HYDROFORMYLATION METHOD AND CATALYST USING RHODIUM-RUTHENIUM DUAL METAL AND TETRADENTATE PHOSPHINE LIGAND
20190337866 ยท 2019-11-07
Inventors
Cpc classification
B01J31/2409
PERFORMING OPERATIONS; TRANSPORTING
B01J31/181
PERFORMING OPERATIONS; TRANSPORTING
B01J2531/0258
PERFORMING OPERATIONS; TRANSPORTING
B01J2231/321
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J31/24
PERFORMING OPERATIONS; TRANSPORTING
B01J31/18
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A homogeneous catalytic reaction method and a catalyst for isomerization and hydroformylation of long-chain internal olefins are disclosed. A rhodium-ruthenium metal complex is used as a catalyst; and the ligands are tetradentate phosphine ligands. By means of the catalytic system, homogeneous internal olefin isomerization aid hydroformylation can be performed under a certain temperature and pressure to obtain aldehyde products having high normal to iso ratios. The present invention is applicable to not only long-chain internal olefins (C8) but also internal olefins having a carbon number less than 8.
Claims
1. A catalyst comprising a rhodium complex and a ruthenium compound, wherein the rhodium complex is formed by complexing a rhodium compound with a biphenyl tetraphosphine ligand.
2. The catalyst according to claim 1, wherein the molar ratio of the rhodium complex to the ruthenium compound is ranged from 1:1 to 5:1, and the molar ratio of the biphenyl tetraphosphine ligand to the rhodium compound is ranged from 1:1 to 10:1.
3. The catalyst according to claim 1, wherein the rhodium compound is selected from a group consisting of: RhCl.sub.3, (Rh(NBD)Cl).sub.2, (Rh(COD)Cl).sub.2, (RH(ethylene).sub.2(CI)).sub.2, RhCl(PPh.sub.3).sub.3, (Rh(CO).sub.2Cl).sub.2 , Rh(acac)(CO).sub.2, Rh(acac)(COD), Rh.sub.6(CO).sub.12, Rh.sub.4(CO).sub.12, Rh.sub.2(OAc).sub.4, Rh(NO.sub.3).sub.3, (Rh(NBD).sub.2)X and (Rh(COD).sub.2)X, wherein X is a conjugated anion, NBD is a bicycloheptadiene; and COD is cyclooctadiene.
4. The catalyst according to claim 1, wherein the biphenyl tetraphosphine ligand has a structure illustrated as follows. ##STR00011## in formula 1, Ar is selected from a group consisting of: benzene, p-methylbenzene. m-trifluoromethylbenzene, p-trifluoromethylbenzene, 3,5-ditrifluoromethylbenzene, 3,5-difluorobenzene, 3,5-dimethylbenzene, 3,5-di-tert-butylbenzene, 3,5-di-tert-butyl-4-methoxybenzene, p-methoxybenzene, p-dimethylaminobenzene, 2-pyridine, p-fluorobenzene, and 2, 3, 4, 5, 6-pentafluorobenzene.
5. The catalyst according to claim 1, wherein the ruthenium compound is selected from a group consisting of: Ru.sub.3(CO).sub.12, RuCl.sub.3, RuCl.sub.2(PPh.sub.3).sub.3, (RuCl.sub.2(CO).sub.3).sub.2, RuH(CO).sub.2(PPh.sub.3).sub.3, Ru(Ar)X.sub.2, Ru(ArH)Cl.sub.2, Ru(Ar)X.sub.2(PPh.sub.3).sub.3, Ru(COD)(COT), Ru(COD)(COT)X, Ru(COD).sub.n, RuCl.sub.2(COD), (Ru(COD).sub.2)X, (RuCl.sub.2(COD)).sub.n, Ru(COD)(methallyl).sub.2, RuX.sub.2(cymene), RuX.sub.2(PN), RuX.sub.2(PN), RuH(CI)(PNN(CO), and RuH(PNN)(CO), wherein Ar is a group having an aromatic ring; X is a conjugated anion, COD is cyclooctadiene; and COT is cyclooctadiene.
6. A reaction method for isomerization and hydroformylation of internal olefins, comprising: first, under inert gas protection, transferring certain amount of a complexed rhodium-ruthenium catalyst solution, certain amount of isopropanol as an additive, certain amount of solvent, and finally a substrate-internal olefin into a reaction flask equipped with a magnetic stirrer; second, charging certain amount of CO and H.sub.2 with a certain pressure into a autoclave containing the reaction flask, and wherein a pressure ratio of H2 to CO is ranged between 1.5:1 and 10:1, and the total pressure is ranged from 0.2 MPa to 4 MPa: and placing the autoclave at oil bath temperature between 80 C. and 140 C. and stirring for 1 to 12 hours.
7. The reaction method according to claim 6, wherein the organic solvent is selected from a group consisting of: methylbenzene, dichloromethane, dichloroethane, hexane, ethyl acetate, methanol, ethanol, trifluoroethanol, isopropanol, dioxane, acetonitrile and tetrahydrofuran.
8. The reaction method according to claim 6, wherein the internal olefin is selected from a group consisting of: 2-butene, cis-trans-2-pentene, cis-trans-2-hexene, cis-trans-3-hexene, cis-trans-2-heptene, cis-trans-3-heptene, cis-trans-2-octene, cis-trans-3-octene, cis-trans-4-octene, cis-trans-2-nonene, cis-trans-3-nonene, cis-trans-4-nonene, cis-trans-2-decene, cis-trans-3-decene, cis-trans-4-decene, and cis-trans-5-decene.
9. Use of the catalyst according to claim 1 for catalyzing isomerization and hydroformylation of internal olefin.
Description
DESCRIPTION OF THE EMBODIMENTS
[0032] The following description is of preferred embodiments by way of example only and without limitation to the combination of features necessary for carrying the invention into effect. However, it should be noted that the present invention is by no means limited or restricted to the below described embodiments and the implementation features thereof but comprises further modifications of the embodiments, in particular those that are comprised by modifications of the features of the described examples and/or by combination of one or more features of the described examples on the basis of the scope of protection of the independent claims.
[0033] Example 1; Isomerization and hydroformylation (S/C=2000, S/C is the molar ratio of reactant to catalyst) using rhodium-ruthenium dual metal (Rh (acac) (CO).sub.2 RuH (CI) (PNN) (CO)) and biphenyl triphosphine ligand (Tribi), rhodium-ruthenium (Rh(acac)(CO).sub.2, RuH(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand (Tetrabi)
[0034] Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO)2 (5.2 mg, 0.02 mmol) and 2,2, 6-tris(diphenylphosphinomethyl)-1, 1-Biphenyl (Tribi) (60 mg, 0.08 mmol) with a glove box into a complex flask, and then placing the deoxygenated/dewatered dichloromethane (2.65 g, 31.2 mmol) solvent into a flask, stirring to dissolve them to obtain a complex of rhodium and biphenyl triphosphine ligand. Subsequently, weighing a ruthenium catalyst RuH(Cl)(PNN)(CO) (9.8 mg, 0.02 mmol) with a glove box, adding it to the complexed rhodium catalyst solution, and stirring at room temperature to dissolve them. Placing the autoclave into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into a reaction flask (5 ml) with magnetic stirrer, and adding 100 l of the internal standard n-decane, 150 l of additive, 350 l of solvent and 2-octene (cis, trans mixture) (224.4 mg. 2 mmol). Then, taking the autoclave containing the reaction flask out from the glove box, and replacing the high-purity argon gas in the vessel with H2 three times, raising the total pressure of the autoclave to 4 bar at a CO/H2 pressure ratio of 1:1, and then placing the autoclave at oil bath temperature 140 C. and stirring for 1 hour and 4 hours, respectively.
[0035] Rh, Ru30 Tetrabi: Weighing the catalyst Rh(acac)(CO)2 (5.2 mg, 0.02 mmol), 2, 2, 6, 6-tetrakis(diphenylphosphinomethyl)-1, 1-biphenyl (Tetrabi) (76 mg. 0.08 mmol) with a glove box and placing them into a complex flask, then adding deoxygenated/dewatered (2.65 g. 31.2 mmol) into the flask and stirring to dissolve them to obtain a complex solution of rhodium and biphenyl tetraphosphine ligand. Subsequently, weighing the ruthenium catalyst RuH(Cl)(PNN)(CO) (9.8 mg, 0.02 mmol) with a glove box and adding it into the complexed rhodium catalyst solution, stiring at room temperature to dissolve them Placing the autoclave into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into a reaction flask (5 ml) with magnetic, stirrer, and adding 100 l internal standard n-decane, 150 l additive and 350 l solvent, and finally 2-octene (cis, trans mixture) (224.4 mg, 2 mmol). Then, taking the autoclave containing the reaction flask out from the glove box, and replacing the high-purity argon gas in the vessel with three rimes, raising the total pressure of the autoclave to 4 bar at a CO/H2 pressure ratio of and then placing the autoclave at oil bath temperature 140 C. and stirring for 1 hour and 4 hours, respectively.
TABLE-US-00001 TABLE 1
[0036] Example 2: Isomerization and hydroformylation (S/C=4000) using rhodium-ruthenium dual metal (Rb(acac)(CO).sub.2RuH(Cl)(PNN)(CO)) andbiphenyl triphosphine ligand (Tribi), rhodium-ruthenium dual metal (Rh(acac) (CO).sub.2, RuII(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand (Teirabi)
[0037] Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO).sub.2 (2.6 mg, 0.01 mmol), 2, 2, 6-Tris(diphenylphosphinomethyl)-1,1-biphenyl (Tiibi) (30 mg, 0.04 mmol) within a glove box and placing them into a complex flask, then adding deoxygenated/dewatered dichloromethane (2.65 g. 31.2 mmol) into the flask, and stirring to dissolve them to obtain a complexed solution of rhodium and biphenyl triphosphine ligand. Subsequently, weighing the ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg. 0.01 mmol) within a glove box and adding it into the complexed rhodium catalyst solution at room temperature. Placing the autoclave into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into reaction flask (5 ml) with magnetic stirrer, and adding 100 l of the internal standard n-decane, 150 l additive and 350 l of solvent, and finally 2-octene (cis. trans mixture) (224.4 mg. 2 mmol). Then, taking the autoclave containing the reaction flask out from the glove box, and replacing the high-purity argon gas in the vessel with H.sub.2 three times, raising the total pressure of the autoclave to 4 bar at a CO/H.sub.2 pressure ratio of 1:1, and then placing the autoclave at oil bath temperature 140 C. and stirring for 1 hour and 4 hours, respectively.
[0038] Rh, Ru+Tetrabi; Weighing the catalyst Rh(acac)(CO).sub.2 (2.6 mg. 0.01 mmol). 2, 2, 6, 6-tetrakis(diphenylphosphinomethyl)-1, 1-biphenyl (Tetrabi) (38 mg, 0.04 mmol) within a glove box and placing them into a complex flask, then adding deoxygenated/dewatered dichloromethane (2.65 g, 31.2 mmol) in a complex flask and stirring to dissolve them to obtain a complex solution of rhodium and biphenyl tetraphosphine ligand. Subsequently, weighing the ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg, 0.01 mmol) within a glove box and adding it into the complexed rhodium catalyst solution at room temperature. Placing the autoclave into the glove box, using a micro syringe to transfer 100 l of die complexed rhodium-ruthenium catalyst solution into a reaction flask (5 ml) with magnetic stirrer, and adding 100 l of internal standard n-decane. 150 l additive and 350 l solvent, and finally 2-octene (cis, trans mixture) (224.4 mg. 2 mmol). Then, taking the autoclave containing the reaction flask out from the glove box, and replacing the high-purity argon gas in the vessel with H.sub.2 three times, raising the total pressure of the autoclave to 4 bar at a CO/H.sub.2 pressure ratio of 1:1, and then placing the autoclave at oil bath temperature 140 C. and stirring for 1 hour and 4 hours, respectively.
TABLE-US-00002 TABLE 2
[0039] Example 3: Isomerization and hydroformylation (S/C=10000) using rhodium-ruthenium dual metal (Rb(acac)(CO).sub.2 RuH(Cl)(PNN)(CO)) and biphenyl triphosphine ligand (Tribi), rhodium-ruthenium dual metal (Rh(acac)(CO).sub.2 , RuH(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand (Tetrabi)
[0040] Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO).sub.2 (2.6 mg, 0.01 mmol), 2, 2,6-Tris(diphenylphosphinomethyl)-1,1-biphenyl (Tribi) (30 mg, 0.04 mmol) within a glove box and placing them into a complex flask, then adding deoxygenated/dewatered dichloromethane (6.63 g, 78.0 mmol) in a flask and stirring lo dissolve them to obtain a complex solution of rhodium and biphenyl triphosphine ligand. Subsequently, weighing a ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg, 0.01 mmol) within a glove box, adding it to the complexed rhodium catalyst solution, and stirring to dissolve them at room temperature. Placing the autoclave into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into a reaction flask (5 ml) with magnetic stirrer, and adding 100 l of internal standard n-decane, 150 l of additive and 350 l of solvent, and finally 2-octene (cis, trans mixture) (224.4 mg, 2 mmol). Then, taking the autoclave containing the reaction flask out from the glove box, and replacing the high-purity argon gas in the vessel with H.sub.2 three times, raising the total pressure of the autoclave to 4 bar at a CO/H.sub.2 pressure ratio of 1:1, and then placing the autoclave at oil bath temperature 140 C. and stirring for 1 hour and 4 hours, respectively.
[0041] Rh, Ru+Tetrabi: Weighing the catalyst Rh(acac)(CO).sub.2 (2.6 mg, 0.01 mmol). 2,2, 6, 6-tetrakis(diphenylphosphinomethyl)-1,1-biphenyl (Tetrabi) (38 mg. 0.04 mmol) within a glove box and placing them into a complex flask, then adding deoxygenated/dewatered dichloromethane (6.63 g. 78.0 mmol) in a complex flask and stirring to dissolve them to obtain a complex solution of rhodium and biphenyl tetraphosphine ligand. Subsequently, weighing the ruthenium catalyst RuH(Cl)(PNN)(CO)(4.9 mg, 0.01 mmol) within a glove box and adding it into the complexed rhodium catalyst solution at room temperature. Placing the autoclave into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into a reaction flask (5 ml) with magnetic stirrer, and adding 100 l of the internal standard n-decane, adding 150 l of additive and 350 l of solvent, finally 2-octene (cis-mixture) (224.4 mg. 2 mmol). Then, taking the autoclave containing the reaction flask out from the glove box, and replacing the high-purity argon gas in the vessel with H.sub.2 three times, raising the total pressure of the autoclave to 4 bar at a CO/H.sub.2 pressure ratio of 1:1, and then placing the autoclave at oil bath temperature 140 C. and stirring for 1 hour and 4 hours, respectively.
TABLE-US-00003 TABLE 3
[0042] Example 4: Isomerization and hydroformylation (S/C=10000) using rhodium-ruthenium dual metal (Rh(acac)(CO).sub.2, RuH(Cl)(PNN)(CO)) and biphenyl triphosphine ligand (Tribi), rhodium-ruthenium dual metal (Rh(acac)) (CO).sub.2, RuH(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand (Tetrabi) (comparison of various -, -, -olefin results)
[0043] Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO).sub.2 (2.6 mg, 0.01 mmol), 2, 2,6-tris(diphenylphosphinomethyl)-1. 1-Biphenyl (30 mg, 0.04 mmol) within a glove box and placing them into a complex flask, and then adding deoxygenated/dewatered dichloromethane (1.33 g. 15.6 mmol) solvent into the flask, stirring to dissolve them to obtain a complex solution of rhodium and biphenyl triphosphine ligand. Subsequently, weighing a ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg, 0.01 mmol) within a glove box, adding it to the complexed rhodium catalyst solution, and stirring at room temperature to dissolve them. Placing the autoclaves into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into a reaction flask (5 ml) with magnetic stirrer, and adding 100 l of the internal standard n-decane, appropriate amount of additives and corresponding solvents, and finally various -, -, - olefin (1 mmol) in batches. Then, taking the autoclaves containing the reaction flasks out from the glove box, and replacing the high-purity argon gas in the vessels with H.sub.2 three times, raising the total pressure of the autoclaves to 4 bar at a CO/H.sub.2 pressure ratio of 1:1, and then placing the autoclaves at oil bath temperature 140 C. and stirring for 2 hours.
[0044] Rh, Ru+Tetrabi: Weighing the catalyst Rh(acac)(CO).sub.2 (2.6 mg, 0.01 mmol), 2,6,6-tetrakis(diphenylphosphinomethyl)-1,1Biphenyl (Tetrabi) (38 mg, 0.04 mmol) within a glove box and placing them into a complex flask, and then adding deoxygenated/dewatered toluene (0.87 g, 9.4 mmol) into the flask and stirring to dissolve to obtain a complex solution of rhodium and biphenyl tetraphosphine ligand. Subsequently, weighing a ruthenium catalyst RuH(CI)(PNN)(CO) (4.9 mg, 0.01 mmol) within a glove box, adding it to the complexed rhodium catalyst solution, and stirring at room temperature to dissolve them. Placing the autoclaves into the glove box, using a micro syringe to transfer 100 l of the complexed rhodium-ruthenium catalyst solution into the reaction flask (5 ml) with magnetic stirrer, and adding 100 l internal standard n-decane, appropriate amount of additives and corresponding solvents, and finally various -, -, - olefin (1 mmol) in batches. Then, taking the autoclaves containing the reaction flasks out from the glove box, and replacing the high-purity argon gas in the vessels with H.sub.2 three times, raising the total pressure of the autoclaves to 4 bar at a CO/H.sub.2 pressure ratio of 1:1, and then placing the autoclaves at oil bath temperature 140 C. and stirring for 2 hours.
TABLE-US-00004 TABLE 4