CN100593540C - Method for preparing 5-amido-1-(2,6-dichlorin-4-trifluoro methylbenzene)-3-cyano pyrazole - Google Patents
Method for preparing 5-amido-1-(2,6-dichlorin-4-trifluoro methylbenzene)-3-cyano pyrazole Download PDFInfo
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- 238000000034 method Methods 0.000 title description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- QPZYPAMYHBOUTC-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole-3-carbonitrile Chemical compound NC1=CC(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl QPZYPAMYHBOUTC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- ITNMAZSPBLRJLU-UHFFFAOYSA-N 2,6-dichloro-4-(trifluoromethyl)aniline Chemical compound NC1=C(Cl)C=C(C(F)(F)F)C=C1Cl ITNMAZSPBLRJLU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- YMJLEPMVGQBLHL-UHFFFAOYSA-N 1h-pyrazole-5-carbonitrile Chemical compound N#CC1=CC=NN1 YMJLEPMVGQBLHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- -1 1,6-dichlor-4-trifluoromethyl phenyl Chemical group 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- ZFGOPCURHTZLST-UHFFFAOYSA-N 4-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1H-pyrazole-5-carbonitrile Chemical compound ClC1=C(C(=CC(=C1)C(F)(F)F)Cl)C=1C(=NNC=1)C#N ZFGOPCURHTZLST-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000008030 elimination Effects 0.000 claims description 3
- 238000003379 elimination reaction Methods 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 2
- MHVNGBBVHJJVPG-UHFFFAOYSA-N ethyl 2,3-dicyanoprop-2-enoate Chemical compound CCOC(=O)C(C#N)=CC#N MHVNGBBVHJJVPG-UHFFFAOYSA-N 0.000 abstract 1
- 235000010344 sodium nitrate Nutrition 0.000 abstract 1
- 239000004317 sodium nitrate Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a preparation method of the 5-amino-1-(2, 6-dichloro-4-trifluoromethyl phenyl)-3-cyano-pyrazole; the 2, 6-dichloro-4-trifluoromethylaniline is used as the raw material;the sulfuric acid of 40 to 98 percent is used as the reaction medium; the aqueous solution of sodium nitrate is dropped for the diazotization at the temperature between 0 and 70 DEG C for 0.5 to 1 hour to get the diazotization reaction solution; the temperature of the diazotization reaction solution is adjusted to be between 15 and 30 DEG C and then the 2, 3-dicyanoacrylate ethyl ester is added;then the cyclization reaction is done in the organic solvent at the temperature between 25 and 50 DEG C under the weakly alkaline condition; after the reaction is finished, the solution is dealt withto get the compound 5-amino-1-(2, 6-dichloro-4-trifluoromethyl phenyl)-3-cyano-pyrazole. The present invention effectively reduces the production cost and the ''three-waste'' emissions; therefore, thepresent invention can maintain the easiness of reaction, improve the collection rate of reaction, and reduce the ''three-waste'' emissions.
Description
(1) technical field
The present invention relates to the preparation method of a kind of 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole
(2) background technology
5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole is the key intermediate of preparation high-efficient broad-spectrum insecticide fluorine worm nitrile (its commodity are called " sharp strength spy ").The method of synthetic this compound mainly contains two classes, and the first kind is with 2, and the 6-dichlor-4-trifluoromethyl aniline is a raw material, obtains target product through steps such as diazotization, cyclisation.Second class is with 2, and 6-dichlor-4-trifluoromethyl phenylhydrazine is a raw material, through the synthetic target product of steps such as acidylate, Guan Huan.The present invention is primarily aimed at first kind method and is optimized improvement.
Patent EP0295117 has reported the synthetic method of following structural compounds:
This method adopts 2, and the 6-dichlor-4-trifluoromethyl aniline is a raw material, carries out diazotization in the mixed acid system of the vitriol oil and glacial acetic acid, and warp is with 2 again, and the cyclisation under weak basic condition of 3-dicyano ethyl propanoate obtains above-claimed cpd.The reaction conditions gentleness, yield＞70% can't be recycled but produce a large amount of spent acid in the reaction process, and especially the difficult separation and recycling of sulfuric acid and acetic acid has not only increased production cost, and environment has been caused pollution.
Ancel, people such as J.E (Tetrahedron Letters 2002, (43), 8319-8321.) reported that the employing methyl-cyanacetate replaces 2, the 3-dicyano ethyl propanoate carries out the method for cyclisation, but only is in laboratory stage at present, still is not suitable for suitability for industrialized production.
(3) summary of the invention
The technical problem to be solved in the present invention provide a kind of preparation easy, easy to use, produce industry " three wastes " less, production cost is relatively low and the preparation method of the 5-amino-1-of suitable suitability for industrialized production (2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole.
For realizing goal of the invention, the technical solution used in the present invention is:
A kind of suc as formula the 5-amino-1-(2 shown in (I), 6-dichlor-4-trifluoromethyl phenyl)-preparation method of 3-cyano pyrazole, comprise the steps: with 2, the 6-dichlor-4-trifluoromethyl aniline is a raw material, sulfuric acid with 40～98% is reaction medium, the aqueous solution that drips Sodium Nitrite carries out diazotization reaction in 0～70 ℃ and got diazotization reaction liquid in 0.5～1 hour, the diazotization reaction liquid temp is adjusted to 15～30 ℃ and adds 2, the 3-dicyano ethyl propanoate, carry out cyclization at 25～50 ℃ in organic solvent again under weak basic condition, reaction finishes after aftertreatment obtains the compound shown in the formula (I); Described 2,6-dichlor-4-trifluoromethyl aniline, Sodium Nitrite, sulfuric acid, 2, the amount of substance ratio that feeds intake of 3-dicyano ethyl propanoate is 1: 1～1.2: 4～6: 1～1.1;
Further, the organic solvent that uses in the cyclization is chloroform, ethylene dichloride or toluene.Described volume of organic solvent consumption is 2,13～16 times (ml/g) of 6-dichlor-4-trifluoromethyl aniline quality.
Particularly, described cyclization is: described diazotization reaction liquid temp is adjusted to 15～30 ℃, adds 2,3-dicyano ethyl propanoate, stirring reaction solution; With the described reaction soln of organic solvent extraction, extraction liquid is regulated PH＞9 with ammoniacal liquor, gets cyclization liquid in 3～10 hours in 25～50 ℃ of stirring reactions.
Preferably, the sulfuric acid concentration that uses in the reaction is 70～80%.
Preferred 20～60 ℃ of described diazotization reaction temperature.
Described aftertreatment is: cyclization liquid is removed by filter the black solid material, the filtrate washing is obtained organic layer, slough organic solvent by Rotary Evaporators again, obtain the product crude product, obtain product 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole with toluene/normal hexane recrystallization at last.
Concrete recommendation is described preparation method carry out according to following steps: in reaction vessel, splash into 2 in 70～80% sulphuric acid solns, the 6-dichlor-4-trifluoromethyl aniline, treat that solid all dissolves, drip the aqueous solution of Sodium Nitrite, drip and finish, be warming up to 20～60 ℃, reaction 30～45min; Be cooled to room temperature, add 2,3-dicyano ethyl propanoate, stirring at normal temperature; Use the chloroform extraction reaction solution, dropping ammonia in extraction liquid to PH＞9, stirred 3～10 hours fast in 25～50 ℃; React and finish back elimination black solid material, chloroform layer gets the product crude product through washing, anhydrous sodium sulfate drying, Rotary Evaporators precipitation, with toluene and normal hexane recrystallization, gets product 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole; Described 2,6-dichlor-4-trifluoromethyl aniline, Sodium Nitrite, sulfuric acid, 2, the amount of substance ratio that feeds intake of 3-dicyano ethyl propanoate is 1: 1.2: 5.4: 1, and the volumetric usage of described chloroform is 2,13～16 times (ml/g) of 6-dichlor-4-trifluoromethyl aniline quality.
The beneficial effect of the method for the invention is mainly reflected in:
(1) directly uses the medium of the sulfuric acid of different concns, avoided the use of glacial acetic acid, greatly reduce raw materials cost as diazotization reaction;
(2) because the solubleness of sulfuric acid in organic solvent is less, the consumption of the alkali of the acetic acid that having reduced is used for neutralizing in the former technology is dissolved in organic solvent has reduced production cost;
(3) the reaction conditions gentleness is easy and simple to handle, and the spent acid (sulfur acid) of reaction gained can directly be recycled the acetic acid that more former technology produced and vitriolic mixing spent acid, environmental protection more.
(4) embodiment
Further set forth technical scheme of the present invention with specific embodiment below, but protection scope of the present invention is not limited thereto:
Embodiment 1
In a four-hole boiling flask of being furnished with electric blender, thermometer, reflux condensing tube, drop into 98% vitriol oil 5.20g and water 2.30g, be diluted to 70% dilute sulphuric acid while stirring; Splash into 2,6-dichlor-4-trifluoromethyl aniline 2.20g makes its abundant salify, treats that solid all dissolves, and drips the 5.0ml aqueous solution of 0.79g Sodium Nitrite, drips and finishes, and is warming up to 55 ℃, keeps 30min; Be cooled to room temperature (20 ℃), impouring 2,3-dicyano ethyl propanoate 1.45g, stirring at normal temperature 2h; With 30ml chloroform extraction reaction solution, in extraction liquid, drip some 25% ammoniacal liquor, to PH＞9, stir 4h fast in 30 ℃; Elimination black solid material, organic layer get brown oil 2.52g through washing, anhydrous sodium sulfate drying, Rotary Evaporators precipitation, with toluene and normal hexane recrystallization, get solid 2.20g, reaction yield 71.65%, mp 140-142 ℃
The physics of gained compound and
1H-NMR character is as follows:
Fusing point: 140-142 ℃
1H-NMR analyzes (CDCl
3, TMS) δ: 7.77 (s, 2H), 6.04 (s, 1H), 3.83 (s, 2H).
Embodiment 2～7
With reference to the method for embodiment 1, do not change 98% vitriol oil consumption of input, change the vitriolic concentration that preparation obtains, other conditions are identical with embodiment 1, gained result such as table 1.
Table 1. sulfuric acid concentration is to the influence of reaction
| Embodiment | Sulfuric acid concentration (%) | Product yield (%) |
| 2 | 40 | 37.21 |
| 3 | 50 | 45.32 |
| 4 | 60 | 52.10 |
| 5 | 80 | 75.43 |
| 6 | 90 | 50.75 |
| 7 | 98 | 43.28 |
Embodiment 8～10
With reference to the method for embodiment 1, change the temperature of diazotization reaction, other conditions are identical with embodiment 1, gained result such as table 2.
Table 2. diazotization reaction temperature is to the influence of reaction
| Embodiment | The diazotization reaction temperature (℃) | Product yield (%) |
| 8 | 0 | 45.63 |
| 9 | 20 | 58.64 |
| 10 | 40 | 68.75 |
| 11 | 60 | 70.86 |
| 12 | 70 | 70.21 |
Embodiment 13～15
With reference to the method for embodiment 1, change the time of diazotization reaction, other conditions are identical with embodiment 1, gained result such as table 3.
The time of table 3. diazotization reaction is to the influence of reaction
| Embodiment | The diazotization reaction time (min) | Product yield (%) |
| 13 | 40 | 71.65 |
| 14 | 50 | 71.22 |
| 15 | 60 | 72.15 |
Embodiment 16～17
With reference to the method for embodiment 1, change adding 2, the temperature during the 3-dicyano ethyl propanoate, other conditions are identical with embodiment 1, gained result such as table 4.
Table 4. adds 2, and the temperature during the 3-dicyano ethyl propanoate is to the influence of reaction
| Embodiment | Temperature (℃) | Product yield (%) |
| 16 | 15 | 71.65 |
| 17 | 30 | 70.62 |
Embodiment 18～20
With reference to the method for embodiment 1, change the temperature of cyclization, other conditions are identical with embodiment 1, gained result such as table 5.
The temperature of table 5. cyclization is to the influence of reaction
| Embodiment | Temperature of reaction (℃) | Product yield (%) |
| 18 | 25 | 71.52 |
| 19 | 40 | 71.65 |
| 20 | 50 | 70.80 |
Embodiment 21～23
With reference to the method for embodiment 1, change the time of cyclization, other conditions are identical with embodiment 1, gained result such as table 6.
The time of table 6. cyclization is to the influence of reaction
| Embodiment | Reaction times (h) | Product yield (%) |
| 21 | 3 | 60.20 |
| 22 | 5 | 71.65 |
| 23 | 10 | 72.13 |
Embodiment 24～29
With reference to the method for embodiment 1, change used organic solvent and the consumption of cyclization, other conditions are identical with embodiment 1, gained result such as table 7.
The used organic solvent of table 7 cyclization is to the influence of reaction
| Embodiment | Organic solvent | Solvent load (ml) | Product yield (%) |
| 24 | Chloroform | 28 | 71.25 |
| 25 | Chloroform | 35 | 71.52 |
| 26 | Ethylene dichloride | 30 | 72.18 |
| 27 | Ethylene dichloride | 35 | 71.90 |
| 28 | Toluene | 30 | 71.51 |
| 29 | Toluene | 35 | 72.05 |
Embodiment 30～33
With reference to the method for embodiment 1, add 2, the amount of 6-dichlor-4-trifluoromethyl aniline is constant, changes the consumption of other reactants, and other conditions are identical with embodiment 1, gained result such as table 8.
The time of table 8. cyclization is to the influence of reaction
| Embodiment | Vitriol oil consumption (g) | Sodium Nitrite consumption (g) | 2,3-dicyano ethyl propanoate consumption (g) | Product yield (%) |
| 30 | 3.83 | 0.66 | 1.45 | 65.32 |
| 31 | 4.52 | 0.71 | 1.60 | 68.61 |
| 32 | 5.74 | 0.79 | 1.50 | 71.65 |
| 33 | 4.33 | 0.79 | 1.45 | 70.33 |
Claims (8)
1. one kind suc as formula the 5-amino-1-(2 shown in (I), 6-dichlor-4-trifluoromethyl phenyl)-preparation method of 3-cyano pyrazole, it is characterized in that described preparation method comprises the steps: with 2, the 6-dichlor-4-trifluoromethyl aniline is a raw material, sulfuric acid with 70～80% is reaction medium, the aqueous solution that drips Sodium Nitrite carries out diazotization reaction in 0～70 ℃ and got diazotization reaction liquid in 0.5～1 hour, the diazotization reaction liquid temp is adjusted to 15～30 ℃ and adds 2, the 3-dicyano ethyl propanoate, carry out cyclization at 25～50 ℃ in organic solvent again under weak basic condition, reaction finishes after aftertreatment obtains the compound shown in the formula (I);
2. the 5-amino-1-(2 shown in claim 1,6-dichlor-4-trifluoromethyl phenyl)-preparation method of 3-cyano pyrazole, it is characterized in that described 2,6-dichlor-4-trifluoromethyl aniline, Sodium Nitrite, sulfuric acid, 2, the amount of substance ratio that feeds intake of 3-dicyano ethyl propanoate is 1: 1～1.2: 4～6: 1～1.1.
3. the preparation method of the 5-amino-1-shown in claim 1 or 2 (2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole is characterized in that described organic solvent is chloroform, ethylene dichloride or toluene.
4. the preparation method of 5-amino-1-as claimed in claim 3 (2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole is characterized in that described volume of organic solvent consumption is 2,13～16 times (ml/g) of 6-dichlor-4-trifluoromethyl aniline quality.
5. 5-amino-1-(2 as claimed in claim 3,6-dichlor-4-trifluoromethyl phenyl)-and the preparation method of 3-cyano pyrazole, it is characterized in that described cyclization is: described diazotization reaction liquid temp is adjusted to 15～30 ℃, adds 2, the 3-dicyano ethyl propanoate, stirring reaction solution; With the described reaction soln of organic solvent extraction, extraction liquid is regulated PH＞9 with ammoniacal liquor, gets cyclization liquid in 3～10 hours in 25～50 ℃ of stirring reactions.
6. the preparation method of the 5-amino-1-shown in claim 1 (2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole is characterized in that described diazotization reaction temperature is 20～60 ℃.
7. 5-amino-1-(2 as claimed in claim 1,6-dichlor-4-trifluoromethyl phenyl)-preparation method of 3-cyano pyrazole, it is characterized in that described aftertreatment is: cyclization liquid is removed by filter the black solid material, the filtrate washing is obtained organic layer, slough organic solvent by Rotary Evaporators again, obtain the product crude product, obtain product 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole with toluene/normal hexane recrystallization at last.
8. the 5-amino-1-(2 shown in claim 1,6-dichlor-4-trifluoromethyl phenyl)-preparation method of 3-cyano pyrazole, it is characterized in that described preparation method is as follows: in reaction vessel, splash into 2 in 70～80% sulphuric acid solns, the 6-dichlor-4-trifluoromethyl aniline treats that solid all dissolves, drip the aqueous solution of Sodium Nitrite, drip and finish, be warming up to 20～60 ℃, reaction 30～45min; Be cooled to room temperature, add 2,3-dicyano ethyl propanoate, stirring at normal temperature; Use the chloroform extraction reaction solution, dropping ammonia in extraction liquid to PH＞9, stirred 3～10 hours fast in 25～50 ℃; React and finish back elimination black solid material, chloroform layer gets the product crude product through washing, anhydrous sodium sulfate drying, Rotary Evaporators precipitation, with toluene and normal hexane recrystallization, gets product 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano pyrazole; Described 2,6-dichlor-4-trifluoromethyl aniline, Sodium Nitrite, sulfuric acid, 2, the amount of substance ratio that feeds intake of 3-dicyano ethyl propanoate is 1: 1.2: 5.4: 1, and the volumetric usage of described chloroform is 2,13～16 times (ml/g) of 6-dichlor-4-trifluoromethyl aniline quality.
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| CN103396366B (en) * | 2013-08-06 | 2015-12-02 | 盐城工学院 | The production method of 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles |
| BR112018007039B1 (en) * | 2015-10-07 | 2021-12-14 | Gharda Chemicals Ltd | PROCESS FOR PREPARATION OF AMINOPYRAZOLE |
| CN106220565A (en) * | 2016-08-17 | 2016-12-14 | 江苏托球农化股份有限公司 | A kind of synthesis technique of 5 amino 3 cyano group 1 (2,6 dichloro-4,4 trifluoromethyl) pyrazoles |
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| CN1027341C (en) * | 1987-06-12 | 1995-01-11 | 罗纳-普朗克农业化学公司 | N-phenylpyrazole derivatives |
| CN1398515A (en) * | 2002-07-30 | 2003-02-26 | 王正权 | N-phenyl pyrazole derivative pesticide |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 氟虫腈及其中间体的合成研究进展. 任青云等.农药，第43卷第12期. 2004 * |
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