CN106831683A - A kind of cumarin aryloxy acetic acids ester type compound and its application on agricultural chemicals - Google Patents
A kind of cumarin aryloxy acetic acids ester type compound and its application on agricultural chemicals Download PDFInfo
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- CN106831683A CN106831683A CN201611224789.4A CN201611224789A CN106831683A CN 106831683 A CN106831683 A CN 106831683A CN 201611224789 A CN201611224789 A CN 201611224789A CN 106831683 A CN106831683 A CN 106831683A
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- 0 *C(C(CC=C1)O)=C1O Chemical compound *C(C(CC=C1)O)=C1O 0.000 description 2
- FGFQLHXKBQFGGR-ZDUSSCGKSA-N Cc(c1c(cc2)C(CCl)=C[C@@H]3[O](C)=C3OC1)c2O Chemical compound Cc(c1c(cc2)C(CCl)=C[C@@H]3[O](C)=C3OC1)c2O FGFQLHXKBQFGGR-ZDUSSCGKSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- General Health & Medical Sciences (AREA)
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Abstract
The invention provides a kind of cumarin aryloxy acetic acids ester type compound and its application on agricultural chemicals, preparation method is as follows：1st, the resorcinol containing different substituents is added in the reaction bulb for filling the concentrated sulfuric acid, stirring and dissolving, acetoacetates is slowly added dropwise under ice-water bath cooling, drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h；It is stirred vigorously down and pours into mixture of ice and water, have yellow mercury oxide to generate, suction filtration, filter cake absolute ethyl alcohol recrystallizes to obtain 7 Hydroxycoumarin class compounds；2nd, 2,4 dichlorphenoxyacetic acids and oxalyl chloride are dissolved in CH2Cl2In solvent, N is added dropwise, N dimethylformamides, room temperature reaction 2h is obtained acyl chlorides；3rd, in the organic solvent containing 7 Hydroxycoumarin class compounds and acyl chlorides, under uniform temperature, catalyst is added, after reaction a period of time, recrystallization obtains final product cumarin aryloxy acetic acids ester type compound.Cumarin aryloxy acetic acids ester type compound of the invention has activity of weeding very high.
Description
Technical field
The present invention relates to a kind of cumarin-aryloxy acetic acids ester type compound and its application on agricultural chemicals, belong to herbicide
Technical field.
Background technology
For a long time, substantial amounts of to use same kind agricultural chemicals, weeds will develop immunity to drugs to it, and be asked in the presence of certain environment
Topic, accordingly, it would be desirable to continually develop the new compound with activity of weeding.It is removing that lead compound is developed with natural products
Careless agent typically have efficiently, low toxicity, degradable and slow resistance development the features such as, meet the development trend of agricultural chemicals.Cumarin is wide
It is general to be present in Rutaceae, Umbelliferae, pulse family, orchid family, Oleaceae, Solanaceae and feverfew.Medical aspect, Coumarins chemical combination
Thing mainly has antitumor, antibacterial, the report of anti-AIDS isoreactivity, and has had the commercial varieties of anticoagulation medicine.Agriculture
With aspect, the existing rat poison commercial varieties of coumarin kind compound also have part document report its bactericidal activity, are lived in weeding
Report in terms of property mainly has CN102146068A, CN105111176A and CN104351179A etc., but as representative of the present invention
Cumarin-aryloxy acetic acids ester type compound is not disclosed.
The content of the invention
The purpose of the present invention is the synthesis (I) and application of a kind of cumarin-aryloxy acetic acids ester type compound.The present invention is provided
Many new chemical constitutions and noval chemical compound.Biological activity determination result shows that chemical compounds I has activity of weeding very high.
The present invention is following logical formula (I) compounds：
Wherein, R1：H, haloalkyl, alkyl；R2：H, alkyl.
The synthetic route of the compounds of this invention (I) is as follows：
The synthesis of umbelliferone class compound (A)：
Wherein, R1：H, haloalkyl, alkyl；R2：H, alkyl.
The synthesis of acyl chlorides (B)：
The synthesis of cumarin-aryloxy acetic acids ester type compound (I)：
Synthetic route of the invention is described below：The synthetic method of cumarin-aryloxy acetic acids ester type compound is according to following
Step is carried out：
Step 1, the resorcinol containing different substituents is added in the reaction bulb for filling the concentrated sulfuric acid, stirring and dissolving,
Acetoacetates are slowly added dropwise under ice-water bath cooling, drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h；
It is stirred vigorously down and pours into mixture of ice and water, have yellow mercury oxide to generate, suction filtration, filter cake absolute ethyl alcohol recrystallizes to obtain faint yellow pin
Shape solid, i.e. umbelliferone class compound (A)；
Step 2,2,4 dichlorophenoxyacetic acid and oxalyl chloride are dissolved in CH2Cl2In solvent, DMF is added dropwise
(DMF), room temperature reaction 2h is obtained acyl chlorides (B)；
Step 3, in the organic solvent containing umbelliferone class compound and acyl chlorides, under uniform temperature, addition is urged
Agent, after reaction a period of time, recrystallization obtains final product cumarin-aryloxy acetic acids ester type compound.
In step 1, the resorcinol containing different substituents is 1 with the mol ratio of acetoacetates:
1；In step 2, the amount ratio of described 2,4- dichlorphenoxyacetic acids, oxalyl chloride and DMF is 3mmol:
9mmol:10μL；In step 3, the mol ratio containing umbelliferone class compound and acyl chlorides is 1:1~1:2, it is described
Organic solvent is from benzene,toluene,xylene, dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, acetone, acetonitrile, ethanol, first
One kind in alcohol, the uniform temperature is 0 DEG C of boiling temperature to organic solvent, the catalyst be Anhydrous potassium carbonate, piperidines,
One kind in pyridine, natrium carbonicum calcinatum, sodium acid carbonate, triethylamine, NaOH, sodium methoxide, caustic alcohol, used by the recrystallization
Solvent be at least one in dichloromethane, chloroform, ethyl acetate, acetone, ethanol, methyl alcohol, DMF, institute
The reaction time is stated for 0.5~5h.
The compound of logical formula (I) of the invention has activity of weeding, especially has high activity to broadleaf weed.
Present invention additionally comprises with logical formula (I) compound be the Herbicidal combinations of active component.Activity in the Herbicidal combinations
The weight percentage of component is between 0.1-99%.Also include agriculturally acceptable carrier in the Herbicidal combinations.
Other embodiments of the present invention are the method for controlling weeds, and the method includes applying Herbicidal combinations of the invention
In on the surface of the somatomedin in the place or the weeds of described weeds or the weeds.What is generally selected more suitably has
Effect amount is 10 grams to 1500 grams of per hectare, and preferably effective dose is 20 grams to 750 grams of per hectare.
Compound of the invention can be administered on soil or blade face in the form of preparation.This compound is generally dissolved in load
It is more readily dispersible in body or when being configured to preparation to be used as herbicide.For example：These chemicals can be made into wettable
Powder or missible oil.In these compositions, a kind of liquid or solid carrier is at least added, and when needed, it is appropriate to mix
Surfactant.
For some applications, one or more other herbicide can be added in Herbicidal combinations of the invention, thus
Additional advantage and effect can be produced.
Compound of the invention both can be used alone can also be with other known insecticide, bactericide, herbicide, plant
Thing growth regulator or fertilizer etc. are mixed together.
It should be appreciated that, in scope defined by the claims of the present invention, various conversion and change can be carried out.
Beneficial effect：
The invention provides the preparation method of the new cumarin of a class-aryloxy acetic acids ester type compound (I).
Compound (I) of the invention has activity of weeding very high, and compared with other coumarin kind compounds, weeding is lived
Property is greatly improved.Compound (I) of the invention is to for examination weeds such as broadleaf weed rape and monocotyledon weed lady's-grass
There is preventive effect very high.
Substantial feature of the invention can be emerged from from following embodiments, but it is not construed as making the present invention
Any limitation.
Specific embodiment
Different substitution resorcinols in the present invention, umbelliferone and acetoacetates can directly be bought.
Embodiment 1：The preparation of Hymecromone (A1)：
Structural formula is：
Resorcinol 0.55g (5mmol) and concentrated sulfuric acid 8.0mL, stirring dissolves it, and second is slowly added dropwise under ice-water bath cooling
Ethyl acetoacetic acid ethyl ester 0.65mL (5mmol), drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h.It is stirred vigorously down and pours into
In a large amount of frozen water, there is precipitation to generate, suction filtration, filter cake is recrystallized with absolute ethyl alcohol, obtains Hymecromone (A1)
0.71g, white powder, yield 81.2%, mp:190~191 DEG C；1H NMR(400MHz,DMSO-d6)δ:2.36(s,3H,
CH3), 4.39 (s, 1H, OH), 6.12 (s, 1H, H-3), 6.71 (d, 1H, J=4.0Hz, H-5), 6.80 (dd, 1H, J=2.4,
8.8Hz, H-6), 7.58 (dd, 1H, J=1.2,8.8Hz, H-8)；13C NMR(400MHz,DMSO-d6)δ:161.6,160.8,
155.3,154.0,127.1,113.3,112.5,110.7,102.6,18.6.Anal.Calcd for C8H8O3:C 68.18,H
4.58；found C68.25,H 4.70.
Embodiment 2：The preparation of 7- hydroxyl -4- chlorocoumarins (A2)：
Structural formula is：
Resorcinol 0.55g (5mmol) and concentrated sulfuric acid 8.0mL, stirring dissolves it, and 4- is slowly added dropwise under ice-water bath cooling
Chloroacetyl acetacetic ester 0.68mL (5mmol), drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h.It is stirred vigorously down
Pour into a large amount of frozen water, there is precipitation to generate, suction filtration, filter cake is recrystallized with absolute ethyl alcohol, obtains 7- hydroxyl -4- chlorocoumarins (A2)
0.85g, white powder, yield 80.9%, mp:211~213 DEG C；1H NMR(400MHz,DMSO-d6)δ:4.12(s,1H,OH),
4.95(s,2H,CH2), 6.42 (s, 1H, H-3), 6.76 (d, 1H, J=2.4Hz, H-5), 6.85 (dd, 1H, J=2.0,
8.4Hz, H-6), 7.67 (d, 1H, J=8.8Hz, H-8)；13C NMR(400MHz,DMSO-d6)δ:161.9,160.6,155.8,
151.5,127.0,113.6,111.5,109.8,103.0,41.8.Anal.Calcd for C15H9O3F:C 57.03,H
3.35；found C57.26,H 3.10.
Embodiment 3：The preparation of 7- hydroxyls -4- trifluoromethyls cumarin (A3)：
Structural formula is：
Resorcinol 0.55g (5mmol) and concentrated sulfuric acid 8.0mL, stirring dissolves it, and 4 are slowly added dropwise under ice-water bath cooling,
4,4- trifluoroacetic ethyl acetoacetate 0.73mL (5mmol), drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h.Acutely
Poured under stirring in a large amount of frozen water, there is precipitation to generate, suction filtration, filter cake is recrystallized with absolute ethyl alcohol, obtains 7- hydroxyl -4- trifluoromethyls
Cumarin (A3) 0.91g, white powder, yield 79.4%, mp:194~195 DEG C；1H NMR(400MHz,DMSO-d6)δ:4.12
(s, 1H, OH), 6.74 (s, 1H, H-3), 6.79~6.85 (m, 1H, H-5), 6.91 (dd, 1H, J=2.0,8.8Hz, H-6),
7.55 (d, 1H, J=8.8Hz, H-8)；13C NMR(400MHz,DMSO-d6)δ:161.3,158.9,158.0,145.1,
137.3,118.6,113.0,105.8,102.4,22.3,21.6.Anal.Calcd for C10H5F3O3:C 52.19,H
2.19；found C 52.14,H 2.05.
Embodiment 4：The preparation of 7- hydroxyls -4,8- diformazans butylcoumariii (A4)：
Structural formula is：
2- methylresorcinols 0.62g (5mmol) and concentrated sulfuric acid 8.0mL, stirring dissolve it, and ice-water bath cooling is lower slow
Ethyl acetoacetate 0.65mL (5mmol) is added dropwise, drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h.It is stirred vigorously
Under pour into a large amount of frozen water, have precipitation generate, suction filtration, filter cake with absolute ethyl alcohol recrystallize, obtain 7- hydroxyl -4,8- dimethyl tonka-beans
Element (A4) 0.71g, white powder, yield 82.2%, mp:252~254 DEG C；1H NMR(400MHz,DMSO-d6)δ:2.15(s,
3H,CH3),2.36(s,3H,CH3), 6.12 (s, 1H, H-3), 6.86 (d, 1H, J=8.4Hz, H-5), 7.43 (d, 1H, J=
8.4Hz,H-6),4.39(s,1H,OH)；13C NMR(400MHz,DMSO-d6)δ:160.9,159.4,154.2,153.3,
123.6,112.4,112.1,111.1,110.3,18.6,8.5.Anal.Calcd for C11H10O3:C 69.46,H 5.30；
found C69.44,H 5.38。
Embodiment 5：The preparation of the chloro- 8- methylcoumarins (A5) of 7- hydroxyls -4-：
Structural formula is：
2- methylresorcinols 0.62g (5mmol) and concentrated sulfuric acid 8.0mL, stirring dissolve it, and ice-water bath cooling is lower slow
4- chloroacetyl acetacetic esters 0.68mL (5mmol) are added dropwise, drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h.Acutely
Poured under stirring in a large amount of frozen water, there is precipitation to generate, suction filtration, filter cake is recrystallized with absolute ethyl alcohol, obtains the chloro- 8- first of 7- hydroxyls -4-
Butylcoumariii (A5) 0.79g, white powder, yield 82.9%, mp:276~278 DEG C；1H NMR(400MHz,DMSO-d6)δ:
2.16(s,3H,CH3),4.94(s,2H,CH2), 6.42 (s, 1H, H-3), 6.90 (d, 1H, J=8.8Hz, H-5), 7.53 (d,
1H, J=8.8Hz, H-6), 10.57 (s, 1H, OH)；13C NMR(400MHz,DMSO-d6)δ:160.8,159.7,153.7,
151.7,123.5,112.4,111.6,111.1,109.8,41.9,8.5.Anal.Calcd for C11H9ClO3:C 58.81,
H 4.04；found C58.93,H 4.22.
Embodiment 6：The preparation of 7- hydroxyls -4- trifluoromethyl -8- methylcoumarins (A6)：
Structural formula is：
2- methylresorcinols 0.62g (5mmol) and concentrated sulfuric acid 8.0mL, stirring dissolve it, and ice-water bath cooling is lower slow
4,4,4- trifluoroacetic ethyl acetoacetates 0.73mL (5mmol) are added dropwise, drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction
24h.It is stirred vigorously down and pours into a large amount of frozen water, have precipitation to generate, suction filtration, filter cake is recrystallized with absolute ethyl alcohol, obtains 7- hydroxyls -4-
Trifluoromethyl -8- methylcoumarin (A6) 0.95g, white powder, yield 78.1%, mp:255~256 DEG C；1H NMR
(400MHz,DMSO-d6)δ:2.17(s,3H,CH3), 6.73 (s, 1H, H-3), 6.96 (d, 1H, J=8.8Hz, H-5), 7.41
(d, 1H, J=8.8Hz, H-6), 10.87 (s, 1H, OH)；13C NMR(400MHz,DMSO-d6)δ:160.5,159.4,154.2,
140.7,123.3,113.3,112.3,111.8,111.8,105.7,8.5.Anal.Calcd for C11H7F3O:C 54.11,
H 2.89；found C54.40,H 2.62.
Embodiment 7：The preparation of 2,4 dichloro benzene oxygen chloroacetic chloride (B)：
Structural formula is：
Under nitrogen protection, 2,4- dichlorphenoxyacetic acids (6.63g, 30.0mmol) are added to dry CH2Cl2(100mL)
In, the 100 dry DMF of μ L are added, to state be dividedly in some parts oxalyl chloride (7.68mL, 90.0mmol), room in mixed liquor then up
Temperature stirring 2h, removes solvent, is directly used in next step reaction.
Embodiment 8：The preparation of 7- (2,4 dichloro benzene oxygen acetoxy) cumarin (I1)：
Structural formula is：
Umbelliferone (0.16g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2(5mL's)
In solution, then dry triethylamine (200 μ L) is dividedly in some parts, 0.5h is stirred at room temperature, TLC detection reactions are complete, and decompression is removed
Solvent is removed, 1% NaOH solution 100mL is added thereto to, is filtered, is washed with distilled water and a small amount of ethanol to pH=7, filtered,
Filter cake ethyl acetate and recrystallize with dichloromethane obtain 7- (2,4- Dichlorophenoxy acetoxyl group) cumarin (I1) 0.30g, yield
83.3%, mp:231~232 DEG C；1H NMR(400MHz,DMSO-d6)δ:5.28(s,2H,CH2), 6.50 (d, J=9.6Hz,
1H, H-3), 7.24 (dd, J=2,8.4Hz, 1H, H-6), 7.31~7.38 (m, 2H, H-4, H-5), 7.41 (dd, J=2.4,
8.8Hz, 1H, H-8), 7.62 (dd, J=2.4,15.6Hz, 1H, ArH), 7.81 (d, J=8.8Hz, 1H, ArH), 8.09 (d, J
=9.6Hz, 1H, ArH)；13C NMR(400M Hz,DMSO-d6)δ:167.2,160.1,154.5,152.6,152.5,144.2,
130.0,130.0,128.6,125.9,122.9,118.9,117.5,116.3,115.9,110.5,66.0.Anal.Calcd
for C17H10Cl2O5:C55.92,H 2.76；found C 55.76,H 2.89.
Embodiment 9：The preparation of 7- (2,4 dichloro benzene oxygen acetoxy) -4- methylcoumarins (I2)：
Structural formula is：
A1 (0.18g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2In the solution of (5mL), so
Dry triethylamine (200 μ L) is dividedly in some parts afterwards, 0.5h is stirred at room temperature, TLC detection reactions are complete, removal of solvent under reduced pressure, to
1% NaOH solution 100mL is wherein added, filtered, washed with distilled water and a small amount of ethanol to pH=7, filtering, filter cake acetic acid
Ethyl ester and recrystallize with dichloromethane obtain 7- (2,4- Dichlorophenoxy acetoxyl group) -4- methylcoumarins (I2) 0.30g, yield
78.2%, mp:239~240 DEG C；1H NMR(400MHz,DMSO-d6)δ:2.51(s,3H,CH3),5.28(s,1H,CH2),
6.42 (s, 1H, H-3), 7.23~7.30 (m, 1H, H-5), 7.37~7.44 (m, 1H, H-6), 7.61~7.67 (m, 1H, H-
8), 7.83~7.95 (m, 3H, ArH)；13C NMR(400MHz,DMSO-d6)δ:166.2,160.5,152.6,152.2,
150.7,130.6,127.8,127.7,124.7,122.4,119.3,118.2,117.7,115.2,115.2,114.6,66.5,
18.9.Anal.Calcd for C18H12Cl2O5:C 57.01,H 3.19；found C 57.26,H 3.30.
Embodiment 10：The preparation of 7- (2,4 dichloro benzene oxygen acetoxy) -4- chlorocoumarins (I3)：
Structural formula is：
A2 (0.21g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2In the solution of (5mL), so
Dry triethylamine (200 μ L) is dividedly in some parts afterwards, 0.5h is stirred at room temperature, TLC detection reactions are complete, removal of solvent under reduced pressure, to
1% NaOH solution 100mL is wherein added, filtered, washed with distilled water and a small amount of ethanol to pH=7, filtering, filter cake acetic acid
Ethyl ester and recrystallize with dichloromethane obtain 7- (2,4- Dichlorophenoxy acetoxyl group) -4- chlorocoumarins (I3) 0.33g, yield
80.6%, mp:251~253 DEG C；1H NMR(400MHz,DMSO-d6)δ:4.67(s,2H,CH2),4.99(s,2H,CH2),
6.58 (s, 1H, H-3), 6.94 (d, J=8Hz, 1H, H-5), 7.17 (d, J=8.8Hz, 1H, H-6), 7.21~7.24 (m, 1H,
), H-8 7.24~7.31 (m, 1H, ArH), 7.39~7.57 (m, 1H, ArH), 7.72 (d, J=8.4Hz, 1H, ArH)；13C NMR
(400MHz,DMSO-d6)δ:166.0,159.7,154.6,152.5,152.2,149.0,130.6,127.9,127.6,
125.4,124.7,117.9,115.7,115.6,115.4,110.6,66.5,41.1.Anal.Calcd for C18H11Cl3O5:
C 52.27,H 2.68；found C 52.14,H 2.84.
Embodiment 11：The preparation of 7- (2,4 dichloro benzene oxygen acetoxy) -4- trifluoromethyls cumarin (I4)：
Structural formula is：
A3 (0.23g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2In the solution of (5mL), so
Dry triethylamine (200 μ L) is dividedly in some parts afterwards, 0.5h is stirred at room temperature, TLC detection reactions are complete, removal of solvent under reduced pressure, to
1% NaOH solution 100mL is wherein added, filtered, washed with distilled water and a small amount of ethanol to pH=7, filtering, filter cake acetic acid
Ethyl ester and recrystallize with dichloromethane obtain 7- (2,4- Dichlorophenoxy acetoxyl group) -4- trifluoromethyls cumarin (I4) 0.33g, yield
77.2%, mp:245~246 DEG C；1H NMR(400MHz,DMSO-d6)δ:5.00(s,2H,CH2),6.82(s,1H,H-3),
6.94 (d, J=8.8Hz, 1H, H-5), 7.21 (dd, J=2.4,8.8Hz, 1H, H-6), 7.25 (dd, J=2.4,8.8Hz, 1H,
H-8), 7.28~7.32 (m, 1H, ArH), 7.46 (d, J=2.4Hz, 1H, ArH), 7.79 (dd, J=1.2,8.8Hz, 1H,
ArH)；13C NMR(400MHz,DMSO-d6)δ:165.9,158.3,155.0,152.1,130.6,128.0,127.8,126.5,
126.5,124.8,118.5,115.8,115.7,115.5,111.8,110.8,66.6.Anal.Calcd for
C18H9Cl2F3O5:C 49.91,H 2.09；found C 49.61,H2.14.
Embodiment 12：The preparation of 7- (2,4 dichloro benzene oxygen acetoxy) -4,8- diformazans butylcoumariii (I5)：
Structural formula is：
A4 (0.19g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2In the solution of (5mL), so
Dry triethylamine (200 μ L) is dividedly in some parts afterwards, 0.5h is stirred at room temperature, TLC detection reactions are complete, removal of solvent under reduced pressure, to
1% NaOH solution 100mL is wherein added, filtered, washed with distilled water and a small amount of ethanol to pH=7, filtering, filter cake acetic acid
Ethyl ester and recrystallize with dichloromethane obtain 7- (2,4- Dichlorophenoxy acetoxyl group) -4,8- diformazans butylcoumariii (I5) 0.32g, yield
81.6%, mp:270~271 DEG C；1H NMR(400MHz,DMSO-d6)δ:2.29(s,1H,CH3),2.46(s,3H,CH3),
5.03(s,2H,CH2), 6.31 (s, 1H, H-3), 6.34~6.58 (m, 1H, H-5), 6.97~7.19 (m, 1H, H-6), 7.16
~7.32 (m, 1H, ArH), 7.33~7.66 (m, 2H, ArH)；13C NMR(400MHz,DMSO-d6)δ:166.2,160.5,
152.6,152.2,150.7,130.6,127.8,127.7,124.7,122.4,119.3,118.2,117.7,115.2,
115.2,114.6,66.5,18.9,9.2.Anal.Calcd for C19H14Cl2O5:C 58.03,H 3.59；found C
58.01,H 3.65。
Embodiment 13：The preparation of the chloro- 8- methylcoumarins (I6) of 7- (2,4 dichloro benzene oxygen acetoxy) -4-：
Structural formula is：
A5 (0.22g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2In the solution of (5mL), so
Dry triethylamine (200 μ L) is dividedly in some parts afterwards, 0.5h is stirred at room temperature, TLC detection reactions are complete, removal of solvent under reduced pressure, to
1% NaOH solution 100mL is wherein added, filtered, washed with distilled water and a small amount of ethanol to pH=7, filtering, filter cake acetic acid
Ethyl ester and recrystallize with dichloromethane obtain 7- (2,4- Dichlorophenoxy acetoxyl group) chloro- 8- methylcoumarins (I6) 0.35g of -4-, receive
Rate 82.5%, mp:298~299 DEG C；1H NMR(400MHz,DMSO-d6)δ:2.94(s,3H,CH3),4.67(s,2H,CH2),
5.03(s,2H,CH2), 6.58 (s, 1H, H-3), 5.95 (dd, J=8.8Hz, 1H, H-5), 7.12 (dd, J=8.4Hz, 1H, H-
6), 7.20~7.33 (m, 1H, ArH), 7.45 (dd, J=2Hz, 1H, ArH), 7.57 (dd, J=28.8Hz, 1H, ArH)；13C
NMR(400MHz,DMSO-d6)δ:166.1,159.9,153.1,152.2,151.0,149.3,130.7,127.9,127.7,
124.7,122.1,119.9,118.1,115.5,115.4,115.3,66.5,41.3.Anal.Calcd for C19H13Cl3O5:
C 53.36,H 3.06；found C 53.19,H 2.99.
Embodiment 14：The preparation of 7- (2,4 dichloro benzene oxygen acetoxy) -4- trifluoromethyl -8- methylcoumarins (I7)：
Structural formula is：
A6 (0.24g, 1.0mmol) is added to and fills B (0.36g, 1.5mmol) and CH2Cl2In the solution of (5mL), so
Dry triethylamine (200 μ L) is dividedly in some parts afterwards, 0.5h is stirred at room temperature, TLC detection reactions are complete, removal of solvent under reduced pressure, to
1% NaOH solution 100mL is wherein added, filtered, washed with distilled water and a small amount of ethanol to pH=7, filtering, filter cake acetic acid
Ethyl ester and recrystallize with dichloromethane obtain 7- (2,4 dichloro benzene oxygen acetoxy) -4- trifluoromethyl -8- methylcoumarins (I7)
0.34g, yield 76.9%, mp:305~306 DEG C；1H NMR(400MHz,DMSO-d6)δ:2.31(s,3H,CH3),5.04(s,
2H,CH2), 6.83 (s, 1H, H-3), 6.95 (dd, J=2,8.8Hz, 1H, H-5), 7.16 (dd, J=9.2Hz, 1H, H-6),
7.20~7.33 (m, 1H, ArH), 7.47 (dd, J=2.4Hz, 1H, ArH), 7.65 (d, J=8.4Hz, 1H, ArH)；13C NMR
(400MHz,DMSO-d6)δ:166.3,155.3,152.2,144.9,144.5,130.6,127.9,127.8,127.7,
124.8,121.3,117.6,117.6,116.3,115.5,105.4,77.8,66.3,21.6.Anal.Calcd for
C19H11Cl2F3O5:C 51.03,H 2.48；found C 51.25,H 2.24.
Embodiment 15：The primary dcreening operation of activity of weeding is determined：
Preliminary activity of weeding is carried out using the compound in rape Plating and barnyard grass small-radius curve track mutual-through type I to test.
Rape Plating：A filter paper of diameter 5.6cm is completed in the culture dish of diameter 6cm, 2mL finite concentrations are added
Test compounds solution, with distill water process be control.Then the rape seed of 4~6h of bubble is invaded in sowing in each culture dish
Son 15, at 28 ± 1 DEG C, radicle length is determined after dark culturing 65h.With compare, measure its suppression long to rape radicle
Percentage processed.The results are shown in Table 1.
Barnyard grass small-radius curve track：Be paved with one layer of glass marble of the same size in 50mL beaker bottoms, then put one it is big with cup bottom
Small consistent filter paper, is separately added into each testing sample, is control with distill water process.10 are sowed in each culture dish
, then be placed on for cuvette 65h cultivated under 28 ± 1 DEG C of illumination conditions by the barnyard grass seed of sprouting, barnyard grass plant height is determined, with contrast ratio
Compared with measuring its suppression percentage to barnyard grass plant height.The results are shown in Table 1.
The activity of weeding (inhibiting rate %) of part of compounds in the formula I of table 1
Claims (6)
1. a kind of cumarin-aryloxy acetic acids ester type compound, it is characterised in that the cumarin-aryloxy acetic acids ester type compound
Formula is as follows：
Wherein, R1：H, haloalkyl, alkyl；R2：H, alkyl.
2. a kind of preparation method of cumarin as claimed in claim 1-aryloxy acetic acids ester type compound, it is characterised in that step
It is rapid as follows：
Step 1, the resorcinol containing different substituents is added in the reaction bulb for filling the concentrated sulfuric acid, stirring and dissolving, frozen water
Acetoacetates are slowly added dropwise under bath cooling, drop finishes, the lower reaction 1h of ice-water bath cooling；In room temperature reaction 24h；Acutely
Poured into mixture of ice and water under stirring, there is yellow mercury oxide to generate, suction filtration, filter cake absolute ethyl alcohol recrystallize faint yellow needle-like consolidate
Body, i.e. umbelliferone class compound；
Step 2,2,4 dichlorophenoxyacetic acid and oxalyl chloride are dissolved in CH2Cl2In solvent, DMF is added dropwise, room temperature is anti-
Answer 2h that acyl chlorides is obtained；
Step 3, in the organic solvent containing umbelliferone class compound and acyl chlorides, under uniform temperature, add catalyst,
After reaction a period of time, recrystallization obtains final product cumarin-aryloxy acetic acids ester type compound.
3. the preparation method of cumarin as claimed in claim 2-aryloxy acetic acids ester type compound, it is characterised in that step 1
In, the resorcinol containing different substituents is 1 with the mol ratio of acetoacetates:1；It is described in step 2
2,4 dichlorophenoxyacetic acid, oxalyl chloride and N,N-dimethylformamide amount ratio be 3mmol:9mmol:10μL；Step 3
In, the mol ratio containing umbelliferone class compound and acyl chlorides is 1:1~1:2, the organic solvent is from benzene, first
One kind in benzene, dimethylbenzene, dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, acetone, acetonitrile, ethanol, methyl alcohol, described one
Constant temperature degree is 0 DEG C of boiling temperature to organic solvent, the catalyst be Anhydrous potassium carbonate, piperidines, pyridine, natrium carbonicum calcinatum,
One kind in sodium acid carbonate, triethylamine, NaOH, sodium methoxide, caustic alcohol, the solvent used by the recrystallization is dichloromethane
At least one in alkane, chloroform, ethyl acetate, acetone, ethanol, methyl alcohol, DMF, the reaction time is
0.5~5h.
4. a kind of Herbicidal combinations, it is characterised in that said composition includes the cumarin-aryloxy acetic acids ester described in claim 1
The weight content of class compound and agriculturally acceptable carrier, wherein active component cumarin-aryloxy acetic acids ester type compound
It is 0.1~99%.
5. the cumarin described in claim 1-aryloxy acetic acids ester type compound or its composition are used to prevent and treat single broadleaf weed
Purposes.
6. a kind of method of controlling weeds, it is characterised in that the method includes the somatomedin or ground to the weeds or the weeds
Using the Herbicidal combinations as claimed in claim 4 of herbicidally effective amount on point.
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| CN109400568A (en) * | 2018-11-06 | 2019-03-01 | 江苏大学 | 7- aroyl acetyl oxygroup isoflavone derivative and its application on pesticide |
| CN110041198A (en) * | 2019-04-03 | 2019-07-23 | 江苏大学 | The synthetic method of aryloxy acetic acids ester type compound containing chalcone and its application on pesticide |
| EP3503727A4 (en) * | 2016-08-23 | 2020-08-12 | Kittrich Corporation | Monoterpenoid/phenylpropanoid-containing compounds and methods of their making and use as herbicides |
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| US5808105A (en) * | 1995-10-10 | 1998-09-15 | American Cyanamid Company | 4-phenoxycoumarins as herbicidal agents |
| CN104592183A (en) * | 2015-01-15 | 2015-05-06 | 青岛农业大学 | N-acyl-N-m-fluorobenzyl-8-aminocoumarin compounds and preparation method and weeding application thereof |
| CN105111176A (en) * | 2015-10-16 | 2015-12-02 | 南开大学 | 3-phenoxyacetyl-4-hydroxycoumarin derivative, synthetic method and application |
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| US5808105A (en) * | 1995-10-10 | 1998-09-15 | American Cyanamid Company | 4-phenoxycoumarins as herbicidal agents |
| CN104592183A (en) * | 2015-01-15 | 2015-05-06 | 青岛农业大学 | N-acyl-N-m-fluorobenzyl-8-aminocoumarin compounds and preparation method and weeding application thereof |
| CN105111176A (en) * | 2015-10-16 | 2015-12-02 | 南开大学 | 3-phenoxyacetyl-4-hydroxycoumarin derivative, synthetic method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3503727A4 (en) * | 2016-08-23 | 2020-08-12 | Kittrich Corporation | Monoterpenoid/phenylpropanoid-containing compounds and methods of their making and use as herbicides |
| CN109400568A (en) * | 2018-11-06 | 2019-03-01 | 江苏大学 | 7- aroyl acetyl oxygroup isoflavone derivative and its application on pesticide |
| CN109400568B (en) * | 2018-11-06 | 2022-10-25 | 江苏大学 | 7-aryloxy acetoxyl isoflavone derivative and application thereof in pesticides |
| CN110041198A (en) * | 2019-04-03 | 2019-07-23 | 江苏大学 | The synthetic method of aryloxy acetic acids ester type compound containing chalcone and its application on pesticide |
| CN110041198B (en) * | 2019-04-03 | 2022-03-22 | 江苏大学 | Synthesis method of chalcone-containing aryloxycarboxylate compound and application of the compound in pesticide |
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