CN1800132A - Arene olefin catalytic oxidation for preparing aromatic aldehyde - Google Patents

Arene olefin catalytic oxidation for preparing aromatic aldehyde Download PDF

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CN1800132A
CN1800132A CN 200510031106 CN200510031106A CN1800132A CN 1800132 A CN1800132 A CN 1800132A CN 200510031106 CN200510031106 CN 200510031106 CN 200510031106 A CN200510031106 A CN 200510031106A CN 1800132 A CN1800132 A CN 1800132A
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catalyzer
flow process
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metal
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CN1800132B (en
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聂亮
李文生
周小平
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Hunan University
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Hunan University
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Abstract

The invention discloses a method using mental oxide or mental salt crystal to catalytic oxidize fragrant olefin, pyridine olefin fragrant and pyridine carboxaldehyde. The reaction uses air or oxygen as oxidant with the pressure 0.1-100 Pa, the reacting temperature 20-400 deg. and the reacting time 0.1-24 h. It separates the product and the crystal after reaction. The crystal can be used after washing and drying.

Description

Arene olefin catalytic oxidation for preparing aromatic aldehyde
The present invention is to be raw material through the carbon-carbon double bond system aromatic aldehyde of catalyzed oxidation alkene, the method for pyridines aldehyde with fragrant alkene, pyridines alkene and air.
At present aromatic aldehyde industrial be to carry out oxide side chain system aromatic aldehyde or chlorination under suitable condition by its methyl substitute, and then produce through peracidity or alkaline hydrolysis and rectifying.Oxidation style such as the low and poor selectivity of toluene oxidation producing benzaldehyde transformation efficiency.Chlorination, and then not high through peracidity or alkaline water solution yield, corrosion contamination is serious.
U.S. Pat 6,458,737 disclose a kind of method of methyl substituted aromatic compound gaseous oxidation system aromatic aldehyde.This method adopts tungsten-based catalyst, under 450 ℃～600 ℃ temperature condition with dioxygen oxidation system aromatic aldehyde.There are shortcomings such as the low poor selectivity of transformation efficiency in this reaction.
In addition, having also had a large amount of documents and patent report utilizes the carbon-carbon double bond cleavage reaction to prepare the method for aromatic aldehyde.Lemieux (E.Can.J.Chem., 1955,33,1701) has reported with potassium permanganate and has made catalyzer that sodium periodate is made oxygenant oxidation fragrance alkene system aromatic aldehyde; Lemieux (J.Org.Chem., 1956,21,478) has reported and has used OsO 4Make catalyzer, sodium periodate is made oxygenant oxidation fragrance alkene system fragrance aldehydes or ketones; U.S. Pat 6,787,671 also disclose and have used OsO 4Olefin oxide system aldehydes or ketones; Sarel (J.Org.Chem., 1959,24,2018) has reported and has used RuO 4Make catalyst olefin oxide system aldehydes or ketones; Smith (J.Org.Chem., 2000,65,3738) has reported the method for utilizing ozone oxidation alkene system aldehyde.Above-mentioned reaction mostly is stoichiometric reaction greatly, and expensive product of oxygenant and catalyzer are not easily separated, are not suitable for large-scale industrial production, and unfriendly to environment.
Again bibliographical information has been arranged in recent years and used H 2O 2Perhaps superoxide is made oxygenant, utilizes the carbon-carbon double bond cleavage reaction to prepare the method for aromatic aldehyde.U.S. Pat 6,303,828 disclose the method for utilizing peroxide catalyzed olefin oxide system aromatic aldehyde.U.S. Pat 6,303,828 disclose and have utilized H 2O 2Make oxygenant, ruthenium molybdenum mixture is made the method for catalyst olefin oxide system aromatic aldehyde.Aforesaid method is owing to adopt superoxide to make oxygenant, cost height not only, and bigger potential safety hazard is arranged.
In addition, also had some bibliographical informations and utilized reductive agent activation oxygen, the carbon-carbon double bond cleavage reaction comes catalyzed oxidation to prepare aromatic aldehyde.Mukaiyama (Bull.Chem.Soc.Jpn.1995,68,17) has reported with aldehyde and has made reductive agent, with the method for dioxygen oxidation.Xavier (J.Org.Chem., 2001,66,4504) has reported with thiophenol and has made reductive agent, with the method for dioxygen oxidation.Because reductive agent is consumptive, the production cost height also is not suitable for large-scale industrial production.
The present invention adopts oxygen or air oxidant, and metal-salt or metal oxide are made catalyst oxidation fragrance alkene, (its alkene is the material shown in chemical structural formula Figure 1A, B, C, D, wherein substituent R to pyridines alkene 1, R 2, R 3, R 4Be :-H, phenyl, alkyl, alkylene ,-CCR, F, Cl, Br, I ,-NH 2,-NHCH 2R ,-N (CH 2R) 2,-NHCHR 2,-N (CHR 2) 2,-OCH 2R ,-OCHR 2With-OOCCH 2R, R is: phenyl, alkyl, alkylene.) oxidation system aromatic aldehyde and pyridines formaldehyde.Be reflected between 20～400 ℃ He under 0.1～50 normal atmosphere and carry out, the reaction times is generally between 0.15～24 hour.Be reflected at and obtain higher yield under the gentle condition, for example, when preparation 4-methoxybenzaldehyde, react maximum per pass conversion and can reach 96.9%, selectivity is 91.6%, and by product seldom.In addition, if adopt after the heterogeneous catalyst reaction finishes, be convenient to very much separated product.Catalyzer can come into operation after washing again.
Figure A20051003110600041
The alkene type
Preparation of Catalyst
WO 3Catalyzer
3.9600gWCl 6Be dissolved in the ethanol, be mixed with 40ml solution, in air, utilize airborne steam hydrolysis 3 days, under 450 ℃ of degree, fire then and got catalyzer in 5 hours.
Nb 2O 5Catalyzer
2.7100gNbCl 5Be dissolved in the ethanol, be mixed with 40ml solution, in air, utilize airborne steam hydrolysis 3 days, under 450 ℃ of degree, fire then and got catalyzer in 5 hours.
80%TiO 2/ 10%Nb 2O 5/ 10%WO 3Catalyzer
TiCl 4, NbCl 5And WCl 6Be 8: 1: 1 mixed (TiCl wherein in molar ratio 4, consumption is 3.8060g), be mixed with 40ml solution, in air, utilize airborne steam hydrolysis 3 days, under 450 ℃ of degree, fired then 5 hours catalyzer.
TiO 2/ SiO 2Catalyzer
1mol oxalic acid is dissolved in the water of 70.0ml, adds the TiCl of 0.050mol 4Stir half an hour, add the solution that water is made into 0.50M then.The Ti solution of getting prepared 0.50M adds Si (OCH 2CH 3) 4, being made into the Ti/Si ratio and being 1: 50,1: 100,1: 200 mixture, these mixtures obtain a titanium silica gel after stirring 6 hours.Titanium silica gel descended dry 6 hours at 50 ℃, burnt 4 hours at 550 ℃ then, made TiO 2/ SiO 2Than being 1/50,1/100,1/200.
TiO 2/ ZrO 2Catalyzer
2ml TiCl 4Be dissolved in the 40.0ml dehydrated alcohol, add 4.2330 gram ZrCl then 4Separated three days in water in air then, in 50 ℃ of dryings 1 day, the gained sample 450 ℃ fired 5 hours catalyzer.
Other catalyzer such as TiO 2, V 2O 5, RuCl 3(content 38.5%) and ZrO 2Be the commercial reagent, without any processing.
Embodiment one
With the titanium dioxide of electronic balance weighing 0.0500 gram, to pack into and be furnished with in the reactor of cover in the tetrafluoroethylene, the vinylbenzene that pipettes 0.800 milliliter with autospencer adds in the reactor, and sealed reactor is put into heating jacket.Reaction is by the thermopair temperature control, and controlled temperature passes through magnetic stirrer at 100 ℃.The oxygen pressure of reaction is controlled at 0.5MPa by reducing valve.After reacting four hours, reactor taken out from heating jacket naturally cool to normal temperature, take reactor then apart, take out product and analyze component, use chromatographic instrument (Agilent6890N) quantitative analysis then with gas chromatograph-mass spectrometer (GC-MS) (GC-MS Agilent6890N-5973N).Again come into operation after the washing of catalyzer process, the drying.Keep other condition constant, change respectively temperature of reaction 80 ℃,
90 ℃ and 100 ℃ of reactions down, the result is as shown in table 1.
The influence of table 1 temperature of reaction
Titanium dioxide (g) Reaction pressure (MPa) Temperature of reaction (℃) Reaction times (h) Transformation efficiency (%) Selectivity (%)
1 0.0500 0.5 80 4 1.69 ＞99
2 0.0500 0.5 90 4 7.02 98.48
3 0.0500 0.5 100 4 75.91 75.35
Embodiment two
With the titanium dioxide of electronic balance weighing 0.0500 gram, to pack into and be furnished with in the reactor of cover in the tetrafluoroethylene, the vinylbenzene that pipettes 0.800 milliliter with autospencer adds in the reactor, and sealed reactor is put into heating jacket.Reaction is by the thermopair temperature control, and controlled temperature passes through magnetic stirrer at 100 ℃.The oxygen pressure of reaction is controlled by reducing valve.After reacting four hours, reactor taken out from heating jacket naturally cool to normal temperature, take reactor then apart, take out product and analyze component, use chromatographic instrument (Agilent6890N) quantitative analysis then with gas chromatograph-mass spectrometer (GC-MS) (Agilent6890N-5973N).Again come into operation after the washing of catalyzer process, the drying.Keep other condition constant, change reaction pressure respectively and react under the condition of 0.5MPa, 1.0MPa, its result is as shown in table 2.
The influence of table 2 reaction pressure
Titanium dioxide (g) Temperature (℃) Reaction pressure (MPa) Reaction times (h) Transformation efficiency (%) Selectivity (%)
1 0.0500 100 0.5 4 75.91 75.35
2 0.0500 100 1.0 4 95.60 77.74
Embodiment three
Catalyst metal oxide catalyst or 0.0100g RuCl with electronic balance weighing 0.0500 gram 3Catalyzer is packed into and is furnished with in the reactor of cover in the tetrafluoroethylene, and the vinylbenzene that pipettes 0.800 milliliter with autospencer adds in the reactor, and sealed reactor is put into heating jacket.Reaction is passed through magnetic stirrer by the thermopair temperature control.The oxygen pressure of reaction is controlled by reducing valve.Behind the reaction certain hour, reactor taken out from heating jacket naturally cool to normal temperature, take reactor then apart, take out product, use chromatographic instrument (Agilent6890N) quantitative analysis then with gas chromatograph-mass spectrometer (GC-MS) (Agilent6890N-5973N) analysis component.Again come into operation after the washing of catalyzer process, the drying.Keep other condition constant, use different metal oxide catalysts, its result is as shown in table 3.
The influence of table 3 catalyzer
Catalyzer Temperature (℃) Reaction pressure (MPa) Reaction times (h) Transformation efficiency (%) Selectivity (%)
1 TiO 2 90 0.5 4 7.02 98.48
2 V 2O 5 90 0.5 4 40.23 81.63
3 ZrO 2 90 0.5 4 13.34 ＞99
4 WO 3 100 1.0 4 87.62 75.92
5 Nb 2O 5 100 1.0 4 52.70 91.18
6 TiO 2/SiO 2(1/200) 90 0.5 4 9.08 ＞99
7 TiO 2/SiO 2(1/100) 90 0.5 4 8.64 ＞99
8 TiO 2/SiO 2(1/50) 90 0.5 4 9.22 ＞99
9 TiO 2/ZrO 2(1/1) 90 0.5 4 20.30 98.66
10 TiO 2/ZrO 2(1/1) 110 1.0 1 26.30 99.41
11 TiO 2/ZrO 2(1/1) 100 1.0 4 59.20 93.21
12 TiO 2/ZrO 2(1/1) 110 1.0 2 60.23 85.84
13 TiO 2/Nb 2O 5/WO 3 90 0.5 4 25.14 99.80
14 RuCl 3 60 1.0 4 71.72 78.51
15 RuCl 3 60 1.0 3 27.31 86.97
16 RuCl 3 60 0.5 4 34.45 93.64
17 RuCl 3 60 0.5 5 58.01 75.04
Embodiment four
TiO with electronic balance weighing 0.0250 gram 2ZrO 2(1/1) catalyzer is packed into and is furnished with in the reactor of cover in the tetrafluoroethylene, and the reaction substrate that pipettes 0.400 milliliter with autospencer adds in the reactor, and sealed reactor is put into heating jacket.Reaction is by the thermopair temperature control, and controlled temperature passes through magnetic stirrer at 100 ℃.The oxygen pressure of reaction is controlled at 1.0Mpa by reducing valve.After reacting four hours, reactor taken out from heating jacket naturally cool to normal temperature, take reactor then apart, take out product and analyze component, use chromatographic instrument (Agilent6890N) quantitative analysis then with gas chromatograph-mass spectrometer (GC-MS) (Agilent6890N-5973N).Again come into operation after the washing of catalyzer process, the drying.Use different reaction substrate reactions, its result is as shown in table 4.
The reaction result of the various reaction substrates of table 4
Substrate Temperature (℃) Transformation efficiency (%) Selectivity (%)
1 The 4-chlorostyrene 100 94.00 80.00
2 The 2-chlorostyrene 100 6.94 84.56
3 The 2-chlorostyrene 110 95.08 76.45
4 The 2-chlorostyrene 120 97.08 68.71
5 The 4-methoxy styrene 100 18.69 95.69
6 The 4-methoxy styrene 110 96.93 91.64
7 The 4-methoxy styrene 120 96.42 89.94
8 1, the 1-distyryl 100 92.00 76.00
9 Trans-stilbene a 100 10.00 100.00
10 The 2-vinyl pyridine 100 1.00 100.00
11 4-vinylpridine 100 1.20 100.00
A 0.2000g is trans-and stilbene is dissolved in 0.88g benzene, and catalyst levels is 0.0500g.

Claims (10)

1. the present invention is one and makes catalyzer with metal oxide or metal-salt, with oxygen or air oxidant, from fragrant alkene and the pyridines alkene new technological process through catalyzed oxidation system fragrance formaldehyde, pyridines formaldehyde.
2. according to claim 1, said flow process reactor can be tank reactor, paste state bed reactor or fixed-bed reactor, after reaction is finished, separation can be adopted distillation or rectifying or underpressure distillation or rectification under vacuum, isolate remaining reactants, product and catalyzer, catalyzer and remaining reactants drop into reactor again and use.
3. according to claim 1, the substituting group on its alkene carbon-carbon double bond of said flow process is except that one of them is phenyl ring, is with substituent phenyl ring, pyridine or is with the substituent pyridine that other substituting group is R 1, R 2, R 3, also be R wherein with substituent phenyl ring or with the substituting group on the substituent pyridine 1, R 2, R 3R 1, R 2And R 3Be :-H, phenyl, alkyl, alkylene ,-CCR, F, Cl, Br, I ,-NH 2,-NHCH 2R ,-N (CH 2R) 2,-NHCHR 2,-N (CHR 2) 2,-OCH 2R ,-OCHR 2With-OOCCH 2R, R is: phenyl, alkyl, alkylene.
4. according to claim 1, the oxygenant that said flow process is used is oxygen or air.
5. according to claim 1, said flow process catalyzer is metal oxide or metal-salt, metal comprises Li, Na, K, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Sn, Pb, Sb, Bi, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Y, Ce, Pr, Nd, Pm, Sm, Eu, GdTb, Dy, La, Ho, Er, Tm, Yb, Lu, Th, U, the oxide compound of Cd, salt and their mixture, or oxide compound that can generate after other after chemical reaction or salt.
6. according to claim 5, said metal-salt is fluorochemical, muriate, bromide, iodide, vitriol, the phosphoric acid salt of metal.
7. according to claim 1, its temperature of reaction of said flow process is between 20 to 400 ℃, and temperature of reaction is between 40 to 200 ℃ preferably, and best temperature of reaction is between 50 to 160 ℃.
8. according to claim 1, the working pressure of said its air or oxygen of flow process is between 0.1 to 200 normal atmosphere, and pressure is between 0.5 to 100 normal atmosphere preferably, preferably between 2 to 60 normal atmosphere.
9. according to claim 1, the mol ratio of its catalyzer of said flow process and alkene is between 1: 100 to 10: 1.
10. according to claim 1, its reaction times of said flow process is between 0.15 hour and 24 hours.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885672A (en) * 2010-07-02 2010-11-17 苏州大学 Method for preparing benzaldehyde through catalytic oxidation of styrene
CN103120933A (en) * 2011-11-18 2013-05-29 中国石油化工股份有限公司 Preparation method of nanometer TiO2/ZrO2 composite material
CN106905121A (en) * 2017-04-21 2017-06-30 南京理工大学 A kind of preparation method of benzaldehyde
CN108250056A (en) * 2018-03-20 2018-07-06 哈尔滨师范大学 A kind of process for catalytic synthesis of benzaldehyde
CN108393084A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of composite metal catalyst and its application in selectivity of styrene oxidation
CN108393094A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of bimetallic catalyst and its application in selectivity of styrene oxidation
CN108393095A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of modified oxidized Co catalysts and its application in selectivity of styrene oxidation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19717181A1 (en) * 1997-04-24 1998-10-29 Hoechst Ag Process for the selective catalytic oxidation of olefins to aldehydes / ketones with C = C bond cleavage

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885672A (en) * 2010-07-02 2010-11-17 苏州大学 Method for preparing benzaldehyde through catalytic oxidation of styrene
CN101885672B (en) * 2010-07-02 2014-11-05 苏州大学 Method for preparing benzaldehyde through catalytic oxidation of styrene
CN103120933A (en) * 2011-11-18 2013-05-29 中国石油化工股份有限公司 Preparation method of nanometer TiO2/ZrO2 composite material
CN108393084A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of composite metal catalyst and its application in selectivity of styrene oxidation
CN108393094A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of bimetallic catalyst and its application in selectivity of styrene oxidation
CN108393095A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of modified oxidized Co catalysts and its application in selectivity of styrene oxidation
CN106905121A (en) * 2017-04-21 2017-06-30 南京理工大学 A kind of preparation method of benzaldehyde
CN108250056A (en) * 2018-03-20 2018-07-06 哈尔滨师范大学 A kind of process for catalytic synthesis of benzaldehyde
CN108250056B (en) * 2018-03-20 2020-12-25 哈尔滨师范大学 Catalytic synthesis method of benzaldehyde

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