CN112457178B - Method for synthesizing valeraldehyde - Google Patents
Method for synthesizing valeraldehyde Download PDFInfo
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- CN112457178B CN112457178B CN202011342953.8A CN202011342953A CN112457178B CN 112457178 B CN112457178 B CN 112457178B CN 202011342953 A CN202011342953 A CN 202011342953A CN 112457178 B CN112457178 B CN 112457178B
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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Abstract
The invention discloses a method for synthesizing valeraldehyde, which is characterized by adding a catalyst and an organic solvent into a reaction kettle, adding n-butene in a closed state, and then fillingCO and H 2 The mixed gas of (3); heating the reaction kettle for reaction; the catalyst is a nitrogen heterocyclic carbene cobalt complex. Compared with the prior art, the N-heterocyclic carbene cobalt complex can be prepared by a direct and rapid method, and meanwhile, a reagent with strong toxicity is not used, and the conditions are mild, so that the N-heterocyclic carbene cobalt complex is a good alternative reaction system of a phosphine ligand catalytic system; the invention has simple synthesis process, low cost and higher industrial application prospect.
Description
Technical Field
The invention relates to a preparation method of a nitrogen heterocyclic carbene cobalt complex catalyst, in particular to application of nitrogen heterocyclic carbene cobalt metal complexes with different substituents or structure types in the hydroformylation reaction of butylene, belonging to the technical field of metal organic and homogeneous catalysis.
Background
In a hydroformylation reaction process, the selection of a catalyst system is crucial, since Otto Roelen discovered olefin hydroformylation in 1938, a hydroformylation catalyst system is subjected to four stages from a cobalt carbonyl high-pressure catalyst system, a triphenylphosphine modified rhodium carbonyl low-pressure catalyst system, a water-soluble rhodium phosphine complex catalyst system to the existing rhodium diphosphine ligand catalyst system, and the like, and the introduction of a phosphine ligand greatly enhances the hydroformylation reaction effect. Therefore, the hydroformylation catalytic system developed at present usually does not separate the existence of the phosphine ligand, but the synthesis process of the phosphine ligand usually requires a reagent with stronger toxicity (such as phosphorus trichloride and the like) and more harsh reaction conditions (temperature < -20 ℃), which leads to higher cost and great challenge on safety of the synthesis process of the phosphine ligand.
The N-heterocyclic carbene is a ligand with strong coordination capability, is similar to the traditional organic phosphine ligand in the coordination property, has higher sigma-electron withdrawing capability and pi electron donating capability, and can form stronger coordination bond when being coordinated with metal due to the property of the N-heterocyclic carbene ligand, so that the complex formed by the coordination of the N-heterocyclic carbene ligand and the metal has higher activity than the phosphine ligand. At present, a great deal of research shows that the nitrogen heterocyclic carbene ligand can be applied to the C-H bond activation reaction after being coordinated with metal palladium, for example, in the direct arylation reaction of azoles, the activity of the nitrogen heterocyclic carbene palladium complex with large steric hindrance is far higher than that of a phosphine ligand system, besides, the ruthenium complex of the carbene ligand is also applied to the olefin metathesis reaction, but the nitrogen heterocyclic carbene ligand is less applied to the hydroformylation reaction.
Rhodium complexes based on azacyclo-carbene ligands have been reported in olefin hydroformylation, and an imidazole-rhodium complex catalyst is firstly reported in U.S. Pat. No. 4, 5663451A, and has a good reaction effect but poor regioselectivity.
The literature (organometallics, 2000,19(18):3459-3461) reports a phosphine-carbene double ligand rhodium complex catalyst 1 which can well catalyze the hydroformylation of styrene and has a positive-to-iso ratio of 5: 95.
rhodium complex catalyst 1
Azacyclocarbene rhodium catalysts of the imidazolium salt type have also been investigated and reported in the literature (organometallics, 2008,27(16):4131-4138) is an Rh (NHC) (COD) X (X ═ Cl, Br, I, SCN) catalyst synthesized from 1-methyl-3-n-butylimidazolium salt, but this catalyst still requires the addition of P (OPh) 3 The ligand can realize the hydroformylation of 1-hexene under mild conditions,
besides, complex catalysts of Rh-bidentate NHC ligands have been studied, and the literature (organometallics, 2006,25(1):300-306) reports that Rh complex catalysts of NHC containing imino group can realize hydroformylation of 1-octene. The yield was only 30%, the normal to iso ratio was 2.5, and the conversion of octenes increased with increasing pressure.
Rh-bidentate NHC ligand complexes
Rhodium is used as a noble metal and is high in price, so that the cost of the NHC-Rh catalyst is increased, the further industrial application process of the NHC-Rh catalyst is limited, cobalt is cheaper than rhodium, and a complex formed after the cobalt is coordinated with carbene can be used as a catalyst in hydroformylation.
Butene hydroformylation based on phosphine ligands has achieved very good results, but the synthesis of highly efficient phosphine ligands usually requires harsh reaction conditions and highly toxic reagents, which leads to high cost and challenging safety of the phosphine ligand synthesis process. The carbene complex has simple synthesis process and becomes a substitute ligand of the phosphine ligand in a plurality of reactions.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: a carbene cobalt complex catalyst is provided which can enhance the reaction effect in the hydroformylation of butene.
In order to solve the technical problems, the invention provides a method for synthesizing valeraldehyde, which is characterized in that a catalyst and an organic solvent are added into a reaction kettle, n-butene is added under a closed state, and then CO and H are charged 2 The mixed gas of (3); heating the reaction kettle for reaction; the catalyst is a nitrogen heterocyclic carbene cobalt complex, and the structure of the catalyst is any one of a general formula (1), a general formula (2), a general formula (3) and a general formula (4):
in the above formula, R 1 、R 2 、R 4 Each independently is substituted or unsubstituted C 1 -C 10 Any one of a substituted or unsubstituted cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, and a substituted or unsubstituted heterocyclic substituent; r is 3 The position (A) is an arbitrary position on the benzene ring or a multiple position on the benzene ringA substituent of a substituent; the valence of Co is monovalent, divalent or trivalent; n represents a carbon number of 1 to 10; z is C 1 -C 5 Alkyl chains of (a) or other heteroatoms; x is any one of halogen, heterocyclic substituent, carbonyl, alkane, alkene, alkyne and alkoxy; m, Y is carbon, nitrogen, oxygen or sulfur.
Preferably, said R is 1 、R 2 Each independently is any one of methyl, methoxy, ethyl, ethoxy, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, cyclohexyl, phenyl, 1,3, 5-trimethylbenzene, m-xylene, p-xylene, benzyl, 1,3, 5-isopropylbenzene, halogen, imidazolyl, pyrazolyl and thiazolyl; the R is 3 Is C 1 -C 10 Alkanoyl of (2), C 1 -C 10 Any one of the alkyl ester group and the halogen; the R is 4 Is any one of methyl, methoxy, ethyl, ethoxy, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, 1,3, 5-trimethylbenzene, m-xylene, p-xylene, benzyl, 1,3, 5-isopropylbenzene, imidazolyl, pyrazolyl and thiazolyl; the other heteroatom is oxygen or sulfur; and X is any one of F, Cl, Br, I, carbonyl (C ═ O), tetrahydrofuran, pyridine, imidazole, thiazole, benzothiazole, benzoxazole and acetylacetone.
Preferably, the organic solvent includes at least one of benzene, toluene, xylene, valeraldehyde, dimethyl sulfoxide, dichloromethane, dichloroethane, acetonitrile, hexane, ethyl acetate, dioxane, tetrahydrofuran, acetone, N-dimethylformamide, N-dimethylacetamide, methanol, ethanol, N-propanol, isopropanol, and N-butanol.
Preferably, the concentration of the catalyst in the organic solvent is 100-3830 ppm; the mol ratio of the n-butene to the catalyst is 38-10000: 1.
preferably, the mixed gas contains CO and H 2 In a molar ratio of 1: 1, the inflation pressure is 1-5 MPa.
More preferably, the gas inflation pressure is 2-4 MPa.
Preferably, the heating reaction is carried out at the temperature of 80-180 ℃ for 12-72 h.
More preferably, the heating reaction is carried out at a temperature of 90-160 ℃ for 12-48 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the N-heterocyclic carbene cobalt complex can be prepared by a direct and rapid method, and meanwhile, a reagent with strong toxicity is not used, and the condition is mild, so that the N-heterocyclic carbene cobalt complex is a good alternative reaction system of a phosphine ligand catalytic system;
(2) the catalyst has the advantages of simple synthesis process, low cost and higher industrial application prospect.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
The synthesis principle of the invention, namely the reaction equation for synthesizing valeraldehyde by hydroformylation of butylene is as follows:
the general operation process of the hydroformylation reaction of the N-heterocyclic carbene catalyst comprises the following steps: adding a certain amount of cobalt complex catalyst into a reaction kettle with a certain volume, then replacing the reaction kettle with mixed gas for 2-3 times, maintaining the pressure, adding n-butene raw material after the pressure maintaining is finished, filling the mixed gas to a certain pressure, and reacting at a certain temperature and pressure. After the reaction, the reaction vessel was cooled, the residual gas was carefully released under ventilation, and an internal standard was added to the reacted solution and analyzed by gas chromatography.
Example 1
0.04mmol of cobalt complex (19.4mg) of catalyst 1 was charged into a 100mL reaction vessel, 40mL of toluene solvent was added using CO/H 2 MixingPerforming replacement operation on the reaction kettle by gas (the molar ratio is 1: 1), after replacing for three times, adding 20mmol (1.72g) of n-butene, and after adding the n-butene, filling the mixture into a reaction kettle with a molar ratio of 1: 1 CO/H 2 The mixed gas is adjusted to 2MPa, and the reaction is carried out at the temperature of 110 ℃. After 24h, cooling the reaction kettle, carefully discharging residual gas under ventilation conditions, adding an internal standard substance into the solution after the reaction, and performing gas chromatography analysis to obtain a product with the n-valeraldehyde yield of 21%, the n-butene conversion rate of 28%, and the n-iso ratio of 3: 1.
example 2
0.025mmol of cobalt complex (16.98mg) of catalyst 2 was charged into a 100mL reactor, 40mL of toluene solvent was added using CO/H 2 The reaction kettle was replaced with a mixed gas (molar ratio 1: 1) three times, 20mmol (1.72g) of n-butene was added, and after addition of n-butene, the reaction kettle was purged with a gas mixture of 1: 1 CO/H 2 The mixed gas is adjusted to 3MPa, and the reaction is carried out at the temperature of 120 ℃. After 24h, cooling the reaction kettle, carefully discharging residual gas under ventilation conditions, adding an internal standard substance into the solution after the reaction, and performing gas chromatography analysis to obtain the product with the n-valeraldehyde yield of 36%, the n-butene conversion rate of 45%, the n-iso ratio of 3.8: 1.
example 3
0.02mmol of cobalt complex (15.92mg) of catalyst 3 was charged into a 100mL reaction vessel, 40mL of toluene solvent was added using CO/H 2 Performing replacement operation on the reaction kettle by using mixed gas (the molar ratio is 1: 1), after replacing for three times, adding 20mmol (1.72g) of n-butene, adding the n-butene, and filling the mixture into a reaction kettle with a molar ratio of 1: 1 CO/H 2 The mixed gas is adjusted to 3MPa, and the reaction is carried out at the temperature of 140 ℃. After 36h, the reaction vessel was cooled, the residual gas was carefully vented under aeration, and the reaction was followedThe internal standard substance is added into the solution to carry out gas chromatography analysis, and the obtained n-valeraldehyde has the yield of 61 percent, the n-butene conversion rate of 70 percent and the n-iso ratio of 6: 1.
example 4
0.02mmol of cobalt complex (12.88mg) of catalyst 4 was charged into a 100mL autoclave, 40mL of toluene solvent was added and CO/H was used 2 Performing replacement operation on the reaction kettle by using mixed gas (the molar ratio is 1: 1), after replacing for three times, adding 20mmol (1.72g) of n-butene, adding the n-butene, and filling the mixture into a reaction kettle with a molar ratio of 1: 1 CO/H 2 The mixed gas is adjusted to 4MPa, and the reaction is carried out at the temperature of 140 ℃. After 36h, the reaction kettle is cooled, residual gas is carefully discharged under ventilation conditions, an internal standard substance is added into the solution after the reaction, and gas chromatography analysis is carried out, so that the yield of n-valeraldehyde is 42%, the n-butene conversion rate is 47.9%, the n-iso ratio is 7.1: 1.
example 5
0.01mmol of cobalt complex (15.32mg) as catalyst 5 was charged into a 100mL reaction vessel, 40mL of a toluene solvent was charged into the reaction vessel, the reaction vessel was subjected to a displacement operation using a CO/H2 mixed gas (molar ratio 1: 1), 20mmol (1.72g) of n-butene was charged after the displacement three times, and after the addition of n-butene, the reaction vessel was charged with a gas mixture having a molar ratio of 1: 1 CO/H2 mixed gas is reacted to 4MPa under the condition of 150 ℃. After 48h, cooling the reaction kettle, carefully discharging residual gas under ventilation conditions, adding an internal standard substance into the solution after the reaction, and performing gas chromatography analysis to obtain the product with the n-valeraldehyde yield of 76%, the n-butene conversion rate of 87%, the n-iso ratio of 6.8: 1.
example 6
0.2mmol of cobalt complex (15.32mg) as catalyst 5 was charged into a 100mL reaction vessel, 40mL of a toluene solvent was charged into the reaction vessel, the reaction vessel was subjected to a displacement operation using a CO/H2 mixed gas (molar ratio 1: 1), 20mmol (1.72g) of n-butene was charged after the displacement three times, and after the addition of n-butene, the reaction vessel was charged with a gas mixture having a molar ratio of 1: 1 CO/H 2 The mixed gas is adjusted to 5MPa, and the reaction is carried out at the temperature of 90 ℃. After 24h, cooling the reaction kettle, carefully discharging residual gas under ventilation conditions, adding an internal standard substance into the solution after the reaction, and performing gas chromatography analysis to obtain the product with the n-valeraldehyde yield of 12%, the n-butene conversion rate of 15.33%, the n-iso ratio of 3.6: 1.
example 7
0.002mmol of cobalt complex (15.32mg) as catalyst 5 was charged into a 100mL reaction vessel, 40mL of a toluene solvent was charged into the reaction vessel, the reaction vessel was replaced with CO/H2 mixed gas (molar ratio 1: 1) three times, 20mmol (1.72g) of n-butene was charged, and after the addition of n-butene, the reaction vessel was charged with a gas mixture having a molar ratio of 1: 1 CO/H 2 The mixed gas is adjusted to 1MPa, and the reaction is carried out at the temperature of 160 ℃. After 36h, cooling the reaction kettle, carefully discharging residual gas under ventilation conditions, adding an internal standard substance into the solution after the reaction, and performing gas chromatography analysis to obtain n-valeraldehyde with the yield of 6%, the n-butene conversion rate of 8.86%, the n-iso ratio of 2.1: 1.
Claims (7)
1. a method for synthesizing valeraldehyde is characterized in that a catalyst and an organic solvent are added into a reaction kettle, n-butene is added under a closed state, and then CO and H are charged 2 The mixed gas of (3); heating the reaction kettle for reaction; the catalyst is a nitrogen heterocyclic carbene cobalt complex, and the structure of the catalyst is any one of a general formula (2), a general formula (3) and a general formula (4):
In the above formula, R 4 Is any one of 1,3, 5-trimethylphenyl and 2-isopropyl-4-methoxyphenyl;
is any one of phenyl and 5, 6-dimethylphenyl; the valence state of Co is divalent; n represents a carbon number of 0 to 1; x is halogen; z, Y, M is nitrogen.
2. A method of synthesizing pentanal as in claim 1, wherein the organic solvent comprises at least one of benzene, toluene, xylene, pentanal, dimethylsulfoxide, dichloromethane, dichloroethane, acetonitrile, hexane, ethyl acetate, dioxane, tetrahydrofuran, acetone, N-dimethylformamide, N-dimethylacetamide, methanol, ethanol, N-propanol, isopropanol, and N-butanol.
3. A process for the synthesis of valeraldehyde as claimed in claim 1 wherein said catalyst concentration in said organic solvent is 100-3830 ppm; the mol ratio of the n-butene to the catalyst is 38-10000: 1.
4. a method of synthesizing pentanal as claimed in claim 1, wherein CO and H in the mixed gas 2 In a molar ratio of 1: 1, the inflation pressure is 1-5 MPa.
5. A method of synthesizing pentanal as claimed in claim 4, wherein said gas aeration pressure is 2 to 4 MPa.
6. A method of synthesizing valeraldehyde according to claim 1 wherein the heating is at a temperature of from 80 to 180 ℃ for a period of from 12 to 72 hours.
7. A method of synthesizing pentanal as claimed in claim 6, wherein the temperature of the heating reaction is 90-160 ℃ and the time is 12-48 h.
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