CN1286838C - Method for preparing 2-arylamino-6H-imidazo[1,2-b]-1,2,4-triazole-6-ketone and its sterilizing activity - Google Patents
Method for preparing 2-arylamino-6H-imidazo[1,2-b]-1,2,4-triazole-6-ketone and its sterilizing activity Download PDFInfo
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- CN1286838C CN1286838C CN 200510019144 CN200510019144A CN1286838C CN 1286838 C CN1286838 C CN 1286838C CN 200510019144 CN200510019144 CN 200510019144 CN 200510019144 A CN200510019144 A CN 200510019144A CN 1286838 C CN1286838 C CN 1286838C
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Abstract
The present invention relates to 2-arylamino-6H-imidazo [1, 2-b]-1, 2, 4-triazole-6-ketone derivatives with bactericidal activity. The general formula of the imidazo triazole ketone derivatives with bactericidal activity is shown as the right formula. In the formula, Ar1 represents phenyl or substituted phenyl whose substituent is 4-chlorine or 4-methoxy; Ar2 represents phenyl or substituted phenyl whose substituent is 4-chlorine; Ar3 represents phenyl or substituted benzene phenyl whose substituent is 3-methyl, 4-methyl, 2-chlorine, 4-chlorine or 4-bromine. The compounds have excellent inhibiting activity on botrytis cinerea pers, sclerotinia rot of colza, magnaporthe grisea, gibberella saubinetii, cercospora leaf spot bacteria and cotton wilt fungi. Thus, the compounds can be used as bactericide.
Description
Technical field
The present invention relates to 2-virtue amino-6H-imidazo [1,2-b]-1,2,4-triazole-6-ketone derivatives, and it is as the application of the effective ingredient of sterilant.
Background technology
Imidazolidinone derivative has good fungicidal activity, as this series bactericidal agent Fenamidone, be 2-alkylthio-1-aminooimidazole quinoline ketone derivatives, belong to the mitochondrial respiratory inhibitor, fruit tree black spot and the oidium that is caused by oomycetes, eqpidemic disease etc. are all had excellent bactericidal activity.Many patent reports have been arranged had imidazolidinone derivative [CN1358714A (2002), CN1358718A (2002), a US6002016 (1999) of fungicidal activity, GB2329180 (1999), GB2327676 (1999), WO9833381 (1998), WO9602538 (1996), EP668270 (1995), EP629616 (1994), WO9401410 (1994), EP599749 (1994), WO9324467 (1993), EP551048 (1993)].Above-mentioned patent is reported is the monocycle imidazolidinone derivative.In view of triazole derivative also is the compound that a class has remarkable fungicidal activity, the preparation and the fungicidal activity of research triazolo imidazolidinone derivative are significant.
Summary of the invention
The objective of the invention is to explore the good compound of fungicidal activity, provide 2-virtue amino-6H-imidazo [1,2-b]-1,2,4-triazole-6-ketone derivatives with fungicidal activity.
The present invention proposes 2-virtue amino-6H-imidazo [1,2-b]-1,2,4-triazole-6-ketone derivatives I:
Among the formula I, Ar
1Be phenyl, substituting group is the substituted-phenyl of 4-chlorine or 4-methoxyl group; Ar
2Be phenyl, substituting group is the substituted-phenyl of 4-chlorine; Ar
3Be phenyl, substituting group is the substituted-phenyl of 3-methyl, 4-methyl, 2-chlorine, 4-chlorine or 4-bromine.
The compound of above-mentioned formula I provided by the invention has good inhibition activity to botrytis cinerea, Sclerotinia sclerotiorum, rice blast fungus, gibberella saubinetii, beet Cercospora bacterium and cotton wilt fusarium, thereby can be used as the effective constituent of sterilant.
With the represented 2-virtue amino-6H-imidazo [1,2-b]-1,2 of general formula I, the preparation of 4-triazole-6-ketone derivatives is to make represented compound of general formula I I and the represented aromatic isocyanate (Ar of general formula III
3NCO) and triphenylphosphine, hexachloroethane and triethylamine with " one kettle way " prepared in reaction,
Ar in II and the III formula
1, Ar
2And Ar
3Identical with the definition in the general formula I; The Ph-phenyl; The Et-ethyl.
In the above-mentioned reaction, the compound that general formula I I is represented and the Ar of general formula III
3NCO and triphenylphosphine and hexachloroethane are 1: 1: 1.2～1.5: 1.2～1.5 in molar ratio, under 10～30 ℃ of room temperatures, mix, reaction is solvent with the anhydrous methylene chloride, drip triethylamine again, the consumption of triethylamine is the twice of triphenylphosphine, and reaction mixture stirred 1～5 hour under 10～30 ℃ of room temperatures, after reaction is finished, reaction solution is under reduced pressure sloughed solvent, and residue gets the general formula I product with ethyl alcohol recrystallization.
With the preparation of the represented 2-virtue amino-3-aminooimidazole quinoline ketone derivatives of general formula I I, be to make represented compound of general formula I V and the represented aromatic isocyanate (Ar of general formula V
2NCO) azepine Wittig reaction takes place, the carbodiimide intermediate VI that obtains, again with hydrazine hydrate VII reaction,
In above-mentioned II, IV, V and the VI formula, Ar
1And Ar
2Identical with the definition in the general formula I.
In the above-mentioned reaction, the represented aromatic isocyanate of compound phosphinimine that equimolar general formula I V is represented and general formula V reacted 2～8 hours under 10～30 ℃ of room temperatures, reaction is solvent with the anhydrous methylene chloride, reacted the back and removed by product triphen phosphine oxide with recrystallization method, resulting carbodiimide again with the hydrazine hydrate of 1.2～2 times of moles under 10～30 ℃ of room temperatures, stirring reaction 5～20 minutes, reaction is a solvent with ethanol, after reaction is finished, filter the solid product that obtains general formula I I.
Embodiment
Be described more specifically the preparation and the effect of compound in I of the present invention and the II formula below by example.
Room temperature is 10～30 ℃ among the embodiment
Embodiment 1
Preparation
Under room temperature and drying nitrogen protection, it (is Ar among the general formula I V that 0.60g (5mmol) phenyl isocyanate is added drop-wise to 2.41g (5mmol) phosphinimine
1Compound for the 4-p-methoxy-phenyl) in the 15mL dichloromethane solution, left standstill the pressure reducing and steaming solvent 6 hours, add ether and sherwood oil volume ratio=1: 2 mixture 20mL, go out the triphen phosphine oxide with recrystallization, filter, filtrate under reduced pressure boils off solvent and promptly gets carbodiimide; Carbodiimide is dissolved in the 15mL ethanol, adds the ethanolic soln that 85wt% hydrazine hydrate 0.35g (6mmol) is dissolved in 5mL, at room temperature stirring reaction is 10 minutes.Filter the 1.26g yellow solid, productive rate 82%, m.p.221～222 ℃.
Ultimate analysis: measured value C% 56.63 H% 3.03 N% 5.57
Calculated value C% 56.40 H% 3.09 N% 5.72
IR(cm
-1)3360，3324(N-H)，1701(C＝O)，1657(C＝C)，1598，1252，1152
1H NMR(δ，ppm)8.10-6.96(m，10H，Ar-H and NH)，6.87(s，1H，＝CH)，4.21(s，2H，NH
2)，3.87(s，3H，OCH
3)
MS(m/z)308(M
+，100)，293(14)，146(54)，91(65)
Adopt above-mentioned similar approach can prepare other II compounds equally.Listedly in the table 1 be the compound of synthetic general formula I I of the present invention.
The implication of ellipsis in the table: Ph-phenyl, 4-Cl-C
6H
4-4-chloro-phenyl-, 4-MeO-C
6H
4-4-methoxyphenyl, the m.p.-fusing point
Table 1
| No. | Ar 1 | Ar 2 | State | Productive rate (%) | m.p./℃ |
| II-1 II-2 II-3 II-4 II-5 | 4-MeO-C 6H 4 Ph 4-Cl-C 6H 4 Ph 4-MeO-C 6H 4 | Ph Ph Ph 4-Cl-C 6H 4 4-Cl-C 6H 4 | Yellow solid yellow solid yellow solid yellow solid yellow solid | 82 76 72 74 80 | 221～222 191～193 239～241 245～246 216～218 |
Embodiment 2
Preparation
At room temperature, the triethylamine of 0.81g (8mmol) being added drop-wise to 0.83g (3mmol) imidazolone (is Ar among the general formula I I
1Be phenyl, Ar
2Compound for phenyl), 0.36g (3mmol) phenyl isocyanate, 1.05g (4mmol) triphenylphosphine and 0.95g (4mmol) C
2Cl
6The 15mL dichloromethane solution in, reaction mixture stirred 1 hour, pressure reducing and steaming solvent, resistates be with ethyl alcohol recrystallization, the 0.81g yellow crystals, productive rate 71%, m.p.241～242 ℃.
Ultimate analysis: measured value C% 72.89 H% 4.44 N% 18.61
Calculated value C% 72.81 H% 4.52 N% 18.46
IR(cm
-1)3358(N-H)，1713(C＝O)，1658(C＝C)，1580，1100
1H NMR(δ，ppm)8.03-7.09(m，16H，Ar-H and＝CH)，6.13(s，1H，NH)
MS(m/z)379(M
+，1)，351(3)，233(7)，116(85)，77(100)
Embodiment 3
At room temperature, the triethylamine of 0.81g (8mmol) being added drop-wise to 0.94g (3mmol) imidazolone (is Ar among the general formula I I
1Be phenyl, Ar
2Compound for the 4-chloro-phenyl-), 0.40g (3mmol) 3-tolyl isocyanic ester, 1.05g (4mmol) triphenylphosphine and 0.95g (4mmol) C
2Cl
6The 15mL dichloromethane solution in, reaction mixture stirred 3 hours, pressure reducing and steaming solvent, resistates be with ethyl alcohol recrystallization, the 1.10g yellow crystals, productive rate 86%, m.p.＞300 ℃.
Ultimate analysis: measured value C% 67.45 H% 4.17 N% 16.20
Calculated value C% 67.37 H% 4.24 N% 16.37
IR(cm
-1)3406(N-H)，1714(C＝O)，1661(C＝C)，1589，1095
1H NMR(δ，ppm)8.93(s，1H，NH)，8.04-6.88(m，14H，Ar-H and＝CH)，2.30(s，3H，CH
3)
MS(m/z)429(28)，427(M
+，82)，399(71)，370(39)，232(75)，116(100)
Embodiment 4
At room temperature, the triethylamine of 0.81g (8mmol) being added drop-wise to 1.03g (3mmol) imidazolone (is Ar among the general formula I I
1Be 4-methoxyphenyl, Ar
2Compound for the 4-chloro-phenyl-), 0.40g (3mmol) 4-tolyl isocyanic ester, 1.05g (4mmol) triphenylphosphine and 0.95g (4mmol) C
2Cl
6The 15mL dichloromethane solution in, reaction mixture stirred 2 hours, pressure reducing and steaming solvent, resistates be with ethyl alcohol recrystallization, the 1.19g yellow crystals, productive rate 87%, m.p.＞300 ℃.
Ultimate analysis: measured value C% 65.65 H% 4.50 N% 15.20
Calculated value C% 65.57 H% 4.40 N% 15.29
IR(cm
-1)3407(N-H)，1722(C＝O)，1665(C＝C)，1606，1093
1H NMR(δ，ppm)9.00(s，1H，NH)，8.00-6.88(m，13H，Ar-H and＝CH)，3.83(s，3H，OCH
3)，2.32(s，3H，CH
3)
MS(m/z) 459(50)，457(M
+，91)，429(73)，414(28)，386(38)，262(51)，132(100)
Adopt above-mentioned similar approach can prepare other compound equally.Listedly in the table 2 be the part of compounds of synthetic general formula I of the present invention.
The implication of ellipsis in the table: Ph-phenyl, 4-Cl-C
6H
4-4-chloro-phenyl-, 2-Cl-C
6H
4-2-chloro-phenyl-, 4-Br-C
6H
4-4-bromophenyl, 4-MeO-C
6H
4-4-methoxyphenyl, 4-Me-C
6H
4-4-tolyl, 3-Me-C
6H
4-3-tolyl, the m.p.-fusing point
Table 2
| No. | Ar 1 | Ar 2 | Ar 3 | State | Productive rate (%) | m.p./℃ |
| I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-8 I-9 I-10 I-11 I-12 I-13 I-14 I-15 | Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 | Ph Ph Ph Ph Ph 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 Ph Ph Ph Ph Ph | Ph 4-Me-C 6H 4 3-Me-C 6H 4 4-Cl-C 6H 4 2-Cl-C 6H 4 Ph 4-Me-C 6H 4 3-Me-C 6H 4 4-Cl-C 6H 4 2-Cl-C 6H 4 Ph 4-Me-C 6H 4 3-Me-C 6H 4 4-Cl-C 6H 4 2-Cl-C 6H 4 | Yellow crystals yellow crystals yellow crystals yellow crystals pale yellow crystals yellow crystals yellow crystals yellow crystals yellow crystals pale yellow crystals yellow crystals yellow crystals yellow crystals yellow crystals pale yellow crystals | 71 79 84 83 77 81 73 86 90 66 87 75 87 88 70 | 241～242 270～271 240～241 ＞300 298～299 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 236～238 ＞300 267～269 |
| I-16 I-17 I-18 I-19 I-20 I-21 I-22 I-23 I-24 I-25 I-26 | 4-Cl-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 4-MeO-C 6H 4 | Ph Ph Ph Ph Ph Ph 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 4-Cl-C 6H 4 | 4-Br-C 6H 4 Ph 4-Me-C 6H 4 3-Me-C 6H 4 4-Cl-C 6H 4 2-Cl-C 6H 4 Ph 4-Me-C 6H 4 3-Me-C 6H 4 4-Cl-C 6H 4 2-Cl-C 6H 4 | Yellow crystals yellow crystals yellow crystals yellow crystals yellow crystals pale yellow crystals yellow crystals yellow crystals yellow crystals yellow crystals yellow crystals | 74 78 92 74 92 71 76 87 89 91 77 | ＞300 247～248 282～283 189～190 ＞300 253～254 240～241 ＞300 ＞300 ＞300 ＞300 |
From following experiment as can be seen, the represented compound of formula I of the present invention has good inhibition activity to cotton wilt fusarium (Fusariumoxysporum), rice blast fungus (Pyricularia oryzae), botrytis cinerea (Botrytis Cinerea Pers.), gibberella saubinetii (Gibberella zeae), Sclerotinia sclerotiorum (Sclerotinia sclerotiorum de Bary) and beet Cercospora bacterium (Cercosporabeticola Sacc.).Wherein best with Compound I-8 and I-23 effect.
Embodiment 5
Fungicidal activity experiment (containing toxic medium method)
Liquor strength 50ppm, get made agar block with the 5mm punch tool, divide and choose into each culture dish, if blank, it was cultivated 48～72 hours for 27 ℃ at constant incubator, check the bacterial plaque diameter, inhibiting rate=(contrast bacterial plaque diameter-sample bacterial plaque diameter)/contrast bacterial plaque diameter * 100% is done a repetition simultaneously.Table 2 is the measurement result of part of compounds I and II.
Table 2
| No. | 50ppm, relative inhibition % | |||||
| Cotton wilt fusarium | Rice blast fungus | Botrytis cinerea | Gibberella saubinetii | Sclerotinia sclerotiorum | The beet Cercospora bacterium | |
| I-8 I-16 I-23 I-25 I-26 II-1 | 93 79 96 62 56 46 | 100 74 93 59 76 56 | 100 100 100 88 89 90 | 97 73 94 48 43 70 | 100 100 100 100 89 95 | 100 / 100 52 44 41 |
When compound of the present invention uses as sterilant, can be with carrier or the mixing diluents that allows in compound of the present invention and other plant protection, whereby it is modulated into normally used various formulation, use as mixture, granule, aqueous emulsion, also can be with other agricultural chemicals such as sterilant, Insecticides (tech) ﹠ Herbicides (tech), plant-growth regulator mixes use or the while is also used.
Claims (4)
1, class 2-virtue amino-6H-imidazo [1,2-b]-1,2,4-triazole-6-ketone derivatives is characterized in that having the structure that general formula I is expressed:
In the formula: Ar
1Be phenyl, substituting group is the substituted-phenyl of 4-chlorine or 4-methoxyl group;
Ar
2Be phenyl, substituting group is the substituted-phenyl of 4-chlorine;
Ar
3Be phenyl, substituting group is the substituted-phenyl of 3-methyl, 4-methyl, 2-chlorine, 4-chlorine or 4-bromine.
2, the described preparation method with the represented derivative of general formula I of claim 1 is characterized in that the compound that makes general formula I I represented
Ar
3NCO III
With the represented aromatic isocyanate of general formula III and triphenylphosphine, hexachloroethane and triethylamine with " one kettle way " prepared in reaction, Ar in II and the III formula
1, Ar
2And Ar
3Identical with the definition among the claim 1 formula of I.
3, preparation method as claimed in claim 2 is characterized in that the compound that general formula I I is represented and the aromatic isocyanate Ar of general formula III
3NCO and triphenylphosphine and hexachloroethane are 1: 1: 1.2～1.5: 1.2～1.5 in molar ratio, under 10～30 ℃ of room temperatures, mix, reaction is solvent with the anhydrous methylene chloride, drip triethylamine again, the consumption of triethylamine is the twice of triphenylphosphine, and reaction mixture stirred 1～5 hour under 10～30 ℃ of room temperatures, after reaction is finished, reaction solution is under reduced pressure sloughed solvent, and residue gets the described general formula I product of claim 1 with ethyl alcohol recrystallization.
4, the application of the described compound of Formula I of claim 1 in the preparation sterilant is characterized in that the effective constituent as sterilant.
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| CN 200510019144 CN1286838C (en) | 2005-07-22 | 2005-07-22 | Method for preparing 2-arylamino-6H-imidazo[1,2-b]-1,2,4-triazole-6-ketone and its sterilizing activity |
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| CN 200510019144 CN1286838C (en) | 2005-07-22 | 2005-07-22 | Method for preparing 2-arylamino-6H-imidazo[1,2-b]-1,2,4-triazole-6-ketone and its sterilizing activity |
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| CN1286838C true CN1286838C (en) | 2006-11-29 |
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