CN113788748A - Method for preparing straight-chain carbonyl compound by catalyzing unsaturated hydrocarbon with multidentate phosphine ligand modified palladium combined catalyst - Google Patents

Method for preparing straight-chain carbonyl compound by catalyzing unsaturated hydrocarbon with multidentate phosphine ligand modified palladium combined catalyst Download PDF

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CN113788748A
CN113788748A CN202111081268.9A CN202111081268A CN113788748A CN 113788748 A CN113788748 A CN 113788748A CN 202111081268 A CN202111081268 A CN 202111081268A CN 113788748 A CN113788748 A CN 113788748A
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刘晔
陈晓超
路勇
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East China Normal University
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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    • 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
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    • C07C231/00—Preparation of carboxylic acid amides
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    • C07C67/00—Preparation of carboxylic acid esters
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Abstract

The invention discloses a method for preparing a linear carbonyl compound by catalyzing unsaturated hydrocarbon with a multidentate phosphine ligand-modified palladium combined catalyst, wherein the linear carbonyl compound comprises carboxylic acid, carboxylic ester and amide; the composite catalyst consists of a divalent or zero-valent palladium compound, a multidentate phosphine ligand and an acidic auxiliary agent. Under the action of a combined catalyst, unsaturated hydrocarbon, carbon monoxide and a nucleophilic reagent are used as raw materials to carry out carbonylation reaction, so as to successfully prepare a straight-chain carbonyl compound; the nucleophilic reagent includes water, alcohol, organic primary amine or inorganic ammonia. The catalyst has the advantages of high catalytic activity, good selectivity of straight-chain carbonyl compounds, good stability and cyclic utilization. The invention is a homogeneous synthesis process by a one-pot method, has simple synthesis process and mild reaction conditions, provides a new technology for synthesizing important chemical straight-chain carbonyl compounds, and has good application and popularization prospects.

Description

Method for preparing straight-chain carbonyl compound by catalyzing unsaturated hydrocarbon with multidentate phosphine ligand modified palladium combined catalyst
Technical Field
The invention belongs to the chemical field of homogeneous catalysis and fine chemical synthesis, and relates to a method for preparing a linear carbonyl compound (comprising organic carboxylic acid, carboxylic ester or amide) by using unsaturated hydrocarbon, carbon monoxide and a nucleophilic reagent as raw materials through carbonylation under the action of a palladium combined catalyst modified by a multidentate phosphine ligand.
Background
Reppe, a German chemist, in the 40's of the 20 th century, first discovered a carboxylic acid synthesis reaction using carbonylation of acetylene, carbon monoxide and water (Reppe, W.; Vetter, H. Liebigs Ann. chem.1953,582,133) and generalized the nucleophile used in the reaction to alcohols (synthetic carboxylic esters) and organic primary amines (synthetic amides), wherein several carbonylation reactions such as BASF, Germany and Toyo Rayon (east Yang) have successfully been put into industrial use (US 3,501,518; US 3,455,989; US 3,437,676; DE OS 1,221,224; Acc. chem. Res.1969,2,144-151; chem. Rev.101(2001) 3435-. Since the carbonylation of unsaturated hydrocarbons (including carboxylation, carbonylation, esterification, and amidation) is 100 atom economical, methods for synthesizing carbonyl compounds (including carboxylic acids, carboxylic esters, and amides) based on this process have been attracting much attention so far (WO 96/19434, WO 01/10551 a1, WO 2004/014552A 1, WO 2005/079981 a1, WO 2007/020379 a1, WO 2008/023338 a1, GB 2529007 a, EP 3121186 a2, US 2017/0341067 Al CN 102531890 a, CN 111116415A, CN 107915630 a).
Unsaturated hydrocarbons (including terminal olefins, dienes or terminal alkynes) are cheap and easily-obtained bulk chemical raw materials, and the carbonylation reaction catalyzed by a phosphine ligand modified transition metal compound catalyst of the eighth subgroup is one of important ways for preparing carbonyl compounds with high added values. However, it is well known that for the carbonylation of terminal alkenes, dienes or alkynes, the products are mainly branched carbonyl compounds (Green Chemistry,2019,21, 5336-.
Disclosure of Invention
The invention aims to provide a method for preparing a linear carbonyl compound by catalyzing unsaturated hydrocarbon through carbonylation reaction by using a palladium combined catalyst modified by a multidentate phosphine ligand.
The invention relates to a method for preparing a linear carbonyl compound by catalyzing unsaturated hydrocarbon with a palladium combined catalyst modified by a multidentate phosphine ligand, which is a process for generating the carbonyl compound (comprising organic carboxylic acid, carboxylic ester and amide) by using unsaturated hydrocarbon, carbon monoxide and a nucleophilic reagent (comprising water, alcohol, organic primary amine or inorganic ammonia (inorganic ammonia comprises ammonia gas, an ammonia substitute (such as ammonium bicarbonate or ammonium chloride) or ammonia water) as raw materials to carry out carbonylation reaction (comprising carbonylation carboxylation reaction, carbonylation esterification reaction and carbonylation amidation reaction) under the action of the combined catalyst of the palladium compound/the multidentate phosphine ligand/an acid assistant.
The specific technical scheme for realizing the purpose of the invention is as follows:
a multidentate phosphine ligand modified palladium composite catalyst is used for catalyzing unsaturated hydrocarbon to prepare straight-chain carbonyl compounds, and the method is characterized in that under the action of the composite catalyst, unsaturated hydrocarbon, carbon monoxide and nucleophilic reagent are used as raw materials to generate straight-chain carbonyl compounds through carbonylation reaction, and specifically comprises the following steps: sequentially adding a palladium compound, a polydentate phosphine ligand, an acidic assistant, unsaturated hydrocarbon and a nucleophilic reagent into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, filling carbon monoxide gas, keeping the pressure of 1.0-5.0MPa, reacting at 80-200 ℃ for 1-48 hours after ensuring the air tightness of the reaction kettle device, and cooling to room temperature after the reaction is finished, wherein the yield of the linear chain carbonyl compound is 50-90%; wherein the unsaturated hydrocarbon comprises a terminal olefin, internal olefin, diene, or terminal alkyne; the composite catalyst is a homogeneous catalyst, is a palladium composite catalyst modified by multidentate phosphine ligands, consists of palladium compounds, multidentate phosphine ligands and acidic auxiliary agents, and is expressed as a 'palladium compound/multidentate phosphine ligand/acidic auxiliary agent' composite catalyst, and the molar ratio of the multidentate phosphine ligands to the palladium compounds is 0.1-100: 1; the molar ratio of the acid auxiliary agent to the palladium compound is 0.1-1000: 1;
the nucleophilic reagent is water, alcohol, organic primary amine or inorganic ammonia;
the inorganic ammonia is ammonia gas, ammonium bicarbonate, ammonium chloride or ammonia water;
the polydentate phosphine ligand is one of or a combination of one of tridentate or tetradentate phosphine ligands of the following structures and a commercially available monodentate or bidentate phosphine ligand, the tridentate or tetradentate phosphine ligand having the following structural formula:
Figure BDA0003264067170000021
in the formula: r1Selected from alkyl, aryl, heterocyclic aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic acid group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; r is selected from hydrogen H, alkyl, cycloalkyl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; the value range of n is 0-2, and represents that the compound in the structural formula has carbon chains with different lengths; the value range of m is 1-4, and the compound in the structural formula has carbon chains with different lengths;
the molar ratio of the commercially available monodentate or bidentate phosphine ligand to the tridentate or tetradentate phosphine ligand is 0.1-50: 1;
the molar ratio of the unsaturated hydrocarbon to the palladium compound is 100-100000: 1;
the molar ratio of the nucleophilic reagent to the unsaturated hydrocarbon is 1-500: 1.
The commercially available monodentate or bidentate phosphine ligands include one or more combinations of triphenylphosphine, triphenylphosphine oxide, 1, 2-bis (diphenylphosphino) methane (dppm), 1, 2-bis (diphenylphosphino) ethane (dppe), 1, 2-bis (diphenylphosphino) propane (dppp), 1, 2-bis (diphenylphosphino) butane (dppb), 1 '-bis (diphenylphosphino) ferrocene (dppf), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (xanthphos), 4, 6-bis (diphenylphosphino) -10H-phenoxazine (nixantpos), 1, 2-bis (di-t-butylphosphinomethyl) benzene, and 1,1' -bis (di-t-butylphosphinomethyl) ferrocene.
The palladium compound is one or more of palladium dichloride, bis (acetonitrile) palladium dichloride, palladium acetate, palladium trifluoroacetate, bis (triphenylphosphine) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride, allyl palladium chloride, tetratriphenylphosphine palladium, bis (acetylacetone) palladium, bis (dibenzylidene acetone) palladium and tris (dibenzylidene acetone) dipalladium.
The acid auxiliary agent is selected from one of formic acid, acetic acid, oxalic acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, dodecylsulfonic acid and aluminum trifluoromethanesulfonate.
Under the action of a palladium combined catalyst modified by a multidentate phosphine ligand, when unsaturated hydrocarbon, carbon monoxide and water are used as raw materials to carry out carbonylation and carboxylation reaction to prepare straight-chain carboxylic acid, the method comprises the following specific processes:
Figure BDA0003264067170000031
in the formula: r2Selected from H, alkyl, alkenyl, heterocyclic aryl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro.
Under the action of a palladium combined catalyst modified by a multidentate phosphine ligand, when unsaturated hydrocarbon, carbon monoxide and alcohol are used as raw materials to carry out carbonylation esterification reaction to prepare straight-chain organic carboxylic ester, the method comprises the following specific processes:
Figure BDA0003264067170000032
in the formula: r2Selected from H, alkyl, alkenyl, heterocyclic aryl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; r3Selected from alkyl or aryl.
Under the action of a palladium combined catalyst modified by a multidentate phosphine ligand, when unsaturated hydrocarbon, carbon monoxide and organic primary amine or inorganic ammonia are used as raw materials to carry out carbonylation and amidation reaction to prepare linear-chain amide, the method comprises the following specific processes:
Figure BDA0003264067170000041
in the formula: r2Selected from H, alkyl, alkenyl, heterocyclic aryl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; r4And R5Selected from H, alkyl or aryl.
The unsaturated hydrocarbon according to the invention is preferably an arylacetylene or an arylethylene.
The invention provides a green synthesis method for preparing a linear chain carbonyl compound (comprising organic carboxylic acid, carboxylic ester or amide) by a carbonylation one-pot method by taking unsaturated hydrocarbon, carbon monoxide and a nucleophilic reagent (comprising water, alcohol, organic primary amine or inorganic ammonia (the inorganic ammonia comprises ammonia gas, ammonia substitute (such as ammonium bicarbonate or ammonium chloride) or ammonia water) as raw materials under the action of a palladium combined catalyst modified by a multidentate phosphine ligand, and the green synthesis method has the following advantages:
(1) the synthesis process has 100% atom economy and no waste discharge.
(2) The palladium combined catalyst modified by the multidentate phosphine ligand has high activity, high chemical and regional selectivity, good stability and long service life.
(3) The reaction process for preparing the straight-chain carbonyl compound is a one-pot homogeneous synthesis process, the synthesis process is simple, and the reaction conditions are mild.
Detailed Description
The present invention is described in more detail in connection with the following examples. However, these examples are only illustrative of the present invention and do not limit the present invention in any way. The reagents mentioned in the examples are all conventional commercial products.
Examples 1 to 14
(1) Reaction result of carbonylation and carboxylation of styrene to prepare phenylpropionic acid by different palladium compounds and phosphine ligands
The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added 0.01mmol of a palladium compound, 0.012mmol of a multidentate phosphine ligand, 0.05mmol of p-toluenesulfonic acid, 20mmol of styrene, 5mL of water, and N-methylpyrrolidone solvent (NMP40mL) in that order. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas, pressurizing to 3.0MPa, reacting for 4 hours in a constant-temperature heating jacket at 120 ℃, cooling to room temperature, and slowly releasing pressure. The conversion of styrene and the selectivity and yield of the product were calculated by GC-MS.
Figure BDA0003264067170000051
Examples 15 to 24
(2) Reaction result of carbonylation and carboxylation of phenylacetylene to prepare phenylacrylic acid by using different palladium compounds and phosphine ligands
The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added 0.01mmol of the procatalyst, 0.012mmol of the ligand, 0.05mmol of p-toluenesulfonic acid, 20mmol of phenylacetylene, 5mL of water, and N-methylpyrrolidone (NMP40mL) in that order. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas, pressurizing to 3.0MPa, reacting for 4 hours in a constant-temperature heating jacket at 120 ℃, cooling to room temperature, and slowly releasing pressure. The conversion of phenylacetylene and the selectivity and yield of the product were calculated by GC-MS.
Figure BDA0003264067170000061
Examples 25 to 34
(3) Reaction result of carbonylation esterification of styrene to prepare methyl phenylpropionate by using different catalytic precursors and different ligands
The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added 0.01mmol of the procatalyst, 0.012mmol of the ligand, 0.05mmol of p-toluenesulfonic acid, 20mmol of styrene, 20mL of methanol, and 40mL of THF in that order. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas, pressurizing to 3.0MPa, reacting for 4 hours in a constant-temperature heating jacket at 140 ℃, cooling to room temperature, and slowly releasing pressure.
The conversion of styrene and the selectivity and yield of the product were calculated by GC-MS.
Figure BDA0003264067170000071
Examples 35 to 44
(4) Reaction result for preparing beta-methyl phenylacrylate by carbonylation and esterification of phenylacetylene with different catalytic precursors and different ligands
The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added 0.01mmol of the procatalyst, 0.012mmol of the ligand, 0.05mmol of p-toluenesulfonic acid, 20mmol of phenylacetylene, 20mL of methanol, and 40mL of THF in that order. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas, pressurizing to 3.0MPa, reacting for 4 hours in a constant-temperature heating jacket at 140 ℃, cooling to room temperature, and slowly releasing pressure.
The conversion of phenylacetylene and the selectivity and yield of the product were calculated by GC-MS.
Figure BDA0003264067170000081
Examples 45 to 55
(5) Reaction result of preparing N-phenyl phenylpropylamide by amidating styrene with different catalytic precursors and different ligands
The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added 0.01mmol of the procatalyst, 0.012mmol of the ligand, 0.05mmol of p-toluenesulfonic acid, 20mmol of styrene, 24mmol of aniline, and 40mL of THF in that order. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas, pressurizing to 3.0MPa, reacting for 10 hours in a constant-temperature heating jacket at 140 ℃, cooling to room temperature, and slowly releasing pressure.
The conversion of styrene and the selectivity and yield of the product were calculated by GC-MS.
Figure BDA0003264067170000091
Examples 55 to 65
(6) Reaction result for preparing N-phenyl benzene acrylamide by carbonylation and amidation of p-phenylacetylene with different catalytic precursors and different ligands
The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added 0.01mmol of the procatalyst, 0.012mmol of the ligand, 0.05mmol of p-toluenesulfonic acid, 20mmol of phenylacetylene, 24mmol of aniline, and 40mL of THF in that order. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas, pressurizing to 3.0MPa, reacting for 10h at 140 ℃ in a constant-temperature heating jacket, cooling to room temperature, and slowly releasing pressure.
The conversion of phenylacetylene and the selectivity and yield of the product were calculated by GC-MS.
Figure BDA0003264067170000101
Example 65
And combining the service life investigation results of the catalyst.
“Pd(OAc)2/L6/MeSO3The H/Nixantphos combined catalyst can be recycled for 10 times in the reaction process of preparing methyl phenylpropionate by carbonylation and esterification of styrene and still maintain good performanceGood activity and stability. The tetradentate phosphine ligand L6 was used in combination with the bidentate phosphine ligand Nixantphos (Nixantphos is 4, 6-bis (diphenylphosphino) -10H-phenoxazine, a commercially available bidentate phosphine ligand) in a 2:1 molar ratio to L6. The specific experimental steps are as follows: to a 200mL polytetrafluoroethylene liner were added, in order, 0.01mmol Pd (OAc)20.012mmol of ligand L6, 0.024mmol of Nixantphos ligand, and MeSO30.2mmol of H, 20mmol of styrene and 50mL of methanol. And (3) placing the lining in a high-pressure reaction kettle, sealing, checking the air tightness of the device, and replacing air in the reaction kettle with carbon monoxide. Then introducing carbon monoxide gas and pressurizing to 3.0MPa, reacting for 4h at 140 ℃ in a constant-temperature heating jacket, cooling to room temperature, slowly decompressing, then adding 20mmol of styrene again, sealing, then injecting 3.0MPa carbon monoxide gas again, and reacting for 4h at 140 ℃. After repeating the above experimental procedure 9 times, the yield of the product methyl phenylpropionate was calculated by GC-MS.

Claims (7)

1. A multidentate phosphine ligand modified palladium composite catalyst is used for catalyzing unsaturated hydrocarbon to prepare a linear carbonyl compound, and is characterized in that under the action of the composite catalyst, unsaturated hydrocarbon, carbon monoxide and a nucleophilic reagent are used as raw materials to generate the linear carbonyl compound through carbonylation reaction, and the method specifically comprises the following steps: sequentially adding a palladium compound, a polydentate phosphine ligand, an acidic assistant, unsaturated hydrocarbon and a nucleophilic reagent into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, filling carbon monoxide gas, keeping the pressure of 1.0-5.0MPa, reacting at 80-200 ℃ for 1-48 hours after ensuring the air tightness of the reaction kettle device, and cooling to room temperature after the reaction is finished, wherein the yield of the linear chain carbonyl compound is 50-90%; wherein the unsaturated hydrocarbon comprises a terminal olefin, internal olefin, diene, or terminal alkyne; the composite catalyst is a homogeneous catalyst, is a palladium composite catalyst modified by a multidentate phosphine ligand, and consists of a palladium compound, the multidentate phosphine ligand and an acidic auxiliary agent, wherein the molar ratio of the multidentate phosphine ligand to the palladium compound is 0.1-100: 1; the molar ratio of the acid auxiliary agent to the palladium compound is 0.1-1000: 1;
the nucleophilic reagent is water, alcohol, organic primary amine or inorganic ammonia;
the inorganic ammonia is ammonia gas, ammonium bicarbonate, ammonium chloride or ammonia water;
the polydentate phosphine ligand is one of or a combination of one of tridentate or tetradentate phosphine ligands of the following structures and a commercially available monodentate or bidentate phosphine ligand, the tridentate or tetradentate phosphine ligand having the following structural formula:
Figure FDA0003264067160000011
in the formula: r1Selected from alkyl, aryl, heterocyclic aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic acid group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; r is selected from hydrogen H, alkyl, cycloalkyl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; the value range of n is 0-2, and represents that the compound in the structural formula has carbon chains with different lengths; the value range of m is 1-4, and the compound in the structural formula has carbon chains with different lengths;
the molar ratio of the commercially available monodentate or bidentate phosphine ligand to the tridentate or tetradentate phosphine ligand is 0.1-50: 1;
the molar ratio of the unsaturated hydrocarbon to the palladium compound is 100-100000: 1;
the molar ratio of the nucleophilic reagent to the unsaturated hydrocarbon is 1-500: 1.
2. The method for preparing linear carbonyl compounds from unsaturated hydrocarbons catalyzed by the multidentate phosphine ligand-modified palladium combination catalyst as claimed in claim 1, characterized in that the commercially available monodentate or bidentate phosphine ligand comprises one or more combinations of triphenylphosphine, triphenylphosphine oxide, 1, 2-bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (diphenylphosphino) propane, 1, 2-bis (diphenylphosphino) butane, 1 '-bis (diphenylphosphino) ferrocene, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene, 4, 6-bis (diphenylphosphino) -10H-phenoxazine, 1, 2-bis (di-tert-butylphosphinomethyl) benzene, and 1,1' -bis (di-tert-butylphosphinomethyl) ferrocene.
3. The method for preparing a linear carbonyl compound from an unsaturated hydrocarbon catalyzed by a polydentate phosphine ligand-modified palladium combination catalyst according to claim 1, wherein the palladium compound is selected from the group consisting of palladium dichloride, bis (acetonitrile) palladium dichloride, palladium acetate, palladium trifluoroacetate, bis (triphenylphosphine) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride, allylpalladium chloride, tetratriphenylphosphine palladium, bis (acetylacetone) palladium, bis (dibenzylideneacetone) palladium, and tris (dibenzylideneacetone) dipalladium.
4. The method for preparing linear carbonyl compounds from unsaturated hydrocarbons catalyzed by the multidentate phosphine ligand-modified palladium composite catalyst according to claim 1, wherein the acidic adjuvant is selected from the group consisting of formic acid, acetic acid, oxalic acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, dodecylsulfonic acid, and aluminum trifluoromethanesulfonate.
5. The method for preparing the linear carbonyl compound by catalyzing unsaturated hydrocarbon with the palladium combination catalyst modified by the multi-dentate phosphine ligand as the claim 1, is characterized in that under the action of the combination catalyst, when unsaturated hydrocarbon, carbon monoxide and water are used as raw materials to carry out carbonylation and carboxylation reaction to prepare linear carboxylic acid, the specific process is as follows:
Figure FDA0003264067160000021
in the formula: r2Selected from H, alkyl, alkenyl, heterocyclic aryl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro.
6. The method for preparing the linear carbonyl compound by catalyzing unsaturated hydrocarbon with the palladium combination catalyst modified by the multi-dentate phosphine ligand as the claim 1, is characterized in that under the action of the combination catalyst, when unsaturated hydrocarbon, carbon monoxide and alcohol are used as raw materials to carry out carbonylation and esterification reaction to prepare linear organic carboxylic ester, the specific process is as follows:
Figure FDA0003264067160000022
in the formula: r2Selected from H, alkyl, alkenyl, heterocyclic aryl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; r3Selected from alkyl or aryl.
7. The method for preparing the linear carbonyl compound by catalyzing unsaturated hydrocarbon with the palladium combination catalyst modified by the multi-dentate phosphine ligand as the claim 1, is characterized in that under the action of the combination catalyst, when unsaturated hydrocarbon, carbon monoxide and organic primary amine or inorganic ammonia are used as raw materials to carry out carbonylation and amidation reaction to prepare linear amide, the specific process is as follows:
Figure FDA0003264067160000031
in the formula: r2Selected from H, alkyl, alkenyl, heterocyclic aryl, aryl or aryl containing substituent, wherein the substituent is halogen, sulfonic group, carboxyl, amino, hydroxyl, trifluoromethyl or nitro; r4And R5Selected from H, alkyl or aryl.
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