CN102690232A - Synthesizing method for fipronil intermediates - Google Patents
Synthesizing method for fipronil intermediates Download PDFInfo
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- CN102690232A CN102690232A CN2012101729594A CN201210172959A CN102690232A CN 102690232 A CN102690232 A CN 102690232A CN 2012101729594 A CN2012101729594 A CN 2012101729594A CN 201210172959 A CN201210172959 A CN 201210172959A CN 102690232 A CN102690232 A CN 102690232A
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Abstract
The invention relates to a synthesizing method for fipronil intermediates. The synthesizing method for the fipronil intermediates effectively solves problems of low production yield in preparation of the fipronil intermediates, complicated operation, low purity and difficulty in industrialized production. The method includes steps of adding 5-amino-3-cyano-1-(2, 6-dichloro-4-trifluoromethyl phenyl) pyrazole into a polar solvent at first and blending the 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl) pyrazole evenly, heating the 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl) pyrazole to 30-70 DEG C under 0.3-0.6 atmosphere, distilling one sixth of the polar solvent, and then cooling the 5-amino-3-cyano-1-(2, 6-dichloro-4-trifluoromethyl phenyl) pyrazole to 20 DEG C, quickly adding sulfur monochloride to react for half an hour under the conditions of 35-40 DEG C and negative pressure of -0.095--0.01MPa, obtaining a mixture which is standing for half an hour under the conditions of 35-50 DEG C and one atmosphere so as to remove hydrogen chloride, adding an amine regulator to regulate a PH value as 7, cooling the mixture to </=5 DEG C, filtering to obtain a filtered object which is washed by water, and drying to obtain 5-amino-1-(2,6-dichloro-4-trifluoromethyl phenyl)-3-cyano pyrazole-4-base double sulfur. The synthesizing method for the fipronil intermediates is prepared by simple process and operated under mild reaction conditions, high in production yield and purity, low in production cost, easy to produce in an industrialized manner and capable of serving as the intermediate to effectively prepare fipronil.
Description
Technical field
The present invention relates to chemical field, particularly a kind of compound method of fluorine worm nitrile midbody.
Background technology
Fluorine worm nitrile is that a kind of phenylpyrazole insecticides, insecticidal spectrum are wide; Is main to insect with stomach poison function; Have concurrently and tag and certain systemic function; Its mechanism of action is to hinder the muriate metabolism of insect γ-An Jidingsuan control, therefore important pests such as aphid, leafhopper, plant hopper, lepidopterous larvae, fly class and Coleoptera is had very high insecticidal activity, and crop is not had poisoning.This medicament can impose on soil, but also foliar spray.Impose on soil effectively chrysomelid, wireworm of control of maize root and cutworm.During foliage spray, small cabbage moth, small white, rice thrips etc. are all had high-level preventive effect, and the lasting period is long.Though China's regulation was from October 1st, 2009; Except that part dry land coating agent for seed such as health usefulness, corn, stop to sell and using the pesticide preparation that is used for otherwise fluorine-containing worm nitrile composition within the border in China, but Ministry of Agriculture's approval fluorine worm nitrile accords with the demands of the market as hygienic insecticide; The fipronil insecticidal spectrum is wide; Can effectively prevent and treat sanitary insect pests such as cockroach, termite, and, be ideal hygienic insecticide kind people and animals' low toxicity.In addition, in the recent period fluorine worm nitrile export volume increases progressively always, has brought the world market opportunity to Chinese Enterprise, and exploitation efficiently, low is polluted, is easy to industrialized technology domestic enterprise is still an opportunity on original technical foundation.
The synthetic of the former medicine of fluorine worm nitrile mainly contains four approach (method) at present, and like Fig. 1,2,3, shown in 4, these four methods, its method shown in Figure 1 are early stage suitability for industrialized production routes, because CF
3SCl is a gas, and toxicity is high, is prone to security incident, and this route is eliminated.Method shown in Figure 2 is present widely used industrial product route, but the midbody CF that this route needs
3SOCl produces difficulty, and facility investment is big.Method shown in Figure 3 is more similar with method shown in Figure 4, and in four few steps of route, route four is as this patent exploitation, improvement route.
Patent (WO 2001030760 A1) has announced that yield is 89.4% from 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole-two sulphur preparing process of 4-base; Patent (CN102060774A) has been announced through 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole-two sulphur of 4-base and has been prepared the route of fluorine worm nitrile, do not have concrete operation steps in the patent; Patent (CN101544607B) is with 5-amino-1-(2; 6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole-two sulphur of 4-base are feedstock production fluorine worm nitrile; Do not relate to 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole-two sulphur preparing process of 4-base; Preparation 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole in " Shanghai Chemical " [Shanghai Huagong, 32 (7) 17-19,2007]-two sulphur of 4-base need be 80 ℃ of back flow reaction 12 hours, and yield is 87%, needs back flow reaction; Agricultural and food chemistry [Journal of Agricultural and Food Chemistry; 58 (8) 4992 – 4998; 2010] synthetic 5-amino-1-(2 in; 6-dichlor-4-trifluoromethyl phenyl)-and the condition of the two sulphur of 3-cyano pyrazole-4-base is harsh, and the temperature that drips sulfur monochloride be-15 ℃, and needs react 12 hours.Be difficult to effectively apply, therefore, the improvement on fluorine worm nitrile is produced is imperative with innovation.
Summary of the invention
To above-mentioned situation, for overcoming the defective of prior art, the present invention's purpose just provides a kind of compound method of fluorine worm nitrile midbody, and it is low effectively to solve preparation fluorine worm nitrile midbody production yield, complicated operation, and purity is low, is difficult for the problem of suitability for industrialized production.
The technical scheme that the present invention solves is, with 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and sulfur monochloride (S
2Cl
2) be raw material, add 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles in the polar solvent, after mixing earlier; Under the 0.3-0.6 normal atmosphere, be heated to 30-70 ℃, boil off 1/6 polar solvent, be cooled to 20 ℃ again; Add rapidly sulfur monochloride, 35-40 ℃ ,-0.095--negative pressure of 0.01MPa under reaction 0.5 hour, mixture, mixture leaves standstill 0.5h under 35-50 ℃, 1 normal atmosphere; Remove de-chlorine hydride, feed the amine regulator, transferring pH is 7, is cooled to≤5 ℃; Cross and filter the filter thing, the filter thing is used water washing, the dry 5-amino-1-(2 that gets; 6-dichlor-4-trifluoromethyl phenyl)-and 3-cyano pyrazole-two sulphur of 4-base, mass content is more than 96%, and yield is more than 93%;
Described 5-amino-3-cyanic acid-1-(2; 6-dichlor-4-trifluoromethyl phenyl) molecular structural formula of pyrazoles is shown in (II) among Fig. 5; The molecular structural formula of 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole-two sulphur of 4-base is shown in (I) among Fig. 5;
Described polar solvent is acetone, butanone, isobutyl ketone, the pentanone of ketone, a kind of or any two kinds mixing of mibk; Or a kind of or any two kinds mixing of the methyl alcohol of alcohols, ethanol, propyl alcohol, Virahol; Or the acetonitrile of nitrile; 5-amino-3-cyanic acid-the 1-(2 that adds 0.1 mole in every 100ml polar solvent; 6-dichlor-4-trifluoromethyl phenyl) sulfur monochloride of pyrazoles and 0.05-0.08 mole (mol ratio that is to say 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and sulfur monochloride is 1 ︰ 0.5-0.8);
Described amine regulator is one or both mixing of ammonia, Monomethylamine, diethylamine, quadrol, triethylamine, n-Butyl Amine 99;
The inventive method is simple; Reaction conditions is gentle, yield is high, simple to operate, purity is high, production cost is low, be easy to the compound method of a kind of fluorine worm nitrile midbody of suitability for industrialized production; Can be effective to prepare fluorine worm nitrile as midbody, to satisfy the needs of market to fluorine worm nitrile.
Description of drawings
Fig. 1-Fig. 4 is the existing chemical reaction process schema of producing fluorine worm nitrile.
Fig. 5 is a chemical reaction process schema of the present invention.
Embodiment
Elaborate below in conjunction with particular case and embodiment specific embodiments of the invention.
By shown in Figure 5, the present invention can be provided by following examples in practical implementation.
Embodiment 1
In 300ml acetone, add 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles of 0.3mol (being 98.3g), under 0.4 normal atmosphere, be heated to 30 ~ 35 ℃, boil off 50mL acetone, be cooled to 20 ℃ again; Add rapidly 0.24 mole of sulfur monochloride (being 33.3g), then 35 ℃ ,-0.03--negative pressure of 0.01MPa under reaction 0.5 hour, mixture, mixture leaves standstill 0.5h under 35 ℃, 1 normal atmosphere; Remove de-chlorine hydride, drip triethylamine again and transfer pH=7, be cooled to 5 ℃, cross and filter the filter thing; The filter thing is used water washing, dry 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole-two sulphur 104.3g of 4-base, the content 97.0% of getting; Yield 95.8%, and 1H NMR (300MHz, DMSO-d6): δ 7.98 (s, 4H; Ph), 6.69 (s, 4H, NH
2).
In 300ml ethanol, add 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles of 0.3mol (being 98.3g), under 0.6 normal atmosphere, be heated to 65 ~ 70 ℃; Boil off 50mL ethanol, be cooled to 20 ℃ again, add 0.18 mole of sulfur monochloride (being 25g) rapidly; Then 40 ℃ ,-0.06--negative pressure of 0.04MPa under reaction 0.5 hour, mixture, mixture leaves standstill 0.5h under 40 ℃, 1 normal atmosphere; Remove de-chlorine hydride, logical again Monomethylamine controlled atmosphere PH=7 is cooled to 5 ℃; Filter row filter thing, the filter thing is used water washing, the dry 5-amino-1-(2 that gets; 6-dichlor-4-trifluoromethyl phenyl)-and 3-cyano pyrazole-two sulphur 101.4g of 4-base, content 96.8%, yield 93.0%.
Embodiment 3
In the 300ml acetonitrile, add 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles of 0.3mol (being 98.3g), under 0.3 normal atmosphere, be heated to 65 ~ 70 ℃; Boil off the 50mL acetonitrile, be cooled to 20 ℃ again, add 0.15 mole of sulfur monochloride (being 20.8g) rapidly; Then 40 ℃ ,-0.08--negative pressure of 0.07MPa under reaction 0.5 hour, mixture, mixture leaves standstill 0.5h under 45 ℃, 1 normal atmosphere; Remove de-chlorine hydride, logical again ammonia is transferred PH=7, is cooled to 5 ℃; Filter row filter thing, the filter thing is used water washing, the dry 5-amino-1-(2 that gets; 6-dichlor-4-trifluoromethyl phenyl)-and 3-cyano pyrazole-two sulphur 103.3g of 4-base, content 97.2%, yield 95.1%.
Embodiment 4
In the mixed solvent of 150ml ethanol and 150ml acetonitrile, add 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles of 0.3mol (being 98.3g), be heated to 65 ~ 70 ℃ at 0.5 normal atmosphere; Boil off the 50mL mixed solvent, be cooled to 20 ℃ again, add 0.21 mole of sulfur monochloride (being 29g) rapidly; Then 40 ℃ ,-negative pressure of 0.095MPa under reaction 0.5 hour, mixture, mixture leaves standstill 0.5h under 50 ℃, 1 normal atmosphere; Remove de-chlorine hydride, add Monomethylamine controlled atmosphere PH=7 again, be cooled to 5 ℃; Filter row filter thing, the filter thing is used water washing, the dry 5-amino-1-(2 that gets; 6-dichlor-4-trifluoromethyl phenyl)-and 3-cyano pyrazole-two sulphur 103.5g of 4-base, content 97.3%, yield 95.4%.
The present invention has all obtained same or analogous satisfactory result through TE and test, shows that method is reliable and stable, and yield is high; Utilization of materials is high, and is easy to operate, energy-conserving and environment-protective, and prepared midbody can be effective to prepare fluorine worm nitrile; Cost is low, and is effective, and pertinent data is following:
The midbody that the present invention makes adopts ordinary method, preparation fluorine worm nitrile; As utilize the compound method of patent (WO 2001030760 A1), and its structure is confirmed with nuclear-magnetism through infrared, confirm as fluorine worm nitrile; IR1637 (C-N), 1762 (C=O), 3068 (C-H); HNMR (CDCl
3, 400MHz) 1.11 (s, 6H, CH
3), 3.58 (s, 4H, CH
2), 8.52 (Py-H), gained fluorine worm nitrile has been obtained satisfied effect through field control effectiveness test for s, 1H, and particular case is following:
Making fluorine worm nitrile with midbody of the present invention is configured to 5%SC and existing fluorine worm nitrile 5%SC (like the product of Anhui Huaxing Chemical Co., Ltd.) and small cabbage moth is carried out the field efficacy experiment, experiment more than 10 times repeatedly.Experiment shows that the pyraclostrobin that utilizes the inventive method preparation is mixed with 5% SC and the fluorine worm nitrile SC of Anhui Huaxing Chemical Co., Ltd. has equal drug effect.
% fluorine worm nitrile suspension agent (SC) is to the control effect of small cabbage moth
A is for to make fluorine worm nitrile and to be configured to SC with instance 3 midbodys of the present invention.
B is Anhui Huaxing Chemical Co., Ltd.'s product.
The c rate of going down is 10 test MVs, every dispenser 1 time, result after 1 day.
Can be found out clearly that by The above results the midbody that the inventive method is processed is effective to the production of fluorine worm nitrile, yield reaches more than 93%; Cost reduces more than 50%, but and suitability for industrialized production, because material is fully used; And working method is simple, and save energy is more than 30%, energy-conserving and environment-protective; Realized the requirement of energy-saving and emission-reduction, good economic and social benefit has been arranged.
Claims (5)
1. the compound method of a fluorine worm nitrile midbody is characterized in that, is raw material with 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and sulfur monochloride; Add 5-amino-3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles in the polar solvent, after mixing, under the 0.3-0.6 normal atmosphere earlier; Be heated to 30-70 ℃, boil off 1/6 polar solvent, be cooled to 20 ℃ again, add sulfur monochloride rapidly; 35-40 ℃ ,-0.095--negative pressure of 0.01MPa under reaction 0.5 hour, mixture, mixture leaves standstill 0.5h under 35-50 ℃, 1 normal atmosphere, remove de-chlorine hydride; Feed the amine regulator, transferring pH is 7, is cooled to≤5 ℃, crosses and filters the filter thing; The filter thing is used water washing, dry 5-amino-1-(2,6-dichlor-4-trifluoromethyl the phenyl)-3-cyano pyrazole-two sulphur of 4-base that get;
Described polar solvent is acetone, butanone, isobutyl ketone, the pentanone of ketone, a kind of or any two kinds mixing of mibk; Or a kind of or any two kinds mixing of the methyl alcohol of alcohols, ethanol, propyl alcohol, Virahol; Or the acetonitrile of nitrile; Add 0.1 mole 5-amino-3-cyanic acid-1-(2, the 6-dichlor-4-trifluoromethyl phenyl) pyrazoles and the sulfur monochloride of 0.05-0.08 mole in every 100ml polar solvent;
Described amine regulator is one or both mixing of ammonia, Monomethylamine, diethylamine, quadrol, triethylamine, n-Butyl Amine 99.
2. the compound method of fluorine worm nitrile midbody according to claim 1 is characterized in that, in 300ml acetone, adds 5-amino-3-cyanic acid-1-(2 of 0.3mol; 6-dichlor-4-trifluoromethyl phenyl) pyrazoles is heated to 30 ~ 35 ℃ under 0.4 normal atmosphere, boil off 50mL acetone; Be cooled to 20 ℃ again, add 0.24 mole of sulfur monochloride rapidly, then 35 ℃ ,-0.03--negative pressure of 0.01MPa under reaction 0.5 hour; Get mixture, mixture leaves standstill 0.5h under 35 ℃, 1 normal atmosphere, removes de-chlorine hydride; Drip triethylamine again and transfer pH=7, be cooled to 5 ℃, cross and filter the filter thing; The filter thing is used water washing, dry 5-amino-1-(2,6-dichlor-4-trifluoromethyl the phenyl)-3-cyano pyrazole-two sulphur of 4-base that get.
3. the compound method of fluorine worm nitrile midbody according to claim 1 is characterized in that, in 300ml ethanol, adds 5-amino-3-cyanic acid-1-(2 of 0.3mol; 6-dichlor-4-trifluoromethyl phenyl) pyrazoles is heated to 65 ~ 70 ℃ under 0.6 normal atmosphere, boil off 50mL ethanol; Be cooled to 20 ℃ again, add 0.18 mole of sulfur monochloride rapidly, then 40 ℃ ,-0.06--negative pressure of 0.04MPa under reaction 0.5 hour; Get mixture, mixture leaves standstill 0.5h under 40 ℃, 1 normal atmosphere, removes de-chlorine hydride; Logical again Monomethylamine controlled atmosphere PH=7 is cooled to 5 ℃, filters row filter thing; The filter thing is used water washing, dry 5-amino-1-(2,6-dichlor-4-trifluoromethyl the phenyl)-3-cyano pyrazole-two sulphur of 4-base that get.
4. the compound method of fluorine worm nitrile midbody according to claim 1 is characterized in that, in the 300ml acetonitrile, adds 5-amino-3-cyanic acid-1-(2 of 0.3mol; 6-dichlor-4-trifluoromethyl phenyl) pyrazoles is heated to 65 ~ 70 ℃ under 0.3 normal atmosphere, boil off the 50mL acetonitrile; Be cooled to 20 ℃ again, add 0.15 mole of sulfur monochloride rapidly, then 40 ℃ ,-0.08--negative pressure of 0.07MPa under reaction 0.5 hour; Get mixture, mixture leaves standstill 0.5h under 45 ℃, 1 normal atmosphere, removes de-chlorine hydride; Logical again ammonia is transferred PH=7, is cooled to 5 ℃, filters row filter thing; The filter thing is used water washing, dry 5-amino-1-(2,6-dichlor-4-trifluoromethyl the phenyl)-3-cyano pyrazole-two sulphur of 4-base that get.
5. the compound method of fluorine worm nitrile midbody according to claim 1 is characterized in that, in the mixed solvent of 150ml ethanol and 150ml acetonitrile, adds 5-amino-3-cyanic acid-1-(2 of 0.3mol; 6-dichlor-4-trifluoromethyl phenyl) pyrazoles is heated to 65 ~ 70 ℃ at 0.5 normal atmosphere, boils off the 50mL mixed solvent; Be cooled to 20 ℃ again, add 0.21 mole of sulfur monochloride rapidly, then 40 ℃ ,-negative pressure of 0.095MPa under reaction 0.5 hour; Get mixture, mixture leaves standstill 0.5h under 50 ℃, 1 normal atmosphere, removes de-chlorine hydride; Add Monomethylamine controlled atmosphere PH=7 again, be cooled to 5 ℃, filter row filter thing; The filter thing is used water washing, dry 5-amino-1-(2,6-dichlor-4-trifluoromethyl the phenyl)-3-cyano pyrazole-two sulphur of 4-base that get.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353251A (en) * | 2017-07-24 | 2017-11-17 | 连云港埃森化学有限公司 | A kind of ethiprole production technology |
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| CN1332730A (en) * | 1999-10-22 | 2002-01-23 | 阿方蒂农科股份有限公司 | Process for preparing insecticide |
| CN101168529A (en) * | 2006-10-24 | 2008-04-30 | 温州大学 | Fipronil, ethiprole and synthesizing method for derivative thereof |
| CN102060774A (en) * | 2009-11-11 | 2011-05-18 | 李家波 | Method for synthesizing fipronil |
| WO2012007938A1 (en) * | 2010-07-12 | 2012-01-19 | Irvita Plant Protection, A Branch Of Celsius Property B.V | Fipronil production process |
-
2012
- 2012-05-30 CN CN2012101729594A patent/CN102690232A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1332730A (en) * | 1999-10-22 | 2002-01-23 | 阿方蒂农科股份有限公司 | Process for preparing insecticide |
| CN101168529A (en) * | 2006-10-24 | 2008-04-30 | 温州大学 | Fipronil, ethiprole and synthesizing method for derivative thereof |
| CN102060774A (en) * | 2009-11-11 | 2011-05-18 | 李家波 | Method for synthesizing fipronil |
| WO2012007938A1 (en) * | 2010-07-12 | 2012-01-19 | Irvita Plant Protection, A Branch Of Celsius Property B.V | Fipronil production process |
Non-Patent Citations (1)
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| QIQI ZHAO，等: "Design, Synthesis and Insecticidal Activity of Novel Phenylpyrazoles Containing a 2,2,2-Trichloro-1-alkoxyethyl Moiety", 《J.AGRIC.FOOD CHEM.》, vol. 58, no. 8, 29 March 2010 (2010-03-29) * |
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| CN107353251A (en) * | 2017-07-24 | 2017-11-17 | 连云港埃森化学有限公司 | A kind of ethiprole production technology |
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Application publication date: 20120926 |