ACID that the embodiment of the present invention 2 obtains.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
The synthetic method of embodiment 1 one kinds of TRICLOPYR ACID, comprises the following steps:
1) etherification reaction
N is added in the 250ml four-hole bottle of dried and clean, N-N,N-DIMETHYLACETAMIDE (DMAC, AR level) 64g, open and stir, add trichloro pyridyl sodium alcoholate 34.3g (content 99% again, 0.15mol) with methyl chloroacetate 18.5g (content 99%), oil bath is heated to 70 DEG C ~ 75 DEG C, insulation reaction 2 hours, HPLC monitors reaction, reaction terminates rear underpressure distillation and reclaims DMAC62.5g, water 60ml is once poured into while hot in system, stir 30min, be cooled to 25 DEG C, filter to obtain light brown particulate solid trichloropyridine fluoroacetic acid methyl esters 70.8g, HPLC purity 96.2%, stand-by, the HPLC spectrogram of product is see Fig. 1, analytical data is see table 1.
Table 1
| Peak number | Retention time (min) | Peak area | Peak height | Content (%) |
| 1 | 8.226 | 214951 | 30568 | 1.620 3 --> |
| 2 | 9.663 | 22531 | 3645 | 0.170 |
| 3 | 12.953 | 224988 | 39326 | 1.696 |
| 4 | 13.135 | 12766473 | 1837599 | 96.228 |
| 5 | 14.074 | 37951 | 5950 | 0.286 |
| Amount to | 13266894 | 1917088 | 100.000 |
2) alkaline hydrolysis acidification reaction
Gained etherificate intermediate trichloropyridine fluoroacetic acid methyl esters and 150ml water are added in 250ml four-hole bottle, add polyoxyethylene glycol (PEG200) 0.1g and benzyl trimethyl ammonium chloride 0.2g again, be warming up to 70 DEG C, drip 30wt% aqueous sodium hydroxide solution 24g, drip Bi Baowen 1h, reaction terminates rear dropping 36wt% hydrochloric acid 18.5g, detect pH=3 ~ 4, be cooled to 25 DEG C, suction filtration, light yellow particulate solid 46.3g is obtained after draining, 80 DEG C of dry 3h in constant temperature convection oven, obtain lurid TRICLOPYR ACID crystallization 37.3g, HPLC purity 99.2%, two step total recoverys 94.2%, product HPLC collection of illustrative plates Fig. 2, analytical data is see table 2, retention time is LC-MS (EI): the m/z255 of 9.64min.
Table 2
The synthetic method of embodiment 2 one kinds of TRICLOPYR ACID, comprises the following steps:
1) etherification reaction
N is added in the 500ml four-hole bottle of dried and clean, dinethylformamide (DMF, AR level) 150g, open and stir, add trichloro pyridyl sodium alcoholate 68.7g (content 99% again, 0.31mol) with methyl chloroacetate 40g (content 99%), oil bath is warming up to 75 DEG C, insulation reaction, be incubated 1.5 hours, HPLC monitors reaction, reaction terminates rear underpressure distillation and reclaims DMF148.3g, in system, once pour 150ml water while hot into stir 30min, be cooled to 25 DEG C, filter to obtain light brown particulate solid trichloropyridine fluoroacetic acid methyl esters 68.8g, HPLC purity 97.2%, stand-by, product HPLC spectrogram is see Fig. 3, analytical data is in table 3.
Table 3
| Peak number | Retention time (min) | Peak area | Peak height | Content (%) |
| 1 | 8.227 | 79195 | 11766 | 1.026 |
| 2 | 9.662 | 52806 | 8591 | 0.684 |
| 3 | 12.953 | 66956 | 12106 | 0.868 |
| 4 | 13.137 | 7499650 | 1123434 | 97.206 |
| 5 | 14.074 | 16630 | 2706 | 0.216 |
| Amount to | 7715238 | 1158603 | 100.000 |
2) alkaline hydrolysis acidification reaction
Gained etherificate intermediate trichloropyridine fluoroacetic acid methyl esters and 250ml water are added in 500ml four-hole bottle, add sodium lauryl sulphate 0.3g and Tetrabutyl amonium bromide 0.5g again, be warming up to 75 DEG C, drip 25wt% potassium hydroxide aqueous solution 72g, drip Bi Baowen 1h, detect starting material left 0.2%, drip 54g sulfuric acid (massfraction 30wt%), detect pH=3, be cooled to 25 DEG C, suction filtration, light yellow particulate solid 97.1g is obtained after draining, in constant temperature convection oven, 80 DEG C of dry 3h obtain light yellow granular TRICLOPYR ACID solid 75.2g, HPLC purity 99.5%, two step total recoverys 94.9%, product HPLC spectrogram is see Fig. 4, analytical data is in table 4.
Table 4
As can be seen from table 1-table 4, etherificate products obtained therefrom HPLC purity > 96% of the present invention, alkaline hydrolysis acidifying products obtained therefrom HPLC purity > 99%.
Claims (10)
1. a production method for TRICLOPYR ACID, comprises the following steps:
1) etherification reaction
Stir in polar organic solvent and add trichloro pyridyl sodium alcoholate and methyl chloroacetate, be heated to 50 ~ 100 DEG C, insulation reaction 2 ~ 4h, after reaction terminates, steam clean polar organic solvent, add water and stir 30min, be cooled to 20 ~ 35 DEG C, filter, obtain intermediate trichloropyridine fluoroacetic acid methyl esters;
2) alkaline hydrolysis, acidifying
To step 1) add water in the intermediate trichloropyridine fluoroacetic acid methyl esters that obtains, dispersion agent and phase-transfer catalyst, be heated to 60 ~ 100 DEG C, add alkali again, insulation reaction 0.5 ~ 3h after reinforced, after reaction terminates, acidifying, regulate pH to 2 ~ 4, be cooled to 20 ~ 45 DEG C, crystallization, filter, obtain TRICLOPYR ACID; Wherein, the water added is 2 ~ 10:1, ml/g with the volume mass ratio of trichloropyridine fluoroacetic acid methyl esters;
Reaction formula is:
2. the production method of TRICLOPYR ACID according to claim 1, is characterized in that, step 2) described dispersion agent is selected from least one in polyoxyethylene glycol series, sodium lauryl sulphate, trisodium phosphate, many sodium-metaphosphates and linolic acid sodium.
3. the production method of TRICLOPYR ACID according to claim 1 and 2, is characterized in that, step 2) consumption of described dispersion agent is 0.1 ~ 1wt.% of trichloropyridine fluoroacetic acid methyl esters.
4. the production method of TRICLOPYR ACID according to claim 1, is characterized in that, step 2) described in phase-transfer catalyst be that crown ether-like is or/and quaternary ammonium salt-type phase transfer catalyst.
5. the production method of TRICLOPYR ACID according to claim 4, it is characterized in that, described crown ether-like phase transfer catalysts is selected from least one in 18 hats 6 and 15 hats 5, and described quaternary ammonium salt-type phase transfer catalyst is selected from least one in benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
6. the production method of the TRICLOPYR ACID according to any one of claim 1-5, is characterized in that, step 2) described in the consumption of phase-transfer catalyst be 0.2 ~ 2wt.% of trichloropyridine fluoroacetic acid methyl esters.
7. the production method of TRICLOPYR ACID according to claim 1, it is characterized in that, step 1) described in polar organic solvent be selected from N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, N-Methyl pyrrolidone and 1, the at least one of 3-dimethyl-2-imidazolinone, described polar organic solvent and the volume ratio of trichloro pyridyl sodium alcoholate are 1 ~ 10:1.
8. the production method of TRICLOPYR ACID according to claim 1, is characterized in that, step 1) described in trichloro pyridyl sodium alcoholate and the mol ratio of methyl chloroacetate be 1:1.0 ~ 1.3.
9. the production method of TRICLOPYR ACID according to claim 1, it is characterized in that, step 2) in alkali be mineral alkali, be selected from least one in sodium-acetate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood and cesium carbonate, the mol ratio of described alkali and trichloropyridine fluoroacetic acid methyl esters is 1.0 ~ 2.0:1.
10. the production method of TRICLOPYR ACID according to claim 1, it is characterized in that, step 2) in utilize mineral acid to carry out acidifying, described mineral acid is selected from least one in hydrochloric acid, sulfuric acid, phosphoric acid, chloric acid, sulfurous acid, phosphorous acid, chlorous acid, nitrous acid, hydroiodic acid HI and Hydrogen bromide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325044A (en) * | 2017-07-08 | 2017-11-07 | 杨子辉 | A kind of preparation method of herbicide triclopyr butoxyethyl ester |
| CN109232401A (en) * | 2018-11-13 | 2019-01-18 | 湖南比德生化科技股份有限公司 | A kind of method of trichlopyr ester distillation residual liquid recycling treatment |
| CN111217720A (en) * | 2018-11-23 | 2020-06-02 | 烟台安诺其精细化工有限公司 | Synthetic method of 3- (N, N-dimethoxycarbonylmethyl) amino-4-methoxyacetanilide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325044A (en) * | 2017-07-08 | 2017-11-07 | 杨子辉 | A kind of preparation method of herbicide triclopyr butoxyethyl ester |
| CN109232401A (en) * | 2018-11-13 | 2019-01-18 | 湖南比德生化科技股份有限公司 | A kind of method of trichlopyr ester distillation residual liquid recycling treatment |
| CN111217720A (en) * | 2018-11-23 | 2020-06-02 | 烟台安诺其精细化工有限公司 | Synthetic method of 3- (N, N-dimethoxycarbonylmethyl) amino-4-methoxyacetanilide |
| CN111217720B (en) * | 2018-11-23 | 2022-09-02 | 烟台安诺其精细化工有限公司 | Synthetic method of 3- (N, N-dimethoxycarbonylmethyl) amino-4-methoxyacetanilide |
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