CN1256320C - Synthesis of p-cyanoacetophenone by direct catalyst selective oxidation - Google Patents
Synthesis of p-cyanoacetophenone by direct catalyst selective oxidation Download PDFInfo
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- CN1256320C CN1256320C CNB031335225A CN03133522A CN1256320C CN 1256320 C CN1256320 C CN 1256320C CN B031335225 A CNB031335225 A CN B031335225A CN 03133522 A CN03133522 A CN 03133522A CN 1256320 C CN1256320 C CN 1256320C
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Abstract
The present invention relates to a method for directly synthesizing p-cyanoacetophenone by one-step catalytic and selective oxidation, which comprises: under the action of a solid catalyst, ethylbenzonitrile is oxidized by oxygen or air to directly synthesize p-cyanoacetophenone in one step. The method comprises the following reaction conditions: the dosage of the catalyst is from 0.5 to 20%, the reaction pressure is from 0.01 to 2.00MPa, the reaction temperature is from 40 to 200 DEG C, the reaction time is from 0.3 to 1.5 hours, the conversion rate can reach 61.0%, and the selectivity can reach 99.3%. The used catalyst is a multi-component compound solid catalyst prepared by a hydro-thermal method which is modified by adopting organic addition agents, and the catalyst comprises the following component: Ag, Al, Ce, Co, Cr, Cu, Fe, Mn, Ni, P, Sn, Ti, V and other elements. The method has the characteristics of no use of reaction solvent, easy separation and cyclic usage of the catalyst, low cost, few byproducts, high selectivity, environmental protection, etc., and has wide industrial application prospects.
Description
Technical field
The present invention relates to the preparation of 4-Acetylbenzonitrile, a specifically a kind of step catalytic selective oxidation is the method for synthetic 4-Acetylbenzonitrile directly.
Background technology
4-Acetylbenzonitrile is a kind of important organic synthesis intermediate, has purposes widely in organic synthesis, medicine in the synthetic and liquid crystal.4-Acetylbenzonitrile synthetic mainly contains following method: 1. pair acetylphenyl halogen or to the cyanide process of acetylphenyl trifluoromethane sulfonic acid ester; 2. to cyano-phenyl halogen or to the acetylation method of cyano-phenyl trifluoromethane sulfonic acid ester; 3. the Grignard reaction method of paracyanobenzoic acid derivative.
German Patent (Ger.Offen.) 10113976 has been reported the method for the synthetic 4-Acetylbenzonitrile of parachloroacetophenone cyaniding, it is catalyzer that this method adopts acid chloride, a kind of bidentate phosphine and a kind of diamines are sequestrant, toluene is solvent, in pressurized vessel, 160 ℃ of reactions 16 hours generate 4-Acetylbenzonitrile by parachloroacetophenone and potassium cyanide, selectivity is 95%, and yield is 86%.European patent EP 771786 has been reported the method for the synthetic 4-Acetylbenzonitrile of acetophenone derivs cyaniding of para-orientation, and this method adopts (Ph
3P)
4Pd and CuI are catalyzer, to be raw material to the acetylphenyl bromine or iodine and to acetylphenyl trifluoromethane sulfonic acid ester, react in tetrahydrofuran (THF) with potassium cyanide, (pertinent literature also has: Bull.Chem.Soc.Jpn. to generate 4-Acetylbenzonitrile, 64 (4), 1118-1121,1991; Chem.Lett., 1957-1958,1989; Tetrahedron Lett., 42 (38), 6707-6710,2001; J.Org.Chem., 60 (21), 6895-6903,1995 etc.).Though this class methods yield is higher, need to use precious metals palladium catalyst and expensive sequestrant, be difficult to reclaim and reuse; And use hypertoxic potassium cyanide to be raw material, there is potential safety hazard.
Document (Tetrahedron; 50 (2); 285-304; 1994) reported being the synthetic method of raw material cyano-phenyl trifluoromethane sulfonic acid ester; the employing acid chloride is a catalyzer, uses N, and N-dimethyl-O-vinyl monoethanolamine is an acetylation reagent; 60 ℃ were reacted 168 hours, and obtained 83% 4-Acetylbenzonitrile.This method is used precious metals palladium catalyst equally, is difficult to reclaim and reuse; And acetylation reagent N, N-dimethyl-O-vinyl monoethanolamine is synthetic complicated, does not have the industrial goods supply.
Document (Tetrahedron Lett., 37 (30), 5381-5384,1996 and 28 (18), 2053-2056,1987) has been reported the method for using the Grignard reagent react of cyano-benzoyl chloride and monobromethane respectively, and the yield of 4-Acetylbenzonitrile reaches 75%; What this method was used is the Grignard reaction, and the Grignard reaction must be carried out under anhydrous condition, often uses low boiling point solvents such as ether, tetrahydrofuran (THF), complex manufacturing.
The synthetic method of above-mentioned various 4-Acetylbenzonitriles does not prepare the ethylbenzene formonitrile HCN with the molecular oxygen direct oxidation, exists the raw materials cost height, pollutes deficiency such as big, processing condition harshness.
Summary of the invention
The objective of the invention is to develop the method that a kind of technology is simple and direct, use the molecular oxygen heterogeneous catalytic oxidation that one step of ethylbenzene formonitrile HCN is directly synthesized 4-Acetylbenzonitrile, develop a kind of solid heterogeneous catalyst that is used for this process simultaneously.
For achieving the above object, the technical solution used in the present invention is:
In the presence of solid catalyst, use oxygen and/or atmospheric oxidation to the ethylbenzene formonitrile HCN, directly synthetic 4-Acetylbenzonitrile of a step; Described solid catalyst is made up of Al component and other component; Other component comprises one or more among Ag, Ce, Co, Cr, Cu, Fe, Mn, Ni, P, Sn, Ti, the V.
Reaction can be carried out in pressure reactor or normal pressure reactor, and reaction pressure is 0.01-2.00MPa, and preferable pressure is 0.05-0.50MPa, and optimum pressure is 0.08-0.15MPa; Temperature of reaction is 40-200 ℃, and preferable temperature of reaction is 100-190 ℃, and best temperature of reaction is 120-180 ℃.Reaction times is 0.3-15 hour, and the preferable reaction times is 0.5-8 hour, and the best reaction times is 0.6-5 hour;
Described catalyzer is a polycomponent composite solid catalyzer, and these components can exist with the form of oxide compound, basic oxide or acid oxide compound in catalyzer; Its usage quantity is the 0.5-20% to ethylbenzene formonitrile HCN quality; When the usage quantity of catalyzer was high, oxidation effectiveness was better, but can increase cost, and therefore, the preferable consumption of the catalyzer that present method adopts is 2-15%, and optimum amount is 3-10%; After reaction finished, catalyzer can separate with reaction system by filtered while hot or cooling back solvent cut after-filtration; The catalyzer that reclaims, can be reused after the oven dry with alcohol immersion, washing;
The Al component is in oxide compound in the catalyzer, and the weight content in catalyzer is 10-40%, is preferably 15-35%, and the best is 20-32%; Other component is in oxide compound, and the add-on of each one-component is 0.1-75%, is preferably 0.5-70%, and the best is 0.8-68%;
The Hydrothermal Preparation that described catalyzer can adopt organic formwork agent to modify, concrete preparation process is: aqueous metal salt, acid solution or the solid precursor of each component precursor are stirred together, then add one or more organic compound as template; Behind the restir, change in the stainless steel encloses container, in 180 ℃ of crystallization 24 hours; Then, after suction filtration, washing, oven dry, 550 ℃ of roastings 2 hours promptly get catalyzer used in the present invention; The organic formwork agent that uses has polyvalent alcohol or amine compounds such as glycerol, tetramethylolmethane, trolamine, diethanolamine, triethylamine, dibutylamine, Tributylamine; Addition is the 0-100% of catalyst component precursor total mass, and preferable consumption is 10-80%, and optimum amount is 15-50%.
The present invention's reaction can be carried out under condition of no solvent, except that catalyzer and oxygen source, in the reaction process, need not to add any other material; Also can carry out having under solvent (for example: acetonitrile, chlorinated benzene, the acetate etc.) condition; React phenomenons such as no polymerization, coking.
The present invention has following advantage:
1. pollute little, efficient is high, simple and direct.The present invention can not use reaction solvent, except that catalyzer and oxygen source, in the reaction process, need not to add any other material, alleviates environmental pollution, reacts phenomenons such as no polymerization, coking;
2. active high, easily separated.The catalyzer that the present invention adopts does not contain precious metal, and its principal feature is that multiple active components and catalyzer have carried out finishing, has higher activity and selectivity, and is easily separated with reaction system, and can reuse.
Embodiment
Embodiment 1: the preparation of catalyst A
Get 12.5g Al (OH)
3, 1.1g Co (NO
3)
26H
2O, 1.6g Ni (NO
3)
26H
2O, 20.0g strong phosphoric acid and 150ml distilled water stir down together, splash into the 25.8g glycerol; After dropwising, stirred one hour; Change in the stainless steel encloses container, in 180 ℃ of crystallization 24 hours; Then, suction filtration, filter cake 550 ℃ of roastings 2 hours, promptly makes catalyst A after distilled water wash 5-6 time, 120 ℃ of oven dry.
Embodiment 2: the preparation of catalyst B-H
Except each active ingredient precursor of catalyzer and composition with organic formwork agent is different, the preparation of catalyst B-G is all identical in catalyst A with the catalytically active assessment method, the composition of catalyzer sees Table 1.
The reactivity worth evaluation result of catalyzer sees Table 2; With dehydrated alcohol reactant is all dissolved, after the filtration, sampling is analyzed (area normalization method) with gas chromatograph.
Embodiment 3: the reaction in the pressure reactor
1.50g is dropped in the 40ml autoclave pressure ethylbenzene formonitrile HCN and 0.075g catalyst A, the envelope still, logical oxygen is stopped leakage in the roof, and takes a breath three times.Under the normal pressure, stir heat temperature raising; When temperature in the kettle was 160 °, aerating oxygen oxygen to the still was pressed and is reached 1.00MPa, begins reaction; When the still internal pressure reached 0.10MPa, supplemental oxygen oxygen to the still was pressed and is reached 1.00MPa, continues reaction; Like this intermittently supplemental oxygen, when the still internal pressure not when descending, stopped reaction; Reaction times is about 4 hours.Be cooled to room temperature, drive still; Reactant is the faint yellow solid shape, below catalyzer is sunken to.
Reactant with 30 milliliters of anhydrous alcohol solutions, after the filtration, is taken a sample, with gas chromatograph analysis (area normalization method).Feed stock conversion is 48.7%, and selectivity is 98.0%.
Embodiment 4: the reaction in the normal pressure reactor
3.0g is equipped with in the reaction flask of prolong and ventpipe ethylbenzene formonitrile HCN and 0.30g catalyst A input, and the oil bath heat temperature raising is answered when oil bath temperature is 180 °; React and stop after 5 hours.If blast air, the reaction times is 10 hours.
Place cooling, reactant is the yellow solid shape, below catalyzer is sunken to.
Embodiment 5: the recovery of catalyzer and regeneration
The recovery of catalyzer has two kinds of methods:
1. after reaction finished, filtered while hot reclaimed catalyzer;
2. after reaction finishes, anhydrous alcohol solution reactant, filtering recovering catalyst.
The catalyzer that reclaims is through dehydrated alcohol dipping back, suction filtration, and absolute ethanol washing is dried, and is promptly renewable; The regenerated catalyzer uses repeatedly through 5 times, does not find that catalytic activity reduces.
Table 1: the composition of catalyzer
| Numbering | Component and consumption (g) | Template and consumption (g) | |||
| A | Co(NO 3) 2·6H 2O 1.1 | Ni(NO 3) 2·6H 2O 1.6 | H 3PO 4 20.0 | - | Glycerol 25.8 |
| B | Cr(NO 3) 3·9H 2O 5.5 | - | - | - | Triethylamine 8.0 |
| C | Fe(NO 3) 3·9H 2O 5.0 | Mn(NO 3) 2·6H 2O 2.9 | SnCl 2 1.0 | - | Trolamine 10.0 |
| D | Ce(NO 3) 3·6H 2O 1.6 | Fe(NO 3) 3·9H 2O 1.2 | AgNO 3 0.5 | H 3PO 4 15.0 | Trolamine 30.0 |
| E | Cr(NO 3) 3·9H 2O 4.5 | Ni(NO 3) 2·6H 2O 1.6 | SnCl 2 2.5 | H 3PO 4 8.0 | Triethylamine 28.6 |
| F | NaVO 3·2H 2O 4.3 | Ti(OPr) 4 0.6 | H 3PO 4 12.0 | - | Glycerol 5.9 |
| G | Cu(OAc) 2·H 2O 2.O | Co(NO 3) 2·6H 2O 3.9 | - | - | Glycerol 15.9 |
Annotate: Al (OH)
3Consumption be 12.5g, the H of use
3PO
4Mass content is 85%.
Table 2: the reaction result of catalyzer
| Catalyzer and consumption | Oxygen source | Reaction pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Transformation efficiency (%) | Selectivity (%) |
| A(5％) | Oxygen | 1.00 | 160 | 4.0 | 48.7 | 98.0 |
| A(10％) | Air | 0.10 | 180 | 10.0 | 57.1 | 97.2 |
| B(0.6％) | Oxygen | 0.50 | 170 | 3.0 | 47.5 | 98.6 |
| B(1％) | Oxygen | 0.50 | 170 | 2.0 | 50.2 | 98.1 |
| B(2％) | Air | 0.10 | 175 | 8.5 | 49.8 | 98.5 |
| C(4％) | Oxygen | 0.60 | 120 | 3.5 | 51.3 | 99.0 |
| C(5％) | Air | 0.10 | 150 | 5.0 | 59.3 | 99.3 |
| D(5％) | Oxygen | 0.30 | 200 | 0.5 | 60.8 | 88.6 |
| D(5％) | Air | 0.10 | 200 | 1.0 | 61.0 | 77.9 |
| E(8％) | Oxygen | 2.00 | 140 | 12.0 | 60.1 | 99.2 |
| E(20％) | Oxygen | 2.00 | 60 | 15.0 | 30.1 | 99.3 |
| E(8％) | Oxygen | 1.50 | 140 | 15.0 | 60.2 | 99.0 |
| F(2.5％) | Oxygen | 0.50 | 150 | 1.0 | 46.9 | 99.3 |
| F(3％) | Air | 0.10 | 150 | 2.0 | 47.6 | 99.0 |
| G(18％) | Oxygen | 0.10 | 190 | 0.4 | 28.8 | 97.0 |
| G(6％) | Oxygen | 0.40 | 100 | 6.0 | 40.5 | 99.1 |
| G(6％) | Air | 0.10 | 110 | 7.5 | 37.8 | 99.0 |
Claims (10)
1. the method for the synthetic 4-Acetylbenzonitrile of direct catalytic selective oxidation of step is characterized in that: in the presence of solid catalyst, use oxygen and/or atmospheric oxidation to the ethylbenzene formonitrile HCN, directly synthetic 4-Acetylbenzonitrile of a step; Described solid catalyst is made up of Al component and other component; Other component comprises one or more among Ag, Ce, Co, Cr, Cu, Fe, Mn, Ni, P, Sn, Ti, the V; Wherein the Al component is in oxide compound, and the mass content in catalyzer is 10-40%; Other component is in oxide compound, and the add-on of each one-component is 0.1-75%.
2. according to the described method of claim 1, it is characterized in that: the usage quantity of catalyzer is the 0.5-20% to ethylbenzene formonitrile HCN quality, and reaction pressure is 0.01-2.00MPa, and temperature of reaction is 40-200 ℃, and the reaction times is 0.3-15 hour.
3. according to the described method of claim 2, it is characterized in that: the usage quantity of catalyzer is the 2-15% to ethylbenzene formonitrile HCN quality, and reaction pressure is 0.05-0.50MPa, and temperature of reaction is 100-190 ℃, and the reaction times is 0.5-8 hour.
4. according to the described method of claim 2, it is characterized in that: the usage quantity of catalyzer is the 3-10% to ethylbenzene formonitrile HCN quality, and reaction pressure is 0.08-0.15MPa, and temperature of reaction is 120-180 ℃, and the reaction times is 0.6-5 hour.
5. according to the described method of claim 1, it is characterized in that: described Al constituent mass content is 15-35%, and the add-on of each one-component of other component is 0.5-70%.
6. according to the described method of claim 1, it is characterized in that: described Al constituent mass content is 20-32%, and the add-on of each one-component of other component is 0.8-68%.
7. according to the described method of claim 1, it is characterized in that: the Hydrothermal Preparation that described catalyzer adopts organic formwork agent to modify, the organic formwork agent that uses is glycerol, tetramethylolmethane, trolamine, diethanolamine, triethylamine, dibutylamine, Tributylamine, and its addition is the 10-100% of catalyst component precursor total mass.
8. according to the described method of claim 7, it is characterized in that: its consumption of described organic formwork agent is 10-80%.
9. according to the described method of claim 7, it is characterized in that: described consumption of template agent is 15-50%.
10. according to the described method of claim 1, it is characterized in that: be reflected under the condition that solvent exists and carry out.
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