Catalyst system and carbonylation reaction method

Abstract

The present invention relates to a catalyst system for carbonylation reaction and a method for carbonylation reaction. The catalyst system comprises (a) a Group VIII metal or a Group VIII metal compound; (b) a bidentate phosphine ligand; and (c) an acidic auxiliary agent; (b) the component is represented by the following formula (I): R 1 >P‑A‑Ar‑B‑P <R 2 (I) wherein P represents a trivalent phosphorus atom; Ar represents an aromatic group; A and B represent an alkylene group, and A and B are located at the ortho position on Ar; R 1 and R 2 Each of them forms together with the P atom to which it is connected a phosphorus-heterocyclic monocyclic group with at least 3 carbon atoms in the ring; the monocyclic group includes an alicyclic group, a lactone group, a lactam group, a cyclic ketone group, an N-containing heterocyclic group and an O-containing heterocyclic group with or without a substituent, and the substituent is connected to the monocyclic group in the form of a single bond or sharing multiple carbon atoms.

Description

Technical Field

[0001] The present invention relates to a catalyst system for carbonylation reaction and a method for olefin carbonylation reaction using the catalyst system. Background Art

[0002] Over the past few decades of chemical research, catalyst systems comprising transition metals and phosphine ligands have been widely used in various reaction types due to their high catalytic activity and high selectivity, such as cross-coupling reactions (Buchwald-Hartwig CN and CO bond formation reactions, Stille reactions, Sonogashira reactions, Suzuki-Miyaura reactions, etc.), asymmetric hydrogenation reactions, and carbonylation reactions. As one example of an olefin carbonylation reaction, as shown in the following Reaction Scheme 1, it involves converting an unsaturated hydrocarbon such as an olefin, CO, and an alcohol into the corresponding saturated carboxylic acid ester in the presence of a metal / ligand or metal complex.

[0003]

[0004] These saturated carboxylic acid esters are important fine chemicals widely used in pharmaceuticals, resins, coatings, food solvents, plasticizers, cosmetics, and other fields. Since the first discovery of olefin carbonylation in 1938, this type of reaction has been a research hotspot in organic synthesis and catalysis. In olefin carbonylation, methyl propionate, the carbonylation product of ethylene, is a key intermediate in the preparation of methyl methacrylate.

[0005] Patent Document 1 discloses a method for ethylene carbonylation and a catalyst system used in the method. The catalyst system comprises a Group VIII metal or a Group VIII metal compound and a bidentate phosphine ligand having a tertiary carbon group and an aryl bridge, the bidentate phosphine ligand being particularly represented by bis(di-tert-butylphosphino)-o-xylene. The catalyst system exhibits a good reaction rate in the olefin carbonylation reaction, but the catalyst system often deactivates during the continuous operation phase due to the palladium compound being reduced to palladium metal, resulting in higher costs and limited industrial applications.

[0006] Patent Document 2 discloses the carbonylation of olefins. It also discloses that the catalyst system used in the carbonylation reaction includes a palladium cation source, an anion source and a bidentate diphosphine source, wherein the bidentate diphosphine has a structure of Formula I, R 1 R 2 P–X–P–R 3 R 4(I), examples of which include 1,3-bis(diisopropylphosphino)propane, 1,3-bis(di-n-butylphosphino)propane, and 1,5-bis(dimethylphosphino)-3-oxapentane. This bidentate diphosphine-containing catalyst system 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 Document 3 discloses a diphosphine containing 2-phospha-tricyclo[3.3.1.1.{3,7}]decyl, which is a bidentate phosphine ligand with a covalent bridging group for the carbonylation reaction of unsaturated compounds. Its structural formula is, R 1 >PR 2 -PR 3 R 4 Specific compounds include 1,3-P,P′-bis(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)propane. This diphosphine ligand requires less ligand at equivalent TON compared to the ligand disclosed in EP0495547A. However, this ligand suffers from low selectivity and a limited substrate application range, leaving room for optimization.

[0008] Patent Document 4 discloses a bidentate phosphine ligand that can be used in a catalyst system. The bidentate phosphine ligand is a bidentate phosphine ligand having a phosphane cyclic group, and its structural formula is, R 1 R 2 M 1 -RM 2 R 3 R 4 . In the bidentate phosphine ligand, two di-tert-alkyl phosphino groups are connected through an alkylene group as a bridge group, or the phosphine cyclic group is connected to phosphorus through a secondary carbon, and the alkylene group is used as a bridge group. Examples of the bidentate phosphine ligand include 2,3-bis(di-tert-butylphosphino)butane, 2,3-P,P'-bis(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3.7}decyl]butane. 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 Document 5 discloses a method for carbonylating an ethylenically unsaturated compound and a catalyst for the method. It extends the teaching of bidentate phosphine ligands in the aforementioned US6156934A to bidentate diphosphines of the type disclosed in the aforementioned WO96019434A1 having a 1,2-substituted aryl bridge. Its structural formula is, R 1 >P–A 1 -R–A 2 -PR 2 R3 Specific examples thereof include 1,2-P,P'-bis(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3.7}decyl]methylenebenzene. The bidentate diphosphine has a certain improvement in the catalytic efficiency in the reaction.

[0010] Patent document 6 discloses a phosphaadamantane catalytic system. This 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 specific examples of the bidentate phosphine ligand include 1,2-bis(diadamantylphosphinomethyl)benzene and 1,2-bis(diadamantylphosphinomethyl)naphthalene. The amount of by-products generated during the reaction using this catalyst system is significantly reduced, and the replenishment of the catalyst 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 document 7 discloses a catalyst system. It is used to catalyze the carbonylation reaction of olefinically unsaturated compounds. The catalyst system includes a VIB group or VIIIB metal or a compound thereof, an acid and a bidentate phosphine, arsine or antimonide ligand. Specific examples of bidentate ligands include 1,2-bis(diadamantylphosphinomethyl)benzene, 1,2-bis(di-3,5-dimethyladamantylphosphinomethyl)benzene, 1,2-bis(di-5-tert-butyladamantylphosphinomethyl)benzene, etc. The bidentate ligand is present in an excess of at least 2:1 molar ratio relative to the metal, and the acid is in a molar excess of at least 2:1 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 this method is large, which directly increases the cost.

[0012] Patent Document 8 discloses the carbonylation of ethylenically unsaturated compounds. The catalyst system employed comprises a Group 8, 9, or 10 metal or compound thereof; and a bidentate phosphine ligand bridged by a non-aromatic cyclic hydrocarbon structure. Specific examples of the bidentate phosphine ligand include cis-1,2-bis(di-tert-butylphosphinomethyl)-4,5-dimethylcyclohexane, cis-1,2-bis(di-tert-butylphosphinomethyl)-5-methylcyclopentane, cis-1,2-bis(2-diphosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxa-adamantyl)-4,5-dimethylcyclohexane, and the like. The use of this catalyst system in alkoxycarbonylation and hydroxycarbonylation reactions can significantly increase the reaction rate and TON, but the amount of ligand used is still relatively high.

[0013] Patent document 9 discloses a carbonylation ligand and its use in the 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 their compounds. Specific examples of the bidentate phosphine ligand include 1,2-bis(di-tert-butyl(phosphinomethyl))-4,5-bis(4'-tert-butylphenyl)benzene, 1,2-bis(di-tert-butyl(phosphinomethyl))-4-tert-butylbenzene, 1,2-bis(di-tert-butyl(phosphinomethyl))-4,5-di-tert-butylbenzene, etc. The catalyst system including the bidentate phosphine ligand is used in the carbonylation reaction to produce a high TON, but the preparation process of the ligand is relatively tedious and complicated, and the yield and purity of some ligands are low.

[0014] Patent Document 10 discloses a method for the carbonylation of ethylenically unsaturated compounds, a novel carbonylation ligand, and a catalyst system incorporating the ligand. The carbonylation ligand employed is a bidentate ligand bridged by a hydrocarbyl aromatic structure having at least one aromatic ring. Specific examples of the bidentate ligand include 1-(di-tert-butylphosphinomethyl)-2-(di-o-tolylphosphinomethyl)benzene and 1-(di-tert-amylphosphinomethyl)-2-(di-o-tolylphosphinomethyl)benzene. The catalyst system containing the bidentate 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-mentioned patent application exhibits high stability and provides a relatively high reaction rate in the olefin carbonylation reaction, it still suffers from 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. These problems limit its industrial application, and therefore there is a need to improve the existing catalyst system.

[0016] References:

[0017] Patent Document 1: WO1996019434A1

[0018] Patent Document 2: EP0495547A

[0019] Patent Document 3: US6156934A

[0020] Patent Document 4: CN1429228A

[0021] Patent Document 5: CN1642646A

[0022] Patent Document 6: CN1674990A

[0023] Patent Document 7: CN103223350A

[0024] Patent Document 8: CN101309753A

[0025] Patent Document 9: CN105153241A

[0026] Patent Document 10: CN106854221A Summary of the Invention

[0027] Problems to be solved by the invention

[0028] The primary object of the present invention is to provide a catalyst system suitable for preparing carboxylic acid ester compounds by carbonylation of unsaturated compounds having double bonds. Furthermore, the present invention also aims to provide a carbonylation method using the catalyst system.

[0029] The catalyst system has high catalytic activity and uses a small amount of bidentate phosphine ligand. In addition, the product carboxylate compound obtained by the carbonylation reaction method of an unsaturated compound with a double bond using the catalyst system has higher selectivity and yield, and the conversion rate of the reaction substrate is also higher.

[0030] Solutions for solving problems

[0031] The present invention can solve the above technical problems by implementing the following technical solutions:

[0032] [1] The present invention first provides a catalyst system for carbonylation reaction, wherein the catalyst system comprises the following components:

[0033] (a) Group VIII metals or Group VIII metal compounds;

[0034] (b) a bidentate phosphine ligand; and

[0035] (c) acidic additives;

[0036] Wherein, the bidentate phosphine ligand of component (b) is represented by the following formula (I):

[0037] R 1 >PA-Ar-BP <R 2 (I)

[0038] Wherein, P represents a trivalent phosphorus atom;

[0039] Ar represents an aromatic group, A and B represent a single bond or an alkylene group, and A and B are located at the ortho position on Ar;

[0040] R 1 and R 2Each of them, together with the P atom to which it is connected, forms a phosphorus-containing monocyclic group having at least 3 carbon atoms in the ring;

[0041] The monocyclic group is selected from an alicyclic group with or without a substituent, a lactone group, a lactam group, a cyclic ketone group, a heterocyclic group containing at least one N atom and a heterocyclic group containing at least one O atom, the substituent is selected from an alkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitrogen-containing group or an oxygen-containing group, and the substituent is connected to the monocyclic group in the form of a single bond or by sharing multiple carbon atoms.

[0042] [2] The catalyst system according to [1], wherein

[0043] A and B each represent a C1-C6 alkylene group;

[0044] Ar represents a phenyl group or a naphthyl group;

[0045] The monocyclic group is selected from monocyclic groups with 3 to 10 carbon atoms in the ring, and the substituent is selected from alkyl groups, cycloalkyl groups, substituted or unsubstituted aryl groups, halogen atoms, nitrogen-containing groups or oxygen-containing groups.

[0046] [3] The catalyst system according to [1] or [2], wherein

[0047] The monocyclic group is selected from phosphacyclopentanyl, phosphapropionolactone, phosphabutyrolactone, phosphavalerolactonyl, phosphahexalactonyl, phosphaheptalactone, phosphatitanone, phosphacyclopentanone, phosphahexanone, phosphaheptanone, phosphaoctanone, phosphatetrahydrofuranyl, phosphatetrahydropyrrolyl, phosphatetrahydropyranyl, phosphahexahydropyridinyl, phosphahexahydropyrimidinyl or dioxaphosphacyclohexaninyl, phosphapropionamyl, phosphabutyrolactamyl, phosphavalerolactamyl, phosphahexanolactamyl or phosphaheptalactamyl, which may be substituted or not;

[0048] The substituent is an alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a chlorine atom, a bromine atom, a cyclohexyl group, a furyl group, a pyridyl group, a pyrrolyl group, or a [2-H]-pyrrolyl group.

[0049] [4] The catalyst system according to any one of [1] to [3], wherein

[0050] The bidentate phosphine ligand is selected from one or more of the following groups:

[0051]

[0052]

[0053] [5] The catalyst system according to any one of [1] to [4], wherein the molar ratio of component (b) to component (a) is 2:1 to 10:1, preferably 2:1 to 5:1;

[0054] The molar ratio of component (c) to component (a) is 2:1 to 100:1, preferably 10:1 to 50:1.

[0055] [6] The catalyst system according to any one of [1] to [5], wherein

[0056] In the component (a):

[0057] The Group VIII metal includes cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum;

[0058] The compound of the Group VIII metal includes: a compound of the Group VIII metal 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 resin, or perhalogen acid; or a complex of zero-valent palladium, rhodium, iridium, platinum, or ruthenium;

[0059] The acidic auxiliary agent of component (c) 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.

[0060] [7] The catalyst system according to any one of [1] to [6], wherein

[0061] The acidic auxiliary agent of component (c) includes 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.

[0062] [8] Furthermore, the present invention also provides a carbonylation reaction method, which comprises reacting an unsaturated compound having a double bond with carbon monoxide and an alcohol in the presence of a catalyst system;

[0063] The catalyst system is the catalyst system according to any one of [1] to [7].

[0064] [9] The method according to [8], wherein the molar ratio of the unsaturated compound having a double bond to the carbon monoxide is 1:1 to 100:1, preferably 2:1 to 50:1;

[0065] The molar ratio of the unsaturated compound having a double bond to the component (a) in the catalyst system is 50:1 to 600:1, preferably 100:1 to 300:1;

[0066] The mass ratio of the alcohol to the component (a) in the catalyst system is 500:1 to 20,000:1, preferably 5,000:1 to 15,000:1.

[0067]

[10] The method according to [8] or [9], wherein the operating conditions of the reaction are:

[0068] The reaction pressure is 1-20 MPa, preferably 1-10 MPa; the reaction temperature is 50-200°C, preferably 60-150°C.

[0069]

[11] The method according to any one of [8] to

[10] , wherein

[0070] The unsaturated compound having a double bond is a substituted or unsubstituted C2-C20 olefin, preferably 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 alkoxy group, a halogen-substituted C6-C12 aryl group, a C2-C6 ester group, or a nitrogen-containing heterocyclic group; the olefin is preferably a C2-C6 olefin;

[0071] 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, preferably a C1-C6 alkyl group or a C6-C10 aryl group; the alcohol is preferably a C1-C6 monohydric alkanol.

[0072] Effects of the Invention

[0073] The catalyst system provided by the present invention contains a specific bidentate phosphine ligand, so it has higher catalytic activity in olefin carbonylation reaction and greatly reduces the amount of bidentate phosphine ligand and Group VIII metal or its compound in the catalyst system.

[0074] Furthermore, the method for carbonylating unsaturated compounds having double bonds using the catalyst system of the present invention can achieve excellent technical effects such as good product selectivity, high product yield, high reaction substrate conversion rate, and long service life of the catalyst system.

[0075] In addition, the catalyst system of the present invention can efficiently catalyze the carbonylation reaction of olefins to synthesize carboxylic acid ester products, thereby improving the catalytic efficiency of the reaction and reducing the residence time of the reaction substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1is the free energy potential energy surface of the olefin carbonylation reaction of palladium catalyst in a strong acid system (wherein the bidentate phosphine ligand is represented by , ethylene is taken as an example of the olefin, methanesulfonic acid is taken as an example of the acid, and methanol is taken as an example of the alcohol). DETAILED DESCRIPTION

[0077] The following is a detailed description of the present invention. The following description of the technical features is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0078] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0079] In this specification, the use of “substantially” or “essentially” means that the standard deviation from a theoretical model or theoretical data is within a range of 5%, preferably 3%, and more preferably 1%.

[0080] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0081] In the present specification, the term "monocyclic group" is used to mean that the phosphorus atom is located in only one ring structure, and is not located on multiple rings at the same time.

[0082] As used herein, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

[0083] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "embodiments," etc., mean that the specific elements (e.g., features, structures, properties, and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0084] The present invention provides a catalyst system that can be used for the carbonylation reaction of unsaturated compounds having double bonds. Since the catalyst system contains a specific bidentate phosphine ligand, the catalytic activity is higher when used in the olefin carbonylation reaction, and the amount of the bidentate phosphine ligand and the Group VIII metal or its compound in the catalyst system is greatly reduced.

[0085] (Bidentate phosphine ligand)

[0086] In the present invention, the bidentate phosphine ligand has a structure represented by the following formula (I):

[0087] R1 >PA-Ar-BP <R 2 (I)

[0088] Here, P represents a trivalent phosphorus atom.

[0089] Ar represents an aromatic group, which may or may not have an alkyl substituent. In some specific embodiments of the present invention, Ar may be a phenyl group or a naphthyl group, preferably a phenyl group.

[0090] A and B are the same or different and may independently represent a single bond or an alkylene group, and A and B are located at the ortho position on the aromatic group Ar. In some preferred embodiments, A or B may be a C1-C6 alkylene group, typically, for example, methylene, ethylene, propylene, butylene, pentylene, or hexylene.

[0091] Further, R 1 and R 2 Each of them forms together with the P atom to which it is connected a phosphorus heterocyclic group with at least 3 carbon atoms on the ring. Preferably, the monocyclic group is a monocyclic group with 3 to 10 carbon atoms on the ring.

[0092] In the present invention, the monocyclic group is selected from an alicyclic group with or without substituents, a lactone group, a lactam group, a cyclic ketone group, a heterocyclic group containing at least one N atom, or a heterocyclic group containing at least one O atom. Among them, lactone groups and lactam groups are preferred, and lactone groups are more preferred.

[0093] Further, the monocyclic group is preferably a phosphacyclopentanyl, a phosphapropionolactone, a phosphabutyrolactone, a phosphavalerolactone, a phosphahexalactone, a phosphaheptalactone, a phosphatitanone, a phosphacyclopentanone, a phosphahexanone, a phosphaheptanone, a phosphaoctanone, a phosphatetrahydrofuranyl, a phosphatetrahydropyrrolyl, a phosphatetrahydropyranyl, a phosphahexahydropyridinyl, a phosphahexahydropyrimidinyl, a dioxaphosphahexacyclohexaninyl, a phosphapropionamyl, a phosphabutyrolactamyl, a phosphavalerolactam, a phosphahexamyl, or a phosphaheptanolactamyl. Among them, preferred are phosphapropiolactone, phosphabutyrolactone, phosphavalerolactone, phosphahexalactone, phosphaheptanolactone, phosphapropiolactam, phosphabutyrolactam, phosphavalerolactam, phosphahexalactam, or phosphaheptanolactam; more preferred are heteropropiolactone, phosphabutyrolactone, phosphavalerolactone, phosphahexalactone, or phosphaheptanolactam.

[0094] The substituent of the monocyclic group is selected from an alkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitrogen-containing group or an oxygen-containing group. Furthermore, the substituent may be connected to the monocyclic group in the form of a single bond or sharing multiple carbon atoms.

[0095] The monocyclic group may have one or more substituents. In some preferred embodiments of the present invention, the alkyl group may be a C1-C10 alkyl group; the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group; the substituted or unsubstituted aryl group may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group; the halogen atom may be a fluorine, chlorine, bromine, or iodine atom; the nitrogen-containing group may be a pyridyl group, a pyrrolyl group, or a [2-H]-pyrrolyl group; and the oxygen-containing group may be a furyl group.

[0096] In a further preferred embodiment, the substituent of the monocyclic group is preferably an alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a chlorine atom, a bromine atom, a cyclohexyl group, a furyl group, a pyridyl group, a pyrrolyl group, or a [2-H]-pyrrolyl group.

[0097] More specifically, specific examples of the bidentate phosphine ligand in the present invention include the following ligands, but the present invention is not limited to the following ligands.

[0098]

[0099]

[0100] The bidentate phosphine ligand in the present invention can cause compression of the CPC bond angle due to the presence of the phosphamonocyclic alicyclic group, phosphamonocyclic lactone group, phosphamonocyclic ketone group, phosphamonocyclic lactam group, phosphamonocyclic N-containing group or phosphamonocyclic O-containing group cyclic structure of the phosphine ligand, so that the bidentate phosphine ligand with such a structure can stably complex with the Group VIII metal to form a square-like planar geometric shape with a suitable chelation angle, and the structure is not easily destroyed.

[0101] Furthermore, the bidentate phosphine ligand is an extremely weak base, resulting in a low ability to donate electrons to the metal. This results in a higher reactivity of the electrophilic metal center, accelerating the rate-determining methanol decomposition step in the olefin carbonylation reaction. Therefore, in a catalyst system containing the bidentate phosphine ligand, the complex of the Group VIII metal and the bidentate phosphine ligand is very stable, resulting in a catalyst system with high catalytic activity and accelerated carbonylation reactions.

[0102] The method for synthesizing the bidentate phosphine ligand provided by the present invention is not particularly limited in principle. In some preferred embodiments of the present invention, the bidentate phosphine ligand can be obtained by borylation of a phosphorus-containing cyclic compound and then reacting it with a halogenated aromatic compound.

[0103] For the borylation reaction, borane can be reacted with a phosphorus-containing cyclic compound to obtain, for example, a phosphine (cycloalkane / cyclic ester / cyclic ketone)-borane complex. Preferably, BH3 can be used as the borane. Furthermore, the present invention does not particularly limit the source of the phosphorus-containing cyclic compound, which can be obtained by conventional synthesis methods in the art or commercially available.

[0104] (Catalyst System)

[0105] The catalyst system provided by the present invention comprises the following components:

[0106] (a) Group VIII metals or compounds of Group VIII metals;

[0107] (b) a bidentate phosphine ligand; and

[0108] (c) acidic additives;

[0109] Wherein, the bidentate phosphine ligand of component (b) is the bidentate phosphine ligand mentioned above.

[0110] In some specific embodiments, according to the catalyst system provided by the present invention, the molar ratio of component (b) to component (a) is 2:1 to 10:1, preferably 2:1 to 5:1; when the molar ratio of component (b) to component (a) is within this range, it can have good catalyst system stability and high catalytic activity. Technical effect.

[0111] In some specific embodiments, according to the catalyst system provided by the present invention, the molar ratio of component (c) to component (a) is 2:1 to 100:1, preferably 10:1 to 50:1; when the molar ratio of component (b) to component (a) is within this range, it can have the technical effects of high reaction conversion rate and selectivity.

[0112] In addition, according to the catalyst system provided by the present invention, in component (a), the Group VIII metal includes one or more of cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum;

[0113] The compound of a Group VIII metal includes one or more of the following compounds: a compound of the Group VIII metal 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 resin, or perhalogen acid; or a complex of zerovalent palladium, rhodium, iridium, platinum, or ruthenium.

[0114] According to the catalyst system provided by the present invention, the acidic auxiliary agent of component (c) 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.

[0115] In some preferred embodiments of the present invention, the acidic auxiliary agent of component (c) includes 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.

[0116] The catalytic process of the catalyst system provided by the present invention can be found as follows:

[0117] See also Figure 1 Based on the existing carbonylation reaction examples of unsaturated compounds with double bonds (ethylene is used as an example below), the present invention uses density functional theory calculations to clarify the microscopic process of olefin carbonylation reaction catalyzed by palladium catalyst in a strong acid system and establishes the free energy potential energy surface changes of the entire catalytic cycle.

[0118] The reaction begins with the active catalyst, a protonated palladium species called int1. It first undergoes coordination with ethylene (int2) and a rapid insertion process (TS3, free energy barrier 1.1 kcal / mol) to form the hydrogen-bonded intermediate int4. This is followed by coordination with carbon monoxide (int5) and a rapid carbonyl migration insertion process (TS3, free energy barrier 3.1 kcal / mol) to form the tricoordinated intermediate int7. At this point, carbon monoxide can undergo additional coordination with int7 to form the more stable tetracoordinated intermediate int8. Subsequently, alcohols such as methanol, assisted by acid anions, undergo nucleophilic attack on the carbonyl group (TS10, free energy barrier 23.1 kcal / mol) to form int11. This difficult carbon-oxygen bond formation process is the rate-determining step in the entire catalytic cycle. Finally, the resulting zerovalent palladium species int12 reacts with strong acid species in the system to regenerate the active catalyst int1.

[0119] Based on theoretical calculations of the catalytic process, the present invention demonstrates, at the microscopic scale, that carbon monoxide (CO) has a certain toxic effect on the ethylene carbonylation reaction in a palladium-catalyzed strong acid system, and that the system requires the presence of an anion capable of acting as a Brönsted base in an acidic medium. The bidentate, bulky sterically hindered ligand framework described in the present invention effectively inhibits the toxic effect of CO, thereby enabling the catalyst system to possess high catalytic activity.

[0120] (Carbonylation reaction)

[0121] According to the present invention, a carbonylation reaction method is provided, which comprises reacting an unsaturated compound having a double bond with carbon monoxide and an alcohol in the presence of a catalyst system; wherein the catalyst system is the catalyst system provided by the present invention.

[0122] According to the carbonylation reaction method provided by the present invention, in a preferred case, the molar ratio of the unsaturated compound having a double bond to carbon monoxide is 1:1 to 100:1, preferably 2:1 to 50:1; the molar ratio of the unsaturated compound having a double bond to component (a) in the catalyst system is 50:1 to 600:1, preferably 100:1 to 300:1; and the mass ratio of the alcohol to component (a) in the catalyst system is 500:1 to 20000:1, preferably 5000:1 to 15000:1.

[0123] According to the carbonylation reaction method provided by the present invention, in a preferred case, the operating conditions of the reaction are: reaction pressure of 1-20 MPa, preferably 1-10 MPa; reaction temperature of 50-200°C, preferably 60-150°C.

[0124] Further, in the present invention, the unsaturated compound having a double bond can typically be a substituted or unsubstituted olefin. In some specific embodiments of the present invention, such a compound can be a substituted or unsubstituted C2-C20 olefin, preferably a substituted or unsubstituted C2-C16 olefin. When the olefin has a substituent, the substituent can be a C1-C10 alkyl, a C6-C12 aryl, a C1-C4 alkoxy, a halogen-substituted C6-C12 aryl, a C2-C6 ester group, or a nitrogen-containing heterocyclic group.

[0125] In a further preferred embodiment of the present invention, the unsaturated compound having a double bond is a C2-C6 olefin.

[0126] Furthermore, the above-mentioned unsaturated compound having a double bond may be used alone or as a mixture of two or more. However, it is preferred to use only one.

[0127] For the alcohol in the above carbonylation reaction, it 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, preferably, the substituent is a C1-C6 alkyl group or a C6-C10 aryl group.

[0128] In a further preferred embodiment of the present invention, the alcohol is a C1-C6 monohydric alkanol.

[0129] The above-mentioned alcohols may be used alone or as a mixture of two or more. However, it is preferred to use only one type.

[0130] According to the carbonylation method provided by the present invention, more preferably, the carbonylation method using ethylene as the unsaturated compound having a double bond is:

[0131] A certain amount of methanol, a Group VIII metal compound, a bidentate phosphine ligand, and an acidic auxiliary are added to an autoclave, which is then sealed. A mixture of ethylene and carbon monoxide in a certain ratio is then introduced into the autoclave under stirring. The pressure is then gradually increased to the reaction pressure. Simultaneously, the autoclave is heated to the reaction temperature. After a certain reaction time, a sample is collected for GC analysis.

[0132] 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.

[0133] The method for carbonylating unsaturated compounds having double bonds using the catalyst system of the present invention can achieve excellent technical effects such as good product selectivity, high product yield, high reaction substrate conversion rate and long service life of the catalyst system.

[0134] Example

[0135] The present invention will be further described below with reference to specific embodiments and comparative examples.

[0136] Preparation Example 1

[0137] Preparation of bidentate phosphine ligand 1

[0138] (1) Preparation of 2,5-dimethylphosphine-borane complex (1-a)

[0139]

[0140] To a solution of 6.0 g (24 mmol) of P(SiMe3)3 in 300 mL of THF was added 25.1 mmol (1.05 equiv / P) of MeLi (15.7 mL, 1.6 M in diethyl ether). The solution was stirred for 12 hours and the solvent was removed under vacuum. The resulting white solid was dissolved in 300 mL of diethyl ether to give a yellow solution. To this was slowly added 4.3 g (24 mmol) of 3,6-hexanediol cyclic sulfate, and the yellow color disappeared. The solution was stirred for 2 hours and 20 mL of methanol was slowly added. The reaction mixture was stirred for 24 hours and the solvent was carefully removed under vacuum at room temperature to give a white (sometimes yellow) solid. (Note: It is difficult to completely remove methanol from this material, which requires the use of excess MeLi in the next step).

[0141] The solid was dissolved in 300 mL of THF and 25.1 mmol of MeLi (15.7 mL, 1.6 M ether solution) was added. The resulting mixture was stirred for 2 hours, and 1.5 to 2 equiv of additional MeLi was added to completely convert the mixture of secondary phosphine and intermediate primary phosphine sulfonate. Next, 48 mmol (2 equiv / P) of BH3-THF solution (48 mL, 1 M THF solution) was added. The resulting residue was extracted with dichloromethane (200 mL), the resulting solution was concentrated under vacuum, and the residue was extracted with hexane (200 mL) and then filtered through a silica gel pad. The solvent was removed in vacuo to obtain a colorless oily substance, 2,5-dimethylphosphine-borane complex (1-a) (1.9 g, 61% yield).

[0142] (2) Preparation of bis(phosphine-borane) (1-b)

[0143]

[0144] To an ice-cooled mixture of 2,5-dimethylphosphine-borane complex (1-a) (1.9 g, 14.6 mmol) and Bu4NBr (158 mg, 0.5 mmol) in 30% aqueous potassium hydroxide solution (100 mL) and toluene (30 mL) was added the appropriate amount of o-dibenzyl bromide (1.73 g, 6.6 mmol, 1.1 equiv P / Br), and the mixture was vigorously stirred at room temperature for 16 hours. Ether (100 mL) was then added and the organic phase was collected. The organic phase was washed with water (3 × 10 mL) and brine (1 × 10 mL) and dried over anhydrous MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by crystallization from hexane to give bis(phosphine-borane) (1-b) (1.6 g, 67% yield) as a white solid.

[0145] (3) Preparation of bidentate phosphine ligand 1

[0146]

[0147] To a 50 mL Schlenk tube was added bis(phosphine-borane) (1-b) (362 mg, 1.0 mmol), DABCO (1,4-diazabicyclo[2,2,2]octane, 247 mg, 2.2 mmol) and toluene (15 mL), and the mixture was stirred at 50° C. for 15 hours. The mixture was cooled to room temperature and filtered through a pad of silica, eluting with 150 mL of degassed hexane / ether (10 / 1). The filtrate was concentrated in vacuo to give the bidentate phosphine ligand 1 (300 mg, 90%) as a colorless oil.

[0148] NMR data of bidentate phosphine ligand 1:

[0149] 1H NMR (400MHz, CDCl3): δ = 7.18–7.09 (m, 4H), 3.62 (dd, J = 6.9, 14.7Hz, 2H), 2.77 (pseudo t,J=15.2Hz,2H),2.26–2.06(m,8H),1.49–1.34(m,4H),1.32(dd,J=6.4,13.0Hz,6H),0.86(dd,J=6.9,15.7Hz,6H).

[0150] 13 C NMR (100MHz, CDCl3): δ = 132.82, 130.58, 127.06, 34.70, 34.44, 34.34, 32.05, 27.17, 15.11, 13.69.

[0151] 31 P NMR (162MHz, CDCl3): δ = 38.68.

[0152] Preparation Example 2

[0153] Preparation of bidentate phosphine ligand 2

[0154] (1) Preparation of 2,5-diphenylphosphine-borane complex (2-a)

[0155]

[0156] At room temperature and under a nitrogen atmosphere, phenylsilane (1.68 g, 15.5 mmol) was added dropwise via a syringe to a stirred suspension of 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) (3.50 g, 12.0 mmol) in toluene (20 mL). Once the addition was complete, the reaction was heated to 110 ° C. After reacting at 110 ° C for 16 hours, it was cooled to room temperature and then concentrated in vacuo to obtain an opaque gum. Under a nitrogen atmosphere, the gum was placed in degassed THF (20 mL) and the solution was cooled to 0 ° C. Borane-methyl sulfide complex (4.88 mL, 51.4 mmol) was added dropwise via a syringe, and once the addition was complete, the reaction was allowed to warm to room temperature. After reacting at room temperature for 16 hours, the reaction solution was concentrated in vacuo to obtain a white solid. The solid was purified by flash column chromatography (heptane:ethyl acetate=9:1) to obtain a white solid product, 2,5-diphenylphosphine-borane complex (2-a) (3.12 g, 95% yield).

[0157] (2) Preparation of bis(2,5-diphenylphosphine-borane) (2-b)

[0158]

[0159] To an ice-cooled mixture of 2,5-diphenylphosphine-borane complex (2-a) (3.7 g, 14.6 mmol) and Bu4NBr (158 mg, 0.5 mmol) in 30% aqueous potassium hydroxide solution (100 mL) and toluene (30 mL) was added the appropriate amount of o-dibenzyl bromide (1.73 g, 6.6 mmol, 1.1 equiv P / Br), and the mixture was vigorously stirred at room temperature for 16 hours. Ether (100 mL) was then added and the organic phase was collected. The organic phase was washed with water (3 × 10 mL) and brine (1 × 10 mL) and dried over anhydrous MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by crystallization from hexane to give bis(2,5-diphenylphosphine-borane) (2-b) (2.4 g, 60% yield) as a white solid.

[0160] (3) Preparation of bidentate phosphine ligand 2

[0161]

[0162] To a 50 mL Schlenk tube was added bis(2,5-diphenylphosphine-borane) (2-b) (610 mg, 1.0 mmol), DABCO (1,4-diazabicyclo[2,2,2]octane, 247 mg, 2.2 mmol) and toluene (15 mL) and the mixture was stirred at 50° C. for 15 hours. The mixture was cooled to room temperature and filtered through a pad of silica, eluting with 150 mL of degassed hexane / ether (10 / 1). The filtrate was concentrated in vacuo to give the bidentate phosphine ligand 2 (495 mg, 85%) as a colorless oil.

[0163] NMR data of bidentate phosphine ligand 2:

[0164] 1 H NMR (400MHz, CDCl3): δ=7.37–7.29(m,4H),7.26–7.17(m,2H),7.15–7.06(m,5H),7.04–6.95(m,1H),3 .20(ddd,J=13.7,1.8,1.1Hz,2H),3.04(tt,J=5.0,1.0Hz,2H),2.16–2.06(m,2H),2.06–1.99(m,2H).

[0165] 13 C NMR (100MHz, CDCl3): δ=138.61,138.59,130.08,129.45,127.94,126.62,126.41,52.74,33.04,31.31.

[0166] 31P NMR (162MHz, CDCl3): δ = 54.36.

[0167] Preparation Example 3

[0168] Preparation of bidentate phosphine ligand 3

[0169]

[0170] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (3-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (3-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (3-b). Finally, the bidentate phosphine ligand 3 (329 mg, 88%) was obtained as a colorless oil.

[0171] NMR data of bidentate phosphine ligand 3:

[0172] 1 H NMR (400MHz, CDCl3): δ = 7.20–7.00 (m, 3H), 3.14 (ddd, J = 13.8, 12.9, 1.1Hz, 1H), 3.07 (ddd, J = 13.7, 12.8, 0.9Hz, 1H), 2.95 (dd, J = 13.7, 1.0Hz, 1H).

[0173] 13 C NMR (100MHz, CDCl3): δ = 137.78, 137.22, 130.05, 126.49, 126.46, 126.40, 126.33, 126.26, 126.23, 40.84, 32.51.

[0174] 31 P NMR (162MHz, CDCl3): δ = 40.79.

[0175] Preparation Example 4

[0176] Preparation of bidentate phosphine ligand 4

[0177]

[0178] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (4-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (4-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (4-b). Finally, the bidentate phosphine ligand 4 (413 mg, 87%) was obtained as a colorless oil.

[0179] NMR data of bidentate phosphine ligand 4:

[0180] 1 H NMR(400MHz, CDCl3):7.72–7.64(m,2H),7.57–7.48(m,3H),7.18(dd,J=5.9,3.7Hz,1H), 7.03(ddt,J=5.7,3.6,1.1Hz,1H), 3.41(d,J=13.7Hz,3H), 3.04(dd,J=13.7,1.1Hz,2H).

[0181] 13 C NMR (100MHz, CDCl3): δ=137.81,136.10,132.45,130.05,127.32,126.43,126.38,124.66,40.86,32.52.

[0182] 31 P NMR (162MHz, CDCl3): δ = 42.53.

[0183] Preparation Example 5

[0184] Preparation of bidentate phosphine ligand 5

[0185]

[0186] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (5-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (5-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (5-b). Finally, the bidentate phosphine ligand 5 (400 mg, 85%) was obtained as a colorless oil.

[0187] NMR data of bidentate phosphine ligand 5:

[0188] 1H NMR(400MHz, CDCl3):7.83–7.75(m,2H),7.65–7.57(m,2H),7.48–7.38(m,4H),7.19(d d,J=5.9,3.7Hz,1H),7.04(ddt,J=5.7,3.7,1.1Hz,1H),3.73(dd,J=13.6,1.0Hz,2H).

[0189] 13 C NMR (100MHz, CDCl3): δ=144.25,138.51,138.29,131.19,130.03,126.26,126.15,125.97,125.76,32.09.

[0190] 31 P NMR (162MHz, CDCl3): δ = 41.62.

[0191] Preparation Example 6

[0192] Preparation of bidentate phosphine ligand 6

[0193]

[0194] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (6-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (6-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (6-b). Finally, the bidentate phosphine ligand 6 (282 mg, 80%) was obtained as a colorless oil.

[0195] NMR data of bidentate phosphine ligand 6:

[0196] 1 H NMR (400MHz, CDCl3): 7.43 (s, 1H), 7.15 (dd, J = 5.9, 3.7Hz, 1H), 7.10–7.03 (m, 1H), 4.26 (d, J = 12.8Hz, 1H), 4.19 (d, J = 12.8Hz, 1H), 3.21 (ddd, J=13.7, 12.8, 0.9Hz, 1H), 3.11 (d, J=13.7Hz, 2H), 2.96 (d, J=13.7Hz, 2H), 2.86 (ddd, J=13.8, 12.9, 1.0Hz, 1H).

[0197] 13C NMR (100MHz, CDCl3): δ=151.13,137.25,130.92,130.63,129.98,126.24,58.79,39.94,39.89,37.85,31.53.

[0198] 31 P NMR (162MHz, CDCl3): δ = 38.21.

[0199] Preparation Example 7

[0200] Preparation of bidentate phosphine ligand 7

[0201]

[0202] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (7-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (7-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (7-b). Finally, the bidentate phosphine ligand 7 (280 mg, 79%) was obtained as a colorless oil.

[0203] NMR data of bidentate phosphine ligand 7:

[0204] 1 H NMR (400MHz, CDCl3): δ = 7.17 (dd, J = 5.9, 3.7Hz, 1H), 7.09 (dddd, J = 5.8, 3.6, 2.9, 1.0Hz, 1H), 7.07 (s, 2H), 3.08 (dd, J = 13.7, 4.6Hz, 6H).

[0205] 13 C NMR (100MHz, CDCl3): δ = 137.79, 137.55, 129.90, 129.44, 126.31, 36.37, 32.52.

[0206] 31 P NMR (162MHz, CDCl3): δ=39.77.

[0207] Preparation Example 8

[0208] Preparation of bidentate phosphine ligand 8

[0209]

[0210] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (8-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (8-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (8-b). Finally, the bidentate phosphine ligand 8 (301 mg, 80%) was obtained as a colorless oil.

[0211] NMR data of bidentate phosphine ligand 8:

[0212] 1 H NMR (400MHz, CDCl3): δ=8.49 (dd, J=3.5, 2.0Hz, 1H), 7.44 (dd, J=7.8, 2.0Hz, 1H), 7.34 (dd, J=7.7, 3.5Hz, 1H), 7.16 (d d,J=5.8,3.7Hz,1H),7.02(ddt,J=5.8,3.7,1.1Hz,1H),3.64–3.55(m,1H),3.37–3.17(m,3H),3.10(d,J=13.7Hz,2H).

[0213] 13 C NMR (100MHz, CDCl3): δ=159.46,147.37,137.76,134.64,132.23,129.98,126.37,121.97,42.05,42.01,40.09,32.48.

[0214] 31 P NMR (162MHz, CDCl3): δ = 40.93.

[0215] Preparation Example 9

[0216] Preparation of bidentate phosphine ligand 9

[0217]

[0218] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (9-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (9-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (9-b). Finally, the bidentate phosphine ligand 9 (524 mg, 80%) was obtained as a colorless oil.

[0219] NMR data of bidentate phosphine ligand 9:

[0220] 1 H NMR (400MHz, CDCl3): δ = 7.12 (dd, J = 6.1, 4.4Hz, 1H), 7.00 (ddd, J = 13.6, 4.1, 2.2Hz, 2H), 6.91 (ddt, J = 5.8, 4.4, 1.1Hz, 1H ),3.52(ddd,J=13.8,12.9,1.0Hz,1H),3.19(ddd,J=13.8,12.8,0.9Hz,1H),2.53(d,J=13.7Hz,1H),1.36–1.28(m,21H).

[0221] 13 C NMR (100MHz, CDCl3): δ=153.29,143.60,137.52,137.14,135.65,129.64,126 .35,124.25,121.73,42.68,36.14,34.87,34.48,32.24,31.44,30.28,29.59.

[0222] 31 P NMR (162MHz, CDCl3): δ = 25.82.

[0223] Preparation Example 10

[0224] Preparation of bidentate phosphine ligand 10

[0225]

[0226] The preparation was carried out in the same manner as in Preparation Example 2, except that the 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (10-a-1), the 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (10-a), and the bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (10-b). Finally, the bidentate phosphine ligand 10 (356 mg, 85%) was obtained as a colorless oil.

[0227] NMR data of bidentate phosphine ligand 10:

[0228] 1H NMR (400MHz, CDCl3): δ = 7.18 (dd, J = 6.0, 4.4Hz, 2H), 7.09–7.01 (m, 2H), 3.46 (td, J = 1 3.6,1.0Hz,2H),3.01(td,J=13.6,1.0Hz,2H),2.49(s,3H),1.36(s,9H),1.21(s,9H).

[0229] 13 C NMR (100MHz, CDCl3): δ=214.52,135.46,131.36,126.31,50.31,40.00,38.68,27.59,23.49,23.47,23.44,23.42,20.41.

[0230] 31 P NMR (162MHz, CDCl3): δ = 15.02.

[0231] Preparation Example 11

[0232] Preparation of bidentate phosphine ligand 11

[0233]

[0234]

[0235] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (11-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (11-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (11-b). Finally, the bidentate phosphine ligand 11 (355 mg, 84%) was obtained as a colorless oil.

[0236] NMR data of bidentate phosphine ligand 11:

[0237] 1 H NMR (400MHz, CDCl3): δ=7.17 (dd, J=6.0, 4.4Hz, 2H), 7.05 (ddt, J=6.6, 4.6, 1.0Hz, 2H) ,3.48(td,J=13.6,1.0Hz,2H),3.03(td,J=13.6,1.0Hz,2H),1.52(s,9H),1.42(s,9H).

[0238] 13C NMR (100MHz, CDCl3): δ=177.43,135.37,131.45,126.38,77.87,49.53,28.30,22.60,22.58,22.55,22.53,20.85.

[0239] 31 P NMR (162MHz, CDCl3): δ = 13.65.

[0240] Preparation Example 12

[0241] Preparation of bidentate phosphine ligand 12

[0242]

[0243] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (12-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (12-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (12-b). Finally, the bidentate phosphine ligand 12 (349 mg, 83%) was obtained as a colorless oil.

[0244] NMR data of bidentate phosphine ligand 12:

[0245] 1 H NMR (400MHz, CDCl3): δ=7.17 (dd, J=5.9, 3.7Hz, 2H), 7.04 (ddt, J=5.8, 3.7, 1.0Hz, 2H), 6.19 ( s,1H),3.33(td,J=13.5,1.0Hz,2H),3.01(td,J=13.5,1.0Hz,2H),1.45(s,9H),1.40(s,9H).

[0246] 13 C NMR (100MHz, CDCl3): δ=177.81,135.71,131.44,126.31,68.67,57.39,28.58,24.13,21.56,21.53,21.51,21.48.

[0247] 31 P NMR (162MHz, CDCl3): δ=11.77.

[0248] Preparation Example 13

[0249] Preparation of bidentate phosphine ligand 13

[0250]

[0251] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (13-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (13-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (13-b). Finally, the bidentate phosphine ligand 13 (383 mg, 80%) was obtained as a colorless oil.

[0252] NMR data of bidentate phosphine ligand 13:

[0253] 1 H NMR (400MHz, CDCl3): δ = 7.16 (dd, J = 6.0, 4.4Hz, 1H), 7.07–6.99 (m, 1H), 4.04 (s, 2H), 3.39 ( td,J=13.5,1.0Hz,1H),2.92(td,J=13.5,1.0Hz,1H),2.35(s,2H),1.18(d,J=8.0Hz,14H).

[0254] 13 C NMR (100MHz, CDCl3): δ=173.06,136.83,131.47,126.34,68.72,46.76,41.62,41.13,27.58,23.72,23.69,23.66,23.63,21.76.

[0255] 31 P NMR (162MHz, CDCl3): δ = 43.13.

[0256] Preparation Example 14

[0257] Preparation of bidentate phosphine ligand 14

[0258]

[0259] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (14-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (14-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (14-b). Finally, the bidentate phosphine ligand 14 (530 mg, 79%) was obtained as a colorless oil.

[0260] NMR data of bidentate phosphine ligand 14:

[0261] 1 H NMR (400MHz, CDCl3): δ=7.40–7.32(m,2H),7.31–7.17(m,6H),7.16–7.09(m, 2H),7.07(dd,J=5.9,3.7Hz,1H),6.94(ddt,J=5.7,3.6,1.0Hz,1H),4.59(dd, J=9.4,5.0Hz,1H),4.30(dd,J=9.4,5.0Hz,1H),3.76(tt,J=6.4,1.0Hz,1H),3 .35–3.20(m,3H),3.17(dd,J=14.8,6.4Hz,1H),2.92(dd,J=14.8,6.4Hz,1H).

[0262] 13 C NMR (100MHz, CDCl3): δ=172.74,139.33,139.29,139.20,139.14,130.17,130.16,130.15,130.15,130.11,1 29.54,128.19,128.11,128.09,126.46,126.40,126.39,126.37,126.36,65.94,47.68,47.44,39.02,32.23.

[0263] 31 P NMR (162MHz, CDCl3): δ = 46.50.

[0264] Preparation Example 15

[0265] Preparation of bidentate phosphine ligand 15

[0266]

[0267] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (15-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (15-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (15-b). Finally, the bidentate phosphine ligand 15 (492 mg, 78%) was obtained as a colorless oil.

[0268] NMR data of bidentate phosphine ligand 15:

[0269] 1 H NMR (400MHz, CDCl3): δ = 7.38 (dt, J = 18.3, 1.5Hz, 2H), 7.21 (dd, J = 5.9, 3.8Hz, 1H), 7.14 (ddt, J = 6.5, 3.8, 1.0Hz, 1H), 6.37 (ddd, J=17.5, 7.8, 1.5Hz, 2H), 6.20 (ddd, J=7.9, 4.0, 1.5Hz, 2H), 4.87 (dd, J=9.4, 5.0Hz, 1H), 4.72 (t, J = 6.4Hz, 1H), 4.54 (dd, J = 9.5, 5.1Hz, 1H), 3.99 (t, J = 5.0Hz, 1H), 3.75 (ddd, J = 13.9, 13.1, 1. 0Hz, 1H), 3.26 (dd, J=14.6, 6.4Hz, 1H), 3.15 (ddd, J=13.8, 13.0, 0.9Hz, 1H), 3.01 (dd, J=14.8, 6.4Hz, 1H).

[0270] 13 C NMR (100MHz, CDCl3): δ=172.72,157.14,157.05,157.03,143.77,139.10,129.50,1 26.41,111.55,111.52,108.50,107.82,107.80,64.62,44.13,38.83,37.83,31.98.

[0271] 31 P NMR (162MHz, CDCl3): δ = 44.25.

[0272] Preparation Example 16

[0273] Preparation of bidentate phosphine ligand 16

[0274]

[0275] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (16-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (16-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (16-b). Finally, the bidentate phosphine ligand 16 (489 mg, 78%) was obtained as a colorless oil.

[0276] NMR data of bidentate phosphine ligand 16:

[0277] 1 H NMR (400MHz, CDCl3): δ = 7.20–7.12 (m, 5H), 7.06 (ddt, J = 5.8, 3.8, 1.1Hz, 1H), 6.03 (td, J = 4.2, 1.3Hz, 4H), 4.84 (t, J = 4.9Hz, 1H), 4.73 (t, J = 6.3Hz, 1H),4.62(dd,J=8.2,4.9Hz,1H),4.31(dd,J=8.2,4.9Hz,1H),3.45(ddd,J =13.8,13.0,0.9Hz,1H),3.05–2.95(m,2H),2.92(dd,J=13.7,6.2Hz,1H).

[0278] 13 C NMR (100MHz, CDCl3): δ=172.76,139.26,129.42,126.42,122.78,122.72,122.67,122.6 1,122.44,110.05,110.04,110.02,110.01,109.94,66.44,63.51,58.28,37.95,29.96.

[0279] 31 P NMR (162MHz, CDCl3): δ = 45.17.

[0280] Preparation Example 17

[0281] Preparation of bidentate phosphine ligand 17

[0282]

[0283] The preparation was carried out in the same manner as in Preparation Example 2, except that the 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (17-a-1), the 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (17-a), and the bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (17-b). Finally, the bidentate phosphine ligand 17 (533 mg, 79%) was obtained as a colorless oil.

[0284] NMR data of bidentate phosphine ligand 17:

[0285] 1 H NMR (400MHz, CDCl3): δ = 8.66 (ddd, J = 4.8, 3.5, 1.5Hz, 2H), 7.64 (tdd, J = 7.7, 2.7, 1.6Hz, 2H), 7. 25(ddd,J=12.9,7.8,1.4Hz,2H),7.24–7.16(m,3H),7.06(ddt,J=5.7,3.6,1.0Hz,1H),5.01(dd ,J=9.4,5.0Hz,1H),4.49(dd,J=9.4,5.0Hz,1H),4.00(t,J=6.4Hz,1H),3.52(dqd,J=14.1,13.0 ,1.0Hz,2H),3.34(dd,J=14.8,6.4Hz,1H),3.26(t,J=5.0Hz,1H),3.01(dd,J=14.8,6.4Hz,1H).

[0286] 13 C NMR (100MHz, CDCl3): δ=172.27,160.28,160.25,160.04,150.38,139.18,137.95,137.93,137.91,1 29.57,126.37,122.23,122.19,122.17,121.17,121.17,121.01,64.86,56.28,49.35,38.28,32.21.

[0287] 31 P NMR (162MHz, CDCl3): δ = 47.98.

[0288] Preparation Example 18

[0289] Preparation of bidentate phosphine ligand 18

[0290]

[0291] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (18-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (18-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (18-b). Finally, the bidentate phosphine ligand 18 (521 mg, 75%) was obtained as a colorless oil.

[0292] NMR data of bidentate phosphine ligand 18:

[0293] 1 H NMR (400MHz, CDCl3): δ = 7.14 (t, J = 4.5Hz, 1H), 7.09–7.03 (m, 1H), 4.35–4.27 (m,1H),4.03–3.95(m,1H),3.35(ddd,J=13.7,12.4,1.0Hz,1H),2.94(ddd,J= 12.3,7.6,1.4Hz,1H),2.80(ddd,J=13.5,12.4,1.0Hz,1H),2.67(ddd,J=12.3 ,7.6,1.4Hz,1H),2.27–2.17(m,1H),1.74–1.42(m,16H),1.34–1.11(m,11H).

[0294] 13 C NMR (100MHz, CDCl3): δ=173.37,139.17,129.54,126.45,63.85,43.33,41.78,41.76,41.71,37.23,31.51, 29.94,27.74,27.68,27.63,27.58,27.16,26.29,26.28,26.26,26.25,26.00,25.96,25.93,25.89,25.78.

[0295] 31 P NMR (162MHz, CDCl3): δ = 36.33.

[0296] Preparation Example 19

[0297] Preparation of bidentate phosphine ligand 19

[0298]

[0299]

[0300] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (19-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (19-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (19-b). Finally, the bidentate phosphine ligand 19 (381 mg, 80%) was obtained as a colorless oil.

[0301] NMR data of bidentate phosphine ligand 19:

[0302] 1 H NMR (400MHz, CDCl3): δ=7.17 (dd, J=5.9, 3.7Hz, 1H), 7.03 (ddt, J=5.8, 3.7, 1.0Hz, 1H), 6.73 (t, J= 5.3Hz,1H),3.35–3.25(m,3H),2.93(td,J=13.6,1.0Hz,1H),2.25(s,1H),1.18(d,J=6.2Hz,12H).

[0303] 13 C NMR (100MHz, CDCl3): δ=172.94,136.70,131.45,126.34,47.30,41.66,41.53,38.89,27.50,23.72,22.61,22.57,22.54,22.51.

[0304] 31 P NMR (162MHz, CDCl3): δ = 40.87.

[0305] Preparation Example 20

[0306] Preparation of bidentate phosphine ligand 20

[0307]

[0308] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (20-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (20-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (20-b). Finally, the bidentate phosphine ligand 20 (324 mg, 83%) was obtained as a colorless oil.

[0309] NMR data of bidentate phosphine ligand 20:

[0310] 1 H NMR (400MHz, CDCl3): δ=7.17 (dd, J=6.0, 4.4Hz, 1H), 7.06 (ddt, J=6.6, 4.4, 1.0Hz, 1H), 3.23 (dd, J=13.7, 1.0Hz, 2H), 1.40 (s, 9H).

[0311] 13 C NMR (100MHz, CDCl3): δ = 207.63, 131.24, 130.75, 126.30, 50.77, 26.94, 22.17.

[0312] 31 P NMR (162MHz, CDCl3): δ = 58.56.

[0313] Preparation Example 21

[0314] Preparation of bidentate phosphine ligand 21

[0315]

[0316] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (21-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (21-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (21-b). Finally, the bidentate phosphine ligand 21 (405 mg, 80%) was obtained as a colorless oil.

[0317] NMR data of bidentate phosphine ligand 21:

[0318] 1 H NMR (400MHz, CDCl3): δ = 7.17 (dd, J = 5.8, 3.7Hz, 2H), 7.04 (ddt, J = 5.7, 3.6, 1.0Hz, 2H), 4.04 (s, 3H), 3.35 (td, J = 13. 4,1.0Hz,2H),2.89(td,J=13.5,1.0Hz,2H),2.33(t,J=8.0Hz,4H),1.69(t,J=8.1Hz,4H),1.18(s,9H),1.12(s,9H).

[0319] 13C NMR (100MHz, CDCl3): δ=172.37,136.83,131.21,126.44,69.41,45.77,38.67,33.36,31.69,27.91,23.60,21.84,21.81,21.77,21.74.

[0320] 31 P NMR (162MHz, CDCl3): δ=36.39.

[0321] Preparation Example 22

[0322] Preparation of bidentate phosphine ligand 22

[0323]

[0324] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (22-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (22-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (22-b). Finally, the bidentate phosphine ligand 22 (394 mg, 78%) was obtained as a colorless oil.

[0325] NMR data of bidentate phosphine ligand 22:

[0326] 1 H NMR (400MHz, CDCl3): δ = 7.17 (dd, J = 5.9, 3.7Hz, 1H), 7.04 (ddt, J = 5.7, 3.6, 1.0Hz, 1H), 6.73 (t, J = 5.3Hz, 1H), 3.37 (dd, J = 12.7, 5. 4Hz,1H),3.35–3.26(m,2H),2.96(td,J=13.4,0.9Hz,1H),2.28(t,J=8.0Hz,2H),1.61(t,J=8.1Hz,2H),1.18(s,4H),1.10(s,4H).

[0327] 13 C NMR (100MHz, CDCl3): δ=173.56,136.80,131.21,126.44,51.18,39.01,38.60,33.87,33.02,27.83,23.73,23.70,23.67,23.64,22.50.

[0328] 31P NMR (162MHz, CDCl3): δ = 34.25.

[0329] Preparation Example 23

[0330] Preparation of bidentate phosphine ligand 23

[0331]

[0332]

[0333] The preparation was carried out in the same manner as in Preparation Example 2, except that the 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (23-a-1), the 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (23-a), and the bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (23-b). Finally, the bidentate phosphine ligand 23 (312 mg, 75%) was obtained as a colorless oil.

[0334] NMR data of bidentate phosphine ligand 23:

[0335] 1 H NMR (400MHz, CDCl3): δ=7.17 (dd, J=5.8, 3.6Hz, 1H), 7.04 (ddt, J=5.7, 3.6, 1.0Hz, 1H), 4. 09–4.00(m,2H),3.45–3.35(m,1H),2.98(td,J=13.4,13.0,1.1Hz,1H),2.21–2.08(m,4H).

[0336] 13 C NMR (100MHz, CDCl3): δ=138.21,138.16,138.13,138.08,129.45,129.42,129.41, 129.37,126.23,126.20,66.26,66.07,31.05,30.95,30.34,30.30,30.15,30.12.

[0337] 31 P NMR (162MHz, CDCl3): δ = 40.25.

[0338] Preparation Example 24

[0339] Preparation of bidentate phosphine ligand 24

[0340]

[0341] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (24-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (24-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (24-b). Finally, the bidentate phosphine ligand 24 (451 mg, 76%) was obtained as a colorless oil.

[0342] NMR data of bidentate phosphine ligand 24:

[0343] 1 H NMR (400MHz, CDCl3): δ=7.16 (dd, J=5.9, 3.8Hz, 1H), 7.10 (dddd, J=5.8, 3.7, 2.9, 1.0Hz, 1H), 3.89 (dddd ,J=5.7,3.7,2.4,1.3Hz,2H),3.46–3.37(m,1H),3.18(ddd,J=13.8,12.9,0.9Hz,1H),2.34–2.20(m,4H).

[0344] 13 C NMR (100MHz, CDCl3): δ=137.92,137.88,137.84,137.79,129.37,129.33,129. 32,129.29,126.25,126.22,51.82,51.64,31.21,31.18,31.12,31.02,31.00.

[0345] 31 P NMR (162MHz, CDCl3): δ = 43.78.

[0346] Preparation Example 25

[0347] Preparation of bidentate phosphine ligand 25

[0348]

[0349] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (25-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (25-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (25-b). Finally, the bidentate phosphine ligand 25 (234 mg, 83%) was obtained as a colorless oil.

[0350] NMR data of bidentate phosphine ligand 25:

[0351] 1 H NMR (400MHz, CDCl3): δ = 7.16 (dd, J = 5.8, 3.7Hz, 1H), 7.04 (ddt, J = 5.8, 3.7, 1.0Hz, 1H), 3.80–3.68 (m, 2H), 3.46 (d, J = 13.7Hz,1H),3.13(ddd,J=13.7,12.8,0.9Hz,1H),2.83(ddd,J=13.8,12.8,0.9Hz,1H),2.38(dt,J=13.7,4.6Hz,2H).

[0352] 13 C NMR (100MHz, CDCl3): δ=138.00,137.96,137.92,137.88,129.95,129.92,129.90,129.87 ,126.26,126.23,69.41,69.22,65.42,65.33,30.47,30.44,30.29,30.25,26.79,26.60.

[0353] 31 P NMR (162MHz, CDCl3): δ = 32.11.

[0354] Preparation Example 26

[0355] Preparation of bidentate phosphine ligand 26

[0356]

[0357] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (26-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (26-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (26-b). Finally, the bidentate phosphine ligand 26 (250 mg, 81%) was obtained as a colorless oil.

[0358] NMR data of bidentate phosphine ligand 26:

[0359] 1 H NMR (400MHz, CDCl3): δ = 7.15 (dd, J = 5.9, 3.7Hz, 1H), 7.06 (ddt, J = 5.8, 3.8, 1.1Hz, 1H), 3.12 (ddd, J = 13.8, 12.9, 1.1Hz, 1H), 3.01 (ddd, J = 11.0, 4.4,3.4Hz,1H),2.92–2.79(m,2H),2.54(d,J=13.5Hz,1H),2.32(s,2H),2.25(tdd,J=13.4,4.3,3.4Hz,1H),1.80(tdd,J=13.4,4.4,3.3Hz,1H).

[0360] 13 C NMR (100MHz, CDCl3): δ = 137.45, 129.78, 126.27, 58.14, 50.05, 40.55, 30.64, 27.66.

[0361] 31 P NMR (162MHz, CDCl3): δ = 33.26.

[0362] Preparation Example 27

[0363] Preparation of bidentate phosphine ligand 27

[0364]

[0365] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (27-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (27-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (27-b). Finally, the bidentate phosphine ligand 27 (245 mg, 79%) was obtained as a colorless oil.

[0366] NMR data of bidentate phosphine ligand 27:

[0367] 1 H NMR (400MHz, CDCl3): δ=7.15 (dd, J=5.9, 3.7Hz, 1H), 7.04 (ddt, J=5.8, 3.7, 1.0Hz, 1H), 3.54–3.43 (m, 4H), 2.93 (dd, J=13.7, 1.0Hz, 2H), 1.78 (dt, J=13.7, 5.6Hz, 4H).

[0368] 13 C NMR (100MHz, CDCl3): δ=137.67,137.63,137.59,137.55,130.06,130.03,130.01, 129.98,126.22,126.19,66.01,65.92,31.65,31.61,31.46,31.43,27.05,26.87.

[0369] 31 P NMR (162MHz, CDCl3): δ=46.74.

[0370] Preparation Example 28

[0371] Preparation of bidentate phosphine ligand 28

[0372]

[0373] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (28-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (28-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (28-b). Finally, the bidentate phosphine ligand 28 (269 mg, 80%) was obtained as a colorless oil.

[0374] NMR data of bidentate phosphine ligand 28:

[0375] 1 H NMR (400MHz, CDCl3): δ = 7.15 (dd, J = 5.9, 3.7Hz, 1H), 7.03 (ddt, J = 5.7, 3.6, 0.9Hz, 1H), 2 .91(dd,J=13.7,1.1Hz,2H),2.50(dd,J=5.3,4.6Hz,4H),2.27(s,2H),1.71–1.62(m,4H).

[0376] 13 C NMR (100MHz, CDCl3): δ = 137.46, 129.74, 126.23, 50.48, 45.48, 31.46, 26.82.

[0377] 31 P NMR (162MHz, CDCl3): δ = 51.68.

[0378] Preparation Example 29

[0379] Preparation of bidentate phosphine ligand 29

[0380]

[0381] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (29-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (29-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (29-b). Finally, the bidentate phosphine ligand 29 (245 mg, 78%) was obtained as a colorless oil.

[0382] NMR data of bidentate phosphine ligand 29:

[0383] 1 H NMR (400MHz, CDCl3): δ=7.17 (dd, J=5.9, 3.7Hz, 1H), 6.97 (ddt, J=5.7, 3.7, 1.0Hz, 1H), 4.68 ( d,J=2.9Hz,1H),4.42(d,J=2.7Hz,1H),3.49(d,J=13.7Hz,3H),3.00(dd,J=13.7,0.9Hz,2H).

[0384] 13C NMR (100MHz, CDCl3): δ=137.94,137.89,137.86,137.81,129.97,129.94,129.92, 129.89,126.20,126.16,96.84,96.77,65.96,65.77,30.29,30.25,30.10,30.07.

[0385] 31 P NMR (162MHz, CDCl3): δ = 48.63.

[0386] Preparation Example 30

[0387] Preparation of bidentate phosphine ligand 30

[0388]

[0389] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (30-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (30-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (30-b). Finally, the bidentate phosphine ligand 30 (286 mg, 78%) was obtained as a colorless oil.

[0390] NMR data of bidentate phosphine ligand 30:

[0391] 1 H NMR (400MHz, CDCl3): δ=7.16 (dd, J=5.9, 3.7Hz, 2H), 7.03 (ddt, J=5.8, 3.8, 1.0Hz, 2 H),3.18(s,3H),2.97(dd,J=13.7,1.0Hz,4H),2.62(d,J=13.5Hz,6H),2.30(s,9H).

[0392] 13 C NMR (100MHz, CDCl3): δ = 136.99, 129.87, 126.28, 74.81, 54.82, 43.68, 32.24.

[0393] 31 P NMR (162MHz, CDCl3): δ = 53.95.

[0394] Preparation Example 31

[0395] Preparation of bidentate phosphine ligand 31

[0396]

[0397] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (31-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (31-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (31-b). Finally, the bidentate phosphine ligand 31 (389 mg, 82%) was obtained as a colorless oil.

[0398] NMR data of bidentate phosphine ligand 31:

[0399] 1 H NMR (400MHz, CDCl3): δ = 7.18 (dd, J = 6.1, 4.4Hz, 1H), 7.08–7.00 (m, 1H), 3.36 (td, J = 13.5, 1.0Hz, 1 H),2.93(td,J=13.4,0.9Hz,1H),2.49–2.37(m,3H),1.65–1.50(m,2H),1.18(s,4H),1.12(s,4H).

[0400] 13 C NMR (100MHz, CDCl3): δ=213.65,136.74,131.45,126.37,43.79,43.70,42.33,40.29,38.78,33.04,27.66,23.74,23.71,23.68,23.64,23.53.

[0401] 31 P NMR (162MHz, CDCl3): δ = 48.98.

[0402] Preparation Example 32

[0403] Preparation of bidentate phosphine ligand 32

[0404]

[0405] The preparation was carried out in the same manner as in Preparation Example 2, except that 1-hydroxy-1-oxo-2,5-diphenylphosphine (2-a-1) in Preparation Example 2 was changed to an equimolar amount of a compound of formula (32-a-1), 2,5-diphenylphosphine-borane complex (2-a) was changed to an equimolar amount of a compound of formula (32-a), and bis(2,5-diphenylphosphine-borane) (2-b) was changed to an equimolar amount of a compound of formula (32-b). Finally, the bidentate phosphine ligand 32 (407 mg, 81%) was obtained as a colorless oil.

[0406] NMR data of bidentate phosphine ligand 32:

[0407] 1 H NMR (400MHz, CDCl3): δ = 7.15 (dd, J = 6.0, 4.4Hz, 1H), 7.06 (ddt, J = 6.6, 4.6, 1.1Hz, 1H), 3.07(dd,J=13.7,0.9Hz,2H),2.41(t,J=8.1Hz,4H),1.58(t,J=8.1Hz,4H),1.13(s,9H).

[0408] 13 C NMR (100MHz, CDCl3): δ=211.53,136.71,131.51,126.46,38.82,36.89,33.51,28.01,23.58.

[0409] 31 P NMR (162MHz, CDCl3): δ = 46.10.

[0410] Preparation Example 33

[0411] Preparation of Bis((di-tert-butylphosphino)methyl)-4-tert-butyl-benzene

[0412]

[0413] 4-tert-Butyl-o-xylene (4.55 g, 28.1 mmol) (Aldrich) was diluted with heptane (100 ml) and NaOBu was added thereto. t (8.1 g, 84.3 mmol), TMEDA (12.6 ml, 84.3 mmol) and Bu n Li (2.5 M 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.

[0414] 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 washings were then removed by cannula. The solid residue was then suspended in pentane (100 ml) and cooled in a cold water bath. But2PCl (7.5 ml, 39.3 mmol) was added dropwise to the suspension. The resulting suspension was stirred for 3 hours and allowed to stand overnight.

[0415] 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 removed by cannula to a clean Schlenk bottle. The pentane extract was dried over sodium sulfate and transferred to a clean Schlenk bottle by 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 matter. The solution was then cooled to room temperature and filtered into a clean Schlenk bottle. The solution was then placed in a freezer at -20° C. overnight to produce a grayish white solid precipitate. The remaining methanol solution was then removed by cannula and the solid was dried under vacuum. The solid was separated in a glove box. Bidentate phosphine ligand 31 (4.20 g, 33% yield) was obtained.

[0416] Preparation Example 34

[0417] Preparation of Bis((di-tert-butylphosphino)methyl)benzene

[0418]

[0419] The same method as Preparation Example 31 was used except that 4-tert-butyl-o-xylene was replaced with an equimolar amount of o-xylene to obtain a white solid bidentate phosphine ligand 32 (4.5 g, yield 40%).

[0420] Example 1

[0421] 1000 g (31.25 mol) of methanol, 91.57 mg (0.10 mmol) of tris(dibenzylideneacetone)dipalladium, 0.77 g (8 mmol) of methanesulfonic acid, and bidentate phosphine ligand 1 (167.21 mg, 0.50 mmol) were placed in a sealed 2 L autoclave. Ethylene and carbon monoxide at a molar ratio of 4:1 were introduced into the autoclave at a carbon monoxide flow rate of 1.2 L / min. The reaction was carried out at a stirring speed of 500 rpm, a reaction pressure of 1.2 MPa, and a reaction temperature of 60°C for 120 min.

[0422] 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.

[0423] Example 2

[0424] In addition, 91.57 mg of tris(dibenzylideneacetone)dipalladium was replaced with diaminopalladium dichloride

[0425] The reaction was carried out in the same manner as in Example 1, except that 42.28 mg (0.20 mmol) of methanol was used, the mass of methanol was changed to 500 g (15.63 mmol), and 291.35 mg (0.50 mmol) of bidentate phosphine ligand 2 was used.

[0426] 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.

[0427] Example 3

[0428] The reaction was carried out in the same manner as in Example 1, except that 91.57 mg of tris(dibenzylideneacetone)dipalladium was replaced by 46.50 mg (0.20 mmol) of dinitrosodiamminepalladium, the mass of methanol was changed to 500 g (15.63 mmol), and 187.20 mg (0.50 mmol) of bidentate phosphine ligand 3 was used.

[0429] 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.

[0430] Example 4

[0431] The reaction was carried out in the same manner as in Example 1, except that 0.77 g of methanesulfonic acid was replaced by 1.27 g (8 mmol) of benzenesulfonic acid and 237.26 mg (0.50 mmol) of bidentate phosphine ligand 4 was used.

[0432] 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.

[0433] Example 5

[0434] The reaction was carried out in the same manner as in Example 1, except that 0.77 g of methanesulfonic acid was replaced with 1.38 g (8 mmol) of p-toluenesulfonic acid and 235.25 mg (0.50 mmol) of bidentate phosphine ligand 5 was used. An appropriate amount of the reaction mixture was weighed and analyzed by GC chromatography. The conversion 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.

[0435] Example 6

[0436] The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed to 80° C. and 176.18 mg (0.50 mmol) of the bidentate phosphine ligand 6 was used.

[0437] 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.

[0438] Example 7

[0439] The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed to 100° C. and 177.17 mg (0.50 mmol) of the bidentate phosphine ligand 7 was used.

[0440] 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.

[0441] Example 8

[0442] In addition, 91.57 mg of tris(dibenzylideneacetone)dipalladium was replaced by [Rh(COD)Cl]2

[0443] The reaction was carried out in the same manner as in Example 1, except that 49.31 mg (0.10 mmol) of methanol was used, the mass of methanol was changed to 500 g (15.63 mmol), and 188.19 mg (0.50 mmol) of bidentate phosphine ligand 8 was used.

[0444] 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.

[0445] Example 9

[0446] In addition, 91.57 mg of tris(dibenzylideneacetone)dipalladium was replaced by [Ir(COD)Cl]2

[0447] The reaction was carried out in the same manner as in Example 1, except that 67.17 mg (0.10 mmol) of methanol was used, the mass of methanol was changed to 500 g (15.63 mmol), and 327.47 mg (0.50 mmol) of bidentate phosphine ligand 9 was used.

[0448] 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.

[0449] Example 10

[0450] The reaction was carried out in the same manner as in Example 1 except that 209.25 mg (0.50 mmol) of the bidentate phosphine ligand 10 was used.

[0451] 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.

[0452] Example 11

[0453] The reaction was carried out in the same manner as in Example 1 except that 211.22 mg (0.50 mmol) of the bidentate phosphine ligand 11 was used.

[0454] 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.

[0455] Example 12

[0456] The reaction was carried out in the same manner as in Example 1 except that 210.24 mg (0.50 mmol) of the bidentate phosphine ligand 12 was used.

[0457] 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.

[0458] Example 13

[0459] The reaction was carried out in the same manner as in Example 1 except that 239.27 mg (0.50 mmol) of the bidentate phosphine ligand 13 was used.

[0460] 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.

[0461] Example 14

[0462] The reaction was carried out in the same manner as in Example 7, except that 335.37 mg (0.50 mmol) of bidentate phosphine ligand 14 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was changed to the same molar ratio of 1-hexene to carbon monoxide.

[0463] 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 heptanoate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0464] Example 15

[0465] The reaction was carried out in the same manner as in Example 7, except that 315.29 mg (0.50 mmol) of the bidentate phosphine ligand 15 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was changed to the same molar ratio of 1-pentene to carbon monoxide.

[0466] 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 hexanoate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0467] Example 16

[0468] The reaction was carried out in the same manner as in Example 7, except that 313.32 mg (0.50 mmol) of bidentate phosphine ligand 16 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was replaced with the same molar ratio of 3-methyl-1-butene to carbon monoxide.

[0469] 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 3-methylvalerate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0470] Example 17

[0471] The reaction was carried out in the same manner as in Example 7, except that 337.34 mg (0.50 mmol) of bidentate phosphine ligand 17 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was replaced with the same molar ratio of 3,3-dimethyl-1-butene to carbon monoxide.

[0472] 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 3,3-dimethylvalerate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0473] Example 18

[0474] The reaction was carried out in the same manner as in Example 7, except that 347.46 mg (0.50 mmol) of the bidentate phosphine ligand 18 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was changed to the molar ratio of styrene to carbon monoxide of styrene.

[0475] 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 phenylpropionate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0476] Example 19

[0477] The reaction was carried out in the same manner as in Example 7, except that 238.29 mg (0.50 mmol) of bidentate phosphine ligand 19 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was changed to the same molar ratio of 2-butene to carbon monoxide.

[0478] 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 2-methylbutyrate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0479] Example 20

[0480] The reaction was carried out in the same manner as in Example 7, except that 195.22 mg (0.50 mmol) of the bidentate phosphine ligand 20 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was changed to the molar ratio of cyclohexene to carbon monoxide of the same ratio.

[0481] 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 cyclohexylcarboxylate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0482] Example 21

[0483] The reaction was carried out in the same manner as in Example 7, except that 253.30 mg (0.50 mmol) of bidentate phosphine ligand 21 was used and the molar ratio of ethylene to carbon monoxide of 4:1 was changed to the same molar ratio of 3-hexene to carbon monoxide.

[0484] 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 2-ethylpentanoate, were calculated based on carbon monoxide. The results are shown in Table 1.

[0485] Example 22

[0486] The reaction was carried out in the same manner as in Example 1 except that 252.32 mg (0.50 mmol) of the bidentate phosphine ligand 22 was used.

[0487] 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.

[0488] Example 23

[0489] The reaction was carried out in the same manner as in Example 1 except that 208.05 mg (0.50 mmol) of the bidentate phosphine ligand 23 was used.

[0490] 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.

[0491] Example 24

[0492] The reaction was carried out in the same manner as in Example 1 except that 296.95 mg (0.50 mmol) of the bidentate phosphine ligand 24 was used.

[0493] 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.

[0494] Example 25

[0495] The reaction was carried out in the same manner as in Example 1 except that 141.13 mg (0.50 mmol) of the bidentate phosphine ligand 25 was used.

[0496] 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.

[0497] Example 26

[0498] The reaction was carried out in the same manner as in Example 1 except that 154.17 mg (0.50 mmol) of the bidentate phosphine ligand 26 was used.

[0499] 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.

[0500] Example 27

[0501] The reaction was carried out in the same manner as in Example 1 except that 155.16 mg (0.50 mmol) of the bidentate phosphine ligand 27 was used.

[0502] 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.

[0503] Example 28

[0504] The reaction was carried out in the same manner as in Example 1 except that 168.20 mg (0.50 mmol) of the bidentate phosphine ligand 28 was used.

[0505] 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.

[0506] Example 29

[0507] The reaction was carried out in the same manner as in Example 1 except that 157.13 mg (0.50 mmol) of the bidentate phosphine ligand 29 was used.

[0508] 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.

[0509] Example 30

[0510] The reaction was carried out in the same manner as in Example 1 except that 183.21 mg (0.50 mmol) of the bidentate phosphine ligand 30 was used.

[0511] 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.

[0512] Example 31

[0513] The reaction was carried out in the same manner as in Example 1 except that 237.30 mg (0.50 mmol) of the bidentate phosphine ligand 31 was used.

[0514] 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.

[0515] Example 32

[0516] The reaction was carried out in the same manner as in Example 1 except that 251.33 mg (0.50 mmol) of the bidentate phosphine ligand 32 was used.

[0517] 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.

[0518] Example 33

[0519] The reaction was carried out in the same manner as in Example 1 except that 177.06 mg (0.37 mmol) of the bidentate phosphine ligand 13, 67.76 mg (0.07 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.57 g (5.92 mmol) of methanesulfonic acid were used.

[0520] 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.

[0521] Example 34

[0522] The reaction was carried out in the same manner as in Example 1 except that 670.73 mg (1.00 mmol) of the bidentate phosphine ligand 14, 183.15 mg (0.20 mmol) of tris(dibenzylideneacetone)dipalladium and 1.54 g (16 mmol) of methanesulfonic acid were used.

[0523] 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.

[0524] Example 35

[0525] The reaction was carried out in the same manner as in Example 1 except that 187.44 mg (0.37 mmol) of the bidentate phosphine ligand 21, 67.76 mg (0.07 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.57 g (5.92 mmol) of methanesulfonic acid were used.

[0526] 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.

[0527] Example 36

[0528] The reaction was carried out in the same manner as in Example 1 except that 957.08 mg (2.00 mmol) of the bidentate phosphine ligand 13 was used.

[0529] 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.

[0530] Example 37

[0531] The reaction was carried out in the same manner as in Example 1 except that 239.27 mg (0.50 mmol) of the bidentate phosphine ligand 13 and 0.04 g (0.4 mmol) of methanesulfonic acid were used.

[0532] 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.

[0533] Example 38

[0534] The reaction was carried out in the same manner as in Example 1 except that 239.27 mg (0.50 mmol) of the bidentate phosphine ligand 13 and 1.92 g (20 mmol) of methanesulfonic acid were used.

[0535] 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.

[0536] Example 39

[0537] The reaction was carried out in the same manner as in Example 1 except that 239.27 mg (0.50 mmol) of the bidentate phosphine ligand 13, 0.96 g (10 mmol) of methanesulfonic acid and 50 g (1.56 mol) of methanol were used.

[0538] 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.

[0539] Example 40

[0540] The reaction was carried out in the same manner as in Example 1 except that 133.99 mg (0.28 mmol) of the bidentate phosphine ligand 13, 51.28 mg (0.06 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (4.48 mmol) of methanesulfonic acid were used.

[0541] 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.

[0542] Example 41

[0543] The reaction was carried out in the same manner as in Example 1 except that 506.59 mg (1.00 mmol) of the bidentate phosphine ligand 21 and 0.19 g (2 mmol) of methanesulfonic acid were used.

[0544] 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.

[0545] Example 42

[0546] The reaction was carried out in the same manner as in Example 1 except that 506.59 mg (1.00 mmol) of the bidentate phosphine ligand 21 and 1.92 g (20 mmol) of methanesulfonic acid were used.

[0547] 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.

[0548] Example 43

[0549] The reaction was carried out in the same manner as in Example 1 except that 506.59 mg (1.00 mmol) of the bidentate phosphine ligand 21 and 0.96 g (10 mmol) of methanesulfonic acid were used.

[0550] 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.

[0551] Comparative Example 1

[0552] The reaction was carried out in the same manner as in Example 1, except that the amount of tris(dibenzylideneacetone)dipalladium was changed to 183.15 mg (0.20 mmol), the amount of methanesulfonic acid was changed to 1.54 g (16 mmol), and 450.66 mg (1.00 mmol) of bidentate phosphine ligand 33 was used.

[0553] 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.

[0554] Comparative Example 2

[0555] The reaction was carried out in the same manner as in Example 1, except that the amount of tris(dibenzylideneacetone)dipalladium was changed to 183.15 mg (0.20 mmol), the amount of methanesulfonic acid was changed to 1.54 g (16 mmol), and 394.55 mg (1.00 mmol) of bidentate phosphine ligand 34 was used.

[0556] 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.

[0557] Table 1

[0558]

[0559]

[0560]

[0561]

[0562]

[0563] As can be seen from Table 1, in the olefin carbonylation method provided by the present invention, Examples 1-43 using a catalyst system comprising a specific bidentate phosphine ligand, compared to Comparative Examples 1-2 using a catalyst system comprising other bidentate phosphine ligands, the amount of bidentate phosphine ligand and Group VIII metal compound used was less, the product selectivity and yield were higher, and the conversion rate of the reaction substrate was also higher. Among them, in Examples 11, 12-19, 21, 22, and 33-43 using a bidentate phosphine ligand in which the monocyclic group was a lactone group or a lactam group in the catalyst system, the product selectivity and yield were further higher, and in Examples 11, 13-18, 21, 33-36, 40, and 43 using a bidentate phosphine ligand in which the monocyclic group was a lactone group, the product selectivity and yield were the highest.

Claims

1. A carbonylation process comprising reacting ethylene with carbon monoxide and an alcohol in the presence of a catalyst system; in, The catalyst system comprises the following components: (a) Group VIII metals or Group VIII metal compounds; (b) a bidentate phosphine ligand; and (c) acidic additives; Wherein, the (b) bidentate phosphine ligand is selected from one or more of the following groups: The acidic auxiliary agent of the component (c) includes 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.

2. The method according to claim 1, wherein The molar ratio of the ethylene to the carbon monoxide is 1:1 to 100:1; The molar ratio of the ethylene to the component (a) in the catalyst system is 50:1 to 600:1; The mass ratio of the alcohol to the component (a) in the catalyst system is 500:1 to 20000:

1.

3. The method according to claim 1 or 2, wherein The operating conditions of the reaction are: The reaction pressure is 1-20 MPa; the reaction temperature is 50-200°C.

4. The method according to claim 1 or 2, wherein: 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.

5. The method according to claim 1 or 2, wherein: The alcohol is a C1-C6 monohydric alkanol.

6. The method according to claim 1, wherein The molar ratio of component (b) to component (a) is 2:1 to 10:1; The molar ratio of component (c) to component (a) is 2:1 to 100:

1.

7. The method according to claim 1 or 6, characterized in that In the component (a): The Group VIII metal includes cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum; The compound of the Group VIII metal includes: a compound formed by 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.

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