CN1915977A - Chlorine-fipronil, prepartion and application - Google Patents
Chlorine-fipronil, prepartion and application Download PDFInfo
- Publication number
- CN1915977A CN1915977A CN 200510095913 CN200510095913A CN1915977A CN 1915977 A CN1915977 A CN 1915977A CN 200510095913 CN200510095913 CN 200510095913 CN 200510095913 A CN200510095913 A CN 200510095913A CN 1915977 A CN1915977 A CN 1915977A
- Authority
- CN
- China
- Prior art keywords
- fluorine worm
- worm nitrile
- compound
- chlorine
- fipronil
- 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
- 239000005899 Fipronil Substances 0.000 title abstract 3
- 229940013764 fipronil Drugs 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000007259 addition reaction Methods 0.000 claims abstract description 4
- 150000002825 nitriles Chemical class 0.000 claims description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003814 drug Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 3
- 241000251468 Actinopterygii Species 0.000 abstract description 7
- 241000143060 Americamysis bahia Species 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 2
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 abstract 2
- 230000000361 pesticidal effect Effects 0.000 abstract 2
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 240000007594 Oryza sativa Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 241000426497 Chilo suppressalis Species 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- AVYVHIKSFXVDBG-UHFFFAOYSA-N N-benzyl-N-hydroxy-2,2-dimethylbutanamide Chemical compound C(C1=CC=CC=C1)N(C(C(CC)(C)C)=O)O AVYVHIKSFXVDBG-UHFFFAOYSA-N 0.000 description 3
- 241000255969 Pieris brassicae Species 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 241000700159 Rattus Species 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GMMUNQTZKMOWNL-UHFFFAOYSA-N 4-(trifluoromethylsulfinyl)-1h-pyrazole Chemical compound FC(F)(F)S(=O)C=1C=NNC=1 GMMUNQTZKMOWNL-UHFFFAOYSA-N 0.000 description 1
- VKLKXFOZNHEBSW-UHFFFAOYSA-N 5-[[3-[(4-morpholin-4-ylbenzoyl)amino]phenyl]methoxy]pyridine-3-carboxamide Chemical compound O1CCN(CC1)C1=CC=C(C(=O)NC=2C=C(COC=3C=NC=C(C(=O)N)C=3)C=CC=2)C=C1 VKLKXFOZNHEBSW-UHFFFAOYSA-N 0.000 description 1
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 235000017647 Brassica oleracea var italica Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000252212 Danio rerio Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000046109 Sorghum vulgare var. nervosum Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000915 fish venom Substances 0.000 description 1
- 231100000731 ichthyotoxin Toxicity 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a method for preparing chlorofipronil and its application in pesticides. Low-toxicity chlorofipronil is prepared by addition reaction between fipronil and chloral. The new compound retains the pesticidal activity and pesticidal spectrum of fipronil, while has reduced toxicity to fishes and shrimps. The method has such advantages as simple process and low cost.
Description
Technical field
The present invention relates to a kind of chlorine fluorine worm nitrile and preparation and purposes, particularly a kind of original fluorine worm nitrile agricultural chemicals is through carrying out addition reaction with trichoro-aldehyde, generates new for lower agricultural chemicals of hydrocoles toxicity such as fish, shrimps.
Background technology
Fluorine worm nitrile is by French Luo Na---Rhone-Poulenc's exploitation; the fluorine-containing pyrazoles broad spectrum insecticide that existing many companies are producing has another name called sharp strength spy, its chemical name: 5-amino-3-cyano group-1-(2; 6-dichlor-4-trifluoromethyl phenyl)-and the 4-trifluoromethyl sulfinyl pyrazole, structural formula:
Relative molecular weight 437.2
Fluorine worm nitrile is active high, applied range, and the insect that insect such as Hemiptera, Thysanoptera, Coleoptera, lepidopteran and chrysanthemum ester class, carbamate insecticides has been produced resistance shows high susceptibility.Can be used for paddy rice, cotton, vegetables, soybean, rape, tobacco leaf, potato, tealeaves, Chinese sorghum, corn, fruit tree, forest, public health, livestock industry etc., is the insecticide variety that Chinese from now on pesticide industry is given priority to.But this kind also exists 2 main shortcomings: (1) production cost is higher relatively; (2) especially very high to hydrocoles toxicity such as fish, shrimps, easily cause poisoning to hydrocoles such as fish, shrimps, to a certain degree placed restrictions on the application and the development of fluorine worm nitrile.
Summary of the invention
The purpose of this invention is to provide a kind of new compound, both can complete reservation fluorine worm nitrile molecular structure, again because by further chemical reaction, the new compound chlorine fluorine worm itrile group that synthesizes originally keeps the insecticidal activity and the insecticidal spectrum of original fluorine worm nitrile, and reduced production cost, especially reduced the high toxicity of original fluorine worm nitrile hydrocoles such as fish, shrimps.
Chlorine fluorine worm nitrile has following array structure:
Relative molecular weight: 584.5
The compound that also contains a small amount of following structural in the product:
Relative molecular weight: 566.5
Chemical equation is as follows:
In raw material fluorine worm nitrile and the disposable input reaction flask of trichoro-aldehyde, slowly rise to reflux temperature, stirring reaction 36 hours, the mixture that 0 ℃ of crystallization 48 hours, filter, oven dry makes above-mentioned two kinds of compounds separates two kinds of compounds by recrystallization then.
Compound I and Compound I I can be used as in sterilant.
Compound provided by the invention reduces more than 15% than the production cost of original fluorine worm nitrile.In general, with fluorine worm nitrile is the new fluorine worm carbonitrile derivatives that raw material is made, its production cost is higher than raw material fluorine worm nitrile, but selecting trichoro-aldehyde for use is the chlorine fluorine worm nitrile that raw material and the addition reaction of fluorine worm nitrile synthesize, three characteristics are arranged: a) atom utilization is 100%, does not produce new waste water,waste gas and industrial residue; B) reaction yield 〉=98%, technological process is very simple; C) molecular weight of the molecular weight ratio fluorine worm nitrile of chlorine fluorine worm nitrile is big by 25%.The combination of these three characteristics makes the production cost of chlorine fluorine worm nitrile be lower than fluorine worm nitrile.
Compound provided by the invention has kept the insecticidal spectrum and the insecticidal activity of original fluorine worm nitrile on substantially.
Chlorine fluorine worm nitrile is to cabbage caterpillar biological activity determination result
| The medicament title | Multiple (ppm) | Total borer population (head) | Dead borer population (head) | Mortality ratio |
| Chlorine fluorine worm nitrile | 20 | 30 | 30 | 100.0 |
| 4 | 30 | 30 | 100.0 | |
| 0.8 | 30 | 29 | 98.0 | |
| 0.16 | 30 | 23 | 76.6 | |
| 0.04 | 30 | 3 | 10.0 | |
| Fluorine worm nitrile | 4 | 30 | 30 | 100.0 |
| 0.16 | 30 | 30 | 100.0 | |
| 0.04 | 30 | 14 | 46.7 | |
| CK | 30 | 0 | 0.0 |
Fluorine worm nitrile is to striped rice borer biological activity determination result
| The medicament title | Multiple (ppm) | Total borer population (head) | Dead borer population (head) | Mortality ratio (%) |
| Chlorine fluorine worm nitrile | 10 | 30 | 30 | 100.0 |
| 2 | 30 | 30 | 100.0 | |
| 0.4 | 30 | 22 | 73.3 | |
| 0.08 | 30 | 3 | 10.0 | |
| Fluorine worm nitrile | 2 | 30 | 30 | 100.0 |
| 0.4 | 30 | 30 | 100.0 | |
| 0.08 | 30 | 14 | 46.7 | |
| CK | 30 | 0 | 0.0 |
More than Shi Yan cabbage caterpillar is a third-instar larvae, and striped rice borer is a second instar larvae, and cabbage caterpillar adopts the broccoli leaf to soak the medicine feeding method, calculates 72 hours mortality ratio; Striped rice borer adopts the test tube rice seedling to soak the medicine method, calculates 72 hours mortality ratio.
Compound provided by the invention has reduced the toxicity of fluorine worm nitrile, has especially reduced the high toxicity of fluorine worm nitrile to hydrocoles such as fish, shrimps.
The former medicine of chlorine fluorine worm nitrile footpath mouthful, test through skin test and to be low toxicity, acute oral LD
50For male rat greater than 506mg/kg, female rats is greater than 502mg/kg, through skin LD
50Greater than 2050mg/L; To zebra fish is middle low toxicity, ichthyotoxin LD
50(96 hours): 6.76mg/L; Test shows, chlorine fluorine worm nitrile has higher activity to various pests such as lepidopterans, particularly the insect activity to aspects such as paddy rice, vegetables has presented and the suitable effectiveness of fluorine worm nitrile, chlorine fluorine worm nitrile is middle low toxicity level to the toxicity of fish, this is its application on crops such as paddy rice, vegetables, has opened up more wide space.
Embodiment
With 100 gram content is that the former medicine of 95% fluorine worm nitrile drops in the 500ml there-necked flask, adds 400ml content and be 96% trichoro-aldehyde, starts and stirs, slowly be warming up to 98 ℃ of reflux temperatures, continuously stirring reaction 36 hours is cooled to 0 ℃, crystallization 48 hours, filter, oven dry, get chlorine fluorine worm nitrile solid 107 grams, product is a mixture, wherein (I) compound 92%, (II) compound 4%, total content 〉=96% boils off trichoro-aldehyde with filtrated stock then, oven dry, chlorine fluorine worm nitrile solid 25 restrains again, product is a mixture, contains (I) compound 86%, and (II) compound 6%, total content 〉=92%, molecular yield is greater than 98%.
Claims (4)
1, chlorine fluorine worm nitrile is the compound with following array structure:
2, according to the preparation method of the described compound of claim 1, its feature in: select for use trichoro-aldehyde and the former medicine of fluorine worm nitrile to carry out addition reaction.
3, with (I) compound in the claim 1 or (II) compound be the sterilant of activeconstituents, it is characterized in that containing in this sterilant (I) compound or (II) compound.
4, can directly serve as sterilant according to the described compound of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100959137A CN1915977B (en) | 2005-08-18 | 2005-08-18 | Chlorine-fipronil, prepartion and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100959137A CN1915977B (en) | 2005-08-18 | 2005-08-18 | Chlorine-fipronil, prepartion and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1915977A true CN1915977A (en) | 2007-02-21 |
| CN1915977B CN1915977B (en) | 2010-04-07 |
Family
ID=37737072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100959137A Expired - Fee Related CN1915977B (en) | 2005-08-18 | 2005-08-18 | Chlorine-fipronil, prepartion and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1915977B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206184A (en) * | 2010-03-29 | 2011-10-05 | 南开大学 | 3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivative insecticide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204123C (en) * | 2002-07-30 | 2005-06-01 | 王正权 | N-phenyl pyrazole derivative pesticide |
-
2005
- 2005-08-18 CN CN2005100959137A patent/CN1915977B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206184A (en) * | 2010-03-29 | 2011-10-05 | 南开大学 | 3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivative insecticide |
| WO2011120312A1 (en) * | 2010-03-29 | 2011-10-06 | 南开大学 | 3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole derivatives as insecticides |
| CN102206184B (en) * | 2010-03-29 | 2013-07-10 | 南开大学 | 3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivative insecticide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1915977B (en) | 2010-04-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: GUANGDONG LIWEI CHEMICAL CO., LTD. Free format text: FORMER OWNER: LI JIAN Effective date: 20100806 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 430074 NO.366, ZHUODAOQUAN ROAD, WUHAN CITY, HUBEI PROVINCE TO: 525000 BESIDE THE MAOGAO HIGHWAY, MAOMING CITY, GUANGDONG PROVINCE |
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| TR01 | Transfer of patent right |
Effective date of registration: 20100806 Address after: 525000 beside Mao Mao highway, Guangdong, Maoming Patentee after: Guangdong Liwei Chemical Industry Co., Ltd. Address before: 430074 Hubei city of Wuhan province zhuodao road 366 Patentee before: Li Jian |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100407 Termination date: 20140818 |
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| EXPY | Termination of patent right or utility model |