CN103333121A - Fluorine-contained pyribenzoxim compound with herbicidal activity and preparation method thereof - Google Patents
Fluorine-contained pyribenzoxim compound with herbicidal activity and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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Abstract
The invention discloses a fluorine-contained pyribenzoxim compound with herbicidal activity and a preparation method thereof. The chemical name of the fluorine-contained pyribenzoxim compound is O-[2,6-bis(4,6-dimethoxy-2-pyrimidyl) oxy] benzophenone (2-trifluoromethyl) formaldoxime, the molecular formula of the fluorine-contained pyribenzoxim compound is C27H22N5O8F3, and the molecular weight of the fluorine-contained pyribenzoxim compound is 601.5. The fluorine-contained pyribenzoxim compound has three isomerides. The invention discloses molecular structural formulas and physical properties of the three isomerides. Meanwhile, the invention discloses a preparation method taking substitute trifluoromethyl-benzaldehyde, 2,6-bis(4,6-dimethyl-2-pyrimidyl-2-oxy) benzoic acid as raw materials. The control effect of the fluorine-contained pyribenzoxim compound reaches at least 94 percent on barnyard grass, Echinochloa colona, Paspalum distichum and Panicum crus in paddy fields. Meanwhile, the fluorine-contained pyribenzoxim compound is highly safe for paddy crops, is friendly to the environment, is low in toxicity and is wide in application prospect in the field of pesticides.
Description
Technical field:
The present invention relates to a kind of new compound of weeding activity and preparation method thereof that has, relate in particular to the phonetic oxime grass of the fluorine with weeding activity ether compound and preparation method thereof.
Background technology:
Last century late nineteen eighties, first commercialization kind found and developed the earliest by pyrimidine salicylic acid weedicide by Japanese combinatorial chemistry two careless ether (Bispyribac-sodium) (CN1035292A), Korea S LG chemical company has developed pyribenzoxim (pyribenzoxim) (EP658549A1) subsequently, Shanghai Organic Chemistry Institute, Chinese Academy of Sciences and Zhejiang Chemical Industry Science and Technology Group Co.,Ltd have developed propyl-ester nitorfen and iso-propyl-ester nitrofen (CN112793C) etc. cooperatively, yet these compounds are to the barnyard grass grass of rice terrace, red pin barnyard grass, Paspalum distichum, the weed control efficacy such as grade of rice barnyard grass is unsatisfactory.
In order to work out a kind of weedicide that can effectively prevent and kill off the barnyard grass grass of rice terrace, red pin barnyard grass, Paspalum distichum, rice barnyard grass.The applicant has carried out research widely to the phonetic oxime grass of fluorine ether compound, find through long term studies and test, specific position at the pyrimidine salicylic acid compounds is introduced trifluoromethyl substituent, the phonetic oxime grass of the fluorine of gained ether compound demonstrates the good performance of preventing and kill off to perennial and annual gramineous weed, and the barnyard grass grass of preventing and kill off rice terrace, red pin barnyard grass, Paspalum distichum, rice barnyard grass are had special efficacy.And the phonetic oxime grass of fluorine ether compound can be realized preventing and kill off barnyard grass grass, red pin barnyard grass, Paspalum distichum, rice barnyard grass and so on weeds with lower dosage, the security that simultaneously rice crop is had height, very effective to preventing and kill off of weeds such as barnyard grass grass, environmentally friendly, low toxicity is with a wide range of applications at pesticide field.
Summary of the invention:
The purpose of this invention is to provide a kind of phonetic oxime grass of fluorine ether compound with weeding activity and preparation method thereof.
This chemical name with the phonetic oxime grass of fluorine ether compound of weeding activity is O-[2, two (4,6-dimethoxy-2-pyrimidyl) the oxygen bases of 6-] Benzoylbenzene (2-trifluoromethyl) formoxime;
Molecular formula is C27H22N5O8F3; Molecular weight 601.5; General formula of molecular structure is as follows:
R=o,m,p-CF3
Wherein: R be adjacent,, to position trifluoromethyl;
When R is the ortho position trifluoromethyl, be referred to as the phonetic oxime grass of fluorine ether A, its chemical name is:
O-[2,6-two (4,6-SDM base-2-base oxygen base) benzoyl] (2-trifluoromethyl) benzaldoxime;
Its physical properties is:
1. pure product are white crystalline solid;
2. fusing point: 157.4 ℃～157.9 ℃;
3. the pH value of pure product is neutrality, i.e. pH value=7;
4. be dissolved in methylene dichloride, acetonitrile solvent, be slightly soluble in methyl alcohol, acetone solvent; Water insoluble.
When R is the ortho position trifluoromethyl, be referred to as the phonetic oxime grass of fluorine ether B, its chemical name is:
O-[2,6-two (4,6-SDM base-2-base oxygen base) benzoyl] (3-trifluoromethyl) benzaldoxime,
Its physical properties is:
1. pure product are white crystalline solid;
2. fusing point: 130.9 ℃～131.2 ℃;
3. the pH value of pure product is neutrality, i.e. pH value=7;
4. be dissolved in methylene dichloride, acetonitrile solvent, be slightly soluble in methyl alcohol, acetone solvent; Water insoluble.
When R is during to position trifluoromethyl, be referred to as the phonetic oxime grass of fluorine ether C, its chemical name is:
O-[2,6-two (4,6-SDM base-2-base oxygen base) benzoyl] (4-trifluoromethyl) benzaldoxime,
Its physical properties is:
1. pure product are white crystalline solid;
2. fusing point: 190.4 ℃～190.8 ℃;
3. the pH value of pure product is neutrality, i.e. pH value=7;
4. be dissolved in methylene dichloride, acetonitrile solvent, be slightly soluble in methyl alcohol, acetone solvent; Water insoluble;
The chemical structural formula of the phonetic oxime grass of fluorine ether A, the phonetic oxime grass ether B of fluorine and the phonetic oxime grass of fluorine ether C is as follows:
The phonetic oxime grass of this fluorine ether compound can be used for preparing efficient, low toxicity, and to rice safety, eco-friendly highly selective weedicide can be prevented and kill off monocotyledon weeds such as the barnyard grass grass in the rice terrace, red pin barnyard grass, Paspalum distichum, rice barnyard grass especially.
The preparation method of the phonetic oxime grass of the fluorine with weeding activity of the present invention ether compound is as follows:
To replace trifluoromethylated benzaldehyde, 2, two (4, the 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid of 6-are the phonetic oxime grass of feedstock production fluorine ether compound, and its synthetic equation is:
The synthetic route of the phonetic oxime grass of Scheme1 fluorine ether compound
This to replace trifluoromethylated benzaldehyde, 2, two (4, the 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid of 6-are the preparation method of the phonetic oxime grass of feedstock production fluorine ether compound, may further comprise the steps:
Step 1: replace the preparation of trifluoromethylated benzaldehyde oxime
With oxammonium hydrochloride with to replace trifluoromethylated benzaldehyde be raw material, add solvent alcohol and inorganic alkali as a catalyst, under 0 ℃～25 ℃ temperature condition, react, react after 1～3 hour, treatedly must replace the trifluoromethylated benzaldehyde oxime;
Wherein, solvent alcohol is methyl alcohol, ethanol, Virahol, propyl carbinol or n-propyl alcohol, particular methanol;
Mineral alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, yellow soda ash or salt of wormwood, preferred sodium hydroxide;
Step 2: the preparation of the phonetic oxime grass of fluorine ether compound
With 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid and above-mentioned replacement trifluoromethylated benzaldehyde oxime are raw material, under organic solvent, catalyzer and dewatering agent effect, reacted at normal temperatures 3～5 hours, reaction finishes after-filtration, and filtrate is under reduced pressure steamed except reclaiming organic solvent, namely gets the phonetic oxime grass of target compound fluorine ether compound;
Wherein, described organic solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, acetone, acetonitrile, tetrahydrofuran (THF), dioxane, N, dinethylformamide, methyl acetate, ethyl ester ethyl ester, propyl acetate or ethanol butyl ester, preferred methylene dichloride;
Described catalyzer is: 4-Dimethylamino pyridine (DMAP) or 4-(1'-Pyrrolidine) pyridine (4-PPY);
Described dewatering agent: N, N'-dicyclohexylcarbodiimide (DCC) or N, N'-DIC (DIC).
With trifluoromethylated benzaldehyde, 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid is that the preparation method of the phonetic oxime grass of feedstock production fluorine ether compound is the synthesis technique of a green cleaning, is fit to a large amount of batches of phonetic oxime grass of preparation of industrialization fluorine ether-derivative herbicidess.
Innovative point of the present invention:
1. the phonetic oxime of a kind of brand-new fluorine grass ether-derivative herbicides is provided, and it is very effective, simultaneously environmentally friendly that it can prevent and kill off barnyard grass grass, red pin barnyard grass, Paspalum distichum, rice barnyard grass to the rice field, and low toxicity is harmless to rice safety.
2. the technology of preparing of the phonetic oxime grass of a kind of highly effective and safe fluorine ether-derivative herbicides is provided, can not only have prepared the phonetic oxime grass of fluorine ether-derivative herbicides in a large number, and the yield height, purity is good.
Main points of the present invention are:
With trifluoromethylated benzaldehyde, 2, two (4, the 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid of 6-are the phonetic oxime grass of the fluorine ether-derivative herbicides that feedstock production has efficient weeding activity.
The phonetic oxime of fluorine grass ether-derivative herbicides has good weeding activity, and the effective active composition of useful as herbicides prepares the various pesticide formulation, wettable powder for example, emulsion, water dispersion granule etc.
The weeding activity determination test of the phonetic oxime grass of fluorine ether compound:
(1), testing laboratory's preventing iron test
Use the phonetic oxime grass of fluorine ether compound that barnyard grass in paddy field is carried out the weeding activity test, test method is as follows:
1, test medicament and preparation:
Take by weighing the former medicine of the phonetic oxime grass ether compound of fluorine of certain mass with analytical balance, be mixed with the little preparation of missible oil of 1.0-5.0% with solvent (among acetone, DMF or the DMSO file mark etc.) dissolving, become finite concentration with the distilled water diluting that contains 0.15%TW-80 then, standby.
2, test design:
3, test
To evenly broadcast respectively in the internal diameter 9cm basin alms bowl for the monocotyledon weed seed of test, in the greenhouse, cultivate, long to the 1-1.5 leaf phase Deng monocotyledon weed, carrying out the back cauline leaf with automatic sprayer handles, handle 3 repetitions, establish blank, left standstill after the processing 4-5 hour, after treating that soup is done on the leaf, move in the greenhouse and cultivate.
Observe the plant strain growth situation every day, the periodic logging symptom of being injured, symptom of chemical damage obviously after, the comprehensive weeding activity of range estimation investigation.
4, result's investigation, the result investigates and adopts range estimation, the visual assessment medicament to plant strain growth inhibition, deformity, yellow, rot, downright bad influence degree, suppress fully according to the plant that comprehensively is injured then, its judgement criteria sees table 1 for details, and the weeding activity measurement result of the phonetic oxime grass of fluorine ether compound sees table 2 for details.
Table 1 greenhouse pot culture weeding activity judgement criteria
| Weeding activity (%) | Weeding activity comment (inhibition, deformity, yellow etc.) |
| 0 | With contrast, resistance is eliminated |
| 12-20 | It is influential slightly to grow, and it is poor to live, and eliminates |
| 30-40 | It is influential to grow, and it is poor to live, and eliminates |
| 50-60 | It is influential to grow, and it is medium to live, and can consider further transformation |
| 70-80 | Responsive, better active, can take into account sieve |
| 90-99 | Extremely responsive, active good, advance sieve |
| 100 | Death, active good, advance sieve |
The phonetic oxime grass of table 2 fluorine ether compound weeding activity measurement result:
Have good inhibition barnyard grass grass, rice barnyard grass, red pin barnyard grass, Paspalum distichum weeds activity from showing to observe the phonetic oxime grass of fluorine ether compound.
(2), the phonetic oxime of fluorine grass ether live early rice and live in the preventing iron test in rice field:
Consumption: with the phonetic oxime grass of 20% fluorine ether A wettable powder (WP) 15～30g/667m
2
Usage: thin up even spraying.
The weeding simultaneous test of the phonetic oxime grass of fluorine ether A:
1, materials and methods
1.1,2.5% the rice outstanding person OF that produces of the phonetic oxime grass of 20% fluorine ether A wettable powder and The Dow Agrosciences, LLC. that the applicant is produced carries out the weeding simultaneous test.
1.2, test design
5 processing are established in test altogether, are respectively:
Handle the phonetic oxime grass of 1:20% fluorine ether A wettable powder (WP), 15g/667m
2
Handle the phonetic oxime grass of 2:20% fluorine ether A wettable powder (WP), 20g/667m
2
Handle the phonetic oxime grass of 3:20% fluorine ether A wettable powder (WP), 30g/667m
2
Handle the outstanding OF of rice of 4:2.5%, 60ml/667m
2
Handle 5: blank;
Every residential quarter area 215m
2, adopt the hand sprayer even spraying during dispenser.
1.3, the experimental plot basic condition
The experimental plot is live early rice and live semilate rice, is located at Jingzhou District Ba Lingshan town, area 1505m
2Clayey soil, preceding crop: blank field.Early rice is in dispenser on April 25, and semilate rice is in dispenser on May 16, and paddy rice is tillering phase during dispenser, and main gramineous weeds is barnyard grass, red pin barnyard grass, Paspalum distichum during the field, and careless ages 4, leaf～7 leaves wholeheartedly.The experimental plot drains dispenser behind the water, pours water water conservation 5～7 days after the dispenser after 48 hours.
1.4, the duration of test weather condition
Early the 3rd day continuous 7 it rains of beginning in back are carried out in test in the rice field, and rainfall amounts to 84.4 millimeters.The 2nd it rains is carried out in test in middle rice field, and arranged in afterwards 10 days 7 day rain day, and rainfall amounts to 19.5 millimeters.Duration of test has certain influence because rainwater is more to drug effect.
2, investigation and method of calculation
2.1 poisoning investigation:
3d, 7d, 14d estimate each treatment zone poisoning situation respectively behind medicine.
2.2 efficacy survey
3d, 7d, 14d estimate each treatment zone drug effect respectively behind medicine, 18d sampling survey behind the medicine.3 points, every some 0.25m are got in every processing at random
2, amount to 0.75m
2Investigate various weeds over-ground part fresh weights respectively, calculate the fresh weight preventive effect.
2.3 preventive effect is calculated
Relative fresh weight preventive effect (%)=[CK-PT]/CK * 100%
In the following formula, PK---check plot weeds fresh weight
CK---outer reason district weeds fresh weight
3, result and analysis
3.1 poisoning situation
Each time observation after dispenser, it is normal that rice growth is respectively distinguished in test, and the phonetic oxime grass ether wettable powder of 20% fluorine (WP) does not have poisoning to paddy rice.
3.2 drug effect situation
The experimental plot gramineous weeds is mainly barnyard grass, red pin barnyard grass and Paspalum distichum, estimate behind the medicine, 3d works the treatment zone weeds lobus cardiacus of playing the phonetic oxime of 20% fluorine grass ether A wettable powder (WP) and begins flavescence behind the medicine, 7d begins death behind the medicine, 14d behind the medicine reaches 99.63% early rice Tanaka to the overall preventive effect of barnyard grass, red pin barnyard grass and Paspalum distichum.
Concrete investigation is calculated as table 3:
Prevent and kill off direct sowing of rice field weed pilot survey table reckoner (table 3) early
Semilate rice Tanaka the overall preventive effect of barnyard grass, red pin barnyard grass and Paspalum distichum is reached 99.57%.
Concrete investigation is calculated as table 4:
Direct sowing of rice field weed pilot survey table (table 4) in preventing and kill off
4, sum up
Test shows, can effectively prevent and kill off morning rice field and middle direct sowing of rice Tanaka's barnyard grass, red pin barnyard grass and Paspalum distichum with the phonetic oxime grass ether A wettable powder of 20% fluorine (WP), wherein, early the preventive effect in rice field reaches 99.63%, and the preventive effect in middle direct sowing of rice field reaches 99.57%.
The advantage of the phonetic oxime grass of fluorine ether herbicide is:
1) have efficient weeding activity, herbicidal effect is good
2) toxicity is low, the person poultry safety
3) easy to use
4) preparation method is simple
The present invention synthesizes first in the world and contains trifluoromethyl pyrimidine salicylic acid weedicide, has tangible novelty and creativeness, measured the activity of the phonetic oxime grass of fluorine ether compound to weedings such as barnyard grass grass, rice barnyard grass, red pin barnyard grass, Paspalum distichums in testing laboratory, wherein the barnyard grass grass of the phonetic oxime of fluorine grass ether A, rice barnyard grass, red pin barnyard grass, Paspalum distichum, activity be respectively 100,98,100,100, the weeding activity of the phonetic oxime grass of three fluorine of the present invention ether compound all is higher than reference product pyribenzoxim and penoxsuam.Therefore, the efficient weeding activity of the phonetic oxime grass of fluorine ether compound has significant practicality in modern agriculture production.
Embodiment:
Further the present invention is done below in conjunction with specific embodiment and to specify:
The weedicide of the phonetic oxime grass of the fluorine that contains trifluoromethylbenzene with efficient weeding activity for preparing ether compound, represent with general formula (I):
R=o,m,p-CF3
Wherein R be adjacent,, to the trifluoromethylbenzene substitution compound.
The phonetic oxime grass of fluorine ether compound has following three kinds of structures:
The phonetic oxime grass of fluorine ether A:O-[2,6-two (4,6-SDM base-2-base oxygen base) benzoyl] (2-trifluoromethyl) benzaldoxime;
The phonetic oxime grass of fluorine ether B:O-[2,6-two (4,6-SDM base-2-base oxygen base) benzoyl] (3-trifluoromethyl) benzaldoxime;
The phonetic oxime grass of fluorine ether C:O-[2,6-two (4,6-SDM base-2-base oxygen base) benzoyl] (4-trifluoromethyl) benzaldoxime;
Experiment one: the preparation of 2-trifluoromethylated benzaldehyde oxime
In the 500ml reaction flask, add methyl alcohol (300 milliliters), oxammonium hydrochloride (8.3g; 120mmol), 50% aqueous sodium hydroxide solution (9.6g; 120mmol), (17.4g 100mmol), reacted 1 hour down for 25 ℃ in nitrogen protection the 2-trifluoromethylated benzaldehyde; after reaction finishes; under reduced pressure steam except methyl alcohol, add water solid 2-trifluoromethylated benzaldehyde oxime, (17.8g; 94.1%) fusing point: 53.5-54.5 ℃.
1H?NMR:(400Hz,CDCl
3),δ(ppm),8.54(s,1H),8.02(d,J=12Hz,1H),7.71(d,J=12Hz,1H),7.49-7.61(m,2H),1.83(s,1H,OH)。
13C?NMR:(100Hz,CDCl
3),δ(ppm),147.2,132.0,129.6,128.6,127.2,126.0,125.7,122.1。
Experiment two: the preparation of 3-trifluoromethylated benzaldehyde oxime
In the 500ml reaction flask, add methyl alcohol (250 milliliters), oxammonium hydrochloride (6.9g; 100mmol), 50% aqueous sodium hydroxide solution (8.0g; 100mmol), 3-trifluoromethylated benzaldehyde (17.4g; 100mmol), reacted 1 hour down for 25 ℃ in nitrogen protection, after reaction finishes; under reduced pressure steam except methyl alcohol; get oily matter 3-trifluoromethylated benzaldehyde oxime, (16.9g, 89.4%).
1H?NMR:(400Hz,DMSO-d
6),δ(ppm),11.53(s,1H,OH),8.27(s,1H),7.85-7.92(m,2H),7.64–7.72(m,2H)。
13C?NMR:(100Hz,DMSO-d
6),δ(ppm),145.6,134.7,129.8,126.1,125.4,123.2，122.6,119.0。
Experiment three: the preparation of 4-trifluoromethylated benzaldehyde oxime
In the 500ml reaction flask, add methyl alcohol (350 milliliters), oxammonium hydrochloride (10.4g; 150mmol), 50% aqueous sodium hydroxide solution (12.0g, 150mmol), the 4-trifluoromethylated benzaldehyde (17.4g, 100mmol); reacted 1 hour down for 25 ℃ in nitrogen protection; after reaction finishes, under reduced pressure steam except methyl alcohol, add water filtration and get solid 4-trifluoromethylated benzaldehyde oxime; (18.1g; 95.7%) fusing point: 101.5 ℃ of 101.0 –
1H NMR:(400Hz, DMSO-d
6), δ (ppm), 11.63 (s, 1H, NOH), 8.25 (s, 1H), 7.81 (dd, J=18Hz, 2H), 7.76 (dd, J=18Hz, 2H).
13CNMR:(100Hz,DMSO-d
6),δ(ppm),147.6,134.6,130.2，127.4,126.1，120.2。
Experiment four: the preparation of the phonetic oxime grass of fluorine ether A
In the 500ml reaction flask, add 280 milliliters of methylene dichloride; add 2 respectively then; 6-two (4; 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid (21.5g; 50mmol), 2-trifluoromethylated benzaldehyde oxime (9.6g; 50.8mmol), DCC(11.3g, 53.7mmol), DMAP(0.63g, 5mmol), under nitrogen protection; reaction is 3 hours under the room temperature; after reaction finishes, filter, filtrate concentrating reclaimed methylene dichloride; get the phonetic oxime grass of white crystal fluorine ether A; (23.5g, 78.2%), fusing point: 157.4 ℃～157.9 ℃.
1HNMR:(400Hz,CDCl
3),δ(ppm),3.720(s,6H,2xCH
3O),3.792(s,6H,2xCH
3O),5.737(s,2H,Pyrimidine?CH),7.219(d,J=8.4Hz,2H,2x?Ph-CH),7.545(d,J=4.0Hz,1H,Ph-CH),7.556(d,J=5.2Hz,1H,Ph-CH),7.588(d,J=8.4Hz,1H,Ph-CH),7.681(m,1H,Ph-CH),8.057(m,1H,Ph-CH),8.44(s,1H,N=CH-)。
13CNMR:(100Hz,CDCl
3),δ(ppm),172.88(4C),163.80,160.44,152.88,151.95,132.51,132.20,132.00,131.55,131.23,130.88,129.48,129.24,128.70,125.95,124.61,120.57,119.05,54.14。
Experiment five: the preparation of the phonetic oxime grass of fluorine ether B
In the 500ml reaction flask, add 250 milliliters of acetone, add 2,6-two (4 more respectively; 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid (21.5g; 50mmol), 3-trifluoromethylated benzaldehyde oxime (9.5g, 50.2mmol), DIC(6.8g, 54.5mmol), HOBt(0.81g; 6mmol), under nitrogen protection; reaction is 1 hour under the room temperature, after reaction finishes, filter the phonetic oxime grass of white crystal fluorine ether B(21.1g; 70.2%) fusing point: 130.9 ℃～131.2 ℃.
1HNMR:(400Hz,CDCl
3),δ(ppm),3.786(s,6H,2xCH
3O),3.805(s,6H,2xCH
3O),5.737(s,2H,Pyrimidine?CH),7.221(d,J=7.6Hz,2H,2x?Ph-CH),7.530(dd,J=15.6Hz,J=8.0,1H,Ph-CH),7.599(dd,J=16.4Hz,J=8.0Hz,1H,Ph-CH),7.710(d,J=8.0Hz,1H,Ph-CH),7.681(d,J=8.0Hz,1H,Ph-CH),7.846(s,1H,Ph-CH),8.156(s,1H,N=CH-)。
13CNMR:(100Hz,CDCl
3),δ(ppm),172.91,163.89,160.44,155.19,152.00,132.44,131.69,131.43,131.32,130.88,129.48,128.24,128.22,125.14,125.11,124.64,120.59,119.05,54.20。
Experiment six: the preparation of the phonetic oxime grass of fluorine ether C
In the 500ml reaction flask, add 200 milliliters of methylene dichloride; add 2 respectively again; 6-two (4; 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid (21.5g; 50mmol), 4-trifluoromethylated benzaldehyde oxime (9.5g; 50.2mmol), DCC(10.3g; 50.1mmol), DMAP(0.6g, 4.9mmol), under nitrogen protection, reaction is 2 hours under the room temperature; after reaction finishes; filter, filtrate concentrating reclaimed methylene dichloride, gets the phonetic oxime grass of white crystal fluorine ether C(18.2g; 60.5%) fusing point: 190.4 ℃～190.8 ℃.
1HNMR:(400Hz,CDCl
3),δ(ppm),3.786(s,6H,2xCH
3O),3.804(s,6H,2xCH
3O),5.736(s,2H,Pyrimidine?CH),7.222(d,J=8.0Hz,2H,2x?Ph-CH),7.590(d,J=8.4,1H,Ph-CH),7.620(dd,J=11.2Hz,J=6.8Hz,2H,Ph-CH),7.649(d,J=8.4Hz,2H,Ph-CH),7.681(d,J=8.0Hz,1H,Ph-CH),7.846(s,1H,Ph-CH),8.156(s,1H,N=CH-)。
13CNMR:(100Hz,CDCl
3),δ(ppm),172.91(4C),163.89,160.42,155.05,151.99,133.42,133.33,133.16,132.71,132.46,128.58,126.23,125.83,125.80,124.69,122.53,120.60,119.01,54.21。
Claims (4)
1. the phonetic oxime grass of the fluorine with weeding activity ether compound, its general structure is as follows:
R=o,m,p-CF3
Wherein: R be adjacent,, to position trifluoromethyl.
2. the preparation method of the phonetic oxime of the described fluorine of claim 1 grass ether compound is characterized in that:
To replace trifluoromethylated benzaldehyde, 2, two (4, the 6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid of 6-are the phonetic oxime grass of feedstock production fluorine ether compound, and concrete preparation process is as follows:
Step 1: replace the preparation of trifluoromethylated benzaldehyde oxime
With oxammonium hydrochloride with to replace trifluoromethylated benzaldehyde be raw material, add solvent alcohol and inorganic alkali as a catalyst, under 0 ℃～25 ℃ temperature condition, react, react after 1～3 hour, treatedly must replace the trifluoromethylated benzaldehyde oxime;
Wherein, solvent alcohol is methyl alcohol, ethanol, Virahol, propyl carbinol or n-propyl alcohol;
Mineral alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, yellow soda ash or salt of wormwood;
Step 2: the preparation of the phonetic oxime grass of fluorine ether compound
With 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid and above-mentioned replacement trifluoromethylated benzaldehyde oxime are raw material, under organic solvent, catalyzer and dewatering agent effect, reacted at normal temperatures 3～5 hours, reaction finishes after-filtration, and filtrate is under reduced pressure steamed except reclaiming organic solvent, namely gets the phonetic oxime grass of target compound fluorine ether compound;
Wherein, described organic solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, acetone, acetonitrile, tetrahydrofuran (THF), dioxane, N, dinethylformamide, methyl acetate, ethyl ester ethyl ester, propyl acetate or ethanol butyl ester;
Described catalyzer is: 4-Dimethylamino pyridine (DMAP) or 4-(1'-Pyrrolidine) pyridine (4-PPY);
Described dewatering agent: N, N'-dicyclohexylcarbodiimide (DCC) or N, N'-DIC (DIC).
3. the preparation method of the phonetic oxime of 1 described fluorine grass ether compound as requested is characterized in that:
In step 1, described solvent alcohol is methyl alcohol, and described mineral alkali is sodium hydroxide; In step 2, described organic solvent is methylene dichloride; Described catalyzer is: 4-Dimethylamino pyridine (DMAP); Described dewatering agent: N, N'-dicyclohexylcarbodiimide (DCC).
4. the purposes of the phonetic oxime grass of the described fluorine of claim 1 ether compound is characterized in that: the barnyard grass grass that is used for preventing and kill off rice terrace.
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| CN201310310166.9A CN103333121B (en) | 2013-07-22 | 2013-07-22 | Fluorine phonetic oxime grass ether compound with weeding activity and preparation method thereof |
| CN201510701775.6A CN105272924B (en) | 2013-07-22 | 2013-07-22 | Fluoropyrimidine grass ether compound with activity of weeding and preparation method thereof |
| PCT/CN2014/081807 WO2015010533A1 (en) | 2013-07-22 | 2014-07-08 | Fluorine pyribenzoxim compound with herbicidal activity and preparation method therefor |
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| CN105272924A (en) | 2016-01-27 |
| CN105272924B (en) | 2016-08-17 |
| WO2015010533A1 (en) | 2015-01-29 |
| CN103333121B (en) | 2015-11-18 |
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