CN1594258A - Process for preparing benzaldehyde by benzene oxidation and carbonylation - Google Patents
Process for preparing benzaldehyde by benzene oxidation and carbonylation Download PDFInfo
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- CN1594258A CN1594258A CN 200410025768 CN200410025768A CN1594258A CN 1594258 A CN1594258 A CN 1594258A CN 200410025768 CN200410025768 CN 200410025768 CN 200410025768 A CN200410025768 A CN 200410025768A CN 1594258 A CN1594258 A CN 1594258A
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- benzene
- benzaldehyde
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Abstract
The invention discloses a process for preparing benzaldehyde by benzene oxidation and carbonylation by using benzene as reaction raw material, cobalt acetate as catalyst, trichloroacetic acid as solvent, oxygen as oxidizing agentconducting oxidation carbonylation reaction at the presence of nitrogen-containing or phosphonium-containing ligand, wherein the pressure of oxygen is 4-15 atm, the pressure of carbon monoxide is 8-40 atm, the reaction temperature is 50-150 deg. C, the reaction time is 10-72 hrs.
Description
Technical field
The present invention relates to the benzene oxidative carbonylation and prepare method of benzaldehyde.
Background technology
Therefore the difficult activation of benzene is converted into useful compound with benzene selective and has great importance.Wherein one of target product is that benzene selective is converted into phenyl aldehyde, but owing to selective control in the reaction process is difficult, the enforcement difficulty of this process is big.
According to the literature, realize that benzene selective oxidative carbonylation producing benzaldehyde has following approach:
One of route is that the close electric attack to the c h bond on the phenyl ring realizes in the environment of super acids.The bibliographical information of this route has N.Yoneda, Y.Takahashi, and F.Fukuhara, A.Suzuki, Bull.Chem.Soc.Jpn.59 (1986) 2819; N.Yoneda, T.Fukuhara, Y.Takahashi, A.Suzuki, Chem.Lett. (1983) 17; I.Akhrem, A.Orlinkov, L.Afanaseva, P.Petrovskii, S.Vitt, Tetrahedron Lett.40 (1999) 5897 and D.S.Sood, S.C.Sherman, A.V.Iretskii, J.C.Kenvin, D.A.Schiraldi, M.G.White, J.Catal.199 (2001) 149.Employed super acids has AlCl
3, HF, and magic sour SbF
5-HF etc.When adopting this path of preparing phenyl aldehyde, to very serious of the corrosion of equipment.
Another synthetic route is under the irradiation of UV-light, and aromatic hydrocarbons can under light-transition metal concerted catalysis carbonylation reaction take place.Relevant bibliographical information has B.J.Fisher, R.Eisenberg, and Organometallics2 (1983) 764; T.Sakakura, T.Sodeyama, K.Sasaki, K.Wada, M.Tanaka, J.Am.Chem.Soc.112 (1990) 7221; T.Sakakura, M.Tanaka, J.Chem.Soc.Commun. (1987) 789.Eisenberg etc. have reported Ir under the optical excitation (CO) (Ph
2CH
2PPh
2) catalysis benzene generation phenyl aldehyde, T.Sakakura etc. have then reported class catalyzer RhCl (CO) (PMe more efficiently
3), the carbonylation of benzene be studies show that generated multiple product.When adopting this route, selectivity is relatively poor, has generated multiple product, and will use precious metal such as rhodium as catalyzer, is not an ideal route therefore.
The third synthetic route is under the catalysis of metal catalyst, makes the benzene activation under the effect of oxygenant, and principal product is a phenylformic acid, and by product is a phenyl aldehyde.Report to this route has US 3414625, M.Asadullah, Y.Taniguchi, T.Kitamura, Y.Fujiwara, Appl.Catal.A:General 443 (2000) 194, H.Sugumoto, I.Kawata, H.Taniguchi, Y.Fujiwara, J.Organomet.Chem., 266 (1984), C14.T.Jintoku, H.Taniguchi, Y.Fujiwara, Chem.Lett., (1987) 1865.Fujiwara etc. find at Pd (OAc)
2/ t-BuOOH/ allyl halide reaction system has further been developed Pd (OAc) again
2/ K
2S
2O
8/ CCl
3The COOH catalyst system makes benzene be converted into phenylformic acid, phenol and a small amount of phenyl aldehyde.Therefore this method is low to the selectivity of phenyl aldehyde, and uses precious metal palladium as catalyzer, and is uneconomical.
Summary of the invention
The object of the present invention is to provide a technology simple, cost is lower, and the benzene oxidative carbonylation that can overcome the described defective of above the whole bag of tricks prepares method of benzaldehyde.
Benzene oxidative carbonylation of the present invention prepares method of benzaldehyde, be to be reaction raw materials with benzene, with the Cobaltous diacetate is catalyzer, and trichoroacetic acid(TCA) is a solvent, and oxygen is oxygenant, nitrogenous or contain in the presence of the phosphine part, carry out oxidation carbonylation, the pressure of oxygen is 4-15atm, and the pressure of carbon monoxide is 8-40atm, temperature of reaction is 50-150 ℃, and the reaction times is 10-72h.
Among the present invention, the consumption of catalyst acetic acid cobalt is the 0.001%-5% of benzene feedstock total amount.The consumption of solvent trichoroacetic acid(TCA) is the 0.1%-10% of benzene feedstock total amount.The part usage quantity is the 0.01%-5% of benzene feedstock total amount.Said containing n-donor ligand comprises single nitrogen ligand and dinitrogen part, contains the phosphine part and comprises monophosphorus ligand and biphosphine ligand, and pyridine, imidazoles, 1 are arranged, 10-phenanthroline, N-Methylimidazole, 2,2 '-dipyridyl, oxine, triphenylphosphine and tri-n-butyl phosphine etc.
The invention has the advantages that: at first, the present invention uses cheap cobalt complex to substitute expensive metallic palladium as catalyzer, thereby the better economic effect is arranged; Secondly, use the less trichoroacetic acid(TCA) of corrodibility to substitute trifluoroacetic acid, AlCl
3, HF, and evil spirit acid (SbF
5-HF) etc. super acids is as solvent, thus reduced corrodibility to equipment, reduced requirement to equipment; The 3rd, the present invention uses oxygen to substitute superoxide as oxygenant, has reduced production cost, and prospects for commercial application is arranged.The selectivity that adopts the present invention to generate phenyl aldehyde can reach more than 90%, and yield can reach 38%.
Embodiment
Below will the present invention is further illustrated by embodiment, but not only sink into following examples.
Embodiment 1
In the 100mL autoclave, add reaction substrate toluene 20mL (0.239mol), trichoroacetic acid(TCA) 0.024mol, Cobaltous diacetate 2.04mmol, pyridine 0.025mol, the pressure of carbon monoxide are 12atm, the pressure of oxygen is 4atm, under 130 ℃ temperature, reaction 24h.Reaction solution is through gas chromatographic analysis, and the yield of phenyl aldehyde is 37.3%.
Embodiment 2
In the 100mL autoclave, add reaction substrate toluene 20mL (0.239mol), trichoroacetic acid(TCA) 0.034mol, Cobaltous diacetate 2.04mmol, pyridine 0.011mol, the pressure of carbon monoxide are 12atm, the pressure of oxygen is 4atm, under 130 ℃ temperature, reaction 24h.Reaction solution is through gas chromatographic analysis, and the yield of phenyl aldehyde is 38.9%.
Embodiment 3
In the 100mL autoclave, add reaction substrate toluene 20mL (0.239mol), trichoroacetic acid(TCA) 0.024mol, Cobaltous diacetate 3.47mmol, pyridine 0.025mol, the pressure of carbon monoxide are 26atm, the pressure of oxygen is 8atm, under 130 ℃ temperature, reaction 36h.Reaction solution is through gas chromatographic analysis, and the yield of phenyl aldehyde is 38.6%.
Embodiment 4
In the 100mL autoclave, add reaction substrate toluene 20mL (0.239mol), trichoroacetic acid(TCA) 0.015mol, Cobaltous diacetate 2.04mmol, 2,2 '-dipyridyl 0.034mol, the pressure of carbon monoxide are 40atm, the pressure of oxygen is 4atm, under 150 ℃ temperature, and reaction 48h.Reaction solution is through gas chromatographic analysis, and the yield of phenyl aldehyde is 37.3%.
Embodiment 5
In the 100mL autoclave, add reaction substrate toluene 20mL (0.239mol), trichoroacetic acid(TCA) 0.024mol, Cobaltous diacetate 2.04mmol, N-Methylimidazole 0.080mol, the pressure of carbon monoxide are 12atm, and the pressure of oxygen is 4atm, under 130 ℃ temperature, reaction 24h.Reaction solution is through gas chromatographic analysis, and the yield of phenyl aldehyde is 24.6%.
Embodiment 6
In the 100mL autoclave, add reaction substrate toluene 20mL (0.239mol), trichoroacetic acid(TCA) 0.024mol, Cobaltous diacetate 2.04mmol, tri-n-butyl phosphine 0.012mol, the pressure of carbon monoxide are 12atm, and the pressure of oxygen is 4atm, under 130 ℃ temperature, reaction 24h.Reaction solution is through gas chromatographic analysis, and the yield of phenyl aldehyde is 11.2%.
Claims (5)
1. the benzene oxidative carbonylation prepares method of benzaldehyde, it is characterized in that with benzene being reaction raw materials, with the Cobaltous diacetate is catalyzer, and trichoroacetic acid(TCA) is a solvent, and oxygen is oxygenant, nitrogenous or contain in the presence of the phosphine part, carry out oxidation carbonylation, the pressure of oxygen is 4-15atm, and the pressure of carbon monoxide is 8-40atm, temperature of reaction is 50-150 ℃, and the reaction times is 10-72h.
2. benzene oxidative carbonylation according to claim 1 prepares method of benzaldehyde, and the consumption that it is characterized in that the catalyst acetic acid cobalt is the 0.001%-5% of benzene feedstock total amount.
3. benzene oxidative carbonylation according to claim 1 prepares method of benzaldehyde, and the consumption that it is characterized in that the solvent trichoroacetic acid(TCA) is the 0.1%-10% of benzene feedstock total amount.
4. benzene oxidative carbonylation according to claim 1 prepares method of benzaldehyde, it is characterized in that the part usage quantity is the 0.01%-5% of benzene feedstock total amount.
5. benzene oxidative carbonylation according to claim 1 prepares method of benzaldehyde, it is characterized in that said containing n-donor ligand comprises single nitrogen ligand and dinitrogen part, contain the phosphine part and comprise monophosphorus ligand and biphosphine ligand, pyridine, imidazoles, 1 are arranged, 10-phenanthroline, N-Methylimidazole, 2,2 '-dipyridyl, oxine, triphenylphosphine and tri-n-butyl phosphine.
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| CN 200410025768 CN1594258A (en) | 2004-06-29 | 2004-06-29 | Process for preparing benzaldehyde by benzene oxidation and carbonylation |
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| CN 200410025768 CN1594258A (en) | 2004-06-29 | 2004-06-29 | Process for preparing benzaldehyde by benzene oxidation and carbonylation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647528A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Synthesis of alkyl aromatic aldehyde catalyst |
| CN109647509A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The catalyst of synthesis of alkyl aromatic aldehyde |
| CN109651113A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of synthesis of alkyl aromatic aldehyde |
| CN109647508A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Synthesize the catalyst of p-tolyl aldehyde |
| CN109651114A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Synthesis of alkyl aromatic aldehyde method |
-
2004
- 2004-06-29 CN CN 200410025768 patent/CN1594258A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647528A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Synthesis of alkyl aromatic aldehyde catalyst |
| CN109647509A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The catalyst of synthesis of alkyl aromatic aldehyde |
| CN109651113A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of synthesis of alkyl aromatic aldehyde |
| CN109647508A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Synthesize the catalyst of p-tolyl aldehyde |
| CN109651114A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Synthesis of alkyl aromatic aldehyde method |
| CN109647508B (en) * | 2017-10-10 | 2022-04-01 | 中国石油化工股份有限公司 | Catalyst for synthesizing p-methyl benzaldehyde |
| CN109647509B (en) * | 2017-10-10 | 2022-04-01 | 中国石油化工股份有限公司 | Catalyst for synthesizing alkyl aromatic aldehyde |
| CN109651113B (en) * | 2017-10-10 | 2022-04-01 | 中国石油化工股份有限公司 | Process for synthesizing alkyl aromatic aldehyde |
| CN109651114B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Method for synthesizing alkyl aromatic aldehyde |
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