CN102558087A - Method for combining high quality fenoxaprop-p-ethyl - Google Patents
Method for combining high quality fenoxaprop-p-ethyl Download PDFInfo
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- CN102558087A CN102558087A CN2011104551940A CN201110455194A CN102558087A CN 102558087 A CN102558087 A CN 102558087A CN 2011104551940 A CN2011104551940 A CN 2011104551940A CN 201110455194 A CN201110455194 A CN 201110455194A CN 102558087 A CN102558087 A CN 102558087A
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- China
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- solvent
- fenoxaprop
- catalyzer
- dichloro benzoxazole
- dichloro
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Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- PQKBPHSEKWERTG-LLVKDONJSA-N ethyl (2r)-2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoate Chemical group C1=CC(O[C@H](C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-LLVKDONJSA-N 0.000 title abstract 4
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- LVVQTPZQNHQLOM-UHFFFAOYSA-N 2,6-dichloro-1,3-benzoxazole Chemical compound C1=C(Cl)C=C2OC(Cl)=NC2=C1 LVVQTPZQNHQLOM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- MPPOHAUSNPTFAJ-UHFFFAOYSA-N 2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 MPPOHAUSNPTFAJ-UHFFFAOYSA-N 0.000 claims description 14
- IQNBTWADYKHANG-UHFFFAOYSA-N ethyl 2-phenoxypropanoate Chemical compound CCOC(=O)C(C)OC1=CC=CC=C1 IQNBTWADYKHANG-UHFFFAOYSA-N 0.000 claims description 12
- 235000015320 potassium carbonate Nutrition 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- -1 Resorcinol-phenoxy-benzoxazoles Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BACHBFVBHLGWSL-JTQLQIEISA-N rac-diclofop methyl Natural products C1=CC(O[C@@H](C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-JTQLQIEISA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LZCLXQDLBQLTDK-BYPYZUCNSA-N ethyl (2S)-lactate Chemical compound CCOC(=O)[C@H](C)O LZCLXQDLBQLTDK-BYPYZUCNSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- AQIHDXGKQHFBNW-ZCFIWIBFSA-N (2r)-2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)[C@@H](C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-ZCFIWIBFSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FHCUXGCMUASJQQ-UHFFFAOYSA-N 2-[(2-chlorophenyl)methylsulfanyl]-5-propyl-1,3,4-oxadiazole Chemical compound O1C(CCC)=NN=C1SCC1=CC=CC=C1Cl FHCUXGCMUASJQQ-UHFFFAOYSA-N 0.000 description 1
- HAASPZUBSZGCKU-UHFFFAOYSA-N 6-chloro-3h-1,3-benzoxazole-2-thione Chemical compound ClC1=CC=C2NC(=S)OC2=C1 HAASPZUBSZGCKU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a method for combining high quality fenoxaprop-p-ethyl, which includes mixing R-phenoxyl ethyl propionate, potassium carbonate and a catalyst in a solvent, heating the mixture to 65-90 DEG C, then slowly adding 2, 6-dichlorobenzeno-oxazole or the 2, 6-dichlorobenzeno-oxazole dissolved in the solvent, keeping the mixture warm for 0.5 hour to 5 hours under the temperature of 70 DEG C to 110 DEG C, and conducting liquid separation through water washing reaction liquid after reaction to separate an oil layer and remove the solvent to obtain the fenoxaprop-p-ethyl. The method can directly obtain the high quality fenoxaprop-p-ethyl with content larger than 98% and the optical effective body larger than 98% without complex postprocessing, and the reaction yield can achieve over 98%.
Description
Technical field
The invention belongs to the synthetic field of agricultural chemicals, be specifically related to a kind of compound method of agricultural chemicals fenoxaprop.
Background technology
Fenoxaprop (chemistry is by name: be phenoxy carboxylic acid herbicides 2-[4-(6-chloro-2-benzoxazole oxygen base) phenoxy] ethyl propionate), its compound method has:
Route 1: with 6-chloro-2-mercaptobenzoxazole (hereinafter to be referred as the sulfydryl thing) is the starting raw material Synthetic 2, and 6-dichloro Bing Ben oxazole (hereinafter to be referred as the dichloro thing) is with the synthetic 6-chloro-2 (to hydroxyl) of Resorcinol-phenoxy-benzoxazoles (hereinafter to be referred as etherate); L-ethyl lactate and p-methyl benzene sulfonic chloride synthetic S () under the effect of triethylamine forms product with above etherate condensation again to Methyl benzenesulfonyl base ethyl propionate.
This technological reaction transformation efficiency is low, and production cost is high; Product purity is low, and specific rotation is low, uses S ()
Methyl benzenesulfonyl base ethyl propionate and phenolic ether are required transposition in reaction process, racemization easily.S (one)
Need use the synthetic preparation under the effect of triethylamine of L-ethyl lactate and p-methyl benzene sulfonic chloride to Methyl benzenesulfonyl base ethyl propionate; To produce a large amount of by product-p-methyl benzenesulfonic acids in this reaction; This by product is difficult to reclaim, and environmental pollution is serious, and resource is also caused very big waste.Former medicine total content is low, generally has only 95%, and the effective body of optics is low, generally has only 95%.
Route 2: with the S-chloropropionic acid is the synthetic R-(+) of starting raw material and Resorcinol-2-(4-hydroxyphenoxy) propionic acid; With the synthetic dichloro thing of sulfydryl thing again with R-(+)-2-(4-hydroxyphenoxy) propionic acid condensation, form product with ethyl esterification again.
Though this technology can obtain high-quality fenoxaprop, reaction conversion ratio is low, and reaction is complicated, and production cost is high.
Route 3: with the synthetic dichloro thing of sulfydryl thing again with 2-(4-hydroxyphenoxy) ethyl propionate condensation, De is Dao oxazole diclofop-methyl product.
This technology uses DMSO 99.8MIN. as solvent, must arrive the oxazole diclofop-methyl, and this process recovery ratio is low, no opticity, and also solvent is difficult to reclaim usefulness again, the cost height.
Also have simultaneously the toluene of use to make solvent, use polyoxyethylene glycol as phase-transfer catalyst, must arrive the oxazole diclofop-methyl, this process recovery ratio has only 80%, no opticity, and cost is high.
Summary of the invention
The objective of the invention is to overcome the various shortcomings in the existing fenoxaprop synthetic route, a kind of fenoxaprop compound method is provided.
The object of the invention can reach through following measure:
A kind of method of synthetic high quality fenoxaprop: after R-mixed in solvent phenoxy propionic acid ethyl ester, salt of wormwood and catalyzer, be warmed up to 65～90 ℃ earlier, slowly add 2 then; 6-dichloro benzoxazole or be dissolved in 2 in the solvent, 6-dichloro benzoxazole is again 70 ℃～110 ℃ insulations 0.5～5 hour down; Reaction back water washing reaction liquid; Separatory divides oil-yielding stratum and removes solvent, must arrive fenoxaprop.
Its reaction equation is following:
R-preferably is warmed up to 70～85 ℃ earlier after phenoxy propionic acid ethyl ester, salt of wormwood and catalyzer are mixed in present method in solvent.2, after adding, 6-dichloro benzoxazole preferably is incubated 0.5～5 hour down at 90 ℃～110 ℃ again, further preferably be incubated 1～5 hour down at 95 ℃～110 ℃ again.
Wherein 2,6-dichloro benzoxazole and R-are 1: 0.7～1.5 to the mol ratio of phenoxy propionic acid ethyl ester; Preferred consumption is 2, and 6-dichloro benzoxazole and R-are 1: 0.9～1.2 to the mol ratio of phenoxy propionic acid ethyl ester.2,6-dichloro benzoxazole generally adds in the reaction system with dropping or other modes that slowly add.2,6-dichloro benzoxazole is dissolved in earlier when adding behind the solvent again, and the mass concentration of this solution is generally 10%～50%, and preferred 20%～30%.
Separatory among the present invention be meant with water layer with separate with water-insoluble non-water layer (referring generally to oil reservoir).
2, the mol ratio of 6-dichloro benzoxazole and salt of wormwood is 1: 1～3; Preferred consumption is 2, and the mol ratio of 6-dichloro benzoxazole and salt of wormwood is 1: 1.1～2.
It is to be suitable for specific phase-transfer catalyst of the present invention that catalyzer is used in this invention; Be mainly crown ether-like, quaternary ammonium salt; As Tetrabutyl amonium bromide, benzyl triethyl ammonium bromide, 15-hat (ether)-5,18-hat (ether)-6, bicyclohexane also-18-hat (ether)-6 etc., be preferably Tetrabutyl amonium bromide, 18-be preced with (ether)-6, is the best with the Tetrabutyl amonium bromide; Consumption is 2, and the mol ratio of 6-dichloro benzoxazole and catalyzer is 1: 0.001～0.03.
This invention can use series such as alkane, halohydrocarbon and aromatic hydrocarbon to make solvent; Like benzene,toluene,xylene, trimethylbenzene, chlorobenzene etc.; The best uses solvent to be toluene and YLENE; The consumption of solvent with can dissolving raw material or the amount of catalyzer be as the criterion, its total consumption is generally every gram raw material and adds 2～12ml, preferred every gram raw material 4～10ml.
Present method uses R-that the phenoxy propionic acid ethyl ester is replaced the phenoxy propionic acid ethyl ester is used the high performance catalyst that is more suitable for this reaction, under the cooperation of concrete intensification and reaction conditions, directly generates high optical rotation De fenoxaprop, improves yield greatly.
Use method of the present invention can need not complicated aftertreatment and directly obtain 98% above content, the high quality fenoxaprop of the effective body of optics more than 98%, reaction yield reaches more than 98%.
Embodiment
Embodiment 1
In 500ml four-hole reaction flask, drop into 60 gram R-to phenoxy propionic acid ethyl ester, 100ml toluene, 60 gram salt of wormwood and 1 gram Tetrabutyl amonium bromide, stir and be warmed up to 70 ℃, drip by 50 grams 2; The solution that 6-dichloro benzoxazole and 150 gram toluene are formed dripped 1 hour, was warming up to 100 ℃ again; Be incubated 2 hours, after insulation finishes, add 200 gram water washings; Layering divides oil-yielding stratum to remove solvent, must arrive fenoxaprop weight 96.24 grams; Content 98.0%, specific rotation 99.5%, molar yield 98.0%.mp：88～91℃.
Data:IR (KB r) 3014,2940,1740,1500,1290,1280,1160; 940,830,620cm-1.1HNMR (CDCl3) D:1.36 (s, 3H), 1.54 (t, 3H); 3.24 (m, 1H), 4.23 (q, 2H), 7.20-8.08 (m, Ar-H). ultimate analysis; Calculated value: C59.75, H4.43, N 3.87, measured value: C59.66, H4.08, N 4.05.
Embodiment 2
In 500ml four-hole reaction flask, drop into 60 gram R-to phenoxy propionic acid ethyl ester, 100ml YLENE, 60 gram salt of wormwood and 2 gram benzyl triethyl ammonium bromides, stir and be warmed up to 70 ℃, drip by 50 grams 2; The solution that 6-dichloro benzoxazole and 150 gram YLENE are formed dripped 1 hour, was warming up to 100 ℃ again; Be incubated 2 hours, after insulation finishes, add 200 gram water washings; Layering divides oil-yielding stratum to remove solvent, must arrive fenoxaprop weight 96.53 grams; Content 98.2%, specific rotation 99.1%, molar yield 98.5%.
Embodiment 3
In 500ml four-hole reaction flask, drop into 70 gram R-to phenoxy propionic acid ethyl ester, 100ml toluene, 60 gram salt of wormwood and 2 gram 18-hat (ether)-6, stir and be warmed up to 70 ℃, drip by 50 grams 2 solution that 6-dichloro benzoxazole and 150 gram toluene are formed; Dripped 1 hour, and be warming up to 100 ℃ again, be incubated 2 hours, after insulation finishes; Add 200 gram water washings, layering divides oil-yielding stratum to remove solvent, must arrive fenoxaprop weight 95.65 grams; Content 98.6%, specific rotation 99.6%, molar yield 98.0%.
Claims (10)
1. the method for a synthetic high quality fenoxaprop after it is characterized in that R-mixed in solvent phenoxy propionic acid ethyl ester, salt of wormwood and catalyzer, is warmed up to 65～90 ℃ earlier; Slowly add 2 then, 6-dichloro benzoxazole or be dissolved in 2 in the solvent, 6-dichloro benzoxazole; Be incubated 0.5～5 hour down at 70 ℃～110 ℃ again, reaction back water washing reaction liquid, separatory; Divide oil-yielding stratum and remove solvent, must arrive fenoxaprop.
2. method according to claim 1 is characterized in that being warmed up to 70～85 ℃ earlier after R-mixes in solvent phenoxy propionic acid ethyl ester, salt of wormwood and catalyzer.
3. method according to claim 1 is characterized in that adding 2, is incubated 0.5～5 hour down at 90 ℃～110 ℃ again behind the 6-dichloro benzoxazole.
4. method according to claim 3 is characterized in that adding 2, is incubated 1～5 hour down at 95 ℃～110 ℃ again behind the 6-dichloro benzoxazole.
5. according to each described method in the claim 1～4, it is characterized in that 2,6-dichloro benzoxazole and R-are 1: 0.7～1.5 to the mol ratio of phenoxy propionic acid ethyl ester.
6. according to each described method in the claim 1～4, it is characterized in that 2, the mol ratio of 6-dichloro benzoxazole and salt of wormwood is 1: 1～3.
7. method according to claim 6 is characterized in that 2, and the mol ratio of 6-dichloro benzoxazole and salt of wormwood is 1: 1.1～2.
8. according to each described method in the claim 1～4, it is characterized in that said catalyzer is a phase-transfer catalyst; 2, the mol ratio of 6-dichloro benzoxazole and catalyzer is 1: 0.001～0.03.
9. method according to claim 8, it is characterized in that said catalyzer be Tetrabutyl amonium bromide, benzyl triethyl ammonium bromide, 15-hat (ether)-5,18-hat (ether)-6, bicyclohexane also-18-is preced with (ether)-6.
10. according to each described method in the claim 1～4, it is characterized in that said solvent is benzene,toluene,xylene, trimethylbenzene or chlorobenzene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965123A (en) * | 2013-01-31 | 2014-08-06 | 湖南化工研究院 | N-oxyl fused heterocycle oxy phenoxy carboxylic acid amide compound having biological activity, and preparation method thereof |
| CN106928131A (en) * | 2017-01-20 | 2017-07-07 | 江苏凯晨化工有限公司 | A kind of preparation method of haloxyfop-r-methyl |
| CN111732553A (en) * | 2020-06-18 | 2020-10-02 | 江苏富鼎化学有限公司 | Method for synthesizing herbicide fenoxaprop-p-ethyl |
| CN113185475A (en) * | 2021-04-29 | 2021-07-30 | 江苏永凯化学有限公司 | Efficient and low-pollution production process of fenoxaprop-p-ethyl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070550A (en) * | 2011-01-25 | 2011-05-25 | 浙江海正化工股份有限公司 | Method for synthesizing fenoxaprop-p-ethyl |
| CN102093305A (en) * | 2011-01-25 | 2011-06-15 | 浙江海正化工股份有限公司 | Method for preparing fenoxaprop-p-ethyl |
-
2011
- 2011-12-30 CN CN2011104551940A patent/CN102558087A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070550A (en) * | 2011-01-25 | 2011-05-25 | 浙江海正化工股份有限公司 | Method for synthesizing fenoxaprop-p-ethyl |
| CN102093305A (en) * | 2011-01-25 | 2011-06-15 | 浙江海正化工股份有限公司 | Method for preparing fenoxaprop-p-ethyl |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965123A (en) * | 2013-01-31 | 2014-08-06 | 湖南化工研究院 | N-oxyl fused heterocycle oxy phenoxy carboxylic acid amide compound having biological activity, and preparation method thereof |
| CN103965123B (en) * | 2013-01-31 | 2016-05-25 | 湖南化工研究院 | There is thick assorted phenoxy carboxylic acid amide compounds of bioactive N-oxygen base and preparation method thereof |
| CN106928131A (en) * | 2017-01-20 | 2017-07-07 | 江苏凯晨化工有限公司 | A kind of preparation method of haloxyfop-r-methyl |
| CN111732553A (en) * | 2020-06-18 | 2020-10-02 | 江苏富鼎化学有限公司 | Method for synthesizing herbicide fenoxaprop-p-ethyl |
| CN111732553B (en) * | 2020-06-18 | 2022-08-05 | 江苏富鼎化学有限公司 | Method for synthesizing herbicide fenoxaprop-p-ethyl |
| CN113185475A (en) * | 2021-04-29 | 2021-07-30 | 江苏永凯化学有限公司 | Efficient and low-pollution production process of fenoxaprop-p-ethyl |
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Application publication date: 20120711 |