CN116217629A - Hydroformylation catalyst, preparation method and application thereof - Google Patents
Hydroformylation catalyst, preparation method and application thereof Download PDFInfo
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- CN116217629A CN116217629A CN202310009204.0A CN202310009204A CN116217629A CN 116217629 A CN116217629 A CN 116217629A CN 202310009204 A CN202310009204 A CN 202310009204A CN 116217629 A CN116217629 A CN 116217629A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 37
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- PRSPLAWXBFRHKV-UHFFFAOYSA-N 3-oxopropyl acetate Chemical compound CC(=O)OCCC=O PRSPLAWXBFRHKV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001299 aldehydes Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- ZEAWSFHWVLOENK-UHFFFAOYSA-N phenanthren-2-amine Chemical compound C1=CC=C2C3=CC=C(N)C=C3C=CC2=C1 ZEAWSFHWVLOENK-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZYHQGITXIJDDKC-UHFFFAOYSA-N 2-[2-(2-aminophenyl)ethyl]aniline Chemical group NC1=CC=CC=C1CCC1=CC=CC=C1N ZYHQGITXIJDDKC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydroformylation catalyst and a method for preparing linear aldehyde by hydroformylation of vinyl acetate. The ligand has the structural general formula of
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a hydroformylation catalyst and a preparation method thereof, and also relates to application of the hydroformylation catalyst in catalyzing the hydroformylation of vinyl acetate to prepare 3-acetoxy propionaldehyde.
Background
The main products of the hydroformylation-hydrolysis method of the vinyl acetate, namely 1, 3-propanediol and 1, 2-propanediol, are important chemical raw materials, and the main products of the hydroformylation-hydrolysis method of the vinyl acetate are widely concerned with the easy rectification and separation of other impurities, so that the key point of obtaining the high-yield 1, 3-propanediol is the process of generating 3-acetoxy propionaldehyde by hydroformylation of the vinyl acetate.
Patent US20070213558A1 discloses a method of using Co 2 (CO) 8 Method for catalyzing hydroformylation of vinyl acetate at minimum reaction temperature of 120 ℃ by using catalyst and pressure of 7.6MPa, but linear product thereofThe selectivity of 3-acetoxy propionaldehyde is lower; patent WO2011075905A1 discloses a method of preparing a complex of metal Co and Rh HRhCo 3 (CO) 13 (PPh 3 ) 3 The method is a method for catalyzing the hydroformylation-hydrolysis of vinyl acetate by a catalyst, and the preparation process of the catalyst is complicated although the reaction condition is mild; patent CN106565485A proposes a method for catalyzing hydroformylation-hydrolysis of vinyl acetate by using Rh as a catalyst and phosphine ligand, wherein the reaction condition is mild, but the selectivity of aldehyde in the total product is low, and the byproduct is difficult to separate, so that the production cost of 1, 3-propanediol is high.
Therefore, a technique for preparing 3-acetoxy propionaldehyde by catalyzing the hydroformylation of vinyl acetate by using a catalyst with mild reaction and high selectivity is needed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a hydroformylation catalyst, wherein the ligand has good stability and high reaction activity.
Another object of the present invention is to provide an application of the catalyst in preparing 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate, which has high reactivity and linear selectivity.
In order to achieve the technical effects, the invention adopts the following technical scheme:
in one aspect, the invention provides a hydroformylation catalyst having a structure as shown in formula I:
in another aspect, the invention also provides a preparation method of the hydroformylation catalyst, which comprises the following steps:
(1) In solvent a, 2-aminophenol
With triethyl formate in the presence of catalyst A to give M1 +.>
(2) Reacting M1 with a dihalide in the presence of butyllithium catalyst in solvent b to form M2
(3) M2 with Co in solvent c 2 (CO) 8 Catalyst produced by catalytic reaction of di (trimethylsilyl) amino potassium
In the step (1) according to the present invention, the amount of triethyl formate added is 0.5 to 1.0 times, preferably 0.5 to 0.6 times the molar amount of 2-aminophenol.
In the step (1), the catalyst A is one of acetic acid, oxalic acid and formic acid, preferably acetic acid; the addition amount of the catalyst A is 0.01-0.05 times, preferably 0.01-0.03 times of the molar amount of the 2-aminophenol; the solvent a is one of ethanol, methanol and propanol, and is preferably ethanol; the amount of the solvent a is 10.0 to 15.0 times, preferably 10.0 to 12.0 times the molar amount of the 2-aminophenol; the reaction temperature is 150-200 ℃, preferably 160-170 ℃, and the reaction time is 2.0-4.0h, preferably 2.5-3.0h.
In the step (2), the addition amount of the butyl lithium is 1.0 to 2.0 times of the molar amount of M1, preferably 1.0 to 1.2 times; the dihalide is one of dibromoethane and dibromomethane, preferably dibromoethane, and the addition amount is 1.5-2.0 times of M1 mol, preferably 1.5-1.7 times of the addition amount; the solvent b is tetrahydrofuran and chloroform, preferably tetrahydrofuran; the amount of the solvent b is 10.0 to 15.0 times, preferably 10.0 to 12.0 times the molar amount of M1; the reaction temperature is room temperature; the reaction time is 2.0 to 4.0 hours, preferably 2.5 to 3.0 hours.
In the step (3), the addition amount of the di (trimethylsilyl) aminopotassium is 1.0-2.0 times, preferably 1.0-1.2 times of the molar amount of the intermediate M2; co (Co) 2 (CO) 8 In an amount of M2 mol of intermediateThe amount is 0.3 to 0.6 times, preferably 0.5 to 0.6 times; the solvent c is one of tetrahydrofuran, chloroform, dichloromethane and benzene, preferably tetrahydrofuran; the amount of the solvent c is 10.0 to 15.0 times, preferably 10.0 to 12.0 times the molar amount of M2; the reaction temperature is room temperature, and the reaction time is 2.0-4.0h, preferably 2.5-3.0h.
The catalyst disclosed by the invention is used for catalyzing the hydroformylation of vinyl acetate to prepare 3-acetoxy propionaldehyde.
Finally, the invention also provides a method for preparing 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate, which comprises the following steps: the catalyst and vinyl acetate are dissolved in a solvent d, then synthesis gas is introduced to the reaction pressure, and the product is obtained through heating reaction.
The catalyst of the present invention is added in an amount of 0.01 to 0.05 times, preferably 0.01 to 0.03 times the molar amount of vinyl acetate.
In the method for preparing 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate, the solvent d is one or more of tetrahydrofuran, dichloromethane, benzene and toluene, and benzene and toluene are preferred.
In the method for preparing 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate, the addition amount of the solvent is 100-500 times, preferably 200-400 times, the molar amount of the transition metal compound.
The hydroformylation reaction pressure of the invention is 1.0 to 10.0MPaG, preferably 1.0 to 3.0MpaG.
The reaction temperature of the hydroformylation reaction is 80-200 ℃, preferably 80-100 ℃.
The reaction time of the hydroformylation reaction described in the present invention is 1.0 to 5.0 hours, preferably 1.0 to 2.0 hours.
The invention has the beneficial effects that:
the ligand of the invention has the principle that the large pi bond of two phenanthrene rings is utilized to attract double bonds in vinyl acetate in the reaction process, thereby improving the reaction rate and reducing the reaction temperature; meanwhile, when the olefin is coordinated with the metal ligand, the linear 3-acetoxyl propionaldehyde is generated by the reaction selectivity due to the insertion of the CO end group with larger steric hindrance of the phenanthrene ring.
The ligand can obtain 3-acetoxyl propionaldehyde with high catalytic activity, good linear selectivity (selectivity can reach 95-98%), strong chelating ability with metal and high reactivity. The method for preparing 3-acetoxyl propionaldehyde has the advantages of simple and convenient process, low cost and energy consumption, good production safety, high quality of the obtained product and the like, and is particularly suitable for large-scale industrialized production.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
The sources of the reagent raw materials used in the examples and comparative examples of the present invention are as follows:
n-butyllithium, triethyl orthoformate was purchased from Sigma-Adrich company; dibromoethane, 2-aminophenyl, vinyl acetate were purchased from Shanghai Ala Biochemical technologies Co., ltd; potassium bis (trimethylsilyl) amide and octahydroxy cobalt were purchased from Angustification Chemie.
The other reagent raw materials are all commercial products unless specified.
All the reagents are purchased and then directly used.
The test methods used in the examples and comparative examples of the present invention are as follows:
the catalyst structure is obtained by a Bruce AVANCE NEO 500M nuclear magnetic analyzer; chromatographic analysis was an Agilent 7890B gas chromatograph: agilent DB-5 chromatographic column, sample inlet temperature: 220 ℃; the temperature of the detector is 250 ℃; h 2 The flow rate is 40/min; air flow rate is 360ml/min. The temperature program of the column box is that the initial temperature is 20 ℃, the temperature rising rate is 20 ℃/min, and the column box is kept for 4min; the temperature is raised at 100-250 deg.c and 15 deg.c/min for 10min.
The invention will be further illustrated with reference to specific examples. It should be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) Preparation of the catalyst
Preparation of M1: 2-Aminophenanthrene (193.25 g,1.0 mol), triethylformate (74.1 g,0.5 mol), acetic acid (0.6 g,0.01 mol) were dissolved in 10mol of ethanol, the temperature was raised to 160℃and after 2.5 hours of reaction, the temperature was lowered to room temperature, and the solvent was removed to give M1 (190.3 g,0.48 mol).
1H NMR(500MHz,Chloroform-d)δ9.41(d,1H),8.50(ddd,2H),8.31(d,1H),8.19(d,1H),8.07(t,1H),8.02–7.95(m,4H),7.89–7.80(m,4H),7.62(ddd,2H),7.55(ddd,2H),7.37(dd,1H),7.27(dd,1H).
Preparation of M2: m1 (190.3 g,0.48 mol), n-butyllithium (30.7 g,0.48 mol), dibromoethane (135.3 g,0.72 mol) were added to 6mol of tetrahydrofuran, and reacted at room temperature for 2.5 hours to give M2 (222.5 g,0.43 mol).
1H NMR(500MHz,Chloroform-d)δ8.55–8.47(m,3H),8.36(s,1H),8.25(d,1H),8.20(t,1H),8.02–7.93(m,3H),7.93–7.90(m,1H),7.89–7.82(m,3H),7.68(t,1H),7.62(ddd,2H),7.55(ddd,2H),7.30(dd,1H),4.25–4.14(m,2H),4.11(dd,1H),4.05(dd,1H),2.21(dddt,2H).
Preparation of the catalyst: m2 (222.5 g,0.43 mol), potassium bis (trimethylsilyl) amide (85.8 g,0.43 mol), co 2 (CO) 8 (75.2 g,0.22 mol) was added to 5mol of tetrahydrofuran and reacted at room temperature for 2.5 hours to obtain a catalyst (231.8 g,0.4 mol).
1H NMR(500MHz,Chloroform-d)δ8.55–8.47(m,3H),8.26(d,1H),8.02–7.93(m,3H),7.89–7.82(m,3H),7.65–7.58(m,3H),7.55(ddd,2H),7.29(t,1H),7.25(ddd,2H),4.40(dd,2H),4.12–4.05(m,2H),2.23–2.11(m,2H).
(2) Preparation of 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate
Vinyl acetate: catalyst molar ratio = 1:0.01 dissolved in toluene and added to the reactor at CO/H 2 The molar ratio is 1:1, the pressure is 1.0MPa, the temperature is 80 ℃, the reaction time is 1.0 hour, and the conversion rate is 99.0 percent; the linear product 3-acetoxy propionaldehyde was obtained by gas chromatography with a selectivity of 96.1%.
Example 2
(1) Preparation of the catalyst
Preparation of M1: preparation of M1: 2-Aminophenanthrene (193.25 g,1.0 mol), triethylformate (88.9 g,0.6 mol), acetic acid (1.8 g,0.03 mol) were dissolved in 15mol ethanol, the temperature was raised to 170℃and after 3.0 hours of reaction, the temperature was lowered to room temperature, and the solvent was removed to give M1 (182.4 g,0.46 mol).
Preparation of M2: m1 (190.3 g,0.48 mol), n-butyllithium (36.8 g,0.576 mol), dibromoethane (154.1 g,0.82 mol) were added to 5.5mol of tetrahydrofuran, and reacted at room temperature for 3.0 hours to give M2 (227.7 g,0.44 mol).
Preparation of the catalyst: m2 (222.5 g,0.43 mol), potassium bis (trimethylsilyl) amide (103.8 g,0.52 mol), co 2 (CO) 8 (88.9 g,0.26 mol) was added to 4mol of tetrahydrofuran and reacted at room temperature for 3.0 hours to obtain a catalyst (237.6 g,0.41 mol).
(2) Preparation of 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate
Vinyl acetate: catalyst molar ratio = 1:0.03 dissolved in toluene and added to the reactor at CO/H 2 The molar ratio is 1:1, the pressure is 3.0MPa, the temperature is 100 ℃, the reaction time is 2.0 hours, and the conversion rate is 99.7%; the linear product 3-acetoxy propionaldehyde was obtained by gas chromatography with a selectivity of 97.7%.
Example 3
(1) Preparation of the catalyst
Preparation of M1: preparation of M1: 2-Aminophenanthrene (193.25 g,1.0 mol), triethylformate (81.5 g,0.55 mol), acetic acid (1.2 g,0.02 mol) were dissolved in 12mol ethanol, the temperature was raised to 165℃and after 3.0 hours of reaction, the temperature was lowered to room temperature, and the solvent was removed to give M1 (186.4 g,0.47 mol).
Preparation of M2: m1 (186.4 g,0.47 mol), n-butyllithium (33.9 g,0.53 mol), dibromoethane (144.7 g,0.77 mol) were added to 4mol of tetrahydrofuran, and reacted at room temperature for 3.0 hours to give M2 (222.5 g,0.43 mol).
Preparation of the catalyst: m2 (222.5 g,0.43 mol), potassium bis (trimethylsilyl) amide (93.8 g,0.47 mol), co 2 (CO) 8 (82.0 g,0.24 mol) was added to 5mol of tetrahydrofuran and reacted at room temperature for 2.8 hours to obtain a catalyst (243.4 g,0.42 mol).
(2) Preparation of 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate
Vinyl acetate: catalyst molar ratio = 1:0.02 dissolved in toluene and added to the reactor at CO/H 2 The molar ratio is 1:1, the pressure is 2.0MPa, the temperature is 90 ℃, the reaction is carried out for 1.5 hours, and the conversion rate is 98.8%; the linear product 3-acetoxy propionaldehyde was obtained by gas chromatography with a selectivity of 97.1%.
Example 4
(1) Preparation of the catalyst
Preparation of M1: preparation of M1: 2-aminophenol (193.25 g,1.0 mol), triethyl formate (148.18 g,1.0 mol), acetic acid (1.2 g,0.02 mol) were dissolved in 12mol of methanol, the temperature was raised to 200℃and after 4.0 hours of reaction, the temperature was lowered to room temperature, and the solvent was removed to give M1 (158.6 g,0.40 mol).
Preparation of M2: m1 (158.6 g,0.40 mol), n-butyllithium (51.24 g,0.8 mol), dibromoethane (150.2 g,0.8 mol) were added to 4mol of tetrahydrofuran and reacted at room temperature for 2.5 hours to give M2 (196.62 g,0.38 mol).
Preparation of the catalyst: m2 (196.62 g,0.38 mol), potassium bis (trimethylsilyl) amide (151.64 g,0.76 mol), co 2 (CO) 8 (77.93 g,0.22 mol) was added to 4mol of methylene chloride and reacted at room temperature for 2.5 hours to obtain a catalyst (208.62 g,0.36 mol).
(2) Preparation of 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate
Vinyl acetate: catalyst molar ratio = 1:0.05 dissolved in toluene and added to the reactor at CO/H 2 The molar ratio is 1:1, the pressure is 10.0MPa, the temperature is 200 ℃, the reaction time is 5.0 hours, and the conversion rate is 99.1 percent; the linear product 3-acetoxy propionaldehyde was obtained by gas chromatography with a selectivity of 92.5%.
Example 5
(1) Preparation of the catalyst
Preparation of M1: preparation of M1: 2-Aminophenanthrene (193.25 g,1.0 mol), triethylformate (118.54 g,0.8 mol), acetic acid (1.8 g,0.03 mol) were dissolved in 14mol of propanol, the temperature was raised to 190℃and after 3.5 hours of reaction, the temperature was lowered to room temperature, and the solvent was removed to give M1 (166.57 g,0.42 mol).
Preparation of M2: m1 (166.57 g,0.42 mol), n-butyllithium (40.35 g,0.63 mol), dibromoethane (157.8 g,0.84 mol) were added to 6mol of tetrahydrofuran, and reacted at room temperature for 4.0 hours to give M2 (201.8 g,0.39 mol).
Preparation of the catalyst: m2 (201.8 g,0.39 mol), potassium bis (trimethylsilyl) amide (139.67 g,0.7 mol), co 2 (CO) 8 (66.65 g,0.195 mol) was added to 4mol of chloroform and reacted at room temperature for 4.0 hours to obtain a catalyst (214.4 g,0.37 mol).
(2) Preparation of 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate
Vinyl acetate: catalyst molar ratio = 1:0.04 dissolved in toluene and added to the reactor at CO/H 2 The molar ratio is 1:1, the pressure is 6.0MPa, the temperature is 150 ℃, the reaction time is 4.0 hours, and the conversion rate is 99.8%; the linear product 3-acetoxy propionaldehyde was obtained by gas chromatography with a selectivity of 93.8%.
Comparative example 1
Preparation of 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate
Vinyl acetate: rh (acac) (CO) 2 =1:0.01 was added to the reaction vessel at CO/H 2 The mass ratio is 1:1, the pressure is 5MPa, the temperature is 110 ℃, the reaction time is 2.0 hours, and the conversion rate is 94.5%; the linear product 3-acetoxy propionaldehyde was obtained by gas chromatography with a selectivity of 72.2%.
Claims (10)
1. A hydroformylation catalyst having a structure according to formula I:
2. the process for preparing a hydroformylation catalyst according to claim 1, comprising the steps of:
(1) In solvent a, 2-aminophenol
With triethyl formate in the presence of catalyst A to produce M1
(2) Reacting M1 with a dihalide in the presence of butyllithium catalyst in solvent b to form M2
(3) M2 with Co in solvent c 2 (CO) 8 Catalyst produced by catalytic reaction of di (trimethylsilyl) amino potassium
3. The process according to claim 2, wherein in step (1), the amount of triethyl formate added is 0.5 to 1.0 times, preferably 0.5 to 0.6 times the molar amount of 2-aminophenol.
4. A process according to claim 2 or 3, wherein in step (1), catalyst a is one of acetic acid, oxalic acid, formic acid, preferably acetic acid; and/or the addition amount of the catalyst A is 0.01 to 0.05 times, preferably 0.01 to 0.03 times of the molar amount of the 2-aminophenol; and/or the solvent a is one of ethanol, methanol and propanol, preferably ethanol; and/or the solvent a is used in an amount of 10.0 to 15.0 times, preferably 10.0 to 12.0 times the molar amount of 2-aminophenol; and/or the reaction temperature is 150-200 ℃, preferably 160-170 ℃, and the reaction time is 2.0-4.0h, preferably 2.5-3.0h.
5. The process according to any one of claims 2 to 4, wherein in step (2), the butyllithium is added in an amount of 1.0 to 2.0 times, preferably 1.0 to 1.2 times the molar amount of M1; and/or the dihalide is one of dibromoethane and dibromomethane, preferably dibromoethane, and the addition amount is 1.5-2.0 times, preferably 1.5-1.7 times of M1 mol.
6. The process according to any one of claims 2 to 5, wherein the solvent b is tetrahydrofuran, chloroform, preferably tetrahydrofuran; the amount of the solvent b is 10.0 to 15.0 times, preferably 10.0 to 12.0 times the molar amount of M1; the reaction temperature is room temperature; the reaction time is 2.0 to 4.0 hours, preferably 2.5 to 3.0 hours.
7. The process according to any one of claims 2 to 6, wherein in step (3), potassium bis (trimethylsilyl) amide is added in an amount of 1.0 to 2.0 times, preferably 1.0 to 1.2 times the molar amount of intermediate M2; co (Co) 2 (CO) 8 The amount of (2) added is 0.3 to 0.6 times, preferably 0.5 to 0.6 times the molar amount of intermediate M2.
8. The preparation method according to any one of claims 2 to 7, wherein the solvent c is one of tetrahydrofuran, chloroform, dichloromethane, benzene, preferably tetrahydrofuran; the amount of the solvent c is 10.0 to 15.0 times, preferably 10.0 to 12.0 times the molar amount of M2; the reaction temperature is room temperature, and the reaction time is 2.0-4.0h, preferably 2.5-3.0h.
9. A process for preparing 3-acetoxy propionaldehyde by hydroformylation of vinyl acetate comprising the steps of: the hydroformylation catalyst according to claim 1 or the hydroformylation catalyst prepared by the preparation method according to any one of claims 2 to 8 and vinyl acetate are dissolved in a solvent d, then synthesis gas is introduced to the reaction pressure, and the reaction is carried out at a temperature rise to obtain the product.
10. The process according to claim 9, wherein the catalyst is added in an amount of 0.01 to 0.05 times, preferably 0.01 to 0.03 times the molar amount of vinyl acetate; and/or the solvent d is one or more of tetrahydrofuran, dichloromethane, benzene and toluene, preferably benzene and toluene.
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