CN1202107C - 2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity - Google Patents
2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity Download PDFInfo
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- CN1202107C CN1202107C CN 03143772 CN03143772A CN1202107C CN 1202107 C CN1202107 C CN 1202107C CN 03143772 CN03143772 CN 03143772 CN 03143772 A CN03143772 A CN 03143772A CN 1202107 C CN1202107 C CN 1202107C
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Abstract
The present invention relates to a 2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity. A general formula of the imidazolidinone derivative with bactericidal activity is disclosed in the specification, wherein in the general formula, Ar represents (substituted) phenyl, and the substituent is 3-chlorine, 4-chlorine and 4-methyl. The compound which has favorable inhibitory activity on magnaporthe grisea, rice sheath blight bacteria, asparagus blown spot bacteria, apple ring grain bacteria, wheat gibberella and cotton blight bacteria can be used as a germicidal agent.
Description
Technical field
The present invention relates to 2-(4-methylthiophenoxy)-5-furfurylidene imidazolidinone derivative, 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.It in field experiment, have tag, infiltration, systemic activity, show excellent protection and therapeutic activity, especially the oidium that caused by oomycetes, eqpidemic disease etc. are had good active.It is a kind of mitochondrial respiratory inhibitor that its germicidal action Study on Mechanism is demonstrated it.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)].Above-mentioned patent is reported is the two substituted imidazoline ketone derivatives of 5-.The preparation and the fungicidal activity of research 5-furfurylidene imidazolidinone derivative are 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-(4-methylthiophenoxy)-5-furfurylidene imidazolidinone derivative (I):
Ar is a phenyl in the formula (I), and substituting group is the substituted-phenyl of 3-chlorine or 4-chlorine or 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) (4-methylthiophenoxy)-5-furfurylidene imidazolidinone derivative, be to make the represented compound of general formula (II)
With aromatic isocyanate ArNCO (III) (definition in the formula in Ar and the general formula I is identical) azepine Wittig reaction takes place, the carbodiimide intermediate (V) that obtains reacts in the presence of catalytic amount solid carbonic acid potassium with 4-methylthiophenol (IV) again.
In the above-mentioned reaction, compound 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 4-methylthiophenol (IV) under catalysis of solid carbonic acid potassium and room temperature, stirring reaction 6～14 hours, reaction is a solvent with the acetonitrile, the mole dosage of solid carbonic acid potassium is 5% 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 and the effect of compound in (I) of the present invention formula below by example.
Embodiment 1
Under room temperature and drying nitrogen protection; 0.77g (5mmol) 4-chloro-phenyl-isocyanic ester is added in the 15mL dichloromethane solution of 2.20g (5mmol) phosphinimine (II); left standstill 4 hours; pressure reducing and steaming flux; added 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 0.70g (5mmol) 4-methylthiophenol and 0.03g solid carbonic acid potassium, at room temperature stirring reaction is 10 hours.Remove by filter potash solid, boil off solvent, resistates is with methylene dichloride/sherwood oil recrystallization, the 1.07g yellow crystals, productive rate 52%, m.p.150～151 ℃.
Ultimate analysis: measured value C% 61.32 H% 3.42 N% 6.94
Calculated value C% 61.39 H% 3.68 N% 6.82
IR(cm
-1)1728(C＝O)，1655(C＝C)，1570(C＝N)，1422，1401，1296
1H NMR (δ, ppm) 7.49～6.48 (m, 12H, Ar-H and=CH), 2.51 (s, 3H, SCH
3)
MS(m/z)411(M
++1，2％)，229(13％)，123(77％)，106(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 state productive rate (%) m.p./℃
I-1 Ph yellow crystals 71 191～192
I-2 4-Me-Ph deep yellow crystal 56 120～121
I-3 4-Cl-Ph yellow crystals 52 150～151
I-4 3-Cl-Ph yellow crystals 57 127～128
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 56 58 63 53 54 50
I-2 6 32 8 0 0 28
I-3 100 100 71 100 31 56
I-4 0 100 75 47 0 0
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-(4-methylthiophenoxy)-5-furfurylidene imidazolidinone derivative, (I) structure expressed that it is characterized in that having general formula:
In the formula: Ar is a phenyl, and substituting group is the substituted-phenyl of 3-chlorine or 4-chlorine or 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 03143772 CN1202107C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03143772 CN1202107C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021154058A Division CN1152019C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methyl) sulfur phenyl) imidazolinone derivant with bactericidal activity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1496988A CN1496988A (en) | 2004-05-19 |
| CN1202107C true CN1202107C (en) | 2005-05-18 |
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| CN 03143772 Expired - Fee Related CN1202107C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity |
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