A method for olefin carbonylation reaction

Abstract

The present invention relates to a method for olefin carbonylation reaction. The method includes reacting olefin with carbon monoxide and alcohol in the presence of a catalyst system; wherein the catalyst system includes the following components: (a) a metal or a compound thereof of Group VIII; (b) a bidentate phosphine ligand; and (c) an acidic auxiliary agent; the bidentate phosphine ligand has a structure represented by the following general formula (I), (R1)(R2)P‑K‑A‑K‑P(R3)(R4)(I). According to the method provided by the present invention, the catalytic activity of the catalyst system used is higher, the amount of bidentate phosphine ligand and Group VIII metal or its compound in the catalyst system is greatly reduced, and the advantages of good product selectivity, high reaction substrate conversion rate and long service life are obtained, and the ester product can be synthesized by efficiently catalyzing the olefin carbonylation reaction, so that the yield of the product is higher, the catalytic efficiency of the reaction can be improved, and the residence time of the reaction substrate can be reduced.

Description

Technical Field

[0001] The present invention relates to a process for the carbonylation of olefins, and more particularly to a process for the carbonylation of olefins in the presence of a catalyst system comprising a specific bidentate phosphine ligand. Background Art

[0002] In the chemical research of the past few decades, the catalyst system including transition metal and phosphine ligand is widely used in various reaction types due to its high catalytic activity and high selectivity, such as cross-coupling reaction (Buchwald-Hartwig CN bond and CO bond formation reaction, Stille reaction, Sonogashira reaction, Suzuki-Miyaura reaction, etc.), asymmetric hydrogenation reaction and carbonylation reaction. As one of the olefin carbonylation reactions, as shown in the following reaction formula 1, it includes converting unsaturated hydrocarbons such as olefins, CO and alcohol into corresponding saturated carboxylic acid esters in the presence of a metal / ligand or metal complex.

[0003]

[0004] This type of saturated carboxylic acid ester is an important fine chemical product, widely used in the fields of medicine, resin, coating, food solvent, plasticizer, cosmetics, etc. Since the first olefin carbonylation reaction was discovered in 1938, this type of reaction has been one of the research hotspots in the field of organic synthesis and catalysis. In the olefin carbonylation reaction, methyl propionate, the carbonylation product of ethylene, is an important intermediate for the preparation of methyl methacrylate.

[0005] Patent WO1996019434A1 discloses a method for ethylene carbonylation and a catalyst system used in the method. The catalyst system includes a VIII group metal or a compound thereof and a bidentate phosphine ligand having a tertiary carbon group and an aromatic bridge, and the bidentate phosphine ligand is particularly represented by bis(di-tert-butylphosphino)-o-xylene. The catalyst system shows a good reaction rate in the olefin carbonylation reaction, but the catalyst is often deactivated during the continuous operation stage due to the reduction of the palladium compound to palladium metal, resulting in high cost and limited industrial application.

[0006] EP0495547A discloses the carbonylation of olefins. The catalyst system used in the carbonylation includes a palladium cation source, an anion source and a bidentate diphosphine, wherein the bidentate diphosphine has a structure of formula I, wherein R 1 R 2 P–X–P–R 3 R 4(I), examples of which include 1,3-bis(diisopropylphosphino)propane, 1,5-bis(dimethylphosphino)-3-oxapentane, etc. The catalyst system containing the bidentate diphosphine provides significantly high reaction rates, product yields and / or selectivities in various monocarbonylation reactions. However, its disadvantage is that the ligand is easily dissociated, resulting in catalyst poisoning and inability to be recycled.

[0007] Patent US6156934A discloses a diphosphine containing 2-phospho-tricyclo[3.3.1.1.{3,7}]decyl, which is a bidentate phosphine ligand with a covalent bridging group for carbonylation of unsaturated compounds, and has the structural formula: R 1 >PR 2 -P <R 1 ; Its specific compound is 1,3-P,P′-bis(2-phospho-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)propane. Compared with the ligand disclosed in the above EP0495547A, the diphosphine ligand has a smaller ligand dosage under the same TON. However, the selectivity of the ligand is low, the application range of the substrate is small, and there is still a certain room for optimization.

[0008] Patent CN1429228A discloses a bidentate ligand that can be used in a catalyst system. The bidentate ligand is a bidentate phosphine ligand having a phosphine cyclic group, and its structural formula is: 1 R 2 M 1 -RM 2 R 3 R 4 In the bidentate ligand, two di-tert-alkyl phosphino groups are connected by an alkylene group as a bridge, or the phosphine cyclic group is connected to phosphorus through a secondary carbon, and the alkylene group is used as a bridge. The bidentate phosphine ligand can provide good selectivity and reduce the production of polymers in the carbonylation reaction, but the catalytic efficiency still needs to be improved.

[0009] Patent CN1642646A discloses a method for carbonylating an ethylenically unsaturated compound and a catalyst for the method. It extends the teaching of the above-mentioned US6156934 to a bidentate phosphine having a 1,2-substituted aryl bridge type of the type disclosed in the above-mentioned WO96019434A1. The catalytic efficiency in the reaction is improved to a certain extent.

[0010] Patent CN1674990A discloses a phosphaadamantane catalytic system. The catalytic system can catalyze the carbonylation reaction of ethylenically unsaturated compounds. The catalytic system uses a bidentate phosphine ligand substituted with a phosphaadamantane side, and the amount of by-products generated during the reaction is significantly reduced, and the catalyst replenishment is reduced. However, the system requires the addition of a polymer dispersant, which needs to be recovered later, increasing the operating process and cost.

[0011] Patent CN103223350A discloses a catalyst system. It is used to catalyze the carbonylation of olefinic unsaturated compounds. The catalyst system includes a VIB group or VIIIB metal or a compound thereof, an acid and a bidentate phosphine ligand, wherein the ligand is present in an excess of at least 2:1 molar ratio relative to the metal, and the acid is present in an excess of at least 2:1 molar ratio relative to the ligand. A polymer dispersant is also used in the method disclosed in the patent. In addition, the amount of acid used in the method is large, which directly increases the cost.

[0012] Patent CN101309753A discloses a method for carbonylating ethylenically unsaturated compounds. The catalyst system used includes a metal of Group 8, 9 or 10 or a compound thereof; and a bidentate phosphine ligand bridged by a non-aromatic cyclic hydrocarbon structure. The use of the catalyst system in alkoxycarbonylation and hydroxycarbonylation reactions can greatly increase the reaction rate and TON, but the amount of ligand used is still relatively high.

[0013] Patent CN105153241A discloses a carbonylation ligand and its use in carbonylation of ethylenically unsaturated compounds. The carbonylation ligand is a bidentate phosphine ligand bridged by a hydrocarbon aromatic structure having 5-22 ring atoms with at least one 5- or 6-membered aromatic ring having a substituent. The bidentate phosphine ligand can form a complex with Group 8, 9, and 10 metals or compounds thereof, and produce a high TON in the carbonylation reaction, but the preparation process of the ligand is relatively cumbersome and complicated, and the yield and purity of some ligands are low.

[0014] Patent CN106854221A discloses a method for carbonylation of ethylenically unsaturated compounds, a novel carbonylation ligand, and a catalyst system incorporating the ligand. The carbonylation ligand employed is a bidentate phosphine ligand bridged by a hydrocarbon aromatic structure having at least one aromatic ring. The catalyst system containing the phosphine ligand exhibits good stability in the carbonylation reaction, but the reaction rate and TON still have room for improvement.

[0015] Although the catalyst system disclosed in the above patent application shows high stability and provides a relatively high reaction rate in the olefin carbonylation reaction, there are still problems such as a relatively high proportion of phosphine ligands, a long reaction residence time, rapid catalyst deactivation, and the need for frequent replenishment of new catalysts. Industrial applications are limited, and therefore there is a need to improve the existing catalyst system. Summary of the invention

[0016] Problem that the invention aims to solve

[0017] In view of the above problems in the prior art, the object of the present invention is to provide a method for olefin carbonylation reaction in which the catalyst system has higher catalytic activity and uses less bidentate phosphine ligand and Group VIII metal or its compound in the catalyst system.

[0018] Solutions for solving problems

[0019] In order to achieve the above object, the present invention provides a method for olefin carbonylation, which comprises reacting olefin with carbon monoxide and alcohol in the presence of a catalyst system;

[0020] Wherein, the catalyst system comprises the following components:

[0021] (a) Group VIII metals or compounds thereof;

[0022] (b) a bidentate phosphine ligand; and

[0023] (c) acidic additives;

[0024] The bidentate phosphine ligand has a structure represented by the following general formula (I),

[0025] (R1)(R2)PKAKP(R3)(R4) (I);

[0026] Wherein, R1 to R4 are the same as or different from each other, and each independently represents a C1 to C10 straight chain or branched alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, a C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a C6 to C20 aryloxy group, or a C6 to C20 heteroaryl group;

[0027] P is a phosphorus atom;

[0028] Each K is the same as or different from each other and is each selected from a single bond or -C(Ra)2-;

[0029] A is selected from -O-, -S-, -N(Rb)-, -OC(Rc)2-O-, -SC(Rc)2-S-, -N(Rf)-C(Rc)2-N(Rf)- , -OC(Rc)2C(Rc)2-O-, -SC(Rc)2C(Rc)2-S- or -N(Rf)-C(Rc)2C(Rc)2-N(Rf)-;

[0030] wherein each Ra is the same as or different from each other, each Rc is the same as or different from each other, and each Ra and each Rc are each independently H, a linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group;

[0031] Rb and Rf are each independently H, a linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group.

[0032] According to the method of the present invention, in the general formula (I), each K is a single bond; and A is -OC(Rc)2-O-, -SC(Rc)2-S-, -N(Rf)-C(Rc)2-N(Rf)-, -OC(Rc)2C(Rc)2-O-, -SC(Rc)2C(Rc)2-S- or -N(Rf)-C(Rc)2C(Rc)2-N(Rf)-.

[0033] According to the method of the present invention, in the structure represented by A in the general formula (I),

[0034] Each Rc is H, or a linear or branched C1-C6 alkyl group, preferably H;

[0035] Rf is H, a linear or branched C1-C6 alkyl group, a substituted or unsubstituted C6-C10 aryl group, or a C3-C8 heteroaryl group; when the C6-C10 aryl group has a substituent, the substituent is a C1-C6 alkyl group or a C1-C6 alkoxy group; Rf is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 4-methoxyphenyl group or a pyridyl group.

[0036] According to the method of the present invention, in the general formula (I), each K is -C(Ra)2-; A is -O-, -S- or -N(Rb)-.

[0037] According to the method of the present invention, in the structure represented by A in the general formula (I),

[0038] Each Ra is independently H or a linear or branched C1-C6 alkyl group, preferably H;

[0039] Rb is H, a linear or branched C1-C6 alkyl group, a substituted or unsubstituted C6-C10 aryl group, or a C3-C8 heteroaryl group; when the C6-C10 aryl group has a substituent, the substituent is a C1-C6 alkyl group or a C1-C6 alkoxy group; Rb is preferably H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, or 4-methoxyphenyl or pyridyl.

[0040] According to the method of the present invention, wherein, in the general formula (I), R1 to R4 are each independently a C1 to C6 straight chain or branched alkyl, a substituted or unsubstituted C6 to C10 aryl, or a C6 to C10 heteroaryl; when the C6 to C10 aryl has a substituent, the substituent is a C1 to C6 alkyl or a C1 to C6 alkoxy; and R1 to R4 are preferably tert-butyl, phenyl, 4-methoxyphenyl, benzyl or pyridyl.

[0041] According to the method of the present invention, wherein in the catalyst system, the molar ratio of component (b) to component (a) is 2:1 to 20:1, preferably 3:1 to 10:1;

[0042] The molar ratio of component (c) to component (a) is 2:1 to 150:1, preferably 50:1 to 100:1.

[0043] According to the method of the present invention,

[0044] The Group VIII metal includes: cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum;

[0045] The compound of the Group VIII metal includes a salt or weakly coordinating anion compound of the Group VIII metal and the following substances: sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid, sulfonated ion exchange resin, or perhalogen acid; or a complex of zero-valent palladium, rhodium, iridium, platinum or ruthenium.

[0046] According to the method of the present invention, the acid auxiliary agent is an acid having a pKa value of less than 5, preferably less than 4, and more preferably less than 3 in an aqueous solution at 25°C;

[0047] The acidic auxiliary agent is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4,6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphoric acid and sulfuric acid; and methanesulfonic acid is most preferred.

[0048] According to the method of the present invention, the operating conditions of the reaction are that the reaction pressure is 1 to 20 MPa, preferably 1 to 10 MPa;

[0049] The reaction temperature is 50 to 200°C, preferably 60 to 150°C.

[0050] According to the method of the present invention, the molar ratio of the olefin to the carbon monoxide is 1:1 to 100:1, preferably 2:1 to 50:1; the molar ratio of the olefin to the component (a) in the catalyst system is 50:1 to 300:1, preferably 100:1 to 200:1.

[0051] The mass ratio of the alcohol to the component (a) in the catalyst system is 500:1 to 20000:1, preferably 5000:1 to 15000:1.

[0052] According to the method of the present invention, the olefin is a substituted or unsubstituted C2-C20 olefin; preferably a substituted or unsubstituted C2-C16 olefin;

[0053] When the olefin has a substituent, the substituent is a C1-C10 alkyl group, a C6-C12 aryl group, a C1-C4 alkyl group or a halogen-substituted C6-C12 aryl group, a C2-C6 ester group, or a nitrogen-containing heterocyclic group;

[0054] The alcohol is a C1-C10 substituted or unsubstituted, linear or branched alkanol; when the alcohol is an alcohol having a substituent, the substituent is a C1-C6 alkyl, a C6-C20 aryl, a C2-C10 heterocyclic group, a halogen, a cyano group or a nitro group, preferably a C1-C6 alkyl or a C6-C10 aryl group;

[0055] The alcohol is preferably a C1-C6 monohydric alkanol.

[0056] Effects of the Invention

[0057] According to the method for olefin carbonylation reaction provided by the present invention, the catalyst system used has higher catalytic activity, greatly reduces the amount of bidentate phosphine ligand and Group VIII metal or its compound in the catalyst system, improves the catalytic efficiency of the reaction, reduces the residence time of the reaction substrate, reduces the gas circulation amount, thereby reducing the required reaction vessel size and reducing the equipment investment.

[0058] According to the method for olefin carbonylation provided by the present invention, the catalyst system used has the advantages of low consumption, good product selectivity, high reaction substrate conversion rate and long service life, and can efficiently catalyze the carbonylation reaction to synthesize ester products, so that the yield of the product is high. Therefore, the method provided by the present invention has good commercial value. DETAILED DESCRIPTION

[0059] The specific embodiments of the present invention will be described in detail below so that the technical solutions of the present invention become apparent.

[0060] The method for olefin carbonylation provided by the present application comprises reacting olefin with carbon monoxide and alcohol in the presence of a catalyst system;

[0061] Wherein, the catalyst system comprises the following components:

[0062] (a) Group VIII metals or compounds thereof;

[0063] (b) a bidentate phosphine ligand; and

[0064] (c) acidic additives;

[0065] Wherein, the bidentate phosphine ligand has a structure represented by the following general formula (I),

[0066] (R1)(R2)PKAKP(R3)(R4) (I);

[0067] wherein R1 to R4 are the same as or different from each other, and each independently represents a C1 to C10 straight chain or branched alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, a C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a C6 to C20 aryloxy group, or a C6 to C20 heteroaryl group;

[0068] P is a phosphorus atom;

[0069] Each K is the same as or different from each other and is each selected from a single bond or -C(Ra)2-;

[0070] A is selected from -O-, -S-, -N(Rb)-, -OC(Rc)2-O-, -SC(Rc)2-S-, -N(Rf)-C(Rc)2-N(Rf)- , -OC(Rc)2C(Rc)2-O-, -SC(Rc)2C(Rc)2-S- or -N(Rf)-C(Rc)2C(Rc)2-N(Rf)-;

[0071] wherein each Ra is the same as or different from each other, each Rc is the same as or different from each other, and each Ra and each Rc are each independently H, a linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C20 aryloxy group, or a C3-C8 heteroaryl group;

[0072] Rb and Rf are each independently H, a linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C20 aryloxy group or a C3-C8 heteroaryl group.

[0073] According to the method for olefin carbonylation provided by the present invention, in a preferred case, in formula (I), R1 to R4 are each independently a C1 to C6 straight chain or branched alkyl, a substituted or unsubstituted C6 to C10 aryl, or a C6 to C10 heteroaryl; when the C6 to C10 aryl has a substituent, the substituent is a C1 to C6 alkyl or a C1 to C6 alkoxy; R1 to R4 are preferably tert-butyl, phenyl, 4-methoxyphenyl, benzyl or pyridyl.

[0074] According to the method for olefin carbonylation provided by the present invention, in a preferred case, in the above formula (I), when each K is a single bond, A is -OC(Rc)2-O-, -SC(Rc)2-S-, -N(Rf)-C(Rc)2-N(Rf)-, -OC(Rc)2C(Rc)2-O-, -SC(Rc)2C(Rc)2-S- or -N(Rf)-C(Rc)2C(Rc)2-N(Rf)-;

[0075] Among them, it is preferred that each Rc is H, or a linear or branched C1-C6 alkyl group, and more preferably all are H;

[0076] Rf is H, a linear or branched C1-C6 alkyl group, a substituted or unsubstituted C6-C10 aryl group, or a C3-C8 heteroaryl group; when the C6-C10 aryl group has a substituent, the substituent is a C1-C6 alkyl group or a C1-C6 alkoxy group; Rf is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a benzyl group, a 4-methoxyphenyl group or a pyridyl group.

[0077] The bidentate phosphine ligands in this case (ie, disulfides, diethers or diamines) have the excellent property of stably complexing with Group VIII metals.

[0078] According to the method for olefin carbonylation provided by the present invention, in a preferred case, in the above formula (I), when each K is -C(Ra)2-; A is -O-, -S- or -N(Rb)-;

[0079] Among them, preferably, each Ra is H or a linear or branched C1-C6 alkyl group, more preferably all are H;

[0080] Rb is H, a linear or branched C1-C6 alkyl group, a substituted or unsubstituted C6-C10 aryl group, or a C3-C8 heteroaryl group; when the C6-C10 aryl group has a substituent, the substituent is a C1-C6 alkyl group or a C1-C6 alkoxy group; Rb is preferably H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 4-methoxyphenyl or pyridyl.

[0081] In this case, the bidentate phosphine ligand (i.e., monosulfide, monoether or monoamine compound) has a suitable flexible arm and chelating angle, can stably complex with the Group VIII metal, and reduce catalyst degradation; and compared with the above-mentioned bidentate phosphine ligand (i.e., disulfide, diether or diamine compound), the performance is better.

[0082] The bidentate phosphine ligands described above can be purchased commercially or prepared by methods known in the art.

[0083] According to the method for olefin carbonylation provided by the present invention, specific compounds of bidentate phosphine ligands are listed below, but the bidentate phosphine ligands described in the present invention are by no means limited to the ligand compounds listed below.

[0084] N,N-bis(di-tert-butylphosphine)-ethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-dimethylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-diethylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-diisopropylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-di-tert-butylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-diphenylethylenediamine, N,N-bis(di-tert-butylphosphine) Phosphine)-N,N-dibenzylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-bis(4-methoxyphenyl)ethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-bis(4-pyridyl)ethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-bis(2-pyridyl)ethylenediamine, N,N-bis(diphenylphosphine)-ethylenediamine, N,N-bis(4-methoxyphenylphosphine)-ethylenediamine, N,N-bis(dibenzylphosphine)- )-ethylenediamine, N,N-bis(2-pyridylphosphine)-ethylenediamine, bis((di-tert-butylphosphine)methyl)methylamine, bis((di-tert-butylphosphine)methyl)ethylamine, bis((di-tert-butylphosphine)methyl)isopropylamine, bis((di-tert-butylphosphine)methyl)tert-butylamine, bis((di-tert-butylphosphine)methyl)phenylamine, bis((di-tert-butylphosphine)methyl)benzylamine, bis((di-tert-butylphosphine)methyl)4-methoxyphenylamine, bis((di-tert-butylphosphine)methyl bis((di-tert-butylphosphino)methyl)methyl)4-pyridylamine, bis((di-tert-butylphosphino)methyl)2-pyridylamine, bis((diphenylphosphino)methyl)methylamine, bis((dibenzylphosphino)methyl)methylamine, bis((di(4-methoxyphenyl)phosphino)methyl)methylamine, and bis((2-pyridylphosphino)methyl)methylamine; ethyl bis((di-tert-butylphosphino)sulfide), ethyl bis((di-tert-butylphosphino)ether), and bis((di-tert-butylphosphino)methyl)sulfane.

[0085] According to the catalyst system provided by the present invention, in a preferred case, the molar ratio of component (b) to component (a) is 2:1 to 20:1, for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 10:1, 12.5:1 or 15:1; the molar ratio is preferably 3:1 to 10:1, more preferably 3:1 to 5:1;

[0086] In addition, the molar ratio of component (c) to component (a) is 2:1 to 150:1, for example 20:1, 50:1, 100:1, 125:1; the molar ratio is preferably 50:1 to 100:1, more preferably 75:1 to 100:1.

[0087] According to the method for olefin carbonylation provided by the present invention, in a preferred case, the Group VIII metal includes cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum;

[0088] Compounds of Group VIII metals include salts or weakly coordinating anionic compounds of the Group VIII metals with sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid, sulfonated ion exchange resins, or perhalogen acids; or complexes of zero-valent palladium, rhodium, iridium, platinum, or ruthenium, for example, bis(triphenylphosphine)palladium chloride, bis(triphenylphosphine)palladium acetate, bis(acetonitrile)palladium chloride, bis(acetylacetone)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)palladium, bis(1,5-cyclooctadiene)palladium chloride, [1,2-bis(diphenylphosphine)ethane] chloride palladium, [1,1-bis(diphenylphosphino)ferrocene]palladium chloride dichloromethane adduct, (carbonyl)bis(triphenylphosphine)rhodium(I) chloride, tris(triphenylphosphine)(carbonyl)rhodium(I) hydride, (triphenylphosphine)(acetylacetonate)carbonylrhodium(I), tris(acetylacetonate)rhodium(II), tris(triphenylphosphine)rhodium(I) chloride, (1,5-cyclooctadiene)rhodium(I) chloride, (carbonyl)bis(triphenylphosphine)iridium(I) chloride, (1,5-cyclooctadiene)iridium(I) chloride dimer, bis(acetylacetonate)platinum, bis(triphenylphosphine)platinum chloride, (1,5-cyclooctadiene)platinum chloride, (1,5-cyclooctadiene)ruthenium chloride, or tris(triphenylphosphine)rhodium(I) chloride ruthenium.

[0089] The compound of Group VIII metal is preferably palladium acetate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)palladium, bis(triphenylphosphine)palladium chloride, (carbonyl)bis(triphenylphosphine)rhodium(I) chloride, tris(triphenylphosphine)(carbonyl)rhodium(I) hydride, or (triphenylphosphine)(acetylacetonate)rhodium(I) carbonyl.

[0090] According to the method for olefin carbonylation provided by the present invention, in a preferred case, the acid auxiliary agent is an acid having a pKa value of less than 5, preferably less than 4, more preferably less than 3 in aqueous solution at 25°C.

[0091] The acidic auxiliary agent is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4,6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphoric acid and sulfuric acid; and methanesulfonic acid is most preferred.

[0092] The method for olefin carbonylation provided by the present invention, in a preferred case, the operating conditions of the reaction are as follows:

[0093] The reaction process is carried out under low pressure or medium pressure, for example, the reaction pressure is 1 to 20 MPa, preferably 1 to 10 MPa, more preferably 1 to 5 MPa;

[0094] The reaction temperature is 50 to 200°C, preferably 60 to 150°C, more preferably 60 to 110°C.

[0095] According to the method for olefin carbonylation provided by the present invention, under normal circumstances, carbon monoxide is used as pure gas or is used by diluting it with an inert gas (such as nitrogen, carbon dioxide, rare gas) in advance, and a small amount of hydrogen may also be present in the carbon monoxide gas, but the content of the hydrogen is generally not more than 5%.

[0096] During the reaction, carbon monoxide and gaseous olefins are both introduced into the reaction system in gas phase through steel cylinders, and the molar ratio of olefin to carbon monoxide introduced into the reaction system is 1:1-100:1, preferably 2:1 to 50:1, and more preferably 3:1 to 5:1; the molar ratio of the amount of olefin to component (a) in the catalyst system is 50:1 to 300:1, preferably 100:1 to 200:1.

[0097] According to the method for olefin carbonylation provided by the present invention, in a preferred case, the mass ratio of alcohol to component (a) in the catalyst system of the present invention is 500:1 to 20000:1, for example, 2000:1, 5000:1, 10000:1, 15000:1; preferably 5000:1 to 15000:1, more preferably 10000:1-12500:1.

[0098] According to the method for olefin carbonylation reaction provided by the present invention, each component in the catalyst system can be added in situ to the reaction vessel for olefin carbonylation reaction, and can directly enter the reaction vessel or form the catalyst system in advance outside the reaction vessel and then add it to the reaction vessel.

[0099] Each component in the catalyst system can be added in any order of addition or added in a specific order of addition to form a catalyst system. Preferably, any two components are mixed and added to a reaction vessel, and then a third component is added to form a catalyst system, or a mixture of the two components is mixed with a third component and then added to a reaction vessel together, thereby easily protonating the ligand. For example, first, a bidentate phosphine ligand of component (b) and an acidic auxiliary agent of component (c) are mixed to form a protonated ligand, which is then added to a component (a) Group VIII metal or a compound thereof to form a catalyst system. More preferably, a bidentate phosphine ligand of component (b) and a Group VIII metal or a compound thereof of component (a) are mixed to form a chelated metal complex to form a metal catalyst precursor, which is then added to an acidic auxiliary agent of component (c) to form a metal-hydrogen catalytic active intermediate, thereby making the catalyst system more active and making the catalyst system more stable.

[0100] According to the method for olefin carbonylation provided by the present invention, in a preferred case, the olefin is a substituted or unsubstituted C2-C20 olefin or cycloolefin; preferably a substituted or unsubstituted C2-C16 olefin;

[0101] When the olefin has a substituent, the substituent is a C6-12 aryl group, a C1-4 alkyl group or a halogen-substituted C6-12 aryl group, a C2-6 ester group, or a nitrogen-containing heterocyclic group.

[0102] Preferred olefins include ethylene, 1-hexene, 1-pentene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, styrene, 2-butene, cyclohexene, 3-hexene, and the like.

[0103] The alcohol is a C1-C10 substituted or unsubstituted, linear or branched alkanol; when the alcohol is an alcohol having a substituent, the substituent is a C1-C6 alkyl, a C6-C10 aryl, a C2-C10 heterocyclic group, a halogen, a cyano group or a nitro group, preferably a C1-C6 alkyl or a C6-C10 aryl group;

[0104] The alcohol is preferably a C1-C6 monohydric alkanol, for example, methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, pentanol, hexanol, chlorooctanol; methanol and ethanol are further preferred; methanol is most preferred.

[0105] Generally, the amount of alcohol used does not play a decisive role in the reaction, and it is usually used in an amount exceeding that of the olefin. In addition, the alcohol can be used as a reaction solvent, and another solvent can also be used during the reaction. When another reaction solvent is used, suitable inert solvents include alkanes, such as hexane, heptane, 2,2,3-trimethylpentane; aromatic compounds, such as benzene, toluene, p-xylene, m-xylene; ketones, such as methyl butyl ketone; ethers, such as anisole, diethyl ether, dimethyl ether; esters, such as methyl acetate, methyl benzoate, dimethyl adipate.

[0106] According to the method for olefin carbonylation reaction provided by the present invention, with respect to the catalyst system, under the condition of ensuring a high reaction rate, compared with the amount of phosphine ligand, Group VIII metal or its compound in the catalyst system recorded in the patent application of the prior art, the advantages of the present invention are: the amount of phosphine ligand, Group VIII metal or its compound is reduced, and the stability of the catalyst system is improved. In addition, with the improvement of the stability of the catalyst system, the amount of metal used in the olefin carbonylation reaction is kept at a relatively low value.

[0107] According to the method for olefin carbonylation provided by the present invention, ethylene is used as an olefin, and when carbonylation is used to synthesize methyl propionate, a specific catalyst system is used, ethylene, carbon monoxide and methanol are used as reaction substrates, and the reaction is carried out at a lower temperature and a lower pressure. Compared with the prior art, the present invention has the following advantages:

[0108] (1) In the specific bidentate phosphine ligand structure contained in the catalyst system, nitrogen, oxygen or sulfur atoms are introduced, and the lone pair electrons on nitrogen, oxygen or sulfur in the formed ligand interact with the Group VIII metal element, thereby stabilizing the catalyst intermediate and greatly reducing the amount of ligand used.

[0109] (2) The solubility of CO and ethylene around the catalyst system is increased, which increases the amount of gas in the catalytic center and thus improves the catalytic efficiency of the reaction.

[0110] (3) The residence time of the reaction substrate is reduced, so that the gas circulation amount is reduced, thereby reducing the size of the required reaction vessel and reducing investment.

[0111] (4) The catalyst system has the advantages of low consumption, good product selectivity, high conversion rate of reaction substrates, and long service life. It can efficiently catalyze the carbonylation of ethylene to synthesize methyl propionate. The reaction result is calculated as carbon monoxide, and the yield of methyl propionate is as high as 96.73%. The whole method has good commercial value.

[0112] According to the method provided by the present invention, more preferably, the method for olefin carbonylation reaction using ethylene as olefin is:

[0113] A certain amount of methanol, a Group VIII metal compound, a bidentate phosphine ligand, and an acidic auxiliary agent are added to the autoclave, and the autoclave is sealed. Subsequently, the air in the autoclave is replaced with 1MPa nitrogen three times, and then a mixture of ethylene and carbon monoxide mixed in a certain proportion is introduced into the autoclave for 5 minutes under stirring, and then the pressure is gradually increased to the reaction pressure. At the same time, the autoclave is heated to the reaction temperature, and after a certain reaction time, a sample is taken for GC chromatography analysis.

[0114] The Group VIII metal compound used may be any one of those listed above; the acidic auxiliary agent used is preferably methanesulfonic acid, benzenesulfonic acid, or p-toluenesulfonic acid.

[0115] The process conditions adopted are:

[0116] The molar ratio of ethylene to CO is 1:1 to 5:1; the molar ratio of ethylene to the Group VIII metal compound is 50:1 to 300:1, preferably 100:1 to 200:1.

[0117] The reaction temperature is 60°C to 110°C;

[0118] The reaction pressure is 1-5 MPa;

[0119] The mass of the Group VIII metal compound is 0.01 to 0.08% of the mass of methanol;

[0120] The molar ratio of the bidentate phosphine ligand to the Group VIII metal compound in the catalyst system is 3:1 to 5:1;

[0121] The molar ratio of the acidic auxiliary agent to the Group VIII metal compound is 75:1 to 100:1;

[0122] The mass of the bidentate phosphine ligand is 0.4-2% of the mass of methanol;

[0123] The mass of the acidic auxiliary agent is 1 to 5.5% of the mass of methanol.

[0124] Example

[0125] The olefin carbonylation reaction is further described below in conjunction with specific examples and comparative examples. However, this should not be construed as limiting the scope of the present invention to the following examples. Various substitutions and changes made according to common technical knowledge and customary means in the art without departing from the technical concept of the present invention should be included within the scope of the present invention.

[0126] Preparation Example 1

[0127] Bis(di-tert-butylphosphine)-ethylenediamine

[0128]

[0129] Tetrahydrofuran (100 mL), ethylenediamine (2.4 g, 40 mmol), and triethylamine (14 mL, 100 mmol) were added to a 250 mL three-necked flask. The obtained solution was then cooled to 0 ° C and chlorodiphenylphosphine (14 mL, 80 mmol) was slowly added. The formation of white salt was observed within a few hours. The resulting solution was then heated to 70 ° C, stirred for 96 hours, and then filtered. The clear filtrate was heated in a vacuum to remove the solvent to obtain 12.3 g of a white solid with a yield of 85%.

[0130] Preparation Example 2

[0131] Preparation of bidentate phosphine ligand 2: N,N-bis(di-tert-butylphosphine)-N,N-dimethylethylenediamine

[0132]

[0133] The same method as in Preparation Example 1 was used except that ethylenediamine was replaced with an equimolar amount of N,N-dimethylethylenediamine to obtain 13.3 g of a white solid with a yield of 88%.

[0134] Preparation Example 3

[0135] Preparation of bidentate phosphine ligand 3: N,N-bis(di-tert-butylphosphine)-N,N-diethylethylenediamine

[0136]

[0137] The same method as in Preparation Example 1 was used except that ethylenediamine was replaced with an equimolar amount of N,N-diethylethylenediamine to obtain 14.6 g of a white solid with a yield of 90%.

[0138] Preparation Example 4

[0139] Bis(di-tert-butylphosphine)-N,N-diisopropylethylenediamine

[0140]

[0141] The preparation was carried out in the same manner as in Preparation Example 1 except that ethylenediamine was replaced with an equimolar amount of N,N-diisopropylethylenediamine to obtain 15.7 g of a white solid with a yield of 91%.

[0142] Preparation Example 5

[0143] Bis(di-tert-butylphosphine)-N,N-di-tert-butylethylenediamine

[0144]

[0145] The preparation was carried out in the same manner as in Preparation Example 1 except that ethylenediamine was replaced with an equimolar amount of N,N-di-tert-butylethylenediamine to obtain 16.4 g of a white solid with a yield of 89%.

[0146] Preparation Example 6

[0147] Bis(di-tert-butylphosphine)-N,N-diphenylethylenediamine

[0148]

[0149] The same method as in Example 1 was used to prepare the product except that ethylenediamine was replaced with an equimolar amount of N,N-diphenylethylenediamine to obtain 17.0 g of a white solid with a yield of 85%.

[0150] Preparation Example 7

[0151] Bidentate phosphine ligand 7: Preparation of N,N-bis(di-tert-butylphosphine)-N,N-bis(4-methoxyphenyl)ethylenediamine

[0152]

[0153] The same method as in Preparation Example 1 was used except that ethylenediamine was replaced with an equimolar amount of N,N-di(p-methoxy)phenylethylenediamine to obtain 19.3 g of a white solid with a yield of 86%.

[0154] Preparation Example 8

[0155] Bis((di-tert-butylphosphine)methyl)methylamine

[0156]

[0157] Methylamine (0.34 g, 10.9 mmol) and diphenylphosphine (4.06 g, 21.8 mmol) were added to a Schlenk flask containing 40 ml of toluene and 0.5 g of paraformaldehyde at 65° C. using a syringe. The mixture was stirred at 65° C. until the solid paraformaldehyde disappeared completely (about 4-5 hours).

[0158] The resulting solution was cooled to room temperature and then filtered through diatomaceous earth. The solvent was removed by rotary evaporation, leaving a clear oil. This was dissolved in about 10 mL of dichloromethane, to which 30 mL of ethanol was added and mixed thoroughly. The flask containing the resulting solution was then evacuated and filled with nitrogen. A white crystalline crude product was formed at this point, and the flask was subsequently cooled to -20 ° C overnight to allow the contents to precipitate completely.

[0159] The white crystalline product was collected on a glass dish, washed with a small amount of ethanol and dried in vacuo to obtain 2.5 g of a white solid with a yield of 67%.

[0160] Preparation Example 9

[0161] Bis((di-tert-butylphosphino)methyl)ethylamine

[0162]

[0163] The same method as in Preparation Example 8 was followed except that methylamine was replaced with an equimolar amount of ethylamine to obtain 2.8 g of a white solid with a yield of 70%.

[0164] Preparation Example 10

[0165] Bis((di-tert-butylphosphino)methyl)isopropylamine

[0166]

[0167] The same method as in Preparation Example 8 was used except that methylamine was replaced with an equimolar amount of isopropylamine to obtain 2.9 g of a white solid with a yield of 72%.

[0168] Preparation Example 11

[0169] Bis((di-tert-butylphosphino)methyl)tert-butylamine

[0170]

[0171] The same method as in Preparation Example 8 was used except that methylamine was replaced with tert-butylamine in an equal molar amount to obtain 3.2 g of a white solid with a yield of 75%.

[0172] Preparation Example 12

[0173] Bis((di-tert-butylphosphino)methyl)phenylamine

[0174]

[0175] The preparation was carried out in the same manner as in Preparation Example 8 except that methylamine was replaced with an equal molar amount of aniline to obtain 3.3 g of a white solid with a yield of 73%.

[0176] Preparation Example 13

[0177] Bis((di-tert-butylphosphine)methyl)benzylamine

[0178]

[0179] The same method as in Preparation Example 8 was used except that methylamine was replaced with an equimolar amount of benzylamine to obtain 3.3 g of a white solid with a yield of 71%.

[0180] Preparation Example 14

[0181] Bis((di-tert-butylphosphino)methyl)4-methoxyphenylamine

[0182]

[0183] The same method as in Preparation Example 8 was used except that methylamine was replaced with an equimolar amount of p-methoxyaniline to obtain 3.8 g of a white solid with a yield of 80%.

[0184] Preparation Example 15

[0185] Bis((diphenylphosphino)methyl)methylamine

[0186]

[0187] The preparation was carried out in the same manner as in Preparation Example 8, except that di-tert-butylphosphine was replaced with an equimolar amount of diphenylphosphine, to obtain 3.8 g of a white solid with a yield of 82%.

[0188] Preparation Example 16

[0189] Bis((di(4-methoxyphenyl)phosphine)methyl)methylamine

[0190]

[0191] The same method as in Preparation Example 8 was used except that di-tert-butylphosphine was replaced with an equimolar amount of 4-methoxyphenylphosphine to obtain 4.6 g of a white solid with a yield of 78%.

[0192] Preparation Example 17

[0193] Bidentate phosphine ligand 17: Preparation of ethyl di((di-tert-butylphosphino)sulfide)

[0194]

[0195] The same method as in Preparation Example 1 was used except that ethylenediamine was replaced with an equimolar amount of 1,2-ethanedithiol to obtain 12.7 g of a white solid with a yield of 83%.

[0196] Preparation Example 18

[0197] Bidentate phosphine ligand 18: Preparation of ethyl bis((di-tert-butylphosphino) ether)

[0198]

[0199] The same method as in Preparation Example 1 was used except that ethylenediamine was replaced with an equimolar amount of 1,2-ethylenediol to obtain 12.3 g of a white solid with a yield of 88%.

[0200] Preparation Example 19

[0201] Bis((di-tert-butylphosphino)methyl)sulfane

[0202]

[0203] The same method as in Preparation Example 8 was used except that methylamine was replaced with an equimolar amount of hydrogen sulfide to obtain 2.5 g of a white solid with a yield of 65%.

[0204] Preparation of Comparative Example 1

[0205] Preparation of bidentate phosphine ligand 20: 1,2-bis((di-tert-butylphosphino)methyl)-4-tert-butyl-benzene

[0206]

[0207] 4-tert-Butyl-o-xylene (4.55 g, 28.1 mmol) (Aldrich) was diluted with heptane (100 ml) and NaOBu t (8.1 g, 84.3 mmol), TMEDA (12.6 ml, 84.3 mmol) and t BuLi (2.5M in hexanes, 33.7 ml, 84.3 mmol). Butyl lithium was added dropwise and produced an immediate color change from colorless to yellow to orange to dark red. The solution was then heated to 65°C for 3 hours, producing a brown / orange suspension.

[0208] The suspension was cooled to room temperature and the supernatant was removed by cannula. The brown precipitate residue was then washed with pentane (100 ml). The pentane wash was then removed by cannula. The solid residue was then suspended in pentane (100 ml) and cooled in a cold water bath. Bu was added dropwise to the suspension. t 2PCl (7.5 ml, 39.3 mmol). The resulting suspension was then stirred for 3 hours and allowed to stand overnight.

[0209] Water (100 ml) was degassed with nitrogen for 30 min and then added to the suspension to obtain a two-phase solution. The upper layer (organic phase) was diluted with pentane (100 ml) and the organic phase was taken out through a cannula into a clean schlenk bottle. The pentane extract was dried with sodium sulfate and transferred to a clean schlenk bottle through a cannula. The solvent was then removed under vacuum to obtain an orange oil. Methanol (100 ml) was added thereto to obtain a two-phase solution. It was then heated to reflux (70° C.) to produce a light yellow solution and some colorless insoluble substances. The solution was then cooled to room temperature and filtered into a clean schlenk bottle. The solution was then placed in a -20° C. freezer overnight to produce an off-white solid deposit. The remaining methanol solution was then removed through a cannula and the solid was dried under vacuum. The solid was separated in a glove box. The amount of the product was 4.20 g, with a yield of 33% and a purity of 95%.

[0210] Preparation of Comparative Example 2

[0211] Preparation of bidentate phosphine ligand 21: 1,2-bis((di-tert-butylphosphino)methyl)benzene

[0212]

[0213] The same method as in Comparative Example 1 was used to prepare the product, except that 4-tert-butyl-o-xylene was replaced with an equimolar amount of o-xylene, to obtain 4.5 g of a white solid with a yield of 40% and a purity of 95%.

[0214] Invention Example 1

[0215] Methanol 1000g (31.25mol), palladium acetate 0.32g (1.43mmol), methanesulfonic acid 5.40g (56.19mmol) and bidentate phosphine ligand 1 (1.22g, 3.50mmol) were added into a 2L autoclave. Ethylene and carbon monoxide in a molar ratio of 4:1 were introduced into the autoclave at a carbon monoxide flow rate of 1.2L / min, and the reaction was carried out under the conditions of a stirring speed of 500r / min, a reaction pressure of 1.2MPa and a reaction temperature of 60°C, and the reaction time was 120min.

[0216] An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion rate and selectivity, as well as the yield of the product methyl propionate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0217] Invention Example 2

[0218] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.32 g (3.51 mmol) of bidentate phosphine ligand 2 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0219] Invention Example 3

[0220] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced by 0.3 g (1.42 mmol) of PdCl2(NH3)2 and 1.42 g (3.51 mmol) of bidentate phosphine ligand 3 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0221] Invention Example 4

[0222] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced by 0.33 g (1.42 mmol) of Pd(NH3)2(NO2)2 and 1.51 g (3.49 mmol) of bidentate phosphine ligand 4 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0223] Invention Example 5

[0224] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 5.40 g of methanesulfonic acid was replaced with 10.41 g (65.81 mmol) of benzenesulfonic acid, and 1.61 g (3.49 mmol) of bidentate phosphine ligand 5 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0225] Invention Example 6

[0226] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced by 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 5.40 g of methanesulfonic acid was replaced by 11.33 g (65.79 mmol) of p-toluenesulfonic acid, and 1.75 g (3.50 mmol) of bidentate phosphine ligand 6 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity, as well as the yield of the product methyl propionate, were calculated in terms of carbon monoxide. The results are shown in Table 1.

[0227] Invention Example 7

[0228] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.96 g (3.50 mmol) of bidentate phosphine ligand 7 was used, and the reaction temperature was 80° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0229] Invention Example 8

[0230] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced by 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.22 g (3.51 mmol) of bidentate phosphine ligand 8 was used, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0231] Invention Example 9

[0232] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced by 0.35 g (0.71 mmol) of [Rh(COD)Cl]2 and 1.27 g (3.51 mmol) of bidentate phosphine ligand 9 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0233] Invention Example 10

[0234] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced by 0.48 g (0.71 mmol) of [Ir(COD)Cl]2 and 1.31 g (3.49 mmol) of bidentate phosphine ligand 10 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0235] Invention Example 11

[0236] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.36 g (3.49 mmol) of bidentate phosphine ligand 11 was used, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0237] Invention Example 12

[0238] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.43 g (3.49 mmol) of bidentate phosphine ligand 12 was used, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0239] Invention Example 13

[0240] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.48 g (3.49 mmol) of bidentate phosphine ligand 13 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0241] Invention Example 14

[0242] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0243] Invention Example 15

[0244] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.50 g (3.51 mmol) of bidentate phosphine ligand 15 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0245] Invention Example 16

[0246] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.92 g (3.51 mmol) of bidentate phosphine ligand 16 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0247] Invention Example 17

[0248] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.34 g (3.50 mmol) of bidentate phosphine ligand 17 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0249] Invention Example 18

[0250] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.23 g (3.51 mmol) of bidentate phosphine ligand 18 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0251] Invention Example 19

[0252] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium and 1.23 g (3.51 mmol) of bidentate phosphine ligand 19 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0253] Invention Comparative Example 1

[0254] The reaction was carried out in the same manner as in Example 2, except that the amount of tri(dibenzylideneacetone)dipalladium was changed to 1.3 g (1.41 mmol) and 3.16 g (7.01 mmol) of bidentate phosphine ligand 20 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0255] Invention Comparative Example 2

[0256] The reaction was carried out in the same manner as in Example 2, except that the amount of tri(dibenzylideneacetone)dipalladium was changed to 1.3 g (1.41 mmol) and 2.76 g (7.00 mmol) of bidentate phosphine ligand 21 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 1.

[0257] Invention Example 20

[0258] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.36 g (3.49 mmol) of bidentate phosphine ligand 11 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of 1-hexene to carbon monoxide, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography, and the conversion rate and selectivity, as well as the yield of the product methyl heptanoate, were calculated in terms of carbon monoxide. The results are shown in Table 1.

[0259] Invention Example 21

[0260] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.43 g (3.49 mmol) of bidentate phosphine ligand 12 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of 1-pentene to carbon monoxide, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography, and the conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl hexanoate. The results are shown in Table 1.

[0261] Invention Example 22

[0262] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used, ethylene and carbon monoxide in a molar ratio of 4:1 were replaced with 3-methyl-1-butene and carbon monoxide in the same molar ratio, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography, and the conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl 3-methylvalerate. The results are shown in Table 1.

[0263] Invention Example 23

[0264] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used, ethylene and carbon monoxide in a molar ratio of 4:1 were replaced with 3,3-dimethyl-1-butene and carbon monoxide in the same molar ratio, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed, and GC chromatography was performed to calculate the conversion rate and selectivity in terms of carbon monoxide, as well as the yield of the product 3,3-dimethylvalerate. The results are shown in Table 1.

[0265] Invention Example 24

[0266] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of styrene to carbon monoxide, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of methyl phenylpropionate. The results are shown in Table 1.

[0267] Invention Example 25

[0268] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of 2-butene to carbon monoxide, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of methyl 2-methylbutyrate. The results are shown in Table 1.

[0269] Invention Example 26

[0270] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of cyclohexene to carbon monoxide, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of methyl cyclohexylcarboxylate. The results are shown in Table 1.

[0271] Invention Example 27

[0272] The reaction was carried out in the same manner as in Example 1, except that 0.32 g of palladium acetate was replaced with 0.65 g (0.71 mmol) of tris(dibenzylideneacetone)dipalladium, 1.54 g (3.50 mmol) of bidentate phosphine ligand 14 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of 3-hexene to carbon monoxide, and the reaction temperature was 100° C. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography, and the conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of methyl 2-ethylpentanoate. The results are shown in Table 1.

[0273] Table 1

[0274]

[0275]

[0276]

[0277] As can be seen from Table 1, in the embodiments 1-27 of the method for olefin carbonylation reaction provided by the present invention, the use amount of phosphorus ligand and Group VIII metal compound is less, and the selectivity and yield of the product are higher, and the conversion rate of the reaction substrate is higher, compared with the comparative examples 1-2 using the catalyst system including other phosphorus ligands. In the embodiments 1-27, the selectivity, conversion rate and yield of the embodiments 1-16 and 20-27 using the catalyst system including nitrogen-containing phosphorus ligands are higher than the embodiments 17-19 using the catalyst system including sulfur-containing or oxygen-containing phosphorus ligands; further, the selectivity, conversion rate and yield of the embodiments 8-16 and 20-27 using the catalyst system including a single nitrogen atom phosphorus ligand are higher than the embodiments 1-7 using the catalyst system including two nitrogen atoms phosphorus ligands.

[0278] Invention Example 28

[0279] Methanol 250g (7.81mol), tri (dibenzylideneacetone) dipalladium 0.1625g (0.177mmol), methanesulfonic acid 1.35g (14.05mmol) and bidentate phosphine ligand 14 (0.385g, 0.876mmol) were added to a 2L autoclave and sealed. Ethylene and carbon monoxide with a molar ratio of 4:1 were introduced into the autoclave, and the reaction was carried out under the conditions of a stirring speed of 500r / min, a reaction pressure of 1.2MPa and a reaction temperature of 60°C for 120min. After the reaction was completed, it was cooled to room temperature, and then an appropriate amount of the reaction mixture was weighed, and GC chromatographic analysis was performed to calculate the conversion rate and selectivity, as well as the yield of the product methyl propionate, in terms of carbon monoxide, and the results were recorded.

[0280] 250 g (7.81 mol) of methanol was added to the autoclave, and ethylene and carbon monoxide were introduced into the autoclave again at a molar ratio of 4:1. The reaction was carried out under the conditions of a stirring speed of 500 r / min, a reaction pressure of 1.2 MPa, and a reaction temperature of 60°C for 120 min. After the reaction was completed, the mixture was cooled to room temperature, and then an appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion rate and selectivity were calculated in terms of carbon monoxide, as well as the yield of the product methyl propionate, and the results were recorded.

[0281] The above steps were repeated three times until a total of 1250 g of methanol was added to the autoclave and the reaction was completed. The reaction results at each stage are recorded in Table 2.

[0282] Table 2

[0283]

[0284] It can be seen from the above embodiments that the catalyst system provided by the present invention comprising a specific bidentate phosphine ligand has good catalytic activity and selectivity at relatively low reaction temperature and reaction pressure. The catalyst system has the advantages of high catalytic efficiency, low consumption, long life, good selectivity, etc., and can efficiently catalyze the carbonylation reaction of olefins. Taking the carbonylation of ethylene to synthesize methyl propionate as an example, the yield can reach 96.73%, which has a good prospect for industrialization.

Claims

1. A method for synthesizing esters by carbonylation of olefins, the method comprising reacting olefins with carbon monoxide and alcohol in the presence of a catalyst system; in, The catalyst system comprises the following components: (a) Group VIII metals or their compounds; (b) bidentate phosphine ligands; and (c) acidic additives; The Group VIII metal includes: cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum; The compound of the Group VIII metal includes a salt or a weakly coordinated anion compound of the Group VIII metal and the following substances: sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid, sulfonated ion exchange resin, or perhalogen acid; or a complex of zero-valent palladium, rhodium, iridium, platinum or ruthenium; The acidic auxiliary agent is at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid and 2,4,6-trimethylmethanesulfonic acid; The bidentate phosphine ligand has a structure represented by the following general formula (I), (R1)(R2)PKAKP(R3)(R4) (I); Wherein, R1 to R4 are the same as or different from each other, and each independently represents a C1 to C10 straight chain or branched alkyl group, a substituted or unsubstituted C6 to C20 aryl group; when the C6 to C20 aryl group has a substituent, the substituent is a C1 to C6 alkyl group or a C1 to C6 alkoxy group; P is a phosphorus atom; Each K is the same as each other and is selected from a single bond or -C(Ra)2-; A is selected from -N(Rb)-, -N(Rf)-C(Rc)2-N(Rf)- or -N(Rf)-C(Rc)2C(Rc)2-N(Rf)-; When each K is a single bond, A is -N(Rf)-C(Rc)2-N(Rf)- or -N(Rf)-C(Rc)2C(Rc)2-N(Rf)-; When each K is -C(Ra)2-, A is -N(Rb)-; wherein each Ra is the same or different from each other, each Rc is the same or different from each other, and each Ra and each Rc are independently H, a linear or branched C1~C6 alkyl group; Rb and Rf are each independently H, a linear or branched C1~C6 alkyl group, or a substituted or unsubstituted C6~C10 aryl group; when the C6~C10 aryl group has a substituent, the substituent is a C1~C6 alkyl group or a C1~C6 alkoxy group.

2. The method according to claim 1, wherein: In the structure represented by A in the general formula (I), Each Rc is H; Rf is methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl or 4-methoxyphenyl.

3. The method according to claim 1, wherein: In the structure represented by A in the general formula (I), Each Ra is H; Rb is H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl or 4-methoxyphenyl.

4. The method according to claim 1, wherein: In the general formula (I), R1 to R4 are each independently a C1 to C6 straight chain or branched alkyl group, or a substituted or unsubstituted C6 to C10 aryl group; when the C6 to C10 aryl group has a substituent, the substituent is a C1 to C6 alkyl group or a C1 to C6 alkoxy group.

5. The method according to claim 4, wherein: In the general formula (I), R1-R4 are each independently tert-butyl, phenyl, 4-methoxyphenyl or benzyl.

6. The method according to claim 1, wherein: The acid auxiliary agent is methanesulfonic acid.

7. The method according to claim 1, wherein: In the catalyst system, the molar ratio of component (b) to component (a) is 2:1 to 20:1; The molar ratio of component (c) to component (a) is 2:1 to 150:

1.

8. The method according to claim 7, wherein: In the catalyst system, the molar ratio of component (b) to component (a) is 3:1 to 10:1; The molar ratio of component (c) to component (a) is 50:1 to 100:

1.

9. The method according to claim 1, wherein: The operating conditions of the reaction are that the reaction pressure is 1-20 MPa; The reaction temperature is 50~200℃.

10. The method according to claim 9, wherein: The operating conditions of the reaction are that the reaction pressure is 1-10 MPa; The reaction temperature is 60~150℃.

11. The method according to claim 1, wherein: The molar ratio of the olefin to the carbon monoxide is 1:1 to 100:1; the molar ratio of the olefin to the component (a) in the catalyst system is 50:1 to 300:1; The mass ratio of the alcohol to the component (a) in the catalyst system is 500:1 to 20000:

1.

12. The method according to claim 11, wherein: The molar ratio of the olefin to the carbon monoxide is 2:1 to 50:1; the molar ratio of the olefin to the component (a) in the catalyst system is 100:1 to 200:1; The mass ratio of the alcohol to the component (a) in the catalyst system is 5000:1 to 15000:

1.

13. The method according to claim 1, wherein: The olefin is a substituted or unsubstituted C2-C20 olefin; when the olefin has a substituent, the substituent is a C1-C10 alkyl group, a C6-C12 aryl group, a C1-C4 alkyl group or a halogen-substituted C6-C12 aryl group, a C2-C6 ester group, or a nitrogen-containing heterocyclic group; The alcohol is a C1-C10 substituted or unsubstituted, linear or branched alkanol; when the alcohol is an alcohol having a substituent, the substituent is a C1-C6 alkyl group, a C6-C20 aryl group, a C2-C10 heterocyclic group, a halogen, a cyano group or a nitro group.

14. The method according to claim 13, wherein: The olefin is a substituted or unsubstituted C2-C16 olefin; when the olefin has a substituent, the substituent is a C1-C10 alkyl group, a C6-C12 aryl group, a C1-C4 alkyl group or a halogen-substituted C6-C12 aryl group, a C2-C6 ester group, or a nitrogen-containing heterocyclic group; The alcohol is a C1-C6 monohydric alkanol.

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