CN102584667B - Arylpyrrole compound with biological activity and preparation method thereof - Google Patents
Arylpyrrole compound with biological activity and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an arylpyrrole compound with insect and acarus killing or bacteria killing biological activity shown in the formula (I), and the preparation method and the application thereof. R is selected from the following groups: I, X refers to halogen; R4 and R5 refer to hydrogen, alkyl and haloalkyl; R6, R7 and R8 refer to hydrogen, halogen, alkyl and haloalkyl; II, Ln is selected from one or five of hydrogen, halogen, alkyl, alkoxyl, alkyl sulphanyl, alkyl sulfinyl, alky sulfonyl, haloalkyl, haloalkoxyl, haloalkyl sulphanyl, haloalkyl sulfinyl, haloalky sulfonyl, alkyl carbonyl and alkoxyl carbonyl; III, n is an integer from 1 to 5; and IV, R1, R2 and R3 are the same or different, and refer to hydrogen, halogen, cyan, nitryl and trifluoromethyl. The arylpyrrole compound with the concentration of 0.5 to 5000 mg/l, shown in the formula (I), has insect and acarus killing or bacteria killing biological activity.
Description
Technical field
The present invention relates to there is desinsection, kill mite, the aryl pyrrole compounds of antifungal bioactivity and preparation method thereof.
Background technology
A series of aryl pyrrole compounds by American Cyanamid Company's development are disclosed in Chinese patent ZL 88106516.1, wherein the bromo-2-of compound 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile (A) has excellence and the biological activity of wide spectrum, but it is very serious to phyto toxicity, can't be as plant protection product; For keeping under the bioactive prerequisite of compound, reduce its poisoning to plant, cyanamide company is by further synthetic and screening, find that again another compound has been developed to desinsection, has killed the 4-bromine 2-(4-chloro-phenyl-) of mite and nematocides-1-ethoxyl methyl-5-trifluoromethyl pyrpole-3-nitrile (B) (test code number: AC303630, logical field title: chlorfenapyr, trade name: kotetsu, eliminate).Eliminating as unique commercial aryl pyrrolines Insecticidal and acaricidal agent, is useful to some insect, evil mite, and some insect, evil mite are had to excellent preventive effect.But eliminate people and animals' toxicity highlyer, it is to female rat acute per os LD
50for 459mg/kg, mouse great and mighty or powerful is 223mg/kg, and simultaneously, it is also higher to the toxicity of fish, honeybee etc., as its LC to Japanese carp
50for 0.5mg/kg.
Heterocycle, fluorochemicals and chipal compounds are the developing direction of modern active substance, low to the person poultry toxicity for obtaining, to fish safety, still there is very satisfied desinsection, miticidal effect simultaneously, even also have the aryl-pyrrole compound of desirable sterilization effect concurrently, we introduce chiral carbon atom or haloalkene wherein, design and synthesize the bioactive aryl pyrrole compounds that has shown in the formula (I) that has no bibliographical information.Wherein part of compounds (as 01,09 etc.) demonstrates and eliminates higher biological activity the part target.
Summary of the invention
The invention provides and there is bioactive aryl pyrrole compounds and isomer thereof shown in formula (I):
Wherein:
I.R is selected from following group:
X is halogen;
R
4, R
5hydrogen, alkyl, haloalkyl;
R
6, R
7, R
8hydrogen, halogen, alkyl, haloalkyl;
II.Ln is selected from 5 of one of following group or as many as: hydrogen, halogen, alkyl, alkoxyl group, alkylthio, alkyl sulphinyl, alkyl sulphonyl, haloalkyl, halogenated alkoxy, halogenated alkylthio, the haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkyl-carbonyl, alkoxy carbonyl;
III.n is the integer of from 1 to 5;
IV.R
1, R
2and R
3identical or different, and representative: hydrogen, halogen, cyano group, nitro, trifluoromethyl;
In the definition of the compound that the above provides (I), no matter separately use or be used in compound word of term used represents following substituting group:
Halogen: refer to fluorine, chlorine, bromine;
Alkyl: the straight or branched alkyl that refers to have 1-6 carbon atom;
Haloalkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom.
Compound shown in the present invention (I), because the two keys of carbon one carbon connect different substituting groups and can form geometrical isomer (meaning different configurations with Z and E respectively), the present invention includes the mixture of Z-type isomer and E-isomer and their any ratios.
Compound of the present invention, can form steric isomer (meaning different configurations with R and S respectively) owing on carbon atom, connecting different substituting groups, the present invention includes the mixture of R type isomer and S type isomer and their any ratios.
Compound of the present invention, not only comprise geometrical isomer (Z/E formula) and steric isomer R/S formula), also relate to the mixture of geometrical isomer and steric isomer.
The aryl pyrrole compounds of general formula of the present invention (I) has broad spectrum activity: but the compound field had on the various crops of control such as the various harmful insects of mythimna separata, small cabbage moth, prodenia litura, beet armyworm, leafhopper, aphid; Some compounds can be used for preventing and treating on various crops the various mite classes such as cotton spider mites, tangerine Panonychus citri; Some compounds can be used for preventing and treating on various crops by multiple fungus-caused diseases such as Haplomycetes, Phycomycetes, Oomycete, Ascomycetes and deuteromycetes; Some compounds not only can be used for preventing and treating on various crops such as the various mite classes of cotton spider mites, tangerine Panonychus citri and/or such as the various harmful insects of mythimna separata, small cabbage moth, prodenia litura, beet armyworm, leafhopper, also can be used for preventing and treating simultaneously on various crops by multiple fungus-caused diseases such as Haplomycetes, Phycomycetes, Oomycete, Ascomycetes and deuteromycetes, and the compound had has very high biological activity and makes under very low dosage and just can obtain good effect.
Can the present invention be described with the compound of listing in following table 1.But do not limit the present invention.In the present invention the fusing point of giving all not calibrated.
Table 1
Can prepare by reaction formula 1 and the reaction formula 2 shown in following by the compound shown in formula of the present invention (I).Substituting group is wherein all limited as front except specializing, and Y is that leavings group is as halogen (chlorine, bromine).
Reaction formula 1-1:
Reaction formula 1-2:
Reaction formula 2:
Can prepare like this by the compound of formula (I): at suitable solvent as tetrahydrofuran (THF), N, in dinethylformamide, compound with suitable alkali as sodium hydride, sodium alkoxide or sodium-hydroxide treatment general formula (II), then add formula (III) or compound (IV).
Preferred solvent is tetrahydrofuran (THF) or DMF.
Preferred alkali is sodium hydroxide, salt of wormwood, and sodium hydride or sodium alkoxide be as sodium methylate, sodium ethylate.
The compound of formula (II) can, according to reaction formula 2, synthesize with reference to pertinent literature.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and the yield in embodiment is all without optimization.
Embodiment 1
The preparation method of this example explanation compound 01.
Synthesizing of 2-(4-chloro-phenyl-)-2-Padil (α-rubigan glycine): by 4-chlorobenzaldehyde (28.1g=0.20mol), bicarbonate of ammonia (39.5g=0.50mol), sodium cyanide (11.8g=0.24mol), ethanol (100ml) and water (100ml) are after 75-80 ℃ of reaction 4-5hr, drip (10%, 180g=0.45mol) aqueous solution of sodium hydroxide, and slough ethanol simultaneously, add subsequently water (50-80ml), in autoclave, at 140-150 ℃ of reaction 4-5hr.After cooling, elimination solid thing wherein, filtrate is adjusted to neutrality with 10% hydrochloric acid, filters, and drying, obtain white solid title product 28.1g, yield 75.6%, fusing point: 228-230 ℃.LC-MS(APCI，Neg)(M
+-1)(relative intensity％)：calc：184，found：184.0.
2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile synthetic: to 2-(4-chloro-phenyl-)-2-Padil (α-rubigan glycine) in acetonitrile (200ml) solution (28.1g=0.15mol), drip successively trifluoroacetic acid (20.9g=0.18mol), triethylamine (13.0g=0.13mol) and phosphorus trichloride (19.3g=0.14mol), after drip finishing, in 60-70 ℃ of reaction 5-6hr, be cooled to room temperature, drip 2-chloroacrylonitrile (7.9g=0.089mol), drip again triethylamine (4.3g=0.04mol), after drip finishing, in 75-85 ℃ of reaction 1-2hr, after cooling, in the impouring frozen water, filter, washing, dry, obtain yellow solid title product 33.6g, yield 80.7%, fusing point: 238-240 ℃.LC-MS(APCI，Neg)(M
+-1)(relative intensity％)：calc：269，found：269.0；GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：270；found：272(25)，270(100)，250(20)，215(20).
Synthesizing of the bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile: in 85-95 ℃, in Glacial acetic acid (200ml) solution of 2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile (33.6g=0.124mol) and sodium acetate (10.1g=0.124mol), drip bromine (21.8g=0.135mol), after drip finishing, react 3-4hr under reflux conditions, after cooling, in the impouring frozen water, filter, washing, drying, obtain white solid title product 32.6g, yield 75.3%, fusing point: 247-249 ℃.LC-MS(APCI，Neg)(M
+-1)(relative intensity％)：calc：347，found：350.6(18)，348.6(100)，346.6(90).
(R/S) synthetic (01 compound) of 1-(the chloro-1-methoxy ethyl of the 2-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile: to sodium hydride (60%, 1.94g=0.048mol) anhydrous tetrahydro furan (40ml) solution in, drip successively the solution and 1 formed by the bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile (14.1g=0.040mol) and anhydrous tetrahydro furan (10ml), the chloro-1-methyl ethyl ether of 2-bis-(6.15g=0.048mol), after drip finishing, back flow reaction 7-8hr.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.For carrying out column chromatography, elutriant obtains faint yellow solid title compound 7.16g, content 96.0%, yield 38.5%, fusing point: 136.5-137.7 ℃ with the mixed solution (1: 40) of ethyl acetate and sherwood oil.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：440，found：440；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：3.463(s，3H，CH
3)，3.580～3.641(q，2H，CH
2)，5.419～5.464(q，1H，CH)，7.368～7.528(m，4H，ph H).
Embodiment 2
The preparation method of this example explanation compound 02.
(R/S) synthetic (02 compound) of 1-(the chloro-1-ethoxyethyl group of the 2-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile:
To sodium hydride (60%, 0.48g=0.012mol) anhydrous tetrahydro furan (20ml) solution in, drip successively the solution that formed by the bromo-2-of 4-(4-chloro-phenyl-) prepared by embodiment 1 method of 3.5g (0.01mol)-5-trifluoromethyl pyrpole-3-nitrile and 8ml anhydrous tetrahydro furan and the chloro-1-Ethoxyethane of 1.2-bis-of 1.72g (0.012mol), after drip finishing, back flow reaction is spent the night.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.For carrying out column chromatography, elutriant obtains white solid title compound 2.2g, content 95.0%, yield 45.7%, fusing point: 167.3-169.5 ℃ with the mixed solution (1: 50) of ethyl acetate and sherwood oil.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：454；found：454；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.208～1.254(t，3H，CH
3)，3.550～3.714(m，4H，2*CH
2)，5.494～5.539(m，1H，CH)，7.380～7.520(m，4H，ph H).
Embodiment 3
The preparation method of this example explanation compound 05.
Synthetic (05 compound) of 1-(the chloro-2-allyl group of 3, the 3-bis-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile:
The solution formed to sodium ethylate (1.1g=0.016mol) and anhydrous tetrahydro furan (20ml), drip successively the solution and 1 that the bromo-2-of 4-(4-chloro-phenyl-) prepared by embodiment 1 method-5-trifluoromethyl pyrpole-3-nitrile (3.50g=0.01mol) and anhydrous tetrahydro furan (10ml) form, 1,3-tri-chloro-2-propenes (1.74g=0.012mol), after drip finishing, back flow reaction 6-7hr.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.For carrying out column chromatography, elutriant obtains yellow viscous liquid title compound 2.42g, content 91.0%, yield 48.0% with the mixed solution (1: 50) of ethyl acetate and sherwood oil.GC-MS(M
+)(EI，70eV，m/z)(relaive intensity％)calc：456；found：456；
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：4.580～4.653(q，2H，CH
2)，6.234～6.358(t，1H，CH)，7.461～7.586(m，4H，ph H).
Embodiment 4
The preparation method of this example explanation compound 06.
Synthetic (06 compound) of 1-(2-the allyl group)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile:
To 0.96g (60%, 0.024mol) in the 20ml anhydrous tetrahydrofuran solution of sodium hydride, drip successively the solution that formed by the bromo-2-of 4-(4-chloro-phenyl-) prepared by embodiment 1 method of 7.1g (0.020mol)-5-trifluoromethyl pyrpole-3-nitrile and 8ml anhydrous tetrahydro furan and the 2-allyl bromide 98 of 2.90g (0.024mol), after drip finishing, room temperature reaction 4-5hr.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.Obtain the white solid title compound of class 5.50g, content 95.0%, yield 67.0%, fusing point: 107.9-109.5 ℃ with mixed solution (1: the 30) recrystallization of ethyl acetate and sherwood oil.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：388，found：388；
1H NMR(CDCl
3/TMS，300Mδ(ppm)：4.592～4.614(d，2H，CH
2)，4.780～5.253(q，2H，CH
2)，5.734～5.858(m，1H，CH)，7.361～7.526(m，4H，ph H).
Embodiment 5
The preparation method of this example explanation compound 07.
Synthetic (07 compound) of 1-(2-methyl-2-allyl group)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile:
To 0.48g (60%, 0.012mol) in the 20ml anhydrous tetrahydrofuran solution of sodium hydride, drip successively the 2-methyl of the solution that formed by the bromo-2-of 4-(4-chloro-phenyl-) prepared by embodiment 1 method of 3.5g (0.01mol)-5-trifluoromethyl pyrpole-3-nitrile and 8ml anhydrous tetrahydro furan and 1.08g (0.012mol)-3-chloro-2-propene, after drip finishing, temperature rising reflux reaction 8-9hr.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.For carrying out column chromatography, elutriant obtains the white solid title compound of class 1.80g, content 95.0%, yield 42.3%, fusing point: 133.5-135.0 ℃ with the mixed solution (1: 40) of ethyl acetate and sherwood oil.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：402；found：402；
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：1.642(s，3H，CH
3)，4.449(s，2H，CH
2)，4.301～4.303(d，1H，CH
2)，4.953～4.967(q，1H，CH)，7.266～7.511(m，4H，ph H).
Embodiment 6
The preparation method of this example explanation compound 08.
(E) synthetic (08 compound) of 1-(the chloro-2-allyl group of the 3-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile:
To sodium hydride (60%, 0.48g=0.012mol) anhydrous tetrahydro furan (20ml) solution in, drip successively the solution that formed by the bromo-2-of 4-(4-chloro-phenyl-) prepared by embodiment 1 method of 3.5g (0.01mol)-5-trifluoromethyl pyrpole-3-nitrile and 8ml In-particular water tetrahydrofuran (THF) and (E) 1 of 1.33g (0.012mol), 3-bis-chloro-2-propenes, after drip finishing, back flow reaction is spent the night.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.For carrying out column chromatography, elutriant obtains white solid title compound 2.45g, content 97.0%, yield 56.0%, fusing point: 127.7-130.1 ℃ with the mixed solution (1: 60) of ethyl acetate and sherwood oil.LC-MS(APCI，Neg)(M
+-1)(relative intensity％)：calc：421，found：421；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：4.787～4.810(m，2H，CH
2)，5.781～5.832(m，1H，CH)，6.153～6.190(m，1H，CH)，7.336～7.565(m，4H，phH).
Embodiment 7
The preparation method of this example explanation compound 09.
(Z) synthetic (09 compound) of 1-(the chloro-2-allyl group of the 3-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile:
To sodium hydride (60%, 0.48g=0.012mol) anhydrous tetrahydro furan (20ml) solution in, drip successively the solution that formed by the bromo-2-of 4-(4-chloro-phenyl-) prepared by embodiment 1 method of 3.5g (0.01mol)-5-trifluoromethyl pyrpole-3-nitrile and 8ml anhydrous tetrahydro furan and (Z) 1 of 1.32g (0.012mol), 3-bis-chloro-2-propenes, after drip finishing, back flow reaction is spent the night.After cooling, by reaction mixture impouring frozen water, be extracted with ethyl acetate 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2sO
4drying, concentrated, obtain thick product.For carrying out column chromatography, elutriant obtains pale solid title compound 2.15g, content 97.0%, yield 49.1%, fusing point: 98.7-101.2 ℃ with the mixed solution (1: 50) of ethyl acetate and sherwood oil.LC-MS(APCI，Neg)(M
+-1)(relative intensity％)：calc：421，found：421；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：4.785～4.809(qq，2H，CH
2)，5.759～5.824(m，1H，CH)，6.151～6.190(tt，1H，CH)，7.262～7.544(m，4H，ph H).
Embodiment 8
Prepare suspension agent: first the wetting dispersing agent of 2-6% is diluted in the frostproofer of 4-10%, and slowly add a certain amount of water in this solution, then under the high speed shear cutter stirs, formula provided by the invention (I) active compound that adds successively 5-80%, the 0.01-0.05% sanitas, 0.01-0.05% defoamer and thickening material etc.Milled in last impouring sand mill, then add solvent to volume.Be diluted with water to required any concentration during use.
Embodiment 9
Prepare emulsifiable concentrates: first the water of certain proportioning, tensio-active agent, antifreezing agent, defoamer, thickening material and sanitas are mixed and form the homogeneous water, then formula provided by the invention (I) compound, suitable solvent and emulsifying agent, co-emulsifier are mixed and make it become even oil phase.Finally under high-speed stirring by the even oil phase emulsifiable concentrates that can be made into mixed with water.Be diluted with water to required any concentration during use.
Embodiment 10
Prepare wettable powder: first the water of certain proportioning, tensio-active agent, antifreezing agent, defoamer, thickening material and sanitas are mixed and form the homogeneous water, then formula provided by the invention (I) compound, suitable solvent and emulsifying agent, co-emulsifier are mixed and make it become even oil phase.Finally under high-speed stirring by the even oil phase emulsifiable concentrates that can be made into mixed with water.Be diluted with water to required any concentration during use.
Embodiment 11
The preparation of 1-(the chloro-1-methoxy ethyl of the 2-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile (in table 1 01) oil slick
Take formula provided by the invention (I) compound: the 1-(the chloro-1-methoxy ethyl of 2-) of (by required the weight percent)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile (01) in right amount, appropriate solubility promoter, appropriate agricultural chemicals used additives and solvent etc. are put into reactor, first add a certain amount of solvent and defoamer to stir 10～30min, add again appropriate stablizer, synergistic agent, the components such as penetration agent, continue to stir 10～30min, regulate pH value, again the solvent of significant quantity is dropped in still, the rear blowing that stirs obtains 1-(the chloro-1-methoxy ethyl of the 2-)-bromo-2-of 4-(4-chloro-phenyl-)-required weight percent missible oil of 5-trifluoromethyl pyrpole-3-nitrile.
The synthesized compound has been carried out desinsection, killed mite, and the fungicidal activity test, now list part of test results.
The evaluated biological activity of 12 pairs of mythimna separatas of embodiment (Mythimna separata)
the Potter spray method: take the appropriate bioactive aryl pyrrole compounds that has provided by the invention, dissolve with DMF, then add a small amount of tween 80 emulsifying agent, stir, add quantitative clear water, be mixed with desired concn, establish clear water for contrast.Get fresh and tender leaf of Semen Maydis and be cut into the basically identical fragment of size, put into the culture dish (Φ 90mm) that is lined with in advance filter paper.Then access 10 of mythimna separata 3 instar larvaes in ware, be put under the Potter spray tower and quantitatively spray, spraying liquid amount 1ml, every concentration repeats for 3 times.Be disposed, cover the ware lid, be placed in the recovery indoor cultivation, routine observation, after 72 hours, record of search examination worm death condition, calculate mortality ratio (%), results averaged.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%-90% is the A level, and mortality ratio 90%-70% is the B level, and mortality ratio 70%-50% is the C level, and mortality ratio 0%-50% is the D level.With the similar unique commodity sterilant shown in formula (B), eliminate as standard control simultaneously.Partial test the results are shown in Table 2 to table 4.
Table 2 part of compounds is the activity to mythimna separata in 1000mg/L concentration
| Compound | 01 | 02 | 05 | 06 | 07 | 08 | 09 | Eliminate |
| Mortality ratio (%) | 100 | 100 | 100 | 100 | 35 | 100 | 100 | 100 |
| Active rank | A | A | A | A | D | A | A | A |
The further the selection result (pickling process 72h mortality ratio (%)) of table 3 part of compounds to mythimna separata
| Compound | 0.5mg/L | 0.25mg/L | 0.125mg/L | 0.0625mg/L |
| 01 | 100 | 93.3 | 6 | 0 |
| 08 | 90 | 30 | 0 | 0 |
| Eliminate | 100 | 93.3 | 10 | 0 |
The further the selection result (pickling process 72h mortality ratio (%)) of table 4 part of compounds to mythimna separata
| Compound | 1.0mg/L | 0.8mg/L | 0.6mg/L | 0.4mg/L | 0.2mg/L |
| 01 | 100 | 100 | 93 | 62 | 3 |
| 02 | 100 | 94 | 55 | 40 | 0 |
| Eliminate | 100 | 100 | 56 | 36 | 3 |
The Insecticidal Activity of 13 pairs of bean aphids of embodiment (Aphis fabae)
Method is as follows: medicament is prepared with embodiment 12, bean aphid is connected on just unearthed bean seedlings, every strain connects more than 20, then bean seedlings are dipped in the aryl pyrrole compounds liquid of different concns provided by the invention together with the examination worm, take out after 5 seconds, suck unnecessary liquid, insert in the sponge of water suction, cover with glass-tube, check survival and dead borer population after 24 hours.Repeat results averaged 3 times.Active blank relatively, in per-cent, is divided into A, B, C, D level Four, and grade scale is with embodiment 12, and partial results is in Table 5.
Table 5 part of compounds is the activity (mortality ratio (%)) to bean aphid in 500mg/L concentration
| Compound | 01 | 02 | 05 | 06 | 07 | 08 | 09 |
| 500mg/L | 100 | 96 | 82 | 100 | 99 | 90 | 86 |
| 100mg/L | 95 | 81 | / | 54 | 38 | / | / |
| 25mg/L | 90 | 63 | / | 44 | 32 | / | / |
| 6.25mg/L | 38 | 50 | / | 19 | 16 | / | / |
*/no test
The acaricidal activity evaluation of 14 pairs of two-spotted spider mites of embodiment (Tetranychus urticae)
Method is as follows: medicament is prepared with embodiment 12, the bean seedlings inoculation red spider that selection is grown fine, after red spider grows surely, by cutting with the mite bean seedlings in the compound liquid provided by the invention prepared, flood 10 seconds, taking-up sucks unnecessary liquid with filter paper, inserts in the beaker that is filled with water, in observing indoor cultivation, check survival and dead mite number after 48 hours, 100-200 mite arranged on every strain bean seedlings.Experiment repeats 3 times.Results averaged.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and grade scale is with embodiment 10, and partial results is in Table 6.
Table 6 part of compounds is the activity to two-spotted spider mite in 500mg/L concentration
| Compound | 01 | 06 | 07 | 09 |
| Mortality ratio (%) | 100 | 79 | 58 | 43 |
| Active rank | A | B | C | D |
The Insecticidal Activity of 15 pairs of planthoppers of embodiment
Method is as follows: medicament is prepared with embodiment 12, adopts to soak plant and connect the worm method and choose two leaf one core rice seedlings, and soaked for 10 seconds in for reagent liquid after, taking-up is dried, and is put in glass test tube (Φ 30 * 250mm), and every pipe 15 strain rice seedlings, repeat for 3 times.Then access 15 of planthopper nymphs in 3～4 age in pipe, the mouth of pipe is tightened with white gauze.Be disposed, be placed in observation ward, check and record death condition after 72 hours, calculate mortality ratio (%), according to probability value analytical method, obtain toxicity regression formula, relation conefficient (r) and median lethal concentration(LC&-{50}) (LC
50), partial results is in Table 7.
The comprehensive toxicity test result (72h) of table 7 part of compounds to planthopper
| Compound | Regression equation (Y=a+bx) | Relation conefficient (r) | LC 50(mg/L) |
| 01 | Y＝-0.2963+3.5294x | 0.9867 | 31.67 |
The fungicidal activity of 16 pairs of Rhizoctonia solani Kuhns of embodiment (Rhizoctonia solani)
Method following (Broad Bean Leaves method): (1) Rhizoctonia solani Kuhn (Rhizoctonia solani) bacterial classification is kept in refrigerator (4-8 ℃), within 2-3 days, from test tube slant, be inoculated in culture dish before test, cultivate for experimental plot under optimal temperature.(2) take appropriate compound provided by the invention, dissolve with DMF, then be diluted with water to desired concn 500mg/L.(3) blade of clip broad bean susceptible variety; put in culture dish; with atomizer by the 500mg/L compound liquid medicine jet wet leaves sheet back side; after natural air drying; with inoculator, by diameter, be that 6.5mm bacterium cake has the one side of mycelia to be inoculated in processing blade central authorities; the protectiveness test is inoculation in 24 hours after chemicals treatment, and inoculation is placed in growth cabinet, under the condition of 26～28 ℃ of temperature, relative humidity 80%～90%, cultivates.Depending on the blank incidence, calculate prevention effect.(4) part of compounds shows obvious fungicidal activity, as compound 09 preventive effect to Rhizoctonia solani Kuhn under 500mg/L concentration reaches 50%, and Rhizoctonia solani Kuhn is not demonstrated to obvious preventive effect except being all under same concentration shown in formula (B).
The fungicidal activity of 17 pairs of wheat powdery mildews of embodiment (Blumeria graminis)
Method following (pot-culture method): (1) wheat powdery mildew (Blumeria graminis) is preserved spore with stem and leaf of Wheat and is for experiment.(2) take appropriate compound provided by the invention, dissolve with DMF, then be diluted with water to desired concn 500mg/L.(3) select the field seedling to grow to the susceptible variety stem and leaf of Wheat of 2 leaves～3 leaf phases; with spray method by 500mg/L compound medicine liquid spray on stem and leaf of Wheat; naturally dry; the fresh spore of Powdery Mildew that the morbidity wheat leaf blade was produced in upper 24 hour is evenly shaken off to be inoculated on stem and leaf of Wheat; every processing is no less than 3 basins; every basin 10 strains, the protectiveness test is inoculation in 24 hours after chemicals treatment, then puts under suitable condition and cultivates.According to blank incidence classification investigation, calculate prevention effect.(4) part of compounds shows obvious fungicidal activity, as compound 09 preventive effect to wheat powdery mildew under 500mg/L concentration reaches 50%, and wheat powdery mildew is not had to obvious preventive effect except being all under 500mg/L concentration shown in formula (B).
The fungicidal activity of 18 pairs of botrytis cinerea pers of embodiment (Botrytis cinerea)
Method following (toxic medium therapy): (1) botrytis cinerea pers (Botrytis cinerea) bacterial classification is kept in refrigerator (4-8 ℃), within 2-3 days, from test tube slant, be inoculated in culture dish before test, cultivate for experimental plot under optimal temperature.(2) take appropriate compound provided by the invention, dissolve with DMF, then be diluted with water to desired concn 500mg/L.Get 500mg/L liquid 2mL, add in the potato agar substratum (PDA) of the 38mL that is cooled to 45 ℃, the pastille culture medium flat plate that to be mixed with concentration be 25mg/L.(3) get 6.5mm diameter mycelia piece from cultured test germ colony edge, move on the pastille substratum, every processing repeats for 4 times.Be disposed, the constant temperature biochemical cultivation case that is placed in 28 ℃ is cultivated, and after 4 days, measures colony diameter, calculates growth inhibition ratio.(4) part of compounds shows obvious fungicidal activity, as compound 02 growth inhibition ratio to botrytis cinerea pers under 25mg/L concentration reaches 50%, compound 09 growth inhibition ratio to botrytis cinerea pers under 25mg/L concentration reaches 36%, and not obvious except being all under 25mg/L concentration the growth-inhibiting to botrytis cinerea pers shown in formula (B).
Claims (3)
1. aryl pyrrole compounds is characterized in that described aryl pyrrole compounds is:
(R/S) 1-(the chloro-1-methoxy ethyl of the 2-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile;
(R/S) 1-(the chloro-1-ethoxyethyl group of the 2-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile;
(Z) 1-(the chloro-2-allyl group of the 3-)-bromo-2-of 4-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile.
2. the preparation method of aryl pyrrole compounds according to claim 1, it is characterized in that at solvents tetrahydrofurane or N, in dinethylformamide, compound by alkali sodium hydride, sodium alkoxide or sodium-hydroxide treatment formula (II), then the compound that adds formula (III) or formula (IV), obtain general formula (I-a) or compound (I-b), as reaction formula 1-1 or reaction formula 1-2:
Reaction formula 1-1:
Reaction formula 1-2:
In formula, Ln is 4-chlorine, R
1cyano group, R
2bromine, R
3trifluoromethyl, R
4methyl or ethyl, R
5hydrogen, R
6chlorine, R
7, R
8be that hydrogen, X are chlorine, Y is the leavings group chlorine or bromine.
3. aryl pyrrole compounds according to claim 1 has the purposes in the medicine of prevention effect to harmful insect, evil mite or germ in preparation.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039807A (en) * | 1987-07-29 | 1990-02-21 | 美国氰胺公司 | Desinsection, kill mite, nematocides aryl-pyrrolidine and preparation method thereof |
| EP0426948A1 (en) * | 1989-08-11 | 1991-05-15 | American Cyanamid Company | Arylpyrrole insecticidal acaricidal and nematicidal agents and methods |
| CN1119184A (en) * | 1990-07-31 | 1996-03-27 | 美国氰胺公司 | Process for the preparation of insecticidal acaricidal and nematicidal 2-aryl-5-(triflumethyl) pyprole compounds |
| CN1224577A (en) * | 1997-08-08 | 1999-08-04 | 美国氰胺公司 | Arylpyrroles for protection of wood, wood products and wooden structures from insect attack |
| CN1670016A (en) * | 2005-04-05 | 2005-09-21 | 湖南化工研究院 | Aryl pyrrole compounds with insecticidal, miticidal and fungicidal bioactivities and process for preparing same |
| CN101348454A (en) * | 2007-07-17 | 2009-01-21 | 南开大学 | N-alkyloxyacyl substituted aryl pyrrole derivatives, preparation and use thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039807A (en) * | 1987-07-29 | 1990-02-21 | 美国氰胺公司 | Desinsection, kill mite, nematocides aryl-pyrrolidine and preparation method thereof |
| EP0426948A1 (en) * | 1989-08-11 | 1991-05-15 | American Cyanamid Company | Arylpyrrole insecticidal acaricidal and nematicidal agents and methods |
| CN1119184A (en) * | 1990-07-31 | 1996-03-27 | 美国氰胺公司 | Process for the preparation of insecticidal acaricidal and nematicidal 2-aryl-5-(triflumethyl) pyprole compounds |
| CN1224577A (en) * | 1997-08-08 | 1999-08-04 | 美国氰胺公司 | Arylpyrroles for protection of wood, wood products and wooden structures from insect attack |
| CN1670016A (en) * | 2005-04-05 | 2005-09-21 | 湖南化工研究院 | Aryl pyrrole compounds with insecticidal, miticidal and fungicidal bioactivities and process for preparing same |
| CN101348454A (en) * | 2007-07-17 | 2009-01-21 | 南开大学 | N-alkyloxyacyl substituted aryl pyrrole derivatives, preparation and use thereof |
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