CN1133619C - Process for preparing 2-fluoro-6-chlorophenyl nitrile - Google Patents
Process for preparing 2-fluoro-6-chlorophenyl nitrile Download PDFInfo
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- CN1133619C CN1133619C CNB021157448A CN02115744A CN1133619C CN 1133619 C CN1133619 C CN 1133619C CN B021157448 A CNB021157448 A CN B021157448A CN 02115744 A CN02115744 A CN 02115744A CN 1133619 C CN1133619 C CN 1133619C
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- fluoro
- mono
- toluene
- chloride
- chlorotoluene
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Abstract
The present invention relates to a preparation method of 2-fluoro-6-chlorobenzonitrile. The required 2-fluoro-6-chlorobenzonitrile is prepared from a five-component catalyst using 2-fluoro-6-chlorotoluene as a raw material, vanadium and phosphorus as main catalysts, and titanium, ferrum, nickel, cobalt or bismuth, manganese, chromium, molybdenum, copper, zinc or tin, boron, sodium, potassium, litium or magnesium as cocatalysts through an ammoxidation reaction under the conditions that the reaction temperature is from 623 to 723K, the molar ratio of the air to the 2-fluoro-6-chlorotoluene is from 8 to 60, the molar ratio of ammonia gas to the 2-fluoro-6-chlorotoluene is from 2 to 12, and the catalyst load is from 30 to 100 g/(kgcat. h). The present invention has the advantages of simple and direct process, continuous progress, high productive capacity, environmental friendliness, easy acquirement of raw materials, etc. Under stable reaction conditions, the conversion rate of the 2-fluoro-6-chlorotoluene is higher than 98%, the mole yield of the 2-fluoro-6-chlorobenzonitrile can reach 71.47%, and the purity of the product can reach higher than 99 %.
Description
Technical field
The present invention relates to the preparation method of 2-fluoro-6-6-chlorophenyl nitrile, it belongs to technical field of organic chemistry, also belongs to organic fine chemical technical field.
Background technology
2-fluoro-6-6-chlorophenyl nitrile (2-chloro-6-fluorobenzonitrile), molecular formula ClC
6H
3FCN, pure product are white crystals.
Making corresponding fluoro virtue nitrile by chloro virtue nitrile through the high temperature fluoro, again by reactions such as hydrolysis, reduction, is one of best method of preparation fluorinated acid, fluoro benzamide.And fluorine-containing novel pesticide and medical kind constantly occurs at present, to the demand sharp increase of fluorinated acid, fluoro benzamide.Set out by 2-fluoro-6-6-chlorophenyl nitrile, can synthesize the many compounds in field such as medicine, agricultural chemicals, photoelectricity record material.
Before the present invention, the 2-fluoro-6-6-chlorophenyl nitrile preparation method of bibliographical information has (1) Journal of FluorineChemistry Vol.35 (1987) p591-596 report, is prepared by 2-nitro-6-6-chlorophenyl nitrile and Potassium monofluoride halogen exchange reaction; (2) World Intellectual Property Organization's patent WO9,805,630 reports are prepared through the aldoxime dehydration by 2-fluoro-6-chlorobenzaldehyde; (3) U.S. Pat P5,2,6-dichlorobenzonitrile halogen exchange prepares 2, the intermediate that relates in the 6-difluorobenzonilyile process as a kind of for 502,235 reports, 2-fluoro-6-6-chlorophenyl nitrile.Preceding two kinds of methods exist the problem of raw material sources difficulty, and the third method is in fact uncontrollable, have shortcomings such as product separation difficulty.So they all are unsuitable for large-scale production.
Summary of the invention
The purpose of this invention is to provide the method that a kind of ammonia oxidation prepares 2-fluoro-6-6-chlorophenyl nitrile, this method have technology simple and direct, can carry out continuously, advantage such as throughput is strong, environmentally friendly and raw material is easy to get.
Technical scheme provided by the invention is: the preparation method of 2-fluoro-6-6-chlorophenyl nitrile, with 2-fluoro-6-toluene(mono)chloride is raw material, with vanadium, phosphorus is Primary Catalysts, titanium, iron, nickel, cobalt or bismuth, manganese, chromium, molybdenum, copper, zinc or tin, boron, sodium, potassium, lithium or magnesium are five component catalysts that promotor is formed, at temperature of reaction 623～723K, the mol ratio of air and 2-fluoro-6-toluene(mono)chloride is 8～60, the mol ratio of ammonia and 2-fluoro-6-toluene(mono)chloride is 2～12, makes required 2-fluoro-6-6-chlorophenyl nitrile through oxidative ammonolysis under the condition of catalyst loading 30～100g/ (kgcath).
Above-mentioned temperature of reaction is preferably 653～693K; The mol ratio of air and 2-fluoro-6-toluene(mono)chloride is preferably 15～40; The mol ratio of ammonia and 2-fluoro-6-toluene(mono)chloride is preferably 4～10.
Consisting of of above-mentioned catalyzer: VPaCbDcEdOx/SiO
2, wherein C is titanium, iron, nickel, cobalt or bismuth, and D is manganese, chromium, molybdenum, copper, zinc or tin, and E is boron, sodium, potassium, lithium or magnesium, a=1, b=0.5～2.5, c=0.1～1.5, d=0.5～2.5, e=0.1～1.5, x then presses the valence state balance according to the content of above each element and decides.Active ingredient element wt content is 3～40%, and preferably scope is 5～30%.Carrier is a microsphere silica gel, and the microsphere diameter scope is 125～450 μ m.
Preparation of catalysts adopts pickling process: the effective ingredient of catalyzer dissolved respectively, mixed, and still aging after fully flooding with carrier silica gel again, under suitable temperature, activate the regular hour then.Generally between 673～923K, preferably temperature range is 723～873K to activation temperature.Soak time was generally 2～20 hours, and the optimum activating time scope is 3～15 hours.
Preparation is during catalyzer, and each component can be with oxide compound, salt or the alkali etc. of this element.For example vanadium can be used V
2O
5Or NH
4VO
3Deng, phosphorus can be used H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, (NH
4) H
2PO
4Or P
2O
5Deng, titanium can be used TiCl
4, Ti
2(C
2O
4)
3Deng, iron can be used FeCl
3, Fe
2O
3, Fe
3O
4, Fe (NO
3)
39H
2O, Fe (OAc)
2, Fe (C
2O
4) 2H
2O or Fe
2(C
2O
4)
36H
2O etc., nickel can be used NiCl
26H
2O or Ni (NO
3)
26H
2O etc., cobalt can be used Co (OAc)
2, Co (NO
3)
26H
2O, Co
3O
4Or CoCl
2Deng, bismuth can be used Bi (NO
3)
39H
2O or Bi
2O
3Deng, manganese can be used MnO
2, MnCl
2, Mn (NO
3)
2Deng, chromium can be used CrCl
3, Cr (NO
3)
39H
2O, Cr
2O
3, CrO
3Or (NH
4)
2Cr
2O
7Deng, molybdenum can be used MoO
3, (NH
4)
6Mo
7O
24Deng, copper can be used CuCl
2Or Cu (NO
3)
2Deng, zinc can be used ZnO, ZnCl
2, Zn (NO
3)
2Or Zn (OAc)
22H
2O etc., tin can be used SnCl
2Or SnCl
4Deng, boron can be used H
3BO
3, sodium can be used NaOH, NaCl, NaNO
3, Na
2CO
3Or Na
2C
2O
4Deng, potassium can be used KOH, KCl, KNO
3, K
2CO
3Or K
2C
2O
4Deng, lithium can be used Li
2O, LiCl, LiNO
3Or Li
2CO
3Deng, magnesium can be used MgO, MgCl
2Or Mg (NO
3)
26H
2O etc.
The ammonia oxidation technology of uses advanced of the present invention, from 2-fluoro-6-toluene(mono)chloride, under catalyst action, labile methyl group in the organic molecule and cheap ammonia and oxygen (air) reaction, a step is converted into cyano group and synthetic important intermediate 2-fluoro-6-6-chlorophenyl nitrile.It has technology simple and direct, can carry out continuously, advantage such as throughput is strong, environmentally friendly and raw material is easy to get.Under stable reaction conditions, the transformation efficiency of 2-fluoro-6-toluene(mono)chloride is higher than 98%, and the molar yield of 2-fluoro-6-6-chlorophenyl nitrile can reach 71.47%, and product purity can reach more than 99%.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
With 7.6930 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, adds 4.7060 grams, 85% strong phosphoric acid, 3.7010 gram V then respectively
2O
5, after the uniform solution to be formed, solution is poured into rapidly in the 30 gram silica gel (φ 125～425 μ m).Stir, after the drying, in muffle furnace, progressively be warmed up to 580 ℃, be incubated 12 hours.Behind the naturally cooling, stand-by.Consisting of of catalyzer: V
1P
1O
4.8/ SiO
2, activity of such catalysts composition weight content is 10%.
At internal diameter is the above-mentioned solid catalyst of filling 15g in the silica tube fixed-bed reactor of 25mm, and the mole proportioning of reaction raw materials is 2-fluoro-6-toluene(mono)chloride: NH
3: Air=1: 7: 30, temperature of reaction was 673 ± 1K, and the load of catalyzer is 50g/ (kgcath).Normal pressure reacted down after 8 hours, the transformation efficiency 99.3% of 2-fluoro-6-toluene(mono)chloride, and the molar yield of 2-fluoro-6-6-chlorophenyl nitrile is 55%, the selectivity of 2-fluoro-6-6-chlorophenyl nitrile is 55.4%.Product purity is 99%.
Embodiment 2
With 11.0103 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, adds 3.3554 grams, 85% strong phosphoric acid, 2.6448 gram V then respectively
2O
5, behind the dark blue solution to be formed, add 1.4556 gram CrO
3, 1.0030 milliliters of 2.92mol/lTiCl
4Solution and 0.3600 gram H
3BO
3, after the uniform solution to be formed, solution is poured into rapidly in the 30 gram silica gel (φ 125～425 μ m).Stir, placement is spent the night.In High Temperature Furnaces Heating Apparatus, progressively be warmed up to 580 ℃, be incubated 12 hours.After treating naturally cooling, preserve stand-by.Consisting of of this catalyzer: V
1P
1Cr
0.5B
0.2Ti
0.1O
6.25/ SiO
2, activity of such catalysts composition weight content is 10%.
The 15g catalyzer is packed in the internal diameter 25mm silica tube fixed-bed reactor, and material mixed gas passes through catalyst bed reaction.The mole of material mixed gas consists of: 2-fluoro-6-toluene(mono)chloride: ammonia: air=1: 6: 20.Temperature of reaction is 673 ± 1K, and the load of catalyzer is 50g/ (kgcath).React after 8 hours 2-fluoro-6-toluene(mono)chloride transformation efficiency 99.3%, 2-fluoro-6-6-chlorophenyl nitrile molar yield 66.4%, selectivity 66.9%, product purity 99.0%.
Can prepare the catalyzer of the present invention that comprises other promotor as stated above, wherein corresponding each active ingredient can be with oxide compound, salt or the alkali etc. of this element, during preparation, with reference to the foregoing description corresponding active ingredient material is proportionally done corresponding replacement and can obtain required catalyzer.
Claims (3)
1. the preparation method of 2-fluoro-6-6-chlorophenyl nitrile, with 2-fluoro-6-toluene(mono)chloride is raw material, with vanadium, phosphorus is Primary Catalysts, titanium, iron, nickel, cobalt or bismuth, manganese, chromium, molybdenum, copper, zinc or tin, boron, sodium, potassium, lithium or magnesium are five component catalysts that promotor is formed, at temperature of reaction 623～723K, the mol ratio of air and 2-fluoro-6-toluene(mono)chloride is 8～60, the mol ratio 2～12 of ammonia and 2-fluoro-6-toluene(mono)chloride makes required 2-fluoro-6-6-chlorophenyl nitrile through oxidative ammonolysis under the condition of catalyst loading 30～100g/ (kgcath).
2. preparation method according to claim 1 is characterized in that: above-mentioned temperature of reaction is 653～693K.
3. preparation method according to claim 1 and 2 is characterized in that: the mol ratio of above-mentioned air and 2-fluoro-6-toluene(mono)chloride is 15～40, and the mol ratio of ammonia and 2-fluoro-6-toluene(mono)chloride is 4～10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157448A CN1133619C (en) | 2002-04-23 | 2002-04-23 | Process for preparing 2-fluoro-6-chlorophenyl nitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157448A CN1133619C (en) | 2002-04-23 | 2002-04-23 | Process for preparing 2-fluoro-6-chlorophenyl nitrile |
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| Publication Number | Publication Date |
|---|---|
| CN1379022A CN1379022A (en) | 2002-11-13 |
| CN1133619C true CN1133619C (en) | 2004-01-07 |
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|---|---|---|---|
| CNB021157448A Expired - Fee Related CN1133619C (en) | 2002-04-23 | 2002-04-23 | Process for preparing 2-fluoro-6-chlorophenyl nitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435949C (en) * | 2006-03-23 | 2008-11-26 | 浙江工业大学 | Integrated member type methyl aromatic hydrocarbon selective oxidizing catalyst and its preparation and use |
| CN102909043B (en) * | 2011-08-04 | 2014-08-27 | 上海泰禾化工有限公司 | Catalyst for preparing 2,6-dichlorobenzonitrile and compositing method and application of catalyst |
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2002
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