CN102093419B - Alpha-amino phosphonate derivative, and preparation and application thereof - Google Patents
Alpha-amino phosphonate derivative, and preparation and application thereof Download PDFInfo
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- CN102093419B CN102093419B CN 201010616343 CN201010616343A CN102093419B CN 102093419 B CN102093419 B CN 102093419B CN 201010616343 CN201010616343 CN 201010616343 CN 201010616343 A CN201010616343 A CN 201010616343A CN 102093419 B CN102093419 B CN 102093419B
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 241000192043 Echinochloa Species 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 16
- 150000002466 imines Chemical class 0.000 abstract description 15
- 101710148054 Ketol-acid reductoisomerase (NAD(+)) Proteins 0.000 abstract description 13
- 101710099070 Ketol-acid reductoisomerase (NAD(P)(+)) Proteins 0.000 abstract description 13
- 101710151482 Ketol-acid reductoisomerase (NADP(+)) Proteins 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000004809 thin layer chromatography Methods 0.000 abstract description 10
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 abstract description 9
- 150000003935 benzaldehydes Chemical class 0.000 abstract description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 8
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 7
- 235000009566 rice Nutrition 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 7
- 238000004440 column chromatography Methods 0.000 abstract description 5
- 239000003480 eluent Substances 0.000 abstract description 5
- 241000196324 Embryophyta Species 0.000 abstract description 3
- 241001233957 eudicotyledons Species 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- 239000003208 petroleum Substances 0.000 abstract 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 235000015241 bacon Nutrition 0.000 abstract 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- 125000001246 bromo group Chemical group Br* 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000009333 weeding Methods 0.000 description 5
- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 210000000582 semen Anatomy 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 3
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000013612 plasmid Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 0 C*CC1=C(C(NC2CC2)P(OC)(OC)=O)C=CCC1=C Chemical compound C*CC1=C(C(NC2CC2)P(OC)(OC)=O)C=CCC1=C 0.000 description 1
- ACFIXJIJDZMPPO-NNYOXOHSSA-N NADPH Chemical compound C1=CCC(C(=O)N)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]2[C@H]([C@@H](OP(O)(O)=O)[C@@H](O2)N2C3=NC=NC(N)=C3N=C2)O)O1 ACFIXJIJDZMPPO-NNYOXOHSSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- -1 chloro hydrogen Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 230000018791 negative regulation of catalytic activity Effects 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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Abstract
The invention discloses an alpha-amino phosphonate derivative shown as a formula (I), and preparation and application thereof. A preparation method comprises the following steps of: (1) reacting substituted benzaldehyde shown as a formula (II) with cyclopropylamine shown as a formula (III) completely at room temperature, tracking the reaction by using thin-layer chromatography and removing residues through spin steaming to prepare imine shown as a formula (IV); and (2) performing reflux reaction on the imine shown as the formula (IV) and methyl phosphate shown as a formula (V), tracking the reaction by using thin-layer chromatography, reacting completely, performing column chromatography by using mixed solution of petroleum ether and ethyl acetate as an eluent, and separating to prepare the alpha-amino phosphonate derivative shown as the formula (I), wherein the volume ratio of the petroleum ether to the ethyl acetate in the reaction solution is 2-4:1. The alpha-amino phosphonate derivative is a new compound which is sensitive to weed effect of dicotyledoneae; and part of the compound has good effects of inhibiting rice KARI enzyme and inhibiting growth of rape bacon under the condition of 100 ppm.
Description
(1) technical field
The present invention relates to a kind of alpha-amino phosphonate derivative and preparation method thereof, and as the application of weedicide.
(2) background technology
The α-aminophosphonicacid ester, as the analogue of natural amino acid, has purposes widely in each side such as biological chemistry, chemistry of pesticide and pharmaceutical chemistry, as can be used as stopper enzyme, microbiotic and pharmacologic mediator, weedicide, haptens catalytic antibody.The α-aminophosphonicacid ester has the activity of spectrum, as antitumour activity, and antiviral activity, fungicidal activity, KARI enzyme inhibition activities etc., for the research and development new drug provides new structure and thinking.Be also a kind of important substrate of synthetic phosphono peptide, so its synthetic method receive much concern simultaneously.The early stage main two step synthesis methods that adopt, in organic solvent, aldehyde reacts dehydration generation imines with amine; Imines synthesizes the α-aminophosphonicacid ester with phosphinate generation nucleophilic addition after purifying again.Because imines is unstable, the existence of organic solvent in reaction, cause imines more to be difficult to purify, and generally adopts " one kettle way " (Kabachnik reaction) to synthesize the α-aminophosphonicacid ester, but the method exists long reaction time, shortcoming that productive rate is low.In order to improve productive rate, Reaction time shorten, scientist has done a large amount of research work in this respect, and has obtained good achievement.Developed in recent years microwave-assisted synthetic, ultrasonic wave is auxiliary synthetic, and the ionic liquid-catalyzed method such as synthetic uses Louis acid catalysis synthetic, as SnCl simultaneously in addition
4, SnCl
2, ZnCl
2or BF
3et
2o.
(3) summary of the invention
The object of the invention is to provide a kind of alpha-amino phosphonate derivative and preparation method thereof and application as weedicide, and the method reaction times is short, and products therefrom purity is high, and separation and purification is simple, has application prospect preferably.
The technical solution used in the present invention is:
It is a kind of suc as formula the alpha-amino phosphonate derivative shown in (I),
R in formula (I)
1for hydrogen, methyl, bromo or chloro.
Described R
1be preferably to methyl, hydrogen, to bromo, adjacent bromo or adjacent chloro, more preferably to bromo or adjacent bromo.
The preparation method of alpha-amino phosphonate derivative of the present invention, according to following steps, carry out: (1) is by the cyclopropylamine shown in the substituted benzaldehyde shown in formula (II) and formula (III), under room temperature, react completely, thin-layer chromatography is followed the tracks of reaction, revolve to steam and remove residue, make the imines shown in formula (IV); (2) by the methyl phosphite shown in the imines shown in formula (IV) and formula (V), back flow reaction, thin-layer chromatography is followed the tracks of reaction, after reacting completely, reaction solution be take volume ratio 2～4: 1 sherwood oil and ethyl acetate mixture, as eluent carries out column chromatography, separate the alpha-amino phosphonate derivative shown in preparation formula (I);
Reaction equation is:
R in formula (I), formula (II) or formula (IV)
1for hydrogen, methyl, bromo or chloro; R in formula (V)
2for methyl, hydrogen, methyl, bromo or chloro.
The ratio of the amount of substance that feeds intake of the cyclopropylamine shown in the substituted benzaldehyde shown in further described formula (II) and formula (III) is 1: 1～3;
Further, the feed intake ratio of amount of substance of the methyl phosphite shown in the imines shown in described formula (IV) and formula (V) is 1: 1～3; In step described here (2), the imines shown in reactant formula (IV) is the imines crude product that step (1) obtains, imines during metering, step (1) made is used as that sterling measures, such metering method, can't exert an influence to effect of the present invention.
Further described R again
2be preferably methyl, hydrogen, to bromo, adjacent bromo or adjacent chloro hydrogen, more preferably to bromo or adjacent bromo.
The another kind of preparation method of alpha-amino phosphonate derivative of the present invention, according to following steps, carry out: the cyclopropylamine shown in the substituted benzaldehyde shown in formula (II), formula (III) is mixed with the dimethylphosphite shown in formula (V-1), back flow reaction 3～5h, thin-layer chromatography is followed the tracks of reaction, after reacting completely, take the volume ratio sherwood oil of 4: 1 and ethyl acetate mixture carries out column chromatography as eluent, separate the alpha-amino phosphonate derivative shown in preparation formula (I), R in formula (I) or formula (II)
1for hydrogen, methyl, bromo or chloro; The feed intake ratio of amount of substance of dimethylphosphite shown in cyclopropylamine shown in substituted benzaldehyde shown in described formula (II), formula (III) and formula (V-1) is 1: 1～3: 1～3;
It is developping agent that thin-layer chromatography of the present invention be take sherwood oil and ethyl acetate, and with the ultraviolet colour developing, raw material point disappearance is and reacts completely, and product is R
fbe worth minimum point.
Described alpha-amino phosphonate derivative is as the application of weedicide, particularly comparatively responsive to the weeds herbicide effect of dicotyledonous class, the present invention specifically applies: the Bacillus coli cells that (1) utilizes recombinant plasmid (containing paddy rice KARI enzyme gene) to transform is expressed paddy rice KARI enzyme in enormous quantities, the interaction of research alpha-amino phosphonate derivative and KARI enzyme under in vitro condition; (2) by alpha-amino phosphonate derivative under dark condition, the growth-inhibiting of rape radicle is carried out the weeding activity of detection compound; (3) by alpha-amino phosphonate derivative under illumination condition, the growth-inhibiting of barnyard grass Seedling Height is carried out the weeding activity of detection compound.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: a kind of new compound that alpha-amino phosphonate derivative of the present invention is comparatively responsive to the weeds effect of dicotyledonous class has this compound of part suppress and under the 100ppm condition, rape Baconic growth-inhibiting had to effect preferably paddy rice KARI enzyme.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
It is developping agent that thin-layer chromatography of the present invention be take sherwood oil and ethyl acetate, volume ratio 2～4: 1, and with the ultraviolet colour developing, raw material point disappearance is and reacts completely, and product is R
fbe worth minimum point.
The preparation of embodiment 1 alpha-amino phosphonate derivative
7.2g (60mmol) p-tolyl aldehyde and 3.42g (60mmol) cyclopropylamine are mixed in the 50mL flask, thin-layer chromatography is followed the tracks of reaction, react 2h under 25 ℃, react completely, then remove remaining cyclopropylamine and water with Rotary Evaporators, obtain brown color oily liquids 9.2g, determine that by GC-MS this product is imines, 4.452g (0.028mol) imines and 3.08g (0.028mol) methyl phosphite are heated to 80 ℃ with oil bath in the 50mL flask, backflow 4h, follow the tracks of reaction by thin-layer chromatography, after reacting completely, isolate product, product is R
fbe worth minimum point, then by column chromatography (mixture that eluent is sherwood oil and ethyl acetate, volume ratio 4: 1), isolate light yellow solid 1.73g, i.e. alpha-amino phosphonate derivative I-1, the yield amount of substance of imines (take) is 23%.
1HNMR(400M，CDCl
3，δppm)：0.89-0.98(m，4H，Cyclopropane-CH
2)，2.37(s，3H，CH
3)，3.00-3.01(m，1H，Cyclopropane-CH)，7.18(d，J＝7.47Hz，2H，Ar-H)，7.57(d，J＝7.47Hz，2H，Ar-H)，8.41(s，1H，HC＝)；EI-MS：160.18，144.27，131.24，118.21，105.25，78.08.
Embodiment 2～5
The substituted benzaldehyde difference, substituted benzaldehyde is identical with the mol ratio of cyclopropylamine, other operate with embodiment 1, the physico-chemical constant of the prepared alpha-amino phosphonate derivative I-1～I-5 of embodiment 1～5 and
1hNMR, FTIR and EI-MS analysis in table 1～3.
The physico-chemical constant of table 1 alpha-amino phosphonate derivative and
1h NMR, IR, MS
Table 2 alpha-amino phosphonate derivative
1h NMR analyzes
The physico-chemical constant of table 3 alpha-amino phosphonate derivative and FTIR and EI-MS analyze
Comparative Examples 1
By dimethylphosphite (0.01mol), substituted benzaldehyde (0.01mol) and cyclopropylamine (0.01mol) join in the 50mL round-bottomed flask according to mol ratio at 1: 1: 1, in oil bath, heat, and 80 ℃ of backflow 3h, solution becomes brown color.Follow the tracks of reaction by thin-layer chromatography, isolate product, product is R
fplant minimum point, then by the column chromatography (mixture that eluent is sherwood oil and ethyl acetate, volume ratio 4: 1) isolate light yellow solid 0.13g, i.e. alpha-amino phosphonate derivative, yield (take p-tolyl aldehyde amount of substance) is 5%.
The biological activity test of embodiment 6 alpha-amino phosphonate derivatives
(1) weeding vitro test method (in vitro)
The Bacillus coli cells that utilizes recombinant plasmid (containing paddy rice KARI enzyme gene) to transform is expressed paddy rice KARI enzyme in enormous quantities, the interaction of research alpha-amino phosphonate derivative and KARI enzyme under in vitro condition.
Reaction adopts dynamic method to carry out, the reduction of the characteristic absorbance of continuous monitoring NADPH (340nm).Reaction system comprises 0.1molL
-1phosphoric acid buffer (pH=8.0) 900uL, 0.2mmolL
-1nADPH 10uL, 1mmolL
-1mgCl
210uL, 0.1mmolL
-1acetylactis 10uL, add prepared alpha-amino phosphonate derivative 10uL and the KARI zymoprotein 20uL of embodiment 1 of concentration 100ppm.Before reaction, various compositions (except acetylactis) are joined in disposable cuvette, start test in 340nm place (30 ℃) with spectrophotometer, after 10min, add 10uL acetylactis solution, continue immediately test 340nm place light absorption value after mixing fast.Calculate the inhibiting rate of alpha-amino phosphonate derivative to paddy rice KARI enzyme according to formula (1), the results are shown in Table 4.
K
icalculating according to formula:
Formula (1)
K in formula (1)
ifor apparent inhibition constant, speed of reaction, I when speed of reaction, Vi when Vu means that enzyme does not have suppressed dose to suppress means that suppressed dose of enzyme suppresses mean inhibitor concentration;
(2) except cursive script build-in test method (in vivo)
The preparation of sample liquid: get the prepared alpha-amino phosphonate derivative I-1～I of embodiment 1～5～5, add the sample liquid of dimethyl sulfoxide (DMSO) (DMSO) solution preparation 10 μ g/mL and 100 μ g/mL.
The preparation of contrast liquid: get the cyclopropane dicarboxylic acid, add DMSO solution, prepare the contrast liquid of 10 μ g/mL and 100 μ g/mL.
1) rape Plating
The pre-treatment of Semen Brassicae campestris: peek grain Semen Brassicae campestris (commercially available), in clear water, 25 degree ℃ seed soaking 1 day, get full complete Semen Brassicae campestris, standby.
Complete the filter paper of a diameter 5.6cm in the culture dish of diameter 6cm, add respectively 10 μ g/mL and 100 μ g/mL sample liquid 2mL, add 10 of pretreated Semen Brassicae campestriss, under 28 ± 1 ℃, radicle length is measured after cultivating 72h in darkroom.By compound under dark condition, the growth-inhibiting of rape radicle is carried out the weeding activity of detection compound.Each sample concentration repeats twice, gets average, and take the cyclopropane dicarboxylic acid as contrast, the results are shown in Table 4.Activity index: radicle elongation inhibiting rate (%).Active graded index: A level: >=80%; B level: 60～79%; C level: 40～59%; D level :≤39%.
2) the little agar diffusion method of barnyard grass
The pre-treatment of barnyard grass seed:
Complete granulated glass sphere and filter paper in the small beaker of 50mL after, add respectively 10 μ g/mL and 100 μ g/mL sample liquid 6mL, add 10, pretreated barnyard grass seed, under 28 ± 1 ℃, measure the height of seedling after illumination cultivation 72h.By compound under illumination condition, the growth-inhibiting of barnyard grass Seedling Height is carried out the weeding activity of detection compound.Each sample liquid concentration repeats twice, gets average, and take the cyclopropane dicarboxylic acid as contrast, the results are shown in Table 4.Activity index: height growth inhibiting rate (%).Active graded index: A level: >=80%; B level: 60～79%; C level: 40～59%; D level :≤39%.
The biological activity of table 4 phosphoramidate
Note:-means that precipitation appears in test macro, fails to obtain data, and CPD means: the cyclopropane dicarboxylic acid
Table 4 can be found out: alpha-amino phosphonate derivative is not clearly to the inhibition situation of KARI enzyme, and Compound I-3 pair KARI inhibition of enzyme activity situation fails to obtain, but the dicotyledons rape is also had in the 10ppm situation to the activity of medium tenacity.
Claims (1)
1. the alpha-amino phosphonate derivative shown in a formula I is as the application of weedicide, it is characterized in that describedly being applied as alpha-amino phosphonate derivative under dark condition to the growth-inhibiting of alpha-amino phosphonate derivative to the barnyard grass Seedling Height under the growth-inhibiting of rape radicle or illumination condition;
R in formula I
1for hydrogen, 4-methyl, 2-bromine, 4-bromine or 2-chlorine.
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| CN1687088A (en) * | 2005-04-04 | 2005-10-26 | 贵州大学 | N-substituted benzothiazolyl-1-substituted phenyl-0,0-dialkyl-alpha-amino phosphonate ester derivatives preparation and application |
| CN101003548A (en) * | 2006-12-12 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Rosinyl diterpene modified alpha - phosphoramidate, preparation method, and application for anti tumors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687088A (en) * | 2005-04-04 | 2005-10-26 | 贵州大学 | N-substituted benzothiazolyl-1-substituted phenyl-0,0-dialkyl-alpha-amino phosphonate ester derivatives preparation and application |
| CN101003548A (en) * | 2006-12-12 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Rosinyl diterpene modified alpha - phosphoramidate, preparation method, and application for anti tumors |
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| Title |
|---|
| PAN Li et al..Solvent- and Catalyst-free Synthesis and Antifungal Activities of α-Aminophosphonate Containing Cyclopropane Moiety.《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》.2010,第26卷(第3期), |
| Solvent- and Catalyst-free Synthesis and Antifungal Activities of α-Aminophosphonate Containing Cyclopropane Moiety;PAN Li et al.;《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》;20100531;第26卷(第3期);第389-393页 * |
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