CN103936630B - The preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane - Google Patents
The preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane Download PDFInfo
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- -1 chloroformyl [4-(trifluoromethoxy) phenyl] Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 20
- MFEIKNAMYARHGK-UHFFFAOYSA-N n,2,3-trifluoro-n-methoxyaniline Chemical compound CON(F)C1=CC=CC(F)=C1F MFEIKNAMYARHGK-UHFFFAOYSA-N 0.000 claims abstract description 13
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 61
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 17
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 6
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000005907 Indoxacarb Substances 0.000 abstract description 8
- VBCVPMMZEGZULK-NRFANRHFSA-N indoxacarb Chemical compound C([C@@]1(OC2)C(=O)OC)C3=CC(Cl)=CC=C3C1=NN2C(=O)N(C(=O)OC)C1=CC=C(OC(F)(F)F)C=C1 VBCVPMMZEGZULK-NRFANRHFSA-N 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000012312 sodium hydride Substances 0.000 abstract description 5
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002917 insecticide Substances 0.000 abstract description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 239000012852 risk material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 241000238631 Hexapoda Species 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 0 *c(cc1)ccc1OC(F)(F)F Chemical compound *c(cc1)ccc1OC(F)(F)F 0.000 description 2
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical compound N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- 108091006146 Channels Proteins 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- XUJFOSLZQITUOI-UHFFFAOYSA-N Nc(cc1)ccc1OC(F)(F)F Chemical compound Nc(cc1)ccc1OC(F)(F)F XUJFOSLZQITUOI-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 108010052164 Sodium Channels Proteins 0.000 description 1
- 102000018674 Sodium Channels Human genes 0.000 description 1
- 241000256247 Spodoptera exigua Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940126121 sodium channel inhibitor Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Indole Compounds (AREA)
Abstract
The present invention relates to the preparation method of a class pharmaceutical intermediate, the preparation method of the intermediate being specifically related to agricultural insecticide indoxacarb chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane.The present invention mainly adopts to trifluoro-methoxyaniline, methyl-chloroformate, solid phosgene as reactant, and the mixed alkali higher by safety in utilization prepares this material.Adopt the present invention, change in prior art the drawback needing to adopt high risk material sodium hydride, operating environment is gentle, and mixed alkali technique improves reactivity, and the ability capturing hydrogen improves, thus accelerate speed of response, reduce the residual of raw material, decrease unnecessary side reaction, reach Reaction time shorten, improve the effect of yield and product content, greatly being better than now commonly using preparation technology, having laid a good foundation for preparing high-purity indoxacarb.
Description
Technical field
The present invention relates to the preparation method of a class pharmaceutical intermediate, the preparation method of the intermediate being specifically related to agricultural insecticide indoxacarb chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane.
Background technology
Indoxacarb is du pont company's exploitation oxadiazine insecticides in 1992, its general indoxacarb by name, chemical name: (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl) [4-(trifluoromethoxy)-phenyl] is amino] carbonyl] indeno [1,2-e] [1,3,4] oxadiazine-4a (3H)-carboxylate methyl esters, trade(brand)name has ammate(homerun 30% water dispersant), vatar(safety hit 15% suspension agent) etc.Its mechanism of action is sodium channel inhibitor, mainly blocks the sodium channel in insect neurocyte, causes target pest to coordinate paralysis, finally death.Medicament enters polypide by tagging and ingesting, and the behavior of insect changes rapidly, causes insect to stop rapidly ingesting, thus fabulous protects Target crops.This kind insecticidal spectrum is wide, and instant effect, has excellent preventive effect to resistant insects such as beet armyworm, small cabbage moth, bollworms.Test shows that indoxacarb and other sterilant are without cross resistance.The typical case of this sterilant Shi oxadiazine insecticides is also first business-like sodium salt carrier frequency channel break type sterilant.
Chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane is an intermediate of indoxacarb, and sterling is white crystal.Existing production technique is generally generate 4-Trifluoromethoxyphen-l-amino formate compounds by reacting trifluoro-methoxyaniline and chloro-formic ester compounds, then sodium hydride 0-5 DEG C of reaction is added, again this reaction solution is added dropwise in solid phosgene, is obtained by reacting chloroformyl [4-(trifluoromethoxy) phenyl] amino formate compounds.Wherein sodium hydride chemical reactivity is very high, energy spontaneous combustion in damp atmosphere, be heated or contact with moisture, acids and namely release heat and hydrogen and cause and burn and explode, with oxygenant, kickback can occur, cause burning or blast, meet moisture and moisture generation oxyhydroxide, corrodibility is very strong, and danger is comparatively large, and raw material molar ratio is larger, reaction time is long, and cost is higher.
Summary of the invention
For the problems referred to above; the present invention proposes the preparation method of a kind of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane; the mixed alkali that use cost is lower, security is stronger instead of harmful influence sodium hydride; simultaneously by the corresponding reaction conditions of adjustment; shorten reaction time, reduce molar ratio, thus reduce cost.
The equation of its reaction is as follows:
Its concrete steps are:
(1) will mix with toluene trifluoro-methoxyaniline, sodium hydroxide, and be cooled to-10-10 DEG C, and drip methyl-chloroformate wherein;
(2) dropwise, be warming up to 30-40 DEG C, insulation reaction 1.5-5h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add mixed alkali, heat up, point cut, to 106-110 DEG C, reacts 2.5-5h;
(4) triphosgene being dissolved in toluene and controlling its temperature is 0-10 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 0-15 DEG C, dropwise, insulation reaction 1-2h;
(6) naturally rise to room temperature, washing, extraction, dry, steaming desolventizes;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product.
First, will mix with toluene trifluoro-methoxyaniline, sodium hydroxide, and then drip methyl-chloroformate wherein and react.In order to ensure to react completely to trifluoro-methoxyaniline, reduce the waste of high cost raw material, to trifluoro-methoxyaniline: sodium hydroxide: methyl-chloroformate=1:1.5-3:1.8-2.5.Decompose in order to avoid methyl-chloroformate and conveniently control reaction process, avoid reaction too violent, dropping temperature is-10-10 DEG C, time for adding 1-5h.
Dropwise, be warming up to 30-40 DEG C, make it continue to react 1.5-5h, preferred 3-5h, liquid phase is followed the tracks of and is got final product stopped reaction to trifluoro-methoxyaniline mass percentage <1%, and then washing is except the salt generated in dereaction.Because next step reaction can add alkali, if there is a large amount of water will inevitably make alkali inactivation, main reaction cannot be carried out, and in order to avoid subsequent reactions is affected, carries out reflux water-dividing until anhydrously to separate after washing to whole reaction system.
In the reaction solution after above-mentioned point of water, add mixed alkali, replace the hydrogen on amine.Contriver is through studying discovery for a long period of time, described mixed alkali adopts the mixture effect of potassium methylate and potassium hydroxide better, potassium methylate is main activating substance, potassium hydroxide enhances the alkalescence of potassium methylate, the two ability strengthening replacement hydrogen used in combination, with the molar ratio computing of pure substance, potassium methylate: potassium hydroxide=3-5:1.Because mixed alkali is unstable, very easily easily deliquescence, causes reaction not exclusively, therefore controls trifluoro-methoxyaniline: be 1:2-5 with the mol ratio of mixed alkali.In this process, can produce the low cut materials such as methyl alcohol, contribute to the carrying out reacted after being isolated out, so the present invention adopts normal pressure fractionation to 106-110 DEG C, make the solvent in whole system be all almost that toluene reacts, the reaction times is 2.5-5h.
Triphosgene high temperature easily decomposes, and discharges a large amount of irritating smell, therefore to control its temperature when being dissolved in toluene be 0-10 DEG C.In order to ensure to react completely, avoid causing wastage of material and increasing post-processing difficulty, trifluoro-methoxyaniline and triphosgene mol ratio 1:3-5.In order to control reaction process, reduce the decomposition of triphosgene, when being added drop-wise in step (4) gained solution by step (3) gained reaction solution, control temperature of reaction is 0-15 DEG C simultaneously; This dropping order can not be exchanged, and drips can produce a large amount of phosgene two replacement by product because anti-.
Rise to room temperature after being added dropwise to complete, washing, extraction, dry, steaming desolventizes, and adds sherwood oil wherein, is scatter by product, can obtain white crystals, be product.
In sum, the present invention is stronger by changing security, more environmental protection, more cheap mixed alkali to replace in existing technique harmful influence sodium hydride to prepare target product, adopt in this way, change in prior art the drawback using high-risk raw material, operating environment is gentle, and mixed alkali technique improves reactivity, the ability capturing hydrogen improves, thus accelerate speed of response, reduce the residual of raw material, decrease unnecessary side reaction, reach Reaction time shorten, improve the effect of yield and product content, reaction time obviously shortens, energy consumption obviously reduces, and reduce production cost, chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane content of final acquisition is all more than 95%, yield reaches more than 92%, have laid a good foundation for preparing high-purity indoxacarb, greatly be better than now commonly using preparation technology.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, those skilled in the art can be made more fully to understand the present invention, but do not limit the present invention in any way.
Embodiment 1
(1) add 0.3mol to trifluoro-methoxyaniline, 0.45mol sodium hydroxide, toluene in the clean anhydrous reaction flask of 1000ml, be cooled to 10 DEG C, drip 0.63mol methyl-chloroformate, control 3.5h drips off;
(2) dropwise, be slowly warming up to 40 DEG C, insulation reaction 3h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add 1.05mol potassium methylate and potassium hydroxide mixes alkali (wherein, with the molar ratio computing of pure substance, potassium methylate: potassium hydroxide=4:1), heat up, point cut to 110 DEG C, reaction 3.5h;
(4) be dissolved in toluene by solid for 0.9mol tri-light, temperature controls at 10 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 15 DEG C, dropwise, insulation reaction 1h;
(6) naturally rise to room temperature, washing, extraction, organic over anhydrous dried over mgso, steaming desolventizes;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product, content 96%, yield 93%.
Embodiment 2
(1) add 0.3mol to trifluoro-methoxyaniline, 0.9mol sodium hydroxide, toluene in the clean anhydrous reaction flask of 1000ml, be cooled to-10 DEG C, drip 0.75mol methyl-chloroformate, control 3.5h drips off;
(2) dropwise, be slowly warming up to 30 DEG C, insulation reaction 5h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add 0.6mol potassium methylate and potassium hydroxide mixes alkali (wherein, with the molar ratio computing of pure substance, potassium methylate: potassium hydroxide=3:1), heat up, point cut to 106 DEG C, reaction 2.5h;
(4) be dissolved in toluene by solid for 1.2mol tri-light, temperature controls at 0 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 0 DEG C, dropwise, insulation reaction 2h;
(6) naturally rise to room temperature, washing, extraction, organic over anhydrous dried over mgso, steam except molten;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product, content 97%, yield 95%.
Embodiment 3
(1) add 0.3mol to trifluoro-methoxyaniline, 0.6mol sodium hydroxide, toluene in the clean anhydrous reaction flask of 1000ml, be cooled to 0 DEG C, drip 0.54mol methyl-chloroformate, control 3.5h drips off;
(2) dropwise, be slowly warming up to 35 DEG C, insulation reaction 1.5h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add 1.5mol potassium methylate and potassium hydroxide mixes alkali (wherein, with the molar ratio computing of pure substance, potassium methylate: potassium hydroxide=4:1), heat up, point cut to 108 DEG C, reaction 5h;
(4) be dissolved in toluene by solid for 15mol tri-light, temperature controls at 5 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 5 DEG C, dropwise, insulation reaction 1.5h;
(6) naturally rise to room temperature, washing, extraction, organic over anhydrous dried over mgso, steaming desolventizes;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product, content 96%, yield 93.8%.
Embodiment 4
(1) add 900mol to trifluoro-methoxyaniline, 2.25kmol sodium hydroxide, toluene in the clean anhydrous reaction flask of 3000L, be cooled to 5 DEG C, drip 1.98kmol methyl-chloroformate, control 3.5h drips off;
(2) dropwise, be slowly warming up to 33 DEG C, insulation reaction 3.2h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add 2.8kmol potassium methylate and potassium hydroxide mixes alkali (wherein, with the molar ratio computing of pure substance, potassium methylate: potassium hydroxide=3:1), heat up, point cut to 110 DEG C, reaction 4.5h;
(4) be dissolved in toluene by solid for 4.05kmol tri-light, temperature controls at 2 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 10 DEG C, dropwise, insulation reaction 1.2h;
(6) naturally rise to room temperature, washing, extraction, organic over anhydrous dried over mgso, steam except molten;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product, content 95%, yield 96.5%.
Embodiment 5
(1) add 900mol to trifluoro-methoxyaniline, 2.43kmol sodium hydroxide, toluene in the clean anhydrous reaction flask of 3000L, be cooled to-5 DEG C, drip 1.71kmol methyl-chloroformate, control 3.5h drips off;
(2) dropwise, be slowly warming up to 37 DEG C, insulation reaction 4h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add 3.6kmol potassium methylate and potassium hydroxide mixes alkali (wherein, with the molar ratio computing of pure substance, potassium methylate: potassium hydroxide=5:1), heat up, point cut to 107 DEG C, reaction 4h;
(4) be dissolved in toluene by solid for 3.15kmol tri-light, temperature controls at 8 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 15 DEG C, dropwise, insulation reaction 1.7h;
(6) naturally rise to room temperature, washing, extraction, organic over anhydrous dried over mgso, steaming desolventizes;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product, content 96.5%, yield 94.5%.
Claims (4)
1. the preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane, is characterized in that: its concrete steps are:
(1) will mix with toluene trifluoro-methoxyaniline, sodium hydroxide, and be cooled to-10-10 DEG C, and drip methyl-chloroformate wherein;
(2) dropwise, be warming up to 30-40 DEG C, insulation reaction 1.5-5h, washing, reflux water-dividing separates to anhydrous;
(3) in step (2) gained reaction solution, add mixed alkali, heat up, point cut, to 106-110 DEG C, reacts 2.5-5h;
(4) triphosgene being dissolved in toluene and controlling its temperature is 0-10 DEG C;
(5) step (3) gained reaction solution is added drop-wise in step (4) gained solution, and to control temperature of reaction be 0-15 DEG C, dropwise, insulation reaction 1-2h;
(6) naturally rise to room temperature, washing, extraction, dry, steaming desolventizes;
(7) in step (6) products obtained therefrom, add sherwood oil, separate out white crystals, namely suction filtration obtains product;
Described mixed alkali is potassium methylate and potassium hydroxide mixed base, with the molar ratio computing of pure substance, and potassium methylate: potassium hydroxide=3-5:1.
2. the preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane according to claim 1, it is characterized in that: with molar ratio computing, to trifluoro-methoxyaniline: sodium hydroxide: methyl-chloroformate: mixed alkali: triphosgene=1:1.5-3:1.8-2.5:2-5:3-5.
3. the preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane according to claim 1, is characterized in that: in step (1), time for adding is 1-5h.
4. the preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane according to claim 1, is characterized in that: in step (2), soaking time is 3-5h.
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| CN107986991A (en) * | 2017-12-18 | 2018-05-04 | 湖南国发精细化工科技有限公司 | The synthetic method of N- chloroformyls-N [(4- trifluoromethoxies) phenyl] methyl carbamate |
| CN109535036B (en) * | 2018-12-26 | 2021-05-25 | 山东华阳农药化工集团有限公司 | Synthetic method of indoxacarb intermediate methyl chloroformyl [4- (trifluoromethoxy) phenyl ] carbamate |
| CN109704994A (en) * | 2018-12-26 | 2019-05-03 | 山东华阳农药化工集团有限公司 | A kind of improved method synthesizing indoxacarb intermediate chloroformyl [4- (trifluoromethoxy) phenyl] methyl carbamate |
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| CN102219712A (en) * | 2011-04-29 | 2011-10-19 | 南开大学 | Synthetic method of methyl-4-(trifluoromethoxy) phenyl carbamate |
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| Title |
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| 茚虫威合成工艺研究;董坤;《中国农药》;20131015;第41页第2.5部分 * |
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