CN105153037B - A kind of azoles worm sulfonylurea compound - Google Patents
A kind of azoles worm sulfonylurea compound Download PDFInfo
- Publication number
- CN105153037B CN105153037B CN201510559068.8A CN201510559068A CN105153037B CN 105153037 B CN105153037 B CN 105153037B CN 201510559068 A CN201510559068 A CN 201510559068A CN 105153037 B CN105153037 B CN 105153037B
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- CN
- China
- Prior art keywords
- compound
- azoles worm
- sulfonylurea compound
- formula
- sulfonylurea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000003851 azoles Chemical class 0.000 title claims abstract description 11
- -1 sulfonylurea compound Chemical class 0.000 title claims abstract description 11
- 229940100389 Sulfonylurea Drugs 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 4
- 230000000361 pesticidal effect Effects 0.000 claims description 3
- 230000000749 insecticidal effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 9
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002917 insecticide Substances 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- DPXOFIHEBFBLOG-UHFFFAOYSA-N CCc1n[nH]c(C(N)=O)c1Cl Chemical compound CCc1n[nH]c(C(N)=O)c1Cl DPXOFIHEBFBLOG-UHFFFAOYSA-N 0.000 description 1
- 0 CCc1n[n](*)c(C(N=C=O)=O)c1Cl Chemical compound CCc1n[n](*)c(C(N=C=O)=O)c1Cl 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
Abstract
The invention discloses a kind of azoles worm sulfonylurea compound, structure is shown in formula I：
Description
Technical field is related to a kind of azoles worm sulfonylurea compound and its application the invention belongs to agricultural insecticide field.
The resistance problem of background technology harmful organism is the main contributor that it is difficult to administer, and developing new pesticide control is
Administer the important channel of resistance.US5039693 discloses preparation and the insecticidal activity of following compounds (KC).The compound commodity
Entitled Tolfenpyrad, has good prevention effect to insects such as diamondback moth, thrips and tea lesser leafhoppers.
In the prior art, as representative of the present invention azoles worm sulfonylurea compound and its desinsection is not disclosed.
The content of the invention
It is an object of the invention to provide the low azoles worm uride chemical combination of a kind of structure novelty, good combination property, cost accounting
Thing, the preventing and treating available for agricultural or forestry primary pest.
Technical scheme is as follows：
A kind of azoles worm sulfonylurea compound, structure is shown in formula I：
The compounds of this invention can be prepared by the following method.
Above two raw material normal-temperature reaction in dichloroethane solvent is to obtain compound of formula I, the pyrazoles in above-mentioned reaction
Prepared by acyl isocyanate sees the embodiment of the present invention.
Advantages and positive effects of the present invention：The compounds of this invention azoles worm uride inherits Tolfenpyrad (KC) insecticide
Design feature, the active group with urea insecticide, has different insecticidal mechanisms, to Tolfenpyrad industry from Tolfenpyrad
The drug-fast insect produced is particularly efficient.And this compound is degradable, Environmental compatibility is good, possesses and is developed into superelevation
Imitate the potentiality of environment-friendlyinsecticide insecticide.
When the compounds of this invention is used to control insect pest purposes, it can be used alone, can also be with other active substance combinations
Use, to improve the comprehensive function of product.
Present invention additionally comprises the Pesticidal combination using compound I as active component, the weight of active component in said composition
Measure between a height of 1-95% of percentage composition, acceptable carrier in agricultural or forestry is also included in the Pesticidal combination.
Embodiment
Following synthesis example and raw test result can be used to further illustrate the present invention, but be not intended to limit this hair
It is bright.
Synthesize example
The preparation of example 1, compound I
(1) synthesis of the chloro- 3- ethyls -1- methylpyrazoles -5- formyl chlorides of 4-
The chloro- 3- ethyls -1- methylpyrazoles -5- formic acid 18.85g (0.1mol) of raw material 4- are added into 250mL reaction bulbs, plus
Enter toluene 100g, stir 5min, instill thionyl chloride 23.8g (0.2mol), be to slowly warm up to backflow.Back flow reaction 4h, decompression
Toluene and unnecessary thionyl chloride is distilled off, brownish red grease 20.70g, yield 100% is obtained.
(2) synthesis of the chloro- 3- ethyls -1- methylpyrazoles -5- formamides of 4-
Added into 250mL reaction bulbs below the ammoniacal liquor of 80g 40%, 0 DEG C of ice bath temperature control, the chloro- 3- ethyls -1- first of 4- is added dropwise
Base pyrazoles -5- formyl chlorides 20.70g (0.1mol), drop finishes, normal-temperature reaction 0.5h, suction filtration, filter cake 20mL × 2 originally water washing,
Obtain white solid 15g, yield 80%.
(3) synthesis of the chloro- 3- ethyls -1- methylpyrazoles -5- formyl based isocyanates of 4-
The chloro- 3- ethyls -1- methylpyrazoles -5- formamides 18.75g (0.1mol) of 4- are separately added into 250mL reaction bulbs,
Dichloroethanes 100mL, is added dropwise oxalyl chloride 31.75g (0.25mol), and drop, which finishes, is warming up to backflow 10h, and vacuum distillation removes two chloroethenes
Alkane and unnecessary oxalyl chloride, obtain brown oil 21.35g, yield 100%.
(4) compound I synthesis
25g dichloroethanes is added into 100mL reaction bulbs, the chloro- 3- of 4- are added dropwise in 2.13g (0.01mol) 4-Methoxybenzylamine
Ethyl -1- methylpyrazole -5- formyl based isocyanate 2.35g (0.011mol), drop finishes normal-temperature reaction 3h, and suction filtration obtains white solid
2.6g, yield 61%.Fusing point：100~103 DEG C.
Compound I's1H NMR (500MHz, DMSO-d6),δ(ppm)：1.153-1.183 (t, 3H), 2.283 (s, 3H),
2.525-2.570 (q, 2H), 3.866 (s, 3H), 4.375-4.387 (d, 2H), 6.896-6.913 (d, 2H), 6.935-6.952
(d, 2H), 7.175-7.192 (d, 2H), 7.328-7.345 (d, 2H), 8.621 (s, 1H), 10.601 (s, 1H).
Biological activity determination
The insecticidal activity assay of example 2
Kill diamondback moth determination of activity：
Using leaf dipping method.The leaf dipping method proposed using international resistance Action Committee (IRAC).With the medicine to be measured prepared
Liquid, impregnates cabbage leaves with straight peen ophthalmology tweezers, time 3-5 second, gets rid of extraction raffinate, 1 tablet once, totally 3, each sample, by sample
Flag sequence is successively placed on processing paper.After decoction is dry, it is put into the straight type pipe for having markd 10cm length, 2 ages of access are small
Diamond-back moth larva 30, the mouth of pipe is covered with gauze.Test process is placed in standard process chamber, 48h inspection results are touched with pulling out pin
Polypide, motionless person is death.Calculate the death rate.3 repetitions are done in experiment, are averaged.It the results are shown in Table 1.
Table 1 kills diamondback moth determination of activity result
The result of table 2 shows that the compounds of this invention azoles worm uride is significantly better than contrast agents Tolfenpyrad (KC) to diamondback moth.
Claims (3)
1. a kind of azoles worm sulfonylurea compound, structure is shown in formula I：
2. according to a kind of purposes of azoles worm sulfonylurea compound described in claim 1, it is characterised in that compound of formula I is used as desinsection
Agent, prevents and treats crop pests.
3. a kind of Pesticidal combination, is that can be connect in active component and agricultural or forestry containing the compound of formula I described in claim 1
The carrier received.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510559068.8A CN105153037B (en) | 2015-09-06 | 2015-09-06 | A kind of azoles worm sulfonylurea compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510559068.8A CN105153037B (en) | 2015-09-06 | 2015-09-06 | A kind of azoles worm sulfonylurea compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105153037A CN105153037A (en) | 2015-12-16 |
| CN105153037B true CN105153037B (en) | 2017-08-22 |
Family
ID=54794135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510559068.8A Active CN105153037B (en) | 2015-09-06 | 2015-09-06 | A kind of azoles worm sulfonylurea compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105153037B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299409B (en) * | 2018-04-02 | 2021-01-29 | 青岛科技大学 | Phenylether oxadiazole pesticide |
| CN114805197B (en) * | 2022-04-11 | 2023-07-11 | 青岛科技大学 | Fluorinated pyridine acyl urea insecticide and acaricide |
| CN114656402B (en) * | 2022-04-11 | 2024-01-30 | 青岛科技大学 | Fluorine-containing nicotinoyl urea compound and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN1183409A (en) * | 1995-09-08 | 1998-06-03 | 化学工业部沈阳化工研究院 | Insecticidal acaricidal pyrazoles compounds and preparation thereof |
-
2015
- 2015-09-06 CN CN201510559068.8A patent/CN105153037B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN1183409A (en) * | 1995-09-08 | 1998-06-03 | 化学工业部沈阳化工研究院 | Insecticidal acaricidal pyrazoles compounds and preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| 吡唑酰胺基脲类化合物的合成及除草活性;谭成侠，等;《农药学学报》;20111231;第13卷(第2期);全文 * |
| 新型吡唑甲酰脲类化合物的合成及其生物活性;刘长令，等;《化学研究与应用》;19971231;第9卷(第5期);全文，尤其实验部分 * |
| 新型吡唑甲酰脲类化合物的合成及其生物活性;刘长令，等;《合成化学》;19970430;第5卷(第4期);全文，尤其实验部分 * |
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| Publication number | Publication date |
|---|---|
| CN105153037A (en) | 2015-12-16 |
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| CB03 | Change of inventor or designer information |
Inventor after: Xu Liangzhong Inventor after: Hu Rao Inventor after: Cui Jianqiang Inventor after: Li Huanpeng Inventor after: Wang Minghui Inventor after: Zhang Huaqing Inventor after: Huang Xuesong Inventor before: Xu Liangzhong Inventor before: Li Huanpeng Inventor before: Wang Minghui Inventor before: Zhang Huaqing Inventor before: Huang Xuesong |
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Effective date of registration: 20191030 Address after: 256200 Changshan Industrial Park, Zouping County, Shandong, Binzhou Patentee after: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Address before: 266000 Shandong province Qingdao City, Zhengzhou Road No. 53, Qingdao University of Science & Technology Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |
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Denomination of invention: Imidazolyl urea compound Effective date of registration: 20211223 Granted publication date: 20170822 Pledgee: Shandong Zouping Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2021980015864 |
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