CN1673228A - Substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate with bactericidal and herbicidal activity and its prepn - Google Patents
Substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate with bactericidal and herbicidal activity and its prepn Download PDFInfo
- Publication number
- CN1673228A CN1673228A CNA2005100185564A CN200510018556A CN1673228A CN 1673228 A CN1673228 A CN 1673228A CN A2005100185564 A CNA2005100185564 A CN A2005100185564A CN 200510018556 A CN200510018556 A CN 200510018556A CN 1673228 A CN1673228 A CN 1673228A
- Authority
- CN
- China
- Prior art keywords
- compound
- general formula
- alkyl
- expression
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention is substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate in the general expression (I) with bactericidal and herbicidal activity. The compound has obvious inhibition effect on cotton blight mold, rice blast mold, cucumber botrytis mold, wheat bakanae fungus, rape rhizoctonia disease mold and other molds and may be used as fungicide. In the same time, the compound has obvious effect of inhibiting the growth of monocotyledon and dicotyledon and may be used as herbicide.
Description
Technical field
The present invention relates to have the substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid of fungicidal activity and weeding activity or salt compound and preparation method thereof, and it is as the biological activity of sterilant, weedicide.
Background technology
Phosphonate derivative is the significant compound of a class biological activity, and existing many phosphonate derivatives are developed to weedicide or plant-growth regulator.Over past ten years, the inventor has developed ten polytype acid derivatives of seeing, and they have all shown weeding activity and plant growth regulating activity in various degree.For example, category-A (He Hongwu etc., Chinese invention patent, the patent No. is ZL 97109095.5), category-B (He Hongwu etc., Chinese invention patent, application number is: 200410012773.8) compound has then shown weeding activity and plant growth regulating activity in various degree.
Summary of the invention
The objective of the invention is to explore and have new texture and have weeding and/or germ-resistant substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid or salt compounds, provide a class to have weeding activity, and with newly see the esters of gallic acid derivative and the synthetic method thereof of fungicidal activity.
The present invention is on the research basis of above-mentioned several compounds, enlarge the structural pattern of above-claimed cpd, the one class phosphonate derivative with above-mentioned all classes of compounds structures different class substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid or salt compound have one by one been proposed, its general structure such as I:
In the formula, R
1Expression C
1-C
3Alkyl; R
2Expression C
1-C
3Alkyl or M, M is Li, Na, K or NH
4 +, R
1With R
2Identical or inequality;
R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl, furyl, thienyl, pyridyl, substituting group are halogen, NO
2, C
1-C
4Alkyl, substituted alkyl, alkoxyl group, alkylthio or OCH
2The substituted-phenyl of O;
R
4Expression H, C
1-C
4Alkyl;
Z and Y represent H, are not halogen, the C of F or CF
1-C
4Alkyl, substituted alkyl or alkoxyl group, alkylthio, NO
2, Z is identical with Y or inequality;
Work as R
1And R
2Expression C
1-C
3Alkyl the time, R
3Expression thienyl, pyridyl, substituting group are C
2-C
4Alkyl, alkylthio, alkoxyl group or OCH
2The substituted-phenyl of O, or remove R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl is beyond aminomethyl phenyl and the furyl.
When M is Na, K, NH
4 +The time, R
3Expression thienyl, pyridyl or substituting group are C
2-C
4Alkyl, alkylthio, alkoxyl group or OCH
2The substituted-phenyl of O;
When M is Li, R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl, furyl, thienyl, pyridyl, substituting group are halogen, NO
2, C
1-C
4Alkyl, substituted alkyl, alkoxyl group, alkylthio or OCH
2The substituted-phenyl of O, but work as R
1Expression Me, Z, Y are 2-Cl, 4-Cl, R
4Be H, the time, R removed
3Expression H, CH
3, n-C
3H
7, Ph, 2-ClPh, 3-ClPh, 2.4-Cl
2Ph, 3.4-OCH
2OPh, 4-FPh, 4-CH
3Ph, 3-NO
2Ph, 2-Pyridyl, 2-Thiophenyl, 2-Furyl, 4-NO
2Beyond the Ph.
The compound that belongs to formula I of the present invention comprises following benzene oxygen acetoxy aromatic heterocyclic alkyl phosphonate with the represented replacement of general formula I-1 in fact, with the represented substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphonic acids monometallic salt of general formula I-2,
Two kinds of All new compounds of proposed by the invention this all are different from the inventor at the represented compound of the aforementioned patent of mentioning, and its All new compounds is defined as follows respectively:
General structure I comprises the structure division of substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid I-1
In substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid I-1, R
1With R
2Expression C
1-C
3Alkyl, R
1With R
2Identical or inequality; R
3Expression thienyl, pyridyl and substituting group are C
2-C
4Alkyl, alkylthio, alkoxyl group or OCH
2The substituted-phenyl of O; R
4Expression H, C
1-C
4Alkyl;
Z and Y represent H, are not F or CF
3Halogen, C
1-C
4Alkyl, substituted alkyl or alkoxyl group, alkylthio, NO
2, Z is identical with Y or inequality.
General structure I comprises the structure division of substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid list salt I-2
In the structure of substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid list salt I-2, R
1Expression C
1-C
4Alkyl;
R
4Expression H, C
1-C
4Alkyl; M is Li, Na, K or NH
4 +
Z and Y represent H, are not F or CF
3Halogen, C
1-C
4Alkyl, substituted alkyl or alkoxyl group, alkylthio, NO
2, Z is identical with Y or inequality;
When M is Na, K, NH
4 +The time, R
3Expression thienyl, pyridyl and substituting group are C
2-C
4Alkyl, alkylthio, alkoxyl group or OCH
2The substituted-phenyl of O;
When M is Li, R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl, furyl, thienyl, pyridyl or substituting group are halogen, NO
2, C
1-C
4Alkyl, substituted alkyl, alkoxyl group, alkylthio or OCH
2The substituted-phenyl of O; But work as R
1Expression Me, Z and Y are 2-Cl, 4-Cl; R
4Be H, the time, R removed
3Expression H, CH
3, n-C
3H
7, Ph, 2-ClPh, 3-ClPh, 2.4-Cl
2Ph, 3.4-OCH
2OPh, 4-FPh, 4-CH
3Ph, 3-NO
2Ph, 2-Pyridyl, 2-Thiophenyl, 2-Furyl, 4-NO
2Beyond the Ph with formula I-2 in R
3Define identical structure.
The compound that the present invention finds to have the new constructional feature of above-mentioned following formula I is to fusarium oxysporum f.sp.vasinfectum, magnaporthe grisea, botrytis cinerea, gibberella saubinetii, sclerotinia rot of colza, multiple bacterial classification such as beet cercospora leaf spot has significant inhibitory effect, can be used as the effective constituent of sterilant.Growth to unifacial leaf or dicotyledons simultaneously has significant inhibitory effect, the effective constituent of useful as herbicides.
With the preparation method of the substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid of general formula I-1 expression is to make the represented compound of the represented compound of general formula I I and following general formula I II react the A method.
R in the formula
1And R
2, R
3, R
4, Z, Y be identical with the definition among the I.
The Alpha-hydroxy phosphonic acid ester in the above-mentioned reaction and the reaction ratio of substituted benzene oxygen Acetyl Chloride 98Min. and alkali are 1: the mol ratio of 0.8-1.2: 0.8-1.6, reaction solvent adopts organic solvent chloroform, methylene dichloride, ethylene dichloride, benzene, acetone or ethyl acetate, in the presence of basic catalyst pyridine or tertiary amine,-20 ℃-80 ℃ reactions 0.1-10 hour, can obtain yield preferably.
The preparation method of the substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid that general formula I-1 is represented, be to utilize the represented compound of the represented compound of general formula I I and following general formula I V to react, obtain the compound that general formula is V, react with the represented compound of general formula VI again and prepare, the B method
R in the formula
1And R
2, R
3, R
4, defined identical in Z, Y and M and the general formula I.
When this B legal system was equipped with the I-1 compound, Alpha-hydroxy phosphonic acid ester and chloroacetyl chloride were in the presence of organic solvent, the employing organic bases is an acid binding agent,-20 ℃-80 ℃ reactions 8 hours, can be converted into alpha-chloro acetyl oxygen alkyl phosphonate smoothly, its yield is about 85-95%.Organic solvent can adopt chloroparaffin such as chloroform, methylene dichloride, ethylene dichloride, ethyl acetate, acetone, dimethyl formamide (DMF) organic solvent.Acid binding agent adopts organic bases tertiary amine or pyridine usually.During by V and phenol or phenates VI prepared in reaction target compound I-1, reactant ratio such as uses excessive slightly at mol ratio or phenol.In acetone, dimethyl formamide, ethyl acetate, chloroform, methylene dichloride polar organic solvent, at K
2CO
3Or react under the existence of NaOH, KOH mineral alkali.Or earlier the phenol preparation is become phenates, in the presence of the above-mentioned solvent of enumerating, react with compound V again.If adding LiI, kI, NaI or ammonium salt in catalysis agent can achieve good results.
Substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphonate in the represented compound of general formula I, preparation method---C method with the compound of general formula I-2 expression, it is substituted phenoxyl acetyloxy hydrocarbyl phosphonate with general formula I-1 expression of preceding method preparation, with metal halides MX such as KI, NaI or LiBr reaction, reaction solvent is selected one or more in benzene, acetone, butanone, ethyl acetate and the hydrochloric ether, at N
2Protection backflow 0.5-8 hour, can obtain corresponding salt down.Compound I in the reaction-1 is 1 with the proportioning of MX: the 1-1.6 mol ratio.
X is a halogen in the formula; R
1And R
2Expression C
1-C
3Alkyl; R
3, R
4, Z, Y be identical with the definition in the general formula I with M.
Embodiment
Specifically describe the compound of formula I of the present invention below by example, comprise the preparation method of compound in I-1, the I-2 formula, only the present invention will be described for these embodiment, rather than limit the invention.
Embodiment 1
The preparation of compound 1
With 0.01 mole 0,0-dimethyl-Alpha-hydroxy-thenyl phosphonic acid ester is dissolved in 10 milliliters of ethylene dichloride, the pyridine that adds 0.012 mole again below 10 ℃, adds 0.012 mole 2,10 milliliters of dichloroethane solutions of 4-Dichlorophenoxy Acetyl Chloride 98Min., 35 ℃ of following stirring reactions 2.5 hours, rise to 60 ℃ of reactions 0.5 hour again, adopt saturated NaCl solution washing after having reacted respectively 2-3 time, tell organic layer, use anhydrous Na 2SO4
4Drying, it is that developping agent carries out Thin-layer separation that the thick product behind the precipitation adopts ethyl acetate and sherwood oil, and the pure product of gained are white solid behind the purifying, and yield is 91%.Mp.92~93℃
Ultimate analysis: calculated value: C%42.37 H%3.56, measured value: C%42.47 H%3.90;
IR(cm
-1)：3072(υph-H)，2972(υC-H)，1763(υC＝O)，1275(υP＝O)，1190(υC-O-C)，1038(υP-O-C)，732(υp-C)；
1H?NMR(δ/ppm)：3.68~3.79(dd，6H，2×(-OCH
3)，J＝10.50Hz)，4.74(d，1H
a，-OCH
2CO-，J＝16.54Hz)，4.77(d，1H
b，-OCH
2CO-，J＝16.54Hz)，6.48~6.53(d，1H，-OCHP，J＝13.50Hz)，6.68~7.01(m，3H，C
4H
3S-)，6.98~7.36(m，3H，-C
6H
3)；
MS(m/z，％)：424(M
+9.05％)，220(36.89％)，205(60.25％)，175(58.32％)，162(75.87％)，145(26.37％)，133(27.72％)，109(33.28％)，94(3.50％)，93(100％)，75(13.87％)，63(25.84％)，44(31.54％)。
Compound 3,4,5,6 can make by compound 1 similar method, and its structure appraising datum is as follows:
Compound 3
The pure product of gained are faint yellow solid, and yield is 86%.Mp.90~91℃
Ultimate analysis: calculated value: C%47.47 H%4.48, measured value: C%47.42 H%4.59;
IR(cm
-1)：3109(υph-H)，2956(υC-H)，1769(υC＝O)，1263(υP＝O)，1171(υC-O-C)，1030(υP-O-C)，728(υp-C)；
1H?NMR(δ/ppm)：2.25(s，3H，CH
3Ph)，3.70~3.80(dd，6H，2×(-OCH
3)，J＝10.62Hz)，4.75(d，1H
a，-OCH
2CO-，J＝16.56Hz)，4.79(d，1H
b，-OCH
2CO-，J＝16.47Hz)，6.54(d，1H，-OCHP，J＝13.56Hz)，6.59~7.02(m，3H，C
4H
3S-)，7.03~7.38(m，3H，-C
6H
3)；
MS(m/z，％)：404(M
+0.93％)，220(14.16％)，205(93.10％)，200(100％)，155(90.95％)，142(67.00％)，125(64.32％)，109(18.54％)，94(3.46％)，93(74.64％)，75(7.71％)，63(27.76％)，44(22.96％)。
Compound 4
The pure product of gained are faint yellow solid, and yield is 88%.Mp.74~75℃
Ultimate analysis: calculated value: C%47.47 H%4.48, measured value: C%47.19 H%4.46;
IR(cm
-1)：3076(υph-H)，2931(υC-H)，1766(υC＝O)，1249(υP＝O)，1174(υC-O-C)，1027(υP-O-C)，725(υp-C)
1H?NMR(δ/ppm)：2.30(s，3H，CH
3Ph)，3.69~3.80(dd，6H，2×(-OCH
3)，J＝10.65Hz)，4.66(d，1H
a，-OCH
2CO-，J＝16.50Hz)，4.70(d，1H
b，-OCH
2CO-，J＝16.44Hz)，6.53(d，1H，-OCHP，J＝13.59Hz)，6.63~7.04(m，3H，C
4H
3S-)，7.18~7.39(m，3H，-C
6H
3)
MS(m/z，％)：404(M
+13.21％)，369(25.58％)，325(60.90％)，250(25.94％)，219(45.97％)，205(100％)，200(44.18％)，155(86.48％)，142(37.21％)，125(74.54％)，109(60.10％)，94(17.03％)，93(99.00％)，75(8.28％)，63(49.59％)，44(22.09％)。
Compound 5, IB-7
The pure product of gained are faint yellow solid, and yield is 72%.Mp.108~110℃
Ultimate analysis: calculated value: C%42.37 H%3.56, measured value: C%42.77 H%3.63;
IR(cm
-1)：3080(υph-H)，2959(υC-H)，1781(υC＝O)，1256(υP＝O)，1178(υC-O-C)，1038(υP-O-C)，776(υp-C)；
1H?NMR(δ/ppm)：3.74~3.84(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.79(d，1H
a，-OCH
2CO-，J＝16.54Hz)，4.82(d，1H
b，-OCH
2CO-，J＝16.44Hz)，6.39(d，1H，-OCHP，J＝15.20Hz)，6.63~7.11(m，3H，C
4H
3S-)，7.13~7.48(m，3H，-C
6H
3)；
MS(m/z，％)：424(M
+3.24％)，220(62.24％)，205(4.49％)，175(39.92％)，162(68.64％)，145(34.53％)，133(30.96％)，109(37.46％)，94(4.50％)，93(13.58％)，75(30.69％)，63(51.51％)，44(66.73％)，40(100％)。
Compound 6
The pure product of gained are white solid, and yield is 74%.Mp.78~79℃
Ultimate analysis: calculated value: C%42.37 H%3.56, measured value: C%41.93 H%3.49;
IR(cm
-1)：3083(υph-H)，2927(υC-H)，1767(υC＝O)，1273(υP＝O)，1180(υC-O-C)，1037(υP-O-C)，727(υp-C)；
1H?NMR(δ/ppm)：3.74~3.84(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.70(d，1H
a，-OCH
2CO-，J＝16.56Hz)，4.74(d，1H
b，-OCH
2CO-，J＝16.47Hz)，6.62(d，1H，-OCHP，J＝13.60Hz)，7.04~7.30(m，3H，C
4H
3S-)，7.31~7.40(m，3H，-C
6H
3)；
MS(m/z，％)：424(M
+14.25％)，220(41.10％)，205(50.10％)，175(89.12％)，162(100％)，145(22.79％)，133(26.36％)，109(36.19％)，94(3.35％)，93(85.92％)，75(17.46％)，63(31.80％)，44(13.80％)。
Embodiment 2
With 0.01 mole 0, O-dimethyl-Alpha-hydroxy-picolyl phosphonic acid ester is dissolved in 10 milliliters of methylene dichloride, the pyridine that adds 0.013 mole again, below 20 ℃, 10 milliliters of dichloromethane solutions that add 0.012 mole of 2,4 dichloro benzene oxygen Acetyl Chloride 98Min. were 25 ℃ of following stirring reactions 0.5 hour, rise to 40 ℃ of reactions 2.0 hours again, reacted the back and adopted the method for example 1 to handle
The pure product of gained are white solid, and yield is 88%.Mp.105~106℃
Ultimate analysis: calculated value: C%45.74 H%3.84 N%3.33, measured value: C%45.97 H%3.79N%2.94;
IR(cm
-1)：3056(υph-H)，2963(υC-H)，1766(υC＝O)，1265(υP＝O)，1190(υC-O-C)，1027(υP-O-C)，755(υp-C)；
1H?NMR(δ/ppm)：3.73~3.79(dd，6H，2×(-OCH
3)，J＝9.95Hz)，4.88(s，2H，-OCH
2CO-)，6.36(d，1H，-OCHP，J＝13.76Hz)，6.81~7.39(m，3H，-C
6H
3)，7.27~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：419(M
++1?13.91％)，220(65.58％)，216(36.89％)，203(7.56％)，200(60.25％)，175(60.80％)，162(100％)，146(27.15％)，109(50.31％)，94(6.68％)，93(40.49％)，79(18.54％)。
Compound 12,15,16 can make by compound 29 similar methods, and its structure appraising datum is as follows:
Compound 12
The pure product of gained are white solid, and yield is 76%.Mp.124~125℃
Ultimate analysis: calculated value: C%49.82 H%4.44 N%3.63, measured value: C%49.90 H%4.21), N%3.66;
IR(cm
-1)：3069(υph-H)，2955(υC-H)，1777(υC＝O)，1255(υP＝O)，1172(υC-O-C)，1038(υP-O-C)，772(υp-C)；
1H?NMR(δ/ppm)：3.66~3.79(dd，6H，2×(-OCH
3)，J＝10.68Hz)，4.80(s，2H，-OCH
2CO-)，6.37(d，1H，-OCHP，J＝1?3.83Hz)，6.82~7.23(m，4H，-C
6H
4)，7.27~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：385(M
++1?7.52％)，258(16.56％)，244(61.27％)，216(7.05％)，201(25.40％)，140(37.78％)，127(5.05％)，109(73.14％)，94(7.19％)，93(100％)，79(52.33％)，75(34.88％)，63(20.18％)。
Compound 15
The pure product of gained are white solid, and yield is 66%.Mp.115~116℃
Ultimate analysis: calculated value: C%45.74 H%3.84 N%3.33, measured value: C%45.90 H%3.63, N%3.38;
IR(cm
-1)：3077(υph-H)，2957(υC-H)，1779(υC＝O)，1252(υP＝O)，1173(υC-O-C)，1053(υP-O-C)，773(υp-C)；
1H?NMR(δ/ppm)：3.73~3.79(dd，6H，2×(-OCH
3)，J＝11.20Hz)，4.92(s，2H，-OCH
2CO-)，6.37(d，1H，-OCHP，J＝14.00Hz)，6.77~7.28(m，3H，-C
6H
3)，7.29~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：419(M
++1?5.85％)，258(18.10％)，244(100％)，216(12.35％)，201(18.31％)，200(7.69％)，182(4.07％)，175(30.65％)，162(5.65％)，145(26.52％)，109(67.98％)，94(6.31％)，93(71.43％)，79(41.83％)，75(13.80％)，63(19.00％)。
Compound 16
The pure product of gained are white solid, and yield is 68%.Mp.125~126℃
Ultimate analysis: calculated value: C%45.74 H% 3.84 N%3.33, measured value: C%45.92 H%3.65), N%3.38;
IR(cm
-1)：3074(υph-H)，2947(υC-H)，1738(υC＝O)，1222(υP＝O)，1156(υC-O-C)，1048(υP-O-C)，785(υp-C)；
1H?NMR(δ/ppm)：3.74~3.80(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.92(s，2H，-OCH
2CO-)，6.37(d，1H，-OCHP，J＝13.80Hz)，6.77~7.29(m，3H，-C
6H
3)，7.45~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：419(M
++1?1.05％)，258(23.60％)，244(62.50％)，216(7.49％)，201(16.83％)，200(5.30％)，182(4.64％)，175(27.45％)，162(16.04％)，145(34.46％)，109(100％)，94(7.74％)，93(70.77％)，79(58.37％)，75(22.27％)，63(38.56％)。
Embodiment 3
Compound 13
O with 0.01 mole, O-dimethyl-Alpha-hydroxy picolyl phosphonic acid ester is dissolved in 10 milliliters of methylene dichloride, the pyridine that adds 0.011 mole again, below 25 ℃, 10 milliliters of dichloromethane solutions that add 0.012 mole of chloroacetyl chloride, descending stirring reaction 3 hours below 10 ℃, at room temperature place and spend the night, wash reaction solution with water, organic phase drying precipitation obtains dimethyl-α-chloroethene acyl-oxygen yl pyridines methylphosphonate crude product, 0.01 mole the O that yield 85%. will make again, O-dimethyl-α-chloroethene acyl-oxygen yl pyridines methylphosphonate is dissolved among 30 milliliters of DMF, adds 2-chloro-5-methyl-phenol sodium salt of 0.11 mole, refluxed 5 hours, cooling,, react the back and adopted the method for example 1 to handle.The pure product of gained are white solid, and yield is 78%.Mp.76~77℃
Ultimate analysis: calculated value: C%51.08 H%4.79 N%3.50, measured value: C%50.74 H%4.93N%3.25;
IR(cm
-1)：3049(υph-H)，2952(υC-H)，1754(υC＝O)，1222(υP＝O)，1182(υC-O-C)，1054(υP-O-C)，778(υp-C)；
1H?NMR(δ/ppm)：2.27(s，3H，CH
3Ph)，3.73~3.79(dd，6H，2×(-OCH
3)，J＝9.03Hz)，4.88(s，2H，-OCH
2CO-)，6.38(d，1H，-OCHP，J＝13.74Hz)，6.67~7.26(m，3H，-C
6H
3)，7.25~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：399(M
++1?0.82％)，216(1.51％)，200(8.69％)，183(1.64％)，155(8.17％)，125(8.54％)，109(9.44％)，95(36.66％)，93(23.52％)，79(100％)，75(9.49％)，63(19.17％)。
Compound 14,17 can make by compound 33 similar methods, and its structure appraising datum is as follows:
Compound 14
The pure product of gained are white solid, and yield is 74%.Mp.83~85℃
Ultimate analysis: calculated value: C%51.08 H%4.79 N%3.50, measured value: C%50.83 H%4.54N%3.52;
IR(cm
-1)：3058(υph-H)，2957(υC-H)，1776(υC＝O)，1258(υP＝O)，1167(υC-O-C)，1035(υP-O-C)，772(υp-C)；
1H?NMR(δ/ppm)：2.31(s，3H，CH
3Ph)，3.71~3.83(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.79(s，2H，-OCH
2CO-)，6.37(d，1H，-OCHP，J＝13.80Hz)，6.66~7.22(m，3H，-C
6H
3)，7.25~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：399(M
+?33.17％)，258(41.95％)，244(99.57％)，216(17.44％)，201(47.25％)，200(20.85％)，182(10.15％)，155(38.74％)，125(75.49％)，109(81.07％)，94(10.36％)，93(100％)，79(67.15％)，75(8.30％)，63(34.44％)。
Compound 17
The pure product of gained are white solid, and yield is 77%.Mp.75~77℃
Ultimate analysis: calculated value: C%51.08 H%4.79 N%3.50, measured value: C%50.78 H%4.99N%3.28;
IR(cm
-1)：3013(υph-H)，2963(υC-H)，1767(υC＝O)，1264(υP＝O)，1177(υC-O-C)，1047(υP-O-C)，755(υp-C)；
1H?NMR(δ/ppm)：2.26(s，3H，CH
3Ph)，3.72~3.79(dd，6H，2×(-OCH
3)，J＝10.40Hz)，4.82(s，2H，-OCH
2CO-)，6.37(d，1H，-OCHP，J＝14.00Hz)，6.62~7.28(m，3H，-C
6H
3)，7.29~8.63(m，4H，-C
5H
4N)；
MS(m/z，％)：399(M
++1?31.22％)，216(21.72％)，201(77.68％)，182(5.68％)，155(35.00％)，141(43.45％)，125(72.49％)，109(78.91％)，108(100％)，94(12.15％)，93(98.32％)，79(74.73％)，75(8.92％)，63(31.67％)。
Embodiment 11
Compound 24
The preparation of intermediate M24
O with 0.01 mole, O-diethyl-Alpha-hydroxy picolyl phosphonic acid ester is dissolved in 10 milliliters of chloroforms, the pyridine that adds 0.014 mole again, below 10 ℃, add 10 milliliters of chloroformic solutions of 0.012 mole of 2,4 dichloro benzene oxygen Acetyl Chloride 98Min., 50 ℃ of following stirring reactions 4.5 hours, rise to 60 ℃ of reactions 1.5 hours again, reacted the back and adopted the method for example 1 to handle, get intermediate M68 behind the purifying.
0.1 mole compound M68 is dissolved in 10 milliliters of acetone, adds 0.011 mole of NaI again, N
2Protection refluxed 6 hours down, sloughed solvent and promptly got thick product, got final product to such an extent that the pure product of gained are white solid through recrystallization, and yield is 79%.Mp.＞231℃
Ultimate analysis: calculated value: C%43.46 H%3.42 N%3.17, measured value: C%43.61 H%3.22N%3.12;
IR(cm
-1)：3070(υph-H)，2980(υC-H)，1748(υC＝O)，1235(υP＝O)，1079(υC-O-C)，1056(υP-O-C)，748(υp-C)；
1H?NMR(δ/ppm)：1.15(t，3H，-OCH
2CH
3，J＝7.07Hz)，3.82~3.91(m，2H，-OCH
2CH
3)，5.00(s，2H，-OCH
2CO-)，6.08(d，1H，-OCHP，J＝13.52Hz)，6.87~7.31(m，3H，-C
6H
3)，7.27~8.47(m，4H，-C
5H
4N)；
MS(m/z，％)：441(M
+0.2％)，248(79.03％)，220(66.01％)，199(7.65％)，175(100.0％)，162(96.21％)，147(72.37％)，145(79.26％)，133(82.32％)，127(18.68％)，121(31.29％)，111(74.27％)，109(69.11％)，108(81.15％)，107(45.62％)，98(66.44％)，94(10.19％)，93(64.74％)，79(80.20％)，75(64.36％)，74(49.65％)，63(84.28％)，44(29.53％)；
LC-MS(m/z，％)：418(M
+-23，negative?64.82％)，219(61.18％)，215(30.87％)，161(100％)；464(M
++23，positive?100％)，442(M
++1?positive?23.58％)，257(78.42％)，243(12.99％)，109(9.17％)。
Embodiment 12
Compound 31
0.01 mole compound 11 is dissolved in 10 milliliters of acetone, adds 0.014 mole of KI again, N
2Protection refluxed 5 hours down, slough solvent and promptly get thick product, through butanone and sherwood oil recrystallization get final product white solid, the pure product of gained are white solid, yield is 78%.Mp.＞235℃
Ultimate analysis: calculated value: C%40.55 H%2.95 N%3.15 K%8.81, measured value: C%40.22H%2.97 N%3.12 K%9.94;
IR(cm
-1)：3048(υph-H)，2944(υC-H)，1740(υC＝O)，1244(υP＝O)，1082(υC-O-C)，1052(υP-O-C)，751(υp-C)；
1H?NMR(δ/ppm)：3.30(d，3H，-OCH
3，J＝10.20Hz)，4.90(d，1H
a，-OCH
2CO-，J＝16.56Hz)，5.01(d，1H
b，-OCH
2CO-，J＝16.56Hz)，5.76(d，1H，-OCHP，J＝12.90Hz)，7.09~7.65(m，3H，-C
6H
3)，7.20~8.42(m，4H，C
5H
4N-)；
MS(m/z，％)：443(M
+0.32％)，234(0.36％)，220(0.57％)，199(0.48％)，175(0.69％)，162(1.93％)，133(0.47％)，127(2.75％)，109(4.21％)，94(1.26％)，93(2.38％)，63(3.84％)，45(100％)；
LC-MS(m/z，％)：404(M
+-39，negative?54.90％)，219(33.39％)，202(13.43％)，161(100％)，127(53.12％)；482(M
++39，positive?100％)，443(19.15％)，273(36.32％)。
Compound 21,22,29,30,87,99 can make by compound 31 similar methods, and compound 22 required phosphonic acid ester intermediates are compound 11, preparation compound 21,29,30,87,99 required corresponding phosphonate intermediate M21, M29, M30, M87, M99, can make its compound 21,22,29 by compound 11 similar methods, 30,87,99 structure appraising datum is as follows:
Compound 21
The pure product of gained are the look solid, and yield is 86%, Mp.83～85 ℃
Ultimate analysis: calculated value: C%43.34 H%2.98 N%4.90, measured value: C%43.22 H%3.07N%5.53;
IR(cm
-1)：3092(υph-H)，2840(υC-H)，1735(υC＝O)，1245(υP＝O)，1079(υC-O-C)，1038(υP-O-C)，734(υp-C)；
1H?NMR(δ/ppm)：3.32(d，3H，-OCH
3，J＝10.02Hz)，4.91(d，1H
a，-OCH
2CO-，J＝14.56Hz)，5.00(d，1H
b，-OCH
2CO-，J＝18.44Hz)，5.70(d，1H，-OCHP，J＝10.67Hz)，5.93(s，2H，-OCH
2OPh)，6.76～7.53(m，6H，-C
6H
3，-C
6H
3)；
MS(m/z，％)：470(M
+0.1％)，234(6.14％)，220(42.87％)，199(12.91％)，196(0.16％)，182(0.28％)，175(2.37％)，174(35.20％)，164(100％)，145(26.05％)，132(35.61％)，110(36.97％)，108(35.91％)，96(10.49％)，94(2.49％)，93(1.27％)，75(2.99％)，74(24.57％)，62(30.59％)，44(23.49％).。
Compound 22
The pure product of gained are white solid, and yield is 88%.Mp.238℃(dec.)
Ultimate analysis: calculated value: C%42.08 H%3.06 N%3.27 (3.26) measured value: C%42.53 H%3.06N%3.26;
IR(cm
-1)：3160(υph-H)，2952(υC-H)，1730(υC＝O)，1249(υP＝O)，1084(υC-O-C)，1052(υP-O-C)，757(υp-C)；
1H?NMR(δ/ppm)：3.34(d，3H，-OCH
3，J＝7.77Hz)，5.02(s，2H，-OCH
2CO-)，5.85(d，1H，-OCHP，J＝13.58Hz)，7.09~7.67(m，3H，-C
6H
3)，7.16~8.45(m，4H，-C
5H
4N).
31PNMR：8.094；
MS(m/z，％)：427(M
+0.3％)，234(80.42％)，220(72.20％)199(100％)，175(90.68％)，162(83.82％)，145(78.37％)，133(78.68％)，111(74.38％)，109(70.39％)，107(81.39％)，98(66.44％)，94(10.19％)，93(64.74％)，75(58.77％)，74(47.65％)，63(69.28％)，44(26.53％)。
Compound 29
The pure product of gained are white solid, and yield is 78%.Mp.152~153℃
Ultimate analysis: calculated value: C%41.90 H%2.90, measured value: C%41.86 H%2.60;
IR(cm
-1)：3076(υph-H)，2950(υC-H)，1754(υC＝O)，1236(υP＝O)，1078(υC-O-C)，1040(υP-O-C)，731(υp-C)；
1H?NMR(δ/ppm)：3.31(d，3H，-OCH
3，J＝9.76Hz)，4.93(d，1H
a，-OCH
2CO-，J＝16.55Hz)，5.02(d，1H
b，-OCH
2CO-，J＝16.56Hz)，5.72(d，1H，-OCHP，J＝11.95Hz)，5.97(s，H，-OCH
2OPh)，6.77~7.58(m，6H，-C
6H
3，-C
6H
3)；
MS(m/z，％)：486(M
+0.2％)，234(2.59％)，220(14.03％)，199(4.28％)，175(16.09％)，162(100％)，133(14.30％)，109(25.85％)，94(1.09％)，93(18.56％)，63(40.42％)；
LC-MS(m/z，％)：447(M
+-39，negative?100％)，245(18.51％)，219(62.04％)，161(96.81％)；525(M
++39，positive?42.73％)，486(100％)，149(59.09％)，136(80.91％)。
Compound 30
The pure product of gained are white solid, and yield is 52%.Mp.102~104℃
Ultimate analysis: calculated value: C%37.43 H%2.69, measured value: C%37.39 H%3.08;
IR(cm
-1)：3028(υph-H)，2941(υC-H)，1723(υC＝O)，1227(υP＝O)，1074(υC-O-C)，1048(υP-O-C)，710(υp-C)；
1H?NMR(δ/ppm)：3.33(d，3H，-OCH
3，J＝9.81Hz)，4.89(d，1H
a，-OCH
2CO-，J＝16.62Hz)，4.98(d，1H
b，-OCH
2CO-，J＝16.65Hz)，6.02(d，1H，-OCHP，J＝12.24Hz)，6.92~7.40(m，3H，-C
4H
3S)，7.03~7.58(m，3H，-C
6H
3)；
MS(m/z，％)：448(M
+?0.85％)，234(1.27％)，220(0.68％)，199(0.55％)，175(1.47％)，162(1.16％)，133(10.04％)，109(10.15％)，94(2.37％)，93(2.70％)，75(19.36％)，63(37.26％)，45(100％)；
LC-MS(m/z，％)：408(M
+-39，negative?6.11％)，292(71.82％)，219(8.50％)，161(2.12％)，126(100％)；487(M
++39，positive?6.09％)，448(2.85％)，205(100％)。
Compound 65
The pure product of gained are white solid, and yield is 74%.Mp.216℃
Ultimate analysis: calculated value: C%38.82 H%2.79, measured value: C%38.61 H%2.83;
IR(cm
-1)：3012(υph-H)，2847(υC-H)，1737(υC＝O)，1245(υP＝O)，1080(υC-O-C)，1036(υP-O-C)，760(υp-C)；
1H?NMR(δ/ppm)：3.35(d，3H，-OCH3，J＝9.90Hz)，4.86(d，1Ha，-OCH2CO-，J＝16.65Hz)，4.97(d，1Hb，-OCH2CO-，J＝16.65Hz)，5.89(d，1H，-OCHP，J＝13.14Hz)，6.39～7.57(m，3H，-C4H3S)，7.04～7.59(m，3H，-C6H3)。
Compound 66
The pure product of gained are white solid, and yield is 71%.Mp.223℃
Ultimate analysis: calculated value: C%42.08 H%3.06 N%3.27, measured value: C%41.95 H%2.78N%2.81;
IR(cm
-1)：3109(υph-H)，2845(υC-H)，1777(υC＝O)，1252(υP＝O)，1080(υC-O-C)，1054(υP-O-C)，749(υp-C)
1H?NMR(δ/ppm)：3.31(d，3H，-OCH3，J＝11.20Hz)，4.98(d，1Ha，-OCH2CO-，J＝16.80Hz)，5.03(d，1Hb，-OCH2CO-，J＝16.80Hz)，5.79(d，1H，-OCHP，J＝12.80Hz)，7.12～7.48(m，3H，-C6H3)，7.50～8.46(m，4H，-C5H4N)
Compound 67
The pure product of gained are white solid, and yield is 79%, Mp.156～158 ℃
Ultimate analysis: calculated value: C%42.08 H%3.06 N%3.27, measured value: C%41.67 H%2.81 N%3.01;
IR(cm
-1)：3104(υph-H)，2846(υC-H)，1777(υC＝O)，1252(υP＝O)，1080(υC-O-C)，1054(υP-O-C)，749(υp-C)；
1H?NMR(δ/ppm)：3.32(d，3H，-OCH3，J＝10.00Hz)，5.00(d，1Ha，-OCH2CO-，J＝16.80Hz)，5.04(d，1Hb，-OCH2CO-，J＝16.80Hz)，5.81(d，1H，-OCHP，J＝12.80Hz)，7.11～7.47(m，3H，-C6H3)，7.50～8.46(m，4H，-C5H4N)。
Embodiment 19
O with 0.01 mole, O-diethyl-Alpha-hydroxy is dissolved in 10 milliliters of methylene dichloride the luorobenzyl phosphonic acid ester, the pyridine that adds 0.012 mole again, below 0 ℃, add 10 milliliters of dichloromethane solutions of 0.012 mole of 2,4 dichloro benzene oxygen Acetyl Chloride 98Min., 10 ℃ of following stirring reactions 5 hours, rise to 40 ℃ of reactions 1.5 hours again, reacted the back and adopted the method for example 1 to handle, just can obtain compound M69.
0.01 mole compound M69 is dissolved in 10 milliliters of ethyl acetate, adds 0.01 mole of LiBr again, N
2Protection refluxed 9 hours down, slough solvent and promptly get thick product, through ethyl acetate and sherwood oil recrystallization get final product white solid.The pure product of (C method) gained are white solid, and yield is 72%.Mp.164～166℃
Ultimate analysis: calculated value C%46.08 H%3.41, measured value: C%46.41 H%3.36;
IR(cm)：3120(υph-H)，2978(υC-H)，1748(υC＝O)，1223(υP＝O)，1104(υC-O-C)，1041(υP-O-C)，715(υp-C)；
1H?NMR(δ/ppm)：1.02(t，3H，-OCH
2CH
3，J＝7.06Hz)，3.64～3.73(m，2H，-OCH
2CH
3)，4.94(d，1H
a，-OCH
2CO-，J＝16.54Hz)，5.06(d，1H
b，-OCH
2CO-，J＝16.61Hz)，5.80(d，1H，-OCHP，J＝12.84Hz)，7.04～7.59(m，8H，-C
6H
4，-C
6H
4)；.
MS(m/z，％)：442(M
+0.44％)，220(1.09％)，175(2.14％)，161(6.04％)，133(14.38％)，127(47.99％)，109(13.49％)，79(26.44％)，75(20.18％)，73(24.92％)，45(100.0％).。
Embodiment 20
Adopt above-mentioned similar method, can prepare other compound equally.Listedly in the table 1 be synthetic part of compounds of the present invention.
The implication of elliptical symbol in the table: Me-methyl Et-ethyl Ph-phenyl Furyl-furyl Pyridy1-pyridyl Thiopheneyl-thienyl
Table 1 synthetic part of compounds of the present invention.
R
1????R
2?????R
3??????????R
4????Z???????Y
1 OMe Me 2-thienyl H 2-Cl 4-Cl
2 OMe Me 2-thienyl H 4-Cl H
3 OMe Me 2-thienyl H 2-Cl 5-CH
3
4 OMe Me 2-thienyl H 4-Cl 5-CH
3
5 OMe Me 2-thienyl H 2-Cl 3-Cl
6 OMe Me 2-thienyl H 2-Cl 6-Cl
7 OMe Me 2-thienyl H 2-CH
34-Cl
8 OEt Et 2-thienyl H 2-Cl 4-Cl
9 OPr Pr 2-thienyl H 4-Cl H
10 OBu Bu 2-thienyl H 2-Cl 5-CH
3
11???????OMe????Me??????2-Pyridyl????H??????2-Cl????4-Cl
12???????OMe????Me??????2-Pyridyl????H??????4-Cl????H
13???????OMe????Me??????2-Pyridyl????H??????2-Cl????5-CH
3
14???????OMe????Me??????2-Pyridyl????H??????4-Cl????5-CH
3
15???????OMe????Me??????2-Pyridyl????H??????2-Cl????3-Cl
16??????OMe????Me??????2-Pyridyl????????H??????2-Cl????????6-Cl
17??????OMe????Me??????2-Pyridyl????????H??????2-CH
3，?????4-Cl
18??????OEt????Et??????2-Pyridyl????????H??????2-Cl????????3-Cl
19??????OPr????Pr??????2-Pyridyl????????H??????2-Cl????????6-Cl
20??????OBu????Bu??????2-Pyridyl????????H??????2-CH
3，?????4-Cl
21??????OMe????Na??????3.4-OCH
2OPh?????H??????2-Cl????????4-Cl
22??????OMe????Na??????2-Pyridyl????????H??????2-Cl????????4-Cl
25??????OMe????Na??????4-CH
3Ph?????????H??????2-Cl????????3-Cl
26??????OMe????Na??????3-NO
2Ph?????????H??????2-Cl????????6-Cl
27??????OMe????Na??????4-NO
2Ph?????????H??????2-CH
3，????4-Cl
28??????OMe????Na??????2-Pyridyl????????H??????2-Cl????????4-Cl
29??????OMe????K???????3，4-OCH
2OPh????H??????2-Cl????????4-Cl
30??????OMe????K???????2-thiophenyl?????H??????2-Cl????????4-Cl
31??????OMe????K???????2-Pyridyl????????H??????2-Cl????????4-Cl
32??????OMe????Li??????H????????????????H??????2-Cl????????4-Cl
33??????OMe????Li??????CH
3?????????????H??????2-Cl????????4-Cl
34??????OMe????Li??????Et???????????????H??????2-Cl????????4-Cl
35??????OMe????Li??????n-C
3H
7????????H??????2-Cl????????4-Cl
36??????OMe????Li??????n-Bu?????????????H??????2-Cl????????4-Cl
37??????OMe????Li??????Ph???????????????H??????2-Cl????????4-Cl
38??????OMe????Li??????2-ClPh???????????H??????2-Cl????????4-Cl
39??????OMe????Li??????3-ClPh???????????H??????2-Cl????????4-Cl
40??????OMe????Li??????2.4-Cl
2Ph???????H??????2-Cl????????4-Cl
41??????OMe????Li??????3.4-OCH
2OPh?????H??????2-Cl????????4-Cl
42??????OMe????Li??????4-FPh????????????H??????2-Cl????????4-Cl
43??????OMe????Li??????4-CH
3Ph?????????H??????2-Cl????????4-Cl
44??????OMe????Li??????3-NO
2Ph?????????H??????2-Cl????????4-Cl
45??????OMe????Li??????2-Pyridy1????????H??????2-Cl????????4-Cl
46??????OMe????Li??????2-Thiopheny1?????H??????2-Cl????????4-Cl
47??????OMe????Li??????2-Fury1??????????H??????2-Cl????????4-Cl
48??????OMe????Li??????4-NO
2Ph?????????H??????2-Cl????????4-Cl
49??????OEt????Li??????H????????????????H??????2-Cl????????4-Cl
50??????OEt????Li??????CH
3?????????????H??????2-Cl????????4-Cl
51??????OEt????Li??????n-C
3H
7????????H??????2-Cl????????5-CH
3
52??????OEt????Li??????n-Bu????????????????????4-Cl????????5-CH
3
53??????OEt??????Li??????Ph??????????????H??????2-Cl????????3-Cl
54??????OEt??????Li??????4-SCH
3Ph???????H??????2-Cl????????6-Cl
55??????OEt??????Li??????CCl
3???????????H??????4-SMe???????H
56??????OEt??????Li??????CCl
3???????????H??????2-Cl????????4-Cl
57??????OEt??????Li??????3.4-OCH
2OPh????H??????2-Cl????????4-Cl
58??????OEt??????Li??????4-FPh???????????H??????2-Cl????????4-Cl
59??????OEt??????Li??????4-CH
3Ph????????H??????2-Cl????????3-Cl
60??????OEt??????Li??????3-NO
2Ph????????H??????2-Cl????????6-Cl
61??????OEt??????Li??????2-Pyridyl???????H??????2-Cl????????5-CH
3
62??????OEt??????Li??????2-Thiophenyl????H??????4-Cl????????3-CH
3
63??????OEt??????Li??????2-Furyl?????????H??????2-CH
3??????4-Cl
64??????OEt??????Li??????4-NO
2Ph????????H??????3-SCH
3?????H
65??????OMe??????Na??????2-Tbiopbenyl????H??????2-Cl????????4-Cl
66??????OMe??????Na??????3-Pyridyl???????H??????2-Cl????????4-Cl
67??????OMe??????Na??????4-Pyridyl???????H??????2-Cl????????4-Cl
68??????OMe??????Na??????4-Pyridyl???????H??????2-Cl????????4-Cl
69??????OEt??????NH
4????3-CH
3OPh??????H??????2-Cl????????3-Cl
70??????OPr??????NH
4????3-CH
3CH
2Ph???H??????2-Cl????????6-Cl
71??????OBu??????NH
4????CCl
3??????????H??????2-CH
3，????4-Cl
Compound of the present invention can granula, but hydrating agents, emulsion flowing agent wait and use.Also can mix and use or also use simultaneously with other agricultural chemicals, sterilant, sterilant, miticide, plant-growth regulator, fertilizer and soil improvement agent etc.
Embodiment 20
The fungicidal activity test
Test materials:
For trying bacterial classification: fusarium oxysporum f.sp.vasinfectum (Fusarium oxysporium), magnaporthe grisea (Pyriculariaoryzae), botrytis cinerea (Botrytis cinereapers), gibberella saubinetii (Gibberella zeae), sclerotinia rot of colza (Sclerotinia sclerotiorum), beet cercospora leaf spot (Cercospora beticola).
Testing method:
Watch-glass isolated activity assay method:
With the 200g peeling potatoes, boil in 700mL distilled water the chopping back, cold filtration, and filtrate is mixed with glucose, agar, adds water to 900mL again, is heated to boiling, promptly gets substratum after the cooling.Substratum, distilled water, culture dish are sterilized together.With electronic balance weighing 3mg left and right sides testing sample, add a small amount of DMF dissolving, drip 1 tween-80, adding distil water is mixed with 1000ppm.
Substratum high temperature decompression sterilization 15 minutes, after the sterilization, measure the 10mL culture medium after sterilization while hot with the scale test tube, with itself and 1mL, the 10mL sample mixing that 1000ppm solution obtains with 10 times of distilled water dilutings, can make the sample that concentration is 50ppm, build the culture dish loam cake, the horizontal positioned cooling.
With diameter is that the punch tool of 5mm is got the blank agar block, chooses in the culture dish with light gage wire, and mycelia faces down, and each culture dish is placed 2-3 kind bacterium.Getting preceding punch tool of bacterium and light gage wire must sterilize with the spirit lamp calcination.Use aforesaid method, do not add testing sample, each bacterial classification is done the primary blank contrast.Place 48-72 hour " Invest, Then Investigate " in the sterile constant-temperature case then.Measure the diameter of bacterial plaque, according to the blank photograph, suppress the expression drug effect with diameter: inhibiting rate %=[(CK-handles)/CK] * 100%
Active is reference with the bacteriostasis rate, rank standard: A level: 〉=90%, and the B level: 70～89%, the C level: 50～69%, D level :≤49%.
The measurement result of segment bounds I compound sees Table 2
The fungicidal activity data of table 2 compound (Plating exsomatizes) 50ppm
| Number 1234567 | Fusarium oxysporum f.sp.vasinfectum | Magnaporthe grisea | Botrytis cinerea | Gibberella saubinetii | Sclerotinia sclerotiorum | Beet Cercospora | ||||||
| Active 44.44 59.26 48.15 51.85 25.93 55.56 48.15 | Rank C C C | Active 34.62 69.23 42.31 69.23 34.62 50.00 50.00 | Rank C C C C | Active 59.52 95.24 66.67 97.62 54.76 92.85 95.24 | Rank C A C A C A A | Active 17.65 61.76 32.35 55.88 26.47 55.88 55.88 | Rank C C C C | Active 65.12 100 88.37 97.67 76.74 100 97.67 | Rank C A B A B A A | Active 22.22 55.56 44.44 55.56 14.81 62.96 37.04 | Rank C C C | |
Embodiment 21
The fungicidal activity test method sees that embodiment 20 is with identical
The fungicidal activity data of table .3-compound (Plating exsomatizes) 50ppm
| Number 29 31 33 34 35 36 41 | Fusarium oxysporum f.sp.vasinfectum | Magnaporthe grisea | Botrytis cinerea | Gibberella saubinetii | The rape sclerotium | Beet Cercospora | ||||||
| Active 22.22 44.44 79.17 95.83 95.83 91.67 58.33 | Rank B A A A C | Active 38.46 46.15 97.06 97.06 100 100 70.59 | Rank A A A A B | Active 64.29 57.14 98.89 100 100 100 91.11 | Rank C C A A A A A | Active 52.94 26.47 79.07 69.77 95.35 97.67 51.16 | Rank C B C A A C | Active 74.42 72.09 100 100 100 100 95.35 | Rank B B A A A A A | Active 25.93 37.04 83.87 98.38 93.55 100 38.71 | Rank B A A A | |
Embodiment 22
The fungicidal activity test method sees that embodiment 20 is with identical
The fungicidal activity data of table .4-compound (Plating exsomatizes) 50ppm
| Number 54 59 | Gibberella saubinetii | Tomato is vaccine early | The withered bacterium of asparagus stem | Apple wheel line bacterium | The peanut Cercospora asparagagas |
| Active % 0.00 0.00 | Active % 6.50 0.00 | Active % 10.0 0.00 | Active % 15.6 0.00 | Active % 15.8 0.00 |
Embodiment 23
The fungicidal activity test method sees that embodiment 20 is with identical
Table 5, the fungicidal activity data of compound (Plating exsomatizes) 50ppm
| Number 32 33 35 37 38 39 40 41 42 43 44 45 46 47 | Fusarium oxysporum f.sp.vasinfectum | Magnaporthe grisea | Botrytis cinerea | Gibberella saubinetii | Sclerotinia sclerotiorum | Beet Cercospora | ||||||
| Active 59.09 54.55 63.64 36.36 36.36 40.91 50.00 40.91 42.86 36.36 50.00 34.14 71.42 28.57 | Rank C C C C C B | Active 66.67 66.67 63.33 33.33 43.33 43.33 53.33 56.67 70.00 36.67 80.00 70.00 90.00 70.00 | Rank C C C C C B B B A B | Active 95.00 90.00 95.00 70.00 50.00 45.00 75.00 75.00 76.00 55.00 100.0 86.00 100.0 66.00 | Rank A A A B C B B B C A B A C | Active 68.75 34.38 65.63 15.63 21.88 18.75 34.38 43.75 34.38 40.63 56.25 28.13 62.50 18.75 | Rank C C C C | Active 100.0 94.44 97.22 75.00 83.33 77.78 80.56 75.00 98.72 83.33 100.0 98.72 100.0 94.87 | Rank A A A B B B B B A B A A A A | Active 48.28 75.86 31.03 82.76 34.48 | Rank B B | |
Embodiment 24
Weeding activity suppresses experiment
Pot-culture method
The soil of quantitatively packing into and sieving with the potted plant box of 30 * 20 * 5.5 centimetres plastics, elder generation's water is drenched, the rape of rudiment, three-coloured amaranth, lady's-grass, each two row of barnyard grass grass on the kind, 10 of every row, cover and sieve native 0.6 centimetre, do seedling pre-treatment and seedling aftertreatment with every mu 100 gram of Compound I immediately, the seedling aftertreatment is generally the 2-3 leaf phase, and two kinds of processing are all handled with emulsion spray, and other establishes the clear water contrast, give out light according to glass room about 15 days, temperature is 25 ℃, cuts over-ground part after the processing, claims fresh weight, according to fresh weight and blank, calculate inhibiting rate.The measurement result of part of compounds I sees Table 9.Active rank: A level 〉=80%, B level 60～79%, C level 40～59%, D level≤39%.
Table 6 compound is to inhibition activity data (the pot-culture method) (consumption: 100g/ mu) of dicotyledons
| Number 1247 11 12 21 22 65 | The seedling pre-treatment | The seedling aftertreatment | ||||||||||
| Rape | Three-coloured amaranth | Clover | Rape | Three-coloured amaranth | Clover | |||||||
| ?％ ? ?94.0 ?91.4 ?63.2 ?95.3 ?88.9 ?89.7 ?95.2 ?100 ?17.3 | Rank A A B A A A A A D | ?％ ? ?83.1 ?83.1 ?66.1 ?83.1 ?93.2 ?69.5 ?99.0 ?100 ?11.9 | Rank A A B A A B A A D | ?％ ? ?96.0 ?81.6 ?87.8 ?87.8 ?93.9 ?81.6 ?96.5 ?100 ?0.00 | Rank A A A A A A A A D | ％ ? 73.3 46.3 44.6 81.0 76.4 60.0 100 41.8 25.1 | Rank B C C A B B A C D | ％ ? 100 52.1 53.8 100 89.7 100 100 100 33.3 | Rank A C C A A A A A D | ％ ? 71.4 36.3 34.1 47.3 40.7 40.7 100 100 31.9 | Rank B D D C C C A A D | |
Embodiment 25
The weeding activity experimental technique is identical with the weeding activity experimental technique of embodiment 24
Table 7 Compound I is to inhibition activity data (the pot-culture method) (consumption: 100g/ mu) of dicotyledons
| Number 24 29 30 31 | The seedling pre-treatment | The seedling aftertreatment | ||||||||||
| Rape | Three-coloured amaranth | Clover | Rape | Three-coloured amaranth | Clover | |||||||
| ??％ ? ??98.1 ??92.3 ??89.7 ??93.6 | Rank A A A A | ?％ ? ?85.2 ?86.4 ?89.8 ?79.7 | Rank A A A B | ?％ ? ?97.5 ?93.9 ?93.9 ?91.8 | Rank A A A A | ％ ? 72.0 67.2 82.6 48.7 | Rank B B A C | ％ ? 54.2 57.3 93.2 74.4 | Rank C C A B | ％ ? 62.1 69.2 64.8 36.3 | Rank C B B D | |
Embodiment 26
The weeding activity experimental technique is identical with the weeding activity experimental technique of embodiment 24
Table 8 Compound I is to monocotyledonous inhibition activity data
(pot-culture method) (consumption: 100g/ mu)
| Compound number | The seedling pre-treatment | The seedling aftertreatment | ||||||
| The barnyard grass grass | Lady's-grass | The barnyard grass grass | Lady's-grass | |||||
| ??％ ? | Rank | ??％ ? | Rank | ??％ ? | Rank | ％ ? | Rank | |
| ????29 ????30 ????31 ????32 ????33 ????37 ????38 ????40 ????41 ????43 ????44 | ??84.6 ??88.2 ??85.5 ??81.2 ??84.4 ??81.2 ??79.7 ??81.2 ??79.7 ??82.8 ??82.8 | ?A ?A ?A ?A ?A ?A ?B ?A ?B ?A ?A | ?98.1 ?96.2 ?96.2 ?94.8 ?100 ?99.0 ?92.8 ?99.0 ?99.5 ?99.0 ?97.1 | ?A ?A ?A ?A ?A ?A ?A ?A ?A ?A ?A | ?32.0 ?41.3 ?38.5 ?23.9 ?45.2 ?40.6 ?36.8 ?25.8 ?34.8 ?46.5 ?39.4 | ??D ??C ??D ??D ??C ??C ??D ??D ??D ??C ??D | ?54.6 ?56.3 ?28.4 ?17.7 ?48.1 ?34.2 ?14.0 ?38.0 ?17.7 ?31.6 ?29.1 | ????C ????C ????D ????D ????C ????D ????D ????D ????D ????D ????D |
Embodiment 27
Weeding activity suppresses experiment
Cucumber culture dish method-IC
50Test
In diameter is 9 centimetres culture dish, put into a sizeable filter paper, 5 milliliters of the soups to be measured that adding has configured in every ware, sow cucumber seeds then through soaking 6 hours, every processing secondary repeats, build the ware lid after, put in 28 ℃ of thermostatic chambers and cultivate, behind the seed germination every day irradiation 10 hours, three days measurement results of cultured continuously.
Measure every strain cucumber primary root length, compared with the control, calculate the long inhibiting rate of root (%).Calculate each medicament then and cucumber primary root length is suppressed 50% concentration (IC
50).
By test and result's calculating, each medicament suppresses 50% effective concentration IC to cucumber primary root length
50List in table 9 respectively.
The IC50 of table 9 compound suppresses activity data
| Compound number | ??IC 50μM ? ? | Compound number | ??IC 50μM ? ? | Compound number | ????IC 50μM ? ? |
| ??1 | ??0.2827 | ??14 | ??2.3679 | ??33 | ????0.5103 |
| ??2 | ??0.5817 | ??15 | ??244.1544 | ??37 | ????0.5962 |
| ??3 | ??50.9750 | ??16 | ??9.3489 | ??38 | ????0.5773 |
| ??4 | ??2.3256 | ??21 | ??0.9820 | ??40 | ????0.4073 |
| ??5 | ??590.9983 | ??22 | ??0.5711 | ??41 | ????0.4983 |
| ??6 | ??178.6842 | ??24 | ??0.4075 | ??42 | ????1.4664 |
| ??7 | ??0.4684 | ??29 | ??0.4433 | ??43 | ????0.4596 |
| ??11 | ??0.3646 | ??30 | ??0.4082 | ??44 | ????0.4164 |
| ??12 | ??0.4321 | ??31 | ??0.5544 | ??46 | ????1.0831 |
| ??13 | ??46.4086 | ??32 | ??0.7573 | ??65 | ????106.5691 |
Claims (12)
1, a class substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid or a salt compound is characterized in that having the represented structural formula of general formula I:
In the formula: R
1Expression C
1-C
3Alkyl; R
2Expression C
1-C
3Alkyl or M, M is Li, Na, K or NH
4 +, R
1With R
2Identical or inequality;
R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl, furyl, thienyl, pyridyl, substituting group are halogen, NO
2, C
1-C
4Alkyl, substituted alkyl, alkoxyl group, alkylthio or OCH
2The substituted-phenyl of O;
R
4Expression H or C
1-C
4Alkyl;
Z and Y represent H, are not halogen, the C of F or CF
1-C
4Alkyl, substituted alkyl or alkoxyl group, alkylthio, NO
2, Z is identical with Y or inequality;
Work as R
1And R
2Expression C
1-C
3Alkyl the time, R
3Expression thienyl, pyridyl, substituting group are C
2-C
4Alkyl, alkylthio, alkoxyl group or OCH
2The substituted-phenyl of O, or remove R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl is beyond aminomethyl phenyl and the furyl.
When M is Na, K, NH
4 +The time, R
3Expression thienyl, pyridyl or substituting group are C
2-C
4Alkyl, alkylthio, alkoxyl group or OCH
2The substituted-phenyl of O;
When M is Li, R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl, furyl, thienyl, pyridyl, substituting group are halogen, NO
2, C
1-C
4Alkyl, substituted alkyl, alkoxyl group, alkylthio or OCH
2The substituted-phenyl of O, but work as R
1Expression Me, Z, Y are 2-Cl, 4-Cl, R
4Be H, the time, R removed
3Expression H, CH
3, n-C
3H
7, Ph, 2-ClPh, 3-ClPh, 2.4-Cl
2Ph, 3.4-OCH
2OPh, 4-FPh, 4-CH
3Ph, 3-NO
2Ph, 2-Pyridyl, 2-Thiophenyl, 2-Furyl, 4-NO
2Beyond the Ph.
2, the preparation method of substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid general formula I-1 in the described compound of representing by general formula I of claim 1, the A method, it is characterized in that making is that the represented compound of the represented compound of general formula I I and following general formula I II is reacted
Among formula II and the III, R
1And R
2, R
3, R
4, Z, Y be identical with the definition in the claim 1 described general formula I.
3, the preparation method of substituted phenoxide acetoxide aryl heterocyclic radical hydrocarbyl phosphine acid in the described compound of representing by general formula I of claim 1, the B method, it is characterized in that making the represented compound of represented compound of general formula I I and following general formula I V to react, resultant general formula is the represented midbody compound of V, reacts with the represented compound of general formula VI to prepare again
Among formula II, IV, V and the VI, R
1And R
2, R
3, R
4, Z, Y, M be identical with the definition in the claim 1 described general formula I.
4, the described compound of representing by general formula I of claim 1-substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphonate, promptly with the preparation method of the compound of general formula I-2 expression, the C method is characterized in that utilizing the represented compound of general formula I-1 and metal halides KI, NaI, LiBr to react and prepare.
R in the formula
1, M, R
3, R
4, in Z, Y and the claim 1 described general formula I definition identical,
R in the formula
1, R
2Expression C
1-C
4Alkyl, R
3, R
4, in Z, Y and the claim 1 described general formula I definition identical.
5, the described application of compound of representing with general formula I of claim 1 is characterized in that the effective ingredient as sterilant.
6, the described application of compound of representing with general formula I of claim 1 is characterized in that as the effective ingredient for the fusarium oxysporum f.sp.vasinfectum sterilant.
7, the described application of compound of representing with general formula I of claim 1 is characterized in that as the effective ingredient for the magnaporthe grisea sterilant.
8, the described application of compound of representing with general formula I of claim 1 is characterized in that as the effective ingredient for the botrytis cinerea sterilant.
9, the described application of compound of representing with general formula I of claim 1 is characterized in that as the effective ingredient for the gibberella saubinetii sterilant.
10, the described application of compound of representing with general formula I of claim 1 is characterized in that as the effective ingredient for the sclerotinia rot of colza sterilant.
11, the described application of compound of representing with general formula I of claim 1 is characterized in that as the effective ingredient for dish brown spot sterilant.
12, the described application of compound of representing with general formula I of claim 1 is characterized in that the effective ingredient as weedicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100185564A CN1274697C (en) | 2005-04-15 | 2005-04-15 | Substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate with bactericidal and herbicidal activity and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100185564A CN1274697C (en) | 2005-04-15 | 2005-04-15 | Substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate with bactericidal and herbicidal activity and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1673228A true CN1673228A (en) | 2005-09-28 |
| CN1274697C CN1274697C (en) | 2006-09-13 |
Family
ID=35046030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100185564A Expired - Fee Related CN1274697C (en) | 2005-04-15 | 2005-04-15 | Substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate with bactericidal and herbicidal activity and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274697C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977147A (en) * | 2011-09-06 | 2013-03-20 | 华中师范大学 | Phosphorus heterocycle-containing substituted phenoxy (isopropyl) acetoxy alkyl phosphonate having weeding activity, and preparation thereof |
| CN103588814A (en) * | 2012-08-13 | 2014-02-19 | 华中师范大学 | Optically active isomer of substituted phenoxyl acetyloxy (amino) hydrocarbyl phosphonate with herbicidal activity and preparation thereof |
| CN104098603A (en) * | 2013-04-02 | 2014-10-15 | 华中师范大学 | O, O-dialkyl-alpha-(substituted phenoxybutyryloxy)alkyl phosphonate with herbicidal activity and preparation method thereof |
| CN105985374A (en) * | 2015-02-15 | 2016-10-05 | 华中师范大学 | Preparation method and production device of clacyfos |
-
2005
- 2005-04-15 CN CNB2005100185564A patent/CN1274697C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977147A (en) * | 2011-09-06 | 2013-03-20 | 华中师范大学 | Phosphorus heterocycle-containing substituted phenoxy (isopropyl) acetoxy alkyl phosphonate having weeding activity, and preparation thereof |
| CN102977147B (en) * | 2011-09-06 | 2016-06-01 | 华中师范大学 | What have weeding activity contains phosphorus heterocycle substituted benzene oxygen second (isopropyl) acyloxyalkyl phosphonic acid ester and preparation |
| CN103588814A (en) * | 2012-08-13 | 2014-02-19 | 华中师范大学 | Optically active isomer of substituted phenoxyl acetyloxy (amino) hydrocarbyl phosphonate with herbicidal activity and preparation thereof |
| CN104098603A (en) * | 2013-04-02 | 2014-10-15 | 华中师范大学 | O, O-dialkyl-alpha-(substituted phenoxybutyryloxy)alkyl phosphonate with herbicidal activity and preparation method thereof |
| CN104098603B (en) * | 2013-04-02 | 2016-08-17 | 华中师范大学 | There is the O of activity of weeding, O-dialkyl group-α-(substituted benzene oxygen butyryl acyloxy) alkyl phosphonate and preparation method |
| CN105985374A (en) * | 2015-02-15 | 2016-10-05 | 华中师范大学 | Preparation method and production device of clacyfos |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1274697C (en) | 2006-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1209016C (en) | Fungicides | |
| CN1067063C (en) | Substituted carboxylic acylaniline derivative and plant disease control agent containing it as active component | |
| CN1291993C (en) | N-substituted benzothiazolyl-1-substituted phenyl-0,0-dialkyl-alpha-amino phosphonate ester derivatives preparation and application | |
| CN1229336C (en) | Photoactive compound used as intermediate for preparing photoactive 2-imidazoline-5-ketone or 2-imdazoline-5-thio-ketone derivative | |
| CN1055686C (en) | Substituted Benzisoxazole and benzisothiazole herbicidal agents | |
| CN1185216C (en) | Fungicidies | |
| CN1078721A (en) | Pyridine carboxylic acid and herbicidal composition | |
| CN100335481C (en) | Poly-substituted pyridino-[4,3d] pyramine with antibacterial and herbicide activity and its production thereof | |
| CN86106281A (en) | Semicarbazone class and thiosemicarbazone class | |
| CN87103150A (en) | Weedicide | |
| CN1070022C (en) | Agrochemical compositions and methods employing 3-hydroxy-5-methylisoxazole | |
| CN1108652A (en) | Alpha-pyrimidinyl acrylic acid derivatives | |
| CN1274697C (en) | Substituted phenoxy acetoxyl aromatic heterocyclic alkyl phosphonate with bactericidal and herbicidal activity and its prepn | |
| CN1484641A (en) | Microbiocidal N-Phenyl-N-[4-pyridyl-pyrimidin-2-yl]-amine derivatives | |
| CN87106830A (en) | Tertiary amine compound | |
| CN1030913C (en) | Benzohyolroxymoylazole derivatives, method for producing same, and insecticide including same | |
| CN1029189C (en) | Isothiazolecarboxylic acid derivatives, rice blast control agents containing same as active ingredients, and rice blast control method applying control agents | |
| CN1319449C (en) | Substituted phenoxy acetyl oxy alkyl phospho acid and phosphonate ester possessing bactericidal insecticidal activity | |
| CN1061406A (en) | Fungicidal 3,3-1,1-bialkyl sulphide-2-pyridyl acrylic acid derivative | |
| CN1246118A (en) | Chromone derivatives and bactericidal and herbicidal agent containing the same as active ingredient | |
| CN1175255A (en) | Hydantoin derivatives, process for producing the same and herbicides comprising the same as active ingredients | |
| CN1042729C (en) | N-sulfonyl carboxylic amide derivative incluoding an N-containing 6-member aromatic ring, or the salf of the game, method for producting the same, and pesticide including herbicide | |
| CN1039009C (en) | Oxazoline derivative, process for preparing the same and agricultural and horticultural chemical for controlling noxious organisms containing the same | |
| CN1560058A (en) | Fluorine substituted phenoxy acetyl oxide alkyl phosphonate ester and salt with weeding active and preparation process thereof | |
| CN1048545A (en) | The benzoxazol quinoline ketone and the quinoline ketone derivatives that replace, their method for making and as the effect of weedicide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060913 Termination date: 20190415 |