CN102093419A - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000002466 imines Chemical class 0.000 claims abstract description 18
- 238000004809 thin layer chromatography Methods 0.000 claims abstract description 13
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003935 benzaldehydes Chemical class 0.000 claims abstract description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 239000003480 eluent Substances 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims description 39
- 125000001246 bromo group Chemical group Br* 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000002363 herbicidal effect Effects 0.000 claims description 5
- 239000004009 herbicide Substances 0.000 claims description 5
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 5
- 235000021050 feed intake Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 17
- 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
- 230000002401 inhibitory effect Effects 0.000 abstract description 9
- 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
- 241000196324 Embryophyta Species 0.000 abstract description 6
- 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
- 239000000047 product Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 241000209094 Oryza Species 0.000 description 6
- 244000025254 Cannabis sativa Species 0.000 description 5
- 241000192043 Echinochloa Species 0.000 description 5
- 238000009333 weeding Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 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
- 230000005764 inhibitory process Effects 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
- 238000005286 illumination Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000004071 biological effect Effects 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
- 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
- 229920001817 Agar Polymers 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
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000000338 in vitro Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 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
- 238000001556 precipitation Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 α-An Jilinsuan ester derivative and preparation method thereof, and as herbicide applications.
(2) background technology
The α-An Jilinsuan ester 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 as the analogue of natural amino acid.The α-An Jilinsuan ester has the spectrographic activity, as antitumour activity, and antiviral activity, fungicidal activity, KARI enzyme inhibition activities etc. are for the research and development new drug provides new structure and thinking.Simultaneously also be a kind of important substrate of synthetic phosphono peptide, so its synthetic method receive much concern.The early stage main two step synthesis methods that adopt, promptly aldehyde and amine reaction dehydration generates imines in organic solvent; After purifying, imines synthesizes the α-An Jilinsuan ester with phosphinate generation nucleophilic addition again.Because the imines instability, the existence of organic solvent in the reaction causes imines more to be difficult to purify, and generally adopts " one kettle way " (Kabachnik reaction) to synthesize the α-An Jilinsuan ester, but this method exists long reaction time, shortcoming that productive rate is low.In order to improve productive rate, to shorten the reaction times, scientist has done a large amount of research work in this respect, and has obtained good achievement.It is synthetic to have developed microwave-assisted in recent years, and ultrasonic wave is auxiliary synthetic, and 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 provide a kind of α-An Jilinsuan ester derivative and preparation method thereof with as herbicide applications, this short in method reaction times, products therefrom purity height, separation and purification is simple, has application promise in clinical practice.
The technical solution used in the present invention is:
It is a kind of suc as formula the α-An Jilinsuan ester derivative shown in (I),
R in the formula (I)
1Be 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 α-An Jilinsuan ester derivative of the present invention, carry out according to following steps: (1) is with the cyclopropylamine shown in substituted benzaldehyde shown in the formula (II) and the formula (III), react completely under the room temperature, thin-layer chromatography is followed the tracks of reaction, revolve to steam and remove residue, make the imines shown in the formula (IV); (2) with imines shown in the formula (IV) and the methyl phosphite shown in the formula V, back flow reaction, thin-layer chromatography is followed the tracks of reaction, after reacting completely, reaction solution is with volume ratio 2～4: 1 sherwood oil and ethyl acetate mixture are that eluent carries out column chromatography, separate the α-An Jilinsuan ester derivative shown in the preparation formula (I);
Reaction equation is:
R in formula (I), formula (II) or the formula (IV)
1Be hydrogen, methyl, bromo or chloro; R in the formula V
2Be methyl, hydrogen, methyl, bromo or chloro.
The ratio of the amount of substance that feeds intake of the cyclopropylamine shown in substituted benzaldehyde shown in the further described formula (II) and the formula (III) is 1: 1～3;
Further, the feed intake ratio of amount of substance of the imines shown in the described formula (IV) and the methyl phosphite shown in the formula V is 1: 1～3; Imines shown in the reactant formula (IV) is the imines crude product that step (1) obtains in the step described here (2), and the imines that during metering step (1) is made is used as that pure product measure, and such metering method can't exert an influence to effect of the present invention.
Further more described R
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 α-An Jilinsuan ester derivative of the present invention, carry out according to following steps: the cyclopropylamine shown in the substituted benzaldehyde shown in the formula (II), the formula (III) is mixed with the dimethylphosphite shown in the formula (V-1), back flow reaction 3～5h, thin-layer chromatography is followed the tracks of reaction, after reacting completely, with 4: 1 sherwood oil of volume ratio and ethyl acetate mixture is that eluent carries out column chromatography, separate the α-An Jilinsuan ester derivative shown in the preparation formula (I), R in formula (I) or the formula (II)
1Be hydrogen, methyl, bromo or chloro; The feed intake ratio of amount of substance of dimethylphosphite shown in cyclopropylamine shown in substituted benzaldehyde shown in the described formula (II), the formula (III) and the formula (V-1) is 1: 1～3: 1～3;
Thin-layer chromatography of the present invention is a developping agent with sherwood oil and ethyl acetate, and with the ultraviolet colour developing, raw material point disappears to be and reacts completely, and product is R
fThe point that value is minimum.
Described α-An Jilinsuan ester derivative is as herbicide applications, particularly comparatively responsive to the weeds herbicide effect of dicotyledonous class, the present invention specifically uses: 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 α-An Jilinsuan ester derivative and KARI enzyme under the condition that exsomatizes; (2) growth-inhibiting of rape radicle is come the weeding activity of detection compound by α-An Jilinsuan ester derivative under the dark condition; (3) by α-An Jilinsuan ester derivative under the illumination condition growth-inhibiting of barnyard grass grass seedling plant height is come 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 α-An Jilinsuan ester derivative of the present invention is comparatively responsive to the weeds effect of dicotyledonous class has this compound of part that paddy rice KARI enzyme is suppressed to reach and under the 100ppm condition rape Baconic growth-inhibiting is had effect preferably.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Thin-layer chromatography of the present invention is a developping agent with sherwood oil and ethyl acetate, volume ratio 2～4: 1, and with the ultraviolet colour developing, raw material point disappears to be and reacts completely, and product is R
fThe point that value is minimum.
The preparation of embodiment 1 α-An Jilinsuan ester 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, 25 ℃ are reacted 2h down, react completely, remove remaining cyclopropylamine and water with Rotary Evaporators then, obtain pale brown look oily liquids 9.2g, determine that by GC-MS this product is an 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, isolate product after reacting completely, product is R
fThe point that value is minimum is isolated light yellow solid 1.73g by column chromatography (eluent is the mixture of sherwood oil and ethyl acetate, volume ratio 4: 1) then, i.e. α-An Jilinsuan ester derivative I-1, and yield (in the amount of substance of imines) 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 are operated with embodiment 1, the physico-chemical constant of embodiment 1～5 prepared α-An Jilinsuan ester derivative I-1～I-5 and
1HNMR, FTIR and EI-MS analysis in table 1～3.
The physico-chemical constant of table 1 α-An Jilinsuan ester derivative and
1H NMR, IR, MS
Table 2 α-An Jilinsuan ester derivative
1H NMR analyzes
The physico-chemical constant of table 3 α-An Jilinsuan ester derivative and FTIR and EI-MS analyze
Comparative Examples 1
With 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 pale brown look.Follow the tracks of reaction by thin-layer chromatography, isolate product, product is R
fPlant minimum point, isolate light yellow solid 0.13g by column chromatography (eluent is the mixture of sherwood oil and ethyl acetate, volume ratio 4: 1) then, i.e. α-An Jilinsuan ester derivative, yield (in the p-tolyl aldehyde amount of substance) is 5%.
The biological activity test of embodiment 6 α-An Jilinsuan ester 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 α-An Jilinsuan ester derivative and KARI enzyme under the condition that exsomatizes.
Reaction adopts dynamic method to carry out the reduction of the characteristic absorbance of continuous monitoring NADPH (340nm).Comprise 0.1molL in the reaction system
-1Phosphoric acid buffer (pH=8.0) 900uL, 0.2mmolL
-1NADPH 10uL, 1mmolL
-1MgCl
210uL, 0.1mmolL
-1Acetylactis 10uL adds prepared α-An Jilinsuan ester derivative 10uL and the KARI zymoprotein 20uL of embodiment 1 of concentration 100ppm.Before the reaction various compositions (except the acetylactis) are joined in the disposable cuvette, in 340nm place (30 ℃), begin test, behind the 10min, add 10uL acetylactis solution, continue test 340nm place light absorption value fast behind the mixing immediately with spectrophotometer.Calculate the inhibiting rate of α-An Jilinsuan ester derivative according to formula (1), the results are shown in Table 4 paddy rice KARI enzyme.
K
iCalculating according to formula:
Formula (1)
K in the formula (1)
iBe apparent inhibition constant, speed of reaction, I when speed of reaction, the Vi when Vu represents that enzyme is not suppressed agent and suppresses represents that enzyme is suppressed agent and suppresses represent inhibitor concentration;
(2) remove cursive script build-in test method (in vivo)
The preparation of sample liquid: get embodiment 1～5 prepared α-An Jilinsuan ester derivative I-1～I～5, add the sample liquid that dimethyl sulfoxide (DMSO) (DMSO) solution is prepared 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, full complete Semen Brassicae campestris is got in 25 degree ℃ seed soaking 1 day, and is standby.
Complete the filter paper of a diameter 5.6cm in the culture dish of diameter 6cm, add 10 μ g/mL and 100 μ g/mL sample liquid 2mL respectively, add 10 of pretreated Semen Brassicae campestriss, under 28 ± 1 ℃, radicle length is measured after cultivating 72h in the darkroom.The growth-inhibiting of rape radicle is come the weeding activity of detection compound by compound under the dark condition.Each sample concentration repeats twice, gets average, and is contrast with cyclopropane dicarboxylic acid, 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 grass
The pre-treatment of barnyard grass grass seed:
After in the small beaker of 50mL, completing granulated glass sphere and filter paper, add 10 μ g/mL and 100 μ g/mL sample liquid 6mL respectively, add 10 of pretreated barnyard grass grass seeds, under 28 ± 1 ℃, measure the height of seedling behind the illumination cultivation 72h.By compound under the illumination condition growth-inhibiting of barnyard grass grass seedling plant height is come the weeding activity of detection compound.Each sample liquid concentration repeats twice, gets average, and is contrast with cyclopropane dicarboxylic acid, the results are shown in Table 4.Activity index: plant height growth inhibition ratio (%).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:-represents that precipitation appears in test macro, fails to obtain data, and CPD represents: the cyclopropane dicarboxylic acid
Table 4 is as can be seen: the α-An Jilinsuan ester derivative is not clearly to the inhibition situation of KARI enzyme, and Compound I-3 pair KARI enzymic activity inhibition situation fails to obtain, but the dicotyledons rape is also had the activity of medium tenacity under the 10ppm situation.
Claims (8)
1. one kind suc as formula the α-An Jilinsuan ester derivative shown in (I),
R in the formula (I)
1Be hydrogen, methyl, bromo or chloro.
2. α-An Jilinsuan ester derivative as claimed in claim 1 is characterized in that described R
1For to methyl, hydrogen, to bromo, adjacent bromo or adjacent chloro.
3. the preparation method of a α-An Jilinsuan ester derivative as claimed in claim 1, it is characterized in that described method carries out according to following steps: (1) is with the cyclopropylamine shown in substituted benzaldehyde shown in the formula (II) and the formula (III), react completely under the room temperature, thin-layer chromatography is followed the tracks of reaction, revolve to steam and remove residue, make the imines shown in the formula (IV); (2) with imines shown in the formula (IV) and the methyl phosphite shown in the formula V, back flow reaction, thin-layer chromatography is followed the tracks of reaction, after reacting completely, reaction solution is with volume ratio 2～4: 1 sherwood oil and ethyl acetate mixture are that eluent carries out column chromatography, separate the α-An Jilinsuan ester derivative shown in the preparation formula (I);
R in formula (I), formula (II) or the formula (IV)
1Be hydrogen, methyl, bromo or chloro; R in the formula V
2Be hydrogen, methyl, bromo or chloro.
4. α-An Jilinsuan ester derivative preparation method as claimed in claim 3 is characterized in that the ratio of the amount of substance that feeds intake of the cyclopropylamine shown in substituted benzaldehyde shown in the described formula (II) and the formula (III) is 1: 1～3.
5. α-An Jilinsuan ester derivative preparation method as claimed in claim 3 is characterized in that the feed intake ratio of amount of substance of imines shown in the described formula (IV) and the methyl phosphite shown in the formula V is 1: 1～3.
6. α-An Jilinsuan ester derivative preparation method as claimed in claim 3 is characterized in that described R
2For to methyl, hydrogen, to bromo, adjacent bromo or adjacent chloro.
7. α-An Jilinsuan ester derivative preparation method as claimed in claim 3 is characterized in that described step (1) or the described thin-layer chromatography of step (2) are developping agent with sherwood oil and ethyl acetate, and with the ultraviolet colour developing, raw material point disappears to be and reacts completely.
8. a α-An Jilinsuan ester derivative as claimed in claim 1 is as herbicide applications.
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|---|---|---|---|
| CN 201010616343 CN102093419B (en) | 2010-12-30 | 2010-12-30 | Alpha-amino phosphonate derivative, and preparation and application thereof |
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|---|---|---|---|
| CN 201010616343 CN102093419B (en) | 2010-12-30 | 2010-12-30 | Alpha-amino phosphonate derivative, and preparation and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087865A (en) * | 2021-02-25 | 2021-07-09 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
Citations (2)
| 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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| 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 |
Non-Patent Citations (2)
| Title |
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| 《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》 20100531 PAN Li et al. Solvent- and Catalyst-free Synthesis and Antifungal Activities of alpha-Aminophosphonate Containing Cyclopropane Moiety 1-8 第26卷, 第3期 * |
| PAN LI ET AL.: "Solvent- and Catalyst-free Synthesis and Antifungal Activities of α-Aminophosphonate Containing Cyclopropane Moiety", 《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》, vol. 26, no. 3, 31 May 2010 (2010-05-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087865A (en) * | 2021-02-25 | 2021-07-09 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
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