CN103965124A - Synthetic method for triazoline-ketone - Google Patents
Synthetic method for triazoline-ketone Download PDFInfo
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- CN103965124A CN103965124A CN201410178956.0A CN201410178956A CN103965124A CN 103965124 A CN103965124 A CN 103965124A CN 201410178956 A CN201410178956 A CN 201410178956A CN 103965124 A CN103965124 A CN 103965124A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
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Abstract
The invention relates to a synthetic method for triazoline-ketone and relates to the field of ketone synthetic production technology. The synthetic method comprises the following steps in sequence: a. synthesizing phenylhydrazine; b. synthesizing the triazoline-ketone; c. chloridizing; d. fluorating. The synthetic method is characterized in that the synthesis of the triazoline-ketone specifically comprises the following steps: (1) putting 79 parts of the phenylhydrazine by weight in a 3 # kettle, pumping 100 parts of tertiary butanol by weight, and pumping 70 parts of acetaldehyde and 45 parts of tertiary butanol by weight in an acetaldehyde metering tank; (2) putting 60 parts of sodium cyanate and 83 parts of water by weight in the 3 # kettle; (3) separating the water below; (4) starting to stir and pumping 320 parts of sodium hypochlorite by weight in a sodium hypochlorite metering tank; (5) separating the water below; (6) adding 200 parts of water by weight in the 3 # kettle; (7) adding 200 parts of water by weight in the 3 # kettle for cooling and discharging. According to the invention, the reaction condition is mild; by adopting the one-pot method, intermediate products don't need to be separated and can be directly synthesized, so that the operation is simple, the yield is high, and the reaction temperature is moderate.
Description
Technical field:
The present invention relates to containing ketone synthetic production technical field, specifically a kind of synthetic method of Triazolinones.
Background technology:
1-(the chloro-2-fluorophenyl of 4-)-3-methyl-4-difluoromethyl-1,2,4-triazoline-5-ketone is the one of Triazolinones, is the synthetic important intermediate of highy potent herbicide carfentrazoneethyl, in the production of weedicide, has a wide range of applications.Existing this Triazolinones mainly contains low temperature fluorate method and two kinds of synthesis modes of high-temperature fluorination method, but pure in some drawbacks in existing synthetic method, in the building-up process of existing intermediate phenylhydrazine, adopt the sub-reduction of tin protochloride, need a large amount of hydrochloric acid, it is also cumbersome reclaiming tin protochloride.Taking phenylhydrazine as raw material, generate hydrazone, then 1-(2-fluorophenyl)-3-methyl isophthalic acid while carrying out synthetic intermediate, 2,4-triazoline-5-ketone, need to adopt two reactors, and intermediate product need to separate, complex operation, yield is low.The trimethyl carbinol recovery problem that reaction is reclaimed, the trimethyl carbinol that reaction is reclaimed, because containing superoxide, can not directly be used, and processes inconvenient.In chlorination reaction, conventional solvent cannot carry out chlorination as chloro thing solvent, and reaction yield is very low.
Summary of the invention:
Technical problem to be solved by this invention is to provide a kind of intermediate 1-(2-fluorophenyl)-3-methyl isophthalic acid, a reactor of the synthetic employing of 2,4-triazoline-5-ketone, intermediate product is without separation, simple to operate, the synthetic method of the Triazolinones that yield is high.
The technical problem solving adopts following technical scheme:
A synthetic method for Triazolinones, comprises the following steps successively: a, phenylhydrazine synthetic, and b, Triazolinones synthetic, c, chlorination, d, fluoridize, and it is characterized in that: the synthetic of described Triazolinones specifically comprises:
The synthetic of described Triazolinones specifically comprises:
(1), in 3# still, drop into phenylhydrazine 79 weight parts, the suction trimethyl carbinol 100 weight parts, open and stir cooling, simultaneously to acetaldehyde test tank suction 70 weight part acetaldehyde and the 45 weight part trimethyl carbinols, when approximately 25 DEG C of still temperature, drip the mixing solutions of the trimethyl carbinol of acetaldehyde and extraction, keep temperature to add for 0.5 hour, continue holding temperature 0.5 hour;
(2), drop into Zassol 60 weight parts, water 83 weight parts in 3# still, 5 DEG C of insulations 7 hours;
(3), leave standstill 0.5 hour, separate lower layer of water;
(4), open and stir, open the cooling of chuck refrigerated water, simultaneously to clorox test tank suction clorox 320 weight parts, 15 DEG C drip clorox, control temperature below 20 DEG C, within approximately 5 hours, add, and continue insulation 3 hours;
(5), leave standstill 0.5 hour, separate lower layer of water;
(6), to 200 weight parts that add water in 3# still, decompression precipitation ,-0.095MPa, 60 DEG C of end;
(7), again to the 200 weight parts coolings that add water in 3# still, be cooled to 30 DEG C, discharging, discharging obtains 1-(2-fluorophenyl)-3-methyl isophthalic acid, 2,4-triazoline-5-ketone.
The synthetic of described phenylhydrazine comprises the following steps:
(1), in 2# still, drop into hydrochloric acid 153 weight parts, inject 306 weight parts waters to water measuring tank simultaneously, take out 70 weight part aniline to aniline test tank, water is put into 2# still, within approximately 0.5 hour, add, continue to be cooled to 10 DEG C, starting to drip 50 weight part concentration is 30% sodium nitrite solution, approximately 1 hour time, 10 DEG C of left and right of temperature control, reaction finishes reaction solution to squeeze into test tank;
(2), in 1# still, drop into sodium bisulfite 125 weight parts, inject 227.5 weight parts waters to water measuring tank simultaneously, water is put into still, open to stir and be cooled to 10 DEG C, take out ammoniacal liquor 60 weight parts to ammoniacal liquor test tank, drip ammoniacal liquor, temperature control is below 30 DEG C, approximately 0.5 hour, continue to be cooled to 5 DEG C;
(3), drip diazonium salt solution to 1# still, temperature control is below 20 DEG C, approximately 1 hour time, regulates PH=8-10;
(4), take out 204 weight part hydrochloric acid to hydrochloric acid test tank, while being warming up to 40 DEG C to 1# still, open tail gas absorbing system, drip hydrochloric acid, within approximately 40 minutes, add, be warming up to 40-45 DEG C, be incubated 2 hours;
(5), 1# still reaction finishes, cooling, takes out 233 weight part ammoniacal liquor to ammoniacal liquor test tank, drips ammoniacal liquor, temperature control, below 50 DEG C, adds for approximately 1 hour, regulates PH=4-5, is cooled to 35 DEG C, discharging, is phenylhydrazine.
Described chlorination comprises the following steps:
(1), check system resistance to air loss and be ready to gas defence articles for use;
(2), drop into triazolone 120 weight parts, acetonitrile 360 weight parts to 4# reactor, open and stir, pass into steam to chuck and be warming up to 37 DEG C;
(3), pass into chlorine 100 weight parts, by 40 DEG C of recirculated water control temperature of reaction, speed DEG C is 6 weight part/10 minute, 90 minutes logical finishing;
(4), insulation 2 hours;
(5), be successively cooled to 15 DEG C with recirculated water and refrigerated water, discharging, use totally 80 weight part acetonitrile washing leaching cakes, send oven dry, obtain 1-(the chloro-2-fluorophenyl of 4-)-3-methyl isophthalic acid, 2,4-triazoline-5-ketone.
Described fluoridizing comprises the following steps:
(1), check system resistance to air loss;
(2), drop into chlorination 75 weight parts, salt of wormwood 40 weight parts, dimethyl formamide 750 weight parts to 5# reactor, open and stir, pass into steam to chuck and heat up;
(3), pass into difluorochloromethane 75 weight parts, the chemical formula of difluorochloromethane is reduced to F22 temperature 115 DEG C of left and right, approximately 1.5 hours time, is cooled to 80 DEG C after maintaining 0.5 hour;
(4), suction filtration 50 DEG C time, filter cake washs with dimethyl formamide, filtrate is sent 6# precipitation still;
(5), ethanol suction alcohol meter measuring tank, negative pressure precipitation under-0.095MPa, 100-120 DEG C has taken off, and with circulating water cooling to 80 DEG C, adds ethanol, is warming up to 70 DEG C, stops stirring refrigerated water cooling;
(6), suction filtration 0 DEG C time, obtain final product 1-(the chloro-2-fluorophenyl of 4-)-3-methyl-4-difluoromethyl-1,2,4-triazoline-5-ketone.
Described adjusting PH regulates with acid or ammoniacal liquor by passing into.
After the building-up reactions of described Triazolinones, the trimethyl carbinol is reclaimed, and the trimethyl carbinol after reclaiming is carried out to alkaline purification.
A, phenylhydrazine synthetic, b, Triazolinones synthetic, c, chlorination, d, the chemical equation of fluoridizing are:
Synthesizing of phenylhydrazine
Triazolinones is synthetic
Chlorination
Fluoridize
The invention has the beneficial effects as follows:
1, in the building-up process of hydrazine, adopting sodium bisulfite is reductive agent, and reaction process is easily controlled, and reduce the conventional tin protochloride Asia that adopts, and needs a large amount of hydrochloric acid, and it is also cumbersome reclaiming tin protochloride.
2, react with acetaldehyde with hydrazine, generate hydrazone, be reacted into ring with Zassol, reaction conditions gentleness adopts one kettle way simultaneously, and intermediate product does not need to separate, and directly carries out next step and synthesizes, and simple to operate, yield is high, and temperature of reaction is moderate.
3, the trimethyl carbinol recovery problem that reaction is reclaimed, the trimethyl carbinol that reaction is reclaimed, because containing superoxide, can not directly be used, and needs to process, and the present invention adopts alkali treatment method, has effectively solved corresponding problem.
4, in chlorination reaction, conventional solvent cannot carry out chlorination as chloro thing solvent, and it is solvent that the present invention adopts acetonitrile, effectively raises reaction yield, reclaims acetonitrile simultaneously and applies mechanically.
Embodiment:
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with specific examples, further set forth the present invention.
A synthetic method for Triazolinones, comprises the following steps successively: a, phenylhydrazine synthetic, and b, Triazolinones synthetic, c, chlorination, d, fluoridize;
The synthetic of Triazolinones specifically comprises:
(1), in 3#2000L still, drop into phenylhydrazine 79kg, suction trimethyl carbinol 100kg, open and stir cooling, simultaneously to acetaldehyde test tank suction 70kg acetaldehyde and the 45kg trimethyl carbinol, when approximately 25 DEG C of still temperature, drip the mixing solutions of the trimethyl carbinol of acetaldehyde and extraction, keep temperature to add for 0.5 hour, continue holding temperature 0.5 hour, it is qualified that sampling gas spectrum is surveyed transformation efficiency 99%;
(2), in 3#2000L still, drop into Zassol 60 weight parts, water 83 weight parts, 5 DEG C of insulations 7 hours, it is qualified that sampling liquid spectrum is surveyed transformation efficiency 99%;
(3), leave standstill 0.5 hour, separate lower layer of water;
(4), open and stir, open the cooling of chuck refrigerated water, simultaneously to clorox test tank suction clorox 320kg, 15 DEG C drip clorox, control temperature below 20 DEG C, within approximately 5 hours, add, continue insulation 3 hours, it is qualified that sampling liquid spectrum is surveyed transformation efficiency 97%;
(5), leave standstill 0.5 hour, separate lower layer of water;
(6), to the 200kg that adds water in 3#2000L still, decompression precipitation ,-0.095MPa, 60 DEG C of end;
(7), again to the 200kg cooling that adds water in 3#2000L still, be cooled to 30 DEG C, discharging.
The synthetic of phenylhydrazine comprises the following steps:
(1), in 2#1000L still, drop into hydrochloric acid 153kg, inject 306L water to water measuring tank simultaneously, take out 70kg aniline to aniline test tank, water is put into 2#1000L still, within approximately 0.5 hour, add, continue to be cooled to 10 DEG C, starting to drip 50kg concentration is 30% sodium nitrite solution, approximately 1 hour time, 10 DEG C of left and right of temperature control, reaction finishes reaction solution to squeeze into test tank;
(2), in 1#2000L still, drop into sodium bisulfite 125kg, inject 227.5L part water to water measuring tank simultaneously, water is put into still, open stirring and be cooled to 10 DEG C, take out ammoniacal liquor 60kg to ammoniacal liquor test tank, drip ammoniacal liquor, temperature control, below 30 DEG C, approximately 0.5 hour, continues to be cooled to 5 DEG C;
(3), drip diazonium salt solution to 1#2000L still, temperature control is below 20 DEG C, approximately 1 hour time, regulates PH=9;
(4), take out 204kg hydrochloric acid to hydrochloric acid test tank, while being warming up to 40 DEG C to 1#2000L still, open tail gas absorbing system, drip hydrochloric acid, within approximately 40 minutes, add, be warming up to 42 DEG C, be incubated 2 hours;
(5), 1#2000L still reaction finishes, cooling, takes out 233kg ammoniacal liquor to ammoniacal liquor test tank, drips ammoniacal liquor, temperature control, below 50 DEG C, adds for approximately 1 hour, regulates PH=4, is cooled to 35 DEG C, discharging, is phenylhydrazine.
Chlorination comprises the following steps:
(1), check system resistance to air loss and be ready to gas defence articles for use;
(2), drop into triazolone 120kg, acetonitrile 360kg to 4#1000L reactor, open and stir, pass into steam to chuck and be warming up to 37 DEG C;
(3), pass into chlorine 100kg, by 40 DEG C of recirculated water control temperature of reaction, speed DEG C be 6kg/10 minute, 90 minutes logical complete;
(4), insulation 2 hours, sampling survey transformation efficiency 98% qualified;
(5), be successively cooled to 15 DEG C with recirculated water and refrigerated water, discharging, with common 80kg acetonitrile washing leaching cake, send oven dry, dries to obtain 113kg, content 95%.
Fluoridize and comprise the following steps:
(1), check system resistance to air loss;
(2), drop into chlorination 75kg, salt of wormwood 40kg, dimethyl formamide 750kg to 5#1000L reactor, open and stir, pass into steam to chuck and heat up;
(3), pass into difluorochloromethane 75kg, temperature is 115 DEG C of left and right, approximately 1.5 hours time, be cooled to 80 DEG C after maintaining 0.5 hour, it is qualified that transformation efficiency 98.5% is surveyed in sampling;
(4), suction filtration 50 DEG C time, filter cake washs with dimethyl formamide, filtrate is sent 6#500L precipitation still;
(5), ethanol suction alcohol meter measuring tank, negative pressure precipitation under-0.095MPa, 110 DEG C have taken off, and with circulating water cooling to 80 DEG C, add ethanol, are warming up to 70 DEG C, stop stirring refrigerated water cooling;
(6), suction filtration 0 DEG C time, dry 57kg, content 95%.
Regulate PH to regulate with acid or ammoniacal liquor by passing into.
After the building-up reactions of Triazolinones, the trimethyl carbinol is reclaimed, and the trimethyl carbinol after reclaiming is carried out to alkaline purification.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. a synthetic method for Triazolinones, comprises the following steps successively: a, phenylhydrazine synthetic, and b, Triazolinones synthetic, c, chlorination, d, fluoridize, and it is characterized in that: the synthetic of described Triazolinones specifically comprises:
(1), in 3# still, drop into phenylhydrazine 79 weight parts, the suction trimethyl carbinol 100 weight parts, open and stir cooling, simultaneously to acetaldehyde test tank suction 70 weight part acetaldehyde and the 45 weight part trimethyl carbinols, when approximately 25 DEG C of still temperature, drip the mixing solutions of the trimethyl carbinol of acetaldehyde and extraction, keep temperature to add for 0.5 hour, continue holding temperature 0.5 hour;
(2), drop into Zassol 60 weight parts, water 83 weight parts in 3# still, 5 DEG C of insulations 7 hours;
(3), leave standstill 0.5 hour, separate lower layer of water;
(4), open and stir, open the cooling of chuck refrigerated water, simultaneously to clorox test tank suction clorox 320 weight parts, 15 DEG C drip clorox, control temperature below 20 DEG C, within approximately 5 hours, add, and continue insulation 3 hours;
(5), leave standstill 0.5 hour, separate lower layer of water;
(6), to 200 weight parts that add water in 3# still, decompression precipitation ,-0.095MPa, 60 DEG C of end;
(7), again to the 200 weight parts coolings that add water in 3# still, be cooled to 30 DEG C, discharging.
2. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: the synthetic of described phenylhydrazine comprises the following steps:
(1), in 2# still, drop into hydrochloric acid 153 weight parts, inject 306 weight parts waters to water measuring tank simultaneously, take out 70 weight part aniline to aniline test tank, water is put into 2# still, within approximately 0.5 hour, add, continue to be cooled to 10 DEG C, starting to drip 50 weight part concentration is 30% sodium nitrite solution, approximately 1 hour time, 10 DEG C of left and right of temperature control, reaction finishes reaction solution to squeeze into test tank;
(2), in 1# still, drop into sodium bisulfite 125 weight parts, inject 227.5 weight parts waters to water measuring tank simultaneously, water is put into still, open to stir and be cooled to 10 DEG C, take out ammoniacal liquor 60 weight parts to ammoniacal liquor test tank, drip ammoniacal liquor, temperature control is below 30 DEG C, approximately 0.5 hour, continue to be cooled to 5 DEG C;
(3), drip diazonium salt solution to 1# still, temperature control is below 20 DEG C, approximately 1 hour time, regulates PH=8-10;
(4), take out 204 weight part hydrochloric acid to hydrochloric acid test tank, while being warming up to 40 DEG C to 1# still, open tail gas absorbing system, drip hydrochloric acid, within approximately 40 minutes, add, be warming up to 40-45 DEG C, be incubated 2 hours;
(5), 1# still reaction finishes, cooling, takes out 233 weight part ammoniacal liquor to ammoniacal liquor test tank, drips ammoniacal liquor, temperature control, below 50 DEG C, adds for approximately 1 hour, regulates PH=4-5, is cooled to 35 DEG C, discharging, is phenylhydrazine.
3. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: described chlorination comprises the following steps:
(1), check system resistance to air loss and be ready to gas defence articles for use;
(2), drop into triazolone 120 weight parts, acetonitrile 360 weight parts to 4# reactor, open and stir, pass into steam to chuck and be warming up to 37 DEG C;
(3), pass into chlorine 100 weight parts, by 40 DEG C of recirculated water control temperature of reaction, speed DEG C is 6 weight part/10 minute, 90 minutes logical finishing;
(4), insulation 2 hours;
(5), be successively cooled to 15 DEG C with recirculated water and refrigerated water, discharging, use totally 80 weight part acetonitrile washing leaching cakes, send oven dry.
4. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: described fluoridizing comprises the following steps:
(1), check system resistance to air loss;
(2), drop into chlorination 75 weight parts, salt of wormwood 40 weight parts, dimethyl formamide 750 weight parts to 5# reactor, open and stir, pass into steam to chuck and heat up;
(3), pass into difluorochloromethane 75 weight parts, temperature is 115 DEG C of left and right, approximately 1.5 hours time, is cooled to 80 DEG C after maintaining 0.5 hour;
(4), suction filtration 50 DEG C time, filter cake washs with dimethyl formamide, filtrate is sent 6# precipitation still;
(5), ethanol suction alcohol meter measuring tank, negative pressure precipitation under-0.095MPa, 100-120 DEG C has taken off, and with circulating water cooling to 80 DEG C, adds ethanol, is warming up to 70 DEG C, stops stirring refrigerated water cooling;
(6), suction filtration 0 DEG C time.
5. the synthetic method of a kind of Triazolinones according to claim 2, is characterized in that: described adjusting PH regulates with acid or ammoniacal liquor by passing into.
6. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: after the building-up reactions of described Triazolinones, the trimethyl carbinol is reclaimed, and the trimethyl carbinol after reclaiming is carried out to alkaline purification.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629015A (en) * | 2017-08-23 | 2018-01-26 | 连云港世杰农化有限公司 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
| CN107698529A (en) * | 2017-08-23 | 2018-02-16 | 连云港世杰农化有限公司 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
| CN113402472A (en) * | 2021-06-16 | 2021-09-17 | 山东潍坊润丰化工股份有限公司 | Synthetic method of sulfentrazone intermediate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041155A (en) * | 1989-04-03 | 1991-08-20 | Fmc Corporation | Herbicidal aryl triazolinones |
| US5756755A (en) * | 1996-08-26 | 1998-05-26 | Fmc Corporation | Difluoromethylation of 4,5-dihydro-1-phenyl-3-methyl-1,2,4-triazol-5(1H)-ones with glymes as solvents |
| CN1067383C (en) * | 1995-12-29 | 2001-06-20 | Fmc有限公司 | Selective chlorination of 1-(2-fluorophenyl)-1,2,4-triazole |
| CN1089748C (en) * | 1995-12-29 | 2002-08-28 | 罗狄亚化学公司 | Method for synthesizing aryl hydrazine through reduction of a diazo compound derivative |
-
2014
- 2014-04-29 CN CN201410178956.0A patent/CN103965124A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041155A (en) * | 1989-04-03 | 1991-08-20 | Fmc Corporation | Herbicidal aryl triazolinones |
| CN1067383C (en) * | 1995-12-29 | 2001-06-20 | Fmc有限公司 | Selective chlorination of 1-(2-fluorophenyl)-1,2,4-triazole |
| CN1089748C (en) * | 1995-12-29 | 2002-08-28 | 罗狄亚化学公司 | Method for synthesizing aryl hydrazine through reduction of a diazo compound derivative |
| US5756755A (en) * | 1996-08-26 | 1998-05-26 | Fmc Corporation | Difluoromethylation of 4,5-dihydro-1-phenyl-3-methyl-1,2,4-triazol-5(1H)-ones with glymes as solvents |
Non-Patent Citations (2)
| Title |
|---|
| LEI WANG，等: "Synthesis, Herbicidal Activities and Comparative Molecular Field Analysis Study of Some Novel Triazolinone Derivatives", 《CHEM BIOL DRUG DES》 * |
| 何普泉，等: "4,5-二氢-3-甲基-1-(4-氯-2-氟苯基) -4-二氟甲基-1,2,4-三唑-5(1H)酮的合成方法", 《安徽化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629015A (en) * | 2017-08-23 | 2018-01-26 | 连云港世杰农化有限公司 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
| CN107698529A (en) * | 2017-08-23 | 2018-02-16 | 连云港世杰农化有限公司 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
| CN113402472A (en) * | 2021-06-16 | 2021-09-17 | 山东潍坊润丰化工股份有限公司 | Synthetic method of sulfentrazone intermediate |
| CN113402472B (en) * | 2021-06-16 | 2022-09-13 | 山东潍坊润丰化工股份有限公司 | Synthetic method of sulfentrazone intermediate |
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Application publication date: 20140806 |