CN105218582B - Compound and preparation method and application thereof - Google Patents
Compound and preparation method and application thereof Download PDFInfo
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- CN105218582B CN105218582B CN201510632831.5A CN201510632831A CN105218582B CN 105218582 B CN105218582 B CN 105218582B CN 201510632831 A CN201510632831 A CN 201510632831A CN 105218582 B CN105218582 B CN 105218582B
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Abstract
The invention provides a compound and a preparation method and application thereof, and particularly relates to a compound shown in the formula I or an enantiomer or a diastereoisomer or racemate or salt acceptable in pharmacy of the compound, a crystalline hydrate or a keto-enol tautomerism compound or solvate, R1 represents at least one halogen or hydrogen, R2 represents any substituted phenyl, and R3 and R4 represent H or any substituted alkyl respectively. The compound has herbicidal activity.
Description
Technical field
The present invention relates to chemical field, specifically, the present invention relates to compound and its preparation method and application, more specifically
, the present invention relates to compound and derivative and its preparation method and application shown in formula Ι.
Background technology
α-aminophosphonicacid is the endogenous substance of organism as a-amino acid containing phosphoramidate analog, and aminophosphonic acid can be effective
Suppress the activity of various enzymes, can be various as antibiotic, antineoplastic, anti-hiv agent, protease inhibitors and catalytic antibody etc.
Medicinal activity and there is the Multiple Pesticides such as weeding, sterilization, anti-plant tobacco mosaic virus (TMV) activity, with mechanism of action
It is various, the advantages of, security low to mammalian toxicity.And uracil herbicide, as PPO inhibitor, have been widely used
In agricultural production.And α-aminophosphonicacid ester of the research containing uracil structure and its activity of weeding are significant.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.For this purpose, the present invention
Purpose is to propose that a class has the compound of activity of weeding.
In a first aspect of the present invention, there is provided a kind of compound.Embodiments in accordance with the present invention, the compound are Formulas I
The enantiomter of compound shown in shown compound or Formulas I, diastereoisomer, racemic modification, pharmaceutically acceptable salt,
Crystalline hydrate or solvate,
Wherein,
R1For at least one halogen, hydrogen；
R2For optionally substituted phenyl；
R3And R4It is separately H or optionally substituted alkyl.
It is surprisingly found by the inventors that, compound according to embodiments of the present invention has effectively activity of weeding.
Embodiments in accordance with the present invention, above-claimed cpd can also have following additional technical feature：
According to one embodiment of present invention, the halogen is F, Cl or Br.
According to one embodiment of present invention, the R3And R4It is separately the alkyl containing 1～5 carbon atom.
According to one embodiment of present invention, the R2For phenyl, 4- aminomethyl phenyls, 3- aminomethyl phenyls, 3- methoxyl groups
Phenyl, 4- chlorphenyls, 2- chlorphenyls, 2,4 dichloro benzene base, 3- bromophenyls, 4- bromophenyls, 4- fluorophenyls, 3- fluorophenyls, 3- nitre
Base phenyl or 4- nitrobenzophenones.
According to one embodiment of present invention, the compound is the right of following compounds or the following compounds
Reflect isomers, diastereoisomer, racemic modification, pharmaceutically acceptable salt, crystalline hydrate or solvate：
In a second aspect of the present invention, the invention provides a kind of method for preparing compound noted earlier, according to this
Bright embodiment, the method include：
Compound shown in compound shown in Formula II, formula III is made to be contacted with compound shown in formula IV, to obtain Formulas I
Shown compound,
Wherein R1、R2、R3、R4It is as defined in any one of Claims 1 to 5.
Embodiments in accordance with the present invention, the contact are by by compound shown in compound, formula III shown in the Formula II
Mix with compound shown in formula IV and catalyst, and 8-12 hours are stirred at 30-120 DEG C,
Optionally, the catalyst be magnesium perchlorate, copper acetate, trifluoroacetic acid copper, copper trifluoromethanesulfcomposite, to toluene sulphur
Acid, phosphoric acid or chiral phosphoric acid.
Embodiments in accordance with the present invention, compound shown in compound shown in Formula II, formula III and compound shown in formula IV and urge
The mol ratio of agent is 1:1.0～1.2:1.0～1.5:0.05-0.06.
Thus, embodiments in accordance with the present invention, the present invention propose a synthetic route, can be used for preparing shown in Formulas I
Compound：
According to inventive embodiments, it is characterized in that under the conditions of 30-120 DEG C, toward the compound shown in Formula II, add aldehyde
III, the compound and magnesium perchlorate shown in formula IV, reactant Formula II and the compound and magnesium perchlorate shown in aldehyde III, formula IV
Mol ratio is 1:1.0～1.2:1.0～1.5:0.05-0.06.Reactant mixture stirs 8-12 hours at 30-120 DEG C, has reacted
Cheng Hou, adds water, and is extracted with dichloromethane or ethyl acetate, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silicon
Glue short column separates to obtain compound shown in Formulas I.
A third aspect of the present invention, the invention provides a kind of agricultural chemicals, which includes compound described above.Inventor
It was found that the agricultural chemicals can be efficiently used for weeding.
In a fourth aspect of the present invention, the invention provides the method that foregoing compound or agricultural chemicals are cut weeds, institute
Weeds are stated for unifacial leaf or dicotyledon；Optionally, the weeds are barnyard grass, Amaranthus retroflexus, lady's-grass, chickweed, summer cypress, lamb's-quarters, dog
Tail grass, black nightshade, black grass wheat, pharbitis nilChoisy, Tong fiber crops or eleusine indica.
Specific embodiment
Embodiments of the invention are described below in detail.It is exemplary below by the embodiment of description, is only used for explaining
The present invention, and be not considered as limiting the invention.
Embodiment 1
Compound I-1
Preparation
3.0mmol amine II-2, benzaldehyde III-1 (3.6mmol), diethyl phosphite is added in 50mL round-bottomed flasks
(3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, and reactant mixture is changed into
Molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to room temperature, plus
Water, dichloromethane or ethyl acetate extraction, anhydrous sodium sulfate drying, slough solvent under decompression, residue is by short column of silica gel point
From white solid, yield 76%, fusing point：183-184℃.
Elementary analysis：Measured value C%：47.63, H%：3.95, N%：7.18；
Calculated value C%：47.60, H%：3.99, N%：7.24；
1H NMR(CDCl3,600MHz)δ(ppm):1.16 (t, J=6.8Hz, 3H, CH3), 1.26 (t, J=6.8Hz, 3H,
CH3),3.51(s,3H,CH3),3.73-4.10(m,4H,2CH2),4.67(dd,J1=7.2Hz, J2=24.6Hz, 1H, PCH),
5.47-5.49 (t, J=7.2Hz, 1H, NH), 6.29 (d, J=7.6Hz, 2H, ArH), 7.27-7.47 (m, 6H, ArH).
31P NMR(CDCl3,162MHz):δ20.34.
EI-MS (m/z, %):579.40(M+,2.88),442.25(100.00),291.14(38.15),255.18
(7.30),213.10(10.98).
Embodiment 2
Compound I-2
Preparation
3.0mmol amine II-1, benzaldehyde III-1 (3.6mmol), diethyl phosphite is added in 50mL round-bottomed flasks
(3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, and reactant mixture is changed into
Molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to room temperature, plus
Water, dichloromethane or ethyl acetate extraction, anhydrous sodium sulfate drying, slough solvent under decompression, residue is by short column of silica gel point
From white solid, yield 80%, fusing point：45.2-47.0℃.
Elementary analysis：Measured value C%：50.53, H%：4.37, N%：7.54；
Calculated value C%：50.61, H%：4.43, N%：7.70；
1H NMR(CDCl3,600MHz)δ(ppm):1.16 (t, J=6.9Hz, 3H, CH3), 1.26 (t, J=7.2Hz, 3H,
CH3),3.78(s,3H,CH3),3.97-4.12(m,4H,2CH2),4.72(dd,J1=7.2Hz, J2=25.2Hz, 1H, PCH),
5.51 (brs, 1H, NH), 6.28 (t, J=6.8Hz, 2H, ArH), 6.49-6.51 (m, 1H, ArH), 7.28-7.46 (m, 6H,
ArH).
31P NMR(CDCl3,162MHz):δ19.86.
ESI-MS (m/z, %):545 (100%)
Embodiment 3
Compound I-3
Preparation
3.0mmol amine II-2,4- chloro- benzaldehyde III-2 (3.6mmol), phosphorous acid two is added in 50mL round-bottomed flasks
Ethyl ester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reactant mixture
It is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to room
Temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue is short by silica gel
Post separation obtains white solid, yield 82%, fusing point：178.2-179.3℃.
Elementary analysis：Measured value C%：45.07, H%：3.49, N%：6.80；
Calculated value C%：44.94, H%：3.61, N%：6.84；
1H NMR(CDCl3,600MHz)δ(ppm):1.20 (t, J=7.2Hz, 3H, CH3), 1.27 (t, J=7.2Hz, 3H,
CH3),3.52(s,3H,CH3),3.83-4.13(m,4H,2CH2),4.63(dd,J1=7.2Hz, J2=25.2Hz, 1H, PCH),
5.43 (t, J=6.8Hz, 1H, NH), 6.24-6.32 (m, 2H, ArH), 7.31-7.48 (m, 5H, ArH).
31P NMR(CDCl3,162MHz):δ19.65.
EI-MS (m/z, %):615(M+,4.07),476(100.00),440(19.67),325(41.53),289
(6.05),213(16.97).
Embodiment 4
Compound I-4
Preparation
3.0mmol amine II-1,4- chloro- benzaldehyde III-2 (3.6mmol), phosphorous acid two is added in 50mL round-bottomed flasks
Ethyl ester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reactant mixture
It is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to room
Temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue is short by silica gel
Post separation obtains white solid, yield 67%, fusing point：173.7-174.2℃.
Elementary analysis：Measured value C%：47.73, H%：3.81, N%：7.07；
Calculated value C%：47.60, H%：3.99, N%：7.24；
1H NMR(CDCl3,600MHz)δ(ppm):1.21 (t, J=7.2Hz, 3H, CH3), 1.27 (t, J=7.2Hz, 3H,
CH3),3.49(s,3H,CH3),3.84-4.13(m,4H,2CH2),4.68(dd,J1=6.6Hz, J2=24.6Hz, 1H, PCH),
5.45 (t, J=6.4Hz, 1H, NH), 6.20 (s, 1H, ArH), 6.30 (s, 1H, ArH), 6.51 (d, J=7.8Hz, 1H, ArH),
7.31-7.40(m,5H,ArH).
31P NMR(CDCl3,162MHz):δ19.94.
EI-MS (m/z, %):581(M+,2.19),442(100.00),291(49.64),255(7.03),179
(17.69).
Embodiment 5
Compound I-5
Preparation
3.0mmol amine II-2,3- nitro-benzaIdehyde III-3 (3.6mmol), phosphorous acid is added in 50mL round-bottomed flasks
Diethylester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reaction mixing
Thing is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to
Room temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silica gel
Short column separates to obtain white solid, yield 88%, fusing point：92.3-94.1℃.
Elementary analysis：Measured value C%：44.01, H%：3.67, N%：8.99；
Calculated value C%：44.18, H%：3.55, N%：8.96；
1H NMR(CDCl3,400MHz)δ(ppm):1.21 (t, J=6.8Hz, 3H, CH3), 1.30 (t, J=7.2Hz, 3H,
CH3),3.48(s,3H,CH3),3.94-4.12(m,4H,2CH2),4.76(dd,J1=6.8Hz, J2=25.2Hz, 1H, PCH),
5.53 (t, J=7.2Hz, 1H, NH), 6.22-6.33 (m, 2H, ArH), 7.50-8.29 (m, 5H, ArH).
31P NMR(CDCl3,162MHz):δ20.05.
ESI-MS (m/z, %):624(M+,100).
Embodiment 6
Compound I-6
Preparation
3.0mmol amine II-1,3- nitro-benzaIdehyde III-3 (3.6mmol), phosphorous acid is added in 50mL round-bottomed flasks
Diethylester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reaction mixing
Thing is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to
Room temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silica gel
Short column separates to obtain white solid, yield 73%, fusing point：155.3-156.2℃.
Elementary analysis：Measured value C%：46.90, H%：3.79, N%：9.36；
Calculated value C%：46.75, H%：3.92, N%：9.48；
IR(KBr)(cm-1):ν 3399 (N-H), 1221 (P=O), 1022 (P-O-C), 816 (P-C).
1H NMR(CDCl3,400MHz)δ(ppm):1.21 (t, J=7.2Hz, 3H, CH3), 1.31 (t, J=7.2Hz, 3H,
CH3),3.47(s,3H,CH3),3.94-4.18(m,4H,2CH2),4.81(dd,J1=6.8Hz, J2=24.6Hz, 1H, PCH),
5.55 (t, J=6.8Hz, 1H, NH), 6.21-6.55 (m, 2H, ArH), 7.40-8.30 (m, 6H, ArH).
EI-MS (m/z, %):590(M+,3.91),453(100.00),302(28.43).
Embodiment 7
Compound I-7
Preparation
3.0mmol amine II-2,4- nitro-benzaIdehyde III-4 (3.6mmol), phosphorous acid is added in 50mL round-bottomed flasks
Diethylester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reaction mixing
Thing is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to
Room temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silica gel
Short column separates to obtain yellow solid, yield 65%, fusing point：178.3-179.8℃.
Elementary analysis：Measured value C%：44.25, H%：3.43, N%：9.02；
Calculated value C%：44.18, H%：3.55, N%：8.96；
1H NMR(CDCl3,400MHz)δ(ppm):1.21 (t, J=6.8Hz, 3H, CH3), 1.28 (t, J=6.8Hz, 3H,
CH3),3.48(s,3H,CH3),3.90-4.14(m,4H,2CH2),4.78(dd,J1=6.8Hz, J2=24.6Hz, 1H, PCH),
5.51 (t, J=6.8Hz, 1H, NH), 6.12 (s, 1H, ArH), 6.25 (s, 1H, ArH), 6.54 (d, J=9Hz, 1H, ArH),
7.41 (d, J=8.4Hz, 1H, ArH), 7.65 (d, J=9Hz, 1H, ArH), 8.19 (d, J=8.4Hz, 2H, ArH).
31P NMR(CDCl3,162MHz):δ18.76.
ESI-MS (m/z, %):625(M+1,100).
Embodiment 8
Compound I-8
Preparation
3.0mmol amine II-1,4- nitro-benzaIdehyde III-4 (3.6mmol), phosphorous acid is added in 50mL round-bottomed flasks
Diethylester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reaction mixing
Thing is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to
Room temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silica gel
Short column separates to obtain yellow solid, yield 83%, fusing point：193.7-195.3℃.
Elementary analysis：Measured value C%：46.62, H%：3.77, N%：9.54；
Calculated value C%：46.75, H%：3.92, N%：9.48；
IR(KBr)(cm-1):ν 3422 (N-H), 1250 (P=O), 1016 (P-O-C), 820 (P-C).
1H NMR(CDCl3,400MHz)δ(ppm):1.23 (t, J=6.8Hz, 3H, CH3), 1.29 (t, J=6.8Hz, 3H,
CH3),3.48(s,3H,CH3),3.93-4.17(m,4H,2CH2),4.81(dd,J1=6.8Hz, J2=25.2Hz, 1H, PCH),
5.53 (t, J=6.2Hz, 1H, NH), 6.13 (s, 1H, ArH), 6.28 (s, 1H, ArH), 6.56 (d, J=9Hz, 1H, ArH),
7.43 (d, J=8.4Hz, 1H, ArH), 7.65 (d, J=9Hz, 2H, ArH), 8.20 (d, J=8.4Hz, 2H, ArH).
31P NMR(CDCl3,162MHz):δ18.84
EI-MS (m/z, %):590(M+,5.12),453(100),302(28).
Embodiment 9
Compound I-9
Preparation
3.0mmol amine II-2,4- fluoro- benzaldehyde III-5 (3.6mmol), phosphorous acid two is added in 50mL round-bottomed flasks
Ethyl ester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reactant mixture
It is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to room
Temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue is short by silica gel
Post separation obtains white solid, yield 79%, fusing point：178.3-179.2℃.
Elementary analysis：Measured value C%：46.03, H%：3.80, N%：6.97；
Calculated value C%：46.17, H%：3.71, N%：7.02；
1H NMR(CDCl3,400MHz)δ(ppm):1.17 (t, J=6.3Hz, 3H, CH3), 1.24 (t, J=7.2Hz, 3H,
CH3),3.48(s,3H,CH3),3.80-4.11(m,4H,2CH2),4.65(dd,J1=6.6Hz, J2=24.6Hz, 1H, PCH),
5.43 (brs, 1H, NH), 6.28 (d, J=7.2Hz, 2H, Ar H), 7.04 (d, J=7.2Hz, 2H, ArH), 7.40-7.47 (m,
3H,ArH).
31P NMR(CDCl3,162MHz):δ19.99.
ESI-MS:597 (M+, 100%)
Embodiment 10
Compound I-10
Preparation
3.0mmol amine II-1,4- fluoro- benzaldehyde III-5 (3.6mmol), phosphorous acid two is added in 50mL round-bottomed flasks
Ethyl ester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reactant mixture
It is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to room
Temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue is short by silica gel
Post separation obtains yellow solid, yield 69%, fusing point：84.2-85.5℃.
Elementary analysis：Measured value C%：48.73, H%：4.04, N%：7.59；
Calculated value C%：48.99, H%：4.11, N%：7.45；
1H NMR(CDCl3,400MHz)δ(ppm):1.19 (t, J=6.9Hz, 3H, CH3), 1.27 (t, J=6.9Hz, 3H,
CH3),3.49(s,3H,CH3),3.83-4.12(m,4H,2CH2),4.69(dd,J1=7.2Hz, J2=25.2Hz, 1H, PCH),
5.46(brs,1H,NH),6.23-6.54(m,3H,Ar H),7.02-7.05(m,2H,ArH),7.39-7.43(m,3H,ArH).
ESI-MS:563 (M+, 100%)
Embodiment 11
Compound I-11
Preparation
3.0mmol amine II-2,4- Methyl-benzaldehyde III-6 (3.6mmol), phosphorous acid is added in 50mL round-bottomed flasks
Diethylester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reaction mixing
Thing is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to
Room temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silica gel
Short column separates to obtain white solid, yield 71%, fusing point：49.3-50.8℃.
Elementary analysis：Measured value C%：46.61, H%：4.30, N%：6.92；
Calculated value C%：48.50, H%：4.24, N%：7.07；
1H NMR(CDCl3,400MHz)δ(ppm):1.16 (t, J=6.9Hz, 3H, CH3), 1.26 (t, J=6.9Hz, 3H,
CH3),2.21(s,3H,CH3),3.51(s,3H,CH3),3.74-4.11(m,4H,2CH2),4.64(dd,J1=6.6Hz, J2=
24.6Hz, 1H, PCH), 5.42 (t, J=7.6Hz, 1H, NH), 6.28-6.36 (m, 2H, ArH), 7.13-7.15 (m, 2H,
ArH),7.28-7.45(m,3H,ArH).
EI-MS (m/z, %):593.4(M+,1.5),456(100),351(5.1),305(35.9),105(7.7).
Embodiment 12
Compound I-12
Preparation
3.0mmol amine II-1,4- Methyl-benzaldehyde III-6 (3.6mmol), phosphorous acid is added in 50mL round-bottomed flasks
Diethylester (3.6mmol, 0.46mL) and anhydrous Mg (ClO4)2(0.15mmol, 0.03g), is heated to 80-100 DEG C, reaction mixing
Thing is changed into molten condition, if stirring is insufficient, can the anhydrous CH of slightly 2mL3CN, reaction time are about 8-10 hours, are cooled to
Room temperature, adds water, and dichloromethane or ethyl acetate are extracted, anhydrous sodium sulfate drying, sloughs solvent under decompression, and residue passes through silica gel
Short column separates to obtain white solid, yield 63%, fusing point：59.2-60.3℃.
Elementary analysis：Measured value C%：51.64, H%：4.57, N%：7.38；
Calculated value C%：51.48, H%：4.68, N%：7.50；
1H NMR(CDCl3,400MHz)δ(ppm):1.17 (t, J=6.9Hz, 3H, CH3), 1.26 (t, J=7.2Hz, 3H,
CH3),2.31(s,3H,CH3),3.49(s,3H,CH3),3.77-4.12(m,4H,2CH2),4.68(dd,J1=7.2Hz, J2=
24.6Hz, 1H, PCH), 5.45 (t, J=5.4Hz, 1H, NH), 6.30 (s, 2H, ArH), 6.48-6.50 (m, 1H, ArH),
7.13-7.14(m,2H,ArH),7.31-7.39(m,3H,ArH).
EI-MS (m/z, %):559(M+,1.8),422(100),271(23.0),179(9.0).
Pharmacological Activity Screening is tested
From following experiment as can be seen that the compound represented by the formula (I) of the present invention is to barnyard grass (Echinochloa
Crusgalli), Amaranthus retroflexus (Amaranthus retroflexus), lady's-grass (Digitaria sanguinalis), chickweed
(Stellaria media), summer cypress (Kochina scoparia), lamb's-quarters (Chenopodium album), green bristlegrass (Setaria
Faberi), black nightshade (Solanum nigrum), black grass wheat (Lolium perenne), pharbitis nilChoisy (Ipomoea
Hederacea), Tong fiber crops (Abutilon theophrasti), the unifacial leaf such as eleusine indica (Eleusine indica) and dicotyledonous
There is weeds excellent activity of weeding to have excellent activity of weeding.
Embodiment 13
Compound is tested to arabidopsis (Arabidopsis thaliana) and annual bluegrass (Poa annua) activity of weeding
(in vitro Plating)
Before seedling processing mode is taken, spraying treatment is carried out to annual bluegrass to arabidopsis, 32ppm speed with 10ppm speed.Survey
The plate of examination is kept for 7 days in being placed on the storage cabinet of control environment, and each sample is repeated 3 times, and 99 represent significant activity of weeding,
0 represents do not have activity.Table 1 is compound shown in segment boundses I to arabidopsis (Arabidopsis thaliana) and annual bluegrass
The measurement result of (Poa annua) activity of weeding.In table：Ph- phenyl.All compounds show excellent weeding to arabidopsis
Activity, wherein compound I-1, I-2, I-3, I-4, I-6, I-8, I-10, I-11, I-12 are shown to arabidopsis and annual bluegrass
Excellent activity of weeding, shows preferable broad-spectrum weed-killing activity；And compound I-7, I-9 are only effective to arabidopsis, to precocity
Standing grain does not have preventive effect, shows preferable selective herbicidal activity.
Table 1
Embodiment 14
Compound is to Amaranthus retroflexus (Amaranthus retroflexus), black grass wheat (Lolium perenne), chickweed
(Stellaria media) and lady's-grass (Digitaria sanguinalis) activity of weeding test (greenhouse pot culture method 1), adopt
Commercial herbicides Atrazine (Atrazine), mesotrione (Mesotrione), glyphosate (Glyphosate) and second grass
Amine (Acetochlor) is used as comparison medicament.
During sample is dissolved in dimethyl sulfoxide, storage is preserved, and is diluted to normal concentration (1000g/ when activity of weeding is tested
ha).Take before seedling and after seedling to process two ways, sample concentration is adopted for 1000g/ to Amaranthus retroflexus, black grass wheat, chickweed and lady's-grass
Ha carries out spraying treatment.Plant is placed on greenhouse and is kept for 12 days, and using more than, four kinds of commercial herbicides are as positive control, right
The toxicity precentagewise of plant represents that 100 expressions control target plant completely, and 0 represents do not have control effect.Table 2 is segment boundses
(I) compound is to Amaranthus retroflexus (Amaranthus retroflexus), black grass wheat (Lolium perenne), chickweed
The measurement result of (Stellaria media) and lady's-grass (Digitaria sanguinalis) activity of weeding.
Compound I-2, I-4, I-6, I-8 and I-10 under 1000 grams/ha of concentration, when no matter before seedling and after seedling are processed,
Wide spectrum, excellent activity of weeding are shown to Amaranthus retroflexus, black grass wheat, chickweed and lady's-grass.Additionally, all compounds in before seedling and
It is during after seedling process, the most excellent to the preventive effect of Amaranthus retroflexus.
Table 2
Embodiment 15
Part of compounds is to pharbitis nilChoisy (Ipomoea hederacea), black nightshade (Solanum nigrum), Amaranthus retroflexus
(Amaranthus retroflexus), faber bristlegrass herb (Setaria faberi), black grass wheat (Lolium perenne) and barnyard grass
Careless (Echinochloa crus-galli) activity of weeding experiment (greenhouse pot culture method 2), processes two kinds of sides using before seedling and after seedling
Formula, using the control effect for changing different liquor strength test six kinds of plants to more than.
Sample is dissolved in storage in dimethyl sulfoxide and preserves, be diluted to when activity of weeding is tested normal concentration (1000g/ha,
500g/ha,250g/ha).Take before seedling and after seedling to process two ways, to pharbitis nilChoisy, black nightshade, Amaranthus retroflexus, faber bristlegrass herb,
Black grass wheat and barnyard grass carry out spraying treatment using different drug concentrations.Plant is placed on greenhouse and is kept for 13 days, the poison to plant
Property precentagewise represent that 100 represent and control target plant completely, 0 represents do not have control effect.Table 3 is chemical combination shown in segment boundses I
Measurement result of the thing to the activity of weeding to pharbitis nilChoisy, black nightshade, Amaranthus retroflexus, faber bristlegrass herb, black grass wheat and barnyard grass.
When further reducing liquor strength to 250 grams/ha, such compound still shows excellent activity of weeding,
The activity of wherein I-2 is optimum, and weed control spectrum is most wide；This kind of compound under 250 grams/ha of concentration, when after seedling is processed to dragon
Certain herbaceous plants with big flowers, Amaranthus retroflexus and pharbitis nilChoisy show 100% herbicidal effect；And when before seedling is processed (under same concentrations), to black nightshade
100% preventive effect is shown with Amaranthus retroflexus.
Table 3
Measuring unit：
Syngenta Co., Ltd of Britain bioactiveity screening center.
When the compound of the present invention is used as herbicide, the load that will can be allowed in the compound of the present invention and other plant protection
Body or diluent mixing, are modulated into the various formulations being usually used whereby, such as mixture, granule, aqueous emulsion etc. using,
Can also be used in mixed way or while be used in combination with other agricultural chemicals such as bactericide, Insecticides (tech) ＆ Herbicides (tech), plant growth regulator etc..
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
Example ", or the description of " some examples " etc. mean specific features with reference to the embodiment or example description, structure, material or spy
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in one or more embodiments or example in an appropriate manner.Additionally, in the case of not conflicting, the skill of this area
The feature of the different embodiments or example described in this specification and different embodiments or example can be tied by art personnel
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (9)
1. a kind of compound, it is characterised in that the compound is that the mapping of compound shown in Formulas I or compound shown in Formulas I is different
Structure body, diastereoisomer, racemic modification, pharmaceutically acceptable salt,
Wherein,
R1For at least one F, Cl, Br or hydrogen；
R2For phenyl, 4- aminomethyl phenyls, 3- aminomethyl phenyls, 3- methoxyphenyls, 4- chlorphenyls, 2- chlorphenyls, 2,4 dichloro benzene
Base, 3- bromophenyls, 4- bromophenyls, 4- fluorophenyls, 3- fluorophenyls, 3- nitrobenzophenones or 4- nitrobenzophenones；
R3、R4It is ethyl.
2. compound according to claim 1, it is characterised in that the compound is following compounds or described following
The enantiomter of compound, diastereoisomer, racemic modification, pharmaceutically acceptable salt：
3. a kind of method for preparing compound described in any one of claim 1～2, it is characterised in that include：Make Formula II shownization
Shown in compound, formula III, compound is contacted with compound shown in formula IV, to obtain compound shown in Formulas I,
Wherein R1、R2、R3、R4It is as defined in any one of claim 1～2.
4. the method for prepare compound according to claim 3, it is characterised in that the contact is by by the Formula II
Shown in shown compound, formula III, compound is mixed with compound shown in formula IV and catalyst, and stirs 8-12 at 30-120 DEG C
Hour,
The catalyst is magnesium perchlorate, copper acetate, trifluoroacetic acid copper, copper trifluoromethanesulfcomposite, p-methyl benzenesulfonic acid, phosphoric acid or hand
Property phosphoric acid.
5. the method for prepare compound according to claim 4, it is characterised in that shown in compound shown in Formula II, formula III
Compound is 1 with the mol ratio of compound and catalyst shown in formula IV:1.0～1.2:1.0～1.5:0.05-0.06.
6. a kind of agricultural chemicals, it is characterised in that including the compound defined in any one of claim 1～2.
7. a kind of method cut weeds, it is characterised in that apply the chemical combination described in any one of claim 1～2 for the weeds
Thing, or the agricultural chemicals described in claim 6.
8. the method cut weeds according to claim 7, it is characterised in that the weeds are unifacial leaf or dicotyledonous plant
Thing.
9. the method cut weeds according to claim 7, it is characterised in that the weeds be barnyard grass, Amaranthus retroflexus, lady's-grass,
Chickweed, summer cypress, lamb's-quarters, green bristlegrass, black nightshade, black grass wheat, pharbitis nilChoisy, Tong fiber crops or eleusine indica.
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