CN115819234B - A method for olefin carbonylation reaction - Google Patents
A method for olefin carbonylation reaction Download PDFInfo
- Publication number
- CN115819234B CN115819234B CN202111573303.9A CN202111573303A CN115819234B CN 115819234 B CN115819234 B CN 115819234B CN 202111573303 A CN202111573303 A CN 202111573303A CN 115819234 B CN115819234 B CN 115819234B
- Authority
- CN
- China
- Prior art keywords
- acid
- group
- reaction
- olefin
- catalyst system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a process for the carbonylation of olefins. The process comprises reacting an olefin with carbon monoxide and an alcohol in the presence of se:Sup>A catalyst system comprising (se:Sup>A) se:Sup>A group VIII metal or compound thereof, (b) se:Sup>A bidentate phosphine ligand having se:Sup>A structure represented by the general formulse:Sup>A (I) (R1) (R2) P-K-A-K-P (R3) (R4) (I), and (c) an acidic auxiliary agent. According to the method provided by the invention, the catalyst system adopted has higher catalytic activity, greatly reduces the consumption of bidentate phosphine ligand and VIII metal or a compound thereof in the catalyst system, has the advantages of good product selectivity, high conversion rate of reaction substrates, long service life and the like, can efficiently catalyze the carbonylation reaction of olefin to synthesize ester products, ensures higher yield of the products, improves the catalytic efficiency of the reaction, and reduces the residence time of the reaction substrates.
Description
Technical Field
The present invention relates to a process for the carbonylation of olefins, and in particular to a process for the carbonylation of olefins in the presence of a catalyst system comprising a specific bidentate phosphine ligand.
Background
In chemical studies of the past few decades, catalyst systems comprising transition metal and phosphine ligands have been widely used in various reaction types, such as cross-coupling reactions (Buchwald-Hartwig C-N bond and C-O bond formation reactions, stille reactions, sonogashira reactions, suzuki-Miyaura reactions, etc.), asymmetric hydrogenation reactions and carbonylation reactions, due to their high catalytic activity and high selectivity. As one of the olefin carbonylation reactions, as shown in the following reaction formula 1, it includes converting an unsaturated hydrocarbon such as an olefin, CO and an alcohol into the corresponding saturated carboxylic acid ester in the presence of one metal/ligand or metal complex.
The saturated carboxylic ester is an important fine chemical product and is widely applied to the fields of medicines, resins, coatings, food solvents, plasticizers, cosmetics and the like. Since the discovery of the first olefin carbonylation reaction in 1938, such reactions have been one of the focus of research in the fields of organic synthesis and catalysis. In the carbonylation of olefins, methyl propionate, the carbonylation reaction product of ethylene, is an important intermediate in the preparation of methyl methacrylate.
Patent WO1996019434A1 discloses a process for the carbonylation of ethylene and a catalyst system for use in the process. The catalyst system comprises a group VIII metal or compound thereof and a bidentate phosphine ligand having a tertiary carbon group and having an aryl bridge, the bidentate phosphine ligand being represented by bis (di-t-butylphosphino) o-xylene, in particular. The catalyst system shows a better reaction rate in olefin carbonylation reactions, but the catalyst tends to be deactivated during the continuous operation phase due to the reduction of the palladium compound to palladium metal, resulting in higher cost and limited industrial application.
EP0495547A discloses the carbonylation of olefins. And discloses that the catalyst system used for the carbonylation comprises a palladium cation source, an anion source and a bidentate diphosphine having the structure of formula I, R 1R2P–X–P–R3R4 (I), examples of which include 1, 3-bis (diisopropylphosphino) propane, 1, 5-bis (dimethylphosphino) -3-oxapentane, and the like. The bidentate diphosphine containing catalyst system provides significantly higher reaction rates, product yields and/or selectivities in various monocarbonylations. However, it has the disadvantage that the ligand is easily dissociated, which results in poisoning of the catalyst and is not recyclable.
Patent US6156934a discloses a 2-phosphorus-tricyclo [3.3.1.1{3,7} ] decyl-containing bisphosphonate which is a bidentate phosphine ligand with a covalent bridging group for the carbonylation of unsaturated compounds, having the formula R 1>P-R2-P<R1, specific compounds such as 1,3-P, P' -bis (2-phosphorus-1, 3,5, 7-tetramethyl-6, 9, 10-trioxytricyclo [3.3.1.1{3,7} ] decyl) propane. The diphosphine ligand is less available at equivalent TON than the ligand disclosed in EP0495547a above. But the ligand has low selectivity and small substrate application range, and also has a certain optimization space.
Patent CN1429228a discloses bidentate ligands useful in catalyst systems. The bidentate ligand is a bidentate phosphine ligand with a phosphane cyclic group, and the structural formula is R 1R2M1-R-M2R3R4. In the bidentate ligand, two di-tertiary alkyl phosphine groups are linked through an alkylene group as a bridging group, or a phosphane cyclic group is linked to phosphorus through a secondary carbon, and an alkylene group is used as a bridging group. The bidentate phosphine ligand can provide good selectivity and reduce the generation of polymer in carbonylation reaction, but the catalytic efficiency is still to be improved.
Patent CN1642646a discloses a process for the carbonylation of ethylenically unsaturated compounds and catalysts for use in the process. It extends the teachings of the above-mentioned US6156934 to bidentate phosphines of the type having A1, 2-substituted aryl bridge in the type disclosed in the above-mentioned WO96019434 A1. The catalytic efficiency in the reaction is improved to a certain extent.
Patent CN1674990a discloses a phosphaadamantane catalytic system. The catalyst system can catalyze the carbonylation reaction of the ethylenically unsaturated compound. The catalyst system adopts a phosphaadamantane side-substituted bidentate phosphine ligand, the production amount of byproducts in the reaction process is obviously reduced, and the supplement of the catalyst is reduced. However, this system requires the addition of polymeric dispersants and subsequent recovery, which increases the operational flow and cost.
Patent CN103223350a discloses a catalyst system. Which are used to catalyze the carbonylation of ethylenically unsaturated compounds. The catalyst system comprises a group VIB or VIIIB metal or compound thereof, an acid, and a bidentate phosphine ligand, wherein the ligand is present in a molar excess of at least 2:1 relative to the metal, and the acid is present in a molar excess of at least 2:1 relative to the ligand. The process disclosed in this patent also uses a polymeric dispersant. In addition, the method has larger acid consumption, and directly increases the cost.
Patent CN101309753a discloses a process for carbonylating ethylenically unsaturated compounds. Wherein the catalyst system employed comprises a group 8, 9 or 10 metal or compound thereof, and a bidentate phosphine ligand comprising a ring hydrocarbon structure bridged with a non-aromatic ring. The use of this catalyst system in the alkoxycarbonylation and hydroxycarbonylation reactions can greatly increase the reaction rate and TON, but the amount of ligand used is also relatively high.
Patent CN105153241a discloses carbonylation ligands and their use in carbonylating ethylenically unsaturated compounds. The carbonylation ligand is a bidentate phosphine ligand bridged by a hydrocarbyl aromatic structure having 5-22 ring atoms of at least one 5 or 6 membered aromatic ring with substituents. The bidentate phosphine ligand can form a complex with group 8, 9 and 10 metals or compounds thereof, and high TON is generated in the carbonylation reaction, but the preparation process of the ligand is complicated, and the yield and purity of part of the ligand are low.
Patent CN106854221a discloses a process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporating the ligands. Wherein the carbonylation ligands employed are bidentate phosphine ligands bridged by a hydrocarbon aromatic structure having at least one aromatic ring. The catalyst system containing the phosphine ligand has better stability in carbonylation reaction, but the reaction rate and TON have a certain improvement space.
Although the catalyst systems disclosed in the above-mentioned patent applications exhibit high stability in olefin carbonylation reactions and provide relatively high reaction rates, there are still problems of relatively high proportion of phosphine ligands, long reaction residence time, rapid catalyst deactivation, need for frequent replenishment of new catalysts, etc., and industrial applications are limited, so that there is a need for improvement of existing catalyst systems.
Disclosure of Invention
Problems to be solved by the invention
In view of the problems of the prior art described above, an object of the present invention is to provide a process for the carbonylation of olefins in which the catalytic activity of the catalyst system is higher and the amount of bidentate phosphine ligand and group VIII metal or compound thereof used in the catalyst system is reduced when the carbonylation of olefins is carried out.
Solution for solving the problem
In order to achieve the above object, the present invention provides a process for the carbonylation of olefins, which comprises reacting an olefin with carbon monoxide and an alcohol in the presence of a catalyst system;
wherein the catalyst system comprises the following components:
(a) A group VIII metal or compound thereof;
(b) Bidentate phosphine ligands, and
(C) An acidic auxiliary agent;
the bidentate phosphine ligand has a structure represented by the following general formula (I),
(R1)(R2)P-K-A-K-P(R3)(R4) (I);
Wherein R1 to R4 are the same or different from each other and each independently represents a C1 to C10 straight or branched chain alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, a C2 to C10 heterocycloalkyl group, a substituted unsubstituted C6 to C20 aryl group, a C6 to C20 aryloxy group or a C6 to C20 heteroaryl group;
P is a phosphorus atom;
Each K is the same or different from each other and is each selected from a single bond or-C (Ra) 2 -;
A is selected from -O-、-S-、-N(Rb)-、-O-C(Rc)2-O-、-S-C(Rc)2-S-、-N(Rf)-C(Rc)2-N(Rf)-、-O-C(Rc)2C(Rc)2-O-、-S-C(Rc)2C(Rc)2-S- or-N (Rf) -C (Rc) 2C(Rc)2 -N (Rf) -;
wherein each Ra is the same or different from each other, each Rc is the same or different from each other, and each Ra and each Rc are each independently H, a straight or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group;
Rb and Rf are each independently H, straight or branched C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, substituted or unsubstituted C6-C10 aryl, C6-C10 aryloxy, or C3-C8 heteroaryl.
The process according to the invention, wherein in the general formula (I), each K is a single bond and A is -O-C(Rc)2-O-、-S-C(Rc)2-S-、-N(Rf)-C(Rc)2-N(Rf)-、-O-C(Rc)2C(Rc)2-O-、-S-C(Rc)2C(Rc)2-S- or-N (Rf) -C (Rc) 2C(Rc)2 -N (Rf) -.
The method according to the present invention, wherein, in the structure represented by A in the general formula (I),
Each Rc is H, or a linear or branched C1-C6 alkyl group, preferably H;
rf is H, linear or branched C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, or C3-C8 heteroaryl, wherein when the C6-C10 aryl has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy, and Rf is preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 4-methoxyphenyl or pyridyl.
The process according to the invention, wherein, in the general formula (I), each K is-C (Ra) 2 -; A is-O-, -S-or-N (Rb) -.
The method according to the present invention, wherein, in the structure represented by A in the general formula (I),
Each Ra is H or straight-chain or branched C1-C6 alkyl, preferably H;
Rb is H, straight-chain or branched-chain C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl or C3-C8 heteroaryl, when the aryl of C6-C10 has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy, and Rb is preferably H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl or 4-methoxyphenyl or pyridyl.
The method according to the invention, wherein in the general formula (I), R1-R4 are each independently C1-C6 linear or branched alkyl, substituted or unsubstituted C6-C10 aryl, C6-C10 heteroaryl, when the C6-C10 aryl has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy, and R1-R4 is preferably tert-butyl, phenyl, 4-methoxyphenyl, benzyl or pyridyl.
The method according to the invention, wherein the molar ratio of component (b) to component (a) in the catalyst system is 2:1 to 20:1, preferably 3:1 to 10:1;
the molar ratio of the component (c) to the component (a) is 2:1 to 150:1, preferably 50:1 to 100:1.
The method according to the invention, wherein,
The VIII group metal comprises cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum;
The compound of the VIII group metal comprises a salt or a weakly coordinated anion compound of the VIII group metal and 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 high halogen acid, or a complex of zero-valent palladium, rhodium, iridium, platinum or ruthenium.
The process according to the invention, wherein the acidic auxiliary is an acid having a pKa value in aqueous solution at 25 ℃ of less than 5, preferably less than 4, more preferably less than 3;
The acid auxiliary is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4, 6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphoric acid and sulfuric acid, and most preferably methanesulfonic acid.
The method of the invention, wherein the operation condition of the reaction is that the reaction pressure is 1-20 MPa, preferably 1-10 MPa;
the reaction temperature is 50 to 200 ℃, preferably 60 to 150 ℃.
The method according to the invention, wherein the molar ratio of the olefin to the carbon monoxide is 1:1 to 100:1, preferably 2:1 to 50:1, and the molar ratio of the olefin to the component (a) in the catalyst system is 50:1 to 300:1, preferably 100:1 to 200:1.
The mass ratio of the alcohol to the component (a) in the catalyst system is 500:1-20000:1, preferably 5000:1-15000:1.
The process according to the invention, wherein the olefin 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, C6-C12 aryl, C1-C4 alkyl or halogen substituted C6-C12 aryl, C2-C6 ester group, or nitrogen-containing heterocyclic group;
The alcohol is a C1-C10 substituted or unsubstituted, straight chain or branched chain 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.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the method for the carbonylation reaction of olefin, the catalyst system adopted has higher catalytic activity, greatly reduces the consumption of bidentate phosphine ligand and VIII metal or the compound thereof in the catalyst system, improves the catalytic efficiency of the reaction, reduces the residence time of reaction substrates, reduces the gas circulation amount, and reduces the size of a required reaction container and equipment investment.
According to the method for the carbonylation of olefin, the adopted catalyst system has the advantages of low consumption, good product selectivity, high conversion rate of reaction substrates, long service life and the like, and can efficiently catalyze the carbonylation to synthesize ester products, so that the yield of the products is higher. Therefore, the method provided by the invention has good commercial value.
Detailed Description
The following detailed description of the present invention will make the technical solution of the present invention apparent.
The present application provides a process for the carbonylation of olefins comprising reacting an olefin with carbon monoxide and an alcohol in the presence of a catalyst system;
wherein the catalyst system comprises the following components:
(a) A group VIII metal or compound thereof;
(b) Bidentate phosphine ligands, and
(C) An acidic auxiliary agent;
wherein the bidentate phosphine ligand has a structure represented by the following general formula (I),
(R1)(R2)P-K-A-K-P(R3)(R4) (I);
Wherein R1 to R4 are the same or different from each other and each independently represents a C1 to C10 linear or branched alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, a C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a C6 to C20 aryloxy group, or a C6 to C20 heteroaryl group;
P is a phosphorus atom;
Each K is the same or different from each other and is each selected from a single bond or-C (Ra) 2 -;
A is selected from -O-、-S-、-N(Rb)-、-O-C(Rc)2-O-、-S-C(Rc)2-S-、-N(Rf)-C(Rc)2-N(Rf)-、-O-C(Rc)2C(Rc)2-O-、-S-C(Rc)2C(Rc)2-S- or-N (Rf) -C (Rc) 2C(Rc)2 -N (Rf) -;
wherein each Ra is the same or different from each other, each Rc is the same or different from each other, and each Ra and each Rc are each independently H, straight or branched C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, substituted or unsubstituted C6-C10 aryl, C6-C20 aryloxy, or C3-C8 heteroaryl;
Rb and Rf are each independently H, straight or branched C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, substituted or unsubstituted C6-C10 aryl, C6-C20 aryloxy, or C3-C8 heteroaryl.
According to the method for the carbonylation reaction of olefin provided by the invention, in a preferable condition, in a formula (I), R1-R4 are respectively and independently C1-C6 linear chain or branched chain alkyl, substituted or unsubstituted C6-C10 aryl and C6-C10 heteroaryl, when the C6-C10 aryl has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy, and R1-R4 are preferably tert-butyl, phenyl, 4-methoxyphenyl, benzyl or pyridyl.
According to the method for the carbonylation of olefins provided by the present invention, in the above formula (I), when each K is a single bond, A is -O-C(Rc)2-O-、-S-C(Rc)2-S-、-N(Rf)-C(Rc)2-N(Rf)-、-O-C(Rc)2C(Rc)2-O-、-S-C(Rc)2C(Rc)2-S- or-N (Rf) -C (Rc) 2C(Rc)2 -N (Rf) -;
Wherein, each Rc is preferably H, or straight-chain or branched-chain C1-C6 alkyl, more preferably H;
rf is H, linear or branched C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, or C3-C8 heteroaryl, wherein when the C6-C10 aryl has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy, and Rf is preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 4-methoxyphenyl or pyridyl.
The bidentate phosphine ligands (i.e. disulfides, diethers or diamines) in this case have excellent properties of stable complexation with the group VIII metals.
According to the process for the carbonylation of olefins provided by the present invention, in the above formula (I), preferably, when each K is-C (Ra) 2 -; A is-O-, -S-or-N (Rb) -;
Wherein, preferably, each Ra is H or straight-chain or branched C1-C6 alkyl, more preferably, each Ra is H;
Rb is H, straight-chain or branched C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl or C3-C8 heteroaryl, when the aryl of C6-C10 has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy, rb is preferably H, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 4-methoxyphenyl or pyridyl.
The bidentate phosphine ligand (namely, a mono-thioether, mono-ether or monoamine compound) in the condition has proper flexible arm and chelating angle, can be stably complexed with the VIII group metal, reduces the degradation of the catalyst, and has more excellent performance compared with the bidentate phosphine ligand (namely, a disulfide, a diether or a diamine compound).
The bidentate phosphine ligands described above are commercially available or may be prepared using methods known in the art.
According to the method for the carbonylation of olefins provided by the present invention, specific compounds of the bidentate phosphine ligands are listed below, but the bidentate phosphine ligands according to the present invention are by no means limited to the ligand compounds listed below.
N, N-bis (di-t-butylphosphine) -ethylenediamine, N-bis (di-t-butylphosphine) -N, N-dimethylethylenediamine, N-bis (di-t-butylphosphine) -N, N-diethylethylenediamine, N-bis (di-t-butylphosphine) -N, N-diisopropylethylenediamine, N, N-bis (di-t-butylphosphine) -N, N-di-t-butylethylenediamine, N-bis (di-t-butylphosphine) -N, N-diphenylethylenediamine, N-bis (di-t-butylphosphine) -N, N-dibenzylethylenediamine, N-bis (di-t-butylphosphine) -N, N-bis (4-methoxyphenyl) ethylenediamine, N-bis (di-t-butylphosphine) -N, N-bis (4-pyridyl) ethylenediamine, N-bis (di-t-butylphosphine) -N, N-bis (2-pyridyl) ethylenediamine, N-bis (diphenylphosphine) -ethylenediamine, N, N-bis (4-methoxyphenylphosphine) -ethylenediamine, N-bis (dibenzylphosphine) -ethylenediamine, N-bis (2-pyridylphosphine) -ethylenediamine, bis ((di-t-butylphosphine) methyl) methylamine, bis ((di-t-butylphosphine) methyl) ethylamine, bis ((di-t-butylphosphinomethyl) isopropylamine, bis ((di-t-butylphosphinomethyl) t-butylamine, bis ((di-t-butylphosphinomethyl) phenylamine, bis ((di-t-butylphosphinomethyl) benzylamine, bis ((di-t-butylphosphinomethyl) 4-methoxyphenylamine, bis ((di-t-butylphosphinomethyl) 4-pyridylamine), bis ((di-t-butylphosphinomethyl) 2-pyridylamine, bis ((diphenylphosphinomethyl) methyl) methylamine, bis ((di (4-methoxyphenyl) phosphinomethyl) methyl) methylamine, and bis ((2-pyridylphosphinomethyl) methylamine, ethyldi ((di-t-butylphosphinomethyl) thio), ethyldi ((di-t-butylphosphinomethyl) ether), and bis ((di-t-butylphosphinomethyl) methyl) sulfane.
According to the catalyst system provided by the invention, the molar ratio of the component (b) to the component (a) is preferably 2:1-20:1, such as 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 10:1, 12.5:1 or 15:1, and the molar ratio is preferably 3:1-10:1, more preferably 3:1-5:1;
in addition, the molar ratio of the component (c) to the component (a) is 2:1 to 150:1, for example, 20:1, 50:1, 100:1, 125:1, preferably 50:1 to 100:1, more preferably 75:1 to 100:1.
According to the process for the carbonylation of olefins provided by the present invention, the group VIII metal preferably comprises cobalt, nickel, palladium, rhodium, ruthenium, iridium or platinum;
The compound of the VIII group metal comprises salts or weakly coordinated anionic compounds of 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 perhalogenated acid; or complexes of zero-valent palladium, rhodium, iridium, platinum or ruthenium, for example bis (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium acetate, bis (acetonitrile) palladium chloride, bis (acetylacetonato) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) palladium, bis (1, 5-cyclooctadiene) palladium chloride, [1, 2-bis (diphenylphosphine) ethane ] palladium chloride, [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloromethane adducts, bis (carbonyl) tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) (carbonyl) rhodium (I), (triphenylphosphine) (acetylacetonato) rhodium (I) carbonyl, tris (acetylacetonato) rhodium (II), tris (triphenylphosphine) rhodium (I), (1, 5-cyclooctadiene) rhodium (I), (carbonyl) chlorobis (triphenylphosphine) iridium (I), (1, 5-cyclooctadiene) iridium (I) chloride dimers, bis (acetylacetonato) platinum Bis (triphenylphosphine) platinum chloride, (1, 5-cyclooctadiene) ruthenium chloride, or tris (triphenylphosphine) rhodium ruthenium chloride.
The group VIII metal compound is preferably palladium acetate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) palladium, bis (triphenylphosphine) palladium chloride, bis (triphenylphosphine) rhodium (I) chloride, (carbonyl) bis (triphenylphosphine) rhodium (I) hydride, tris (triphenylphosphine) (carbonyl) rhodium (I), or rhodium (triphenylphosphine) (acetylacetonate) carbonyl (I).
According to the process for the carbonylation of olefins provided by the present invention, the acidic auxiliary is preferably an acid having a pKa value in aqueous solution at 25 ℃ of less than 5, preferably less than 4, more preferably less than 3.
The acid auxiliary is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4, 6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphoric acid and sulfuric acid, and most preferably methanesulfonic acid.
The process for the carbonylation of olefins provided by the present invention is preferably operated under the following conditions:
The reaction process is carried out under low-pressure or medium-pressure conditions, for example, the reaction pressure is 1-20 MPa, preferably 1-10 MPa, and more preferably 1-5 MPa;
the reaction temperature is 50 to 200 ℃, preferably 60 to 150 ℃, more preferably 60 to 110 ℃.
According to the method for the carbonylation of olefins provided by the present invention, carbon monoxide is used in a pure gas or is used beforehand by dilution with an inert gas (e.g. nitrogen, carbon dioxide, noble gas), and a small amount of hydrogen may also be present in the carbon monoxide gas, but the content of this hydrogen is generally not more than 5%.
In the reaction process, carbon monoxide and olefin in a gas state are all input into a reaction system in a gas phase form through a steel cylinder, the mol ratio of the olefin to the carbon monoxide input into the reaction system is 1:1-100:1, preferably 2:1 to 50:1, more preferably 3:1 to 5:1, and the mol ratio of the olefin to the component (a) in the catalyst system is 50:1 to 300:1, preferably 100:1 to 200:1.
According to the method for the carbonylation of olefins provided by the invention, the mass ratio of the alcohol to the component (a) in the catalyst system of the invention is preferably 500:1-20000:1, such as 2000:1, 5000:1, 10000:1, 15000:1, preferably 5000:1-15000:1, more preferably 10000:1-12500:1.
According to the method for the carbonylation of olefin provided by the invention, each component in the catalyst system can be added into a reaction vessel for the carbonylation of olefin in situ, and can directly enter the reaction vessel or be added into the reaction vessel after the catalyst system is formed outside the reaction vessel in advance.
The components of the catalyst system may be added in any order of addition, or in a particular order of addition to form the catalyst system. Preferably, any two components are mixed and then added to the reaction vessel followed by the addition of the third component to form the catalyst system, or a mixture of two components is mixed with the third component and then added together to the reaction vessel, thereby facilitating the identity of the ligand. For example, component (b) the bidentate phosphine ligand and component (c) the acid promoter are first mixed to form a protonated ligand, which is then added to component (a) the group VIII metal or compound thereof to form the catalyst system. More preferably, component (b) the bidentate phosphine ligand and component (a) the group VIII metal or compound thereof are mixed to form a chelated metal complex to form a metal catalyst precursor, which is then added to component (c) the acid promoter to form a metal-hydrogen catalytically active intermediate, thereby allowing the catalyst system to be more active and to be more stable.
According to the process for the carbonylation of olefins provided by the present invention, the olefin is preferably a substituted or unsubstituted C2-C20 alkene or cyclic olefin, preferably a substituted or unsubstituted C2-C16 alkene;
When the olefin has a substituent, the substituent is a C6-12 aryl, C1-4 alkyl or halogen substituted C6-12 aryl, C2-6 ester group, or nitrogen-containing heterocyclic group.
Preferred olefins include ethylene, 1-hexene, 1-pentene, 3-methyl-1-butene, 3-dimethyl-1-butene, styrene, 2-butene, cyclohexene, 3-hexene and the like.
When the alcohol is an alcohol having a substituent, the substituent is a C1-C6 alkyl group, a C6-C10 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, for example, methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, pentanol, hexanol, chlorooctanol, more preferably methanol, ethanol, most preferably methanol.
In general, the amount of alcohol used does not determine the reaction, and is generally used in excess of the amount of olefin. In addition, alcohols may be used as reaction solvents, and additional solvents may also be used during the reaction. When additional reaction solvents are used, suitable inert solvents include alkanes such as hexane, heptane, 2, 3-trimethylpentane, aromatics such as benzene, toluene, para-xylene, meta-xylene, ketones such as methyl butyl ketone, ethers such as anisole, diethyl ether, dimethyl ether, esters such as methyl acetate, methyl benzoate, dimethyl adipate.
According to the method for olefin carbonylation reaction provided by the invention, with respect to the catalyst system, under the condition of ensuring high reaction rate, compared with the dosage of phosphine ligand, VIII metal or compound thereof in the catalyst system disclosed in the prior art application, the method has the advantages that the dosage of phosphine ligand, VIII metal or compound thereof is reduced, and the stability of the catalyst system is improved. And, as the stability of the catalyst system increases, the amount of metal used in the olefin carbonylation reaction remains relatively low.
According to the method for the carbonylation reaction of the olefin, provided by the invention, when ethylene is taken as olefin and methyl propionate is synthesized by carbonyl, a specific catalyst system is adopted, and ethylene, carbon monoxide and methanol are taken as reaction substrates to react at a lower temperature and a lower pressure. Compared with the prior art, the invention has the following advantages:
(1) In the specific bidentate phosphine ligand structure contained in the catalyst system, nitrogen, oxygen or sulfur atoms are introduced, and the formed ligand is subjected to the combined action of lone pair electrons on the nitrogen, oxygen or sulfur and VIII group metal elements, so that the catalyst intermediate is stabilized, and the dosage of the ligand is greatly reduced.
(2) The solubility of CO and ethylene around the catalyst system is improved, so that the gas quantity of the catalytic center is more, and the catalytic efficiency of the reaction is improved.
(3) The residence time of the reaction substrate is reduced, resulting in a reduction in the gas circulation, thus resulting in a reduction in the size of the required reaction vessel and in a reduction in investment.
(4) The catalyst system has the advantages of low consumption, good product selectivity, high conversion rate of reaction substrates, long service life and the like, can efficiently catalyze ethylene to oxo to synthesize methyl propionate, and the yield of the methyl propionate is up to 96.73 percent based on carbon monoxide as a reaction result, so that the whole method has good commercial value.
According to the method provided by the invention, more preferably, the method for the carbonylation of olefin by using ethylene as olefin is as follows:
A certain amount of methanol, a VIII group metal compound, a bidentate phosphine ligand and an acidic auxiliary agent are added into an autoclave, and the autoclave is sealed. Then, the air in the autoclave was replaced three times with 1MPa nitrogen, then, a mixed gas of ethylene and carbon monoxide mixed in a certain ratio was introduced into the autoclave with stirring for 5 minutes, and then, the pressure was gradually increased to the reaction pressure, and at the same time, the autoclave was heated to the reaction temperature, and after a certain period of reaction, samples were taken for GC chromatography.
The group VIII metal compound used may be any of those listed above, and the acidic auxiliary used is preferably methanesulfonic acid, benzenesulfonic acid, or p-toluenesulfonic acid.
The adopted process conditions are as follows:
The molar ratio of ethylene to CO is 1:1-5:1, and the molar ratio of ethylene to the VIII group metal compound is 50:1-300:1, preferably 100:1-200:1.
The reaction temperature is 60-110 ℃;
the reaction pressure is 1-5 MPa;
The mass of the VIII group metal compound is 0.01-0.08% of the mass of methanol;
the molar ratio of the bidentate phosphine ligand to the VIII group metal compound in the catalyst system is 3:1-5:1;
the molar ratio of the acid auxiliary agent to the VIII metal compound is 75:1-100:1;
The mass of the bidentate phosphine ligand is 0.4-2% of that of methanol;
the mass of the acid auxiliary agent is 1-5.5% of the mass of the methanol.
Examples
The olefin carbonylation reaction is further described below with reference to specific examples and comparative examples. It should not be construed that the scope of the invention is limited to the following examples. Various substitutions and alterations are also possible, without departing from the technical spirit of the present invention, and are intended to be within the scope of the present invention.
Preparation example 1
Preparation of bidentate phosphine ligand 1N, N-bis (di-t-butylphosphine) -ethylenediamine
Tetrahydrofuran (100 mL), ethylenediamine (2.4 g,40 mmol), and triethylamine (14 mL,100 mmol) were sequentially added to a 250mL three-necked flask. The resulting solution was then cooled to 0 ℃ and chlorodiphenylphosphine (14 ml,80 mmol) was slowly added. White salt formation was observed within a few hours. The resulting solution was then heated to 70 ℃, stirred for 96 hours, and then filtered. The clear filtrate was heated in vacuo to remove solvent to give 12.3g of white solid in 85% yield.
Preparation example 2
Preparation of bidentate phosphine ligand 2N, N-bis (di-t-butylphosphine) -N, N-dimethylethylenediamine
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to an equimolar amount of N, N-dimethylethylenediamine, to obtain 13.3g of a white solid in 88% yield.
Preparation example 3
Preparation of bidentate phosphine ligand 3N, N-bis (di-t-butylphosphine) -N, N-diethyl ethylenediamine
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to an equimolar amount of N, N-diethyl ethylenediamine, to obtain 14.6g of a white solid in a yield of 90%.
Preparation example 4
Preparation of bidentate phosphine ligand 4N, N-bis (di-t-butylphosphine) -N, N-diisopropylethylenediamine
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to N, N-diisopropylethylenediamine in an equimolar amount, to obtain 15.7g of a white solid in a yield of 91%.
Preparation example 5
Preparation of bidentate phosphine ligand 5N, N-bis (di-t-butylphosphine) -N, N-di-t-butylethylenediamine
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to N, N-di-t-butylethylenediamine in an equimolar amount, to obtain 16.4g of a white solid in 89% yield.
Preparation example 6
Preparation of bidentate phosphine ligand 6N, N-bis (di-t-butylphosphine) -N, N-diphenylethylenediamine
Prepared in the same manner as in example 1 except that ethylenediamine was changed to an equimolar amount of N, N-diphenylethylenediamine, 17.0g of a white solid was obtained in a yield of 85%.
Preparation example 7
Preparation of bidentate phosphine ligand 7N, N-bis (di-t-butylphosphine) -N, N-bis (4-methoxyphenyl) ethylenediamine
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to an equimolar amount of N, N-di (p-methoxy) phenylethanediamine, to obtain 19.3g of a white solid in 86% yield.
Preparation example 8
Preparation of bidentate phosphine ligand 8 bis ((di-tert-butylphosphine) methyl) methylamine
Methylamine (0.34 g,10.9 mmol) and diphenylphosphine (4.06 g,21.8 mmol) were added at 65℃using a syringe to a Schlenk flask containing 40ml toluene and 0.5g paraformaldehyde. The mixture was stirred at 65 ℃ until the solid paraformaldehyde completely disappeared (about 4 to 5 hours).
The resulting solution was cooled to room temperature and then filtered through celite. The solvent was removed by rotary evaporation leaving a clear oil. It was dissolved in about 10mL of dichloromethane, 30mL of ethanol was added thereto, and mixed well. The flask containing the resulting solution was then evacuated and filled with nitrogen. At this point a white crystalline crude product formed, followed by cooling the flask to-20 ℃ overnight to allow the contents to precipitate completely.
The white crystalline product was collected on a glass dish, washed with a small amount of ethanol and dried in vacuo to give 2.5g of a white solid in 67% yield.
Preparation example 9
Preparation of bidentate phosphine ligand 9 bis ((di-tert-butylphosphine) methyl) ethylamine
The same procedure as in production example 8 was conducted except that methylamine was changed to ethylamine in an equimolar amount, whereby 2.8g of a white solid was obtained in a yield of 70%.
Preparation example 10
Preparation of bidentate phosphine ligand 10 bis ((di-tert-butylphosphine) methyl) isopropyl amine
Preparation was carried out in the same manner as in preparation example 8 except that methylamine was changed to isopropylamine in an equimolar amount, to obtain 2.9g of a white solid in a yield of 72%.
Preparation example 11
Preparation of bidentate phosphine ligand 11 bis ((di-tert-butylphosphine) methyl) tert-butylamine
Preparation was carried out in the same manner as in preparation example 8 except that methylamine was changed to an equimolar amount of tert-butylamine, to obtain 3.2g of a white solid in 75% yield.
Preparation example 12
Preparation of bidentate phosphine ligand 12 bis ((di-tert-butylphosphine) methyl) phenylamine
Preparation was carried out in the same manner as in preparation example 8 except that methylamine was changed to aniline in an equimolar amount, to obtain 3.3g of a white solid in 73% yield.
Preparation example 13
Preparation of bidentate phosphine ligand 13 bis ((di-tert-butylphosphine) methyl) benzylamine
Preparation was performed in the same manner as in preparation example 8 except that methylamine was changed to an equimolar amount of benzylamine, to obtain 3.3g of a white solid in 71% yield.
Preparation example 14
Preparation of bidentate phosphine ligand 14 bis ((di-tert-butylphosphine) methyl) 4-methoxyphenylamine
Preparation was carried out in the same manner as in preparation example 8 except that methylamine was changed to p-methoxyaniline in an equimolar amount, to obtain 3.8g of a white solid in 80% yield.
Preparation example 15
Preparation of bidentate phosphine ligand 15 bis ((diphenylphosphine) methyl amine
Preparation was carried out in the same manner as in preparation example 8 except that di-t-butylphosphine was changed to an equimolar amount of diphenylphosphine, to obtain 3.8g of a white solid in 82% yield.
Preparation example 16
Preparation of bidentate phosphine ligand 16 bis ((di (4-methoxyphenyl) phosphine) methyl) methylamine
Preparation was carried out in the same manner as in preparation example 8 except that di-t-butylphosphine was changed to an equimolar amount of 4-methoxyphenylphosphine, to obtain 4.6g of a white solid, yield 78%.
Preparation example 17
Preparation of bidentate phosphine ligand 17 Ethylbis ((di-tert-butylphosphino) thio) s
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to an equimolar amount of 1, 2-ethanedithiol, to obtain 12.7g of a white solid, and a yield was 83%.
Preparation example 18
Preparation of bidentate phosphine ligand 18 ethyl di ((di-tert-butylphosphino) ether)
Preparation was carried out in the same manner as in preparation example 1 except that ethylenediamine was changed to an equimolar amount of 1, 2-ethanediol, to obtain 12.3g of a white solid, and a yield was 88%.
Preparation example 19
Preparation of bidentate phosphine ligand 19 bis ((di-tert-butylphosphine) methyl) sulfane
Preparation was carried out in the same manner as in preparation example 8 except that methylamine was changed to an equimolar amount of hydrogen sulfide, to obtain 2.5g of a white solid in 65% yield.
Preparation of comparative example 1
Preparation of bidentate phosphine ligand 20:1, 2-bis ((di-t-butylphosphine) methyl) -4-t-butyl-benzene
4-Tert-butyl-o-xylene (4.55 g,28.1 mmol) was diluted with heptane (100 ml) (Aldrich) and NaOBu t (8.1 g,84.3 mmol), TMEDA (12.6 ml,84.3 mmol) and t BuLi (2.5M in hexane, 33.7ml,84.3 mmol) were added thereto. Butyl lithium was added dropwise and an immediate discoloration was produced from colorless to yellow to orange to dark red. The solution was then heated to 65 ℃ for 3 hours, resulting in a brown/orange suspension.
The suspension was cooled to room temperature and the supernatant removed by cannula. The brown precipitate residue was then washed with pentane (100 ml). The pentane washes were then removed through the cannula. The solid residue was then suspended in pentane (100 ml) and cooled in a cold water bath. Bu t 2 PCl (7.5 ml,39.3 mmol) was added dropwise to the suspension. The resulting suspension was then stirred for 3 hours and allowed to stand overnight.
Water (100 ml) was degassed with nitrogen for 30min and then added to the suspension to give a two-phase solution. The upper layer (organic phase) was diluted with pentane (100 ml) and the organic phase was taken out through a cannula into a clean schlenk flask. The pentane extract was dried over sodium sulfate and transferred through a cannula into a clean schlenk flask. The solvent was then removed under vacuum to give an orange oil. Methanol (100 ml) was added thereto to obtain a two-phase solution. It was then heated to reflux (70 ℃) to give a pale yellow solution and some colorless insoluble material. The solution was then cooled to room temperature and filtered into a clean schlenk flask. The solution was then placed in a freezer at-20 ℃ overnight, yielding an off-white solid deposit. The remaining methanol solution was then removed through a cannula and the solid was dried under vacuum. The solids were isolated in a glove box. The amount of the product was 4.20g, the yield was 33% and the purity was 95%.
Preparation of comparative example 2
Preparation of bidentate phosphine ligand 21:1, 2-bis ((di-tert-butylphosphine) methyl) benzene
Preparation was carried out in the same manner as in preparation comparative example 1 except that 4-t-butyl-orthoxylene was changed to an equimolar amount of orthoxylene, to obtain 4.5g of a white solid in 40% yield and 95% purity.
Inventive example 1
1000G (31.25 mol) of methanol, 0.32g (1.43 mmol) of palladium acetate, 5.40g (56.19 mmol) of methanesulfonic acid and 1 (1.22 g,3.50 mmol) of bidentate phosphine ligand were charged into a 2L autoclave. Ethylene and carbon monoxide in a molar ratio of 4:1 were introduced into the autoclave at a carbon monoxide flow rate of 1.2L/min, and reacted at a stirring speed of 500r/min, a reaction pressure of 1.2MPa and a reaction temperature of 60℃for 120min.
An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 2
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.32g (3.51 mmol) of bidentate phosphine ligand 2 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 3
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.3g (1.42 mmol) of PdCl 2(NH3)2 and 1.42g (3.51 mmol) of bidentate phosphine ligand 3 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 4
A reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.33g (1.42 mmol) of Pd (NH 3)2(NO2)2) and 1.51g (3.49 mmol) of bidentate phosphine ligand 4 was used.
Inventive example 5
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 5.40g of methanesulfonic acid was changed to 10.41g (65.81 mmol) of benzenesulfonic acid, and 1.61g (3.49 mmol) of bidentate phosphine ligand 5 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 6
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 5.40g of methanesulfonic acid was changed to 11.33g (65.79 mmol) of p-toluenesulfonic acid, and 1.75g (3.50 mmol) of bidentate phosphine ligand 6 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 7
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.96g (3.50 mmol) of bidentate phosphine ligand 7 was used and the reaction temperature was 80 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 8
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 1.22g (3.51 mmol) of bidentate phosphine ligand 8 was used and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 9
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.35g (0.71 mmol) of [ Rh (COD) Cl ] 2 and 1.27g (3.51 mmol) of the bidentate phosphine ligand 9 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 10
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.48g (0.71 mmol) of [ Ir (COD) Cl ] 2 and 1.31g (3.49 mmol) of the bidentate phosphine ligand 10 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 11
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 1.36g (3.49 mmol) of bidentate phosphine ligand 11 was used, and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 12
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 1.43g (3.49 mmol) of bidentate phosphine ligand 12 was used, and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 13
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.48g (3.49 mmol) of bidentate phosphine ligand 13 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 14
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 15
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.50g (3.51 mmol) of bidentate phosphine ligand 15 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 16
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.92g (3.51 mmol) of bidentate phosphine ligand 16 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 17
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.34g (3.50 mmol) of bidentate phosphine ligand 17 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 18
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.23g (3.51 mmol) of bidentate phosphine ligand 18 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 19
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.23g (3.51 mmol) of bidentate phosphine ligand 19 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Comparative example 1 of the invention
The reaction was carried out in the same manner as in example 2 except that the amount of tris (dibenzylideneacetone) dipalladium was changed to 1.3g (1.41 mmol) and 3.16g (7.01 mmol) of bidentate phosphine ligand 20 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive comparative example 2
The reaction was carried out in the same manner as in example 2 except that the amount of tris (dibenzylideneacetone) dipalladium was changed to 1.3g (1.41 mmol) and 2.76g (7.00 mmol) of bidentate phosphine ligand 21 was used. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl propionate as a product, the results of which are shown in table 1.
Inventive example 20
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 1.36g (3.49 mmol) of bidentate phosphine ligand 11 was used, 1-hexene to carbon monoxide in a molar ratio of 4:1 was changed to the same molar ratio, and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of the product methyl heptanoate, the results of which are shown in table 1.
Inventive example 21
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 1.43g (3.49 mmol) of bidentate phosphine ligand 12 was used, 1-pentene and carbon monoxide in a molar ratio of 4:1 were changed to the same molar ratio, and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl caproate as a product, the results of which are shown in table 1.
Inventive example 22
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used, that ethylene and carbon monoxide were changed to the same molar ratio of 4:1, and that 3-methyl-1-butene and carbon monoxide were used at a reaction temperature of 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of the product methyl 3-methylpentanoate, the results of which are shown in table 1.
Inventive example 23
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used, the molar ratio of ethylene to carbon monoxide was changed to the same molar ratio of 3, 3-dimethyl-1-butene to carbon monoxide, and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of the product methyl 3, 3-dimethylvalerate, the results of which are shown in Table 1.
Inventive example 24
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used, that styrene and carbon monoxide were changed to the same molar ratio of ethylene to carbon monoxide in a molar ratio of 4:1, and that the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity as carbon monoxide, and the yield of methyl phenylpropionate, and the results are shown in table 1.
Inventive example 25
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used, that ethylene and carbon monoxide were changed to the same molar ratio of 2-butene and carbon monoxide in a molar ratio of 4:1, and that the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl 2-methylbutyrate, and the results are shown in Table 1.
Inventive example 26
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used, cyclohexene and carbon monoxide in a molar ratio of 4:1 were changed to the same molar ratio, and the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl cyclohexylformate, and the results are shown in table 1.
Inventive example 27
The reaction was carried out in the same manner as in example 1 except that 0.32g of palladium acetate was changed to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and 1.54g (3.50 mmol) of bidentate phosphine ligand 14 was used, that ethylene and carbon monoxide were changed to 3-hexene and carbon monoxide in the same molar ratio of 4:1, and that the reaction temperature was 100 ℃. An appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity in terms of carbon monoxide, and the yield of methyl 2-ethyl valerate, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, examples 1-27 of the process for the carbonylation of olefins according to the present invention employing a catalyst system comprising a specific phosphorus ligand have lower amounts of phosphorus ligand and group VIII metal compound, and have higher selectivity and yield of product and higher conversion of reaction substrate than comparative examples 1-2 employing a catalyst system comprising other phosphorus ligands. In examples 1-27, examples 1-16 and 20-27 employing a catalyst system comprising a nitrogen-containing phosphorus ligand have higher selectivity, conversion and yield than examples 17-19 employing a catalyst system comprising a sulfur-or oxygen-containing phosphorus ligand, and further examples 8-16 and 20-27 employing a catalyst system comprising a phosphorus ligand of a single nitrogen atom have higher selectivity, conversion and yield than examples 1-7 employing a catalyst system comprising a phosphorus ligand of two nitrogen atoms.
Inventive example 28
250G (7.81 mol) of methanol, 0.1625g (0.177 mmol) of tris (dibenzylideneacetone) dipalladium, 1.35g (14.05 mmol) of methanesulfonic acid and 14 (0.385 g,0.876 mmol) of bidentate phosphine ligand were charged into a 2L autoclave and sealed. Ethylene and carbon monoxide in a molar ratio of 4:1 were introduced into the autoclave and reacted at a stirring speed of 500r/min, a reaction pressure of 1.2MPa and a reaction temperature of 60℃for 120min. After the reaction was completed, the reaction mixture was cooled to room temperature, and then a proper amount of the reaction mixture was weighed, GC analysis was performed, the conversion and selectivity were calculated as carbon monoxide, and the yield of methyl propionate as a product was recorded.
250G (7.81 mol) of methanol was fed into the autoclave, and ethylene and carbon monoxide in a molar ratio of 4:1 were introduced again into the autoclave, and the reaction was carried out at a stirring speed of 500r/min, a reaction pressure of 1.2MPa and a reaction temperature of 60℃for 120 minutes. After the completion of the reaction, the reaction mixture was cooled to room temperature, and then an appropriate amount of the reaction mixture was weighed, GC analysis was performed, the conversion and selectivity as well as the yield of methyl propionate as a product were calculated in terms of carbon monoxide, and the results were recorded.
The above procedure was repeated three times until 1250g of methanol was finally added to the autoclave and the reaction was completed, and the results of the reactions at each stage were recorded in Table 2.
TABLE 2
The catalyst system containing the specific bidentate phosphine ligand has good catalytic activity and selectivity at lower reaction temperature and reaction pressure, has the advantages of high catalytic efficiency, less consumption, long service life, good selectivity and the like, can efficiently catalyze olefin carbonylation reaction, takes ethylene carbonylation to synthesize methyl propionate as an example, and has good industrial prospect, and the yield can reach 96.73%.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111573303.9A CN115819234B (en) | 2021-12-21 | 2021-12-21 | A method for olefin carbonylation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111573303.9A CN115819234B (en) | 2021-12-21 | 2021-12-21 | A method for olefin carbonylation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819234A CN115819234A (en) | 2023-03-21 |
| CN115819234B true CN115819234B (en) | 2025-04-29 |
Family
ID=85515504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111573303.9A Active CN115819234B (en) | 2021-12-21 | 2021-12-21 | A method for olefin carbonylation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819234B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116237086B (en) * | 2023-03-23 | 2023-11-03 | 中国科学院长春应用化学研究所 | Efficient catalyst system for preparing methyl propionate by ethylene carbonylation based on antioxidant strategy |
| CN117380282B (en) * | 2023-09-12 | 2026-01-27 | 浙江新化化工股份有限公司 | Composite catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063277A (en) * | 1991-01-15 | 1992-08-05 | 国际壳牌研究有限公司 | Carbonylation of alkenes |
| CN1252015A (en) * | 1997-04-07 | 2000-05-03 | Dsm有限公司 | Carbonylation catalyst system |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69204691T2 (en) * | 1991-01-15 | 1996-04-11 | Shell Int Research | Process for carbonylation of olefin. |
| BE1007944A3 (en) * | 1993-12-30 | 1995-11-21 | Dsm Nv | PROCESS FOR THE PREPARATION OF 5-formylvaleric AND ester. |
| GB9425911D0 (en) * | 1994-12-22 | 1995-02-22 | Ici Plc | Process for the carbonylation of olefins and catalyst system for use therein |
| CN109364996B (en) * | 2018-10-22 | 2020-11-03 | 厦门大学 | Bidentate phosphorus ligand coordinated metal catalyst and method for preparing 3-hydroxy propionate by catalysis of bidentate phosphorus ligand coordinated metal catalyst |
-
2021
- 2021-12-21 CN CN202111573303.9A patent/CN115819234B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063277A (en) * | 1991-01-15 | 1992-08-05 | 国际壳牌研究有限公司 | Carbonylation of alkenes |
| CN1252015A (en) * | 1997-04-07 | 2000-05-03 | Dsm有限公司 | Carbonylation catalyst system |
Non-Patent Citations (2)
| Title |
|---|
| Hydroesterification Reactions with Palladium-Complexed PAMAM Dendrimers Immobilized on Silica;Reynhardt, Jan P. K. et al;《Journal of Organic Chemistry》;20030927;第68卷(第22期);8353-8360 * |
| Ligand-enabled palladium-catalyzed hydroesterification of vinyl arenes with high linear selectivity to access 3-arylpropanoate esters;Deng, Zhixin et al;《Chemical Communications 》;20220224;第58卷(第24期);3921-3924 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819234A (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7116127B2 (en) | Methods for the carbonylation of ethylenically unsaturated compounds, novel carbonylating ligands and catalyst systems incorporating such ligands | |
| US6156934A (en) | Diphosphines | |
| JP3051986B2 (en) | Carbonylation catalyst | |
| EP0499329B1 (en) | Carbonylation catalyst system | |
| CN107580593B (en) | Process for preparing unsaturated carboxylate | |
| TWI488691B (en) | Carbonylation process of ethylenically unsaturated compounds, novel carbonyl ligands, and catalyst systems incorporating the ligands | |
| US20060235241A1 (en) | Process for the carbonylation of a conuugated diene | |
| KR20170010800A (en) | Process for preparing an unsaturated carboxylic acid salt | |
| KR19990022086A (en) | Synthesis of fluoro-substituted bidentate phosphine ligands and hydroformylation using the same | |
| CN115819234B (en) | A method for olefin carbonylation reaction | |
| US9809611B2 (en) | Carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds | |
| ES2430224T3 (en) | Hydroformylation procedure | |
| ZA200503932B (en) | Carbonylation of vinyl ester | |
| US5189003A (en) | Carbonylation catalyst system | |
| US5258546A (en) | Carbonylation catalyst system | |
| CN116139939B (en) | Catalyst system and carbonylation reaction method | |
| Marko et al. | Asymmetric homogeneous hydrogenation and related reactions | |
| EP1735263A1 (en) | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds | |
| US5352813A (en) | Carbonylation of methanol using a novel transition metal catalyst | |
| US7265242B2 (en) | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds | |
| CN118834125A (en) | Method for preparing tricyclodecane dicarboxylic acid (TCD-dicarboxylic acid) from dicyclopentadiene | |
| CN116444563A (en) | A kind of synthetic method of novel triphosphine ligand | |
| JP6551922B2 (en) | Process for producing alcohol by hydrogenation of carboxylic acid compound, and ruthenium complex used in the process | |
| EP4448172A2 (en) | Cationic cobalt complexes for asymmetric hydrogenation and methods of making the same | |
| CN115298157A (en) | Catalytic process for preparing alpha, beta-ethylenically unsaturated carboxylic acid salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |