CN1850776A - Method for preparing trinexapac-ethyl - Google Patents
Method for preparing trinexapac-ethyl Download PDFInfo
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- CN1850776A CN1850776A CN 200610050826 CN200610050826A CN1850776A CN 1850776 A CN1850776 A CN 1850776A CN 200610050826 CN200610050826 CN 200610050826 CN 200610050826 A CN200610050826 A CN 200610050826A CN 1850776 A CN1850776 A CN 1850776A
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- ester
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- acetonyl
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- 238000000034 method Methods 0.000 title description 8
- RVKCCVTVZORVGD-UHFFFAOYSA-N trinexapac-ethyl Chemical group O=C1CC(C(=O)OCC)CC(=O)C1=C(O)C1CC1 RVKCCVTVZORVGD-UHFFFAOYSA-N 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims abstract description 11
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- -1 sodium alkoxide Chemical class 0.000 claims description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 9
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010719 annulation reaction Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Natural products OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- PFMUYGVPUBEGSQ-UHFFFAOYSA-N cyclohexane-1,3-dione ethyl formate Chemical compound C(=O)OCC.C1CC(CC(C1)=O)=O PFMUYGVPUBEGSQ-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- TULILRZWOVSTLQ-UHFFFAOYSA-N 2-ethyl-4-oxopentanoic acid Chemical compound CCC(C(O)=O)CC(C)=O TULILRZWOVSTLQ-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical class OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention discloses anti inverse ester preparation method. 2-acetonyl-1, 4 diethyl succiante is high pressure condensed by diethyl maleate and acetone under organic amine condition. Then it cycles to get 3, 5-dioxygen hexahydrobenzoic acid ethyl esterunder sodium alcoholate condition, finally anti inverse ester is got by reacting with ring third formic anhydride under alkali condition. The operation is simple, reaction is wild, material is easy to get, yield is high, product purity is high, and generating cost is reduced, so it is propitious to industrial manufacure.
Description
Technical field
The present invention relates to the anti-preparation method of ester of cyclohexane dicarboxylic acid class efficient plant growth regulator.
Background technology
The existing anti-main preparation methods of ester has: and method one (US 4,693, and 745; JP 59; 163,346) by 3, the 5-resorcylic acid is a starting raw material; obtain 3 through hydro-reduction; 5-cyclohexanedione-1-formic acid obtains 3 through esterification again, 5-cyclohexanedione-1-ethyl formate; itself and the ring third formyl chloride generation acylation reaction are obtained 3-ethoxycarbonyl-5-oxygen hexamethylene-1-enol cyclopropane ester, rearrangement reaction takes place under the DMAP katalysis obtain the anti-ester of target product.(EP 0126713 for method two; US4803268) be to be starting raw material with ethyl maleate and acetone; make 2-acetonyl-butyric acid diethyl ester through addition; cyclic condensation obtains 3 under the condition that sodium ethylate exists then; 5-cyclohexanedione-1-ethyl formate; encircle third formyl chloride and metal cyanides react intermediate cyclopropane carbonyl formonitrile HCN, again with 3, the reaction of 5-cyclohexanedione-1-ethyl formate obtains the anti-ester that falls of target product.
In the method one 3, the 5-resorcylic acid is reduced into 3, and the hydrogen pressure during 5-cyclohexanedione-1-formic acid need reach 95.28atm, and yield is also lower, and needs to use expensive DMAP as rearrangement catalyst, has increased production cost; The metal cyanides severe toxicity is unfavorable for environmental protection in the method two.
Summary of the invention
The anti-method of ester of preparation that the purpose of this invention is to provide a kind of high yield, low cost and constant product quality.
The anti-preparation method of ester of the present invention in turn includes the following steps:
The first step is a raw material with ethyl maleate and acetone, in the presence of organic amine, in autoclave, in 140～160 ℃, condensation gets 2-acetonyl-1 under 5～15atm, 4-diethyl succinate, the mol ratio of ethyl maleate and acetone are 0.1～0.5: 1, and the mol ratio of organic amine and ethyl maleate is 0.1～0.5: 1;
The second step 2-acetonyl-1, the 4-diethyl succinate refluxes into ring and obtains 3 in mass percent concentration is 10～30% sodium alkoxide, 5-dioxy cyclohexyl ethyl formate, sodium alkoxide and 2-acetonyl-1, the mol ratio of 4-diethyl succinate is 1～1.5: 1;
The 3rd step 3,5-dioxy cyclohexyl ethyl formate and cyclopropanecarboxylic acid acid anhydride under alkaline condition, react the anti-ester that falls, 3, the mol ratio of 5-dioxy cyclohexyl ethyl formate and cyclopropanecarboxylic acid acid anhydride is 1: 1～1: 1.5, used alkali and 3, the mol ratio of 5-dioxy cyclohexyl ethyl formate is 1: 1～1: 1.5.
Concrete synthetic route is as follows:
Among the preparation method of the present invention:
The used organic amine of the first step can be dimethylamine, diethylamine, dibutylamine, Trimethylamine 99 or triethylamine, and the pressure of condensation reaction is 5～20atm in autoclave, 10atm the best.
The used sodium alkoxide of the second step annulation can be sodium methylate, sodium ethylate or sodium tert-butoxide.
In the 3rd step 3,5-dioxy cyclohexyl ethyl formate and cyclopropanecarboxylic acid acid anhydride react under alkaline condition, and used alkali can be sodium hydroxide, sodium methylate, sodium ethylate or sodium tert-butoxide.
Preparation provided by the invention is anti-, and to fall the method for ester simple to operate, reaction temperature and, raw material is easy to get, yield is higher, good product purity need only be made with extra care once and just can be reached requirement, production cost can descend significantly, is easy to realize industrialization.Wherein, the first step condensation pressure is 5～20atm, far below the pressure of literature method, the 3rd step did not need 3,5-cyclohexanedione-1-ethyl formate is reacted into ester with ring third formyl chloride earlier, resets again, promptly gets target product and resists ester but directly react under alkaline condition with the cyclopropanecarboxylic acid acid anhydride.
Embodiment
Embodiment 1
1) 2-acetonyl-1, the preparation of 4-diethyl succinate
Ethyl maleate (34.4g, 0.2mol), acetone (95.3g, 1.64mol) and dimethylamine (1.8g, 0.04mol) input 500ml autoclave is heated to 150 ℃, the still internal pressure is 10atm, insulation reaction 21h is cooled to room temperature, and normal pressure is removed underpressure distillation behind the low-boiling-point substance, collect 155～160 ℃ of cut/5mmHg, get the 39.8g weak yellow liquid, yield is 86.5%, and content is more than 99%.
2) 3, the preparation of 5-cyclohexanedione-1-ethyl formate
(10.8g, methanol solution 0.056mol) drip 2-acetonyl-1 to drop into 40ml 28% sodium methylate in the reaction flask, (12g 0.052mol), dropwised the post-heating back flow reaction 5 hours to the 4-diethyl succinate, the reaction solution cooling concentrates and reclaims methyl alcohol, adds 80ml water in resistates, with the removal of impurity of 50ml ethylene dichloride extracting twice, the HCl that aqueous phase adds 80ml 1N uses 50ml ethylene dichloride extracting twice, the organic phase drying again, concentrate, get the 8.2g light yellow viscous liquid.Yield is 85.7%, and content is 93.1%.
3) anti-ester is synthetic
To having reflux condensing tube, thermometer, the ethanolic soln of the sodium ethylate of adding 13.2g 15% in the 250ml round-bottomed flask of agitator, drip 3,5-cyclohexanedione-1-ethyl formate 5.73g (content is by 93.1%, 0.029mol), and reflux 2h, decompression steams ethanol, in remaining solid, add 5.0g (0.032mol) cyclopropanecarboxylic acid acid anhydride, reflux 2.5h, cooling, add cryosel acid then and transfer pH value 1～2, with reaction solution CH
2Cl
2Extraction, the organic phase drying concentrates, and underpressure distillation obtains the anti-5.22g of falling the ester, yield 71.4%, 35 ℃ of fusing points.
Embodiment 2
1) 2-acetonyl-1, the preparation of 4-diethyl succinate
Ethyl maleate (34.4g, 0.2mol), acetone (95.3g, 1.64mol) and Trimethylamine 99 (2.4g, 0.041mol) input 500ml autoclave is heated to 140 ℃, the still internal pressure is 15atm, insulation reaction 18h is cooled to room temperature, and normal pressure is removed underpressure distillation behind the low-boiling-point substance, collect 155～160 ℃ of cut/5mmHg, get the 39.6g weak yellow liquid, yield is 86.1%, and content is more than 99%.
2) 3, the preparation of 5-cyclohexanedione-1-ethyl formate
(25g, ethanolic soln 0.055mol) drip 2-acetonyl-1 to drop into 40ml 15% sodium ethylate in the reaction flask, (12g 0.052mol), dropwised the post-heating back flow reaction 5 hours to the 4-diethyl succinate, the reaction solution cooling concentrates and reclaims ethanol, adds 80ml water in resistates, with the removal of impurity of 50ml ethylene dichloride extracting twice, the HCl that aqueous phase adds 80ml 1N uses 50ml ethylene dichloride extracting twice, the organic phase drying again, concentrate, get the 8.3g light yellow viscous liquid.Yield is 86.7%, and content is more than 93%.
3) anti-ester is synthetic
To having reflux condensing tube, thermometer adds the 20ml dehydrated alcohol in the 250ml round-bottomed flask of agitator, add 1.2g sodium hydroxide again, stirring and dissolving drips 3 then, 5-cyclohexanedione-1-ethyl formate 5.73g (content is by 93%, 0.029mol), and reflux 2h, decompression steams ethanol, in remaining solid, add 5.8g (0.038mol) cyclopropanecarboxylic acid acid anhydride, reflux 2.5h, cooling, add cryosel acid then and transfer pH value 1～2, with reaction solution CH
2Cl
2Extraction, the organic phase drying concentrates, and underpressure distillation obtains the anti-5.27g of falling the ester, yield 72.1%, 35 ℃ of fusing points.
Embodiment 3
1) 2-acetonyl-1, the preparation of 4-diethyl succinate
Ethyl maleate (34.4g, 0.2mol), acetone (95.3g, 1.64mol) and diethylamine (2.9g, 0.04mol) input 500ml autoclave is heated to 160 ℃, the still internal pressure is 6atm, insulation reaction 24h is cooled to room temperature, and normal pressure is removed underpressure distillation behind the low-boiling-point substance, collect 155～160 ℃ of cut/5mmHg, get the 38.9g weak yellow liquid, yield is 84.6%, and content is more than 99%.3, the preparation of 5-cyclohexanedione-1-ethyl formate
Drop into 40ml 10% sodium tert-butoxide (51.8g in the reaction flask, 0.054mol) t-butanol solution, drip 2-acetonyl-1,4-diethyl succinate (12g, 0.052mol), dropwised the post-heating back flow reaction 5 hours, the reaction solution cooling, concentrate and reclaim the trimethyl carbinol, add 80ml water in resistates, with the removal of impurity of 50ml ethylene dichloride extracting twice, aqueous phase adds the HCl of 80ml 1N, use 50ml ethylene dichloride extracting twice again, the organic phase drying concentrates, and gets the 8.5g light yellow viscous liquid, yield is 88.8%, and content is more than 93%.
3) anti-ester is synthetic
To having reflux condensing tube, thermometer, the methanol solution of the sodium methylate of adding 5g 28% in the 250ml round-bottomed flask of agitator, drip 3,5-cyclohexanedione-1-ethyl formate 5.73g (content is by 93.1%, 0.029mol), and reflux 2h, decompression steams ethanol, in remaining solid, add 6.7g (0.0435mol) cyclopropanecarboxylic acid acid anhydride, reflux 2.5h, cooling, add cryosel acid then and transfer pH value 1～2, with reaction solution CH
2Cl
2Extraction, the organic phase drying concentrates, and underpressure distillation obtains the anti-5.37g of falling the ester, yield 73.5%, 35 ℃ of fusing points.
Claims (5)
1. the anti-preparation method of ester in turn includes the following steps:
The first step is a raw material with ethyl maleate and acetone, in the presence of organic amine, in autoclave, in 140～160 ℃, condensation gets 2-acetonyl-1 under 5～20atm, 4-diethyl succinate, the mol ratio of ethyl maleate and acetone are 0.1～0.5: 1, and the mol ratio of organic amine and ethyl maleate is 0.1～0.5: 1;
The second step 2-acetonyl-1, the 4-diethyl succinate refluxes into ring and obtains 3 in mass percent concentration is 10～30% sodium alkoxide, 5-dioxy cyclohexyl ethyl formate, sodium alkoxide and 2-acetonyl-1, the mol ratio of 4-diethyl succinate is 1～1.5: 1;
The 3rd step 3,5-dioxy cyclohexyl ethyl formate and cyclopropanecarboxylic acid acid anhydride under alkaline condition, react the anti-ester that falls, 3, the mol ratio of 5-dioxy cyclohexyl ethyl formate and cyclopropanecarboxylic acid acid anhydride is 1: 1～1: 1.5, used alkali and 3, the mol ratio of 5-dioxy cyclohexyl ethyl formate is 1: 1～1: 1.5.
2. by the described anti-preparation method of ester of claim 1, it is characterized in that the used organic amine of the first step is dimethylamine, diethylamine, dibutylamine, Trimethylamine 99 or triethylamine.
3. by the described anti-preparation method of ester of claim 1, the pressure that it is characterized in that the first step condensation reaction is 10atm.
4. by the described anti-preparation method of ester of claim 1, it is characterized in that the used sodium alkoxide of the second step annulation is sodium methylate, sodium ethylate or sodium tert-butoxide.
5. by the described anti-preparation method of ester of claim 1, it is characterized in that used alkali is sodium hydroxide, sodium methylate, sodium ethylate or sodium tert-butoxide in the 3rd step.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100508264A CN100398508C (en) | 2006-05-19 | 2006-05-19 | Method for preparing trinexapac-ethyl |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100508264A CN100398508C (en) | 2006-05-19 | 2006-05-19 | Method for preparing trinexapac-ethyl |
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| CN1850776A true CN1850776A (en) | 2006-10-25 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101830A (en) * | 2010-12-06 | 2011-06-22 | 张家港田由新材料科技有限公司 | Method for preparing trinexapac-ethyl |
| CN102295563A (en) * | 2011-07-13 | 2011-12-28 | 迈克斯(如东)化工有限公司 | Preparation method of trinexapac-ethyl |
| CN102911058A (en) * | 2012-11-19 | 2013-02-06 | 江苏扬农化工股份有限公司 | Synthetic method of plant growth regulator trinexapac-ethyl intermediate 3-carbethoxy-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate |
| CN105085270A (en) * | 2015-08-19 | 2015-11-25 | 迈克斯(如东)化工有限公司 | Preparation method of trinexapac-ethyl and intermediate thereof |
| CN107162907A (en) * | 2017-05-27 | 2017-09-15 | 安阳全丰生物科技有限公司 | The synthetic method of Prohexadione calcium and TrinexAN_SNacethyl |
| CN110776421A (en) * | 2019-11-29 | 2020-02-11 | 厦门本素药业有限公司 | Preparation method and intermediate of hexahydroquinoline diketone compound |
| CN111972410A (en) * | 2020-09-07 | 2020-11-24 | 安徽省四达农药化工有限公司 | Preparation and application of trinexapac-ethyl emulsion in water |
| CN112441919A (en) * | 2020-12-29 | 2021-03-05 | 江苏傲伦达科技实业股份有限公司 | Improved synthetic method of trinexapac-ethyl |
| CN115073291A (en) * | 2022-06-09 | 2022-09-20 | 鹤壁全丰生物科技有限公司 | Production process for producing intermediate acetonyl diethyl succinate from prohexadione calcium |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59163346A (en) * | 1983-03-07 | 1984-09-14 | Ihara Chem Ind Co Ltd | Preparation of acetonylsuccinic acid ester |
| EP0126713B1 (en) * | 1983-05-18 | 1989-01-18 | Ciba-Geigy Ag | Cyclohexanedione-carboxylic-acid derivatives having a herbicidal and plant growth regulating activity |
| US4803286A (en) * | 1987-08-19 | 1989-02-07 | Merck & Co., Inc. | Amino-2-hydroxypropyloximinoheterocycle α-blockers |
-
2006
- 2006-05-19 CN CNB2006100508264A patent/CN100398508C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101830A (en) * | 2010-12-06 | 2011-06-22 | 张家港田由新材料科技有限公司 | Method for preparing trinexapac-ethyl |
| CN102295563A (en) * | 2011-07-13 | 2011-12-28 | 迈克斯(如东)化工有限公司 | Preparation method of trinexapac-ethyl |
| CN102911058A (en) * | 2012-11-19 | 2013-02-06 | 江苏扬农化工股份有限公司 | Synthetic method of plant growth regulator trinexapac-ethyl intermediate 3-carbethoxy-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate |
| CN102911058B (en) * | 2012-11-19 | 2015-04-08 | 江苏优嘉化学有限公司 | Synthetic method of plant growth regulator trinexapac-ethyl intermediate 3-carbethoxy-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate |
| CN105085270A (en) * | 2015-08-19 | 2015-11-25 | 迈克斯(如东)化工有限公司 | Preparation method of trinexapac-ethyl and intermediate thereof |
| CN105085270B (en) * | 2015-08-19 | 2017-01-11 | 迈克斯(如东)化工有限公司 | Preparation method of trinexapac-ethyl and intermediate thereof |
| CN107162907A (en) * | 2017-05-27 | 2017-09-15 | 安阳全丰生物科技有限公司 | The synthetic method of Prohexadione calcium and TrinexAN_SNacethyl |
| CN107162907B (en) * | 2017-05-27 | 2020-06-16 | 鹤壁全丰生物科技有限公司 | Synthesis method of prohexadione calcium and trinexapac-ethyl |
| CN110776421A (en) * | 2019-11-29 | 2020-02-11 | 厦门本素药业有限公司 | Preparation method and intermediate of hexahydroquinoline diketone compound |
| CN110776421B (en) * | 2019-11-29 | 2022-06-07 | 厦门本素药业有限公司 | Preparation method and intermediate of hexahydroquinoline diketone compound |
| CN111972410A (en) * | 2020-09-07 | 2020-11-24 | 安徽省四达农药化工有限公司 | Preparation and application of trinexapac-ethyl emulsion in water |
| CN112441919A (en) * | 2020-12-29 | 2021-03-05 | 江苏傲伦达科技实业股份有限公司 | Improved synthetic method of trinexapac-ethyl |
| CN115073291A (en) * | 2022-06-09 | 2022-09-20 | 鹤壁全丰生物科技有限公司 | Production process for producing intermediate acetonyl diethyl succinate from prohexadione calcium |
| CN115073291B (en) * | 2022-06-09 | 2024-07-05 | 鹤壁全丰生物科技有限公司 | Production process of intermediate diethyl acetonylsuccinate for producing prohexadione calcium |
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