CN100503563C - Arylpyrrole N-oxalate derivatives, and their preparation and use as pesticide - Google Patents
Arylpyrrole N-oxalate derivatives, and their preparation and use as pesticide Download PDFInfo
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- CN100503563C CN100503563C CNB2005100143858A CN200510014385A CN100503563C CN 100503563 C CN100503563 C CN 100503563C CN B2005100143858 A CNB2005100143858 A CN B2005100143858A CN 200510014385 A CN200510014385 A CN 200510014385A CN 100503563 C CN100503563 C CN 100503563C
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Abstract
This invention relates to the method for synthesizing the derivates of pyrrole-aryl N- oxalic ester and its application. Its structure shows as formula (I) (see the specification of each group in the directions). The described compound has a favorable insecticidal activity widely used in pest control for the crops. The insecticide has a broad prospect.
Description
Technical field
The present invention relates to as sterilant, particularly aryl-pyrrolidine N-oxalic acid ester derivative and preparation and application.
Background technology
1987 American Cyanamid Company (CR2anamid) the researchist from the meta-bolites of microorganism streptomycete (StreptomR2cesfumanus), isolate dioxapR2rrolomR2cin, and find that it has the desinsection of medium tenacity, acaricidal activity.Subsequently, American Cyanamid Company has developed the brand-new insecticidal/acaricidal agent 2-aryl pyrrolines pesticide bromine worm cyanogen (chlorfenapR2r) of structure by the further investigation to this natural antibiotics.Addor?R.R3.；Babcock?T.J.；Black?B.C.et?al.SR2nthesis?and?ChemistrR2?of?Agrochemincals?III，ACS?SR2mp.504，pp283-297.(1992)；
Companies of American Cyanamid Company (CR2anamid) in 1992 have synthesized the N-substituted azole derivatives of aminoalkyl group carboxylicesters structure, and as Ia and Ib, 10mg/L is 100% to the lethality rate of southern mythimna separata.Kuhn?D.G.；Donovan?S.F.；Furch?J.A.US5,286,743(1992)。
Company of American Cyanamid Company (CR2anamid) had synthesized N-cycloalkyl carboxylicesters pyrrole derivative II in 1992, as IIa and IIb, 10mg/L to southern mythimna separata, corn is chrysomelid and cigarette aphid pretty young woman at night, 100mg/L is 100% to the lethality rate of the tetranychid of organophosphorus resistant strain.Kuhn?D.G.；Donovan?S.F.；Furch?J.A.US?5,232,980(1992)。
Company of American Cyanamid Company (CR2anamid) had synthesized III in 1993, as IIIa and IIIb to the adult of the tetranychid of western potato leaf hopper and organophosphorus resistant strain and the superior activity of ovum, 100mg/L lethality rate 100%.Kuhn?D.G.；KamesR3aran?V.US?5,302,383(1993)。
BaR2er companies in 1993 have reported the aryl-pyrrolidine derivative that the N-carbamate replaces, and at 100mg/L the lethality rate of the tetranychid of organophosphorus resistant strain are 98% as IVa and IVb, are higher than bromine worm cyanogen (lethality rate is 80%).Uhr?H.；Erdelen?C.；R3achendorff-Neumann?U.，Stendel?R3.US?5521211(1993)。
Summary of the invention
The purpose of this invention is to provide a kind of aryl-pyrrolidine N-oxalic acid ester derivative and preparation and application, this compounds has excellent insecticidal activity.
The present invention is that chemical general formula is the aryl-pyrrolidine N-oxalic acid ester derivative of (I):
In the formula, R
1Represent hydrogen, Cl, Br or CF
3R
2Represent Cl, Br, CF
3, CN or NO
2R
3Represent CN, NO
2Or S (O
2) CF
3R
4Represent hydrogen, Cl, Br or CF
3Y represents O, S or N; R represents 1-6 carbon alkoxyl groups; 1-6 halocarbons are for alkoxyl group; 1-6 carbon alkoxyalkoxy groups; 3-6 carbene oxygen bases; 3-6 halo carbene oxygen bases; 3-6 carbon alkynyloxy groups; 3-7 carbocyclic ring alkoxyl groups; 3-6 carbon cyanogen are for alkoxyl group; phenoxy group; benzyloxy; hydroxyl; 1-4 carbon alkoxyalkyls; 1-4 carbon alkyl; phenyl; naphthyloxy or phenyl ring are replaced by one or more following radicals: halogen; 1-4 carbon alkyl; 1-4 carbon alkoxyl groups; 1-4 halocarbon substituted alkyls; 1-4 halocarbons are for alkoxyl group; 1-4 carbon alkoxyalkyls; 1-4 carbon alkylthios; 1-4 carbon alkyl sulphinyls; 1-4 carbon alkyl sulphonyls; nitro; cyano group; hydroxyl; carboxyl; 1-4 carbon burn basic carbonyl; 1-4 carbon alkoxy carbonyl or imido grpups.
General formula goes out excellent especially insecticidal activity for the compound exhibits of (Ia), and R represents 1-6 carbon alkoxyl groups in the formula; 1-6 halocarbons are for alkoxyl group; 1-6 carbon alkoxyalkoxy groups; 3-6 carbene oxygen bases; 3-6 halo carbene oxygen bases; 3-6 carbon alkynyloxy groups; 3-7 carbocyclic ring alkoxyl groups; 3-6 carbon cyanogen are for alkoxyl group; phenoxy group; benzyloxy; hydroxyl; 1-4 carbon alkoxyalkyls; 1-4 carbon alkyl; phenyl; naphthyloxy or phenyl ring are replaced by one or more following radicals: halogen; 1-4 carbon alkyl; 1-4 carbon alkoxyl groups; 1-4 halocarbon substituted alkyls; 1-4 halocarbons are for alkoxyl group; 1-4 carbon alkoxyalkyls; 1-4 carbon alkylthios; 1-4 carbon alkyl sulphinyls; 1-4 carbon alkyl sulphonyls; nitro; cyano group; hydroxyl; carboxyl; 1-4 carbon alkyl-carbonyls; 1-4 carbon alkoxy carbonyl or imido grpups.
The compound of general formula of the present invention (I) can be as follows a preparation: with compd A and B in organic solvent, make acid binding agent (mol ratio of compd A and compd B and acid binding agent is 1:1:1-2) with mineral alkali or organic bases,-10-80 ℃ were reacted 2-12 hours down, tell organic phase, organic solvent, recycle silicon glue chromatographic column purifying are sloughed in decompression.Organic solvent is toluene, benzene, hexanaphthene, acetonitrile, acetone, tetrahydrofuran (THF), ether, dioxane, DMF (, dimethyl formamide) or DMSO (dimethyl sulfoxide (DMSO)); Mineral alkali is NaOH, KOH, Na
2CO
3, K
2CO
3, NaHCO
3, KHCO
3Organic bases is pyridine, triethylamine or 4-N, the N dimethylamine yl pyridines.
Method one:
X is Cl or Br.
With compd A and oxalic acid in organic solvent, make acid binding agent (mol ratio of compd A and oxalic acid and acid binding agent is 1:1:1-2) with mineral alkali or organic bases,-10-80 ℃ were reacted 2-12 hours down, tell organic phase, decompression is sloughed organic solvent and is obtained Compound C, Compound C is with oxidation sulfoxide or oxalyl chloride or phosgene chloride, obtains Compound I with alcohol or phenol or oxime reaction again.Organic solvent is toluene, benzene, hexanaphthene, acetonitrile, acetone, tetrahydrofuran (THF), ether, dioxane, DMF or DMSO (dimethyl sulfoxide (DMSO)); Mineral alkali is NaOH, KOH, Na
2CO
3, K
2CO
3, NaHCO
3, KHCO
3Organic bases is pyridine, triethylamine or 4-N, the N dimethylamine yl pyridines.
Method two:
X is Cl or Br.
The compound of general formula of the present invention (Ia) can prepare as follows: 2-(4-chloro-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (D) and equimolar acetate kharophen methylene radical ester are dissolved in the tetrahydrofuran (THF), in the presence of 1-1.5 moles sodium hydride, behind the back flow reaction 8h, cooling, filter, filtrate concentrates, residuum is through the silica gel chromatographic column column chromatography that reduces pressure, get 1-kharophen methylene radical-2-(4-chloro-the phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (E) of white crystal, after three oxyhalogen phosphorus of compd E and 1-1.5 moles are mixed, be warming up to backflow, behind the back flow reaction 1h, cooling, reaction mixture is poured in the frozen water, ethyl acetate extraction, organic layer washes with water successively, the saturated salt washing, anhydrous sodium sulfate drying, filter back decompression precipitation, the gained solid obtains compound F 17-hydroxy-corticosterone through ethyl acetate and sherwood oil mixed solvent recrystallization.With compound F 17-hydroxy-corticosterone and G in organic solvent, make acid binding agent (mol ratio of compound F 17-hydroxy-corticosterone and compound G and acid binding agent is 1:1:1-2) with mineral alkali or organic bases ,-10-80 ℃ were reacted 2-12 hours down, tell organic phase, organic solvent, recycle silicon glue chromatographic column purifying are sloughed in decompression.Organic solvent is toluene, benzene, hexanaphthene, acetonitrile, acetone, tetrahydrofuran (THF), ether, dioxane, DMF or DMSO; Mineral alkali is NaOH, KOH, Na
2CO
3, K
2CO
3, NaHCO
3, KHCO
3Organic bases is pyridine, triethylamine or 4-N, the N dimethylamine yl pyridines.
X＝Cl，Br。
Compound D can be commercially available or with (referring to the US5777132) of currently known methods preparation.
The present invention goes back the compound of listing in the free list 1 and illustrates, but does not limit the present invention.
The compound of general formula of the present invention (I) has excellent, can be used to prevent and treat the lepidopteran class, stick up wing order class, Heteroptera class, Diptera class, Orthoptera class and Homoptera class pest.
The insecticidal activity of the insecticidal activity of the part of compounds of general formula of the present invention (I) and commercialization kind bromine worm cyanogen is suitable.
The compound of general formula of the present invention (I) can directly use, and can add that also the carrier that agricultural go up to be accepted uses, also can with other sterilants and (or) the composite use of miticide.
Embodiment
Further specify the present invention below in conjunction with embodiment:
Embodiment 1:
Acetate kharophen methylene radical ester
9.0g (0.1mol) N-hydroxy methylene-ethanamide is dissolved in 25g (0.25mol) aceticanhydride, drips 10 pyridines, stirred overnight at room temperature, concentrating under reduced pressure adds the underpressure distillation of 50mL toluene remaining aceticanhydride is all taken out of, cool off white solid 13.0g, Yield:99.2%, mp:32-35 ℃.
1H NMR: δ: 2.04 (s, 3H, CH3); 2.08 (s.3H.CH3); 5.23 (d, 2H, J=7.5HR1, CH2); 6.95 (s, 1H, br, NH) .Anal.Calcd. (%) for C
5H
9NO
3: C:45.80; H:6.92; N:10.68.found (%): C:45.70; H:6.92; N:10.57.
Embodiment 2:
1-kharophen methylene radical-2-(4-chloro-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (E)
17.5g (0.05mol) 2-(4-chloro-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (D) is dissolved in 50mL in sodium Metal 99.5 dewaters the exsiccant tetrahydrofuran (THF), add 4.32g (50%, 0.09mol) hydrogenation receive, be warming up to backflow, behind the back flow reaction 30min, be cooled to room temperature, add 9.65g (0.074mol) acetate kharophen methylene radical ester, be warming up to backflow, TLC follows the tracks of reaction, behind the backflow 8h, cooling is filtered, and filtrate concentrates, residuum is through the silica gel chromatographic column column chromatography that reduces pressure, elutriant is ethyl acetate and sherwood oil mixed solvent, gets white crystal 8.0g, reclaims raw material 2.58g, Yield:44.7%, mp:149-151 ℃.
1Anal.Calcd. (%) for C
15H
10BrClF
3N
3O:C:42.83; H:2.40; N:9.99.found (%): C:42.86; H:2.41; N:9.82.
Embodiment 3:
1-halogen methylene radical-2-(4-chloro-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (F)
After the three oxyhalogen phosphorus of 1-kharophen methylene radical-2-(4-chloro-the phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (E) of 2.9mmol and 8.2mmol are mixed, be warming up to backflow, behind the back flow reaction 1h, cooling is poured reaction mixture in the frozen water into, ethyl acetate extraction, organic layer washes with water successively, saturated salt washing, anhydrous sodium sulfate drying, filter back decompression precipitation, the gained solid is through ethyl acetate and sherwood oil mixed solvent recrystallization.
F
a：X＝Cl，Yield：60.1％，mp：131-133℃.
1H?NMR：δ：5.60(s，2H，CH2)；7.56(dd，J＝9HR1，Ph).Anal.Calcd.(％)for?C
13H
6BrCl
2F
3N
2：C：39.23；H：1.52；N：7.04.found(％)：C：39.04；H：1.80；N：7.21.F
b：X＝Br，Yield：80.2％，mp：136-138℃.
1H?NMR：δ：5.61(s，2H，CH
2)；7.57(dd，J＝9HR1，Ph).Anal.Calcd.(％)for?C
13H
6Br
2ClF
3N
2：C：35.29；H：1.37；N：6.33.found(％)：C：35.32；H：1.54；N：6.57.
Embodiment 4:
Uncle's fourth oxygen oxalic acid potassium salt
To dropwise be added drop-wise under 16.0g (0.5mol) the methyl alcohol room temperature in the new distillatory oxalyl chloride of 61.25g (0.5mol), stirring at room 2h, reaction finishes, and 119-125 ℃ cut is collected in air distillation, gets colourless liquid Dikalii Clorazepas ester 122.15g, Yield:36.2%.
4.74g (64.05mmol) trimethyl carbinol is dissolved in the 100mL anhydrous diethyl ether, add 5.06g (64.05mmol) pyridine, 5.0g (40.8mmol) Dikalii Clorazepas ester dropwise is added drop-wise in the above-mentioned solution, behind the stirring at room 1h, water, saturated sodium bicarbonate and water washing successively, anhydrous sodium sulfate drying gets colourless oil liquid methoxy oxalic acid tert-butyl ester 3.36g, Yield:51.4%. behind the decompression precipitation
1H NMR: δ: 1.56 (s, 9H, C (CH
3)
3); 3.87 (s, 3H, CH
3)
3.22g (20.1mmol) the methoxy oxalic acid tert-butyl ester is dissolved in 10mL acetonitrile and the 10mL water, with 1.373g (82%, 20.1mmol) potassium hydroxide is ground into powder, add in the above-mentioned solution, stir 2h under the room temperature, dissolve fully to potassium hydroxide, the vacuum precipitation gets clear crystal uncle fourth oxygen oxalic acid potassium salt 3.18g, Yield:86.0%.
1H NMR: δ (D
2O): 1.41 (9H, C (CH
3)
3).
Embodiment 5:
Alcoxyl oxalic acid
Under the ice bath cooling, 5mL water slowly is added drop-wise in the 7mmol chlorine oxalic acid alkyl ester, drip and finish, with dilute hydrochloric acid reaction solution is transferred to PH=2, extracted with diethyl ether, anhydrous sodium sulfate drying gets oily liquids behind the decompression precipitation.
G1：R＝CH
3，Yield：77.9％.
1H?NMR：δ：3.96(s，3H，CH
3)；9.17(s，1H，COOH).
G2：R＝C
2H
5，Yield：75.8％.
1H?NMR：δ：1.40(t，3H，J＝7.5HR1，CH
3)；4.40(q，2H，J＝7.5HR1，CH
2)；9.03(s，1H，COOH).
G3：R＝n-C
4H
9.Yield：77.0％.
1H?NMR：δ：0.96(t，3H，J＝7.5HR1，CH
3)；1.37～1.50(m，2H，CH
2CH
3)；1.70～1.80(m，2H，OCH
2CH
2)；4.35(t，3H，J＝7.5HR1，OCH
2)；9.52(s，1H，COOH).
Embodiment 6:
Target compound I's is synthetic:
1-bromine methylene radical-2-(4-oxygen-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (Fb) of 0.227mmol is dissolved in the 3mL toluene, the aqueous sodium hydroxide solution (1mL water), the alcoxyl oxalic acid of 0.681mmol and the tetra-n-butyl ammonium bromide of catalytic amount that add 0.681mmol, stirred overnight at room temperature, reaction finishes, add 15mL ethyl acetate dilute reaction solution, washing, anhydrous sodium sulfate drying spends the night, filter, the filtrate decompression precipitation, the gained solid gets white solid through sherwood oil and ether mixed solvent recrystallization.
Embodiment 7:
Target compound I's is synthetic:
1-chlorine methylene radical-2-(4-chloro-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles (F with 0.227mmol
a) be dissolved in the 3mL toluene, drip the aqueous solution (1mL water) of the alcoxyl oxalic acid potassium salt of 0.678mmol under the room temperature, add the tetra-n-butyl ammonium bromide of catalytic amount, stirring at room 8h, TLC follows the tracks of reaction, reaction finishes, and adds 15mL ethyl acetate dilute reaction solution, washing, anhydrous sodium sulfate drying spends the night, filter, the filtrate decompression precipitation, the gained solid gets white solid through sherwood oil and ether mixed solvent recrystallization.
Equally, can synthesize other compound of the present invention.See Table 1:
The present invention has carried out the mensuration of insecticidal activity, and the mensuration program is as follows:
For the examination insect is southern mythimna separata [MR2thimna (=Pseudaletia) separata (R3alker), the normal population that indoor leaf of Semen Maydis is raised.Mythimna separata is adopted leaf dipping method, and sample is mixed with the solution of different concns with acetone, and dipping leaf of Semen Maydis in seedling stage is put into the 7cm culture dish after drying, insert 4 instar larvaes, repeats 2-4 times.Contrast acetone soln soaking maize leaf breeding grub.
Table 1 is the test result of part of compounds:
Claims (7)
1, a kind of aryl-pyrrolidine N-oxalic acid ester derivative is characterized in that it has structure shown in the following general formula (I):
In the formula, R
1Represent hydrogen, Cl, Br or CF
3R
2Represent Cl, Br, CF
3, CN or NO
2R
3Represent CN, NO
2Or S (O
2) CF
3R
4Represent hydrogen, Cl, Br or CF
3Y represents O or S; R represents 1-6 carbon alkoxyl groups; 1-6 halocarbons are for alkoxyl group; 3-6 carbene oxygen bases; 3-6 halo carbene oxygen bases; 3-6 carbon alkynyloxy groups; 3-7 carbocyclic ring alkoxyl groups; 3-6 carbon cyanogen are for alkoxyl group; phenoxy group; benzyloxy; hydroxyl; 1-4 carbon alkyl; phenyl; naphthyloxy or the phenyl ring that is replaced by one or more following radicals: halogen; 1-4 carbon alkyl; 1-4 carbon alkoxyl groups; 1-4 halocarbon substituted alkyls; 1-4 halocarbons are for alkoxyl group; 1-4 carbon alkylthios; 1-4 carbon alkyl sulphinyls; 1-4 carbon alkyl sulphonyls; nitro; cyano group; hydroxyl; carboxyl; 1-4 carbon alkyl-carbonyls or 1-4 carbon alkoxy carbonyls.
2, aryl-pyrrolidine N-oxalic acid ester derivative according to claim 1 is characterized in that R
1Represent CF
3R
2Represent Br; R
3Represent CN; R
4Represent oxygen; Y represents O; R represents 1-6 carbon alkoxyl groups; 1-6 halocarbons are for alkoxyl group; 3-6 carbene oxygen bases; 3-6 halo carbene oxygen bases; 3-6 carbon alkynyloxy groups; 3-7 carbocyclic ring alkoxyl groups; 3-6 carbon cyanogen are for alkoxyl group; phenoxy group; benzyloxy; hydroxyl; 1-4 carbon alkyl; phenyl; naphthyloxy or the phenyl ring that is replaced by one or more following radicals: halogen; 1-4 carbon alkyl; 1-4 carbon alkoxyl groups; 1-4 halocarbon substituted alkyls; 1-4 halocarbons are for alkoxyl group; 1-4 carbon alkylthios; 1-4 carbon alkyl sulphinyls; 1-4 carbon alkyl sulphonyls; nitro; cyano group; hydroxyl; carboxyl; 1-4 carbon alkyl-carbonyls or 1-4 carbon alkoxy carbonyls.
3, the preparation method of the described aryl-pyrrolidine N-of claim 1 oxalic acid ester derivative is characterized in that it comprises the steps:
Compd A and B in organic solvent, are made acid binding agent with mineral alkali or organic bases, and the mol ratio of compd A and compd B and acid binding agent is 1:1:1-2,-10-80 ℃ were reacted 2-12 hours down, tell organic phase, organic solvent, recycle silicon glue chromatographic column purifying are sloughed in decompression;
X is Cl or Br, and Y is O or S.
4, the preparation method of the described aryl-pyrrolidine N-of claim 1 oxalic acid ester derivative is characterized in that it comprises the steps:
With compd A and oxalic acid in organic solvent, make acid binding agent with mineral alkali or organic bases, the mol ratio of compd A and oxalic acid and acid binding agent is 1:1:1-2,-10-80 ℃ were reacted 2-12 hours down, tell organic phase, decompression is sloughed organic solvent and is obtained Compound C, and Compound C obtains Compound I with alcohol or phenol reaction again with sulfur oxychloride or oxalyl chloride or phosgene chloride;
X is Cl or Br, R be 1-6 carbon alkoxyl groups, 1-6 halocarbons for alkoxyl group, 3-6 carbene oxygen bases, 3-6 halo carbene oxygen bases, 3-6 carbon alkynyloxy groups, 3-7 carbocyclic ring alkoxyl groups, 3-6 carbon cyanogen for alkoxyl group, phenoxy group or benzyloxy.
5, the preparation method of the described aryl-pyrrolidine N-of claim 2 oxalic acid ester derivative is characterized in that it comprises the steps:
2-(4-chloro-phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles D and equimolar acetate kharophen methylene radical ester are dissolved in the tetrahydrofuran (THF), in the presence of 1-1.5 moles sodium hydride, behind the back flow reaction 8h, cooling, filter, filtrate concentrates, residuum is through the silica gel chromatographic column column chromatography that reduces pressure, get 1-kharophen methylene radical-2-(4-chloro-the phenyl)-3-cyano group-4-bromo-5-trifluoromethyl-pyrroles E of white crystal, after three oxyhalogen phosphorus of compd E and 1-1.5 moles are mixed, be warming up to backflow, behind the back flow reaction 1h, cooling, reaction mixture is poured in the frozen water, ethyl acetate extraction, organic layer washes with water successively, saturated salt washing, anhydrous sodium sulfate drying, filter back decompression precipitation, the gained solid obtains compound F 17-hydroxy-corticosterone through ethyl acetate and sherwood oil mixed solvent recrystallization, with compound F 17-hydroxy-corticosterone and G in organic solvent, make acid binding agent with mineral alkali or organic bases, the mol ratio of compound F 17-hydroxy-corticosterone and compound G and acid binding agent is 1:1:1-2, and-10-80 ℃ were reacted 2-12 hours down, tell organic phase, organic solvent, recycle silicon glue chromatographic column purifying are sloughed in decompression;
X＝Cl，Br。
6, according to the preparation method of claim 3 or 4 or 5 described aryl-pyrrolidine N-oxalic acid ester derivatives, it is characterized in that described organic solvent is toluene, benzene, hexanaphthene, acetonitrile, acetone, tetrahydrofuran (THF), ether, dioxane, N, dinethylformamide or dimethyl sulfoxide (DMSO); Described mineral alkali is NaOH, KOH, Na
2CO
3, K
2CO
3, NaHCO
3Or KHCO
3Organic bases is pyridine, triethylamine or 4-N, the N dimethylamine yl pyridines.
7, the application of the described aryl-pyrrolidine N-of claim 1 oxalic acid ester derivative is characterized in that it is used as sterilant, control lepidopteran class, Coleoptera class, Heteroptera class, Diptera class, Orthoptera class or Homoptera class insect.
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| 新型二芳酰肼类和芳基吡咯类杀虫剂的合成及生物活性研究. 毛春晖.南开大学博士学位论文. 2005 * |
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