CN1687086A - Substituted phenoxy-acetoxy-aromatic heterocyclic radical-alkyl ester phisphinic acid possessing bactericidal and herbicidal activity, and preparation - Google Patents

Substituted phenoxy-acetoxy-aromatic heterocyclic radical-alkyl ester phisphinic acid possessing bactericidal and herbicidal activity, and preparation Download PDF

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CN1687086A
CN1687086A CNA200510018611XA CN200510018611A CN1687086A CN 1687086 A CN1687086 A CN 1687086A CN A200510018611X A CNA200510018611X A CN A200510018611XA CN 200510018611 A CN200510018611 A CN 200510018611A CN 1687086 A CN1687086 A CN 1687086A
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CN100375748C (en
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贺红武
王涛
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Huazhong Normal University
Central China Normal University
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Abstract

The present invention relates to a substituted phenoxyacetoxyl aromatic heterocyclic radical hydroxy phosphinic acid ester or salt with bactericidal and weedicidal activity. Said invention also provides its structure formula, and said compound has the obvious effect for inhibiting cotton wilt mycosis, rice blastmycin, cucumber mildew, wheat mildew and others, and can be used as bacteriocide, also can be used as weedicide.

Description

Substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate salt and preparation with bactericidal and herbicidal activity
Technical field
The present invention relates to substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate salt compound that has fungicidal activity and weeding activity 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 phosphonate derivatives, and they have all shown weeding activity and plant growth regulating activity in various degree.For example, in recent years, the inventor had developed following a few class phosphonate derivative: category-A (patent No. is ZL 97109095.5 for He Hongwu etc., Chinese invention patent), category-B (patent No. is ZL 00131149.2 for He Hongwu etc., Chinese invention patent).C class ((He Hongwu etc., Chinese invention patent application number are 200410012773.8).Result of study shows, and category-A, category-B, C compounds have then shown weeding activity and plant growth regulating activity in various degree.
Figure A20051001861100041
Summary of the invention
The objective of the invention is to explore and have new texture and have weeding and/or germ-resistant substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate and salt compounds, provide a class to have weeding activity, and with the novel phosphinic acids ester 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, propose a class phosphonate derivative-substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate and the salt compounds I different with above-mentioned all classes of compounds structures, its general structure is suc as formula I:
Figure A20051001861100042
In the formula, R 1Expression C 1-C 4Alkyl;
R 2Expression C 1-C 4Alkyl 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 or substituting group are halogen, NO 2, C 1-C 4Alkyl, substituted alkyl, alkoxyl group, alkylthio or CH 2The substituted-phenyl of O;
R 4Expression H or C 1-C 4Alkyl;
Z and Y represent H, halogen, C 1-C 4Alkyl, substituted alkyl or alkoxyl group, alkylthio or NO 2, Z is identical with Y or inequality; Work as R 2During the expression alkyl, Z and Y are not F or CF 3Halogen, R 3Do not represent furyl, C 1Alkyl.
The compound that belongs to formula I of the present invention comprises following with the represented substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of general formula I-1 in fact, with the represented substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate metal-salt of general formula I-2.
Figure A20051001861100051
The structure of two kinds of compounds of proposed by the invention this all is 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 benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate I-1
In the structure of substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate I-1, R 1And R 2Expression C 1-C 4Alkyl, R 1With R 2Identical or inequality; R 4Expression H or 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 or NO 2, Z is identical with Y or inequality; R 3Expression thienyl, pyridyl or substituting group are C 2-C 4Alkyl, alkylthio, alkoxyl group or OCH 2The substituted-phenyl of O.General structure I comprises the structure division of substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate salt I-2,
Figure A20051001861100053
In the structure of substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate salt I-2, R 1Expression C 1-C 4Alkyl; M is Li, Na, K or NH 4 +R 4Expression H, C 1-C 4Alkyl; 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; Z and Y represent H, halogen, C 1-C 4Alkyl, substituted alkyl or alkoxyl group, alkylthio or NO 2, Z is identical with Y or inequality.
The compound that the present invention finds to have above-mentioned new constructional feature not only has good weeding activity, also has good fungicidal activity simultaneously.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, thereby can be used as the effective constituent of weedicide.
The preparation method of the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate I-1 that represents with general formula I makes the represented compound of the represented compound of general formula I I and following general formula I II react the A method.
Among formula II and the III, R 1And R 2, R 3, R 4, Z and Y be identical with the definition in the general formula I.
The Alpha-hydroxy phosphinate 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 acetone, ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, benzene, the chlorobenzene organic solvent, in the presence of basic catalyst pyridine or tertiary amine,-20 ℃-80 ℃ reactions 1-8 hour, can obtain target compound I-1 of the present invention
Figure A20051001861100062
Another preparation method of the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate 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.
II??????????IV??????????????V?????????????????????????I-1
R among formula II and IV, V, the VI 1And R 2, R 3, R 4, Z, Y and M be identical with the definition in the general formula I.
When this B legal system was equipped with the I-1 compound, Alpha-hydroxy phosphinate and chloroacetyl chloride were in the presence of organic solvent, and the employing organic bases is an acid binding agent ,-20 ℃-80 ℃ reactions 0.5-8 hour, can be converted into alpha-chloro acetyl oxygen alkyl hypophosphorous ester V smoothly.Organic solvent can adopt chloroparaffin such as chloroform, methylene dichloride, ethylene dichloride, ethyl acetate, acetone, multiple organic solvent such as DMF.Acid binding agent adopts organic basess such as 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 various polarity organic solvents such as acetone, dimethyl formamide, ethyl acetate, chloroform, methylene dichloride, at K 2CO 3Or react under the existence of mineral alkalis such as NaOH, KOH.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 catalyzer such as MI or ammonium salt can achieve good results.
Substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinates in the represented compound of general formula I of the present invention, promptly with the preparation method of the compound of general formula I-2 expression, the C method, be with the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of general formula I-1 expression of preceding method preparation, react with metal halides MX (as KI, NaI or LiBr).Reaction solvent can be 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: 1～1.5 mol ratios with the proportioning of MX,
Figure A20051001861100071
R in the formula 1And R 2Expression C 1-C 4Alkane, M, H; X is a halogen, R 3And R 4, Z, Y and M be identical with the definition in the general formula I.
Specifically describe the represented compound of general formula I of the present invention below by example, comprise the preparation method of compound in I-1 and 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, the A method,
0.01 mole methyl-O-methyl-alpha-hydroxy-2-thenyl phosphinate is dissolved in 30 milliliter 1, in the 2-ethylene dichloride, add 0.011 mole pyridine again, below 10 ℃, add 0.009 mole 2,10 milliliter 1 of 4-Dichlorophenoxy Acetyl Chloride 98Min., the 2-dichloroethane solution was 40 ℃ of following stirring reactions 4.5 hours, rise to 70 ℃ of reactions 0.5 hour again, react the back and adopted saturated NaCl solution washing 2-3 time, told organic layer, used anhydrous Na 2SO 4Drying, it is that developping agent carries out Thin-layer separation that the thick product behind the precipitation adopts ethyl acetate and sherwood oil, purifying, the pure product of gained are light yellow viscous liquid, yield is 64%, n D 20=1.5121.
Ultimate analysis: measured value C%44.40 H%3.72, calculated value C%44.03 H%3.69;
IR(cm -1)：3075(ph-H)?1749(C＝O)?1246(P＝O)?1182(C-O-C)?1042(P-O-C)；
1HNMR(δppm)：1.47～1.62(dd，3H，-CH 3，J＝15.6Hz)，3.68～3.74(dd，3H，-OCH 3，J＝12.4Hz)，4.82(d，1H a，-OCH 2CO-，J＝14.0Hz)，4.83(d，1H b，-OCH 2CO-，J＝12.8Hz)，6.49～6.54(dd，1H，-OCHP，J＝10.4Hz)，6.72～7.40(m，6H，-C 4H 3S，-C 6H 3)；
MS(m/z)：408(M +?11.68％)。
Compound 2,5,6 listed in the table 1 can make by compound 1 similar method, and the structure appraising datum of its compound 2,5,6 is as follows
Compound 2:
Figure A20051001861100081
Yellow thick liquid, yield: 62%, n D 20=1.4868
Ultimate analysis: measured value C%47.95 H%4.00, calculated value C%48.07 H%4.30;
IR(cm -1)：3092(ph-H)?1739(C＝O)?1236(P＝O)?1174(C-O-C)?1042(P-O-C)；
1HNMR(δppm)：1.47～1.54(dd，3H，-CH 3，J＝14.4Hz)，3.68～3.74(dd，3H，-OCH 3，J＝12.4Hz)，4.82(d，1H a，-OCH 2CO-，J＝15.6Hz)，4.84(d，1H b，-OCH 2CO-，J＝15.4Hz)，6.45～6.53(dd，1H，-OCHP，J＝9.8Hz)，6.85～7.39(m，7H，-C 4H 3S，-C 6H 4)；MS(m/z)：374(M +?15.62％)。
Compound 5:
Light yellow viscous liquid, yield: 63%, n D 20=1.5186
Ultimate analysis: measured value C%43.55 H%3.74, calculated value C%44.03 H%3.69;
IR(cm -1)：3076(ph-H)?1775(C＝O)?1227(P＝O)?1175(C-O-C)?1042(P-O-C)；
1HNMR(δppm)：1.51～1.57(dd，3H，-CH 3，J＝14.0Hz)，3.70～3.77(dd，3H，-OCH 3，J＝10.8Hz)，4.75(d，1H a，-OCH 2CO-，J＝14.8Hz)，4.76(d，1H b，-OCH 2CO-，J＝14.6Hz)，6.51～6.60(dd，1H，-OCHP，J＝7.6Hz)，7.03～7.40(m，6H，-C 4H 3S，-C 6H 3)；
MS(m/z)：408(M +?5.89％)。
Compound 6:
Figure A20051001861100091
Light yellow viscous liquid, yield: 61%, n D 20=1.5241
Ultimate analysis: measured value C%43.72 H%3.72, calculated value C%44.03 H%3.69;
IR(cm -1)：3081(ph-H)?1770(C＝O)?1232(P＝O)?1178(C-O-C)?1042(P-O-C)；
1HNMR(δppm)：1.45～1.50(dd，3H，-CH 3，J＝14.4Hz)，3.67～3.73(dd，3H，-OCH 3，J＝12.4Hz)，4.83(d，1H a，-OCH 2CO-，J＝15.6Hz)，4.87(d，1H b，-OCH 2CO-，J＝15.4Hz)，6.44～6.52(dd，1H，-OCHP，J＝8.8Hz)，6.75～7.39(m，6H，-C 4H 3S，-C 6H 3)；；
MS(m/z)：408(M +?4.68％)
Embodiment 2
The preparation of compound 9, the A method,
0.01 mole methyl-O-methyl-alpha-hydroxy-2-picolyl phosphinate is dissolved in 30 milliliters of methylene dichloride, the triethylamine that adds 0.012 mole again, below 10 ℃, add 0.011 mole 2,10 milliliters of dichloromethane solutions of 4-Dichlorophenoxy Acetyl Chloride 98Min., 25 ℃ of following stirring reactions 5 hours, rise to 50 ℃ of reactions 1 hour again, react the method processing of back employing embodiment 1.The pure product of gained are for being light yellow viscous liquid, and yield is 73%, n D 20=1.5412.
Ultimate analysis: measured value: C%47.33 H%3.95 N%3.09,
Calculated value: C%47.55 H%3.99 N%3.47;
IR(cm -1)：3070(ph-H)?1770(C＝O)?1246(P＝O)?1167(C-O-C)?1040(P-O-C)；
1HNMR(δppm)：1.51～1.61(dd，3H，-CH 3，J＝14.4Hz)，3.69～3.73(dd，3H，-OCH 3，J＝12.4Hz)，4.90～4.92(d，2H，-OCH 2CO-，J＝10.0Hz)，6.21～6.31(dd，1H，-OCHP，J＝10.4Hz)，6.81～8.62(m，7H，-C 5H 4N，-C 6H 3)；
MS(m/z)：403(M ++1?41.51％)
Compound 10,13,14 listed in the table 1 can make by compound 9 similar methods, and the structure appraising datum of its compound 10,13,14 is as follows:
Compound 10:
Light yellow viscous liquid, yield: 76%, n D 20=1.5198
Ultimate analysis: measured value C%51.71 H%4.56 N%3.33,
Calculated value C%51.98 H%4.63 N%3.79;
IR(cm -1)：3070(ph-H)?1770(C=O)?1218(P＝O)?1142(C-O-C)?1042(P-O-C)；
1HNMR(δppm)：1.50～1.60(dd，3H，-CH 3，J＝14.8Hz)，3.68～3.73(dd，3H，-OCH 3，J＝12.4Hz)，4.82～4.84(d，2H，-OCH 2CO-，J＝10.4Hz)，6.21～6.32(dd，1H，-OCHP，J＝12.4Hz)，6.84～8.63(m，8H，-C 5H 4N，-C 6H 4)；
MS(m/z)：369(M ++1?39.42％)。
Compound 13:
Figure A20051001861100102
Light yellow viscous liquid, yield: 64%, n D 20=1.5026
Ultimate analysis: measured value C%47.08 H%3.95 N%2.98,
Calculated value C%47.55 H%3.99 N%3.47;
IR(cm -1)：3068(ph-H)?1774(C＝O)?1232(P＝O)?1178(C-O-C)?1043(P-O-C)；
1HNMR(δppm)：1.58～1.66(dd，3H，-CH 3，J＝14.8Hz)，3.72～3.79(dd，3H，-OCH 3，J＝12.4Hz)，4.83～4.86(d，2H，-OCH 2CO-，J＝10.4Hz)，6.30～6.42(dd，1H，-OCHP，J＝12.4Hz)，7.04～8.63(m，7H，-C 5H 4N，-C 6H 3)；
MS(m/z)：403(M ++1?28.68％)。
Compound 14:
Light yellow viscous liquid, yield: 61%, n D 20=1.5162
Ultimate analysis: measured value C%47.64 H%3.98 N%3.07,
Calculated value C%47.55 H%3.99 N%3.47;
IR(cm -1)：3076(ph-H)?1769(C＝O)?1224(P＝O)?1147(C-O-C)?1041(P-O-C)；
1HNMR(δppm)：1.50～1.61(dd，3H，-CH 3，J＝14.4Hz)，3.69～3.73(dd，3H，-OCH 3，J＝12.4Hz)，4.93～4.95(d，2H，-OCH 2CO-，J＝10.0Hz)，6.22～6.32(dd，1H，-OCHP，J＝12.4Hz)，6.79～8.62(m，7H，-C 5H 4N，-C 6H 3)；
MS(m/z)：403(M ++1?39.30％)。
Embodiment 3
The preparation of compound 3, the B method,
0.01 mole methyl-O-methyl-alpha-hydroxy-2-thenyl phosphinate is dissolved in 15 milliliters of chloroforms, the pyridine that adds 0.011 mole again, below 15 ℃, 5 milliliters of chloroformic solutions that add 0.011 mole of chloroacetyl chloride, stirring reaction is 1 hour under this temperature, place at normal temperatures and spend the night, wash reaction solution with water, the organic phase anhydrous Na 2SO 4Dry precipitation obtains:
Crude product, yield 85%.
The 0.01 mole of methyl-O-methyl-α-chloroethene acyloxy-2-thenyl phosphinate that makes is dissolved in 25 milliliters of acetone, adds 0.011 mole 2-chloro-5-methylphenol and 0.006 mole K 2CO 3Solid, the KI that adds catalytic amount again refluxed two hours, and solvent is sloughed in cooling, and through silica gel (G type) column chromatography gradient elution, eluent is acetone and sherwood oil, and the pure product of gained are light yellow viscous liquid, yield is 75%, n D 20=1.5382.
Ultimate analysis: measured value C%49.55 H%4.66, calculated value C%49.43 H%4.67;
IR(cm -1)：3077(ph-H)?1770(C＝O)?1271(P＝O)?1180(C-O-C)?1051(P-O-C)；
1HNMR(δppm)：1.49～1.53(dd，3H，-CH 3，J＝13.8Hz)，2.27(s，3H，PhCH 3)，3.70～3.77(dd，3H，-OCH 3，J＝12.4Hz)，4.80(d，1H a，-OCH 2CO-，J＝15.5Hz)，4.82(d，1H b，-OCH 2CO-，J＝15.4Hz)，6.56～6.62(dd，1H，-OCHP，J＝10.4Hz)，6.68～7.27(m，6H，-C 4H 3S，-C 6H 3)；
MS(m/z)：388(M +?1.77％)。
Compound 4 listed in the table 1 can make by compound 3 similar methods,
The structure appraising datum of its compound 4 is as follows:
Compound 4:
Figure A20051001861100121
Light yellow viscous liquid, yield: 72%, n D 20=1.5423
Ultimate analysis: measured value C%49.56 H%4.21, calculated value C%49.43 H%4.67;
IR(cm -1)：3059(ph-H)?1771(C＝O)?1224(P＝O)?1170(C-O-C)?1041(P-O-C)；
1HNMR(δppm)：1.47～1.54(dd，3H，-CH 3，J＝14.0Hz)，2.28(s，3H，PhCH 3)，3.69～3.75(dd，3H，-OCH 3，J＝12.4Hz)，4.80(d，1H a，-OCH 2CO-，J＝15.2Hz)，4.83(d，1H b，-OCH 2CO-I，J＝15.4Hz)，6.52～6.60(dd，1H，-OCHP，J＝10.4Hz)，6.90～7.36(m，6H，-C 4H 3S，-C 6H 3)；
MS(m/z)：388(M +?3.06％)。
Embodiment 4
Figure A20051001861100122
The preparation of compound 11, the B method
0.01 mole methyl-O-methyl-alpha-hydroxy-2-picolyl phosphinate is dissolved in 15 milliliters of methylene dichloride, the Trimethylamine 99 that adds 0.011 mole again, below 20 ℃, 5 milliliters of dichloromethane solutions that add 0.012 mole of chloroacetyl chloride, stirring reaction is 1 hour under this temperature, place at normal temperatures and spend the night, after having reacted, slough solvent, through silica gel (G type) column chromatography gradient elution, eluent is acetone and sherwood oil, can obtain the crude product of methyl-O-methyl-α-chloracetyl chloryl-2-pyridyl phosphinate, yield 90%.
0.01 mole of the above-mentioned crude product that makes is dissolved in 30 milliliters of acetone, adds 0.011 mole 2-chloro-5-methylphenol sodium salt, refluxed 2.5 hours, cooling adopts the method for embodiment 1 to handle, and is light yellow viscous liquid behind the product purification, and yield is 70%, n D 20=1.5131.
Ultimate analysis: measured value C%53.37 H%4.87 N%3.31,
Calculated value C%53.21 H%4.99 N%3.65;
IR(cm -1)：3057(ph-H)?1771(C＝O)?1225(P＝O)?1169(C-O-C)?1041(P-O-C)；
1HNMR(δppm)：1.50～1.58(dd，3H，-CH 3，J＝13.7Hz)，2.28(s，3H，PhCH 3)，3.69～3.73(dd，3H，-OCH 3，J＝12.4Hz)，4.90～4.92(d，2H，-OCH 2CO-，J＝9.6Hz)，6.23～6.35(dd，1H，-OCHP，J＝12.4Hz)，6.67～8.63(m，7H，-C 5H 4N，-C 6H 3)；
MS(m/z)：383(M ++1?100％)。
Compound 12 listed in the table 1 can make by compound 11 similar methods,
The structure appraising datum of its compound 12 is as follows:
Compound 12:
Figure A20051001861100131
Light yellow viscous liquid, yield: 70%, n D 20=1.5275
Ultimate analysis: measured value C%52.72 H%5.20 N%3.14,
Calculated value C%53.21 H%4.99 N%3.65;
IR(cm -1)：3217(ph-H)?1761(C＝O)?1218(P＝O)?1183(C-O-C)?1043(P-O-C)；
1HNMR(δppm)：1.50～1.60(dd，3H，-CH 3，J＝14.8Hz)，2.27(s，3H，PhCH 3)，3.68～3.72(dd，3H，-OCH 3，J＝12.4Hz)，4.83～4.86(d，2H，-OCH 2CO-，J＝10.4Hz)，6.21～6.32(dd，1H，-OCHP，J＝12.4Hz)，6.62～8.63(m，7H，-C 5H 4N，-C 6H 3)；
MS(m/z)：383(M ++1?51.34％)。
Embodiment 5
The preparation of compound 25, the C method,
0.002 mole of the methyl-O-methyl-2-chloro-5-methylenedioxy phenoxy acetoxyl group that makes earlier by the method for embodiment 4-2-pyridyl phosphinate; 20 milliliters in the acetone that adding was handled with molecular sieve; under lucifuge and nitrogen protection; add 0.002 mole of sodium iodide, white solid is separated out in stirring and refluxing reaction 6 hours; filter; obtain white crystal with recrystallizing methanol, yield is 70.0%, m.p.＞265 ℃.
Ultimate analysis: measured value C%49.62 H%4.03 N%3.19,
Calculated value C%49.06 H%4.12 N%3.58;
IR(cm -1)：3139(ph-H)?1739(C＝O)?1206(P＝O)?1061(C-O-C)?1026(P-O-C)；
1HNMR(δppm)：0.96～1.00(d，3H，-CH 3，J＝14.0Hz)，2.22(s，3H，CH 3Ph)，5.03(s，2H，-OCH 2CO-)，5.65～5.68(d，1H，-OCHP，J＝10.8Hz)，6.78～8.48(m，7H，-C 5H 4N，-C 6H 3)。
Compound 27,28 listed in the table 1 can make by compound 25 similar methods,
The structure appraising datum of its compound 27,28 is as follows:
Compound 27:
White solid, yield: 72%, m.p.=163-165 ℃
Ultimate analysis: measured value C%49.73 H%3.58, calculated value C%49.77 H%3.69;
IR(cm -1)：3125(ph-H)?1742(C＝O)?1198(P＝O)?1070(C-O-C)?1046(P-O-C)；
1HNMR(δppm)：0.78～0.83(d，3H，-CH 3，J＝14.8Hz)，5.09(s，2H，-OCH 2CO-)，5.56～5.62(d，1H，-OCHP，J＝16.64Hz)，7.01～7.56(m，9H，-C 6H 5，-C 6H 4)。
Compound 28:
Figure A20051001861100142
White solid, yield: 76%, m.p.＞282 ℃
Ultimate analysis: measured value C%42.30 H%2.94, calculated value C%42.61 H%2.73;
IR(cm -1)：3111(ph-H)?1757(C＝O)?1188(P＝O)?1066(C-O-C)?1041(P-O-C)；
1HNMR(δppm)：0.79～0.84(d，3H，-CH 3，J＝15.4Hz)，5.05(s，2H，-OCH 2CO-)，5.86～5.89(d，1H，-OCHP，J＝10.8Hz)，7.05～7.58(m，7H，-C 6H 3，-C 6H 4)。
Embodiment 6
Figure A20051001861100151
The preparation of compound 22, the C method,
Methyl-O-the methyl-2 that makes earlier by the method for embodiment 2; 0.002 mole of 4-Dichlorophenoxy acetoxyl group-2-picolyl phosphinate; 25 milliliters in the acetone that adding was handled with molecular sieve under lucifuge and nitrogen protection, adds 0.002 mole of sodium iodide; stirring and refluxing reaction 5 hours; separate out white solid, filter, obtain white crystal with recrystallizing methanol; yield is 76.0%, m.p.=229-230 ℃.
Ultimate analysis: measured value C%44.01 H%3.32 N%3.10,
Calculated value C%43.71 H%3.18 N%3.40;
IR(cm -1)：3147(ph-H)?1754(C＝O)?1200(P＝O)?1080(C-O-C)?1057(P-O-C)；
1HNMR(δppm)：0.85～0.88(d，3H，-CH 3，J＝13.6Hz)，5.07(s，2H，-OCH 2CO-)，5.60～5.63(d，1H，-OCHP，J＝11.2Hz)，7.16～8.48(m，7H，-C 5H 4N，-C 6H 3)；
LC-MS(m/z)：388(M +-23，negative?100％)，434(M ++23，positive?100％)。
Compound 19,23,24,26 listed in the table 1 can make by compound 22 similar methods, and the structure appraising datum of its compound 19,23,24,26 is as follows:
Compound 19:
White solid, yield: 78%, m.p.=162-164 ℃
Ultimate analysis: measured value C%46.47 H%3.28, calculated value C%46.74 H%3.43;
IR(cm -1)：3092(ph-H)?1770(C＝O)?1224(P＝O)?1102(C-O-C)?1046(P-O-C)；
1HNMR(δppm)：0.77～0.82(d，3H，-CH 3，J＝15.0Hz)，4.88～5.09(m，2H，-OCH 2CO-，J＝6.3Hz)，5.57～5.63(d，1H，-OCHP，J＝18.0Hz)，7.02～7.54(m，8H，-C 6H 5，-C 6H 3)。
Compound 23:
White solid, yield: 68%, m.p.＞276 ℃
Ultimate analysis: measured value C%49.92 H%4.44 N%3.48,
Calculated value C%49.87 H%3.91 N%3.88;
IR(cm -1)：3132(ph-H)?1752(C＝O)?1199(P＝O)?1113(C-O-C)?1062(P-O-C)；
1HNMR(δppm)：0.85～0.89(d，3H，-CH 3，J＝13.6Hz)，5.03(s，2H，-OCH 2CO-)，5.58～5.60(d，1H，-OCHP，J＝10.4Hz)，6.95～8.45(m，8H，-C 5H 4N，-C 6H 4)。
Compound 24:
White solid, yield: 66%, m.p.=234-235 ℃
Ultimate analysis: measured value C%47.53 H%4.21 N%3.26,
Calculated value C%47.70 H%3.74 N%3.71;
IR(cm -1)：3117(ph-H)?1754(C＝O)?1199(P＝O)?1095(C-O-C)?1054(P-O-C)；
1HNMR(δppm)：0.87～0.91(d，3H，-CH 3，J＝14.0Hz)，5.02(s，2H，-OCH 2CO-)，5.59～5.62(d，1H，-OCHP，J＝10.4Hz)，6.94～8.47(m，8H，-C 5H 4N，-C 6H 4)。
Compound 26:
Figure A20051001861100162
White solid, yield: 64%, m.p.＞257 ℃
Ultimate analysis: measured value C%43.51 H%3.26 N%3.00,
Calculated value C%43.71 H%3.18 N%3.40;
IR(cm -1)：3121(ph-H)?1765(C＝O)?1193(P＝O)?1073(C-O-C)?1048，936(P-O-C)762(P-C)；
1HNMR(δppm)：0.86～0.90(d，3H，-CH3，J＝14.0Hz)，5.10(s，2H，-OCH 2CO-)，5.61～5.64(d，1H，-OCHP，J＝11.2Hz)，7.16～8.49(m，7H，-C 5H 4N，-C 6H 3)。
Embodiment 7
The preparation of compound 20 (C method)
Methyl-O-the methyl-2 that makes earlier with reference to the method for embodiment 21; 0.002 mole of 4-two chloro-benzene oxygen acetoxy-2,4 dichloro benzene base phosphinate add 20 milliliters of the ethyl acetate handled with molecular sieve; under nitrogen protection; add 0.002 mole of sodium iodide, white solid is separated out in stirring and refluxing reaction 6 hours; filter; obtain white crystal with recrystallizing methanol, yield is 82.0%, m.p.=225-227 ℃.
Ultimate analysis: measured value C%46.47 H%3.28, calculated value C%46.74 H%3.43;
IR(cm -1)：3026(ph-H)?1765(C＝O)?1193(P＝O)?1073(C-O-C)?1047(P-O-C)；
1HNMR(δppm)：0.94～0.98(d，3H，-CH 3，J＝16.8Hz)，5.03(s，2H，-OCH 2CO-)，5.94～5.96(d，1H，-OCHP，J＝8.0Hz)，7.03～7.58(m，6H，-C 6H 3，-C 6H 3)；
LC-MS(m/z)：455(M +-23，negative?100％)，434(M ++23，positive?100％)。
The preparation method of compound 21 can make compound by compound 20 similar methods.
Compound 21:
Figure A20051001861100172
White solid, yield: 63%, m.p.＞280 ℃
Ultimate analysis: measured value C%42.73 H%2.94, calculated value C%43.13 H%2.94;
IR(cm -1)：3043(ph-H)?1761(C＝O)?1178(P＝O)?1059(C-O-C)?1043(P-O-C)；
1HNMR(δppm)：0.97～1.01(d，3H，-CH 3，J＝13.6Hz)，5.04(s，2H，-OCH 2CO-)，6.02～6.05(d，1H，-OCHP，J＝10.8Hz)，7.04～7.59(m，7H，-C 6H 4，-C 6H 3)。
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 Pyridyl-pyridyl Thiopheneyl-thienyl
Table 1 synthetic part of compounds of the present invention.
?R 1 ??R 2 ??R 3 ?R 4 ?Z ????Y
????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 ????19 ????20 ????21 ????22 ????23 ????24 ????25 ????26 ????27 ????28 ????29 ????30 ????31 ????32 ????33 ????34 ????35 ????36 ????37 ????38 ????39 ?Me ?Me ?Me ?Me ?Me ?Me ?Et ?Pr ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Et ?Pr ?Bu ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Et ?Pr ?Bu ?Me ??Me ??Me ??Me ??Me ??Me ??Me ??Et ??Pr ??Me ??Me ??Me ??Me ??Me ??Me ??Me ??Et ??Pr ??Bu ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Na ??Li 2-thienyl 2-thienyl 2-thienyl 2-thienyl 2-thienyl 2-thienyl 2-thienyl 2-thienyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl 2-Pyridyl Ph 2.4-Cl2Ph ??2-ClPh ??2-Pyridyl ??2-Pyridyl ??2-Pyridyl ??2-Pyridyl ??2-Pyridyl ??Ph ??2.4-Cl 2Ph ??2-Thiophenyl ??3.4-OCH 2OPh ??4-CH 3Ph ??3-NO 2Ph ??4-NO 2Ph ??2-Furyl ??3-Pyridyl ??CH 3??CH 3??CH 3??H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?H ?2-Cl ?4-Cl ?2-Cl ?4-Cl ?2-Cl ?2-Cl ?2-Cl ?4-Cl ?2-Cl ?4-Cl ?2-Cl ?4-Cl ?2-Cl ?2-Cl ?2-CH 3， ?2-Cl ?2-Cl ?2-CH 3， ?2-Cl ?2-Cl ?2-Cl ?2-Cl ?2-F ?4-Cl ?2-Cl ?2-Cl ?3-CF 3?3-CF 3?2-Cl ?2-Cl ?2-Cl ?2-Cl ?2-CH 3， ?2-Cl ?2-Cl ?H ?2-Cl ?2-CH 3， ?2-Cl ????4-Cl ????H ????5-CH 3????5-CH 3????6-Cl ????3-Cl ????4-Cl ????H ????4-Cl ????H ????5-CH 3????5-CH 3????6-Cl ????3-Cl ????4-Cl ????3-Cl ????6-Cl ????4-Cl ????4-Cl ????4-Cl ????4-Cl ????4-Cl ????H ????H ????5-CH 3????6-Cl ????H ????H ????4-Cl ????4-Cl ????3-Cl ????6-Cl ????4-Cl ????4-Cl ????4-Cl ????4-Br ????4-OCH 3????4-Cl ????4-Cl
????40 ????41 ????42 ????43 ????44 ????45 ????46 ????47 ????48 ????49 ????50 ? ????51 ????52 ????53 ????54 ????55 ????56 ????57 ????58 ????59 ????60 ????61 ????62 ????63 ????64 ????65 ????66 ? ????67 ????68 ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Me ?Et ?Me ? ?Me ?Me ?Me ?Me ?Et ?Et ?Pr ?Bu ?Me ?Me ?Et ?Pr ?Bu ?Me ?Et ?Pr ? ?Bu ?Me ?Li ?Li ?Li ?Li ?Li ?Li ?Li ?Li ?Li ?NH 4?K ? ?K ?K ?K ?K ?K ?K ?K ?K ?K ?NH 4?K ?K ?K ?Me ?Et ?Pr ? ?Bu ?Me ?CH 3?n-C 3H 7?n-Bu ?CCl 3?4-CH 3Ph ?3-NO 2Ph ?2-Pyridyl ?2-Thiophenyl ?2-Furyl ?3-ClPh ?3， ?4-OCH 2OPh ?2-Pyridyl ?Ph ?2.4-Cl 2Ph ?2-Thiophenyl ?4-NO 2Ph ?CH 32-Furyl 2-Furyl 2-thienyl 2-thienyl CH 3?2-Furyl ?2-Furyl ?4-SCH 3Ph ?3-CH 3OPh ?3-CH 3CH 2?Ph ?CCl 3?2-ClPh ??H ??H ??Me ??H ??H ??H ??H ??H ??H ??H ??H ? ??Me ??H ??H ??H ??H ??H ??H ??H ??Me ??H ??H ??H ??H ??H ??H ??H ? ??H ??H ?2-F ?4-Cl ?2-Cl ?2-Cl ?2-Cl ?2-Cl ?2-Cl ?2-Cl ?2-Cl ?4-SMe ?2-Cl ? ?2-Cl ?3-CF 3?3-CF 3?2-Cl ?3-SCH 3?3-SCH 3?2-Cl ?2-Cl ?H ?H ?2-CH 3， ?H ?2-Cl ?2-CH 3， ?2-Cl ?2-Cl ? ?2-CH 3， ?H ????H ????H ????5-CH 3????4-Cl ????4-Cl ????4-Cl ????4-Cl ????4-Cl ????4-Cl ????H ????4-Cl ? ????6-Cl ????H ????H ????4-Cl ????H ????H ????3-NO 2????3-NO 2????4-Br ????4-Br ????4-Cl ????4-Br ????4-OCH 3????4-Cl ????3-Cl ????6-Cl ? ????4-Cl ????4-F
But granula, 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 8
The fungicidal activity test
Test materials:
For trying bacterial classification: fusarium oxysporum f.sp.vasinfectum (Fusarium oxysporium), magnaporthe grisea (Pyricularia oryzae), botrytis cinerea (Botrytis cinereapers), gibberella saubinetii (Gibberella zeae), sclerotinia rot of colza (Sclerotiniasclerotiorum), 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
Numbering Fusarium oxysporum f.sp.vasinfectum Magnaporthe grisea Botrytis cinerea Gibberella saubinetii Sclerotinia sclerotiorum Beet Cercospora
Active rank Active rank Active rank Active rank Active rank Active rank
????1 ????2 ????3 ????4 ????5 ????6 ??34.78 ??39.13 ??34.78 ??26.09 ??56.52????C ??30.43 ??28.57 ??57.14????C ??35.71 ??28.57 ??50.00????C ??50.00????C ??18.75 ??90.63????A ??37.50 ??40.63 ??87.50????B ??59.38????C ??23.53 ??55.88????C ??29.41 ??29.41 ??47.06 ??41.18 ??41.18 ??94.12????A ??58.82????C ??70.59????B ??88.24????B ??64.71????C ??21.43 ??53.57????C ??32.14 ??39.29 ??46.43 ??28.57
Embodiment 9
The fungicidal activity test method is identical with embodiment 8
The fungicidal activity data of table 3 compound (Plating exsomatizes) 50ppm
Numbering Fusarium oxysporum f.sp.vasinfectum Magnaporthe grisea Botrytis cinerea Gibberella saubinetii Sclerotinia sclerotiorum Beet Cercospora
Active rank Active rank Active rank Active rank Active rank Active rank
??9 ??10 ??11 ??12 ??13 ??14 34.78 30.43 34.78 34.78 47.83 43.48 42.85 28.57 42.85 28.57 42.85 50.00?????C 78.13?????B 28.13 40.63 40.63 75.00?????B 84.38?????B 47.06 26.47 32.35 29.41 35.29 35.29 82.35?????B 29.41 70.59?????B 70.59?????B 82.35?????B 76.47?????B 57.14?????C 10.71 42.86 67.86?????C 50.00?????C 64.29?????C
Embodiment 10
The fungicidal activity test method is identical with embodiment 8
The fungicidal activity data of table 4 compound (Plating exsomatizes) 50ppm
Numbering Fusarium oxysporum f.sp.vasinfectum Magnaporthe grisea Botrytis cinerea Gibberella saubinetii Sclerotinia sclerotiorum Beet Cercospora
Active rank Active rank Active rank Active rank Active rank Active level is not (
19 20 21 22 23 24 25 26 28 11.11 22.22 33.33 33.33 50.00 27.78 22.22 38.89 33.33 70.00 80.00?????B 80.00?????B 90.00?????A 80.00?????B 70.00 60.00 90.00?????A 90.00?????A 29.27 31.71 39.02 92.68?????A 90.24?????A 46.34 48.78 82.93?????B 53.66 23.53 23.53 26.47 52.94 47.06 23.53 20.59 67.65 29.41 84.62?????B 76.92 84.62?????B 92.31?????A 84.62?????B 76.92 69.23 100???????A 76.92 37.50 43.75 46.88 56.25 53.13 40.63 46.88 59.38 31.25
Embodiment 11
Active culture ware method
Get the 10ppm of 10 milliliters of formula I compounds, 100ppm solution, put into respectively and be lined with two filter paper, diameter is in 10 centimetres the culture dish, wheat that again will be after vernalization, each 10 culture dish of putting into different concns respectively of barnyard grass grass seed are inserted (25 ℃) in the thermostat container with culture dish, illumination/dark processing (8/16 hour), measure the long and clear water contrast of root length, stem of plant after 96 hours, calculate different medicine samples, different concns, the root length of different examination materials, the long percentage that suppresses of stem respectively.
Table 5 Compound I is to the inhibition activity data (culture dish method) of single dicotyledons
Compound number Barnyard grass grass barnyard grass Rape rape
???????Stalk ?10ppm??????100ppn ???????Root ?10ppm??????100ppm ??????Stalk ?10ppm??????100ppm ????????Root ?10ppm??????100ppm
??1 ??2 ??3 ??4 ??5 ??6 ??9 ??10 ??11 ??12 ??13 ??14 ?39.3???????89.3??B ?46.4???????64.3 ?57.1???????60.7 ?35.7???????53.6 ?67.8???????67.8 ?67.8???????82.1??B ?55.5???????66.6 ?40.7???????51.8 ?35.1???????27.8 ?60.7???????78.6??B ?57.1???????57.1 ?67.8???????67.8 ?97.8??A????97.8??A ?95.5??A????97.8??A ?57.8???????82.2??B ?95.5??A????97.8??A ?75.5??B????86.6??B ?60.0???????95.5??A ?94.8??A????97.4??A ?92.3??A????97.4??A ?48.7???????79.5??B ?97.8??A????97.8??A ?42.2???????82.2??B ?62.2???????91.1??A ?97.4??A????100???A ?92.3??A????97.4??A ?7.7????????56.4 ?94.8??A????97.4??A ?20.5???????92.3??A ?2.6????????53.8 ?91.6??A????94.4??A ?91.6??A????94.4??A ?66.6???????88.8??B ?94.8??A????94.8??A ?20.5???????71.8??B ?5.1????????84.6??B ?100???A????100???A ?98.8??A????100???A ?39.5???????94.2??A ?100???A????100???A ?46.5???????96.5??A ?25.6???????93.0??A ?98.8??A????98.8??A ?96.6??A????98.8??A ?95.5??A????96.6??A ?97.6??A????98.8??A ?46.5???????89.5??A ?29.1???????94.2??A
Embodiment 12
The weeding activity experimental technique is identical with the weeding activity experimental technique of embodiment 11
Table 6 compound is to the inhibition activity data (culture dish method) of single dicotyledons
Compound Barnyard grass grass barnyard grass Rape rape
?????Stalk 10ppm????100ppm ?????Root 10ppm????100ppm ??????Stalk 10ppm??????100ppm ??????Root 10ppm?????100ppm
Numbering
????19 ????20 ????21 ????22 ????24 ????25 ????26 ????27 ??65.2??C????73.9??C ??-17???C????-8.7??D ??60.7???????60.7 ??21.4???????32.1 ??28.6???????57.1 ??64.3???????64.3 ??7.1????????25.0 ??43.5??D????47.8??D ?94.6??A????100???A ?91.9??A????97.3??A ?64.4???????86.6??B ?95.5??A????97.8??A ?93.3??A????97.8??A ?64.4???????88.9??B ?97.8??A????97.8??A ?97.3??A????97.3??A ?91.4??A????94.3??A ?88.6??B????94.3??A ?58.9???????97.4??A ?94.8??A????97.4??A ?92.3??A????97.4??A ?35.9???????94.8??A ?94.8??A????97.4??A ?91.4??A????94.3??A ?98.8??A????98.8??A ?97.7??A????98.8??A ?95.3??A????100???A ?100???A????100???A ?100???A????100???A ?75.6??B????98.8??A ?98.8??A????100???A ?97.3??A????97.3??A
Embodiment 13
Test method
Adopt the greenhouse pot culture method
Take by weighing the former medicine of certain mass with analytical balance (0.0001g), from water, acetone, tetrahydrofuran (THF), DMF and DMSO equal solvent, screen one by one solvability good make solvent, and add 10% tween-80 and do dispersion agent and be made into little formulation, be configured to the soup of above-mentioned concentration gradient again with distilled water diluting, stand-by.
Adopt the greenhouse pot culture spray method, under the concentration of treatment weeds target carried out bud before, spraying is handled behind the bud.The bud aftertreatment time: carry out during the broadleaf weeds leaf period; The bud pre-treatment time: in 24h after planting.Every processing is established once and is repeated.
10 ℃～25 ℃ of growth temperatures, examination material normal management.Handle the back and regularly observe plant growing way and toxicity symptom, and behind 20d, press the comprehensive weeding activity of 0-100% staging visual assessment
Table 7 compound is to the inhibition activity data of dicotyledons
Leaf mustard Amaranthus retroflexus Lamb's-quarters
Compound Dosage Before the bud Behind the bud Before the bud Behind the bud Before the bud Behind the bud
19 60 ??80 ??80 ??20 ??80 ??20 ??90
68 30 ??30 ??80 ??20 ??70 ??20 ??40
68 20 ??0 ??75 ??0 ??30 ??0 ??30
68 10 ??0 ??50 ??0 ??10 ??0 ??0
。

Claims (12)

1, a class substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate 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 4Alkyl; R 2Expression C 1-C 4Alkyl, M, M is Li, Na, K or NH 4 +, R 1With R 2Identical or inequality; R 4Expression H, C 1-C 4Alkyl; R 3Expression H, C 1-C 4Alkyl or substituted alkyl, phenyl, furyl, thienyl, pyridyl, substituting group are halogen or NO 2, C 1-C 4Alkyl, substituted alkyl, alkoxyl group, alkylthio or OCH 2The substituted-phenyl of O; Z and Y represent H, halogen, C 1-C 4Alkyl, substituted alkyl or alkoxyl group, alkylthio or NO 2, Z is identical with Y or inequality; Work as R 2During the expression alkyl, Z and Y are not F or CF 3Halogen, R 3Do not represent furyl, C 1Alkyl.
2, substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate in the described compound of representing by general formula I of claim 1, be the preparation method of the compound of general formula I-1 expression, it is characterized in that making the represented compound of represented compound of general formula I I and following general formula I II to react the A method
In I-1, II and III formula, R 1With R 2Expression C 1-C 4Alkyl, R 1With R 2Identical or inequality; 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 or NO 2, Z is identical with Y or inequality; R 3Expression thienyl, pyridyl, substituting group are C 2-C 4Alkyl, alkylthio, alkoxyl group or OCH 2The substituted-phenyl of O.
3, substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate in the described compound of representing by general formula I of claim 1, be the preparation method of the compound of general formula I-1 expression, it is characterized in that utilizing the represented compound of 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, the B method
Figure A2005100186110002C3
Among formula I-1, II, IV, V and the VI, R 1And R 2, R 3, R 4, Z and Y be identical with claim 2 described definition, M represents Li, Na, K or NH 4 +
4, substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate salt compounds in the described compound of representing by general formula I of claim 1, promptly with the preparation method of the compound of general formula I-2 expression, it is characterized in that it being to make the represented substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate compounds of general formula I-1 and metal halides KI, NaI or LiBr reaction, the C method
Figure A2005100186110003C1
In the I-2 formula, R 1Expression C 1-C 4Alkyl; M is Li, Na, K or NH 4 +R 4Expression H, C 1-C 4Alkyl; 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 2Substituted-phenyl Z and the Y of O represent H, halogen, C 1-C 4Alkyl, substituted alkyl or alkoxyl group, alkylthio, NO 2, etc. Z identical with Y or inequality.
5, the described substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of representing with general formula I of claim 1 or the application of salt compounds is characterized in that the effective ingredient as sterilant.
6, the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of representing with general formula I as claimed in claim 5 or the application of salt compounds is characterized in that as the effective ingredient to the fusarium oxysporum f.sp.vasinfectum sterilant.
7, the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of representing with general formula I as claimed in claim 1 or the application of salt compounds is characterized in that as the effective ingredient to the magnaporthe grisea sterilant.
8, the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of representing with general formula I as claimed in claim 1 or the application of salt compounds is characterized in that as the effective ingredient to the botrytis cinerea sterilant.
9, the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl phosphinate of representing with general formula I as claimed in claim 1 or the application of salt compounds is characterized in that as the effective ingredient to the gibberella saubinetii sterilant.
10, the application of the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl of representing with general formula I time acid esters as claimed in claim 1 or salt compounds is characterized in that as the effective ingredient to the sclerotinia rot of colza sterilant.
11, the application of the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl of representing with general formula I time acid esters as claimed in claim 1 or salt compounds is characterized in that as the effective ingredient to the beet Cercospora sterilant.
12, the application of the substituted benzene oxygen acetoxy fragrant heterocyclic alkyl of representing with general formula I time acid esters as claimed in claim 1 or salt compounds is characterized in that the effective ingredient as weedicide.
CNB200510018611XA 2005-04-26 2005-04-26 Substituted phenoxy-acetoxy-aromatic heterocyclic radical-alkyl ester phisphinic acid possessing bactericidal and herbicidal activity, and preparation Expired - Fee Related CN100375748C (en)

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CN110452266A (en) * 2018-09-30 2019-11-15 华中师范大学 A kind of phosphine oxide-type compound and its preparation method and application

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DE3313070A1 (en) * 1983-04-12 1984-10-18 Bayer Ag, 5090 Leverkusen CHLORINE PHOSPHORYLMETHYLCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PLANT PROTECTION PRODUCTS
EP0196026B1 (en) * 1985-03-28 1989-05-31 Hoechst Aktiengesellschaft Functional derivatives of phosphorus containing acetic acids, process for their preparation and herbicidal and plant growth regulator composition containing them
DE3721868A1 (en) * 1987-07-02 1989-01-12 Bayer Ag 1-ARYLPYRAZOLE
TW263511B (en) * 1990-10-10 1995-11-21 Hoechst Ag
TW353663B (en) * 1991-04-06 1999-03-01 Hoechst Ag Process for the preparation of phosphorus-containing L-amino acids, their derivatives and intermediates for this process
CN1060480C (en) * 1997-04-30 2001-01-10 华中师范大学 Substituted phenoxyl acetyloxy hydrocarbyl phosphonate with phytocidal activity and its preparation
CN1151162C (en) * 2000-11-15 2004-05-26 华中师范大学 Substituted phenoxy acetoxyl alkyl hypophosphorous ester with herbicide activity and preparation
CN1528764A (en) * 2003-10-14 2004-09-15 华中师范大学 Herbicide O,O-dimethyl-1-(2,4-dichlorphenoxyacethoxy ethyl phosphate ester and weeding composition thereof
CN100412078C (en) * 2004-02-26 2008-08-20 华中师范大学 Fluorine substituted phenoxy acetyl oxide alkyl phosphonate ester and salt with weeding active and preparation process thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452266A (en) * 2018-09-30 2019-11-15 华中师范大学 A kind of phosphine oxide-type compound and its preparation method and application

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