CN105153037A - Pyrazole ureide compound - Google Patents
Pyrazole ureide compound Download PDFInfo
- Publication number
- CN105153037A CN105153037A CN201510559068.8A CN201510559068A CN105153037A CN 105153037 A CN105153037 A CN 105153037A CN 201510559068 A CN201510559068 A CN 201510559068A CN 105153037 A CN105153037 A CN 105153037A
- Authority
- CN
- China
- Prior art keywords
- compound
- pyrazole
- formula
- azoles worm
- methylpyrazole
- 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.)
- Granted
Links
- -1 Pyrazole ureide compound Chemical class 0.000 title claims abstract description 9
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 4
- 150000003851 azoles Chemical class 0.000 claims description 9
- 229940100389 Sulfonylurea Drugs 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 230000000749 insecticidal effect Effects 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- 238000000034 method Methods 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
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 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
- 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a pyrazole ureide compound. A structural formula I is as shown in the accompanying drawing. The compound as shown in the formula I has excellent insecticidal activity and can be used for prevention and treatment of agricultural or forestry pests.
Description
Technical field the invention belongs to agricultural insecticide field, relates to a kind of azoles worm sulfonylurea compound and application thereof.
The resistance problem of background technology harmful organism is the main contributor that it is difficult to administer, and development of new pesticide control is the important channel administering resistance.US5039693 discloses preparation and the insecticidal activity of following compounds (KC).This compound trade name is Tolfenpyrad, has good prevention effect to insects such as small cabbage moth, thrips and tea lesser leafhoppers.
In the prior art, azoles worm sulfonylurea compound as representative of the present invention and desinsection thereof have no open.
Summary of the invention
The azoles worm sulfonylurea compound that the object of the present invention is to provide a kind of novel structure, good combination property, cost accounting low, can be used for the control of agricultural or forestry primary pest.
Technical scheme of the present invention is as follows:
A kind of azoles worm sulfonylurea compound, structure is such as formula shown in I:
The compounds of this invention can be prepared by the following method.
Namely above-mentioned two kinds of raw materials normal-temperature reaction in dichloroethane solvent obtains formula I, and the embodiment of the present invention is shown in the Pyrazole Acyl isocyanic ester preparation in above-mentioned reaction.
Advantage of the present invention and positively effect: the compounds of this invention azoles worm uride inherits the constructional feature of Tolfenpyrad (KC) sterilant, there is again the active group of urea insecticide, have different insecticidal mechanisms from Tolfenpyrad, the drug-fast insect already produced Tolfenpyrad is particularly efficient.And this compound is easily degraded, Environmental compatibility is good, possesses the potentiality that exploitation becomes ultra-high efficiency environment-friendlyinsecticide insecticide.
When the compounds of this invention is for controlling insect pest purposes, can be used alone, also can use with other active substance combination, to improve the comprehensive function of product.
The present invention also comprises the insect-killing composition using Compound I as active ingredient, and in said composition, the weight percentage height of active ingredient is between 1-95%, also comprises acceptable carrier in agricultural or forestry in this insect-killing composition.
Embodiment
Following synthesis example and raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthesis example
The preparation of example 1, Compound I
(1) synthesis of the chloro-3-ethyl of 4--1-methylpyrazole-5-formyl chloride
In 250mL reaction flask, add the chloro-3-ethyl of raw material 4--1-methylpyrazole-5-formic acid 18.85g (0.1mol), add toluene 100g, stir 5min, instillation sulfur oxychloride 23.8g (0.2mol), is slowly warming up to backflow.Back flow reaction 4h, underpressure distillation removing toluene and unnecessary sulfur oxychloride, obtain red-brown oily matter 20.70g, yield 100%.
(2) synthesis of the chloro-3-ethyl of 4--1-methylpyrazole-5-methane amide
In 250mL reaction flask, add 80g40% ammoniacal liquor, ice bath temperature control less than 0 DEG C, drip 4-chloro-3-ethyl-1-methylpyrazole-5-formyl chloride 20.70g (0.1mol), drip and finish, normal-temperature reaction 0.5h, suction filtration, filter cake 20mL × 2 tap water, obtain white solid 15g, yield 80%.
(3) synthesis of the chloro-3-ethyl of 4--1-methylpyrazole-5-formyl radical isocyanic ester
The chloro-3-ethyl of 4--1-methylpyrazole-5-methane amide 18.75g (0.1mol) is added respectively in 250mL reaction flask, ethylene dichloride 100mL, drip oxalyl chloride 31.75g (0.25mol), drip to finish and be warming up to backflow 10h, underpressure distillation removing ethylene dichloride and unnecessary oxalyl chloride, obtain brown oil 21.35g, yield 100%.
(4) synthesis of Compound I
25g ethylene dichloride is added in 100mL reaction flask; 2.13g (0.01mol) 4-Methoxybenzylamine, drips 4-chloro-3-ethyl-1-methylpyrazole-5-formyl radical isocyanic ester 2.35g (0.011mol), drips complete normal-temperature reaction 3h; suction filtration obtains white solid 2.6g, yield 61%.Fusing point: 100 ~ 103 DEG C.
Compound I
1hNMR (500MHz, DMSO-d
6), 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
Example 2 insecticidal activity assay
Kill small cabbage moth determination of activity:
Adopt leaf dipping method.Adopt the leaf dipping method that international resistance Action Committee (IRAC) proposes.With the liquid to be measured prepared, with straight peen ophthalmology tweezers dipping cabbage leaves, time 3-5 second, get rid of remaining liquid, each 1, totally 3, each sample, is successively placed in treatment paper by sample flag sequence.After liquid is dry, put into the straight type pipe that the markd 10cm of tool is long, access 2 age diamondback moth larvae 30, build the mouth of pipe with gauze.Test process be placed in standard treatment chamber, 48h check result touches polypide to pull out pin, and motionless person is dead.Calculate mortality ratio.3 repetitions are done in test, average.The results are shown in Table 1.
Table 1 kills small cabbage moth determination of activity result
Table 2 result shows, the compounds of this invention azoles worm uride is significantly better than contrast agents Tolfenpyrad (KC) to small cabbage moth.
Claims (3)
1. an azoles worm sulfonylurea compound, structure is such as formula shown in I:
2. according to the purposes of a kind of azoles worm sulfonylurea compound according to claim 1, it is characterized in that formula I is used as sterilant, control crop pests.
3. an insect-killing composition is active ingredient and acceptable carrier in agricultural or forestry containing formula I according to claim 1.
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 true CN105153037A (en) | 2015-12-16 |
| CN105153037B 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299409A (en) * | 2018-04-02 | 2018-07-20 | 青岛科技大学 | A kind of Ben Mi oxadiazole insecticides |
| CN114656402A (en) * | 2022-04-11 | 2022-06-24 | 青岛科技大学 | Fluorine-containing nicotinoyl urea compound and application thereof |
| CN114805197A (en) * | 2022-04-11 | 2022-07-29 | 青岛科技大学 | Fluorine-containing pyridine acyl urea insecticide and acaricide |
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 |
|---|
| 刘长令，等: "新型吡唑甲酰脲类化合物的合成及其生物活性", 《化学研究与应用》 * |
| 刘长令，等: "新型吡唑甲酰脲类化合物的合成及其生物活性", 《合成化学》 * |
| 谭成侠，等: "吡唑酰胺基脲类化合物的合成及除草活性", 《农药学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299409A (en) * | 2018-04-02 | 2018-07-20 | 青岛科技大学 | A kind of Ben Mi oxadiazole insecticides |
| CN108299409B (en) * | 2018-04-02 | 2021-01-29 | 青岛科技大学 | Phenylether oxadiazole pesticide |
| CN114656402A (en) * | 2022-04-11 | 2022-06-24 | 青岛科技大学 | Fluorine-containing nicotinoyl urea compound and application thereof |
| CN114805197A (en) * | 2022-04-11 | 2022-07-29 | 青岛科技大学 | Fluorine-containing 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105153037B (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103232431B (en) | Dihalogenated pyrazole amide compound and its use | |
| TW377346B (en) | Use of 2-{(dihydro)pyrazolyl-3'-oxymethylene}-anilides as pest-control agents and fungicides | |
| CN105153113A (en) | 3, 5-thiobenzamide dihalide insecticide | |
| CN104710436B (en) | A kind of pyrazolyl pyrimidines aminated compounds and purposes | |
| CN103130769B (en) | 3-difluoro ethoxy-pyrazole amides compounds and application thereof | |
| CN105153114A (en) | Pyrazolopyridine ureide compound and application thereof | |
| CN105153037A (en) | Pyrazole ureide compound | |
| CN103214461B (en) | Quinoline derivative and application thereof | |
| CN103755700B (en) | A kind of pyrazol acid amide compounds and uses thereof | |
| CN103641782A (en) | Pyrazol acylhydrazone compounds and application thereof | |
| TWI244892B (en) | Synergistic mixtures | |
| CN105254625B (en) | One kind class compound of yl-benzamide containing chloro-thiazole and its application | |
| CN109232550A (en) | One kind base -1,3,4- oxadiazoles -2- ketone compounds of chloro-5-trifluoromethylpyridine containing 3- and its application | |
| CN105712973B (en) | A kind of pyrazol acid amide compounds and its application | |
| CN104920409A (en) | Thioamide insecticidal and acaricidal agent containing urethane group | |
| CN113549053B (en) | Pyrazoloquine (azolyl) ether compound and application thereof | |
| CN109336879B (en) | 3-pyridyl-1, 2, 4-oxadiazole compound and application thereof | |
| CN106749225A (en) | A kind of pyrazol acid amide compounds of difluoroethoxy containing thiadiazoles and its application | |
| CN106831752B (en) | One kind propoxyl group pyridine of tetrafluoro containing thiadiazoles connects pyrazol acid amide compounds | |
| CN103755681A (en) | 3-(2,2,3,3-tetrafluoropropoxy)-pyrazole amide compound and application thereof | |
| CN105061412A (en) | Fluorine-containing N-furoamide compound and application thereof | |
| CN103232432A (en) | 3-difluoroethoxy-4-chloropyrazole amide compound and use thereof | |
| DE3306697A1 (en) | SUBSTITUTED MALEINIC ACID IMIDES | |
| CN109336882B (en) | Fluorine-containing pyridine acyl piperazine compound and application thereof | |
| CN109320506A (en) | A kind of difluorophenyl furodiazole insecticidal/acaricidal agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
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 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220523 Granted publication date: 20170822 Pledgee: Shandong Zouping Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2021980015864 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A imidazolyl urea compound Effective date of registration: 20220527 Granted publication date: 20170822 Pledgee: Shandong Zouping Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2022980006587 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20170822 Pledgee: Shandong Zouping Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2022980006587 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |