CN105272924A - O-[2,6-bis(4,6-dimethoxy-2-pyrimidinyl) oxyl] benzoylbenzene (2-trifluoromethyl) formaldoxime compounds with herbicidal activity and preparation method of compounds - Google Patents
O-[2,6-bis(4,6-dimethoxy-2-pyrimidinyl) oxyl] benzoylbenzene (2-trifluoromethyl) formaldoxime compounds with herbicidal activity and preparation method of compounds Download PDFInfo
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Abstract
The invention discloses O-[2,6-bis(4,6-dimethoxy-2-pyrimidinyl) oxyl] benzoylbenzene (2-trifluoromethyl) formaldoxime compounds with herbicidal activity and a preparation method of the compounds. The chemical name of the O-[2,6-bis(4,6-dimethoxy-2-pyrimidinyl) oxyl] benzoylbenzene (2-trifluoromethyl) formaldoxime compounds is O-[2,6-bis(4,6-dimethoxy-2-pyrimidinyl) oxyl] benzoylbenzene (2-trifluoromethyl) formaldoxime, the molecular formula is C27H22N5O8F3, the molecular weight is 601.5, the compounds include three isomerides, and molecular structural formulae and physical properties of the isomerides are disclosed. Meanwhile, the invention further discloses a preparation method utilizing substituted trifluoromethylbenzaldehyde and 2,6-bis(4,6-dimethoxy-2-pyrimidinyl-2-oxyl) benzoic acid as raw materials. The control effects of the compounds on barnyard grass, echinochloa colona, paspalum distichum and water barnyardgrass in the rice field are all higher than 94%. Besides, the compounds have high safety on rice crop, are environment-friendly and low-toxic, and have the broad application prospect in the field of pesticides.
Description
Technical field:
The present invention relates to and a kind of there is new compound of weeding activity and preparation method thereof, particularly relate to 5-FU grass ether compound with weeding activity and preparation method thereof.
Background technology:
Last century late nineteen eighties, pyrimidinylthiobenzoate herbicides is found the earliest by Japanese combinatorial chemistry and develops two careless ether (Bispyribac-sodium) (CN1035292A) of first commercial varieties, Korea S LG chemical company develops 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, but these compounds are to the barnyard 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 effectively preventing and kill off the barnyard grass of rice terrace, red pin barnyard grass, Paspalum distichum, rice barnyard grass.Applicant conducts extensive research 5-FU grass ether compound, find through long-term research and test, the specific position of pyrimidine salicylic acid compounds introduces trifluoromethyl substituent, the 5-FU grass ether compound of gained demonstrates perennial and annual gramineous weed and excellent prevents and kill off performance, and to preventing and kill off the barnyard grass of rice terrace, red pin barnyard grass, Paspalum distichum, rice barnyard grass have special efficacy.And 5-FU grass ether compound can realize preventing and kill off barnyard grass, red pin barnyard grass, Paspalum distichum, rice barnyard grass and so on weeds with lower dosage, rice crop is had to the security of height simultaneously, very effective to preventing and kill off of the weeds such as barnyard grass, environmentally friendly, low toxicity, is with a wide range of applications at pesticide field.
Summary of the invention:
The object of this invention is to provide a kind of 5-FU grass ether compound with weeding activity and preparation method thereof.
This chemical name with the 5-FU grass ether compound of weeding activity is O-[two (4,6-dimethoxy-2-pyrimidyl) the oxygen base of 2,6-] 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 ortho position trifluoromethyl, be referred to as 5-FU grass ether A, its chemical name is:
O-[two (4, the 6-SDM base-2-base oxygen base) benzoyl of 2,6-] (2-trifluoromethyl) benzaldoxime;
Its physical properties is:
1. sterling is white crystalline solid;
2. fusing point: 157.4 DEG C ~ 157.9 DEG C;
3. the pH value of sterling 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 ortho position trifluoromethyl, be referred to as 5-FU grass ether B, its chemical name is:
O-[two (4, the 6-SDM base-2-base oxygen base) benzoyl of 2,6-] (3-trifluoromethyl) benzaldoxime,
Its physical properties is:
1. sterling is white crystalline solid;
2. fusing point: 130.9 DEG C ~ 131.2 DEG C;
3. the pH value of sterling 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 to position trifluoromethyl, be referred to as 5-FU grass ether C, its chemical name is:
O-[two (4, the 6-SDM base-2-base oxygen base) benzoyl of 2,6-] (4-trifluoromethyl) benzaldoxime,
Its physical properties is:
1. sterling is white crystalline solid;
2. fusing point: 190.4 DEG C ~ 190.8 DEG C;
3. the pH value of sterling 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 5-FU grass ether A, 5-FU grass ether B and 5-FU grass ether C is as follows:
This 5-FU grass ether compound can be used for preparing efficient, low toxicity, and to rice safety, eco-friendly highly selective weedicide, can prevent and kill off the monocotyledon weeds such as the barnyard grass in rice terrace, red pin barnyard grass, Paspalum distichum, rice barnyard grass especially.
The preparation method of the 5-FU grass ether compound with weeding activity of the present invention is as follows:
To replace trifluoromethylated benzaldehyde, 2,6-pairs of (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid are that 5-FU grass ether compound prepared by raw material, and its synthesis equation is:
The synthetic route of Scheme1 5-FU grass ether compound
This to replace trifluoromethylated benzaldehyde, 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid are the preparation method that 5-FU grass ether compound prepared by raw material, comprise the following steps:
Step 1: the preparation replacing trifluoromethylated benzaldehyde oxime
With oxammonium hydrochloride with replace trifluoromethylated benzaldehyde for raw material, add solvent alcohol and inorganic alkali as a catalyst, react under 0 DEG C ~ 25 DEG C temperature condition, react after 1 ~ 3 hour, treatedly must replace 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, sodium carbonate or salt of wormwood, preferred sodium hydroxide;
Step 2: the preparation of 5-FU grass ether compound
With 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid and above-mentioned replacement trifluoromethylated benzaldehyde oxime be raw material, under organic solvent, catalyzer and dewatering agent effect, react 3 ~ 5 hours at normal temperatures, reaction terminates rear filtration, and filtrate is under reduced pressure steamed except reclaiming organic solvent, obtains target compound 5-FU grass ether compound;
Wherein, described organic solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, acetone, acetonitrile, tetrahydrofuran (THF), dioxane, DMF, methyl acetate, EtOAc, propyl acetate or ethanol butyl ester, preferred methylene dichloride;
Described catalyzer is: DMAP (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) the clean synthesis technique of phenylformic acid to be the preparation method that 5-FU grass ether compound prepared by raw material a be green, be applicable to a large amount of batches of preparation of industrialization 5-FUs grass ether-derivative herbicidess.
Innovative point of the present invention:
1. provide a kind of brand-new 5-FU grass ether-derivative herbicides, it can prevent and kill off barnyard grass, red pin barnyard grass, Paspalum distichum, rice barnyard grass very effectively to rice field, simultaneously environmentally friendly, and low toxicity is harmless to rice safety.
2. provide the technology of preparing of a kind of highly effective and safe 5-FU grass ether-derivative herbicides, can not only prepare 5-FU grass ether-derivative herbicides in a large number, and yield is high, purity is good.
Main points of the present invention are:
Be the 5-FU grass ether-derivative herbicides that raw material preparation has efficient weeding activity with trifluoromethylated benzaldehyde, 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid.
5-FU grass ether-derivative herbicides has good weeding activity, can be used as the effective active composition of weedicide, prepares the various pesticide formulation, such as wettable powder, emulsion, water dispersion granule etc.
The Herbicidal test of 5-FU grass ether compound:
(1), testing laboratory's preventing iron test
Use 5-FU grass ether compound to carry out weeding activity test to barnyard grass in paddy field, test method is as follows:
1, medicament and preparation is tested:
The former medicine of 5-FU grass ether compound of certain mass is taken with analytical balance, the little preparation of missible oil being mixed with 1.0-5.0% is dissolved with solvent (acetone, DMF or DMSO file mark etc.), then finite concentration is become with the distilled water diluting containing 0.15%TW-80, for subsequent use.
2, test design:
3, test
Monocotyledon weed seed for test is evenly sown in internal diameter 9cm basin alms bowl respectively, cultivate in greenhouse, the 1-1.5 leaf phase is grown to Deng monocotyledon weed, rear cauline leaf process is carried out with automatic sprayer, process 3 repetitions, if blank, after process, leave standstill 4-5 hour, after liquid on leaf is dry, move into warm indoor cultivation.
Observe plant strain growth situation every day, periodic logging damage symptoms, after symptom of chemical damage is obvious, the comprehensive weeding activity of range estimation investigation.
4, result investigation, result investigation adopts range estimation, visual assessment medicament is to plant strain growth suppression, deformity, yellow, rotten, downright bad influence degree, then suppress completely according to the plant that is comprehensively injured, its judgement criteria refers to table 1, and the Herbicidal of 5-FU grass ether compound is the results detailed in Table 2.
Table 1 greenhouse pot culture weeding activity judgement criteria
| Weeding activity (%) | Weeding activity comment (suppression, deformity, yellow etc.) |
| 0 | With contrast, resistance, eliminates |
| 12-20 | Growth slightly affects, and lives poor, eliminates |
| 30-40 | Growth has impact, lives poor, eliminates |
| 50-60 | Growth has impact, lives medium, can consider further transformation |
| 70-80 | More responsive, better active, can sieve be taken into account |
| 90-99 | Extremely responsive, active good, enter sieve |
| 100 | Death, active good, enter sieve |
Table 2 5-FU grass ether compound Herbicidal result:
Show to observe 5-FU grass ether compound from above and there is good suppression barnyard grass, rice barnyard grass, red pin barnyard grass, Paspalum distichum weeds activity.
(2), the preventing iron test of 5-FU grass ether in ridged pot without plow and live middle rice field:
Consumption: with 5-FU grass ether A wettable powder (WP) 15 ~ 30g/667m of 20%
2.
Usage: thin up even spraying.
The weeding simultaneous test of 5-FU grass ether A:
1, materials and methods
The outstanding OF of rice of 1.1,20% 5-FU grass ether A wettable powder of applicant's production and The Dow Agrosciences, LLC. are produced 2.5% carries out weeding simultaneous test.
1.2, test design
5 process are established in test altogether, respectively:
Process 1:20% 5-FU grass ether A wettable powder (WP), 15g/667m
2;
Process 2:20% 5-FU grass ether A wettable powder (WP), 20g/667m
2;
Process 3:20% 5-FU grass ether A wettable powder (WP), 30g/667m
2;
Rice outstanding OF, the 60ml/667m of process 4:2.5%
2;
Process 5: blank;
Every plot area 215m
2, during dispenser, adopt hand sprayer even spraying.
1.3, experimental plot basic condition
Experimental plot is ridged pot without plow and live semilate rice, is located at Ba Lingshan town, Jingzhou District, area 1505m
2; Clayey soil, preceding crop: blank field.Early rice is in dispenser on April 25, and semilate rice is in dispenser on May 16, and during dispenser, paddy rice is tillering phase, and during field, main gramineous weeds is barnyard grass, red pin barnyard grass, Paspalum distichum, and grass leaf ~ 7 leaf in age 4 wholeheartedly.Experimental plot drains dispenser after water, pours water after dispenser after 48 hours, water conservation 5 ~ 7 days.
1.4, duration of test weather condition
Early rice field starts continuous 7 it rains in the 3rd day after test is carried out, and rainfall amounts to 84.4 millimeters.The 2nd it rains is carried out in test in middle rice field, and have 7 day rain day in afterwards 10 days, rainfall amounts to 19.5 millimeters.Duration of test due to rainwater more, have certain influence to drug effect.
2, investigation and method of calculation
2.1 poisoning investigation:
After medicine, 3d, 7d, 14d estimate each treatment zone poisoning situation respectively.
2.2 efficacy survey
After medicine, 3d, 7d, 14d estimate each treatment zone drug effect respectively, 18d sampling survey after medicine.Often process and get 3 points at random, often some 0.25m
2, amount to 0.75m
2.Investigate various weeds over-ground part fresh weight respectively, calculate fresh weight preventive effect.
2.3 preventive effects calculate
Relative fresh weight preventive effect (%)=[CK-PT]/CK × 100%
In above formula, PK---check plot weeds fresh weight
CK---Wai Li district weeds fresh weight
3, results and analysis
3.1 poisoning situations
Observe for each time after dispenser, test each district rice growth normal, 20% 5-FU grass ether wettable powder (WP) to paddy rice without poisoning.
3.2 drug effect situations
Experimental plot gramineous weeds is mainly barnyard grass, red pin barnyard grass and Paspalum distichum, estimate after medicine, after medicine 3d rise beat 20% 5-FU grass ether A wettable powder (WP) treatment zone weeds lobus cardiacus start turn yellow, after medicine, 7d starts death, 14d after medicine, reaches 99.63% at the overall preventive effect of early rice Tanaka to barnyard grass, red pin barnyard grass and Paspalum distichum.
Concrete investigation calculates as table 3:
Prevent and kill off early direct seeded rice weeds pilot survey table reckoner (table 3)
| 3 | 0.0 | 100 | 0.0 | 100 | 0.0 | 100 | 0.0 | 100 |
| 4 | 0.0 | 100 | 37.1 | 71.9 | 1.2 | 76.9 | 38.3 | 80.2 |
| CK | 55.5 | 0 | 132.3 | O | 5.2 | 0 | 193.0 | 0 |
99.57% is reached at the overall preventive effect of semilate rice Tanaka to barnyard grass, red pin barnyard grass and Paspalum distichum.
Concrete investigation calculates as table 4:
Prevent and kill off middle direct sowing of rice field weed pilot survey table (table 4)
4, sum up
Test shows, with 20% 5-FU grass ether A wettable powder (WP) can to morning rice field and the barnyard grass of middle direct sowing of rice Tanaka, red pin barnyard grass and Paspalum distichum effectively prevent and kill off, 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 5-FU grass ether herbicide is:
1) have efficient weeding activity, herbicidal effect is good
2) toxicity is low, person poultry safety
3) easy to use
4) preparation method is simple
The present invention's synthesis first is in the world containing trifluoromethyl pyrimidine salicylic acid weedicide, there is obvious novelty and creativeness, 5-FU grass ether compound is determined to the activity of the weedings such as barnyard grass, rice barnyard grass, red pin barnyard grass, Paspalum distichum in testing laboratory, wherein 5-FU grass ether A to barnyard grass, rice barnyard grass, red pin barnyard grass, Paspalum distichum, activity be respectively 100,98,100,100, the weeding activity of three 5-FUs grass ether compound of the present invention is all higher than reference product pyribenzoxim and penoxsuam.Therefore, the efficient weeding activity of 5-FU grass ether compound has significant practicality in modern agricultural production.
Embodiment:
Further the present invention is illustrated below in conjunction with specific embodiment:
The weedicide with the grass of the 5-FU containing the trifluoromethylbenzene ether compound of efficient weeding activity to be prepared, represents with general formula (I):
R＝o，m，p-CF3
Wherein R be adjacent, to trifluoromethyl aromatics.
5-FU grass ether compound has following three kinds of structures:
5-FU grass ether A:O-[two (4, the 6-SDM base-2-base oxygen base) benzoyl of 2,6-] (2-trifluoromethyl) benzaldoxime;
5-FU grass ether B:O-[two (4, the 6-SDM base-2-base oxygen base) benzoyl of 2,6-] (3-trifluoromethyl) benzaldoxime;
5-FU grass ether C:O-[two (4, the 6-SDM base-2-base oxygen base) benzoyl of 2,6-] (4-trifluoromethyl) benzaldoxime;
The preparation of experiment one: 2-trifluoromethylated benzaldehyde oxime
Methyl alcohol (300 milliliters), oxammonium hydrochloride (8.3g is added in 500ml reaction flask; 120mmol), 50% aqueous sodium hydroxide solution (9.6g; 120mmol), 2-trifluoromethylated benzaldehyde (17.4g, 100mmol), at nitrogen protection 25 DEG C react 1 hour; after reaction terminates; under reduced pressure steam except methyl alcohol, add water and obtain solid 2-trifluoromethylated benzaldehyde oxime, (17.8g; 94.1%), fusing point: 53.5-54.5 DEG C.
1HNMR：(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)。
13CNMR：(100Hz，CDCl
3)，δ(ppm)，147.2，132.0，129.6，128.6，127.2，126.0，125.7，122.1。
The preparation of experiment two: 3-trifluoromethylated benzaldehyde oxime
Methyl alcohol (250 milliliters), oxammonium hydrochloride (6.9g is added in 500ml reaction flask; 100mmol), 50% aqueous sodium hydroxide solution (8.0g; 100mmol), 3-trifluoromethylated benzaldehyde (17.4g; 100mmol), react 1 hour at nitrogen protection 25 DEG C, after reaction terminates; under reduced pressure steam except methyl alcohol; obtain oily matter 3-trifluoromethylated benzaldehyde oxime, (16.9g, 89.4%).
1HNMR：(400Hz，DMSO-d
6)，6(ppm)，11.53(s，1H，OH)，8.27(s，1H)，7.85-7.92(m，2H)，7.64-7.72(m，2H)。
13CNMR：(100Hz，DMSO-d
6)，δ(ppm)，145.6，134.7，129.8，126.1，125.4，123.2，122.6，119.0。
The preparation of experiment three: 4-trifluoromethylated benzaldehyde oxime
Methyl alcohol (350 milliliters), oxammonium hydrochloride (10.4g is added in 500ml reaction flask; 150mmol), 50% aqueous sodium hydroxide solution (12.0g, 150mmol), 4-trifluoromethylated benzaldehyde (17.4g, 100mmol); react 1 hour at nitrogen protection 25 DEG C; after reaction terminates, under reduced pressure steam except methyl alcohol, add water filtration and obtain solid 4-trifluoromethylated benzaldehyde oxime; (18.1g; 95.7%), fusing point: 101.0-101.5 DEG C
1hNMR:(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 5-FU grass ether A
Methylene dichloride 280 milliliters is added in 500ml reaction flask; then 2 are added respectively; 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; react 3 hours under room temperature; after reaction terminates, filter, filtrate concentration and recovery methylene dichloride; obtain white crystal 5-FU grass ether A; (23.5g, 78.2%), fusing point: 157.4 DEG C ~ 157.9 DEG C.
1HNMR：(400Hz，CDCl
3)，δ(ppm)，3.720(s，6H，2xCH
3O)，3.792(s，6H，2xCH
3O)，5.737(s，2H，PyrimidineCH)，7.219(d，J＝8.4Hz，2H，2xPh-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 5-FU grass ether B
250 milliliters of acetone are added in 500ml reaction flask; add 2 respectively again; 6-two (4; 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; react 1 hour under room temperature, after reaction terminates, filter to obtain white crystal 5-FU grass ether B (21.1g; 70.2%), fusing point: 130.9 DEG C ~ 131.2 DEG C.
1HNMR：(400Hz，CDCl
3)，δ(ppm)，3.786(s，6H，2xCH
3O)，3.805(s，6H，2xCH
3O)，5.737(s，2H，PyrimidineCH)，7.221(d，J＝7.6Hz，2H，2xPh-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 5-FU grass ether C
200 milliliters of methylene dichloride are added in 500ml reaction flask; 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, react 2 hours under room temperature; after reaction terminates; filter, filtrate concentration and recovery methylene dichloride, obtain white crystal 5-FU grass ether C (18.2g; 60.5%), fusing point: 190.4 DEG C ~ 190.8 DEG C.
1HNMR：(400Hz，CDCl
3)，δ(ppm)，3.786(s，6H，2xCH
3O)，3.804(s，6H，2xCH
3O)，5.736(s，2H，PyrimidineCH)，7.222(d，J＝8.0Hz，2H，2xPh-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 (10)
1. have a compound for weeding activity, its general structure is as follows:
Wherein: R be adjacent, to position trifluoromethyl.
2. compound according to claim 1, wherein: R is ortho position trifluoromethyl.
3. compound according to claim 1, wherein: R is to position trifluoromethyl.
4. weedicide, it comprises compound according to claim 1.
5. weedicide according to claim 4, it is wettable powder.
6. the preparation method of compound according to claim 1, is characterized in that:
To replace trifluoromethylated benzaldehyde, 2,6-pairs of (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid are that 5-FU grass ether compound prepared by raw material, and concrete preparation process is as follows:
Step 1: the preparation replacing trifluoromethylated benzaldehyde oxime
With oxammonium hydrochloride with replace trifluoromethylated benzaldehyde for raw material, add solvent alcohol and inorganic alkali as a catalyst, react under 0 DEG C ~ 25 DEG C temperature condition, react after 1 ~ 3 hour, treatedly must replace 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, sodium carbonate or salt of wormwood;
Step 2: the preparation of 5-FU grass ether compound
With 2,6-two (4,6-dimethoxy-2-pyrimidyl-2-oxygen base) phenylformic acid and above-mentioned replacement trifluoromethylated benzaldehyde oxime be raw material, under organic solvent, catalyzer and dewatering agent effect, react 3 ~ 5 hours at normal temperatures, reaction terminates rear filtration, and filtrate is under reduced pressure steamed except reclaiming organic solvent, obtains target compound 5-FU grass ether compound;
Wherein, described organic solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, acetone, acetonitrile, tetrahydrofuran (THF), dioxane, DMF, methyl acetate, EtOAc, propyl acetate or ethanol butyl ester;
Described catalyzer is: DMAP (DMAP) or 4-(1 '-Pyrrolidine) pyridine (4-PPY);
Described dewatering agent: N, N '-dicyclohexylcarbodiimide (DCC) or N, N '-DIC (DIC).
7. the preparation method of the compound as requested described in 6, 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: DMAP (DMAP); Described dewatering agent: N, N '-dicyclohexylcarbodiimide (DCC).
8. compound according to claim 1 is as the purposes of weedicide.
9. the purposes of compound according to claim 8, is characterized in that: for preventing and kill off the weeds of rice terrace.
10. the purposes of compound according to claim 9, wherein: weeds are barnyard grass, rice barnyard grass, red pin barnyard grass, Paspalum distichum.
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| CN110278953A (en) * | 2019-07-31 | 2019-09-27 | 河南省农业科学院植物保护研究所 | Herbicidal composition and its application of the ether of grass containing fluoropyrimidine and pyraclonil |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031081A (en) * | 1987-08-07 | 1989-02-15 | 纳幕尔杜邦公司 | The weedicide of control weeds in paddy field |
| CN1033050A (en) * | 1987-11-04 | 1989-05-24 | 古米埃(Kumiai)化学工业株式会社 | Pyrimidine derivatives and preparation method thereof and its herbicidal composition and herbicidal methods |
| CN1035292A (en) * | 1987-12-22 | 1989-09-06 | 古米埃化学工业株式会社 | Pyrimidine derivatives and preparation method thereof and herbicidal methods and composition |
| US4986846A (en) * | 1988-12-19 | 1991-01-22 | Mitsui Toatsu Chemicals, Incorporated | 2-(4,6-dimethoxy-2-pyrimidinyloxy)benzaldoximes, preparation processes thereof, herbicides containing the same, and herbicidal compositions containing the same along with other active ingredient |
| CN1111623A (en) * | 1993-11-13 | 1995-11-15 | 株式会社乐喜 | Novel herbicidal pyrimidine derivatives, process for preparation thereof and their use as herbicide |
| WO1996041799A1 (en) * | 1995-06-12 | 1996-12-27 | Hoechst Schering Agrevo Gmbh | Sulphonamides as herbicides and plant-growth regulators |
| CA2194080A1 (en) * | 1995-12-28 | 1997-06-29 | Kun-Tai Kim | Novel process for preparing 2,6-di(4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272924B (en) * | 2013-07-22 | 2016-08-17 | 金坛市信德农业科技有限公司 | Fluoropyrimidine grass ether compound with activity of weeding and preparation method thereof |
-
2013
- 2013-07-22 CN CN201510701775.6A patent/CN105272924B/en active Active
- 2013-07-22 CN CN201310310166.9A patent/CN103333121B/en active Active
-
2014
- 2014-07-08 WO PCT/CN2014/081807 patent/WO2015010533A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031081A (en) * | 1987-08-07 | 1989-02-15 | 纳幕尔杜邦公司 | The weedicide of control weeds in paddy field |
| CN1033050A (en) * | 1987-11-04 | 1989-05-24 | 古米埃(Kumiai)化学工业株式会社 | Pyrimidine derivatives and preparation method thereof and its herbicidal composition and herbicidal methods |
| CN1035292A (en) * | 1987-12-22 | 1989-09-06 | 古米埃化学工业株式会社 | Pyrimidine derivatives and preparation method thereof and herbicidal methods and composition |
| US4986846A (en) * | 1988-12-19 | 1991-01-22 | Mitsui Toatsu Chemicals, Incorporated | 2-(4,6-dimethoxy-2-pyrimidinyloxy)benzaldoximes, preparation processes thereof, herbicides containing the same, and herbicidal compositions containing the same along with other active ingredient |
| CN1111623A (en) * | 1993-11-13 | 1995-11-15 | 株式会社乐喜 | Novel herbicidal pyrimidine derivatives, process for preparation thereof and their use as herbicide |
| WO1996041799A1 (en) * | 1995-06-12 | 1996-12-27 | Hoechst Schering Agrevo Gmbh | Sulphonamides as herbicides and plant-growth regulators |
| CA2194080A1 (en) * | 1995-12-28 | 1997-06-29 | Kun-Tai Kim | Novel process for preparing 2,6-di(4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid oxime ester derivatives |
Non-Patent Citations (4)
| Title |
|---|
| ARZU，KARAKURT等: "《Synthesis of some novel 1-(2-naphthyl)-2-(imidazol-1-yl)ethanone oxime ester derivatives and evaluation of their anticonvulsant activity》", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》 * |
| TRACEY，PIRALI等: "《Stereospecific Synthesis of syn-α-Oximinoamides by a Three-Component Reaction of Isocyanides,syn-Chlorooximes,and Carboxylic Acids》", 《ORGANIC LETTERS》 * |
| 李元祥: "《新型4,6-二甲氧基嘧啶类衍生物的合成及除草活性研究》", 《华中师范大学博士学位论文》 * |
| 田志高等: "《新型除草剂嘧啶肟草醚的合成研究》", 《现代农药》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311982A (en) * | 2017-06-26 | 2017-11-03 | 杨子辉 | A kind of bispyribac-sodium derivative and preparation method and application |
| CN107616185A (en) * | 2017-10-31 | 2018-01-23 | 安徽蓝田农业开发有限公司 | A kind of herbicidal composition containing mesosulfuron and fluoropyrimidine grass ether |
| CN110278953A (en) * | 2019-07-31 | 2019-09-27 | 河南省农业科学院植物保护研究所 | Herbicidal composition and its application of the ether of grass containing fluoropyrimidine and pyraclonil |
| CN110278953B (en) * | 2019-07-31 | 2021-11-05 | 河南省农业科学院植物保护研究所 | Herbicide composition containing pyriftalid and pyraclonil and application thereof |
Also Published As
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| CN103333121A (en) | 2013-10-02 |
| CN103333121B (en) | 2015-11-18 |
| CN105272924B (en) | 2016-08-17 |
| WO2015010533A1 (en) | 2015-01-29 |
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