CN108863845A - A kind of preparation method of trifloxystrobin and its intermediate - Google Patents
A kind of preparation method of trifloxystrobin and its intermediate Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of trifloxystrobin；The preparation reaction of trifloxystrobin is as follows：R is selected from：C2~C5Straight chained alkyl or C3~C5Branched alkyl；In bromination reaction, bromating agent selects NBS or 1, bromo- 5, the 5- Dimethyl Hydan of 3- bis-.
Description
Technical field
The present invention relates to the preparation methods of compound, specifically trifloxystrobin and its intermediate 2- methyl-α-methoxy imino
The preparation method of phenyl acetamide.
Background technique
Trifloxystrobin (Trifloxystrbin, trade name Flint) chemical name：(2Z) -2- methoxyimino -2- [2-
[[1- [3- (trifluoromethyl) phenyl] ethyleneimino] oxygen methyl] phenyl] methyl acetate：
Trifloxystrobin is a kind of efficient, safe, environmental-friendly methoxy acrylic bactericide, as a kind of novel
Mitochondrial respiratory inhibitor has the characteristics that efficient, wide spectrum, low toxicity, environmentally friendly and mechanism of action are unique, has become at present
For the hot spot of fungicide research.Be mainly used for cauline leaf process, have special efficacy to powdery mildew, leaf spot, to rust, downy mildew, stand it is withered
Disease, scab of apple also have good activity.
Chinese patent [CN 1049426C, 2000] using O-bromo methyl methyl phenylacetate as starting material, first with benzene first azanol
Etherification reaction occurs for acid, then reacts to obtain adjacent methoxy aminophenyl acetic acid methyl esters with methanol in acid condition, then with m-trifluoromethyl
Acetophenone carries out oximation reaction, and trifloxystrobin, total recovery is made through alpha..alpha.-dimethylethyl nitrite lactazone and dimethyl sulfate methylation of ester
40.5%：
The route shares five steps, and reaction step is relatively reasonable, but the O-bromo methyl benzene second for having used price more expensive in reaction
Sour methyl esters.
World patent [WO 9520569,1995] studies trifloxystrobin, first by O-bromo methyl phenyl boric acid and
Trifluoromethyl acetophenone oxime carries out etherification reaction, then is condensed instead under the catalysis of palladium with the chloro- 2- methoxyiminoacetic acid methyl esters of 2-
Trifloxystrobin should be generated：
The synthetic route is shorter, but raw material O-bromo methyl phenyl boric acid price；Due to the chloro- 2- methoxyiminoacetic acid first of 2-
The synthesis condition of ester is excessively harsh and there are isomerization, causes yield low.
United States Patent (USP) [US 5194662,1993] obtains after bromination reaction using o-Tolylacetic acid methyl esters as initial feed
It is condensed to O-bromo methyl methyl phenylacetate, then with (TrifluoroMethyl)acetophenone oxime, then through oxidation and oximation reaction, obtains oxime bacterium
Ester：
The third step oxidation reaction of the route is more difficult.
Ni Yuebiao etc. [CN 101941921,2011] and Jiang Wentao etc. [organic chemistry, 2014,34 (4), 774-782] with
Toluene replaces toluene to be raw material, and under Catalyzed by Anhydrous Aluminium Chloride, friedel-crafts acylation reaction occurs with Methyl oxatyl chloride,
Again through oximate and chloro, trifloxystrobin, total recovery 50.2% are finally condensed to yield with (TrifluoroMethyl)acetophenone oxime again：
Friedel-crafts acylation reaction in the route, selectivity is lower, causes yield lower；Methyl oxatyl chloride price compared with
It is high.
Li Yan etc. [Central China Normal University's journal, 2005,39 (1), 54-56] is using o-bromotoluene as raw material, in organic copper lithium
Reagent effect is lower to obtain o-methyl-benzene formic acid methyl esters with ethanedioly chloride mono-methyl generation coupling reaction, then with methoxamine hydrochloric acid
Salt oximate obtains intermediate oxime ester, then obtains trifloxystrobin, total recovery 25% through bromination and oximation reaction：
The coupling reaction of the route first step is complicated, and condition is harsh, and by-product is more, technique the high requirements on the equipment.
Chinese patent [CN 1560027,2005；CN 1793115,2006]] using o-methyl-benzene ethyl ketone as raw material, in weak base
Property under the conditions of aoxidized with potassium permanganate, then through esterification, oximate, bromo, be finally condensed again with (TrifluoroMethyl)acetophenone oxime
Obtain trifloxystrobin, total recovery 39%：
Chen Wei etc. [chemical research, 2014,25 (1), 16-19] first exists through potassium permanganate using o-Tolylacetic acid as raw material
It is aoxidized under alkaline condition, then through esterification, oximate and bromo-reaction, most generates trifloxystrobin, total recovery 17% through condensation reaction afterwards：
In the method for potassium permanganate oxidation, it is difficult to control reaction process using Potassium Permanganate as Oxidant, methyl may also
It is oxidized.
World patent [WO 2013144924, US 5221762,1993], Chen Can etc. [fine-chemical intermediate, 2004,34
(5), 25-26] and sieve just etc. [fine-chemical intermediate, 2016,46 (2), 19-21] using o-toluic acid as raw material, with two
Chlorine sulfoxide flows back to obtain o-methyl-benzene formyl chloride；Afterwards by cyanalation, esterification, the obtained intermediate of oximate and bromination again with a trifluoro
Methyl acetophenone oxime is etherified to obtain trifloxystrobin, total recovery 16.2%：
The route raw material is cheap, easy to operate, but second step reacts the Cymag for having used toxicity big.
Lu Cuijun etc. [pesticide, 2011,50 (3), 187-191] and Chinese patent [CN 101139308,2008] are with adjacent hydroxyl
Methyl benzoic acid lactone is raw material, generates o-chloromethyl benzoic acid chlorides through open loop, then using Cymag as cyanogen source, reacts and neighbour is made
Chloromethylbenzene formyl nitrile, the intermediate and (TrifluoroMethyl)acetophenone oxime most obtained afterwards through esterification, oximate are etherified to obtain trifloxystrobin,
Total recovery 22%：
Route phthalide open loop generates acyl chlorides and chloromethyl, each to walk reaction condition all relatively mildly；But second step reacts
The Cymag that toxicity is big is used.
Chinese patent [CN 103524378,2015] is using o-Tolylacetic acid as raw material, through cyclization, oxidation, hydrolysis, oxime
Change, chloro and etherificate have synthesized trifloxystrobin, yield 50.6%：
The route raw material is cheap and easy to get, and yield is higher.But oxidation process uses expensive oxidant
CAT9901。
Chinese patent [CN 105294490,2016] and world patent [WO 2010089267] are with adjacent hydroxymethylphenylacetic acid
Lactone process is raw material, reacts to obtain trifloxystrobin, total recovery 25% through 4 steps：
Route raw material neighbour's hydroxymethylphenylacetic acid lactone price is higher, and first step oximation reaction needs anhydrous and oxygen-free to operate.
Bavin soldier etc. [pesticide, 2013,52 (4), 258-259] and Li Yan etc. [organic chemistry, 2006,26 (1), 110-115]
Using o-toluidine as raw material, by diazo-reaction, methylation reaction, bromo-reaction, finally and (TrifluoroMethyl)acetophenone
Oxime is etherified to obtain trifloxystrobin, total recovery 31%：
The diazo-reaction condition requirement that the route is taken is harsher, and by-product is more.
Li Renhong [Hebei University of Science and Technology's Master's thesis, 2015] using o-methyl-benzene acetonitrile as raw material, through oximate, methylation,
Hydrolysis, hydrolysis, bromo and etherificate have synthesized trifloxystrobin, yield 30.8%：
The route raw material is cheap and easy to get, and reaction condition is relatively mild.But the concentrated sulfuric acid has been used in esterification process, to equipment
Corrosivity is strong.
Zhu little Meng [Shandong Normal University's Master's thesis, 2013] is using adjacent methyl benzyl chloride as starting material, through cyanalation, oxime
Change, methylate, esterification and bromo have obtained trifloxystrobin key intermediate 2- bromomethyl-α-methoxy imino methyl phenylacetate, receipts
Rate 41.6%.
The route conditions are relatively mild, but have used the Cymag of severe toxicity.
United States Patent (USP) [US 5145980,1992] using o-tolualdehyde as raw material, by it is cyanalation, oxidation after with methoxy
The reaction of base amine hydrochlorate, then 2- bromomethyl-α-methoxy imino methyl phenylacetate, total recovery 16% are obtained through bromo：
The route is longer, and gross production rate is very low, and the first step reacts the potassium cyanide for having used toxicity big.
Wei Xinghui etc. [Zhejiang chemical industry, 2013,44 (2), 7-9] using o-Tolylacetic acid as raw material, through over-churning, oximate,
Methylation and bromination synthesize 2- bromomethyl-α-methoxy imino methyl phenylacetate, total recovery 32%：
The route reaction condition is milder, is that a kind of to prepare 2- bromomethyl-α-methoxy imino methyl phenylacetate preferable
Method.
Chinese patent [CN 101711232,2010] using o-chloro benzyl chloride as raw material, with morpholine protect methylene after by lattice
Formula reaction, esterification, 4 step of oximate react to obtain 2- chloromethyl-α-methoxy imino methyl phenylacetate, total recovery 22%：
The route second step grignard reaction is difficult to control, yield 30.3%.
For world patent [WO 9714688,1997] using o-methyl-benzene acetonitrile as raw material, 5 steps react to obtain 2- chloromethyl-α-first
Oxygen imido grpup methyl phenylacetate, total recovery 23%：
The third step reaction of the route needs anhydrous and oxygen-free to operate.
For United States Patent (USP) [US 5756811,1998] with N, N- dimethyl benzylamine and dimethyl oxalate are raw material, are reacted through 3 steps
Obtain intermediate 2- chloromethyl-α-methoxy imino methyl phenylacetate of trifloxystrobin, total recovery 55%：
The route is relatively easy, and yield is higher, but first step reaction is needed with n-BuLi, severe reaction conditions.
In conclusion the technology of existing preparation trifloxystrobin is difficult and expensive there are raw material sources, synthetic route is long, anti-
It answers condition harshness, technique to be difficult to control, require production equipment height, safety and environmental protection pressure big and the disadvantages such as yield is low.
Summary of the invention
The purpose of the present invention is to provide the preparations of 2- methyl-α shown in chemical structural formula I-methoxy imino phenyl acetamide
Method；It is characterized in that it, which is prepared, reacts as follows：
R is selected from：C2~C5Straight chained alkyl or C3~C5Branched alkyl.
The purpose of the present invention is to provide 2- methyl-α-methoxy imino phenyl acetamide preparation methods：It is characterized in that
Its preparation manipulation process is as follows：
5mmol o-methyl-benzene acetonitrile is added in 12mmol sodium hydroxide and 10mL methanol, 40 DEG C of stirring and dissolvings, is added
7.5mmol nitrite tert-butyl is warming up to 60 DEG C, reacts 1h.It is post-treated to obtain 2- methyl-α-hydroxyl imido grpup benzene acetonitrile, it receives
Rate 100%.
4mmol 2- methyl-α-hydroxyl imido grpup benzene acetonitrile, 15mL acetonitrile and 8mmol KOH or NaOH are stirred at 35~40 DEG C
0.5h is mixed, it is cooling, at lower than 10 DEG C, 4.8mmol dimethyl suflfate is slowly added dropwise, 3h is stirred at 35 DEG C, it is post-treated to obtain
0.626g pale yellow oily liquid, yield 90%.
In 5mmol 2- methyl-α-methoxy imino benzene acetonitrile and 5mL ethyl alcohol, it is molten that 20% potassium hydroxide of 5mmol is added
Liquid, reacts 3h at 60 DEG C, and (E) -2- methyl-α-methoxy imino phenyl acetamide of post-treated 0.900g single configuration is received
Rate 92.5%, 123~125 DEG C of fusing point.
The purpose of the present invention is additionally provided through 2- methyl-α shown in chemical structural formula I-methoxy imino phenyl acetamide preparation
The method of trifloxystrobin；It is characterized in that it, which is prepared, reacts as follows：
R is selected from：C2~C5Straight chained alkyl or C3~C5Branched alkyl；In bromination reaction, bromating agent selects NBS or 1,3- bis-
Bromo- 5,5- Dimethyl Hydan.
The present invention has the following advantages that compared with prior art:Reaction condition is mild, raw material is more cheap and easy to get, post-processing is simple
Just high (43.5%) with total recovery.The present invention is used for the first time through 2- methyl-α-methoxy imino phenyl acetamide key intermediate system
Standby trifloxystrobin.
Specific embodiment
Following embodiment is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1
The preparation of 2- methyl-α-hydroxyl imido grpup benzene acetonitrile
0.655g (5mmol) adjacent methyl is added in 0.480g (12mmol) sodium hydroxide and 10mL methanol, 40 DEG C of stirring and dissolvings
0.773g (7.5mmol) nitrite tert-butyl is added in benzene acetonitrile, is warming up to 60 DEG C, and 1h is reacted in TLC monitoring.Depressurize precipitation recycling
20mL water is added in methanol, and salt acid for adjusting pH to neutrality, ethyl acetate extraction, anhydrous sodium sulfate is dry, and precipitation recycles acetic acid second
Ester, yield 100% are directly used in next step.(E) -2- methyl-α-hydroxyl imido grpup benzene acetonitrile：1H NMR (400MHz, CDCl3)δ：
13.78 (s, 1H, OH), 7.53~7.32 (m, 4H, C6H4), 2.44 (s, 3H, CH3) (Z) -2- methyl-α-hydroxyl imido grpup benzene second
Nitrile：1H NMR (400MHz, CDCl3)δ：13.78 (s, 1H, OH), 7.46~7.33 (m, 4H, C6H4), 2.25 (s, 3H, CH3)。
Embodiment 2
The preparation of 2- methyl-α-methoxyimino benzene acetonitrile
0.640g (4mmol) 2- methyl-α-hydroxyl imido grpup benzene acetonitrile, 15mL acetonitrile, 0.448g (8mmol) powdered KOH,
0.5h is stirred at 35~40 DEG C, it is cooling, it is lower than at 10 DEG C, 0.605g (4.8mmol) dimethyl suflfate is slowly added dropwise, is stirred at 35 DEG C
Mix 3h, TLC monitoring.It stands, filters, revolving recycling acetonitrile.Ethyl acetate dissolves residue, and dilute hydrochloric acid neutralizes, washing, saturation food
Salt washing, anhydrous sodium sulfate is dry, precipitation, column chromatography for separation (PE:EA=8:1) 0.626g 2- methyl-α-methoxy imino is obtained
Benzene acetonitrile, yield 90%.(E) -2- methyl-α-methoxy imino benzene acetonitrile：1H NMR (400MHz, CDCl3)δ：7.56~7.25
(m, 4H, C6H4), 4.20 (s, 3H, NOCH3), 2.51 (s, 3H, CH3)；(Z) -2- methyl-α-methoxy imino benzene acetonitrile：1H
NMR (400MHz, CDCl3)δ：7.38~7.25 (m, 4H, C6H4), 4.06 (s, 3H, NOCH3), 2.31 (s, 3H, CH3)。
Embodiment 3
The preparation of 2- methyl-α-methoxyimino phenyl acetamide
0.870g (5mmol) 2- methyl-α-methoxy imino benzene acetonitrile and 5mL ethyl alcohol add 20% hydrogen of 1.400g (5mmol)
Potassium oxide or NaOH solution react 3h, TLC monitoring at 60 DEG C.Recycling design is rotated, residue pours into 20mL ice water, solid
It is precipitated, filters, washing.Filter cake drying, filtrate are extracted with ethyl acetate, dry with anhydrous sodium sulfate, and precipitation is dry, obtain
0.900g 2- methyl-α-methoxyimino phenyl acetamide, yield 92.5%, 123~125 DEG C of fusing point.1H NMR (400MHz,
DMSO-d6)δ：7.97 (s, 1H, NH2), 7.73 (s, 1H, NH2), 7.40~7.22 (m, 4H, C6H4), 3.89 (s, 3H, NOCH3),
2.42 (s, 3H, CH3)。
Embodiment 4
The preparation of 2- methyl-α-methoxy imino methyl phenylacetate
0.960g (5mmol) 2- methyl-α-methoxy imino phenyl acetamide and methanol, are passed through hydrogen chloride gas, at 60 DEG C
12h is stirred, TLC monitoring depressurizes precipitation, adds 20mL water, be extracted with ethyl acetate, saturated sodium bicarbonate washing, washing, anhydrous sulphur
Sour sodium is dry, depressurizes precipitation, is dried to obtain 2- methyl-α-methoxy imino methyl phenylacetate, yield 90.5%, fusing point 69~71
℃。1H NMR (400MHz, DMSO-d6)δ：7.34~7.09 (m, 4H, C6H4), 3.94 (s, 3H, NOCH3), 3.76 (s, 3H,
OCH3), 2.09 (s, 3H, CH3)。
Embodiment 5
(E) -2- bromomethyl-α-methoxyimino methyl phenylacetate preparation
0.414g (2.00mmol) (E) -2- methyl-α-methoxyimino-methyl phenylacetate, 5mL dichloroethanes, 0.300g
Bis- bromo- 5,5- Dimethyl Hydan (abbreviation C5H6Br2N2O2) of (1.05mmol) 1,3-, 0.100g (0.61mmol) AIBN are anti-at 82 DEG C
Answer 5.0h, TLC monitoring, precipitation.5mL water is added, ethyl acetate extraction, sodium hydroxide solution washing, anhydrous sodium sulfate is dry, takes off
It is molten, column chromatography for separation (PE:EA=20:1) (E) -2- bromomethyl-α-methoxyimino methyl phenylacetate 0.472g, yield, are obtained
82.5%.1H NMR (400MHz, CDCl3)δ：7.52~7.35,7.17~7.12 (m, 4H, C6H4), 4.34 (s, 2H, CH2),
4.07 (s, 3H, NOCH3), 3.88 (s, 3H, OCH3)。
Embodiment 6
The preparation of (TrifluoroMethyl)acetophenone oxime
1.000g (5.0mmol) (TrifluoroMethyl)acetophenone, 0.5g (7.0mmol) hydroxylamine hydrochloride, 10mL ethyl alcohol are added
0.350g (8.8mmol) sodium hydroxide tune pH8.0, flow back 1.0h, pours into ice water, hydrochloric acid tune pH2.0, and it is solid that a large amount of whites are precipitated
Body, filters, and washing and drying obtains 0.965g white solid (TrifluoroMethyl)acetophenone oxime, yield 95.5%.1H NMR (400MHz,
CDCl3)δ：7.92~7.48 (m, 4H, C6H4), 2.32 (s, 3H, CH3)。
Embodiment 7
The preparation of trifloxystrobin trifloxystrobin
0.25g (1.22mmol) (TrifluoroMethyl)acetophenone, 4mLDMF, 0.133g (2.46mmol) sodium methoxide, room temperature are stirred
15min is mixed, is cooled to 5 DEG C, 0.422g (1.47mmol) (E) -2- bromomethyl-α-methoxyimino methyl phenylacetate, room is added
Temperature reaction 5h, is poured into ice water, ethyl acetate extraction, dilute hydrochloric acid washing, washing, column chromatography for separation (PE:EA=20:1)
0.375g trifloxystrobin, yield 70%.1H NMR (400MHz, CDCl3)δ：7.90~7.15 (m, 8H, 2 × C6H4), 5.15 (s,
2H, CH2), 4.03 (s, 3H, NOCH3), 3.82 (s, 3H, OCH3), 2.22 (s, 3H, CH3)；13C NMR (100 MHz, CDCl3)
δ：163.34,153.66,149.58,137.23,135.99,129.84,129.42,129.28,128.83,128.80,
128.56,127.79,125.65,125.61,122.91,122.87,74.94,63.81,52.90,12.54.
Claims (2)
1. 2- methyl-α-methoxy imino phenyl acetamide preparation method shown in a kind of chemical structural formula I；It is characterized in that it
Preparation reaction it is as follows：
Wherein, R is selected from：C2~C5Straight chained alkyl or C3~C5Branched alkyl；
2- methyl-α-methoxy imino phenyl acetamide preparation manipulation process is as follows：
12mmol sodium hydroxide and 10mL methanol, 40 DEG C of stirring and dissolvings, 5mmol o-methyl-benzene acetonitrile and 7.5mmol nitrous acid uncle
Butyl ester is in 60 DEG C of reaction 1h；It is post-treated to obtain 2- methyl-α-hydroxyl imido grpup benzene acetonitrile, yield 100%；
4mmol 2- methyl-α-hydroxyl imido grpup benzene acetonitrile, 15mL acetonitrile and 8mmol KOH stir 0.5h at 35~40 DEG C, cooling
To at lower than 10 DEG C, 4.8mmol dimethyl suflfate is added dropwise, 3h is stirred at 35 DEG C, it is post-treated to obtain 0.626g 2- methyl-α-first
Oxygen imido grpup benzene acetonitrile, yield 90%；
In 5mmol 2- methyl-α-methoxy imino benzene acetonitrile and 5mL ethyl alcohol, 20% potassium hydroxide solution of 5mmol is added,
3h, post-treated (the E) -2- methyl-α-methoxy imino phenyl acetamide for obtaining 0.900g single configuration, yield are reacted at 60 DEG C
92.5%, 123~125 DEG C of fusing point.
2. a kind of preparation method of trifloxystrobin；It is characterized in that it, which is prepared, reacts as follows：
Wherein, R is selected from：C2~C5Straight chained alkyl or C3~C5Branched alkyl；In bromination reaction, bromating agent selects NBS or 1,3- bis-
Bromo- 5,5- Dimethyl Hydan.
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