CN1358714A - 2-(4-methyl) sulfur phenyl) imidazolinone derivant with bactericidal activity and preparation method thereof - Google Patents
2-(4-methyl) sulfur phenyl) imidazolinone derivant with bactericidal activity and preparation method thereof Download PDFInfo
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- CN1358714A CN1358714A CN 02115405 CN02115405A CN1358714A CN 1358714 A CN1358714 A CN 1358714A CN 02115405 CN02115405 CN 02115405 CN 02115405 A CN02115405 A CN 02115405A CN 1358714 A CN1358714 A CN 1358714A
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Abstract
The present invention relates to a kind of 2-(4-methylthiophenoxy) imidazolidinone derivative with antifungal activity and its preparation method. Said invention provides the general formula of said imidazolidinone derivative. For rice blastmycin, rice sheath blight disease, asparagus brown spot, ring rot of apple, wheatgrass scab fusarium wilt of cotton said invented compound possesses good inhibiting activity, so that it can be used as fungicide.
Description
Technical field
The present invention relates to have 2-(4-methylthiophenoxy) imidazolidinone derivative of fungicidal activity and preparation method thereof, 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-aryl methylene imidazolidinone derivative are significant.
Summary of the invention
The objective of the invention is to explore the good compound of fungicidal activity, imidazolidinone derivative and preparation method with fungicidal activity are provided.
The present invention proposes 2-(4-methylthiophenoxy) imidazolidinone derivative (I):
Ar in the formula (I)
1Be 2-furyl or substituted-phenyl, substituting group is 2-chlorine, 3-chlorine, 4-chlorine, 2,4-dichloro, 3-bromine, 4-methoxyl group, Ar
2Be (replacement) phenyl, 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 method of the represented 2-of general formula (I) (4-methylthiophenoxy) imidazolidinone derivative, be to make the represented compound of general formula (II)
(Ar in the formula
1Identical with the definition in the general formula I) and aromatic isocyanate Ar
2NCO (III) (Ar in the formula
2Identical with the definition in the general formula I) 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 Ar
2NCO (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 method and the effect of compound in (I) of the present invention formula below by example.
Embodiment 1
Under room temperature and drying nitrogen protection, 0.66g (5mmol) 4-tolyl isocyanic ester is added drop-wise to 2.41g (5mmol) phosphinimine (II, Ar
1Be the 4-p-methoxy-phenyl) the 15mL dichloromethane solution in, left standstill 6 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 0.70g (5mmol) 4-methylthiophenol and 0.03g solid carbonic acid potassium, at room temperature stirring reaction is 12 hours.Remove by filter potash solid, boil off solvent, resistates is with methylene dichloride/sherwood oil recrystallization, the 1.91g yellow crystals, productive rate 89%, m.p.171～172 ℃.
Ultimate analysis: measured value C% 69.83 H% 5.31 N% 6.38
Calculated value C% 69.75 H% 5.15 N% 6.51
IR(cm
-1)1724(C＝O)，1654(C＝C)，1564(C＝N)，1401，1295，1159
1H NMR (δ, ppm) 7.90～6.81 (m, 13H, Ar-H and=CH), 3.80 (s, 3H, OCH
3), 2.50 (s, 3H,
SCH
3)，2.39(s，3H，CH
3)
MS(m/z)431(M
++1，6％)，270(7％)，209(11％)，146(83％)，123(88％)，45(100％)
Embodiment 2
Under room temperature and drying nitrogen protection, 0.77g (5mmol) 4-chloro-phenyl-isocyanic ester is added to 2.60g (5mmol) phosphinimine (II, Ar
1Be the 2,4 dichloro benzene base) the 15mL dichloromethane solution in, 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 0.70g (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 1.42g pale yellow crystals, productive rate 58%, m.p.187～189 ℃.
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)1746(C＝O)，1652(C＝C)，1565(C＝N)，1426，1397，1094
1H NMR (δ, ppm) 8.43～7.14 (m, 12H, Ar-H and=CH), 2.51 (s, 3H, SCH
3)
MS(m/z)489(M
++1，1％)，227(2％)，184(8％)，123(39％)，45(100％)
Embodiment 3
Under room temperature and drying nitrogen protection, 0.77g (5mmol) 4-chloro-phenyl-isocyanic ester is added to 2.65g (5mmol) phosphinimine (II, Ar
1Be the 3-bromophenyl) the 15mL dichloromethane solution in, 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 0.70g (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 1.40g pale yellow crystals, productive rate 56%, m.p.179～180 ℃.
Ultimate analysis: measured value C% 55.02 H% 3.45 N% 5.48
Calculated value C% 55.27 H% 3.23 N% 5.60
IR(cm
-1)1740(C＝O)，1656(C＝C)，1573(C＝N)，1421，1398，1293
1H?NMR(δ，ppm)8.20～7.13(m，12H，Ar-H)，6.96(s，1H，＝CH)，2.51(s，3H，SCH
3)
MS(m/z)501(M
++1，1％)，320(5％)，196(20％)，123(79％)，45(100％)
Embodiment 4
Under room temperature and drying nitrogen protection, 0.77g (5mmol) 4-chloro-phenyl-isocyanic ester is added to 2.20g (5mmol) phosphinimine (II, Ar
1Be the 2-furyl) the 15mL dichloromethane solution in, 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 0.70g (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％)
Embodiment 5
Under room temperature and drying nitrogen protection, 0.77g (5mmol) 3-chloro-phenyl-isocyanic ester is added drop-wise to 2.60g (5mmol) phosphinimine (II, Ar
1Be the 2,4 dichloro benzene base) the 15mL dichloromethane solution in, 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 0.70g (5mmol) 4-methylthiophenol and 0.03g solid carbonic acid potassium, at room temperature stirring reaction is 12 hours.Remove by filter potash solid, boil off solvent, resistates is with methylene dichloride/sherwood oil recrystallization, the 2.13g yellow crystals, productive rate 87%, m.p.176～178 ℃.
Ultimate analysis: measured value C% 56.18 H% 2.95 N% 5.80
Calculated value C% 56.40 H% 3.09 N% 5.72
IR(cm
-1)1738(C＝O)，1651(C＝C)，1570(C＝N)，1412，1302，1138
1H NMR (δ, ppm) 8.42～7.12 (m, 12H, Ar-H and=CH), 2.51 (s, 3H, SCH
3)
MS(m/z)489(M
++1，1％)，227(2％)，184(6％)，123(24％)，45(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, the 4-Cl-Ph-4-chloro-phenyl-, 3-Cl-Ph-3-chloro-phenyl-, 2-Cl-Ph-2-chloro-phenyl-, 2,4-2Cl-Ph-2,4-dichlorophenyl, 3-Br-Ph-3-bromophenyl, the 4-MeO-Ph-4-methoxyphenyl, the 4-Me-Ph-4-tolyl, 2-Furyl-2-furyl, m.p.-fusing point
Table 1No. Ar
1Ar
2State productive rate (%) m.p./℃ I-1 4-Cl-Ph Ph pale yellow crystals 78 160～161I-2 3-Cl-Ph Ph pale yellow crystals 83 140～141I-3 2-Cl-Ph Ph pale yellow crystals 74 151～152I-4 2; 4-2Cl-Ph Ph yellow crystals 84 162～163I-5 3-Br-Ph Ph pale yellow crystals 71 138～139I-6 4-MeO-Ph Ph pale yellow crystals 73 161～162I-7 2-Furyl Ph yellow crystals 71 191～192I-8 4-Cl-Ph 4-Me-Ph pale yellow crystals 62 150～151I-9 3-Cl-Ph 4-Me-Ph pale yellow crystals 66 140～141I-10 2-Cl-Ph 4-Me-Ph yellow crystals 58 118～119I-11 2; 4-2Cl-Ph 4-Me-Ph pale yellow crystals 75 148～149I-12 3-Br-Ph 4-Me-Ph yellow crystals 64 155～156I-13 4-MeO-Ph 4-Me-Ph yellow crystals 89 171～172I-14 2-Furyl 4-Me-Ph buff crystal 56 120～121I-15 4-Cl-Ph 4-Cl-Ph pale yellow crystals 54 188～190I-16 3-Cl-Ph 4-Cl-Ph pale yellow crystals 60 165～166I-17 2-Cl-Ph 4-Cl-Ph yellow crystals 57 181～182I-18 2; 4-2Cl-Ph 4-Cl-Ph pale yellow crystals 58 187～189I-19 3-Br-Ph 4-Cl-Ph pale yellow crystals 56 179～180I-20 4-MeO-Ph 4-Cl-Ph pale yellow crystals 84 184～185I-21 2-Furyl 4-Cl-Ph yellow crystals 52 150～151I-22 4-Cl-Ph 3-Cl-Ph pale yellow crystals 74 175～176I-23 3-Cl-Ph 3-Cl-Ph pale yellow crystals 57 145～147I-24 2-Cl-Ph 3-Cl-Ph yellow crystals 77 161～162I-25 2,4-2Cl-Ph 3-Cl-Ph yellow crystals 87 176～178I-26 3-Br-Ph 3-Cl-Ph pale yellow crystals 70 159～160I-27 4-MeO-Ph 3-Cl-Ph pale yellow crystals 86 153～154I-28 2-Furyl 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).Wherein best with Compound I-18 and I-19 effect.
Embodiment 6
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 250ppm, relative inhibition %No.
I-1 63 100 63 100 15 56I-2 6 42 75 100 69 6I-3 19 100 33 60 15 39I-4 6 42 29 47 8 28I-5 25 37 54 40 0 56I-6 56 11 100 100 69 56I-7 56 58 63 53 54 50I-8 31 21 100 53 54 44I-9 6 5 54 73 46 0I-10 13 63 50 53 31 22I-11 44 26 79 80 31 39I-12 31 100 83 27 46 72I-13 100 58 75 100 38 61I-14 6 32 8 0 0 28I-15 13 63 50 20 23 28I-16 0 21 33 40 0 0I-17 44 100 71 100 38 39I-18 100 100 100 100 54 67I-19 100 100 100 100 54 67I-20 50 100 75 100 46 61I-21 100 100 71 100 31 56I-22 6 53 63 33 8 22I-23 25 68 67 20 23 39I-24 0 0 38 27 8 17I-25 50 100 75 100 46 39I-26 50 100 75 100 54 22I-27 31 74 67 100 38 17I-28 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 (4)
1, a class 2-(4-methylthiophenoxy) imidazolidinone derivative, (I) structure expressed that it is characterized in that having general formula
In the formula: Ar
1Be 2-furyl or substituted-phenyl, substituting group is 2-chlorine, 3-chlorine, 4-chlorine, 2,4-dichloro, 3-bromine, 4-methoxyl group
Ar
2Be (replacement) phenyl, substituting group is 3-chlorine, 4-chlorine, 4-methyl
2, the described preparation method with the represented derivative of general formula (I) of claim 1 is characterized in that making the represented compound of general formula (II)
(Ar in the formula
1Identical with the definition in the claim 1) elder generation and aromatic isocyanate Ar
2NCO (III) (Ar in the formula
2Identical with the definition in the claim 1), reaction obtains intermediate, reacts with 4-methylthiophenol (IV) again.
3, preparation method as claimed in claim 2 is characterized in that: make represented compound phosphine imido of equimolar general formula (II) and aromatic isocyanate Ar
2The anhydrous methylene chloride of NCO (III) is that solvent at room temperature reacted 2～8 hours, react the back recrystallization and removed by product, resulting intermediate, with the acetonitrile solvent with equimolar 4-methylthiophenol (IV) again, under catalysis of solid carbonic acid potassium and room temperature, stirring reaction 6～14 hours, the mole dosage of solid carbonic acid potassium is 5% of (II) consumption, after having reacted, slough solvent, get product (I) with methylene dichloride/sherwood oil recrystallization.
4, the described application with the represented derivative of general formula (I) of claim 1 is characterized in that the effective constituent as sterilant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021154058A CN1152019C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methyl) sulfur phenyl) imidazolinone derivant with bactericidal activity and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021154058A CN1152019C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methyl) sulfur phenyl) imidazolinone derivant with bactericidal activity and preparation method thereof |
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|---|---|---|---|
| CN 03143772 Division CN1202107C (en) | 2002-01-04 | 2002-01-04 | 2-(4-methiophnoxy)-5-furfural imidazolone derivative with bactericiding activity |
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| CN1358714A true CN1358714A (en) | 2002-07-17 |
| CN1152019C CN1152019C (en) | 2004-06-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408409A (en) * | 2011-10-11 | 2012-04-11 | 华中师范大学 | Preparation and fungicidal activity of 3-(1H-imidazole-1-yl)quinoline derivative |
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408409A (en) * | 2011-10-11 | 2012-04-11 | 华中师范大学 | Preparation and fungicidal activity of 3-(1H-imidazole-1-yl)quinoline derivative |
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