CN113956289A - Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction - Google Patents

Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction Download PDF

Info

Publication number
CN113956289A
CN113956289A CN202111187127.5A CN202111187127A CN113956289A CN 113956289 A CN113956289 A CN 113956289A CN 202111187127 A CN202111187127 A CN 202111187127A CN 113956289 A CN113956289 A CN 113956289A
Authority
CN
China
Prior art keywords
reaction
substituent
catalyst
solvent
ligand
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111187127.5A
Other languages
Chinese (zh)
Inventor
梁观峰
茹童
陈芬儿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CN202111187127.5A priority Critical patent/CN113956289A/en
Publication of CN113956289A publication Critical patent/CN113956289A/en
Pending legal-status Critical Current

Links

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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Abstract

The invention belongs to the technical field of homogeneous catalyst ligands, and particularly relates to a nitrogen phosphine ligand, a preparation method thereof and application thereof in aryl ethylene hydroformylation. The structural formula of the nitrogen phosphine ligand is shown as the following formula; wherein X is in the form of a sodium, potassium or lithium salt of a sulfonate or carboxylate group, and R is methyl, methoxy or phenyl; the nitrogen phosphine ligand and the catalyst based on the nitrogen phosphine ligand react with synthesis gas consisting of carbon monoxide and hydrogen in aryl ethylene hydroformylation reaction to obtain an isomeric aldehyde product 2-aryl propionaldehyde with high regioselectivity, and can be efficiently separated and recovered after the reaction is finished.

Description

Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction
Technical Field
The invention belongs to the technical field of homogeneous catalyst ligands, and particularly relates to a nitrogen phosphine ligand, a preparation method thereof and application thereof in aryl ethylene hydroformylation.
Background
The hydroformylation reaction refers to a chemical process in which olefin, under the action of a transition metal catalyst, undergoes an oxidative addition reaction with carbon monoxide and hydrogen to obtain a product aldehyde. Hydroformylation is currently the largest scale homogeneous catalytic reaction in industrial applications. The metal components in the hydroformylation catalyst are mainly Rh, Co and Ru. Ligands are a core problem in the design of hydroformylation catalysts, and the structure of the ligand influences the chemoselectivity, regioselectivity and stereoselectivity of the reaction process. The Rh metal catalyst complexed by the organic phosphine ligand has excellent catalytic performance in olefin hydroformylation.
For the olefin hydroformylation reaction catalyzed by the Rh complex, the rhodium complex formed by the water-soluble phosphine ligand and the Rh precursor compound can catalyze the olefin hydroformylation reaction in a water/organic two-phase system, so that the product and the catalyst in the catalytic reaction can be quickly separated. The sodium trisulfonate (TPPTS) with good water solubility of triphenylphosphine is used as a phosphine ligand for hydroformylation reaction, and shows good reactivity and chemoselectivity to product aldehyde in the hydroformylation reaction of low-carbon-number olefin with the carbon number less than 5. In the subsequent research, novel water-soluble phosphine ligands with different structures, such as BISBI, BINAS, NORBOS, Sulfonated-Xantphos, phosphine-modified polyethylene glycol-based ligands and the like, are developed, but the ligands have the problems of poor reaction activity and low regioselectivity in aryl ethylene hydroformylation reaction.
Based on the current situation of aryl ethylene hydroformylation reaction, the invention develops a water-soluble nitrogen phosphine ligand which has good water solubility and unique spatial configuration and electronic effect and can efficiently catalyze aryl ethylene to be converted into corresponding aryl propionaldehyde in a water-organic two-phase high selectivity manner.
Disclosure of Invention
The invention aims to provide a nitrogen phosphine ligand with excellent catalytic performance in aryl ethylene hydroformylation reaction, a preparation method thereof and application in catalyzing aryl ethylene hydroformylation reaction. The nitrogen phosphine ligand is used as a catalyst, and in aryl ethylene hydroformylation, an isomeric aldehyde product 2-aryl propionaldehyde can be obtained in a high regioselectivity manner.
The nitrogen phosphine ligand used as the aryl ethylene hydroformylation reaction catalyst provided by the invention has water solubility, can efficiently convert aryl ethylene into aldehyde in a water-organic two-phase system, and has good regioselectivity on 2-aryl propionaldehyde. The structural formula of the nitrogen phosphine ligand is as follows:
Figure BDA0003299726900000021
wherein X is in the form of sodium salt, potassium salt or lithium salt of sulfonate or carboxylate, and R is methyl, ethyl, isopropyl, methoxy or phenyl.
Preferably, the nitrogen phosphine ligand has a structural formula shown in the specification, wherein R1 is a sodium carboxylate or sodium sulfonate functional group and is connected at any position of a benzene ring from C2 to C6; r2 is methoxyl, and is connected at any position of C2 to C6 of a benzene ring.
Figure BDA0003299726900000022
The preparation method of the nitrogen phosphine ligand provided by the invention comprises two steps:
the synthesis reaction formula of the method I is as follows:
Figure BDA0003299726900000023
the method comprises the following specific steps:
in the presence of a solvent, performing coupling reaction on benzoyl chloride analogue connected with a substituent and a compound 2 (bis (2- (diphenylphosphino) ethyl) amine hydrochloride) under the action of an alkali catalyst to generate an intermediate product benzamide;
wherein, -COOMe is at any position of C2-C6 on the benzene ring; the chemical structure of the substituent R2 is-COOMe or H, and the connecting position is any position from C2 to C6 on the benzene ring; the molar ratio of the benzoyl chloride-containing analogue to compound 2 (bis (2- (diphenylphosphino) ethyl) amine hydrochloride) was 1:1 to 1:10 is between; the catalyst is triethylamine TEA, and the molar ratio of the triethylamine TEA to the benzoyl chloride analogue is 0.1-1.5; the solvent is tetrahydrofuran, and the reaction temperature is between-30 ℃ and room temperature;
in the presence of a solvent, an intermediate product benzamide undergoes a hydrolysis reaction under the action of an inorganic base, the chemical structure of a substituent is converted from-COOMe to corresponding sodium carboxylate-COONa, and finally a nitrogen phosphine ligand is obtained;
wherein, the substituent R1 on the benzene ring in the benzoyl chloride analogue has a chemical structural formula:
R1＝-COONa；
the chemical structure of the second substituent:
r2 ═ OMe, and the linking position of the substituent R2 is any position on the benzene ring other than R1.
In particular, when R1 ═ 2-COONa, R2 ═ H, the resulting phosphorane ligand is denoted as L1; when R1 ═ 3-COONa and R2 ═ H, the resulting aminophosphine ligand is designated as L2; when R1 ═ 3-COONa and R2 ═ 5-OMe, the resulting phosphorane ligand is designated as L3; when R1 ═ 4-COONa, R2 ═ H, the resulting phosphorane ligand was designated L4.
The solvent is a mixed solvent of tetrahydrofuran and water, and the ratio of the tetrahydrofuran to the water is 1:10 to 10: 1, the catalyst is an inorganic base catalyst, and is specifically selected from one or more of LiOH, NaOH and KOH;
the second method has the synthesis reaction formula as follows:
Figure BDA0003299726900000031
the method comprises the following specific steps:
in the presence of a solvent, catalyzing a benzoyl chloride analogue containing a substituent group by a catalyst to react with a compound 2 (bis (2- (diphenylphosphino) ethyl) amine hydrochloride) to generate an intermediate product benzamide;
wherein, the mass ratio of the benzoyl chloride containing substituent groups to the compound 2 (bis (2- (diphenylphosphino) ethyl) amine hydrochloride) is 1:1 to 1:10 is between; the catalyst is triethylamine TEA, and the molar ratio of the triethylamine TEA to the benzoyl chloride analogue is 0.1-1.5; the solvent is tetrahydrofuran, and the reaction temperature is between-30 ℃ and room temperature;
and step two, in the presence of a solvent, the intermediate product benzamide undergoes a hydrolysis reaction under the action of an inorganic salt, the chemical structure of the substituent is converted into a corresponding sodium sulfonate salt, and finally the nitrogen phosphine ligand is obtained.
Wherein, the chemical structural formulas of the substituents R2 and R3 on the benzene ring are as follows: r2 ═ OMe, R3 ═ SO3Na; wherein, the connecting position of the substituent R3 is any position from C2 to C6 on the benzene ring, and the connecting position of the substituent R2 is any position except R3 on the benzene ring.
In particular, when R2 ═ H, R3 ═ 2-SO3When Na is contained, the obtained nitrogen phosphine ligand is marked as L5; when R2 is H, R3 is 3-SO3When Na is contained, the obtained nitrogen phosphine ligand is marked as L6; when R2 is 4-OMe, R3 is 3-SO3When Na is contained, the obtained nitrogen phosphine ligand is marked as L7; when R2 is H, R3 is 4-SO3Na, and the obtained nitrogen phosphine ligand is marked as L8; when R2 is 3-OMe, R3 is 4-SO3When Na is used, the obtained nitrogen phosphine ligand is marked as L9.
The solvent is an organic solvent, and the ligand is obtained by carrying out reflux operation under the condition of adding NaI. The invention also provides the application of the nitrogen phosphine ligand in aryl ethylene hydroformylation. Experiments show that the N-phosphine ligand can obtain an isomeric aldehyde product 2-aryl propionaldehyde in high regioselectivity in aryl ethylene hydroformylation reaction, and can be efficiently separated and recovered after the reaction is finished.
The invention also provides an application of the nitrogen phosphine ligand in aryl ethylene hydroformylation reaction, which comprises the following specific steps:
(1) first, a catalyst was prepared: in-situ complexing a rhodium metal compound and an azapinphosphine ligand in an organic solvent to form an Rh metal complex catalyst; wherein:
the rhodium metal compound is selected from one or more of rhodium halide, rhodium carbonyl complex, rhodium acetylacetonate complex and cyclooctadienyl rhodium complex; the preferred rhodium metal compound is RhCl3、Rh(CO)2acac、Rh4(CO)12Or Rh6(CO)16Diphenylphosphine (1, 5-cyclooctadiene) rhodium (I) dimer, (1, 5-cyclooctadiene)Alkene) chlororhodium (I) dimer.
The molar ratio of the rhodium metal compound to the phosphine nitride ligand is 1:1 to 1:100(1: 1 to 100)), preferably 1:10 to 1: 50.
(2) The Rh metal complex catalyst is used for catalyzing aryl ethylene hydroformylation reaction, the selected reaction medium is water and an organic phase, the water is used as a solvent for dissolving the catalyst, and the organic phase is one or more of benzene, toluene, m-xylene, p-xylene, o-xylene, mesitylene, diethyl ether, chloralkane, cyclohexane, n-hexane and methyl tert-butyl ether. Preferably one or more of toluene, m-xylene, p-xylene, o-xylene and mesitylene. Wherein:
preferably, in the aryl ethylene hydroformylation reaction, the aryl olefin is selected from styrene or aryl ethylene with substituent groups on aryl; the substituent on the aryl ethylene comprises one or more of methyl, ethyl, n-propyl, isopropyl, tert-butyl, isobutyl, methoxy, cyano, hydroxyl and halogen atoms.
Preferably, the aryl ethylene also comprises aryl ethylene with the following special structure, which is sequentially marked as a compound 6, a compound 7, a compound 8 and a compound 9; the structure is as follows:
Figure BDA0003299726900000041
preferably, in the aryl ethylene hydroformylation reaction, aryl ethylene reacts with the mixed gas of carbon monoxide and hydrogen under the action of a catalyst, and the reaction temperature is 40-120 ℃, and preferably 60-100 ℃; the reaction time is 0.5-48 h; the pressure of the mixed gas of the carbon monoxide and the hydrogen required by the hydroformylation reaction is 0.1-5MPa, and preferably 1-4 MPa.
Preferably, in the aryl ethylene hydroformylation reaction, the amount of the catalyst used in the reaction system is 0.001 to 1%, preferably 0.05 to 0.5%, based on the mass of the rhodium metal compound; the molar ratio of carbon monoxide to hydrogen is from 3:1 to 1:3, preferably from 2:1 to 1: 2.
The technical scheme of the invention has the following effects:
in the aryl ethylene hydroformylation reaction, the nitrogen phosphine ligand provided by the invention is complexed with an Rh metal salt precursor and then efficiently catalyzes the aryl ethylene to react with the mixed gas of carbon monoxide and hydrogen, so that an isomeric aldehyde product, namely 2-aryl propionaldehyde is obtained with high regioselectivity; the catalyst prepared based on the nitrogen phosphine ligand has one nitrogen atom and two phosphorus atoms as electron donors to coordinate with rhodium metal, can improve the proportion of isomeric aldehyde in an aryl ethylene hydroformylation reaction product, has water solubility, can be separated and recycled after the reaction is finished, has simple operation process, can be recycled, and is suitable for industrial production and application.
Detailed Description
The preparation method of the phosphine nitride ligand and the catalyst of the present invention and the application thereof in the hydroformylation of aryl ethylene will be further illustrated by the following examples, but it should be specifically noted that the present invention is not limited to the following examples.
Example 1 preparation of ligand L1
Figure BDA0003299726900000051
Step 1, add 1a (2mmol), 2(2mmol) and DCM (4mL) to the reaction flask, add TEA (8mmol) at 0 deg.C, then move to room temperature for 24h, evaporate the solvent and perform column separation to obtain the product (3 a: 83%).
Step 2, THF (2mL) dissolved 3a (1mmol), then LiOH. H2O (1.5mmol) was dissolved in 1ml of water and added to a reaction flask, when the starting material had reacted completely, 5% HCl was added to adjust the pH to 2, THF was distilled off and extracted with DCM, Na2SO4Drying, evaporating the solvent to dryness to give a colorless oily product, then eluting with THF (1ml) and H2O (1mL) was dissolved, NaOH (1mmol) was added, the mixture was stirred at room temperature for 2 hours, and the solvent was evaporated to dryness to give the product (L1: 95%).
Example 2 preparation of ligand L5
Figure BDA0003299726900000052
Step 1, 4a (2mmol), 2(2mmol) and THF (4mL) were added to a reaction flask, TEA (8mmol) was added at 0 deg.C, then the reaction was allowed to move to room temperature for 24h, and the solvent was evaporated to dryness for column separation to give the product (5 a: 89%).
Step 2, adding NaI (1.5mmol), 5a (1mmol) and acetone into a reaction flask, heating and refluxing until the reaction is completed, evaporating the solvent product and washing with acetone to obtain the product (L5: 83%).
Example 3 preparation of ligand L6
Figure BDA0003299726900000061
Step 1, 4b (2mmol), 2(2mmol) and THF (4mL) were added to a reaction flask, TEA (8mmol) was added at 0 deg.C, then the reaction was allowed to move to room temperature for 24h, and the solvent was evaporated to dryness for column separation to give the product (5 b: 85%).
Step 2, adding NaI (1.5mmol), 5b (1mmol) and acetone into a reaction bottle, heating and refluxing until the reaction is completed, evaporating the solvent product and washing with acetone to obtain the product (L6: 81%).
Example 4 preparation of ligand L8
Figure BDA0003299726900000062
Step 1, the reaction flask was charged with 4d (2mmol), 2(2mmol) and THF (4mL), TEA (8mmol) was added at 0 deg.C, then moved to room temperature for 24h, and the solvent was evaporated to dryness to give product 5d (90%).
Step 2, adding NaI (1.5mmol), 5d (1mmol) and acetone into a reaction flask, heating and refluxing until the reaction is completed, evaporating the solvent product and washing with acetone to obtain L8 (82%).
Example 5 preparation of ligand L9
Figure BDA0003299726900000063
Step 1, 4f (2mmol), 2(2mmol) and THF (4mL) were added to a reaction flask, TEA (8mmol) was added at 0 deg.C, then the reaction was allowed to move to room temperature for 24h, and the solvent was evaporated to dryness for column separation to give the product (5 f: 87%).
Step 2, adding NaI (1.5mmol), 5f (1mmol) and acetone into a reaction bottle, heating and refluxing until the reaction is completed, evaporating the solvent product and washing with acetone to obtain the product (L9: 85%).
Example 6 use of the Nitrogen phosphine ligand in the hydroformylation of styrene
In the embodiment, parallel miniature high-pressure reaction kettles are adopted, and five reaction tubes with the numbers of 1, 2, 3, 4 and 5 are arranged in the kettles. 0.0015mmol of (1, 5-cyclooctadiene) chlororhodium (I) dimer was added to the reaction tubes of 1, 2, 3, 4 and 5, respectively, under an anhydrous and oxygen-free atmosphere, and then 0.018mmol of each of ligands L1, L5, L6, L8 and L9 was added to the reaction tubes of 1, 2, 3, 4 and 5. Then, the mixture was dissolved in 1.5mL of toluene and stirred at 0.1MPa of nitrogen for 2 hours at room temperature to obtain a catalyst solution. 3mmol of styrene, 1.5mL of water, and 5mM of sodium dodecylbenzenesulfonate (surfactant) were added to the reaction tubes of 1, 2, 3, 4, and 5 under nitrogen. Introducing 4.0MPa of synthetic gas (CO/H)21: 1). Heating to 60 ℃, stirring and reacting for 24h, cooling to room temperature and discharging gas, wherein the upper layer of the reaction solution is an organic product layer, and the lower layer is a catalyst aqueous solution layer. After the organic product layer is diluted, the conversion rate is more than 99 percent and the selectivity of normal and isomeric product aldehyde is more than 99 percent through gas chromatography analysis. The results are shown in Table 1.
TABLE 1 Activity representation of different ligands in the benzoyl reaction of styrene
Figure BDA0003299726900000071
Example 7 hydroformylation of Arylethylene having a particular Structure
In this example, parallel miniature high-pressure reaction kettles are used, and five reaction tubes with numbers of 1, 2, 3, 4 and 5 are arranged in the kettles. 0.0015mmol of (1, 5-cyclooctadiene) chlororhodium (I) dimer and 0.018mmol of the nitrogen phosphine ligand L5 were dissolved in 1.5mL of toluene under an anhydrous oxygen-free atmosphereStirring the mixture for 2 hours at the room temperature in nitrogen with the pressure of 0.1MPa to obtain a catalyst solution. 3mmol of aryl ethylene compounds 6, 7, 8 and 9 with special structures are respectively added into reaction tubes No. 1, 2, 3 and 4 under the nitrogen purging. Then 1.5mL of water, surfactant sodium dodecylbenzenesulfonate (5mM) was added. Introducing 4.0MPa of synthetic gas (CO/H)21: 1). Heating to react stably, stirring to react for 24h, cooling to room temperature to release gas, wherein the upper layer of the reaction solution is an organic product layer, and the lower layer is a catalyst aqueous solution layer. Drying the organic product layer by anhydrous sodium sulfate, then spin-drying, and carrying out flash column chromatography to obtain the target product aldehyde. The results are shown in Table 2.
TABLE 2 results of hydroformylation reaction of arylethenes having specific structures
Figure BDA0003299726900000072
Figure BDA0003299726900000081

Claims (10)

1. A phosphorane ligand having the formula:
Figure FDA0003299726890000011
wherein X is in the form of sodium salt, potassium salt or lithium salt of sulfonate or carboxylate, and R is methyl, ethyl, isopropyl, methoxy or phenyl.
2. The phosphorane ligand of claim 1, wherein the phosphorane ligand has the formula: wherein R1 is sodium carboxylate or sodium sulfonate functional group, and is connected at any position of a benzene ring C2 to C6; r2 is hydrogen atom or methoxyl.
Figure FDA0003299726890000012
3. A process for the preparation of the phosphorane ligand of claim 2, wherein the ligand is classified into two types:
the synthesis reaction formula of the method I is as follows:
Figure FDA0003299726890000013
the method comprises the following specific steps:
in the presence of a solvent, performing coupling reaction on benzoyl chloride analogue connected with a substituent and compound 2 bis (2- (diphenylphosphino) ethyl) amine hydrochloride under the action of an alkali catalyst to generate an intermediate product benzamide;
wherein, for benzoyl chloride analogues, -COOMe is at any position on the phenyl ring from C2 to C6; the chemical structure of a substituent R2 on a benzene ring is-COOMe or H, and the connecting position is any position from C2 to C6 on the benzene ring; the molar ratio of the benzoyl chloride-containing analogue to the compound 2 bis (2- (diphenylphosphino) ethyl) amine hydrochloride was 1:1 to 1:10 is between; the catalyst is triethylamine TEA, and the molar ratio of the triethylamine TEA to the benzoyl chloride analogue is 0.1-1.5; the solvent is tetrahydrofuran, and the reaction temperature is between-30 ℃ and room temperature;
in the presence of a solvent, an intermediate product benzamide undergoes a hydrolysis reaction under the action of an inorganic base, the chemical structure of a substituent is converted from-COOMe to corresponding sodium carboxylate-COONa, and finally a nitrogen phosphine ligand is obtained;
wherein, the substituent R1 on the benzene ring in the benzoyl chloride analogue has a chemical structural formula:
R1＝-COONa；
the chemical structure of the second substituent:
r2 ═ OMe, and the linking position of the substituent R2 is any position on the benzene ring other than R1;
the solvent is a mixed solvent of tetrahydrofuran and water, and the ratio of the tetrahydrofuran to the water is 1:10 to 10: 1, the catalyst is an inorganic base catalyst, and is specifically selected from one or more of LiOH, NaOH and KOH;
the second method has the synthesis reaction formula as follows:
Figure FDA0003299726890000021
the method comprises the following specific steps:
in the presence of a solvent, catalyzing a benzoyl chloride analogue containing a substituent group by a catalyst to react with a compound 2 bis (2- (diphenylphosphino) ethyl) amine hydrochloride to generate an intermediate product benzamide;
wherein, the chemical structural formula of a substituent R1 on a benzene ring in the benzoyl chloride analogue is as follows:
R1＝2-SO3CH2CH2(CH3)2or R1 ═ 3-SO3CH2CH2(CH3)2Or R1 ═ 3-SO3CH2CH2(CH3)2Or R1 ═ 4-SO3CH2CH2(CH3)2Or R1 ═ 4-SO3CH2CH2(CH3)2(ii) a The structural formula of the second substituent R2 is-OMe or H; wherein the connecting position of the substituent R2 is any position of C2 to C6 on the benzene ring except R1;
wherein, the mass ratio of the benzoyl chloride containing substituent groups to the compound 2 is 1:1 to 1:10 is between; the catalyst is triethylamine TEA, and the molar ratio of the triethylamine TEA to the benzoyl chloride analogue is 0.1-1.5; the solvent is tetrahydrofuran, and the reaction temperature is between-30 ℃ and room temperature;
in the presence of a solvent, the intermediate product benzamide undergoes a hydrolysis reaction under the action of an inorganic salt, the chemical structure of a substituent is converted into a corresponding sodium sulfonate salt, and finally a nitrogen phosphine ligand is obtained; wherein, the structural formula of the substituent R2 is-OMe or H, and the connecting position is any position of C2 to C6 on the benzene ring except R3;
the solvent is an organic solvent, and the ligand is obtained by carrying out reflux operation under the condition of adding NaI.
4. The use of a phosphorane ligand according to claim 1 or 2 in the hydroformylation of arylethenes, characterised by the specific steps of:
(1) first, a catalyst was prepared: complexing a rhodium metal compound with the phosphorane ligand of claim 1 in situ in an organic solvent to form a Rh metal complex catalyst; wherein:
the rhodium metal compound is selected from one or more of rhodium halide, rhodium carbonyl complex, rhodium acetylacetonate complex and cyclooctadienyl rhodium complex;
the molar ratio of the rhodium metal compound to the nitrogen-phosphine ligand is 1 (1-100);
(2) the Rh metal complex catalyst is used for catalyzing aryl ethylene hydroformylation reaction, a reaction medium is water and an organic phase, the water is used as a solvent for dissolving the catalyst, and the organic phase is one or more of benzene, toluene, m-xylene, p-xylene, o-xylene, mesitylene, diethyl ether, chloralkane, cyclohexane, n-hexane and methyl tert-butyl ether.
5. Use according to claim 4, wherein the rhodium metal compound is selected from RhCl3、Rh(CO)2acac、Rh4(CO)12、Rh6(CO)16One or more of diphenylphosphine (1, 5-cyclooctadiene) rhodium (I) dimer, and (1, 5-cyclooctadiene) chlororhodium (I) dimer.
6. The use of claim 4, wherein in the aryl ethylene hydroformylation reaction, aryl ethylene reacts with a mixed gas of carbon monoxide and hydrogen under the action of a catalyst to obtain aldehydes; wherein the molar ratio of the carbon monoxide to the hydrogen is 3:1-1: 3.
7. The use according to claim 4 or 5, wherein in the hydroformylation of arylethene, the arylalkene is selected from styrene or arylethene with substituents present on the aryl group; the substituent on the aryl ethylene is selected from one or more of methyl, ethyl, n-propyl, isopropyl, tert-butyl, isobutyl, methoxy, cyano, hydroxyl and halogen atoms.
8. Use according to claim 6, characterized in that the arylethylene is of one of the following formulae (6), (7), (8), (9):
Figure FDA0003299726890000031
9. the use according to claim 4, 5 or 7, characterized in that in the arylethene hydroformylation reaction, the reaction temperature is 40-120 ℃, and the reaction time is 0.5-48 h; the reaction pressure is 0.1-5 MPa.
10. The use according to claim 4, 5 or 7, wherein the catalyst is used in the reaction system in an amount of 0.001 to 1% by mass based on the mass of the rhodium metal compound.
CN202111187127.5A 2021-10-12 2021-10-12 Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction Pending CN113956289A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111187127.5A CN113956289A (en) 2021-10-12 2021-10-12 Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111187127.5A CN113956289A (en) 2021-10-12 2021-10-12 Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction

Publications (1)

Publication Number Publication Date
CN113956289A true CN113956289A (en) 2022-01-21

Family

ID=79464063

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111187127.5A Pending CN113956289A (en) 2021-10-12 2021-10-12 Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction

Country Status (1)

Country Link
CN (1) CN113956289A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003231A (en) * 2023-01-17 2023-04-25 山东京博石油化工有限公司 Method for synthesizing aldehyde compound by hydroformylation of 1, 1-disubstituted olefin

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063668A1 (en) * 2003-12-31 2005-07-14 Council Of Scientific & Industrial Research Process for synthesis of alpha-substituted acroleins
WO2008071508A1 (en) * 2006-12-13 2008-06-19 Evonik Oxeno Gmbh Bisphosphite ligands for hydroformylation catalyzed by transition metals
CN101298460A (en) * 2008-06-25 2008-11-05 中国科学院上海有机化学研究所 Bidentate phosphite ester ligand, synthetic method and use thereof in alkene unsymmetrical catalysis hydroformylation reaction
CN101775035A (en) * 2009-12-25 2010-07-14 青岛科技大学 Synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation
CN103130623A (en) * 2011-12-05 2013-06-05 中国石油化工集团公司 Reaction system and reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene
WO2013176345A1 (en) * 2012-05-24 2013-11-28 (주)엘지화학 Catalyst composition for hydroformylation reaction and hydroformylation method using the same
KR20160032528A (en) * 2014-09-16 2016-03-24 한화케미칼 주식회사 Aqueous hydroformylation having improved iso-aldehyde selectivity
WO2018103536A1 (en) * 2016-12-08 2018-06-14 武汉凯特立斯科技有限公司 Reaction method and catalyst for internal olefin isomerization and hydroformylation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063668A1 (en) * 2003-12-31 2005-07-14 Council Of Scientific & Industrial Research Process for synthesis of alpha-substituted acroleins
WO2008071508A1 (en) * 2006-12-13 2008-06-19 Evonik Oxeno Gmbh Bisphosphite ligands for hydroformylation catalyzed by transition metals
CN101298460A (en) * 2008-06-25 2008-11-05 中国科学院上海有机化学研究所 Bidentate phosphite ester ligand, synthetic method and use thereof in alkene unsymmetrical catalysis hydroformylation reaction
CN101775035A (en) * 2009-12-25 2010-07-14 青岛科技大学 Synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation
CN103130623A (en) * 2011-12-05 2013-06-05 中国石油化工集团公司 Reaction system and reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene
WO2013176345A1 (en) * 2012-05-24 2013-11-28 (주)엘지화학 Catalyst composition for hydroformylation reaction and hydroformylation method using the same
KR20160032528A (en) * 2014-09-16 2016-03-24 한화케미칼 주식회사 Aqueous hydroformylation having improved iso-aldehyde selectivity
WO2018103536A1 (en) * 2016-12-08 2018-06-14 武汉凯特立斯科技有限公司 Reaction method and catalyst for internal olefin isomerization and hydroformylation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GAO PENG ET AL.: "Synthesis of rac-α-aryl propionaldehydes via branched-selective hydroformylation of terminal arylalkenes using water-soluble Rh-PNP catalyst", CHINESE CHEMICAL LETTERS, vol. 33, no. 2, pages 830 - 834, XP086970487, DOI: 10.1016/j.cclet.2021.07.068 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003231A (en) * 2023-01-17 2023-04-25 山东京博石油化工有限公司 Method for synthesizing aldehyde compound by hydroformylation of 1, 1-disubstituted olefin

Similar Documents

Publication Publication Date Title
Yu et al. Pd/C-catalyzed direct formylation of aromatic iodides to aryl aldehydes using carbon dioxide as a C1 resource
Dongol et al. Iron‐catalysed sp3–sp3 cross‐coupling reactions of unactivated alkyl halides with alkyl Grignard reagents
Stefani et al. Homocoupling reactions of alkynes, alkenes and alkyl compounds
CN111087306B (en) Method for preparing organic carboxylic ester by aryl bidentate phosphine ligand combined catalysis
Zheng et al. Difunctionalization of ketones via gem-bis (boronates) to synthesize quaternary carbon with high selectivity
CN113416211A (en) Vinyl functional group phosphine ligand synthesis method, phosphine ligand and application
CN106513048A (en) Catalyst for nonterminal olefin hydroformylation reaction and preparation method and application of catalyst
Zhou et al. Pd/tetraphosphine catalytic system for Cu-free Sonogashira reaction “on water”
Geng et al. Copper-catalyzed hydroformylation and hydroxymethylation of styrenes
CN113956289A (en) Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction
Zhang et al. Copper-catalyzed direct couplings of terminal alkynes with primary and secondary benzyl bromides
JP5920834B2 (en) Metal complex compound, hydrogen production catalyst and hydrogenation reaction catalyst containing the metal complex compound, and hydrogen production method and hydrogenation method using the catalyst
Lei et al. Nickel-catalysed SET-reduction-based access to functionalized allenes via 1, 4-carbohydrogenation of 1, 3-enynes with alkyl bromides
CN113004326B (en) Phosphine ligand for butadiene hydroformylation reaction and preparation method thereof
CN110229080B (en) Alpha-diimine nickel metal organic ligand, porous organic polymer and application thereof
CN101195641A (en) Novel phosphine ligand, production and uses in catalytic reaction thereof
Iranpoor et al. 1, 3, 2, 4-Diazadiphosphetidines as ligand and base for palladium-catalyzed Suzuki–Miyaura, Sonogashira–Hagihara, and homocoupling reactions of aryl halides under heterogeneous conditions in water
CN113980052B (en) Monophosphate ligand, preparation method thereof and application thereof in hydroformylation reaction
JP5738021B2 (en) Method for producing hexafluoro-1,3-butadiene
JP7019912B2 (en) Catalyst composition for the process of producing unsaturated carboxylates and their derivatives from carbon dioxide and olefins
CN111116285B (en) Efficient preparation method of 1-aryl-4-butene compound
CN114163476A (en) Monodentate phosphine ligand, hydroformylation catalyst and method for preparing linear aldehyde by olefin hydroformylation
Aydemir et al. Cationic and neutral ruthenium (II) complexes containing both arene or Cp* and functionalized aminophosphines. Application to hydrogenation of aromatic ketones
WO2017193288A1 (en) Synthesis of phosphine ligands bearing tunable linkage: methods of their use in catalysis
CN114588945B (en) Catalyst and method for preparing alpha-acetoxy acetone by hydroformylation of vinyl acetate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20220121