CN1962674A - Substituted phenoxyl acetyloxy furyl methyl phosphonate and its preparation - Google Patents
Substituted phenoxyl acetyloxy furyl methyl phosphonate and its preparation Download PDFInfo
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- CN1962674A CN1962674A CN 200610125215 CN200610125215A CN1962674A CN 1962674 A CN1962674 A CN 1962674A CN 200610125215 CN200610125215 CN 200610125215 CN 200610125215 A CN200610125215 A CN 200610125215A CN 1962674 A CN1962674 A CN 1962674A
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Abstract
The invention discloses a preparing method of substituted phenoxyaceto oxyfuryl methyl phosphonate compound with general formula I, wherein X and Y is H, halogen, C1-3 alkyl and halogenated alkyl at the same time or different. The compound possesses obvious inhibiting action for multiple bacteria such as rice withertip, cotton wilt fungus, rice mycoses, cucumber mildew and so on, which inhibits some fungus effectively.
Description
Technical field
The present invention relates to substituted benzene oxygen acetoxy furyl methyl phosphonate ester compound that has fungicidal activity and preparation method thereof, and it is as the biological activity of sterilant.
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, wherein, the category-A compound has then shown weeding activity in various degree, plant growth regulating activity and fungicidal activity (He Hongwu etc., Chinese invention patent, ZL 97109095.5,200510018556.4).
The inventor had once proposed to have the substituted phenoxyl acetyloxy hydrocarbyl phosphonate and the preparation of weeding activity in Chinese invention patent ZL 97109095.5, though the substituted phenoxyl acetyloxy hydrocarbyl phosphonate that in this patent, proposes (structure type of the Compound I that proposes with patent of the present invention has certain similarity), but the compound among the patent ZL 97109095.5 does not relate to fungicidal activity, and does not comprise the concrete structure of the Compound I that the application's patent is invented in tabulation of the compound of this patent and example yet.In addition, the inventor is also at Chinese invention patent: the substituted benzene oxygen acetyl oxygen aromatic heterocyclic alkyl phosphonate salt and the preparation that have proposed to have bactericidal and herbicidal activity among the ZL 200510018556.4, the substituted benzene oxygen acetyl oxygen aromatic heterocyclic alkyl phosphonate that in this patent, proposes (though the structure type of the Compound I that proposes with patent of the present invention has certain similarity), the compound of being invented simultaneously also relates to fungicidal activity, but does not comprise in the claim to the compound invented in ZL 200510018556.4 and work as R
1And R
2Expression C
1-C
3Alkyl the time, R
3Expression H, C
1-C
4Alkyl or substituted alkyl, phenyl, the situation of aminomethyl phenyl and furyl, (this moment, the compound of patent of the present invention was R to the substituted benzene oxygen acetoxy furyl methyl phosphonate ester compound that does not comprise patent of the present invention in other words and proposed
1And R
2Expression C
1Alkyl the time, R
3The expression furyl).Therefore, the concrete structure that does not also comprise the Compound I that the application's patent is invented in tabulation of the compound in ZL 200510018556.4 and the example.The inventor is at Chinese invention patent ZL 97109095.5,200510018556.4 the research basis on, by further to the substituent composition optimizes of substituted phenoxyl acetyloxy hydrocarbyl phosphonate, synthetic and bioactive research, find that substituted benzene oxygen acetoxy furyl methyl phosphonate ester compound has than patent of invention: the compound of being invented among the ZL200510018556.4 has more excellent fungicidal activity, better practicality and potentiality to be exploited.Not only when isolated measuring, to rice sheath blight disease, fusarium oxysporum f.sp.vasinfectum, magnaporthe grisea, gibberella saubinetii, botrytis cinerea and Sclerotinia sclerotiorum show excellent fungicidal activity for they.To graw mold of tomato, grey mould fruit rot of strawberry has certain fungicidal activity, and in the potted plant test of pesticide effectiveness or field test to wheat powdery mildew, southern corn leaf blight, rice sheath blight disease, sclerotinia rot of colzas etc. show excellent live body fungicidal activity.
Summary of the invention
The objective of the invention is to explore and have the substituted benzene oxygen acetoxy furyl methyl phosphonate ester compound that new chemical structure has fungicidal activity simultaneously, provide a class to have the novel phosphonate ester derivative and the synthetic method thereof of fungicidal activity.
The present invention on the research basis of ZL 97109095.5,200510018556.4, has further optimized substituent structure type at Chinese invention patent, has proposed a class substituted benzene oxygen acetoxy furyl methyl phosphonate ester compound, its general structure such as I:
In the formula: X and Y are H, halogen, C
1-C
3Alkyl, haloalkyl, X is identical with Y or inequality.
Can be with the substituted benzene oxygen acetoxy furyl methyl phosphonic acid ester that general formula I is represented by following two kinds of methods preparation.
The A method:
In the formula: X is identical with the definition in the above-mentioned general formula I with Y.
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 B method:
In the formula: X is identical with the definition in the above-mentioned general formula I with Y; M is Li, Na, K or NH
3 +
When the B legal system was equipped with compound of Formula I, 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 85-95%.Organic solvent can adopt chloroparaffin such as chloroform, methylene dichloride, ethylene dichloride, ethyl acetate, acetone, dimethyl formamide (DMF) etc.Acid binding agent adopts organic bases tertiary amine or pyridine usually.Alpha-chloro acetyl oxygen alkyl phosphonate is during again with phenol or phenates prepared in reaction target compound I, and reactant ratio such as uses excessive slightly at mol ratio or phenol.In acetone, dimethyl formamide, ethyl acetate, chloroform, methylene dichloride isopolarity organic solvent, at K
2CO
3Or react under the existence of NaOH or KOH mineral alkali, or earlier the phenol preparation is become phenates, in the presence of the above-mentioned solvent of enumerating, react with alpha-chloro acetyl oxygen alkyl phosphonate again.If adding LiI, kI, NaI or ammonium salt are made catalyzer and can be achieved good results.
The compound that the present invention finds to have above-mentioned general formula I can be used as the effective constituent of sterilant.To fusarium oxysporum f.sp.vasinfectum (Fusarium oxysporium), magnaporthe grisea (Pyricularia oryzae), botrytis cinerea (Botrytis cinereapers), gibberella saubinetii (Gibberella zeae), sclerotinia rot of colza (Sclerotinia sclerotiorum), beet cercospora leaf spot multiple bacterial classifications such as (Cercosporabeticola) has significant inhibitory effect.To graw mold of tomato, grey mould fruit rot of strawberry has certain restraining effect.Indoor live body test and preliminary field plot trial result show: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum), corn southern leaf blight, wheat powdery mildew (Blumeria graminis), rice sheath blight disease (Rhizoctoniasolani) are had remarkable preventive effect.
But compound of the present invention can adopt formulations such as granule, suspension agent, emulsion, microemulsion flowing agent to use.Also can mix and use or also use simultaneously with other agricultural chemicals such as sterilant, sterilant, miticide, plant-growth regulator, fertilizer and soil improvement agent etc.
Embodiment
The preparation method and the fungicidal activity that specifically describe compound of Formula I of the present invention below by example are measured, and only the present invention will be described for these embodiment, rather than limit the invention.
Embodiment 1
Compound 1:
O, the preparation (A method) of O-dimethyl-1-(2-chloro-5-methylphenoxy acetoxyl group) furfuryl phosphonic acid ester
O with 0.01 mole, O-dimethyl-Alpha-hydroxy furfuryl phosphonic acid ester is dissolved in 10 milliliters of ethylene dichloride, the pyridine that adds 0.012 mole again, below 10 ℃, add 10 milliliters of dichloroethane solutions of 0.012 mole of 2-chloro-5-methylenedioxy phenoxy 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
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, and the pure product of gained are white solid behind the purifying, and yield is 85%.Fusing point .97～98 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%49.43, H%4.67; Measured value: C%49.23, H%4.47;
IR(cm
-1)：3115，2953，2848，1774，1585，1493，1448，1265，1170，1059，930，780；
1H NMR(δ/ppm)：2.27(s，3H，CH
3Ph)，3.73～3.84(dd，6H，2×(-OCH
3)，J＝10.76Hz)，4.75(d，1H
a，-OCH
2CO-，J＝16.53Hz)，4.78(d，1H
b，-OCH
2CO-，J＝16.52Hz)，6.39(d，1H，-OCHP，J＝11.18Hz)，6.42～6.77(m，3H，C
4H
3O-)，6.63～7.47(m，3H，-C
6H
3)；
MS(m/z，％)：388(M
+ 1.31％)，205(2.86％)，200(53.59％)，189(9.12％)，165(18.30％)，155(27.48％)，142(36.15％)，125(43.78％)，109(12.35％)，94(5.61％)，93(12.01％)，91(54.43％)，77(89.69％)，63(40.63％)，44(70.27％)。
Embodiment 2
Compound 2:
O, the preparation (B method) of O-dimethyl-1-(3-methyl-4-chlorophenoxy acetoxyl group) furfuryl phosphonic acid ester
O with 0.01 mole, O-dimethyl-Alpha-hydroxy furfuryl phosphonic acid ester is dissolved in 10 milliliters of methylene dichloride, the pyridine that adds 0.011 mole again, below 25 ℃, add 10 milliliters of dichloromethane solutions of 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 acyloxy furfuryl phosphonic acid ester crude product, yield 85%.0.01 mole the O that will make again, O-dimethyl-α-chloroethene acyloxy furfuryl phosphonic acid ester is dissolved among 30 milliliters of DMF, 3-methyl-4-chlorophenol the sodium salt that adds 0.11 mole, refluxed 5 hours, cooling, adopt saturated NaCl solution washing after having reacted respectively 2-3 time, tell organic layer, use 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.The pure product of gained are white solid, and yield is 78%.Fusing point .47～48 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%49.43, H%4.67; Measured value: C%49.53, H%4.56;
IR(cm
-1)：3081，2937，2846，1774，1576，1478，1447，1269，1170，1055，939，755：
1H NMR(δ/ppm)：2.31(s，3H，CH
3Ph)，3.73～3.82(dd，6H，2×(-OCH
3)，J＝10.74Hz)，4.66(d，1H
a，-OCH
2CO-，J＝16.44Hz)，4.69(d，1H
b，-OCH
2CO-，J＝16.41Hz)，6.38(d，1H，-OCHP，J＝12.84Hz)，6.42～6.76(m，3H，C
4H
3O-)，6.65～7.47(m，3H，-C
6H
3)；
MS(m/z，％)：388(M
+ 10.52％)，309(56.50％)，234(29.08％)，205(49.27％)，200(49.11％)，189(100％)，165(10.28％)，155(85.94％)，142(40.67％)，125(79.16％)，109(69.91％)，94(18.39％)，93(96.42％)，91(50.99％)，77(52.72％)，63(39.14％)，44(26.57％)。
Embodiment 3
Compound 3:
O, the preparation of O-dimethyl-1-(2,4 dichloro benzene oxygen base acetoxyl group) furfuryl phosphonic acid ester
Compound 3 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 87%.Fusing point .62～63 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%44.03, H%3.70; Measured value: C%44.08, H%3.67;
IR(cm
-1)：3074，2971，2852，1765，1583，1483，1439，1285，1188，1036，934，753；
1H NMR(δ/ppm)：3.74～3.85(dd，6H，2×(-OCH
3)，J＝10.77Hz)，4.76(d，1H
a，-OCH
2CO-，J＝16.54Hz)，4.78(d，1H
b，-OCH
2CO-，J＝16.54Hz)，6.38(d，1H，-OCHP，J＝14.83Hz)，6.42～6.76(m，3H，C
4H
3O-)，7.12～7.47(m，3H，-C
6H
3)；
MS(m/z，％)：408(M
+ 13.19％)，220(65.58％)，205(52.67％)，203(7.56％)，189(74.91％)，175(60.80％)，162(100％)，145(32.22％)，133(37.16％)，109(50.31％)，94(6.68％)，93(70.49％)，75(18.39％)，63(27.67％)，44(28.95％)。
Embodiment 4
Compound 4:
O, the preparation of O-dimethyl-1-(3-4-trifluoromethylphenopendant acetoxyl group) furfuryl phosphonic acid ester
Compound 4 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 68%.Fusing point .78～79 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%47.07, H%3.95; Measured value: C%46.75, H%3.54;
IR(cm
-1)：3132，2960，2852，1766，1594，1494，1456，1251，1173，1033，932，754；
1H NMR(δ/ppm)：3.73～3.82(dd，6H，2×(-OCH
3)，J＝10.12Hz)，4.75(d，1H
a，-OCH
2CO-，J＝16.44Hz)，4.78(d，1H
b，-OCH
2CO-，J＝16.49Hz)，6.39(d，1H，-OCHP，J＝11.03Hz)，6.42～7.15(m，3H，C
4H
3O-)，7.04～7.47(m，4H，-C
6H
4)；
MS(m/z，％)：408(M
+ 58.76％)，220(41.56％)，205(80.88％)，203(16.18％)，189(87.31％)，175(100％)，162(37.61％)，145(82.39％)，133(10.65％)，109(68.68％)，94(28.33％)，93(97.13％)，75(17.91％)，63(23.73％)，44(18.02％)。
Embodiment 5
Compound 5:
O, the preparation of O-dimethyl-1-(4-chlorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 5 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are white solid, and yield is 76%.Fusing point .107～108 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%48.08, H%4.30; Measured value: C%48.13, H%4.37;
IR(cm
-1)：3023，2911，2849，1777，1589，1494，1446，1255，1171，1037，945，771；
1H NMR(δ/ppm)：3.72～3.79(dd，6H，2×(-OCH
3)，J＝10.77Hz)，4.77(d，1H
a，-OCH
2CO-，J＝16.54Hz)，4.80(d，1H
b，-OCH
2CO-，J＝16.54Hz)，6.37(d，1H，-OCHP，J＝12.96Hz)，6.38～7.26(m，3H，C
4H
3O-)，7.00～7.71(m，4H，-C
6H
4)；
MS(m/z，％)：374(M
+ 0.76％)，258(20.00％)，244(77.22％)，205(1.12％)，201(22.42％)，189(1.18％)，186(13.02％)，148(10.35％)，141(26.27％)，109(43.10％)，94(8.11％)，93(58.34％)，75(30.28％)，63(37.20％)，44(66.45％)。
Embodiment 6
Compound 6:
O, the preparation of O-dimethyl-1-(4-fluorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 6 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are white solid, and yield is 65%.Fusing point .69～71 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%50.29, H%4.50; Measured value: C%50.72, H%4.42;
IR(cm
-1)：3075，2940，2858，1777，1596，1502，1453，1247，1177，1055，944，761；
1H NMR(δ/ppm)：3.73～3.83(dd，6H，2×(-OCH
3)，J＝10.74Hz)，4.66(d，1H
a，-OCH
2CO-，J＝16.53Hz)，4.69(d，1H
b，-OCH
2CO-，J＝16.44Hz)，6.38(d，1H，-OCHP，J＝11.13Hz)，6.42～6.94(m，3H，C
4H
3O-)，6.87～7.48(m，4H，-C
6H
4)；
MS(m/z，％)：358(M
+ 15.53％)，205(23.77％)，189(56.67％)，170(54.22％)，125(92.34％)，112(33.59％)，109(23.08％)，95(100％)，93(56.53％)，75(15.90％)，63(6.30％)，44(22.77％)。
Embodiment 7
Compound 7:
O, the preparation of O-dimethyl-1-(2,3-dichlorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 7 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 62%.Fusing point .81～82 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%44.03, H%3.70; Measured value: C%44.56, H%3.50;
IR(cm
-1)：3081，2959，2846，1779，1581，1463，1427，1270，1172，1054，938，750；
1H NMR(δ/ppm)：3.70～3.80(dd，6H，2×(-OCH
3)，J＝13.60Hz)，4.79(d，1H
a，-OCH
2CO-，J＝16.52Hz)，4.82(d，1H
b，-OCH
2CO-，J＝16.55Hz)，6.54(d，1H，-OCHP，J＝9.90Hz)，6.68～7.09(m，3H，C
4H
3O-)，7.12～7.39(m，3H，-C
6H
3)；
MS(m/z，％)：408(M
+ 59.84％)，377(10.61％)，271(20.37％)，249(33.98％)，220(20.09％)，205(92.43％)，203(32.91％)，189(97.50％)，175(90.26％)，162(38.22％)，145(63.21％)，133(22.25％)，109(81.40％)，94(24.91％)，93(100％)，75(34.32％)，63(43.62％)，44(15.52％)。
Embodiment 8
Compound 8:
O, the preparation of O-dimethyl-1-(2,6-dichlorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 8 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 60%.Fusing point .92～93 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%44.03, H%3.70; Measured value: C%44.44, H%3.48;
IR(cm
-1)：3126，2932，2857，1767，1567，1458，1428，1271，1189，1032，937，763；
1H NMR(δ/ppm)：3.77～3.87(dd，6H，2×(-OCH
3)，J＝10.02Hz)，4.68(d，1H
a，-OCH
2CO-，J＝16.53Hz)，4.71(d，1H
b，-OCH
2CO-，J＝16.44Hz)，6.42(d，1H，-OCHP，J＝14.60Hz)，6.65～7.00(m，3H，C
4H
3O-)，7.03～7.46(m，3H，-C
6H
3)；
MS(m/z，％)：408(M
+ 19.54％)，220(40.45％)，205(11.43％)，203(32.91％)，189(97.50％)，175(31.71％)，162(100％)，145(16.76％)，133(25.09％)，109(20.95％)，94(1.81％)，93(27.41％)，75(13.81％)，63(21.23％)，44(26.06％)。
Embodiment 9
Compound 9:
O, the preparation of O-dimethyl-1-(2-fluorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 9 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 66%.Fusing point .56～58 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%50.29, H%4.50; Measured value: C%50.67, H%4.38;
IR(cm
-1)：3124，2931，2857，1765，1613，1510，1435，1263，1181，1029，933，755；
1H NMR(δ/ppm)：3.72～3.82(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.76(d，1H
a，-OCH
2CO-，J＝16.64Hz)，4.78(d，1H
b，-OCH
2CO-，J＝16.50Hz)，6.38(d，1H，-OCHP，J＝14.70Hz)，6.61～6.94(m，3H，C
4H
3O-)，6.95～7.45(m，4H，-C
6H
4)；
MS(m/z，％)：358(M
+ 25.35％)，205(66.71％)，189(52.99％)，170(56.31％)，125(100％)，112(67.01％)，109(32.14％)，95(81.46％)，93(83.55％)，75(20.13％)，63(10.65％)，44(23.52％)。
Embodiment 10
Compound 10:
O, the preparation of O-dimethyl-1-(2,4 difluorobenzene oxygen base acetoxyl group) furfuryl phosphonic acid ester
Compound 10 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 68%.Fusing point .180～181 ℃.
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%47.88, H%4.02; Measured value: C%47.53, H%4.36;
IR(cm
-1)：3025，2913，2850，1777，1590，1572，1494，1256，1186，1032，945，753；
1H NMR(δ/ppm)：3.71～3.81(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.72(d，1H
a，-OCH
2CO-，J＝16.44Hz)，4.78(d，1H
b，-OCH
2CO-，J＝16.51Hz)，6.54(d，1H，-OCH P，J＝13.60Hz)，6.76～7.03(m，3H，C
4H
3O-)，6.09～7.40(m，3H，-C
6H
3)；
MS(m/z，％)：376(M
+ 13.59％)，205(12.59％)，189(98.28％)，151(100％)，145(71.28％)，127(66.58％)，109(91.49％)，94(67.63％)，93(71.09％)，75(10.58％)，63(25.78％)，45(71.15％)。
Embodiment 11
Compound 11:
O, the preparation of O-dimethyl-1-(3-fluorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 11 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow liquid, and yield is 70%.n
D 20 1.5238。
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%50.29, H%4.50; Measured value: C%50.60, H%4.39;
IR(cm
-1)：3054，2959，2855，1736，1596，1491，1459，1234，1169，1038，939，763；
1H NMR(δ/ppm)：3.74～3.84(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.67(d，1H
a，-OCH
2CO-，J＝16.52Hz)，4.71(d，1H
b，-OCH
2CO-，J＝16.52Hz)，6.41(d，1H，-OCHP，J＝14.40Hz)，6.64～6.85(m，3H，C
4H
3O-)，6.95～7.48(m，4H，-C
6H
4)；
MS(m/z，％)：358(M
+ 34.01％)，205(17.28％)，189(76.92％)，170(5.94％)，125(72.33％)，112(10.11％)，109(56.40％)，95(100％)，93(76.97％)，75(32.91％)，63(8.52％)，44(3.52％)。
Embodiment 12
Compound 12:
O, the preparation of O-dimethyl-1-(2-chloro-4-fluorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 12 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are yellow liquid, and yield is 77%.n
D 20 1.5385。
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%45.88, H%3.85; Measured value: C%45.73, H%3.69;
IR(cm
-1)：3123，2960，2846，1721，1589，1495，1424，1246，1192，1044，929，751；
1H NMR(δ/ppm)：3.73～3.80(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.76(d，1H
a，-OCH
2CO-，J＝16.44Hz)，4.80(d，1H
b，-OCH
2CO-，J＝16.52Hz)，6.53(d，1H，-OCHP，J＝13.60Hz)，6.71～6.03(m，3H，C
4H
3O-)，7.11～7.40(m，3H，-C
6H
3)；
MS(m/z，％)：392(M
+ 6.23％)，204(10.42％)，189(4.26％)，159(11.08％)，146(18.75％)，129(18.75％)，109(100％)，95(54.77％)，93(33.99％)，79(77.26％)，63(24.11％)，44(7.96％)。
Embodiment 13
Compound 13:
O, the preparation of O-dimethyl-1-(2-methyl-4-chlorophenoxy acetoxyl group) furfuryl phosphonic acid ester
Compound 13 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are yellow liquid, and yield is 79%.n
D 20 1.5016。
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%49.43, H%4.67; Measured value: C%49.72, H%4.52;
IR(cm
-1)：3078，2959，2855，1772，1598，1492，1447，1235，1171，1039，932，754；
1H NMR(δ/ppm)：2.25(s，3H，CH
3Ph)，3.74～3.83(dd，6H，2×(-OCH
3)，J＝11.00Hz)，4.70(d，1H
a，-OCH
2CO-，J＝16.51Hz)，4.73(d，1H
b，-OCH
2CO-，J＝16.53Hz)，6.39(d，1H，-OCHP，J＝12.00Hz)，6.52～6.66(m，3H，C
4H
3O-)，7.07～7.48(m，3H，-C
6H
3)；
MS(m/z，％)：388(M
+ 16.91％)，234(38.10％)，205(22.51％)，200(9.41％)，189(100％)，165(1.26％)，155(58.25％)，142(18.96％)，125(51.14％)，109(45.50％)，94(9.20％)，93(67.23％)，91(27.86％)，77(35.26％)，63(25.21％)，44(7.87％)。
Embodiment 14
Compound 14:
O, the preparation of O-dimethyl-1-(4-4-trifluoromethylphenopendant acetoxyl group) furfuryl phosphonic acid ester
Compound 14 can be by embodiment 1 (A method) or similarly method preparation of embodiment 2 (B method).Pure product are light yellow solid, and yield is 67%.n
D 20 1.5182。
The structure appraising datum is as follows:
Ultimate analysis: calculated value: C%47.07, H%3.95; Measured value: C%47.58, H%3.54;
IR(cm
-1)：3029，2962，2854，1732，1594，1494，1456，1284，1124，1065，928，743；
1H NMR(δ/ppm)：3.74～3.80(dd，6H，2×(-OCH
3)，J＝10.80Hz)，4.79(d，1H
a，-OCH
2CO-，J＝16.44Hz)，4.82(d，1H
b，-OCH
2CO-，J＝16.45Hz)，6.38(d，1H，-OCHP，J＝13.60Hz)，6.84～7.28(m，3H，C
4H
3O-)，7.43～8.64(m，4H，-C
6H
4)；
MS(m/z，％)：408(M
+ 32.26％)，220(31.76％)，205(60.18％)，203(11.11％)，189(89.91％)，175(100％)，162(47.31％)，145(52.49％)，133(13.62％)，109(64.28％)，94(48.13％)，93(93.12％)，75(13.31％)，63(25.74％)，44(13.62％)。
Embodiment 15
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 200 gram peeling potatoes, boil in 700 ml distilled waters the chopping back, cold filtration, and filtrate is mixed with glucose, agar, adds water to 900 milliliters again, is heated to boiling, promptly gets substratum after the cooling.Substratum, distilled water, culture dish are sterilized together.With 3 milligrams of left and right sides testing samples of electronic balance weighing, 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 10 milliliters of culture medium after sterilization while hot with the scale test tube, with itself and 1 milliliter, 10 milliliters of sample mixings 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 5 millimeters punch tool 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,, suppress the expression drug effect with diameter according to the blank photograph:
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 fungicidal activity data of table 1 compound 1～14 (Plating exsomatizes) 50ppm
| Compound | 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 7 8 9 10 | 90.91 59.09 13.64 31.82 68.18 27.27 63.64 31.82 68.18 50.00 | A C C C C C | 96.67 83.33 40.00 40.00 73.33 36.67 70.00 40.00 66.67 46.67 | A B B B C | 100.0 95.00 65.00 25.00 100.0 45.00 100.0 60.00 90.00 60.00 | A A C A A C A C | 90.63 68.75 31.25 25.00 65.63 15.63 65.63 25.00 46.88 59.38 | A C C C C | 100.0 100.0 80.56 63.89 100.0 83.33 100.0 83.33 100.0 80.56 | A A B C A B A B A B | ||
| 11 12 13 14 | 27.27 44.44 33.33 37.04 | 36.67 38.46 23.08 26.92 | 30.00 71.43 14.29 50.00 | B C | 21.88 38.24 23.53 35.29 | 38.89 76.74 58.14 76.74 | B C B | 33.33 7.41 33.33 |
Experimental result shows:
Compound is generally better to the activity of botrytis cinerea and Sclerotinia sclerotiorum, wherein has 5 compounds to reach the A level, and 6 reach the B level, illustrate that this series compound has the certain selectivity fungicidal activity.Compound 1 (X, Y:2-Cl, 5-CH
3) and compound 2 (X, Y:3-CH
3, 4-Cl) to fusarium oxysporum f.sp.vasinfectum, magnaporthe grisea, gibberella saubinetii, botrytis cinerea and Sclerotinia sclerotiorum show excellent fungicidal activity.
Embodiment 16
The mensuration of 1 pair of corn southern leaf blight prevention effect of compound
Adopt the potted plant test of pesticide effectiveness method of sterilant to carry out, select the southern corn leaf blight bacterial classification for use, the southern corn leaf blight spore is advisable with 100 spores in (10 * 15) every visual field under low power lens.With the disease index is judging quota:
Disease index (%)=[∑ (onset grade * diseased plant numbers at different levels or sick number of sheets)]/(total sample number * highest ranked rank) * 100
Calculate relative control effect with disease index:
Relative control effect (%)=(check plot disease index-treatment zone disease index)/check plot disease index * 100
Grade scale:
0 grade: the expansion blade is normal, does not have any bacterial plaque;
The I level: the tikka area accounts for below 1/3 of blade area;
The II level: the tikka area accounts for below 1/2 of blade area;
The III level: the tikka area accounts for below 2/3 of blade area;
The IV level: whole blade is withered.
1 pair of corn southern leaf blight prevention effect of table 2 compound
| Handle | Onset grade | Disease index | Relative protection effect (%) | ||||
| 0 | I | II | III | IV | |||
| Southern corn leaf blight southern corn leaf blight+compound 1 (50ppm) southern corn leaf blight+compound 1 (100ppm) | 0 23 24 | 1 7 5 | 5 0 1 | 9 0 0 | 15 0 0 | 81.67 5.83 5.83 | 92.86 92.86 |
Experimental result shows:
1 pair of southern corn leaf blight of compound shows excellent live body fungicidal activity.
Embodiment 17
Compound is to Sclerotinia sclerotiorum and wheat powdery mildew efficiency test
Wheat powdery mildew is preserved spore with stem and leaf of Wheat and is for experiment, and accurately takes by weighing an amount of new compound to be measured, with suitable solvent dissolving and adding small amounts of emulsifiers, is diluted to finite concentration with clear water earlier.Adopt potted plant blade bacterination process, spraying medicine concentration is 500ppm, and test-results sees Table 3.
Table 3 pair Sclerotinia sclerotiorum and wheat powdery mildew prevention effect
| Compound | Sclerotinia sclerotiorum | Wheat powdery mildew | ||
| Preventive effect (%) | The virulence rank | Preventive effect (%) | The virulence rank | |
| 1 7 | 90.0 90.0 | A A | 20.0 15.0 | D D |
Embodiment 18
Compound is measured the graw mold of tomato bacteriostatic activity
Adopt indoor isolated growth rate determination method that the graw mold of tomato bacteriostatic activity is measured, the results are shown in Table 4.
Table 4 compound is to the bacteriostatic activity measurement result of graw mold of tomato
| Compound | Inhibiting rate, % | ||
| 1000 mcg/ml | 100 mcg/ml | 10 mcg/ml | |
| 1 2 3 5 7 | 17.8％ 16.7％ 30.6％ 19.4％ 35.6％ | 0 3.7％ 25％ 4.2％ 22.2％ | 0 1.9％ 15.3％ 0 17.6％ |
Embodiment 19
Compound is to grey mould fruit rot of strawberry bacteriostatic activity test EC
50Test result
Adopt the growth velocity assay method.With acetone is solvent, and with compound 1,2,3,5,6,7 are mixed with 5 concentration of 10,5,2.5,1.25,0.625 μ g/ml respectively, and the acetone contrast is set.Experimental result sees the following form:
Table 5 compound is to grey mould fruit rot of strawberry bacteriostatic activity test EC
50Test result
| Compound | EC 50(μg/ml) |
| 1 2 | 40.058 38.528 |
| 3 4 5 7 | 61.945 11.259 60.395 94.271 |
Embodiment 20
Compound is to the bacteriostatic activity measurement result of rice sheath blight disease
Adopt the growth velocity assay method, prepare each drug concentration with sterilized water, and measure the inhibition growth rate of each concentration.Compound sees Table 6 to the bacteriostatic activity measurement result of rice sheath blight disease.The contrast medicament is a jingganmycin.
Table 6 compound is to the bacteriostatic activity measurement result of rice sheath blight disease
| Compound | Inhibiting rate, % | |||||||
| 1000 mcg/ml | 160 mcg/ml | 100 mcg/ml | 80 mcg/ml | 40 mcg/ml | 20 mcg/ml | 10 mcg/ml | 5 mcg/ml | |
| 12357 jingganmycins | 100 100 51.3 22.6 100 91.2 | 100 100 100 | 80.6 100 3.5 3.2 100 40.2 | 100 100 100 | 100 100 100 | 100 100 100 | 81.5 88.3 0 0 83.6 29.7 | 73.2 77.5 71.5 |
Interpretation of result: the bacteriostatic activity measurement result of 1,2,7 pairs of rice sheath blight diseases of compound shows that when drug concentration was 20 mcg/ml, the inhibiting rate of three kinds of medicaments was 100%; When drug concentration was 10 mcg/ml, the inhibiting rate of three kinds of medicaments was all more than 80%; Bacteriostatic activity under three concentration being measured all is higher than contrast medicament jingganmycin (10 mcg/ml, 29.7%).The result shows that 1,2,7 pairs of rice sheath blight diseases of compound have tangible bacteriostatic activity, in the control to rice sheath blight disease, have the value of further research and development.
Embodiment 21
Compound 1 is prevented and treated rice sheath blight disease (Rhizoctonia solani) field control effectiveness test
10% compound, 1 missible oil is prevented and treated the rice sheath blight disease field control effectiveness test, the result shows: it is remarkable that 10% compound, 1 missible oil is prevented and treated the rice sheath blight disease effect, the preventive effect of diluting 1000 times behind the medicine has reached more than 70%, the average preventive effect of diluting behind 500 times the medicine is: 81.8057%, preventive effect strengthens with concentration and improves, and is best to dilute 500 times preventive effect.10% compound, 1 missible oil is prevented and treated the rice sheath blight disease effect and contrast medicament 25% jingganmycin WP preventive effect suitable: (effective ingredient: 12 gram/mus) average preventive effect is 88.54% to jingganmycin.(effective ingredient: 10 gram/mus) average preventive effect is 83% to 10% compound, 1 missible oil.
Influence to crop and beneficial organism: through observing, 10% compound, 1 missible oil is compared with the blank district, does not find that this medicament is to doing deposits yields poisoning and other detrimentally affect.Do not find that this medicament produces detrimentally affect to beneficial organism.
Embodiment 22
Compound 2 is prevented and treated rice sheath blight disease (Rhizoctonia solani) field control effectiveness test
5% compound, 2 missible oil are prevented and treated rice sheath blight disease field control effectiveness test result and shown: the preventive effect of diluting 1000 times behind 5% compound, the 2 missible oil medicines has reached more than 70%, the average preventive effect of diluting behind 500 times the medicine is: 80%, preventive effect strengthens with concentration and improves, and is best to dilute 500 times preventive effect.5% compound, 2 missible oil are prevented and treated the rice sheath blight disease effect and compared with contrast medicament 25% jingganmycin WP preventive effect: (effective ingredient: 12.5 gram/mus) average preventive effect is 88.54% to jingganmycin; (effective ingredient: 5 gram/mus) average preventive effect is 79.78% to 5% compound, 2 missible oil.As seen work as 5% compound, 2 missible oil under the condition of low dosage 5 gram/mus by the result, its drug effect also can reach 79.78%.
Influence to crop and beneficial organism: through observing, three used concentration of treatment of 5% compound, 2 missible oil are compared with the blank district, do not find that this medicament is to doing deposits yields poisoning and other detrimentally affect.Do not find that this medicament produces detrimentally affect to beneficial organism.
Embodiment 23
Compound 1 control sclerotinia rot of colza field plot trial
Compound 1 is carried out the field plot trial of control sclerotinia rot of colza, found that, to rape plant safety, compared no poisoning with blank behind the administered compound 1 control sclerotinia rot of colza.
The effect of compound 1 control sclerotinia rot of colza is obvious.Be respectively 89.13%, 73.98%, 73.93% by the preventive effect after 500ppm, 250ppm, the 50ppm dispenser,
Table 7 compound 1 control sclerotinia rot of colza field plot trial enquiry data and drug effect calculation result
| The medicament title | Spraying medicine concentration | Lesion area (millimeter 2) | Prevention effect (%) | The significance of difference 0.05 0.01 |
| Compound 1 | 500ppm | 50.21 | 89.13 | b B |
| 250ppm | 120.17 | 73.98 | b B | |
| 50ppm | 120.43 | 73.93 | b B | |
| 40% dimetachlone WP | 500ppm | 16.00 | 96.53 | a A |
| The clear water contrast | 461.76 | —— |
Though compound 1 still has effect preferably in the prevention effect of the 500ppm prevention effect not as contrast medicament 40% dimetachlone WP 500ppm under low dosage 50ppm.Therefore compound 1 is a new compound that potentiality to be exploited is arranged very much.
Embodiment 24
Compound 2 control sclerotinia rot of colza field plot trials
Compound 2 control sclerotinia rot of colzas have tangible prevention effect.Be respectively 95.62%, 83.98%, 83.92% by the preventive effect after 500ppm, 250ppm, the 50ppm dispenser,
Table 8 compound 2 control sclerotinia rot of colza plot experiment enquiry data and drug effect calculation result
| The medicament title | Spraying medicine concentration | Lesion area (millimeter 2) | Prevention effect (%) | The significance of difference 0.05 0.01 |
| Compound 2 | 500ppm | 20.24 | 95.62 | a A |
| 250ppm | 73.96 | 83.98 | b B | |
| 50ppm | 74.25 | 83.92 | b B | |
| 40% dimetachlone WP | 500ppm | 16.00 | 96.53 | a A |
| The clear water contrast | 461.76 | -- |
To rape plant safety, compare no poisoning with blank behind the administered compound 2 control sclerotinia rot of colzas.The commercialization sterilant that this test and Selection is prevented and treated the sclerotinia rot of colza best results at present is the contrast medicament, and compound 2 is suitable with the prevention effect of contrast medicament dimetachlone WP 500ppm in the prevention effect of 500ppm, still has effect preferably under low dosage 50ppm.Compound 2 is the novel cpds that potentiality to be exploited is arranged very much.
Claims (13)
1, a class substituted benzene oxygen acetoxy furyl methyl phosphonate compound is characterized in that having the represented structural formula of general formula I:
In the formula: X and Y are H, halogen, C
1-C
3Alkyl, haloalkyl, X is identical with Y or inequality.
2, the preparation method of the described compound of representing by general formula I of claim 1, the A method is characterized in that by following reaction path preparation,
In the formula: X is identical with the definition in the described general formula I of claim 1 with Y.
3, the preparation method of the described compound of representing by general formula I of claim 1, the B method is characterized in that by following reaction path preparation,
In the formula: X is identical with the definition in the described general formula I of claim 1 with Y; M is Li, Na, K or NH
3 +
4, the described application of compound of representing with general formula I of claim 1 is characterized in that the effective ingredient as sterilant.
5, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the fusarium oxysporum f.sp.vasinfectum sterilant.
6, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the magnaporthe grisea sterilant.
7, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the botrytis cinerea sterilant.
8, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the gibberella saubinetii sterilant,
9, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the sclerotinia rot of colza sterilant.
10, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the grey mould fruit rot of strawberry sterilant.
11, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the corn southern leaf blight sterilant.
12, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the wheat powdery mildew sterilant.
13, the described application of compound of representing with general formula I of claim 4 is characterized in that as the effective ingredient for the rice sheath blight disease sterilant.
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ID=38081919
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2006
- 2006-12-01 CN CN 200610125215 patent/CN1962674A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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