CN1508135A - 2-(1H-1,2,4,-triazole-1-radical)-5-furan methylene imidazolidinone derivatives and bactericidal activity - Google Patents
2-(1H-1,2,4,-triazole-1-radical)-5-furan methylene imidazolidinone derivatives and bactericidal activity Download PDFInfo
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- CN1508135A CN1508135A CNA031542662A CN03154266A CN1508135A CN 1508135 A CN1508135 A CN 1508135A CN A031542662 A CNA031542662 A CN A031542662A CN 03154266 A CN03154266 A CN 03154266A CN 1508135 A CN1508135 A CN 1508135A
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Abstract
The present invention relates to a kind of 2-(1H-1,2,4-triazole-1-radicle)-5-furfuralimidazolone derivative and its germ-killing activity. Said invention also provides its general formula, and its application for inhibiting rice blast, rice stripe, puccinia asparagilucidili, apple-tree canker, wheat grass scab and cotton wilt, etc. Said invention can be used as mycocide.
Description
Technical field
The present invention relates to 2-(1H-1,2,4-triazol-1-yl)-5-furfurylidene imidazolidinone derivative and fungicidal activity, and it is as the application of the effective ingredient of sterilant.
Background technology
1993, the researchist of French Rhone-Poulenc found that this compounds shows good fungicidal activity, thereby develops first imidazolone series bactericidal agent (RPA407213) when research 2-thiamazole quinoline ketone derivatives.After this, again many patent reports have been arranged and had imidazolidinone derivative [US6002016 (1999), GB2329180 (1999), a GB2327676 (1999) of fungicidal activity, WO9833381 (1998), WO9602538 (1996), EP668270 (1995), EP629616 (1994), WO9401410 (1994), EP599749 (1994), WO9324467 (1993), EP551048 (1993)].And 1,2, the 4-triazole bactericidal agent demonstrates good interior suction fungicidal activity as ergosterol biosynthesis inhibitor, has characteristics such as efficient, wide spectrum, low toxicity.With 1,2, the 4-triazolyl is incorporated into 2 of imidazolone, and the 2-with fungicidal activity is provided, and (1H-1,2,4-triazol-1-yl)-5-furfurylidene imidazolidinone derivative is significant.
Summary of the invention
The objective of the invention is to explore the good compound of fungicidal activity, the imidazolidinone derivative with fungicidal activity is provided.The present invention proposes 2-(1H-1,2,4-triazol-1-yl)-5-furfurylidene imidazolidinone derivative (I):
Ar is (replacement) phenyl in the formula (I), and substituting group is 3-chlorine, 4-chlorine, 4-methyl
The compound of above-mentioned formula provided by the invention (I) has good inhibition activity to rice blast fungus, rice banded sclerotial blight bacterium, asparagus splash bacterium, apple wheel line bacterium, gibberella saubinetii and cotton wilt fusarium, thereby can be used as the effective constituent of sterilant.
With the preparation of the represented 2-of general formula (I) (1H-1,2,4-triazol-1-yl) imidazolidinone derivative, be to make the represented compound of general formula (II)
Azepine Wittig reaction takes place with aromatic isocyanate ArNCO (III) (definition in the formula in Ar and the general formula I is identical), the carbodiimide intermediate (V) that obtains, again with 1H-1,2,4-triazole (IV) is reacted in the presence of excessive solid carbon acid potassium.
In the above-mentioned reaction, phosphine imido that equimolar general formula (II) is represented and aromatic isocyanate ArNCO (III) at room temperature reacted 2～8 hours, and reaction is a solvent with the anhydrous methylene chloride, had reacted the back and had removed by product triphen phosphine oxide with recrystallization method.Resulting carbodiimide (V) again with equimolar 1H-1,2,4-triazole (IV) under excessive solid carbon acid potassium catalysis and room temperature, stirring reaction 10～45 minutes, reaction is a solvent with the acetonitrile, the mole dosage of solid carbonic acid potassium is 5～10 times of (II) consumption.After reaction was finished, reaction solution was under reduced pressure sloughed solvent, and residue gets product (I) with methylene dichloride/sherwood oil recrystallization.
Embodiment
Be described more specifically the preparation of compound in (I) of the present invention formula and as the application of sterilant effective ingredient below by example.
Embodiment 1
Under room temperature and drying nitrogen protection; 0.77g (5mmol) 4-chloro-phenyl-isocyanic ester is added drop-wise in the 15mL dichloromethane solution of 2.20g (5mmol) phosphinimine (II); left standstill 4 hours; pressure reducing and steaming flux; add V (ether)/V (sherwood oil) (1:2; 20mL) go out the triphen phosphine oxide with recrystallization, filter, filtrate under reduced pressure boils off solvent and promptly gets carbodiimide (V).(V) is dissolved in the 15mL acetonitrile, adds 0.34g (5mmol) 1H-1,2,4-triazole (IV) and 6.9g (50mmol) solid carbonic acid potassium, at room temperature stirring reaction is 15 minutes.Remove by filter potash solid, boil off solvent, resistates is with methylene dichloride/sherwood oil recrystallization, the 0.76g yellow crystals, productive rate 45%, m.p.199～201 ℃.
Ultimate analysis: measured value C% 56.38 H% 2.75 N% 20.73
Calculated value C% 56.57 H% 2.97 N% 20.61
IR(cm
-1)1717(C＝O)，1649(C＝C)，1557(C＝N)，1479，1239，1153
1H NMR (δ, ppm) 7.66～6.61 (m, 8H, Ar-H and=CH), 8.95 (s, 1H, triazolyl-5-H), 7.88 (s, 1H, triazolyls-3-H)
MS(m/z)339(M
+，63％)，341(21％)，205(64％)，151(100％)
Adopt above-mentioned similar approach can prepare other compound equally.Listedly in the table 1 be the part of compounds of synthetic general formula of the present invention (I).
The implication of ellipsis in the table: Ph-phenyl, 4-Cl-Ph-4-chloro-phenyl-, 3-Cl-Ph-3-chloro-phenyl-, 4-Me-Ph-4-tolyl, m.p.-fusing point
Table 1
No. Ar
2State productive rate (%) m.p./℃
I-1 Ph yellow crystals 80 192～194
I-2 4-Cl-Ph yellow crystals 45 199～201
I-3 3-Cl-Ph yellow crystals 57 166～167
I-4 4-Me-Ph yellow crystals 76 202～203
From following experiment as can be seen, the represented compound of formula of the present invention (I) has good inhibition activity to rice blast fungus (Pyriculariaoryzae), rice banded sclerotial blight bacterium (Pellicularia sasakii), asparagus splash bacterium (Cercospora asparagagas), apple wheel line bacterium (Physalospora piricola), gibberella saubinetii (Gibberella zeae) and cotton wilt fusarium (Fusariumoxysporum).
Embodiment 2
Fungicidal activity experiment (containing toxic medium method)
Liquor strength 50ppm, get made agar block with the 5mm device that fans the air, 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).
Table 2
50ppm, relative inhibition %
No.
Rice blast fungus rice banded sclerotial blight bacterium asparagus splash bacterium apple wheel line bacterium gibberella saubinetii cotton wilt fusarium
I-1 67 80 50 83 60 70
I-2 83 33 56 67 53 57
I-3 13 22 63 58 63 48
I-4 46 82 69 75 50 70
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, wait as mixture, granule, aqueous emulsion and to use, also can mix and use or simultaneously and use with other agricultural chemicals such as sterilant, Insecticides (tech) ﹠ Herbicides (tech), plant-growth regulator etc.
Claims (2)
1, a class 2-(1H-1,2,4-triazol-1-yl)-5-furfurylidene imidazolidinone derivative, (I) structure expressed that it is characterized in that having general formula:
In the formula: Ar is (replacement) phenyl, and substituting group is 3-chlorine, 4-chlorine, 4-methyl.
2, the described application with the represented derivative of general formula (I) of claim 1 is characterized in that the effective constituent as sterilant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03154266 CN1208334C (en) | 2002-01-04 | 2002-01-04 | 2-(1H-1,2,4,-triazole-1-radical)-5-furan methylene imidazolidinone derivatives and bactericidal activity |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03154266 CN1208334C (en) | 2002-01-04 | 2002-01-04 | 2-(1H-1,2,4,-triazole-1-radical)-5-furan methylene imidazolidinone derivatives and bactericidal activity |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021154066A Division CN1150188C (en) | 2002-01-04 | 2002-01-04 | Preparation for 2-(1H-1,2,4-pyrrodiazole-1) imidazolinone derivant and bactericidal activity |
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| Publication Number | Publication Date |
|---|---|
| CN1508135A true CN1508135A (en) | 2004-06-30 |
| CN1208334C CN1208334C (en) | 2005-06-29 |
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| CN 03154266 Expired - Fee Related CN1208334C (en) | 2002-01-04 | 2002-01-04 | 2-(1H-1,2,4,-triazole-1-radical)-5-furan methylene imidazolidinone derivatives and bactericidal activity |
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