CN115819234A - Method for olefin carbonylation reaction - Google Patents
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- CN115819234A CN115819234A CN202111573303.9A CN202111573303A CN115819234A CN 115819234 A CN115819234 A CN 115819234A CN 202111573303 A CN202111573303 A CN 202111573303A CN 115819234 A CN115819234 A CN 115819234A
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Abstract
The invention relates to a method for olefin carbonylation reaction. The process 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) a bidentate phosphine ligand; and (c) an acidic adjuvant; the bidentate phosphine ligand has A structure represented by the following general formulA (I), (R1) (R2) P-K-A-K-P (R3) (R4) (I). According to the method provided by the invention, the adopted catalyst system has higher catalytic activity, the dosage of bidentate phosphine ligand and VIII group metal or compound thereof in the catalyst system is greatly reduced, the method has the advantages of good product selectivity, high reaction substrate conversion rate, long service life and the like, and the catalyst can efficiently catalyze olefin carbonylation reaction to synthesize ester products, so that the product yield is higher, the reaction catalytic efficiency can be improved, and the residence time of reaction substrates can be reduced.
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 decades, catalyst systems comprising transition metals 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 scheme 1, it comprises 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.
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 a reaction has been one of the research hotspots in the field of organic synthesis and catalysis. In the olefin carbonylation reaction, methyl propionate, a carbonylation reaction product of ethylene, is an important intermediate for 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 an aryl bridge, which is represented inter alia by bis (di-tert-butylphosphino) o-xylene. The catalyst system shows a better reaction rate in the olefin carbonylation reaction, but the catalyst is often inactivated due to the reduction of palladium compound into palladium metal during continuous operation stage, which results in higher cost and limited industrial application.
EP0495547A discloses the carbonylation of olefins. And discloses that the catalyst system used in the carbonylation comprises a source of palladium cations, a source of anions and a bidentate diphosphine having the structure of formula I, R 1 R 2 P–X–P–R 3 R 4 (I) Examples thereof include 1, 3-bis (diisopropylphosphino) propane, 1, 5-bis (dimethylphosphino) -3-oxapentane and the like. The catalyst systems containing bidentate diphosphines provide significantly higher reaction rates, product yields and/or selectivity in various monocarbonylation reactions. However, the disadvantage is that the ligand is liable to dissociate, causing catalyst poisoning and making recycling impossible.
Patent US6156934A discloses a 2-phosphorus-containing tricyclo [3.3.1.1.{3,7 })]A diphosphinate of decyl groups, which is a bidentate phosphine ligand with a covalent bridging group for the carbonylation of unsaturated compounds, of the formula R 1 >P-R 2 -P<R 1 (ii) a Specific compounds thereof are, for example, 1,3-P, P' -bis (2-phosphorus-1, 3,5, 7-tetramethyl-6, 9, 10-trioxatricyclo [3.3.1.1 f 3,7}]Decyl) propane. The diphosphine ligand is used in a smaller amount than the ligand disclosed in the above mentioned EP0495547A at the same TON. But the ligand has low selectivity, small substrate application range and 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 of the bidentate ligand is shown in the specification, R 1 R 2 M 1 -R-M 2 R 3 R 4 . In the bidentate ligand, the two di-tert-alkyl phosphino groups are linked by an alkylene group as a bridge, or the phosphane cyclic group is linked to the phosphorus by a secondary carbon and the alkylene group is the bridge. The bidentate phosphine ligand can provide good selectivity and reduce polymer production 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 a catalyst for use in the process. Which extends the teaching of the above-mentioned US6156934 to bidentate phosphines of the type having a1,2-substituted aryl bridge of 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 catalytic system can catalyze carbonylation reaction of ethylenic unsaturated compounds. The catalyst system adopts a bidentate phosphine ligand substituted by the phospho-adamantane side, the generation amount of by-products in the reaction process is obviously reduced, and the supplement of the catalyst is reduced. However, this system requires the addition of a polymeric dispersant, which subsequently requires recovery, increasing the process flow and cost.
Patent CN103223350A discloses a catalyst system. Which is 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. The process disclosed in this patent also uses a polymeric dispersant. In addition, the method has large acid consumption, which directly increases the cost.
Patent CN101309753A discloses a process for the carbonylation of ethylenically unsaturated compounds. Wherein the catalyst system employed comprises a group 8, 9 or 10 metal or compound thereof; and bidentate phosphine ligands bridged with a cyclic hydrocarbon structure of a non-aromatic ring. The use of this catalyst system in alkoxycarbonylation and hydroxycarbonylation reactions greatly increases the reaction rate and TON, but the amount of ligand used is relatively high.
Patent CN105153241A discloses carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds. The carbonylation ligand is a bidentate phosphine ligand bridged by a substituted hydrocarbyl aromatic structure having 5-22 ring atoms of at least one 5 or 6 membered aromatic ring. The bidentate phosphine ligand can form a complex with metals of groups 8, 9 and 10 or compounds thereof, and high TON is generated in 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 such ligands. Wherein the carbonylation ligand employed is a bidentate phosphine ligand bridged by a hydrocarbyl aromatic structure having at least one aromatic ring. The catalyst system containing the phosphine ligand shows better stability in carbonylation reaction, but the reaction rate and TON have certain improvement space.
Although the catalyst systems disclosed in the above patent applications show high stability in olefin carbonylation and provide relatively high reaction rates, there still exist problems of relatively high proportion of phosphine ligands, long reaction residence time, rapid catalyst deactivation, frequent need for new catalyst replenishment, etc., and industrial application is limited, and thus 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, it is an object of the present invention 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 ligands and group VIII metal or compounds thereof used in the catalyst system is less when carrying out the carbonylation of olefins.
Means for solving the problems
In order to achieve the above object, the present invention provides a process for the carbonylation of olefins, which process 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) A bidentate phosphine ligand; and
(c) An acidic adjuvant;
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 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 independently selected from the group consisting of 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) 2 C(Rc) 2 -O-、-S-C(Rc) 2 C(Rc) 2 -S-or-N (Rf) -C (Rc) 2 C(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 linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group;
rb and Rf are each independently H, a linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group.
The method according to the present 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) 2 C(Rc) 2 -O-、-S-C(Rc) 2 C(Rc) 2 -S-or-N (Rf) -C (Rc) 2 C(Rc) 2 -N(Rf)-。
The method of the invention, wherein in the structure represented by A in the general formula (I),
each Rc is independently H or a linear or branched C1-C6 alkyl group, preferably all H;
rf is H, linear 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; 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 of the invention is characterized in that in the structure represented by A in the general formula (I),
each Ra is independently H or a linear or branched C1-C6 alkyl group, preferably both H;
rb is H, linear 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, or 4-methoxyphenyl or pyridyl.
The method of the invention, wherein in the general formula (I), R1-R4 are respectively and independently C1-C6 straight chain or branched chain alkyl, substituted or unsubstituted C6-C10 aryl, and C6-C10 heteroaryl; when the aryl of C6-C10 has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy; r1 to R4 are 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;
the molar ratio of component (c) to component (a) is from 2 to 150, preferably from 50.
The method according to the present invention, wherein,
the group VIII metals include: cobalt, nickel, palladium, rhodium, ruthenium, iridium, or platinum;
the group VIII metal compound includes a salt or weakly coordinating anion 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 resins, or perhalogenic acids; or complexes of zero-valent palladium, rhodium, iridium, platinum or ruthenium.
The method according to the invention, wherein the acidic adjuvant is an acid having a pKa value below 5, preferably below 4, more preferably below 3, in an aqueous solution at 25 ℃;
the acid auxiliary agent is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4, 6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphoric acid and sulfuric acid; most preferred is methanesulfonic acid.
The method of the invention, wherein the reaction is carried out under the operating conditions that the reaction pressure is 1-20 MPa, preferably 1-10 MPa;
the reaction temperature is 50 to 200 ℃, preferably 60 to 150 ℃.
The process according to the invention, wherein the molar ratio of the olefin to the carbon monoxide is from 1 to 100, preferably from 2 to 1; the molar ratio of the olefin to component (a) in the catalyst system is from 50 to 300, preferably from 100 to 1.
The mass ratio of the alcohol to component (a) in the catalyst system is from 500 to 20000, preferably from 5000 to 15000.
The method according to the present invention, wherein the olefin is a substituted or unsubstituted C2-C20 olefin; preferably a substituted or unsubstituted C2-C16 alkene;
when the olefin has a substituent, the substituent is 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 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 monoalkanol.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the method for the olefin carbonylation reaction, the adopted catalyst system has higher catalytic activity, the dosage of bidentate phosphine ligand and VIII group metal or compounds thereof in the catalyst system is greatly reduced, the catalytic efficiency of the reaction is improved, the retention time of reaction substrates is reduced, and the gas circulation volume is reduced, so that the size of a required reaction container is reduced, and the equipment investment is reduced.
According to the method for the olefin carbonylation reaction, 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 reaction to synthesize ester products, so that the yield of the products is high. Therefore, the method provided by the invention has good commercial value.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail so that the technical aspects of the present invention will become apparent.
The process for the carbonylation of olefins provided herein 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) A bidentate phosphine ligand; and
(c) An acidic adjuvant;
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 independently selected from the group consisting of 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) 2 C(Rc) 2 -O-、-S-C(Rc) 2 C(Rc) 2 -S-or-N (Rf) -C (Rc) 2 C(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 linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C20 aryloxy group, or a C3-C8 heteroaryl group;
rb and Rf are each independently H, linear 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 olefin carbonylation provided by the invention, in the formula (I), R1-R4 are respectively and independently C1-C6 straight-chain or branched-chain alkyl, substituted or unsubstituted C6-C10 aryl, and C6-C10 heteroaryl; when the aryl of C6-C10 has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy; r1 to R4 are preferably tert-butyl, phenyl, 4-methoxyphenyl, benzyl or pyridyl.
According to the process for the carbonylation of olefins provided by the present invention, in the above formula (I), preferably, 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) 2 C(Rc) 2 -O-、-S-C(Rc) 2 C(Rc) 2 -S-or-N (Rf) -C (Rc) 2 C(Rc) 2 -N(Rf)-；
Among them, each Rc is preferably H or a linear or branched C1 to C6 alkyl group, and more preferably H;
rf is H, linear 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; rf is preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 4-methoxyphenyl or pyridyl.
The bidentate phosphine ligand (i.e. disulfide, diether or diamine) in this case has the excellent property of stable complexation with the group VIII metal.
According to the present invention there is provided a process for the carbonylation of olefins, preferably wherein in formula (I) above, when each K is-C (Ra) 2 -when; a is-O-, -S-or-N (Rb) -;
among them, each Ra is preferably independently H or a linear or branched C1 to C6 alkyl group, more preferably both are H;
rb is H, linear 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, the monosulfide, the monoether or the monoamine compound) in the condition has a proper flexible arm and a chelating angle, can be stably complexed with the VIII group metal, and reduces the degradation of the catalyst; and is superior to the above-mentioned bidentate phosphine ligands (i.e., disulfide, diether or diamine compounds).
The bidentate phosphine ligands described above are commercially available or may be prepared using methods known in the art.
According to the process for the carbonylation of olefins provided by the present invention, specific compounds of bidentate phosphine ligands are listed below, but the bidentate phosphine ligands described in the present invention are by no means limited to the ligand compounds listed below.
<xnotran> N, N- ( ) - , N, N- ( ) -N, N- , N, N- ( ) -N, N- , N, N- ( ) -N, N- , N, N- ( ) -N, N- , N, N- ( ) -N, N- , N, N- ( ) -N, N- , N, N- ( ) -N, N- (4- ) , N, N- ( ) -N, N- (4- ) , N, N- ( ) -N, N- (2- ) , N, N- ( ) - , N, N- (4- ) - , N, N- ( ) - , N, N- (2- ) - , (( ) ) , (( ) ) , (( ) ) , </xnotran> Bis ((di-tert-butylphosphino) methyl) -tert-butylamine, bis ((di-tert-butylphosphino) methyl) phenylamine, bis ((di-tert-butylphosphino) methyl) benzylamine, bis ((di-tert-butylphosphino) methyl) 4-methoxyphenylamine, bis ((di-tert-butylphosphino) methyl) 4-pyridylamine, bis ((di-tert-butylphosphino) methyl) 2-pyridylamine, bis ((diphenylphosphino) methyl) methylamine, bis ((dibenzylphosphine) methyl) methylamine, bis ((4-methoxyphenyl) phosphine) methyl) methylamine, and bis ((2-pyridylphosphine) methyl) methylamine; ethylbis ((di-tert-butylphosphino) thio), ethylbis ((di-tert-butylphosphino) ether), and bis ((di-tert-butylphosphino) methyl) sulfane.
According to the catalyst system provided by the present invention, the molar ratio of component (b) to component (a) is 2; the molar ratio is preferably 3;
furthermore, the molar ratio of component (c) to component (a) is from 2 to 150, for example 20; the molar ratio is preferably 50.
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;
compounds of group VIII metals include salts or weakly coordinating anionic compounds of the group VIII metals with: sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid sulfonated ion exchange resin, or perhalogenic 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 (acetylacetonate) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) palladium, bis (1, 5-cyclooctadiene) palladium chloride, [1, 2-bis (diphenylphosphino) ethane ] palladium chloride, [1, 1-bis (diphenylphosphino) ferrocene ] palladium chloride dichloromethane adduct, bis (triphenylphosphine) -rhodium (I) chloride, tris (triphenylphosphine) (carbonyl) rhodium hydride (I), (triphenylphosphine) (acetylacetonate) rhodium (I), tris (acetylacetonate) rhodium (II), tris (triphenylphosphine) rhodium (I) chloride, (1, 5-cyclooctadiene) rhodium (I) chloride, (carbonyl) chlorobis (triphenylphosphine) iridium (I), (1, 5-cyclooctadiene) rhodium (I) chloride dimer, bis (acetylacetonate) platinum, bis (triphenylphosphine) platinum, (1, 5-cyclooctadiene) rhodium (I) chloride, or (1, 5-cyclooctadiene) platinum chloride.
The compound of the group VIII metal is preferably palladium acetate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) palladium, bis (triphenylphosphine) palladium chloride, (carbonyl) bis (triphenylphosphine) rhodium (I) chloride, (triphenylphosphine) (carbonyl) rhodium (I) hydride, or (triphenylphosphine) (acetylacetonato) rhodium (I) carbonyl.
According to the olefin carbonylation process provided by the present invention, the acidic adjuvant is preferably an acid having a pKa value of less than 5, preferably less than 4, more preferably less than 3, in an aqueous solution at 25 ℃.
The acidic auxiliary agent is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4, 6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphonic acid and sulfuric acid; most preferred is methanesulfonic acid.
The method for olefin carbonylation provided by the invention has the following operating conditions in a preferable condition:
the reaction process is carried out under low pressure or medium pressure, for example, the reaction pressure is 1 to 20MPa, preferably 1 to 10MPa, more preferably 1 to 5MPa;
the reaction temperature is 50 to 200 ℃, preferably 60 to 150 ℃, and more preferably 60 to 110 ℃.
According to the process for the carbonylation of olefins provided by the present invention, carbon monoxide is used as a pure gas or previously diluted with an inert gas (e.g., nitrogen, carbon dioxide, noble gas) in a usual case, and a small amount of hydrogen gas may also be present in the carbon monoxide gas, but the content of hydrogen gas is generally not more than 5%.
During the reaction, carbon monoxide and the olefin in a gaseous state are both fed into the reaction system through the steel cylinder in a gas phase, and the molar ratio of the olefin to the carbon monoxide fed into the reaction system is 1-100, preferably 2; the molar ratio of the olefin used to component (a) in the catalyst system is from 50 to 300, preferably from 100 to 1.
According to the process for the carbonylation of olefins provided by the present invention, the mass ratio of the alcohol to component (a) in the catalyst system of the present invention is from 500 to 20000 1, for example 2000, 1, 5000, 10000 1, 15000; preferably from 5000 to 15000, more preferably from 10000 to 12500.
According to the method for the olefin carbonylation reaction provided by the invention, all components in the catalyst system can be added into the reaction vessel for the olefin carbonylation reaction in situ, and can directly enter the reaction vessel or form the catalyst system outside the reaction vessel in advance and then be added into the reaction vessel.
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 added to the reaction vessel and then the third component is added 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 easily protonating the ligand. For example, the component (b) bidentate phosphine ligand and the component (c) acidic promoter are first mixed to form the protonated ligand, which is then added to the component (a) group VIII metal or compound thereof to form the catalyst system. More preferably, the bidentate phosphine ligand of component (b) and the group VIII metal or compound thereof of component (a) are mixed to form a chelated metal complex to form a metal catalyst precursor, which is then added to the acidic adjuvant of component (c) to form a metal-hydrogen catalytically active intermediate, thereby rendering the catalyst system more active and the catalyst system more stable.
According to the method for olefin carbonylation provided by the invention, the olefin is substituted or unsubstituted C2-C20 alkene or cycloolefine in a preferable case; preferably a substituted or unsubstituted C2-C16 alkene;
when the olefin has a substituent, the substituent is a C6-12 aryl group, a C1-4 alkyl group, a halogen-substituted C6-12 aryl group, a C2-6 ester group, or a nitrogen-containing heterocyclic group.
Preferred olefins include: ethylene, 1-hexene, 1-pentene, 3-methyl-1-butene, 3-dimethyl-1-butene, styrene, 2-butene, cyclohexene, or 3-hexene, and the like.
The alcohol is a C1-C10 substituted or unsubstituted, straight or branched chain alkanol; 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 monoalkanol, for example methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, pentanol, hexanol, chlorooctanol; further preferred are methanol and ethanol; methanol is most preferred.
In general, the amount of alcohol used is not critical to the reaction and is generally used in excess of the amount of olefin. In addition, alcohols may be used as a reaction solvent, 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; aromatic compounds such as benzene, toluene, p-xylene, m-xylene; ketones, such as methyl butyl ketone; ethers such as anisole, diethyl ether, dimethyl ether; esters, such as methyl acetate, methyl benzoate, dimethyl adipate.
According to the method for olefin carbonylation provided by the invention, the catalyst system has the advantages that under the condition of ensuring high reaction rate, compared with the dosage of phosphine ligand, VIII group metal or compound thereof in the catalyst system described in the prior patent application, the method has the following advantages: the dosage of phosphine ligand, VIII group metal or compound thereof is reduced, and the stability of the catalyst system is improved. Also, the amount of metal used in the olefin carbonylation reaction is kept relatively low as the stability of the catalyst system is increased.
According to the method for the olefin carbonylation reaction, when ethylene is used as olefin and methyl propionate is synthesized by carbonylation, a specific catalyst system is adopted, and ethylene, carbon monoxide and methanol are used as reaction substrates and react at a lower temperature and a lower pressure. Compared with the prior art, the invention has the following advantages:
(1) In a specific bidentate phosphine ligand structure contained in a catalyst system, nitrogen, oxygen or sulfur atoms are introduced, and lone pair electrons on nitrogen, oxygen or sulfur and VIII family metal elements act together in the formed ligand, so that a 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 amount 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, so that the gas circulation amount is reduced, thereby reducing the size of the required reaction vessel and reducing the 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 carbonylation to synthesize methyl propionate, and has the reaction result that the yield of methyl propionate is up to 96.73 percent calculated by carbon monoxide, so that the whole method has good commercial value.
According to the method provided by the invention, more preferably, the method for olefin carbonylation by using ethylene as olefin comprises the following steps:
adding a certain amount of methanol, VIII group metal compound, bidentate phosphine ligand and acid auxiliary agent into a high-pressure autoclave, and sealing the high-pressure autoclave. And then replacing the air in the autoclave with 1MPa nitrogen for three times, introducing mixed gas of ethylene and carbon monoxide mixed according to a certain proportion into the autoclave under stirring for 5min, gradually increasing the pressure to the reaction pressure, simultaneously raising the temperature of the autoclave to the reaction temperature, and sampling for GC analysis after reacting for a certain time.
The group VIII metal compound employed may be any of those listed above; the acidic adjuvant 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 1-5; the molar ratio of ethylene to group VIII metal compound is 50 to 300, preferably 100.
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 that of the methanol;
the molar ratio of the bidentate phosphine ligand to the VIII group metal compound in the catalyst system is 3-1;
the molar ratio of the acid auxiliary agent to the VIII group metal compound is 75-100;
the mass of the bidentate phosphine ligand is 0.4-2% of that of the methanol;
the mass of the acid additive is 1-5.5% of the mass of the methanol.
Examples
The olefin carbonylation reaction will be further described with reference to specific examples and comparative examples. It should be understood that the scope of the present invention is limited only by the following examples. Various substitutions and alterations made according to the knowledge and conventional means of ordinary skill in the art without departing from the technical idea of the present invention should be included in the scope of the present invention.
Preparation of example 1
Bidentate phosphine ligand 1: preparation of N, N-bis (di-tert-butylphosphino) -ethylenediamine
Tetrahydrofuran (100 mL), ethylenediamine (2.4g, 40mmol) and triethylamine (14mL, 100mmol) were sequentially added to a 250mL three-necked flask. The resulting solution was then cooled to 0 ℃ and chlorodiphenylphosphine (14ml, 80mmol) was added slowly. The formation of a white salt 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 the solvent to give 12.3g of a white solid in 85% yield.
Preparation of example 2
Bidentate phosphine ligand 2: preparation of N, N-bis (di-tert-butylphosphino) -N, N-dimethylethylenediamine
The preparation was carried out in the same manner as in preparation example 1 except for changing ethylenediamine to an equimolar amount of N, N-dimethylethylenediamine to obtain 13.3g of a white solid with a yield of 88%.
Preparation of example 3
Bidentate phosphine ligand 3: preparation of N, N-bis (di-tert-butylphosphino) -N, N-diethylethylenediamine
The preparation was carried out in the same manner as in preparation example 1 except for changing ethylenediamine to an equimolar amount of N, N-diethylethylenediamine, to obtain 14.6g of a white solid with a yield of 90%.
Preparation of example 4
Bidentate phosphine ligand 4: preparation of N, N-bis (di-tert-butylphosphino) -N, N-diisopropylethylenediamine
The preparation was carried out in the same manner as in preparation example 1 except for changing ethylenediamine to an equimolar amount of N, N-diisopropylethylenediamine, and 15.7g of a white solid was obtained in a yield of 91%.
Preparation of example 5
Bidentate phosphine ligand 5: preparation of N, N-bis (di-tert-butylphosphino) -N, N-di-tert-butylethylenediamine
The preparation was carried out in the same manner as in preparation example 1 except for changing ethylenediamine to an equimolar amount of N, N-di-t-butylethylenediamine, to obtain 16.4g of a white solid with a yield of 89%.
Preparation of example 6
Bidentate phosphine ligand 6: preparation of N, N-bis (di-tert-butylphosphino) -N, N-diphenylethylenediamine
The preparation was carried out in the same manner as in example 1 except for changing ethylenediamine to an equimolar amount of N, N-diphenylethylenediamine, to obtain 17.0g of a white solid with a yield of 85%.
Preparation of example 7
Bidentate phosphine ligand 7: preparation of N, N-bis (di-tert-butylphosphino) -N, N-bis (4-methoxyphenyl) ethylenediamine
The preparation was carried out in the same manner as in preparation example 1 except for changing ethylenediamine to an equimolar amount of N, N-di (p-methoxy) phenylethylenediamine, whereby 19.3g of a white solid was obtained in a yield of 86%.
Preparation of example 8
Bidentate phosphine ligand 8: preparation of bis ((di-tert-butylphosphino) methyl) methylamine
Methylamine (0.34g, 10.9mmol) and diphenylphosphine (4.06g, 21.8mmol) were added at 65 ℃ to a Schlenk flask containing 40ml of toluene and 0.5g of paraformaldehyde using a syringe. The mixture was stirred at 65 ℃ until the solid paraformaldehyde was completely disappeared (about 4 to 5 hours).
The resulting solution was allowed to cool to room temperature and then filtered through celite. The solvent was removed by rotary evaporation, leaving a clear oil. This was dissolved in about 10mL of dichloromethane, to which 30mL of ethanol was added, and mixed well. The flask containing the resulting solution was then evacuated and filled with nitrogen. At this point a white crystalline crude product was formed, and the flask was subsequently cooled to-20 ℃ overnight to allow complete precipitation of the contents.
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 of example 9
Bidentate phosphine ligand 9: preparation of bis ((di-tert-butylphosphino) methyl) ethylamine
The procedure was carried out in the same manner as in preparation example 8, except that methylamine was changed to an equimolar amount of ethylamine, to give 2.8g of a white solid in a yield of 70%.
Preparation of example 10
Bidentate phosphine ligand 10: preparation of bis ((di-tert-butylphosphino) methyl) isopropylamine
The preparation was carried out in the same manner as in preparation example 8 except for changing methylamine to an equimolar amount of isopropylamine, to obtain 2.9g of a white solid in a yield of 72%.
Preparation of example 11
Bidentate phosphine ligand 11: preparation of bis ((di-tert-butylphosphino) methyl) tert-butylamine
The preparation was carried out in the same manner as in preparation example 8 except for changing methylamine to an equimolar amount of tert-butylamine, and 3.2g of a white solid was obtained in a yield of 75%.
Preparation of example 12
Bidentate phosphine ligand 12: preparation of bis ((di-tert-butylphosphino) methyl) phenylamine
The preparation was carried out in the same manner as in preparation example 8 except for changing methylamine to an equimolar amount of aniline, whereby 3.3g of a white solid was obtained in a yield of 73%.
Preparation of example 13
Bidentate phosphine ligand 13: preparation of bis ((di-tert-butylphosphino) methyl) benzylamine
The preparation was carried out 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 with a yield of 71%.
Preparation of example 14
Bidentate phosphine ligand 14: preparation of bis ((di-tert-butylphosphino) methyl) 4-methoxyphenylamine
The preparation was carried out in the same manner as in preparation example 8 except for changing methylamine to an equimolar amount of p-methoxyaniline, and 3.8g of a white solid was obtained in a yield of 80%.
Preparation of example 15
Bidentate phosphine ligand 15: preparation of bis ((diphenylphosphino) methyl) methylamine
The preparation was carried out in the same manner as in preparation example 8 except that di-tert-butylphosphine was changed to an equimolar amount of diphenylphosphine, giving 3.8g of a white solid with a yield of 82%.
Preparation of example 16
Bidentate phosphine ligand 16: preparation of bis ((bis (4-methoxyphenyl) phosphine) methyl) methylamine
The preparation was carried out in the same manner as in preparation example 8 except for changing di-tert-butylphosphine to an equimolar amount of 4-methoxyphenylphosphine, and 4.6g of a white solid was obtained in a yield of 78%.
Preparation of example 17
Bidentate phosphine ligand 17: preparation of ethylbis ((di-tert-butylphosphino) thio)
The preparation was carried out in the same manner as in preparation example 1 except for changing the ethylenediamine to an equimolar amount of 1, 2-ethanedithiol, and 12.7g of a white solid was obtained in a yield of 83%.
Preparation of example 18
Bidentate phosphine ligand 18: preparation of ethylbis ((di-tert-butylphosphino) ether)
The preparation was carried out in the same manner as in preparation example 1 except for changing ethylenediamine to 1, 2-ethanediol in an equimolar amount to obtain 12.3g of a white solid, with a yield of 88%.
Preparation of example 19
Bidentate phosphine ligand 19: preparation of bis ((di-tert-butylphosphino) methyl) sulfane
The preparation was carried out in the same manner as in preparation example 8 except for changing methylamine to an equimolar amount of hydrogen sulfide, so as to obtain 2.5g of a white solid with a yield of 65%.
Preparation of comparative example 1
Bidentate phosphine ligand 20: preparation of 1, 2-bis ((di-tert-butylphosphino) methyl) -4-tert-butyl-benzene
4-tert-butyl-o-xylene (4.55g, 28.1 mmol) (Aldrich) was diluted with heptane (100 ml) and NaOBu was added thereto t (8.1g, 84.3mmol), TMEDA (12.6ml, 84.3mmol) and t BuLi (2.5M, 33.7ml,84.3mmol in hexane). Butyl lithium was added dropwise and an immediate color change from colorless to yellow to orange to dark red was produced. The solution is then heated to 65 ℃ for 3 hours, resulting in a brown colorAn 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 wash was then removed through a cannula. The solid residue was then suspended in pentane (100 ml) and cooled in a cold water bath. Bu was added dropwise to the suspension t 2 PCl (7.5ml, 39.3mmol). 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 biphasic solution. The upper layer (organic phase) was diluted with pentane (100 ml) and the organic phase was removed via cannula into a clean schlenk bottle. The pentane extract was dried over sodium sulfate and transferred through a cannula into a clean schlenk bottle. 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 ℃ C.) to yield a pale yellow solution and some colorless insoluble material. 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 ℃ overnight, resulting in an off-white solid deposit. The remaining methanol solution was then removed via cannula and the solid was dried under vacuum. The solids were separated in a glove box. The amount of product was 4.20g, yield 33%, purity 95%.
Preparation of comparative example 2
Bidentate phosphine ligand 21: preparation of 1, 2-bis ((di-tert-butylphosphino) methyl) benzene
Preparation was carried out in the same manner as in preparation comparative example 1 except for changing 4-tert-butyl-o-xylene to an equimolar amount of o-xylene, and 4.5g of a white solid was obtained in a yield of 40% and a purity of 95%.
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 (1.22g, 3.50mmol) of bidentate phosphine ligand were charged into a 2L autoclave. Ethylene and carbon monoxide in a molar ratio of 4.
The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 2
The reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and using 1.32g (3.51 mmol) of bidentate phosphine ligand 2. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 3
Except that 0.32g of palladium acetate was changed to 0.3g (1.42 mmol) of PdCl 2 (NH 3 ) 2 And a reaction was carried out in the same manner as in example 1 except for using 1.42g (3.51 mmol) of the bidentate phosphine ligand 3. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 4
Except that 0.32g of palladium acetate was changed to 0.33g (1.42 mmol) of Pd (NH) 3 ) 2 (NO 2 ) 2 And a reaction was carried out in the same manner as in example 1 except for using 1.51g (3.49 mmol) of the bidentate phosphine ligand 4. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
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. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 6
The reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium, 5.40g of methanesulfonic acid to 11.33g (65.79 mmol) of p-toluenesulfonic acid and using 1.75g (3.50 mmol) of bidentate phosphine ligand 6. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results 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 employed and the reaction temperature was 80 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results 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 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 9
Except that 0.32g of palladium acetate was changed to 0.35g (0.71 mmol) of [ Rh (COD) Cl] 2 The same procedures used in example 1 were repeated except for using 1.27g (3.51 mmol) of the bidentate phosphine ligand 9The method carries out the reaction. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 10
Except that 0.32g of palladium acetate was changed to 0.48g (0.71 mmol) [ Ir (COD) Cl] 2 And a reaction was carried out in the same manner as in example 1 except for using 1.31g (3.49 mmol) of the bidentate phosphine ligand 10. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results 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 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results 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 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 13
The reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and using 1.48g (3.49 mmol) of bidentate phosphine ligand 13. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 14
A reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and using 1.54g (3.50 mmol) of bidentate phosphine ligand 14. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 15
The reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and using 1.50g (3.51 mmol) of the bidentate phosphine ligand 15. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 16
A 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. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 17
A 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. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 18
A 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. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Inventive example 19
A reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and using 1.23g (3.51 mmol) of the bidentate phosphine ligand 19. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results 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. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results are shown in table 1.
Comparative example 2 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 2.76g (7.00 mmol) of bidentate phosphine ligand 21 was used. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl propionate, based on carbon monoxide, and the results 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, ethylene and carbon monoxide in a molar ratio of 4 were changed to 1-hexene and carbon monoxide in the same molar ratio, and the reaction temperature was 100 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatographic analysis to calculate the conversion and selectivity, and the yield of the product methyl heptanoate, based on carbon monoxide, and the results 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, ethylene and carbon monoxide in a molar ratio of 4 were changed to 1-pentene and carbon monoxide in the same molar ratio, and the reaction temperature was 100 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity, as well as the yield of the product methyl hexanoate, based on carbon monoxide, and the results are shown in Table 1.
Inventive example 22
The reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and changing 1.54g (3.50 mmol) of bidentate phosphine ligand 14, ethylene and carbon monoxide in a molar ratio of 4 to the same molar ratio of 3-methyl-1-butene and carbon monoxide and the reaction temperature was 100 ℃. The reaction mixture was weighed in an appropriate amount and subjected to GC chromatography to calculate conversion and selectivity based on carbon monoxide and yield of the product methyl 3-methylpentanoate, and the results are shown in Table 1.
Inventive example 23
The reaction was carried out in the same manner as in example 1 except for changing 0.32g of palladium acetate to 0.65g (0.71 mmol) of tris (dibenzylideneacetone) dipalladium and using 1.54g (3.50 mmol) of bidentate phosphine ligand 14, changing the molar ratio of ethylene to carbon monoxide to 4 to the same molar ratio of 3, 3-dimethyl-1-butene to carbon monoxide and the reaction temperature to 100 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity, and the yield of the product methyl 3, 3-dimethylpentanoate, based on carbon monoxide, and the results 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, ethylene and carbon monoxide in a molar ratio of 4 were changed to the same molar ratio of styrene and carbon monoxide, and the reaction temperature was 100 ℃. The reaction mixture was weighed in an appropriate amount and subjected to GC chromatography to calculate conversion and selectivity, and yield of methyl phenylpropionate in terms of carbon monoxide, 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, ethylene and carbon monoxide in a molar ratio of 4 were changed to the same molar ratio of 2-butene and carbon monoxide, and the reaction temperature was 100 ℃. The reaction mixture was weighed in an appropriate amount and subjected to GC chromatography to calculate the conversion and selectivity, and the yield of methyl 2-methylbutyrate in terms of carbon monoxide, 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, ethylene and carbon monoxide in a molar ratio of 4 were changed to the same molar ratio of cyclohexene and carbon monoxide, and the reaction temperature was 100 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity, and the yield of methyl cyclohexylcarboxylate in terms of carbon monoxide, 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, ethylene and carbon monoxide in a molar ratio of 4 were changed to the same molar ratio of 3-hexene to carbon monoxide, and the reaction temperature was 100 ℃. The appropriate amount of the reaction mixture was weighed and subjected to GC chromatography to calculate the conversion and selectivity, and the yield of methyl 2-ethylpentanoate based on carbon monoxide, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1, examples 1 to 27 of the method for the carbonylation of olefins according to the present invention using a catalyst system comprising a specific phosphorus ligand used less phosphorus ligand and a group VIII metal compound, and the selectivity and yield of the product were higher and the conversion of the reaction substrate was higher, compared to comparative examples 1 to 2 using catalyst systems comprising other phosphorus ligands. In examples 1-27, examples 1-16 and 20-27 using catalyst systems comprising nitrogen-containing and phosphorous-containing ligands gave higher selectivity, conversion and yield than examples 17-19 using catalyst systems comprising sulfur-containing or oxygen-containing phosphorous ligands; further, examples 8-16 and 20-27, which employ a catalyst system comprising a phosphorus ligand containing a single nitrogen atom, showed higher selectivity, conversion and yield than examples 1-7, which employ a catalyst system comprising a phosphorus ligand containing 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 0.385g (0.876 mmol) of bidentate phosphine ligand 14 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 rate of 500r/min, a reaction pressure of 1.2MPa and a reaction temperature of 60 ℃ for 120min. After the reaction is finished, cooling to room temperature, then weighing a proper amount of reaction mixed liquid, carrying out GC chromatographic analysis, calculating the conversion rate and selectivity and the yield of the methyl propionate product by using carbon monoxide, and recording the result.
250g (7.81 mol) of methanol were additionally added to the autoclave, and ethylene and carbon monoxide were again introduced into the autoclave in a molar ratio of 4. After the reaction is finished, the reaction mixture is cooled to room temperature, then an appropriate amount of reaction mixture is weighed, GC chromatographic analysis is carried out, the conversion rate and selectivity are calculated according to carbon monoxide, the yield of the methyl propionate product is calculated, and the result is recorded.
The above procedure was repeated three times until a total of 1250g of methanol was finally added to the autoclave and the reaction was completed, and the results of the reactions at each stage are reported in Table 2.
TABLE 2
The embodiments show that the catalyst system containing the specific bidentate phosphine ligand provided by the invention has good catalytic activity and selectivity at lower reaction temperature and reaction pressure, has the advantages of high catalytic efficiency, low consumption, long service life, good selectivity and the like, can efficiently catalyze olefin carbonylation, takes the example of synthesizing methyl propionate by ethylene carbonylation, has a yield of 96.73%, and has good industrial prospect.
Claims (12)
1. A process for the carbonylation of olefins, the process 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) A bidentate phosphine ligand; and
(c) An acidic adjuvant;
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 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 independently selected from the group consisting of 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) 2 C(Rc) 2 -O-、-S-C(Rc) 2 C(Rc) 2 -S-or-N (Rf) -C (Rc) 2 C(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 linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group;
rb and Rf are each independently H, a linear or branched C1-C6 alkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, a C6-C10 aryloxy group, or a C3-C8 heteroaryl group.
2. The process according to claim 1, wherein in 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) 2 C(Rc) 2 -O-、-S-C(Rc) 2 C(Rc) 2 -S-or-N (Rf) -C (Rc) 2 C(Rc) 2 -N(Rf)-。
3. The method according to claim 1 or 2, wherein in the structure represented by A in the general formula (I),
each Rc is independently H or a linear or branched C1-C6 alkyl group, preferably all H;
rf is H, linear 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; rf is preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 4-methoxyphenyl or pyridyl.
4. The process according to claim 1, wherein in the formula (I), each K is-C (Ra) 2 -; a is-O-, -S-or-N (Rb) -.
5. The method according to claim 1 or 4, wherein in the structure represented by A in the general formula (I),
each Ra is independently H or a linear or branched C1-C6 alkyl group, preferably both H;
rb is H, linear 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, or 4-methoxyphenyl or pyridyl.
6. The method according to any one of claims 1 to 5, wherein in the general formula (I), R1 to R4 are each independently a C1 to C6 linear or branched alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a C6 to C10 heteroaryl group; when the aryl of C6-C10 has a substituent, the substituent is C1-C6 alkyl or C1-C6 alkoxy; r1 to R4 are preferably tert-butyl, phenyl, 4-methoxyphenyl, benzyl or pyridyl.
7. The process according to any one of claims 1 to 6, wherein the molar ratio of component (b) to component (a) in the catalyst system is from 2 to 1, preferably from 3 to 1;
the molar ratio of component (c) to component (a) is from 2 to 150, preferably from 50.
8. The method of any one of claims 1-7,
the group VIII metals include: cobalt, nickel, palladium, rhodium, ruthenium, iridium, or platinum;
the group VIII metal compound includes a salt or weakly coordinating anion 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 resins, or perhalogenic acids; or complexes of zero-valent palladium, rhodium, iridium, platinum or ruthenium.
9. A process according to any one of claims 1 to 8, wherein the acidic adjuvant is an acid having a pKa in aqueous solution at 25 ℃ of less than 5, preferably less than 4, more preferably less than 3;
the acid auxiliary agent is preferably at least one of methanesulfonic acid, trifluoromethanesulfonic acid, tert-butylsulfonic acid, p-toluenesulfonic acid, 2-hydroxypropyl-2-sulfonic acid, 2,4, 6-trimethylmethanesulfonic acid, perchloric acid, phosphoric acid, methylphosphoric acid and sulfuric acid; most preferred is methanesulfonic acid.
10. The process according to claim 1, wherein the reaction is carried out under conditions such that the reaction pressure is between 1 and 20MPa, preferably between 1 and 10MPa;
the reaction temperature is 50 to 200 ℃, preferably 60 to 150 ℃.
11. The process according to claim 1, wherein the molar ratio of the olefin to the carbon monoxide is from 1 to 1, preferably from 2 to 50; the molar ratio of the olefin to component (a) in the catalyst system is from 50 to 300, preferably from 100 to 1;
the mass ratio of the alcohol to component (a) in the catalyst system is from 500 to 20000, preferably from 5000 to 15000.
12. The process of claim 1, wherein the olefin is a substituted or unsubstituted C2-C20 olefin; preferably a substituted or unsubstituted C2-C16 alkene;
when the olefin has a substituent, the substituent is 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 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 monoalkanol.
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| CN116237086A (en) * | 2023-03-23 | 2023-06-09 | 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 |
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| CN116237086A (en) * | 2023-03-23 | 2023-06-09 | 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 |
| 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 |
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