CN111617808A - For CO2Catalyst for participating in alkyne carbonylation esterification reaction - Google Patents
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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
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 17
- 230000006315 carbonylation Effects 0.000 title claims abstract description 15
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 15
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract 2
- -1 alcohol hydrogen Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940052810 complex b Drugs 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 abstract 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical class Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 159000000011 group IA salts Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- SUBDBMMJDZJVOS-UHFFFAOYSA-N 5-methoxy-2-{[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]sulfinyl}-1H-benzimidazole Chemical compound N=1C2=CC(OC)=CC=C2NC=1S(=O)CC1=NC=C(C)C(OC)=C1C SUBDBMMJDZJVOS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229960000381 omeprazole Drugs 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003699 antiulcer agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table 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
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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
- 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
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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
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:
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:
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:
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
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
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
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
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
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.
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:
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:
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:
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.
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