CN111617808A - For CO2Catalyst for participating in alkyne carbonylation esterification reaction - Google Patents

For CO2Catalyst for participating in alkyne carbonylation esterification reaction Download PDF

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CN111617808A
CN111617808A CN202010588928.1A CN202010588928A CN111617808A CN 111617808 A CN111617808 A CN 111617808A CN 202010588928 A CN202010588928 A CN 202010588928A CN 111617808 A CN111617808 A CN 111617808A
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alkyne
esterification reaction
catalyst
carbonylation
complex
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严文忠
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C07F15/004—Iridium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/82—Metals of the platinum group
    • B01J2523/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane

Abstract

The invention relates to a method for CO2Catalyst structure participating in carbonylation and esterification reaction of alkyne and preparation method thereof, and relates to catalysis of alkyne and CO by using catalyst2And (3) carbonylation and esterification reaction. The invention develops a metal organic catalyst of a dinitrogen ligand of benzimidazole, which uses CO2Is a C1 source, catalyzes alkyne and CO2And (3) carrying out carbonylation esterification reaction to convert alkyne into α -unsaturated carbonate with high added value, thereby realizing the construction of C-C bond.

Description

For CO2Catalyst for participating in alkyne carbonylation esterification reaction
Technical Field
The invention belongs to the technical field of homogeneous catalysis, and particularly relates to a catalyst for CO2A catalyst participating in the carbonylation and esterification reaction of alkyne.
Background
Greenhouse gas CO2Mainly produced by the combustion of fossil fuels, and is also an extremely abundant and inexpensive resource of C1 on earth. Chemical fixation of CO2The method can relieve the greenhouse effect, can convert the greenhouse effect into chemical products with higher added values, has high atom economy and environmental economy, and becomes an important research direction in the world (nat. Commun.2015,6,5933; Angew. chem. int. Ed.2018,57,15948). With CO2The carbonylation of olefins to a source of C1 to CO2One of the important reaction types for catalytic conversion. The existing reports focus on the research of carboxylic acid products, and the active centers of the developed organometallic catalysts are mainly: nickel, iron, cobalt, palladium, etc. (chem. rev.2001,101, 3435; org. lett.2003,5,4329;chem. 2003,68, 8353; j.am.chem.soc.2008,130, 14936; j.am.chem.soc.2012,134, 11900; chem.lett.2014,43,565). The carboxylic ester compound has a plurality of purposes, such as wines, foods, cosmetics, important chemical intermediates and the like (org.Lett.2011,13, 5; J.Am.chem.Soc.2012,134, 11900; Greenchem.2018,20,5533; nat.Commun.2014,5,3091). The industrial report shows that the synthesis of carboxylic ester compounds mainly uses poisonous CO as carbonyl source and organic alcohol as solvent to carry out the hydrogen esterification reaction on olefin under the conditions of high temperature and high pressure; noble metal catalysis such as Pd, Rh and the like, and expensive phosphine ligands (WO2007057640A1, US6476255B1, CN101665432A, US6294687B 1); selecting CO in consideration of unsafety of CO2Instead of CO, cheap metal is used as a metal catalyst, so that the reaction becomes simple, safe, economic and easy to operate. In recent years, groups of Beller (ChemCatchem2014,6,2805; NatCommun.2014,5,3091; Nat Commun.2015,6,5933; Catal. Sci. Technol.2016, 6,4712), Dupont (ChemSusChem.2015,8,586) and Charuen millet (Green chem.2018,20, 5533) reported in sequence as CO2The catalyst is a carbonyl source, and the Ru-catalyzed alkene carbonyl esterification reaction does not need any sensitive ligand, but needs chloridion liquid/salt as an additive, and has the problems of small substrate range, poor selectivity, high reaction temperature, difficult product separation and the like.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a method for CO2A catalyst structure participating in the carbonylation and esterification reaction of alkyne and a preparation method thereof.
In the first aspect, the catalyst provided by the invention is applied to alkyne and CO2The direct carbonylation esterification reaction with alcohol is shown in scheme 1.
Scheme 1:
Figure RE-GDA0002604804330000021
wherein R is1Is phenyl or phenyl containing substituent; r2Is a hydrogen atom or C1-C3Alkyl groups of (a); r is cyclohexyl or C1-C4Alkyl group of (1).
In a second aspect, the invention relates to a ligand represented by the structural formula X, Y:
Figure RE-GDA0002604804330000022
wherein R is3、R4、R5、R6Can be independently H, C1-C6Alkyl, methoxy, trifluoromethyl and the like.
The reference for the preparation of class X ligands (clever. synthesis of omeprazole process impurities of antiulcer drug [ D ], university of southeast, 2019.) includes the following synthetic steps:
the method comprises the following steps: adding 1H-benzimidazole-2-thiol compounds into a reactor, adding distilled water as a solvent, adding alkaline salt as an auxiliary agent, stirring at room temperature for 10min, slowly adding 2-chloromethylpyridine hydrochloride compounds, and continuing to react at room temperature for 10 hours after the addition is finished.
And step two, removing distilled water from the reaction solution after the reaction is finished through rotary evaporation, dissolving residues with methanol, removing insoluble impurities, and then obtaining the target ligand through column chromatography.
Preferably, the alkaline salt is sodium carbonate or potassium carbonate; the molar ratio of the basic salt to the 1H-benzimidazole-2-thiol compound is 3-4:1.
preferably, the molar ratio of the 1H-benzimidazole-2-thiol compound to the 2-chloromethylpyridine hydrochloride compound is 1: 1.5-2.
Preparation reference of Y-type ligand (synthesis of omeprazole process impurity [ D ], university of southeast, 2019.) was synthesized by the following method:
the method comprises the following steps: adding 1H-benzimidazole-2-thiol compounds into a reactor, adding distilled water as a solvent, adding alkaline salt as an auxiliary agent, stirring at room temperature for 10min, slowly adding 2-chloromethylpyridine hydrochloride compounds, and continuing to react at room temperature for 10 hours after the addition is finished.
And step two, removing distilled water from the reaction solution after the reaction is finished through rotary evaporation, dissolving the residue with methanol, removing insoluble impurities, and then obtaining the target intermediate through column chromatography.
And step three, adding the intermediate into a round-bottom flask, adding dichloromethane serving as a solvent, adding potassium bicarbonate serving as an auxiliary agent, slowly dropwise adding m-CPBA (m-chloroperoxybenzoic acid) under the stirring condition of 0 ℃, and continuously keeping the temperature of 0 ℃ for reacting for 6 hours after dropwise adding. Filtering and recrystallizing to obtain the Y-type ligand.
Preferably, the alkaline salt is sodium carbonate or potassium carbonate; the molar ratio of the basic salt to the 1H-benzimidazole-2-thiol compound is 3-4:1.
preferably, the molar ratio of the 1H-benzimidazole-2-thiol compound to the 2-chloromethylpyridine hydrochloride compound is 1: 1.5-2.
Preferably, the step three comprises the following steps of: potassium bicarbonate: m-CPBA ═ 1:3-4: 1.2-1.5.
In a third aspect, the catalyst of the present invention is represented by the structural formulae of complex a and complex B:
Figure RE-GDA0002604804330000031
wherein M is metal such as Ru, Co, Ir, Ni, Cu, Mn, Zn, Fe and the like;
the preparation method of the complex A or the complex B comprises the following steps:
under the protection of inert gas, 1-2 millimoles of ligand are dissolved in 50-60 millimoles of acetonitrile, 1 millimole of precursor metal salt is added, the mixture is heated to 50 ℃, stirred for 2 hours, cooled to low temperature, crystals are precipitated, filtered and dried, and the catalyst is obtained.
The ligand and the catalyst related to the invention are detected by a nuclear magnetic resonance method, and are proved to be the ligand and the catalyst.
The invention has the following beneficial effects:
the invention realizes alkyne and CO by using a catalyst of cheap and more stable bidentate nitrogen ligand2And the carbonylation and esterification reaction of organic alcohol.
Drawings
FIG. 1 is a hydrogen spectrum of example 3; FIG. 2 is a carbon spectrum of example 3.
Detailed Description
In order to better understand the invention, the following examples are further provided to illustrate the invention, but the invention is not limited to the following examples, and should not be construed as being limited thereto.
Example 1
Synthesis of class X ligand 2- ((pyridyl-2-methyl) thio) -1H-benzo [ d ] imidazole
Figure RE-GDA0002604804330000041
The implementation method comprises the following steps:
1H-benzimidazole-2-thiol (1.5g,10mmol) was added to a round-bottomed flask under nitrogen atmosphere, 10mL of distilled water was added as a solvent, sodium carbonate (3.18g, 30mmol) was added, stirring was carried out at room temperature for 10min, a methanol solution of 2-chloromethylpyridine hydrochloride (2.46g,15mmol) was slowly added dropwise, and the mixture was allowed to react at room temperature for 10 hours after completion of the dropwise addition. After the reaction is finished, spinning dry, dissolving with methanol, filtering to remove impurities, performing column chromatography with EA/PE ═ 1:5, and spinning dry the solvent to obtain 2.10g of X ligand 2- ((pyridyl-2-methyl) sulfenyl) -1H-benzo [ d ] b]Imidazole ligand, yield 87%.1H NMR(400MHz,CDCl3)8.52(s,1H), 7.67(s,1H),7.56(d,J＝6.8Hz,2H),7.21(dd,J＝18.9,12.1Hz,4H),6.85(s,1H), 4.51–4.46(m,2H).13C NMR(100MHz,CDCl3)154.3,154.1148.9,140.8,140.0, 139.0,124.2,122.6,122.3,119.5,116.2,110.8,36.1.[M+H]＝242.31
Example 2
Synthesis of class Y ligand 2- ((pyridin-2-ylmethyl) sulfinyl) -1H-benzo [ d ] imidazole
Figure RE-GDA0002604804330000042
Under nitrogen atmosphere, 1.5g (10 mmol) of 1H-benzimidazole-2-thiol was added to a round-bottomed flask, 10mL of distilled water was added as a solvent, and carbon was addedSodium (3.18g, 30mmol), stirred at room temperature for 10min, slowly added dropwise with a methanol solution of 2-chloromethylpyridine hydrochloride (2.46g,15mmol), and after completion of the dropwise addition, the reaction was carried out at room temperature for 10 hours. After the reaction is finished, the product is dried by spinning, dissolved by methanol, filtered to remove impurities, and then is subjected to column chromatography by using EA/PE (1: 5) column, and the solvent is dried by spinning to obtain 2.10g of 2- ((pyridyl-2-methyl) sulfenyl) -1H-benzo [ d]An imidazole intermediate; dissolving 2.10g of intermediate by using dichloromethane, adding potassium bicarbonate (2.61g, 26.1mmol), cooling to 0 ℃, dropwise adding a dichloromethane solution of m-chloroperoxybenzoic acid (1.8g,10.44mmol) while stirring, keeping the temperature at 0 ℃ for reacting for 6 hours after dropwise adding, filtering after the reaction is finished to obtain a filter cake, recrystallizing the filter cake by using methanol, and drying to obtain the 2.1gY type ligand 2- ((pyridine-2-ylmethyl) sulfinyl) -1H-benzo [ d]Imidazole ligand, yield 91.9%.1H NMR(400MHz,CDCl3)8.52(s,1H),7.68 (s,1H),7.58(d,J＝1.9Hz,2H),7.32–7.11(m,5H),4.20–4.10(m,2H).13C NMR (100MHz,CDCl3)153.7,148.1,141.4,140.0,139.0,126.4,122.6,122.3,120.4, 116.2,110.8.[M+H]＝258.06.
Example 3
Preparation of Complex A1
Figure RE-GDA0002604804330000051
Under the protection of nitrogen, 1.5mmol of the ligand prepared in example 1 is dissolved in 3mL of acetonitrile in a pressure resistant tube, 1mmol of iridium trichloride is added, the mixture is heated to 50 ℃, stirred for 2 hours, cooled to-10 ℃ to precipitate crystals, and the complex A1 catalyst is obtained after filtration and drying. The hydrogen spectrum and the carbon spectrum are shown in FIG. 1 and FIG. 21H NMR(400MHz,CDCl3)8.67(s,1H),7.56(d,J＝6.8Hz,2H),7.67(m,1H), 7.21(dd,J＝18.9,12.1Hz,4H),6.95(s,1H),4.51–4.46(m,2H).13C NMR(100 MHz,CDCl3)157.3,157.1,153.9,148.8,148.0,144.0,134.2,125.6,125.3,119.5, 118.2,112.8,40.1[M+H]＝540.90。
Example 4
Preparation of Complex B1
Figure RE-GDA0002604804330000052
Under the protection of nitrogen, 1.5mmol of the ligand prepared in example 1 is dissolved in 3mL of acetonitrile in a pressure resistant tube, 1mmol of iridium trichloride is added, the mixture is heated to 50 ℃, stirred for 2 hours, cooled to-10 ℃ to precipitate crystals, and the complex A1 catalyst is obtained after filtration and drying.1H NMR(400MHz,CDCl3) 9.30(s,1H),7.86(d,J＝6.8Hz,2H),7.67(m,2H),7.41(dd,J＝18.9,12.1Hz,4H), 4.51(m,2H).13C NMR(100MHz,CDCl3)156.3,156.1,152.9,147.8,147.0,144.0, 134.2,125.6,124.3,118.5,117.2,111.8,39.1.[M+H]＝556.90。
Example 5
Figure RE-GDA0002604804330000061
Adding 2mmol of phenylacetylene, 2.2mmol of methanol, 2mL of acetonitrile, methanesulfonic acid (0.1-0.4mmol), and catalyst (5% -10%) into a high-pressure reaction kettle, and introducing 50bar of CO2Reacting at 80-160 ℃ for 12-36 hours, cooling to room temperature, adding an internal standard substance of n-hexadecane (1mmol,0.5equiv.), and analyzing the conversion rate of the phenylacetylene and the selectivity of branched chains and straight chains of the product by using GC.
Figure RE-GDA0002604804330000062
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (5)

1. For CO2Participate in the carbonylation and esterification reaction of alkyneThe catalyst is characterized in that the catalyst is a metal organic complex with stable structure, and the structural formula of the metal organic complex is as follows:
Figure FDA0002554751570000011
wherein M is metal such as Ru, Co, Ir, Ni, Cu, Mn, Zn, Fe and the like; the structural formula of the dinitrogen ligand with stable structural performance is as follows:
Figure FDA0002554751570000012
wherein R is3、R4、R5、R6Can be independently H, C1-C6Alkyl, methoxy, trifluoromethyl and the like.
2. The method of claim 1 for CO2The catalyst participating in the carbonylation and esterification reaction of alkyne is characterized in that the metal center M is Ru, Co, Ir, Ni, Cu, Mn, Zn and Fe; preferably Ir; r in ligand X, Y3、R4、R5、R6Preferably H.
3. CO (carbon monoxide)2A process for participating in an alkyne carbonylation esterification reaction comprising reacting an alkene with CO in the presence of a catalyst of the formula complex a or complex B according to claim 12And the scheme of the direct alcohol hydrogen esterification reaction:
Figure FDA0002554751570000013
。
4. CO according to claim 32A method for participating in the carbonylation and esterification reaction of alkyne, wherein R1Is phenyl or phenyl containing substituent; r2Is a hydrogen atom or C1-C3Alkyl groups of (a); r is cyclohexyl or C1-C4Alkyl group of (1).
5. The catalyst complex A or the complex B according to claim 1 for use in catalyzing direct carbonylation and esterification of an alkyne with CO2 and an organic alcohol.
CN202010588928.1A 2020-06-24 2020-06-24 For CO2Catalyst for participating in alkyne carbonylation esterification reaction Withdrawn CN111617808A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957012A (en) * 2022-05-20 2022-08-30 湖南工程学院 Preparation method for synthesizing unsaturated organic carboxylic ester by carbon dioxide and alkyne

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957012A (en) * 2022-05-20 2022-08-30 湖南工程学院 Preparation method for synthesizing unsaturated organic carboxylic ester by carbon dioxide and alkyne

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Application publication date: 20200904