CN105272924B - Fluoropyrimidine grass ether compound with activity of weeding and preparation method thereof - Google Patents
Fluoropyrimidine grass ether compound with activity of weeding and preparation method thereof Download PDFInfo
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
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- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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Abstract
The invention discloses a kind of fluoropyrimidine grass ether compound with activity of weeding and preparation method thereof; the chemical name of fluoropyrimidine grass ether compound is O [2; 6 pairs (4; 6 dimethoxy 2 pyrimidine radicals) epoxide] Benzoylbenzene (2 trifluoromethyl) formaldoxime; molecular formula is C27H22N5O8F3; molecular weight 601.5, it has three isomerss, discloses their molecular structural formula and physical property；Also disclose a kind of with replace trifluoromethylated benzaldehyde, 2,6 pairs (4,6 dimethoxy 2 pyrimidine radicals 2 epoxides) benzoic acid is method for preparing raw material, the barnyard grass of its rice terrace, red foot barnyard grass, Paspalum distichum, rice barnyard grass preventive effect all more than 94%.Rice crop is had the safety of height simultaneously, environmentally friendly, low toxicity, it is with a wide range of applications at pesticide field.
Description
Technical field:
The present invention relates to a kind of there is new compound of activity of weeding and preparation method thereof, particularly relate to that there is activity of weeding
Fluoropyrimidine grass ether compound and preparation method thereof.
Background technology:
Last century late nineteen eighties, pyrimidinylthiobenzoate herbicides by Japan combinatorial chemistry find the earliest and develop first
The bispyribac-sodium (Bispyribac-sodium) (CN1035292A) of individual commercial varieties, Korea S LG chemical company develops subsequently
Pyribenzoxim (pyribenzoxim) (EP658549A1), Shanghai Organic Chemistry Institute, Chinese Academy of Sciences and Zhejiang chemical industry section
Skill Group Co., Ltd has developed propyl-ester nitorfen and iso-propyl-ester nitrofen (CN112793C) etc. cooperatively, but these compounds are to water
The barnyard grass in rice field, red foot barnyard grass, Paspalum distichum, rice barnyard grass etc. weed control efficacy unsatisfactory.
A kind of the barnyard grass of rice terrace, red foot barnyard grass, Paspalum distichum, the herbicide of rice barnyard grass can be effectively prevented and kill off in order to work out.Shen
Ask someone fluoropyrimidine grass ether compound is conducted extensive research, find, pyrimidine bigcatkin willow through long-term research and test
Introducing trifluoromethyl substituent on the ad-hoc location of acid compounds, the fluoropyrimidine grass ether compound of gained is to perennial and one
Year raw grassy weed demonstrates excellent prevents and kill off performance, and to preventing and kill off the barnyard grass of rice terrace, red foot barnyard grass, Paspalum distichum, rice barnyard grass have
Specially good effect.And fluoropyrimidine grass ether compound can be to realize barnyard grass, red foot barnyard grass, Paspalum distichum, rice barnyard grass etc than relatively low dosage
Preventing and kill off of weeds, has the safety of height simultaneously, prevents and kill off highly effective to weeds such as barnyard grasses rice crop, to environment friend
Good, low toxicity, it is with a wide range of applications at pesticide field.
Summary of the invention:
It is an object of the invention to provide a kind of fluoropyrimidine grass ether compound with activity of weeding and preparation method thereof.
The chemical name of this fluoropyrimidine grass ether compound with activity of weeding be O-[2,6-double (4,6-dimethoxies-
2-pyrimidine radicals) epoxide] Benzoylbenzene (2-trifluoromethyl) formaldoxime；
Molecular formula is C27H22N5O8F3；Molecular weight 601.5；General formula of molecular structure is as follows:
R=o, m, p-CF3
Wherein: R is o-, m-, to position trifluoromethyl；
When R is ortho position trifluoromethyl, referred to as fluoropyrimidine grass ether A, its chemical name is:
O-[2,6-double (4,6-SDM base-2-base epoxide) benzoyls] (2-trifluoromethyl) benzaldoxime；
Its physical property 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. it is dissolved in dichloromethane, acetonitrile solvent, is slightly soluble in methanol, acetone solvent；Water insoluble.
When R is ortho position trifluoromethyl, referred to as fluoropyrimidine grass ether B, its chemical name is:
O-[2,6-double (4,6-SDM base-2-base epoxide) benzoyls] (3-trifluoromethyl) benzaldoxime,
Its physical property 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. it is dissolved in dichloromethane, acetonitrile solvent, is slightly soluble in methanol, acetone solvent；Water insoluble.
When R is to position trifluoromethyl, referred to as fluoropyrimidine grass ether C, its chemical name is:
O-[2,6-double (4,6-SDM base-2-base epoxide) benzoyls] (4-trifluoromethyl) benzaldoxime,
Its physical property 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. it is dissolved in dichloromethane, acetonitrile solvent, is slightly soluble in methanol, acetone solvent；Water insoluble；
The chemical structural formula of fluoropyrimidine grass ether A, fluoropyrimidine grass ether B and fluoropyrimidine grass ether C is as follows:
This fluoropyrimidine grass ether compound can be used for preparing efficiently, low toxicity, to rice safety, and eco-friendly high selection
Property herbicide, can prevent and kill off the monocotyledon weeds such as the barnyard grass in rice terrace, red foot barnyard grass, Paspalum distichum, rice barnyard grass especially.
The preparation method of the fluoropyrimidine grass ether compound with activity of weeding of the present invention is as follows:
With replace trifluoromethylated benzaldehyde, 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-is raw material system
Standby fluoropyrimidine grass ether compound, its synthesis equation is:
The synthetic route of Scheme1 fluoropyrimidine grass ether compound
This with replace trifluoromethylated benzaldehyde, 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-is former
The preparation method of fluoropyrimidine grass ether compound prepared by material, comprises the following steps:
Step 1: replace the preparation of trifluoromethylated benzaldehyde oxime
With oxammonium hydrochloride. with replace trifluoromethylated benzaldehyde as raw material, add solvent alcohol and inorganic alkali as a catalyst, at 0 DEG C
～react under 25 DEG C of temperature conditionss, after reacting 1～3 hour, treated must replace trifluoromethylated benzaldehyde oxime；
Wherein, solvent alcohol is methanol, ethanol, isopropanol, n-butyl alcohol or normal propyl alcohol, preferably methanol；
Inorganic base is sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium carbonate or potassium carbonate, preferably sodium hydroxide；
Step 2: the preparation of fluoropyrimidine grass ether compound
With 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-and above-mentioned replacement trifluoromethylated benzaldehyde oxime
For raw material, under organic solvent, catalyst and dehydrant effect, reaction 3～5 hours at normal temperatures, reaction is filtered after terminating, is filtered
Liquid is under reduced pressure evaporated off reclaiming organic solvent, obtains object fluoropyrimidine grass ether compound；
Wherein, described organic solvent be dichloromethane, chloroform, 1,2-dichloroethanes, acetone, acetonitrile, oxolane,
Dioxane, DMF, methyl acetate, EtOAc, propyl acetate or ethanol butyl ester, preferably dichloromethane；
Described catalyst is: DMAP (DMAP) or 4-(1 '-nafoxidine) pyridine (4-PPY)；
Described dehydrant: N, N '-dicyclohexylcarbodiimide (DCC) or N, N '-DIC (DIC).
With trifluoromethylated benzaldehyde, 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-is that fluorine prepared by raw material
The preparation method of pyrimidine grass ether compound is the synthesis technique of a green cleaning, is suitable for a large amount of batches of preparation of industrialization fluoropyrimidines
Grass ether-derivative herbicides.
The innovative point of the present invention:
1. providing a kind of brand-new fluoropyrimidine grass ether-derivative herbicides, barnyard grass, red foot barnyard grass, double fringe passeris montani saturati can be prevented and kill off in rice field by it
Barnyard grass, rice barnyard grass are highly effective, the most environmentally friendly, and low toxicity is harmless to rice safety.
2. provide the technology of preparing of a kind of highly effective and safe fluoropyrimidine grass ether-derivative herbicides, fluoropyrimidine can not only be prepared in a large number
Grass ether-derivative herbicides, and yield is high, and purity is good.
The method is characterized in that
With trifluoromethylated benzaldehyde, 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-is raw material preparation tool
There is the fluoropyrimidine grass ether-derivative herbicides of efficient activity of weeding.
Fluoropyrimidine grass ether-derivative herbicides has good activity of weeding, can be used as the effective active composition of herbicide, preparation
The various formulations of pesticide, such as wettable powder, Emulsion, water dispersion granule etc..
The Herbicidal test of fluoropyrimidine grass ether compound:
(1), test chamber preventing iron test
Using fluoropyrimidine grass ether compound that barnyard grass in paddy field is carried out activity of weeding test, test method is as follows:
1, test medicament and preparation:
The fluoropyrimidine former medicine of grass ether compound of certain mass is weighed, with solvent (acetone, DMF or DMSO with analytical balance
Middle file mark etc.) dissolve the little preparation of cream being configured to 1.0-5.0%, then with the distilled water diluting containing 0.15%TW-80
Become finite concentration, standby.
2, EXPERIMENTAL DESIGN:
3, test
To the most uniformly be sown in internal diameter 9cm basin alms bowl for the monocotyledon weed seed of test, cultivate in greenhouse, wait list
Leaf weeds grow to the 1-1.5 leaf phase, carry out rear stem and leaf process with automatic sprayer, process 3 repetitions, if blank, process
Rear standing 4-5 hour, after medicinal liquid on leaf is dry, moves into temperature indoor cultivation.
Observing plant strain growth situation, periodic logging damage symptoms every day, after symptom of chemical damage is obvious, range estimation investigation comprehensively removes
Grass activity.
4, result investigation, result investigation uses range estimation, and visual assessment medicament is to plant strain growth suppression, deformity, yellow, corruption
Rotten, downright bad influence degree, then completely inhibits according to the plant that is comprehensively injured, and its evaluation criterion refers to table 1, fluoropyrimidine grass ethers
The Herbicidal of compound is the results detailed in Table 2.
Table 1 greenhouse pot culture activity of weeding evaluation criterion
| Activity of weeding (%) | Activity of weeding comment (suppression, deformity, yellow etc.) |
| 0 | With comparison, drug resistance, eliminate |
| 12-20 | Growth slightly affects, and lives poor, eliminates |
| 30-40 | Growth has an impact, and lives poor, eliminates |
| 50-60 | Growth has an impact, and lives medium, it is contemplated that transform further |
| 70-80 | More sensitive, activity is preferably, it is contemplated that enter sieve |
| 90-99 | Extremely sensitive, activity is good, enters sieve |
| 100 | Death, activity is good, enters sieve |
Table 2 fluoropyrimidine grass ether compound Herbicidal result:
Fluoropyrimidine grass ether compound can be observed on upper table there is good suppression barnyard grass, rice barnyard grass, red foot barnyard grass, double fringe
Ditch millet weeds activity.
(2), fluoropyrimidine grass ether is at ridged pot without plow and the preventing iron test in live middle rice field:
Consumption: with fluoropyrimidine grass ether A wettable powder (WP) 15～30g/667m of 20%2。
Usage: dilute even spraying.
The weeding contrast test of fluoropyrimidine grass ether A:
1, materials and methods
1.1,20% fluoropyrimidine grass ether A wettable powder applicant produced and The Dow Agrosciences, LLC. produce
The rice outstanding person OF of 2.5% carries out weeding contrast test.
1.2, EXPERIMENTAL DESIGN
Test sets 5 process, respectively altogether:
Process 1:20% fluoropyrimidine grass ether A wettable powder (WP), 15g/667m2；
Process 2:20% fluoropyrimidine grass ether A wettable powder (WP), 20g/667m2；
Process 3:20% fluoropyrimidine grass ether A wettable powder (WP), 30g/667m2；
Process the rice outstanding person OF, 60ml/667m of 4:2.5%2；
Process 5: blank；
Every plot area 215m2, during dispenser, use 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 1505m2；Clayey soil, front
Stubble crop: blank field.Early rice is in dispenser on April 25, and semilate rice is in dispenser on May 16, main during during dispenser, Oryza sativa L. is tillering stage, field
Wanting grassy weed is barnyard grass, red foot barnyard grass, Paspalum distichum, and grass leaf in age 4～7 leaves are wholeheartedly.Experimental plot drains dispenser after water, after dispenser 48
Pour water after hour, water conservation 5～7 days.
1.4, weather condition during test
Early rice field starts continuous 7 it rains in the 3rd day after test is carried out, and rainfall amounts to 84.4 millimeters.Middle rice field is in test
Carrying out the 2nd it rains, have 7 day rain day in 10 days afterwards, rainfall amounts to 19.5 millimeters.During test more due to rainwater, right
Drug effect has certain impact.
2, investigation and computational methods
2.1 poisoning investigation:
After medicine, 3d, 7d, 14d estimate each treatment region poisoning situation respectively.
2.2 efficacy survey
After medicine, 3d, 7d, 14d estimate each treatment region drug effect, 18d sampling survey after medicine respectively.Often process and take 3 points at random,
Every some 0.25m2, 0.75m altogether2.Investigate various weeds aerial parts 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, result and analysis
3.1 poisoning situations
Observe for each time after dispenser, test each district rice growth normal, 20% fluoropyrimidine grass ether wettable powder
(WP) to Oryza sativa L. without poisoning.
3.2 drug effect situations
Experimental plot grassy weed is mainly barnyard grass, red foot barnyard grass and Paspalum distichum, estimates after medicine, and after medicine, 3d rises and beat 20% fluorine
The treatment region weeds lobus cardiacus of pyrimidine grass ether A wettable powder (WP) starts to turn yellow, and after medicine, 7d starts death, and 14d after medicine, in early rice
Tanaka reaches 99.63% to the overall preventive effect of barnyard grass, red foot barnyard grass and Paspalum distichum.
Concrete investigation calculates such as table 3:
Prevent and kill off early direct seeded rice weeds test survey table computational chart (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 |
Semilate rice Tanaka, the overall preventive effect of barnyard grass, red foot barnyard grass and Paspalum distichum is reached 99.57%.
Concrete investigation calculates such as table 4:
Prevent and kill off middle direct sowing of rice field weed test survey table (table 4)
4, sum up
Test shows, with 20% fluoropyrimidine grass ether A wettable powder (WP) can to rice field morning and the barnyard grass of middle direct sowing of rice Tanaka,
Red foot barnyard grass and Paspalum distichum are effectively prevented and kill off, and wherein, early the preventive effect in rice field reaches 99.63%, and middle direct sowing of rice field
Preventive effect reaches 99.57%.
The advantage of fluoropyrimidine grass ether herbicide is:
1) having efficient activity of weeding, herbicidal effect is good
2) toxicity is low, person poultry safety
3) easy to use
4) preparation method is simple
The present invention synthesizes the salicylic acid herbicide Han trifluoromethyl pyrimidine first, have obvious novelty and
Creativeness, determines the work to weedings such as barnyard grass, rice barnyard grass, red foot barnyard grass, Paspalum distichums of the fluoropyrimidine grass ether compound in test chamber
Property, wherein fluoropyrimidine grass ether A to barnyard grass, rice barnyard grass, red foot barnyard grass, Paspalum distichum, activity be respectively 100,98,100,100, this
The activity of weeding of three bright fluoropyrimidine grass ether compounds is above reference product pyribenzoxim and penoxsuam.Cause
This, the efficient activity of weeding of fluoropyrimidine grass ether compound has significant practicality in modern agricultural production.
Detailed description of the invention:
Further the present invention is illustrated below in conjunction with specific embodiment:
The weeding of the fluoropyrimidine grass ether compound containing trifluoromethylbenzene with efficient activity of weeding to be prepared
Agent, represents by logical formula (I):
R=o, m, p-CF3
Wherein R is o-, m-, to trifluoromethyl aromatics.
Fluoropyrimidine grass ether compound has following three kinds of structures:
Fluoropyrimidine grass ether A:O-[2,6-double (4,6-SDM base-2-base epoxide) benzoyls] (2-trifluoromethyl)
Benzaldoxime；
Fluoropyrimidine grass ether B:O-[2,6-double (4,6-SDM base-2-base epoxide) benzoyls] (3-trifluoromethyl)
Benzaldoxime；
Fluoropyrimidine grass ether C:O-[2,6-double (4,6-SDM base-2-base epoxide) benzoyls] (4-trifluoromethyl)
Benzaldoxime；
The preparation of experiment one: 2-trifluoromethylated benzaldehyde oxime
Methanol (300 milliliters), oxammonium hydrochloride. (8.3g, 120mmol), 50% sodium hydroxide is added in 500ml reaction bulb
Aqueous solution (9.6g, 120mmol), 2-trifluoromethylated benzaldehyde (17.4g, 100mmol), react 1 little at nitrogen protects 25 DEG C
Time, after reaction terminates, methanol is under reduced pressure evaporated off, adds water and obtain solid 2-trifluoromethylated benzaldehyde oxime, (17.8g, 94.1%),
Fusing point: 53.5-54.5 DEG C.
1H NMR:(400Hz, CDCl3), 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, CDCl3), 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
Methanol (250 milliliters), oxammonium hydrochloride. (6.9g, 100mmol), 50% sodium hydroxide is added in 500ml reaction bulb
Aqueous solution (8.0g, 100mmol), 3-trifluoromethylated benzaldehyde (17.4g, 100mmol), react 1 little at nitrogen protects 25 DEG C
Time, after reaction terminates, methanol is under reduced pressure evaporated off, obtains grease 3-trifluoromethylated benzaldehyde oxime, (16.9g, 89.4%).
1H NMR:(400Hz, DMSO-d6), 6 (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-d6), 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
Methanol (350 milliliters), oxammonium hydrochloride. (10.4g, 150mmol), 50% sodium hydroxide is added in 500ml reaction bulb
Aqueous solution (12.0g, 150mmol), 4-trifluoromethylated benzaldehyde (17.4g, 100mmol), react 1 little at nitrogen protects 25 DEG C
Time, after reaction terminates, methanol is under reduced pressure evaporated off, adds water filtration and obtain solid 4-trifluoromethylated benzaldehyde oxime, (18.1g,
95.7%), fusing point: 101.0-101.5 DEG C,1H NMR:(400Hz, DMSO-d6), 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-d6), δ (ppm), 147.6,134.6,130.2,127.4,126.1,120.2.
Experiment four: the preparation of fluoropyrimidine grass ether A
Adding dichloromethane 280 milliliters in 500ml reaction bulb, be then respectively adding 2,6-is double, and (4,6-dimethoxy-2-are phonetic
Piperidinyl-2-epoxide) benzoic 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 dichloromethane, obtains white crystal fluoropyrimidine grass ether A, (23.5g, 78.2%), fusing point: 157.4 DEG C～157.9 DEG C.
1HNMR:(400Hz, CDCl3), δ (ppm), 3.720 (s, 6H, 2xCH3O), 3.792 (s, 6H, 2xCH3O), 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, CDCl3), 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 fluoropyrimidine grass ether B
In 500ml reaction bulb, add 250 milliliters of acetone, then be separately added into 2,6-pair (4,6-dimethoxy-2-pyrimidine radicals-
2-epoxide) benzoic 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 in vain
Color crystal fluoropyrimidine grass ether B (21.1g, 70.2%), fusing point: 130.9 DEG C～131.2 DEG C.
1HNMR:(400Hz, CDCl3), δ (ppm), 3.786 (s, 6H, 2xCH3O), 3.805 (s, 6H, 2xCH3O), 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, CDCl3), 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 fluoropyrimidine grass ether C
In 500ml reaction bulb, add 200 milliliters of dichloromethane, then be separately added into 2, double (4, the 6-dimethoxy-2-pyrimidines of 6-
Base-2-epoxide) benzoic 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, filter
Liquid concentration and recovery dichloromethane, obtains white crystal fluoropyrimidine grass ether C (18.2g, 60.5%), fusing point: 190.4 DEG C～190.8 DEG C.
1HNMR:(400Hz, CDCl3), δ (ppm), 3.786 (s, 6H, 2xCH3O), 3.804 (s, 6H, 2xCH3O), 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, CDCl3), 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 (7)
1. having a compound for activity of weeding, its general structure is as follows:
Wherein: R is o-, m-, to position trifluoromethyl.
2. the compound described in claim 1, wherein: R is ortho position trifluoromethyl.
3. the compound described in claim 1, wherein: R is to position trifluoromethyl.
4. herbicide, it includes the compound described in claim 1.
5. the herbicide described in claim 4, it is wettable powder.
6. the preparation method of the compound described in claim 1, is characterized in that:
With replace trifluoromethylated benzaldehyde, 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-is that fluorine prepared by raw material
Pyrimidine grass ether compound, concrete preparation process is as follows:
Step 1: replace the preparation of trifluoromethylated benzaldehyde oxime
With oxammonium hydrochloride. with replace trifluoromethylated benzaldehyde as raw material, add solvent alcohol and inorganic alkali as a catalyst, at 0 DEG C～25
React under DEG C temperature conditions, after reacting 1～3 hour, treated must replace trifluoromethylated benzaldehyde oxime；
Wherein, solvent alcohol is methanol, ethanol, isopropanol, n-butyl alcohol or normal propyl alcohol；
Inorganic base is sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium carbonate or potassium carbonate；
Step 2: the preparation of fluoropyrimidine grass ether compound
With 2, double (4, the 6-dimethoxy-2-pyrimidine radicals-2-epoxide) benzoic acid of 6-and above-mentioned replacement trifluoromethylated benzaldehyde oxime are former
Material, under organic solvent, catalyst and dehydrant effect, reaction 3～5 hours at normal temperatures, to react and filter after terminating, filtrate exists
It is evaporated off under decompression reclaiming organic solvent, obtains object fluoropyrimidine grass ether compound；
Wherein, described organic solvent be dichloromethane, chloroform, 1,2-dichloroethanes, acetone, acetonitrile, oxolane, dioxy
Six rings, DMF, methyl acetate, EtOAc, propyl acetate or ethanol butyl ester；
Described catalyst is DMAP or 4-(1'-nafoxidine) pyridine；
Described dehydrant is N, N'-dicyclohexylcarbodiimide or N, N'-DIC.
The preparation method of the compound described in 6 the most as requested, is characterized in that:
In step 1, described solvent alcohol is methanol, and described inorganic base is sodium hydroxide；In step 2, described organic solvent is
Dichloromethane；Described catalyst is DMAP；Described dehydrant is N, N'-dicyclohexylcarbodiimide.
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| CN103333121B (en) * | 2013-07-22 | 2015-11-18 | 金坛市信德农业科技有限公司 | Fluorine phonetic oxime grass ether compound with weeding activity and preparation method thereof |
| CN104302629B (en) * | 2013-12-03 | 2015-12-30 | 南京慧博生物科技有限公司 | The pyrimidine salicylic acid compounds of weeding activity, its preparation method and the purposes as weedicide thereof |
| CN103783066B (en) * | 2014-03-07 | 2015-06-24 | 赵邦斌 | Fluorine pyribenzoxim herbicide composition |
| CN104823984A (en) * | 2015-05-13 | 2015-08-12 | 广东中迅农科股份有限公司 | Weeding composition containing fluoropyribenzoxim and triafamone |
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| CN104886065A (en) * | 2015-06-04 | 2015-09-09 | 广东中迅农科股份有限公司 | Weeding composition containing fluoropyrimidine oxime ether and benzobicylon |
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| CN108041048A (en) * | 2017-11-23 | 2018-05-18 | 江苏省农用激素工程技术研究中心有限公司 | Composition pesticide and its application of the ether of grass containing fluoropyrimidine and bentazone |
| CN108041046A (en) * | 2018-01-24 | 2018-05-18 | 安徽蓝田农业开发有限公司 | A kind of herbicidal composition of humulone containing dichloroquinoline and the phonetic oxime grass ether of fluorine |
| CN108558777B (en) * | 2018-07-31 | 2021-01-26 | 河北大学 | Pyrimidine salicylic acid derivative and preparation method and application thereof |
| CN110317177B (en) * | 2019-07-30 | 2022-05-17 | 常州大学 | Preparation method of pyrimidine salicylic acid oxime ester compound and application of pyrimidine salicylic acid oxime ester compound as herbicide |
| 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 |
| CN113651760B (en) * | 2021-09-26 | 2023-07-25 | 常州大学 | Pyrimidine selenobenzoic acid derivative, preparation method thereof and application of pyrimidine selenobenzoic acid derivative as herbicide |
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| CN103333121B (en) | 2015-11-18 |
| WO2015010533A1 (en) | 2015-01-29 |
| CN105272924A (en) | 2016-01-27 |
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