CN100357263C - Preparation process of oxime strain ester - Google Patents
Preparation process of oxime strain ester Download PDFInfo
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- CN100357263C CN100357263C CNB2004100167491A CN200410016749A CN100357263C CN 100357263 C CN100357263 C CN 100357263C CN B2004100167491 A CNB2004100167491 A CN B2004100167491A CN 200410016749 A CN200410016749 A CN 200410016749A CN 100357263 C CN100357263 C CN 100357263C
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Abstract
The present invention discloses a preparation method of trifloxystrobin, which comprises the following steps: (a)ortho-methyl hypnone is taken as a raw material and oxidized to 2-(2'-methylphenyl)-2-carbonyl acetic acid by potassium permanganate; (b)the product in step (a) reacts with methanol to obtain 2-(2'-methylphenyl)-2-carbonyl methyl acetate; (c)the product in step (b) is brominated to 2-(2'-bromomethylphenyl)-2-carbonyl methyl acetate; (d)the product in step (c) reacts with methoxy amine to obtain (E)-2-(2'-bromomethylphenyl)-2-carbonyl methyl acetate-O-methyl ketone oxime; (e)the product in step (d) reacts with meta-trifluoromethyl hypnone oxime to obtain the product trifloxystrobin. The synthesis technology of the present invention reduces the discharge of a great amount of waste water in the oxidation reaction and avoids adopting methyl chloroformate to carry out esterification, and most of the operation conditions are mild; the present invention has the advantage of easy operation, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of the organic compound as agricultural chemicals, relate in particular to a kind of oxime bacterium ester ((E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-2-carbonylic acetic acid methyl esters-O-ketoxime) synthetic method.
Background technology
Oxime bacterium ester class wide-spectrum bactericide is the new fluorine-containing sterilant of successfully developing as the sterilant lead compound from natural product Strobilurins of a class.Be characterized in: efficient, wide spectrum, protection, treat, root out, infiltration, systemic activity, resistance of rainwater washing against, characteristic such as the lasting period is long.To 1, the bacterial strain of 4-demethylation enzyme inhibitors, benzamides, dicarboxylic dihydrazides amine and benzimidazoles generation resistance is effective, does not have cross resistance with at present existing sterilant.Nearly all Eumycetes (Ascomycetes, Basidiomycetes, Oomycete and imperfect fungi) disease such as Powdery Mildew, rust, Ying's rot, net blotch, oidium, rice blast etc. all there is good activity.Except that Powdery Mildew, leaf spot are had the special efficacy, rust, oidium, damping-off, apple apple scab there is good activity.To crop safety, capable of being fast degraded in soil, water because of it, so environmentally safe.
Document J.Chem.Soc., 1965:5298, Tetrahedron Lett., 1980,21:4957.J.Org.Chem., 1981,46 (1): 211, EP0363818A1, US5041618, Angew.Chem., 1959,71:349, US5194662 and CN1109686 skill.
Summary of the invention
The object of the invention be to provide a kind of oxime bacterium ester ((E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-2-carbonylic acetic acid methyl esters-O-ketoxime) complete synthesis technique.
The present invention is achieved through the following technical solutions:
1,2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid is synthetic
In water and organic solvent mixed solvent, pH is controlled at 8-13, preferably the pH value is 9, temperature is-10-40 ℃, and preferred range is 0-30 ℃, best temperature is 0 ℃, add the potassium permanganate aqueous solution earlier, add the potassium permanganate solid again and react, the mol ratio of o-methyl-benzene ethyl ketone and potassium permanganate is 1: 0.8-2.5, preferred mol ratio is 1: 1.1.
2,2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters is synthetic
This synthetic used catalyzer is the acidic resins and the vitriol oil, and the amount of catalyzer is 0.1-1%.The mol ratio of methyl alcohol and 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid is 1-20: 1, and temperature of reaction is 20-65 ℃.
3,2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters is synthetic
Bromination reaction adopts the direct bromination of bromine or carries out bromination with N-bromo-succinimide (NBS).Reaction solvent is tetracol phenixin, methylene dichloride and trichloromethane etc.Temperature of reaction is 10-70 ℃, and preferred temperature is 50 ℃.
4, (E)-2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime
Reaction medium is ethanol, methyl alcohol, and the pH value is 8-13, and preferred pH value is 10.Alkali
Reaction medium is ethanol, methyl alcohol, and the pH value is 8-13, and preferred pH value is 10.Alkaline conditioner is pyridine, triethylamine, diethylamine, sodium hydroxide, potassium hydroxide etc.Temperature of reaction is 10-80 ℃, and preferred temperature is 60 ℃.5, (E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-the 2-carbonyl
Synthesizing of guanidine-acetic acid methyl esters-O-ketoxime
Reaction is sodium hydride, hydrolith, sodium hydroxide, potassium hydroxide, sodium amide etc. with alkali.Temperature of reaction is 20-70 ℃, and preferred temperature is 60 ℃.Reaction medium is N, dinethylformamide, tetrahydrofuran (THF).The mol ratio of alkali and trifluoromethyl acetophenone oxime is 0.8-2.5: 1, and preferred molar ratio is 1.2: 1.The trifluoromethyl acetophenone oxime with (E)-mol ratio of 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime is 0.8-1.5: 1, preferred molar ratio is 1: 1.
Synthesis technique provided by the invention is compared with traditional synthesis process, on the basis that does not change oxime bacterium ester performance, has reduced discharge of wastewater a large amount of in the oxidizing reaction, avoided the employing methyl-chloroformate to carry out esterification, most of operational condition gentleness, easy and simple to handle, be fit to suitability for industrialized production.
Embodiment
How further specify the present invention below by embodiment realizes:
Embodiment 1
Synthesizing of 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid
In the 500ml round-bottomed flask, add 2ml (0.015mol) o-methyl-benzene ethyl ketone, 6g sodium hydroxide, 200ml water,, 7g potassium permanganate is added in the flask in batches at ice-water bath with under stirring.A collection of to the end potassium permanganate adds, color in the reaction system continue to keep 1 hour constant, reaction finishes, and drips sodium sulfite solution the red-purple of mixed solution is taken off, suction filtration is removed the Manganse Dioxide solid, and the aqueous solution is removed unreacted raw material with extracted with diethyl ether.Water is acidified to pH=4 with concentrated hydrochloric acid, and the adularescent solid occurs, and with 2 * 50ml extracted with diethyl ether, white solid is dissolved in ether.Collect the organic phase anhydrous magnesium sulfate drying, boil off ether, obtain 2g xanchromatic 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid liquid, productive rate 80%.
IR(KBr)：1749，1686cm
-1.
1HNMR (CDCl
3): (s, 3H), (m, 4H), 9.1 (s, 1H) .2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters is synthetic for 7.26-7.69 in δ=2.61
Under agitation, the 1ml vitriol oil slowly added fill 1g (0.006mol) 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid, in the 100ml round-bottomed flask of methyl alcohol 20ml, TLC (ethyl acetate: sherwood oil=1: 8) follow the tracks of reaction, reflux finishes after about 5 hours, reaction solution is poured in the 100ml beaker, with saturated sodium hydrogen carbonate solution adjust pH is neutral, with 3 * 25ml extracted with diethyl ether, merge organic layer, anhydrous magnesium sulfate drying boils off the debris behind the ether, through purification by silica gel column chromatography (ethyl acetate: sherwood oil=1: 30), obtain 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters liquid of 0.55g yellow oily, productive rate 51%.IR (KBr): 1749,1686,1609,1455,1315,1287,1203,1001,735cm
-1.
1HNMR (CDCl
3): (s, 3H), 3.96 (s, 3H), (m, 4H) .3,2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters is synthetic for 7.26-7.69 in δ=2.61
1g (0.006mol) 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters is dissolved in the 20ml tetracol phenixin and places the 100ml three-necked bottle, getting 1.5ml (0.03) bromine is dissolved in the 10ml tetracol phenixin and places constant pressure funnel to be added dropwise to three-necked bottle, shine with the 250W mercury lamp, color takes on a red color after the dripping bromine, reaction was less than 10 minutes, color promptly shoals, and continues point and adds bromine, and color fade is very fast.(ethyl acetate: sherwood oil=1: 8) follow the tracks of reaction process, TLC shows that the basic disappearance of raw material point finishes reaction after 5 hours with TLC in the reaction process.To its solution earlier once, saturated sodium bicarbonate (NaHCO with the 50ml washing
3) solution gives a baby a bath on the third day after its birth time.The organic phase anhydrous magnesium sulfate drying steams solvent, obtains the tawny product.Through purification by silica gel column chromatography (ethyl acetate: sherwood oil=1: 10), obtain 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters liquid of 0.78g yellow oily, productive rate 54%.
IR (KBr): 2955,1742,1686,1435,1318,1207,999
1HNMR (CDCl
3): (s, 3H), 4.90 (s, 2H), (m, 4H) .4, (E)-2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime is synthetic for 7.4-7.8 in δ=3.99
In the 100ml three-necked bottle, add 1g (0.004mol) 2-(2-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters, 0.8g (0.01mol) methoxy amine hydrochlorate and 20ml95% ethanol, adding 1ml triethylamine adjusting pH is alkalescence, TLC (ethyl acetate: sherwood oil=1: 9) follow the tracks of reaction, stirring and refluxing was poured in the frozen water after 4 hours, with extracted with diethyl ether (3 * 30ml), organic phase with the 50ml washing once, the anhydrous sodium sulfate drying organic phase, boil off the debris behind the ether, through purification by silica gel column chromatography (ethyl acetate: sherwood oil=1: 9), obtain 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime liquid of 0.58g yellow oily, productive rate 52%.
HNMR (CDCl
3): (s, 3H), 3.97 (s, 3H), 4.05 (s, 2H) (m, 4H) .5 m-trifluoromethyl acetophenone oxime is synthetic for 7.2-7.9 in δ=3.85
In the 100ml three-necked bottle, add 1g (0.005mol) m-trifluoromethyl methyl phenyl ketone, 0.7g (0.01mol) oxammonium hydrochloride, 20ml dehydrated alcohol, add sodium hydrate solid, the pH that transfers solution is an alkalescence, about pH=8, after the stirring and refluxing 3 hours, pour in the frozen water, with the concentrated hydrochloric acid adjust pH is 2, there are this moment a large amount of white solid things to occur in the solution, filter, with distilling the washing white solid to neutral, drain, the gained solid is carried out recrystallization with sherwood oil, obtain white needle-like crystals 1.05g, productive rate 97%.
1HNMR(CDCl
3)：δ＝2.35(s，3H)，7.4-7.8(m，4H).
6, oxime bacterium ester is synthetic
0.5g (0.02mol) NaH is joined in the 50ml tetrahydrofuran (THF), at room temperature, add 0.7g (0.0034mol) m-trifluoromethyl acetophenone oxime, after the heated and stirred 1 hour, add 1 g (0.0034mol) (E)-2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime and 20ml tetrahydrofuran (THF), continue the heated and stirred reaction, with TLC (ethyl acetate: sherwood oil=1: 9) follow the tracks of reaction mechanism, raw material point disappears on thin-layer chromatography, stopped reaction is poured in the frozen water, separates out solid, filter, water and ether drip washing solid are collected solid sherwood oil recrystallization respectively, obtain 0.78g (E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-2-carbonylic acetic acid methyl esters-O-ketoxime solid, productive rate 55%.Fusing point: 70 ℃.
1HNMR(CDCl
3)：δ＝2.21(s，3H)，3.82(s，3H)，3.93(s，3H)，5.13(s，2H)，7.1-7.8(m，7H)。
Embodiment 2
Other steps repeat embodiment 1 by same steps as, just wherein the synthetic of 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters in the 3rd step undertaken by following step: 1g (0.006mol) 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters is dissolved in the 20ml tetracol phenixin and places the 100ml three-necked bottle, add 1.5g (0.012mol) NBS (N-bromo-succinimide) and 0.2g BPO (benzoyl peroxide), with the irradiation of 250W mercury lamp.(ethyl acetate: sherwood oil=1: 8) follow the tracks of reaction process, TLC shows that the basic disappearance of raw material point finishes reaction with TLC in the reaction process.To its solution earlier once, saturated sodium bicarbonate (NaHCO with the 50ml washing
3) solution gives a baby a bath on the third day after its birth time.The organic phase anhydrous magnesium sulfate drying steams solvent, obtains the tawny product.Through purification by silica gel column chromatography (ethyl acetate: sherwood oil=1: 10), obtain 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters liquid of 0.88g yellow oily, productive rate 61%.IR(KBr)：2955，1742，1686，1435，13?18，1207，999
1HNMR(CDCl
3)：δ＝3.99(s，3H)，4.90(s，2H)，7.4-7.8(m，4H).
The above is preferred embodiment of the present invention only, is not to be used for limiting scope of the present invention, and is all according to equalization variation and modification that the present invention did, is all claim of the present invention and contains.
Claims (7)
1, a kind of synthesis type (I) oxime bacterium ester promptly (E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-method of 2-carbonylic acetic acid methyl esters-O-ketoxime, comprise the steps:
Oxime bacterium ester (I)
(a), 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid is synthetic
With the o-methyl-benzene ethyl ketone is that starting raw material gets 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid with potassium permanganate oxidation under alkaline condition;
(b), 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters is synthetic
2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid gets 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters with the methyl alcohol effect under acidic resins and sulphuric acid catalysis;
(c), 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters is synthetic
2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters gets 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters through bromination;
(d), 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime
2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters and methoxyl group amine react (E)-2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime;
(e), (E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-2-carbonylic acetic acid methyl esters-O-ketoxime synthetic
(E)-2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime and m-trifluoromethyl acetophenone oxime react product (E, E)-2-[1 '-(3 '-trifluoromethyl)-ethyl-imines-oxygen-tolyl]-2-carbonylic acetic acid methyl esters-O-ketoxime.
2, the preparation method of a kind of oxime bacterium ester according to claim 1 is characterized in that:
Solvent in the step (a) is the mixed solvent of water and organic solvent, and temperature of reaction is 0-30 ℃, and the mol ratio of o-methyl-benzene ethyl ketone and potassium permanganate is 1: 0.8-2.5, the pH value is 8-13, adds the potassium permanganate aqueous solution earlier, adds the potassium permanganate solid again and reacts.
3, according to the preparation method of the described a kind of oxime bacterium ester of claim 2, it is characterized in that:
Step (a) reaction pH value is 9, and temperature of reaction is 0 ℃, and the mol ratio of o-methyl-benzene ethyl ketone and potassium permanganate is 1: 1.1.
4, the preparation method of a kind of oxime bacterium ester according to claim 1 is characterized in that:
The amount of the acidic resins and the vitriol oil is 0.1-1% in step (b) reaction, and the mol ratio of methyl alcohol and 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid is 1-20: 1, and temperature of reaction is 20-65 ℃.
5, the preparation method of a kind of oxime bacterium ester according to claim 1 is characterized in that:
The reaction of step (c) is with a kind of bromination of carrying out in bromine or the N-bromo-succinimide, and temperature of reaction is 10-70 ℃.
6, the preparation method of a kind of oxime bacterium ester according to claim 1 is characterized in that:
Used reaction medium is ethanol and methyl alcohol in the step (d), and used alkaline conditioner is a kind of in pyridine, triethylamine, diethylamine, sodium hydroxide or the potassium hydroxide, and the pH value is 10-80 ℃ for the 8-13 temperature of reaction.
7, the preparation method of a kind of oxime bacterium ester according to claim 1 is characterized in that:
Reaction is N with reaction medium in described (e) step, a kind of in dinethylformamide or the tetrahydrofuran (THF), alkali is a kind of in sodium hydride, hydrolith, sodium hydroxide, potassium hydroxide or the sodium amide, temperature of reaction is 20-70 ℃, the mol ratio of alkali and trifluoromethyl acetophenone oxime is 0.8-2.5: 1, the trifluoromethyl acetophenone oxime with (E)-mol ratio of 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters-O-methyl ketoxime is 0.8-1.5: 1.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334070C (en) * | 2005-11-18 | 2007-08-29 | 上海同纳环保科技有限公司 | Tech. for synthesizing high productivity oxime kresoxim |
| CN101941921B (en) * | 2010-09-03 | 2013-10-02 | 岳阳迪普化工技术有限公司 | Method for preparing trifloxystrobin |
| CN103787916B (en) * | 2014-01-15 | 2016-07-13 | 京博农化科技股份有限公司 | A kind of preparation method of trifloxystrobin |
| CN103922924A (en) * | 2014-04-29 | 2014-07-16 | 南京工业大学 | Preparation method of 2-(2'-methyl phenyl)-2-carbonyl acetic acid |
| CN111333535B (en) * | 2020-04-20 | 2022-03-01 | 江苏食品药品职业技术学院 | Preparation method of trifloxystrobin |
| CN115490612A (en) * | 2022-10-24 | 2022-12-20 | 河北威远生物化工有限公司 | Synthesis method of trifloxystrobin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0460575A1 (en) * | 1990-06-05 | 1991-12-11 | Ciba-Geigy Ag | Aromatic compounds |
| WO1992018494A1 (en) * | 1991-04-19 | 1992-10-29 | Ciba-Geigy Ag | Methyl esters of aldimino- or ketimino-oxy-orthotolylacrylic acid, manufacturing process and fungicides containing them |
| US5346902A (en) * | 1990-08-22 | 1994-09-13 | Imperial Chemical Industries Plc | Fungicidal diazinyl dioxime |
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2004
- 2004-03-05 CN CNB2004100167491A patent/CN100357263C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0460575A1 (en) * | 1990-06-05 | 1991-12-11 | Ciba-Geigy Ag | Aromatic compounds |
| US5346902A (en) * | 1990-08-22 | 1994-09-13 | Imperial Chemical Industries Plc | Fungicidal diazinyl dioxime |
| WO1992018494A1 (en) * | 1991-04-19 | 1992-10-29 | Ciba-Geigy Ag | Methyl esters of aldimino- or ketimino-oxy-orthotolylacrylic acid, manufacturing process and fungicides containing them |
Non-Patent Citations (2)
| Title |
|---|
| HALIDE-DIRECTED NITRILE HYDROLYSIC JAMES.M.TETRAHEDRON LETT.,Vol.21 No.37. 1980 * |
| SYNTHESIS OF 8-SUBSITUTED5H,9H-6-OXO-7-AZABENZOCYCLONONENE-10,11-DIONE-11-O-METHYLOXIMES,A NEW [1,2]-OXAZONINE RINGSYSTEM. ALFONS PASCUAL.TETRAHEDRON LETT.,Vol.41 . 2000 * |
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