CN110590658B - Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound - Google Patents

Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound Download PDF

Info

Publication number
CN110590658B
CN110590658B CN201910961915.1A CN201910961915A CN110590658B CN 110590658 B CN110590658 B CN 110590658B CN 201910961915 A CN201910961915 A CN 201910961915A CN 110590658 B CN110590658 B CN 110590658B
Authority
CN
China
Prior art keywords
reaction
catalyst
nitrogen
unsaturated heterocyclic
containing unsaturated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910961915.1A
Other languages
Chinese (zh)
Other versions
CN110590658A (en
Inventor
刘强
王玉杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN201910961915.1A priority Critical patent/CN110590658B/en
Publication of CN110590658A publication Critical patent/CN110590658A/en
Application granted granted Critical
Publication of CN110590658B publication Critical patent/CN110590658B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J31/20—Carbonyls
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • C07D221/12—Phenanthridines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
    • C07F13/005—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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese

Abstract

The invention provides a method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compounds, belonging to the technical field of catalytic hydrogenation. The invention provides a method for catalytically hydrogenating nitrogen-containing unsaturated heterocyclic compounds, which comprises the following steps: in the presence of hydrogen and a manganese catalyst, a nitrogen-containing unsaturated heterocyclic compound is used as a substrate for hydrogenation reaction. The manganese catalyst adopted by the invention is an NNP type pincerlike manganese catalyst, and has the advantages of low price, easy obtainment and low toxicity compared with a noble metal catalyst; compared with the existing cheap metal iron catalyst or cobalt catalyst, the method has the advantages of wide substrate applicability and high yield of target products; compared with a PNP type pincerlike manganese catalyst, the catalyst has stronger electron-donating ability and smaller steric hindrance, so the catalyst shows higher reaction activity in a series of hydrogenation reactions, and the yield of a target product can reach 99 percent at most.

Description

Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a method for catalytically hydrogenating a nitrogen-containing unsaturated heterocyclic compound.
Background
The hydrogenation reaction of the unsaturated heterocyclic compound is a very important reaction in organic synthesis, and can be used for conveniently synthesizing various compounds containing a saturated heterocyclic structure and providing a material basis for medicinal active molecules taking the saturated heterocyclic structure as a core skeleton. The hydrogenation of unsaturated heterocyclic compounds destroys the aromaticity of the unsaturated heterocyclic compounds, and compared with the hydrogenation of common unsaturated substrates such as ketone, imine and the like, the aromatic stabilizing energy of the heterocyclic compounds is additionally overcome, so that the hydrogenation of the unsaturated heterocyclic compounds is relatively more difficult. The hydrogenation of unsaturated heterocyclic compounds has now made considerable progress thanks to noble metal catalysts (j.am. chem. soc.2003,125, 10536; j.am. chem. soc.2011,133,9878) and the development of hindered lewis acids and bases on catalysts (FPLs) (org.lett.2015,17,6266; angelw. chem. int. ed.2019,58,4664). However, the hindered lewis acid-base is very complicated for catalyst synthesis and has poor self-stability; the noble metal catalyst depends on the use of noble metal, and the storage amount of the noble metal in the earth crust is limited and the noble metal catalyst is expensive. Therefore, the development of cheaper and efficient catalysts for catalyzing the hydrogenation of unsaturated heterocyclic compounds is a very important and urgent scientific problem to be solved in the organic chemistry at present.
At present, there are reports of catalytic hydrogenation of unsaturated heterocyclic compounds by using cheap metal catalysts, such as iron catalysts or cobalt catalysts (j.am. chem.soc.2014,136, 8564; ACS catal.2015,5,6350; angelw. chem.int.ed.2017,56,3216), but the substrate application range of the above catalysts is limited, and the catalytic effect needs to be improved.
Disclosure of Invention
The invention aims to provide a method for catalytically hydrogenating a nitrogen-containing unsaturated heterocyclic compound, which adopts an NNP type pincerlike manganese catalyst to catalytically hydrogenate the nitrogen-containing unsaturated heterocyclic compound and has the advantages of wide substrate applicability and good catalytic effect.
In order to achieve the above object, the present invention provides the following technical solutions:
a process for the catalytic hydrogenation of a nitrogen-containing unsaturated heterocyclic compound comprising the steps of:
in the presence of hydrogen and a manganese catalyst, a nitrogen-containing unsaturated heterocyclic compound is used as a substrate to carry out hydrogenation reaction; the manganese catalyst is any one of structural compounds shown in formulas I to IV:
Figure BDA0002229223460000021
preferably, the nitrogen-containing unsaturated heterocyclic compound comprises
Figure BDA0002229223460000022
Figure BDA0002229223460000023
Preferably, the molar ratio of the manganese catalyst to the nitrogen-containing unsaturated heterocyclic compound is (1-2): 100.
preferably, the hydrogenation reaction is carried out in the presence of an alkaline agent and an organic solvent.
Preferably, the alkaline reagent comprises potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide or sodium ethoxide, and the molar ratio of the alkaline reagent to the nitrogen-containing unsaturated heterocyclic compound is (20-30): 100.
preferably, the organic solvent comprises tetrahydrofuran, toluene or dioxane, and the dosage ratio of the organic solvent to the nitrogen-containing unsaturated heterocyclic compound is (0.5-1.0) mL: 0.25 mmol.
Preferably, the pressure of the hydrogen is 60 to 80 bar.
Preferably, the temperature of the hydrogenation reaction is 120 ℃, and the time is 8-16 h.
Preferably, the preparation method of the manganese catalyst having the structure shown in formula II comprises the following steps:
mixing 2-chloroethylamine hydrochloride, trimethylchlorosilane, triethylamine and dichloromethane, and then carrying out a first substitution reaction to obtain 2-chloro-N, N-bis (trimethylsilyl) ethylamine;
in a protective atmosphere, mixing diphenylphosphine hydrogen, N-butyllithium and tetrahydrofuran, then carrying out an acid-base reaction, adding the 2-chloro-N, N-bis (trimethylsilyl) ethylamine into the obtained product system, carrying out a second substitution reaction, and then removing trimethylsilyl to obtain diphenylphosphine ethylamine;
in a protective atmosphere, mixing the diphenylphosphine ethylamine, imidazole formaldehyde and tetrahydrofuran, then carrying out a condensation reaction, removing the tetrahydrofuran in an obtained product system, and adding toluene and diisobutyl aluminum hydride to carry out a reduction reaction to obtain an imidazole NNP ligand;
and in a protective atmosphere, mixing the imidazole NNP ligand with manganese pentacarbonyl bromide, and then carrying out a coordination substitution reaction to obtain the manganese catalyst with the structure shown in the formula II.
Preferably, the temperature of the first substitution reaction is room temperature, and the time is 10-15 h;
the temperature of the acid-base reaction is room temperature, and the time is 1.5-2.5 h;
the temperature of the second substitution reaction is 80 ℃, and the time is 10-15 h;
the condensation reaction is carried out at room temperature for 50-70 min;
the temperature of the reduction reaction is room temperature, and the time is 1.5-2.5 h;
the temperature of the coordination substitution reaction is 110 ℃, and the time is 10-15 h.
The invention provides a method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compounds, which comprises the following steps: in the presence of hydrogen and a manganese catalyst, a nitrogen-containing unsaturated heterocyclic compound is used as a substrate to carry out hydrogenation reaction; the manganese catalyst is any one of structural compounds shown in formulas I to IV. The invention adopts the cheap metal manganese catalyst to realize the hydrogenation reduction of the nitrogen-containing unsaturated heterocyclic compound, and has the advantages of low price, easy obtaining and low toxicity compared with the noble metal catalyst; compared with the existing cheap metal iron catalyst or cobalt catalyst, the method has the advantages of wide substrate applicability and high yield of target products. The manganese catalyst adopted by the invention is an NNP type pincerlike manganese catalyst, and compared with a PNP type pincerlike manganese catalyst, the NNP type pincerlike manganese catalyst has stronger electron-donating capability and smaller steric hindrance, so the NNP type pincerlike manganese catalyst has higher reaction activity in a series of hydrogenation reactions, and the yield of a target product can reach 99 percent at most.
Drawings
FIG. 1 is a schematic diagram of the transition state structure of hydrogenation of NNP type pincerlike manganese catalyst [ Mn ] -1;
FIG. 2 is a schematic diagram of the transition state structure of hydrogenation of PNP type pincerlike manganese catalyst [ Mn ] -5.
Detailed Description
The invention provides a method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compounds, which comprises the following steps:
in the presence of hydrogen and a manganese catalyst, a nitrogen-containing unsaturated heterocyclic compound is used as a substrate to carry out hydrogenation reaction; the manganese catalyst is any one of structural compounds shown in formulas I to IV:
Figure BDA0002229223460000041
in the present invention, unless otherwise specified, the required reactants and reagents are commercially available products well known to those skilled in the art.
In the present invention, the nitrogen-containing unsaturated heterocyclic compound preferably includes
Figure BDA0002229223460000042
Figure BDA0002229223460000043
Figure BDA0002229223460000051
In the present invention, the nitrogen-containing unsaturated heterocyclic compound is preferably used in an amount of at least 0.25 mmol.
In the invention, the molar ratio of the manganese catalyst to the nitrogen-containing unsaturated heterocyclic compound is preferably (1-2): 100, more preferably 2: 100.
in the present invention, the hydrogenation reaction is preferably carried out in the presence of an alkaline agent and an organic solvent; the alkaline reagent preferably comprises potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide or sodium ethoxide, more preferably potassium tert-butoxide, and the molar ratio of the alkaline reagent to the nitrogen-containing unsaturated heterocyclic compound is preferably (20-30): 100, more preferably 20: 100, respectively; the organic solvent preferably comprises tetrahydrofuran, toluene or dioxane, more preferably tetrahydrofuran, and the dosage ratio of the organic solvent to the nitrogen-containing unsaturated heterocyclic compound is preferably (0.5-1.0) mL: 0.25mmol, more preferably 0.5 mL: 0.25 mmol.
In the invention, the pressure of the hydrogen is preferably 60 to 80bar, and more preferably 70 to 80 bar.
In the invention, the temperature of the hydrogenation reaction is preferably 120 ℃, and the time is preferably 8-16 h, more preferably 12-16 h, and further preferably 16 h. In the present invention, the hydrogenation reaction is preferably carried out under stirring conditions, and the rotation speed of the stirring is not particularly limited in the present invention, so that the hydrogenation reaction can be smoothly carried out.
In the present invention, it is preferable that the alkali agent, the manganese catalyst, the organic solvent and the nitrogen-containing unsaturated heterocyclic compound are mixed in a protective atmosphere, then the protective gas is replaced with hydrogen gas, and the hydrogenation reaction is carried out in a hydrogen atmosphere. In the embodiment of the invention, specifically, in a glove box filled with argon, an alkaline reagent, a manganese catalyst, an organic solvent and a nitrogen-containing unsaturated heterocyclic compound are sequentially added into a glass bottle with a stirrer, a bottle cap is covered, a needle head (the length is preferably 3-4 cm, and the aperture of the vent hole is preferably 1-2 mm) with a vent hole is inserted into the bottle cap, the glass bottle is placed into an autoclave, then the autoclave is taken out from the glove box, argon (3 x 10bar) in the autoclave is replaced by hydrogen, then 60-80 bar hydrogen is filled, and hydrogenation reaction is carried out for 8-16 h under the conditions of stirring and 120 ℃.
After the hydrogenation reaction is finished, the invention preferably cools the autoclave by using an ice water bath, then carefully releases the gas in the autoclave, samples the obtained reaction product system for GC quantification and obtains the target product by column chromatography separation. The chromatographic conditions for the GC quantification and the reagents for the column chromatographic separation are not particularly limited in the present invention, and may be those well known to those skilled in the art depending on the specific type of the target product.
In the invention, the manganese catalyst is any one of structural compounds shown in formulas I to IV and is respectively marked as manganese catalysts [ Mn ] -1, [ Mn ] -2, [ Mn ] -3 and [ Mn ] -4:
Figure BDA0002229223460000061
the manganese catalyst adopted by the invention is an NNP type pincerlike manganese catalyst, and has the advantages of low price, easy obtainment and low toxicity compared with a noble metal catalyst; compared with the existing cheap metal iron catalyst or cobalt catalyst, the method has the advantages of wide substrate applicability and high yield of target products; compared with a PNP type pincerlike manganese catalyst, the catalyst has stronger electron-donating ability and smaller steric hindrance, so the catalyst shows higher reaction activity in a series of hydrogenation reactions, and the yield of a target product can reach 99 percent at most. In the present invention, the manganese catalysts [ Mn ] -1, [ Mn ] -3 and [ Mn ] -4 are preferably synthesized by reference methods (chem.Sci.2017,8,3576; J.Am.chem.Soc.2017,139, 11941; Angew.chem.int.Ed.2018,57,13439), and the preparation method of the manganese catalyst [ Mn ] -2 preferably comprises the steps of:
mixing 2-chloroethylamine hydrochloride, trimethylchlorosilane, triethylamine and dichloromethane, and then carrying out a first substitution reaction to obtain 2-chloro-N, N-bis (trimethylsilyl) ethylamine;
in a protective atmosphere, mixing diphenylphosphine hydrogen, N-butyllithium and tetrahydrofuran, then carrying out an acid-base reaction, adding the 2-chloro-N, N-bis (trimethylsilyl) ethylamine into the obtained product system, carrying out a second substitution reaction, and then removing trimethylsilyl to obtain diphenylphosphine ethylamine;
in a protective atmosphere, mixing the diphenylphosphine ethylamine, imidazole formaldehyde and tetrahydrofuran, then carrying out a condensation reaction, removing the tetrahydrofuran in an obtained product system, and adding toluene and diisobutyl aluminum hydride to carry out a reduction reaction to obtain an imidazole NNP ligand;
and in a protective atmosphere, mixing the imidazole NNP ligand with manganese pentacarbonyl bromide, and then carrying out a coordination substitution reaction to obtain a manganese catalyst with a structure shown in a formula II, namely a manganese catalyst [ Mn ] -2.
The invention uses 2-chloroethylamine hydrochloride, trimethylchlorosilane and triethylamine (NEt)3) And mixing with dichloromethane, and carrying out a first substitution reaction to obtain the 2-chloro-N, N-bis (trimethylsilyl) ethylamine. In the present invention, the ratio of the amount of 2-chloroethylamine hydrochloride, trimethylchlorosilane and triethylamine is preferably 40 mmol: (130-135) mmol: (11-12) mL, more preferably 40 mmol: 132 mmol: 11.4 mL; the dosage of the dichloromethane is not specially limited, and the first substitution reaction can be ensured to be smoothly carried out; wherein triethylamine is used as a binding agent to neutralize hydrochloric acid generated in the substitution process, and dichloromethane is used as a solvent for the first substitution reaction. In the invention, the 2-chloroethylamine hydrochloride and the trimethylchlorosilaneThe mixing of triethylamine and dichloromethane is preferably carried out by dissolving trimethylchlorosilane in dichloromethane to obtain a dichloromethane solution of trimethylchlorosilane, adding 2-chloroethylamine hydrochloride and triethylamine to dichloromethane, and then adding the dichloromethane solution of trimethylchlorosilane to the obtained system.
In the present invention, the temperature of the first substitution reaction is preferably room temperature, and the room temperature does not need additional heating or cooling; in the examples of the present invention, room temperature specifically means 25 ℃. In the present invention, the time of the first substitution reaction is preferably 10 to 15 hours, and more preferably 12 hours. In the present invention, the first substitution reaction is preferably carried out under stirring conditions, and the rotation speed of the stirring is not particularly limited in the present invention, and the first substitution reaction can be smoothly carried out.
After the first substitution reaction is finished, the excessive triethylamine, trimethylchlorosilane and dichloromethane in the obtained product system are preferably removed under reduced pressure, normal hexane is added into the obtained residue, the mixture is stirred for 25-35 min at room temperature, and NEt is removed through filtration3And HCl, performing rotary evaporation on the filtrate by using a rotary evaporator to remove N-hexane, and performing reduced pressure distillation by using an oil pump to obtain a fraction which is a target product, namely 2-chloro-N, N-bis (trimethylsilyl) ethylamine.
After 2-chloro-N, N-bis (trimethylsilyl) ethylamine is obtained, diphenyl phosphine hydrogen, N-butyllithium and tetrahydrofuran are mixed in protective atmosphere and then subjected to acid-base reaction, the 2-chloro-N, N-bis (trimethylsilyl) ethylamine is added into the obtained product system, and trimethylsilyl is removed after secondary substitution reaction to obtain the diphenyl phosphine ethylamine. In the present invention, the molar ratio of diphenylphosphine hydride, N-butyllithium and 2-chloro-N, N-bis (trimethylsilyl) ethylamine is preferably 10: (10.5-11.5): (10.5 to 11.5), more preferably 10: 11: 11; the n-butyllithium is preferably used in the form of an n-hexane solution of n-butyllithium, and the concentration of the n-hexane solution of n-butyllithium (commercially available) is preferably 2.5 mol/L; the dosage of the tetrahydrofuran is not specially limited, and the second substitution reaction can be ensured to be smoothly carried out; wherein tetrahydrofuran is used as a solvent for the second substitution reaction.
In the invention, the diphenyl phosphine hydrogen, the n-butyl lithium and the tetrahydrofuran are mixed, preferably, the tetrahydrofuran solution of the diphenyl phosphine hydrogen is added into a Schlenk bottle under the protection of argon gas and at the temperature of-75 to-80 ℃, and then the n-hexane solution of the n-butyl lithium is slowly dropped; after the dropwise addition is finished, the temperature of the reaction system is adjusted to the temperature required by the acid-base reaction, and the acid-base reaction is carried out. The dropping rate of the n-hexane solution of n-butyllithium in the present invention is not particularly limited, and may be a dropping rate known to those skilled in the art.
In the invention, the temperature of the acid-base reaction is preferably room temperature, and the time is preferably 1.5-2.5 h, and more preferably 2 h; the acid-base reaction is preferably carried out under stirring conditions, and the stirring speed is not particularly limited in the invention, and the conventional stirring speed is only required. In the acid-base reaction process, the n-butyl lithium can pull out the proton of the hydrogen of the diphenylphosphine to form diphenylphosphine anions, which is beneficial to the occurrence of the subsequent substitution reaction.
After the acid-base reaction is completed, the method does not need to carry out post-treatment on the obtained product system, and directly adds the 2-chloro-N, N-di (trimethylsilyl) ethylamine into the product system, carries out a second substitution reaction, and then removes the trimethylsilyl group to obtain the diphenylphosphine ethylamine. Preferably, a product system obtained after the acid-base reaction is cooled to 0 ℃ by using an ice water bath, and 2-chloro-N, N-bis (trimethylsilyl) ethylamine is slowly dripped; and after the dropwise addition is finished, adjusting the temperature of the reaction system to the temperature required by the second substitution reaction, and carrying out the second substitution reaction. The dropping rate of the 2-chloro-N, N-bis (trimethylsilyl) ethylamine is not particularly limited in the present invention, and may be a dropping rate well known to those skilled in the art.
In the present invention, the temperature of the second substitution reaction is preferably 80 ℃, and specifically, the reaction system may be maintained in a reflux state; the time of the second substitution reaction is preferably 10-15 h, and more preferably 12 h.
In the embodiment of the invention, the system obtained after the second substitution reaction is cooled to room temperature, water is added to quench possible residual n-butyl lithium, then sulfuric acid (the concentration is preferably 2.0mmol/mL) is added, stirring is carried out for 50-70 min to remove trimethylsilyl groups, then sodium hydroxide solution (the concentration is preferably 4.0mmol/mL) is added, and stirring is carried out for 25-35 min to neutralize sulfuric acid; and (3) separating an organic phase, extracting the water phase with diethyl ether for 3-4 times, combining the obtained organic phases, drying the organic phases with anhydrous sodium sulfate, and then carrying out spin-drying on the diethyl ether with a rotary evaporator to obtain a crude product containing the diphenylphosphine ethylamine, wherein the crude product is directly used for the next feeding without further column chromatography separation.
After the diphenylphosphine ethylamine is obtained, the diphenylphosphine ethylamine, imidazole formaldehyde and tetrahydrofuran are mixed and then subjected to condensation reaction in a protective atmosphere, the tetrahydrofuran in an obtained product system is removed under reduced pressure, and toluene and diisobutylaluminum hydride are added for reduction reaction to obtain the imidazole NNP ligand. In the present invention, the molar ratio of the diphenylphosphinoethylamine to the imidazolecarboxaldehyde is preferably 1: 1, specifically, the amount of the substance of diphenylphosphinoethylamine is the amount of the substance of diphenylphosphinoethylamine in the crude product obtained in the above step; the amount of the tetrahydrofuran is not particularly limited, and the tetrahydrofuran is used as a solvent for the condensation reaction, so that the condensation reaction can be smoothly carried out.
In the present invention, the mixture of diphenylphosphinoethylamine, imidazolecarboxaldehyde and tetrahydrofuran is preferably a tetrahydrofuran solution of diphenylphosphinoethylamine added dropwise to a tetrahydrofuran solution of imidazolecarboxaldehyde, and the addition rate of the tetrahydrofuran solution of diphenylphosphinoethylamine is not particularly limited in the present invention, and may be any one known to those skilled in the art.
In the invention, the condensation reaction is preferably performed at room temperature, and the time is preferably 50-70 min, and more preferably 60 min.
After the condensation reaction is finished, tetrahydrofuran in the obtained product system is removed, and toluene and diisobutylaluminum hydride are added for reduction reaction to obtain the imidazole NNP ligand. In the present invention, the tetrahydrofuran is preferably removed by pumping with an oil pump through a schlenk line connected to a cold trap. In the invention, toluene is used as a solvent for the reduction reaction, and the amount of toluene used in the invention is not particularly limited, so that the reduction reaction can be carried out smoothly. In the present invention, the diisobutylaluminum hydride is used as a reducing agent; the molar ratio of diisobutylaluminum hydride to diphenylphosphinoethylamine is preferably (1.5-2.0): 1, more preferably 1.8: 1, the diisobutylaluminum hydride is preferably used in the form of a toluene solution of diisobutylaluminum hydride, the concentration of the toluene solution of diisobutylaluminum hydride (commercially available) being preferably 1.5 mol/L.
In the invention, the temperature of the reduction reaction is preferably room temperature, and the time is preferably 1.5-2.5 h, and more preferably 2 h.
After the reduction reaction is completed, the method preferably adds water to the obtained product system for quenching reaction, separates out an organic phase, extracts a water phase for 3-4 times by using diethyl ether, combines the obtained organic phases, dries the organic phase by spinning after drying by using anhydrous sodium sulfate, and obtains a light yellow oily liquid after column chromatography separation as a target product, namely the imidazole NNP ligand (2- (diphenylphosphine) -N- ((1-methyl-1H-imidozol-2-yl) methyl) ethane-1-amine). In the invention, the eluent used for column chromatography separation is preferably a mixed solution of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is preferably 20: 1.
after obtaining the imidazole NNP ligand, the invention mixes the imidazole NNP ligand with manganese pentacarbonyl bromide in protective atmosphere and then carries out coordination substitution reaction to obtain the manganese catalyst with the structure shown in formula II, namely the manganese catalyst [ Mn ] -2. In the invention, the molar ratio of the imidazole NNP ligand to the manganese pentacarbonyl bromide is preferably (0.60-0.70): 0.60, more preferably 0.65: 0.60. in the present invention, the mixing of the imidazole NNP ligand with manganese pentacarbonyl bromide and subsequent coordination substitution reactions are preferably performed in a glove box with argon shield.
In the invention, the temperature of the coordination substitution reaction is preferably 110 ℃, and specifically the coordination substitution reaction is carried out in a system reflux state; the time of the coordination substitution reaction is preferably 10 to 15 hours, and more preferably 12 hours.
After the coordination substitution reaction is finished, the obtained system is preferably cooled to room temperature, yellow precipitate is separated out, the yellow filter cake is washed by toluene for 2-3 times after filtration, the filter cake is washed by diethyl ether for 3-4 times, and then the target product, namely the manganese catalyst [ Mn ] -2, is obtained after vacuum drying. The specific conditions of the vacuum drying are not particularly limited, and the materials can be fully dried.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a manganese catalyst having a structure represented by formula II, namely, a manganese catalyst [ Mn ] -2, comprising the steps of:
(1) synthesis of 2-chloro-N, N-bis (trimethylsilyl) ethylamine
Figure BDA0002229223460000101
2-Chloroethylamine hydrochloride (4.6g,40mmol), triethylamine (NEt) were added to a Schlenk bottle318mL,132mmol) and 50mL of dichloromethane, adding a solution of trimethylchlorosilane (TMSCl,90mmol,9.8g,11.4mL) in dichloromethane (20mL) to the obtained system, and stirring the reaction at room temperature for 12 h; after the reaction is finished, removing excessive triethylamine, trimethylchlorosilane and dichloromethane under reduced pressure, adding 60mL of normal hexane into the obtained residue, stirring for 30min at room temperature, and filtering to remove NEt3HCl, and after n-hexane was removed by rotary evaporation of the filtrate using a rotary evaporator, the filtrate was distilled under reduced pressure using an oil pump to obtain a fraction of the objective product (yield 6.0g, yield 68%).
1H NMR(400MHz,CDCl3)3.37–3.21(m,2H),3.18–2.99(m,2H),0.14(s,18H).13CNMR(101MHz,CDCl3)47.38,44.83,1.89。
(2) Synthesis of diphenylphosphinoethylamine
Figure BDA0002229223460000111
Under the protection of argon and at-78 ℃, adding a tetrahydrofuran solution (20mL) of diphenylphosphine hydrogen (1.86g,10mmol) into a Schlenk bottle, then slowly dropwise adding an n-hexane solution (2.5mol/L,4.4mL, 11mmol of n-butyllithium) of n-butyllithium, after dropwise adding, slowly heating the reaction system to room temperature, and stirring for 2 hours at the room temperature; then cooling the Schlenk bottle to 0 ℃ by using an ice water bath, slowly adding 2-chloro-N, N-bis (trimethylsilyl) ethylamine (2.45g,11mmol), and carrying out reflux reaction for 12h at 80 ℃; after the reaction is finished, cooling the obtained system to room temperature, adding 5mL of water and 6mL of 2.0mmol/mL sulfuric acid, stirring for 1h, then adding 7mL of 4.0mmol/mL sodium hydroxide solution, and stirring for 0.5 h; the organic phase was separated, the aqueous phase was extracted with ether (3 × 20mL), the organic phases were combined, dried over anhydrous sodium sulfate and dried to give the crude product (crude yield 2.06g, crude yield 95%) which was used directly in the next step without further column chromatography.
(3) Synthesis of imidazole NNP ligands
Figure BDA0002229223460000112
Under the protection of argon and at room temperature, adding a tetrahydrofuran solution (6mL) of imidazole formaldehyde (110mg,1.0mmol) into a Schlenk bottle, then dropwise adding a tetrahydrofuran solution (6mL) of diphenylphosphine ethylamine (290mg,1.0mmol), and reacting at room temperature for 1 h; then, tetrahydrofuran is pumped out by an oil pump through a Schlenk pipeline connected with a cold trap, 6mL of toluene is added, a toluene solution of diisobutylaluminum hydride (DIBAL) (1.5mol/L,1.2mL, 1.8mmol) is added under the condition of ice-water bath, the mixture reacts for 2h under the condition of room temperature, 10mL of water is added for quenching reaction, an organic phase is separated, an aqueous phase is extracted by diethyl ether (3X 20mL), the obtained organic phases are combined, dried by anhydrous sodium sulfate and dried by spinning, and column chromatography separation (the adopted eluent is a mixture of dichloromethane and methanol, the volume ratio of the dichloromethane to the methanol is 20: 1) is carried out to obtain a light yellow oily liquid which is the target product (the yield is 210mg, and the yield is 65%).
1H NMR(400MHz,CDCl3)7.41(ddt,J＝7.4,5.4,2.7Hz,4H),7.35–7.29(m,6H),6.91(d,J＝1.3Hz,1H),6.80(d,J＝1.3Hz,1H),3.82(s,2H),3.64(s,3H),2.86–2.74(m,2H),2.31–2.23(m,2H),1.77(b,1H)。
13C NMR(101MHz,CDCl3)146.3,138.3(d,J＝12.4Hz),132.7(d,J＝18.7Hz),128.6,128.4(d,J＝6.7Hz),127.1,121.2,46.2(d,J＝20.3Hz),45.6,32.7,28.9(d,J＝12.4Hz)。
31PNMR(162MHz,CDCl3)-20.76(s)。
HRMS(ESI)calcd.forC19H22N3P[M+H]+:324.1624；found:324.1610。
(4) Synthesis of manganese catalyst [ Mn ] -2
Figure BDA0002229223460000121
In a glove box filled with argon, imidazole NNP ligand (210mg,0.65mmol) and manganese pentacarbonyl bromide (165mg,0.60mmol) were added to a Schlenk bottle and reacted at 110 ℃ under reflux for 12 h; after the reaction was completed, the obtained system was cooled to room temperature, a yellow precipitate was precipitated, and after filtration, the yellow filter cake (2X 1mL) was washed with toluene, and the filter cake (3X 5mL) was washed with ether, followed by vacuum drying to obtain the objective catalyst (yield 260mg, yield 80%).
1H NMR(400MHz,DMSO-d6)7.76(t,J＝7.6Hz,2H),7.55(m,3H),7.45–7.34(m,5H),7.07(s,1H),6.42(s,1H),4.32(d,J＝16.8Hz,1H),4.08(d,J＝16.8Hz,1H),3.56(s,3H),3.14(m,1H),2.87–2.69(m,1H),2.27(m,2H)。
13C NMR(101MHz,DMSO-d6)149.8,132.7,132.3,132.0,131.9,131.7,131.4,131.0,130.9,129.7(d,J＝9.5Hz),129.4(d,J＝9.3Hz),128.1,125.2,54.9(d,J＝11.4Hz),49.7,34.7,22.5(d,J＝22.6Hz)。
31PNMR(162MHz,DMSO-d6)63.97(s)。
HRMS(ESI)calcd.for C22H22BrMnN3O3P[M-Br]+:462.0774；found:462.0775。
Example 2
Sequentially adding potassium tert-butoxide (5.6mg,0.05mmol), a manganese catalyst (0.005 mmol) which is respectively a manganese catalyst with a structure shown in formulas I-IV (namely manganese catalysts [ Mn ] -1, [ Mn ] -2, [ Mn ] -3, [ Mn ] -4), tetrahydrofuran (0.5mL) and quinoline (0.25mmol) into a 4mL glass bottle filled with an argon gas, covering the glass bottle, inserting a needle head (the length is 3cm, and the aperture of the vent hole is 1mm) with a vent hole into the glass bottle, putting the glass bottle into an autoclave, taking the autoclave out of the glove box, replacing the argon gas (3 x 10bar) in the autoclave with hydrogen gas, filling 80bar of hydrogen gas, and reacting for 16 hours at 120 ℃; after the reaction is finished, cooling in ice water bath, carefully discharging the gas in the autoclave, sampling the obtained reaction product system, carrying out GC quantification, and carrying out column chromatography separation to obtain the target product.
Taking manganese catalyst [ Mn ] -1 as an example, the reaction flow is as follows:
Figure BDA0002229223460000131
the structure of each manganese catalyst and the yield of the target product are specifically listed in table 1.
TABLE 1 Structure of manganese catalyst and yield of target product
Figure BDA0002229223460000132
Example 3
The substituted quinolines were catalytically hydrogenated using the manganese catalyst [ Mn ] -1 according to the method of example 2, and the structural formula and yield of each of the objective products are shown in Table 2 (the structure of quinolines and the yield of the objective products after catalytic hydrogenation of quinolines using the manganese catalyst [ Mn ] -1 are also shown in Table 2).
TABLE 2 structural formulae and yields of the respective target products
Figure BDA0002229223460000141
From example 2, it can be seen that the hydrogenation reaction of the quinoline nitrogen-containing unsaturated heterocyclic compound catalyzed by the manganese catalyst has good substrate applicability, and is well compatible with substituents having different electronic effects and steric effects on quinoline.
Example 4
Other types of nitrogen-containing unsaturated heterocyclic compounds were catalytically hydrogenated using manganese catalyst [ Mn ] -4 according to the method of example 2, and the structural formula and the yield of each target product are specifically shown in Table 3.
TABLE 3 structural formulae and yields of the respective target products
Figure BDA0002229223460000151
As can be seen from example 4, the manganese catalyst is used to catalyze the hydrogenation reaction of the nitrogen-containing unsaturated heterocyclic compound, so that the catalytic effect on quinoline or substituted quinoline is good, and the catalytic effect on other types of nitrogen-containing unsaturated heterocyclic compounds such as isoquinoline, quinoxaline and naphthyridine, and polycyclic compounds such as phenanthroline is good.
Comparative example
Quinoline is catalytically hydrogenated according to the method of example 2 using PNP type pincerlike manganese catalysts (manganese catalysts [ Mn ] -5, [ Mn ] -6, [ Mn ] -7) and N-Me protected NNP type pincerlike manganese catalysts (manganese catalysts [ Mn ] -8), the structure of each manganese catalyst and the yield of the desired product being specified in Table 4.
TABLE 4 Structure of each manganese catalyst and yield of target product
Figure BDA0002229223460000152
Comparing the results in tables 1 and 4, it can be seen that, with quinoline as a model substrate, the NNP type pincerlike manganese catalysts adopted in the invention, namely the manganese catalysts [ Mn ] -1, [ Mn ] -2, [ Mn ] -3 and [ Mn ] -4, have good catalytic effects, and the N-Me protected NNP type pincerlike manganese catalyst [ Mn ] -8 has no reaction activity at all, which indicates that the existence of-NH-structure on the catalyst is very important, and polar unsaturated compounds can be hydrogenated through the synergistic effect of metal ligands.
In addition, the yield of the target product of the PNP type pincerlike manganese catalyst, namely the manganese catalysts [ Mn ] -5, [ Mn ] -6 and [ Mn ] -7 for catalytic hydrogenation is less than 20%, which shows that the reaction activity of the NNP type pincerlike manganese catalyst adopted by the invention is higher than that of the PNP type pincerlike manganese catalyst. In order to study the difference between the reactivity of the NNP-type pincerlike manganese catalyst and the reactivity of the PNP-type pincerlike manganese catalyst, the electron effect and the steric hindrance effect of representative NNP-type pincerlike manganese catalyst [ Mn ] -1 and PNP-type pincerlike manganese catalyst [ Mn ] -5 were studied, as follows:
electronic effect: mixing 0.1mmol of manganese catalyst [ Mn ] -1 with 0.1mmol of potassium tert-butoxide and 3mL of tetrahydrofuran, stirring and reacting for 0.5h at room temperature, and removing one molecule of hydrogen bromide and one molecule of carbon monoxide to obtain a compound [ Mn ] -1a with the following structural formula:
removing one molecule of hydrogen bromide from manganese catalyst [ Mn ] -5 by referring to the above reaction, and obtaining a compound [ Mn ] -5a having the following structural formula:
Figure BDA0002229223460000161
para compound [ Mn]-1a and a compound [ Mn]5a, infrared test shows that the compound [ Mn ]]V of-1 a1＝1801cm-1，ν2＝1882cm-1(ii) a Compound [ Mn]V of-5 a1＝1809cm-1，ν2＝1884cm-1(ii) a Wherein, v1For antisymmetric telescopic vibration, v2Symmetrical telescopic vibration. Infrared test results show that carbonyl infrared absorption on the manganese catalyst chelated with the imidazole NNP ligand is more red shifted than that of a PNP analog, which indicates that the bond length of CO on the NNP-type pincerlike manganese catalyst is longer due to stronger pi bond feedback of the metal to CO, the stronger the feedback, the weaker the CO bond level, and the weaker the bond level, the longer the CO bond length, the red shift of infrared absorption will occur. While goldThe stronger the feedback pi bond of the metal is, the richer the electron in the metal center is, so that the NNP-type pincerlike ligand has stronger electron-donating capability, which is beneficial to transferring negative hydrogen on the metal to an unsaturated substrate, and therefore, the hydrogenation capability of the NNP-type pincerlike manganese catalyst is higher.
Steric effect: FIG. 1 is a schematic diagram of a hydrogenated transition state structure of an NNP type pincerlike manganese catalyst [ Mn ] -1 (the left side is a schematic diagram of a ball-and-stick model, and the right side is a corresponding structural formula), and FIG. 2 is a schematic diagram of a hydrogenated transition state structure of a PNP type pincerlike manganese catalyst [ Mn ] -5 (the left side is a schematic diagram of a ball-and-stick model, and the right side is a corresponding structural formula).
In summary, the NNP type pincerlike manganese catalyst has stronger electron-donating capability and smaller steric hindrance compared with the corresponding PNP type pincerlike manganese catalyst, so that the NNP type pincerlike manganese catalyst has higher reaction activity in a series of hydrogenation reactions.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A process for the catalytic hydrogenation of a nitrogen-containing unsaturated heterocyclic compound, comprising the steps of:
in the presence of hydrogen and a manganese catalyst, a nitrogen-containing unsaturated heterocyclic compound is used as a substrate to carry out hydrogenation reaction; the manganese catalyst is any one of structural compounds shown in formulas I to IV:
Figure FDA0002570960770000011
the nitrogen-containing unsaturated heterocyclic compound is selected from
Figure FDA0002570960770000012
Figure FDA0002570960770000013
Figure FDA0002570960770000021
2. The method according to claim 1, wherein the molar ratio of the manganese catalyst to the nitrogen-containing unsaturated heterocyclic compound is (1-2): 100.
3. the process according to claim 1, wherein the hydrogenation reaction is carried out in the presence of an alkaline agent and an organic solvent.
4. The method according to claim 3, wherein the alkaline reagent is selected from potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide or sodium ethoxide, and the molar ratio of the alkaline reagent to the nitrogen-containing unsaturated heterocyclic compound is (20-30): 100.
5. the method according to claim 3, wherein the organic solvent is selected from tetrahydrofuran, toluene or dioxane, and the ratio of the amount of the organic solvent to the nitrogen-containing unsaturated heterocyclic compound is (0.5-1.0) mL: 0.25 mmol.
6. The method according to any one of claims 1 to 5, wherein the pressure of the hydrogen gas is 60 to 80 bar.
7. The method according to claim 6, wherein the temperature of the hydrogenation reaction is 120 ℃ and the time is 8-16 h.
8. The method according to claim 1, wherein the preparation method of the manganese catalyst having the structure shown in formula II comprises the following steps:
mixing 2-chloroethylamine hydrochloride, trimethylchlorosilane, triethylamine and dichloromethane, and then carrying out a first substitution reaction to obtain 2-chloro-N, N-bis (trimethylsilyl) ethylamine;
in a protective atmosphere, mixing diphenylphosphine hydrogen, N-butyllithium and tetrahydrofuran, then carrying out an acid-base reaction, adding the 2-chloro-N, N-bis (trimethylsilyl) ethylamine into the obtained product system, carrying out a second substitution reaction, and then removing trimethylsilyl to obtain diphenylphosphine ethylamine;
in a protective atmosphere, mixing the diphenylphosphine ethylamine, imidazole formaldehyde and tetrahydrofuran, then carrying out a condensation reaction, removing the tetrahydrofuran in an obtained product system, and adding toluene and diisobutyl aluminum hydride to carry out a reduction reaction to obtain an imidazole NNP ligand;
and in a protective atmosphere, mixing the imidazole NNP ligand with manganese pentacarbonyl bromide, and then carrying out a coordination substitution reaction to obtain the manganese catalyst with the structure shown in the formula II.
9. The method according to claim 8, wherein the temperature of the first substitution reaction is room temperature and the time is 10-15 h;
the temperature of the acid-base reaction is room temperature, and the time is 1.5-2.5 h;
the temperature of the second substitution reaction is 80 ℃, and the time is 10-15 h;
the condensation reaction is carried out at room temperature for 50-70 min;
the temperature of the reduction reaction is room temperature, and the time is 1.5-2.5 h;
the temperature of the coordination substitution reaction is 110 ℃, and the time is 10-15 h.
CN201910961915.1A 2019-10-11 2019-10-11 Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound Active CN110590658B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910961915.1A CN110590658B (en) 2019-10-11 2019-10-11 Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910961915.1A CN110590658B (en) 2019-10-11 2019-10-11 Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound

Publications (2)

Publication Number Publication Date
CN110590658A CN110590658A (en) 2019-12-20
CN110590658B true CN110590658B (en) 2020-09-22

Family

ID=68866460

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910961915.1A Active CN110590658B (en) 2019-10-11 2019-10-11 Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound

Country Status (1)

Country Link
CN (1) CN110590658B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112774734B (en) * 2021-02-22 2022-03-25 江南大学 Copper catalyst for synthesizing quinoline compound and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445995B (en) * 2017-08-08 2019-09-24 清华大学 The method that a kind of novel manganese catalysis ethanol condensation prepares butanol

Also Published As

Publication number Publication date
CN110590658A (en) 2019-12-20

Similar Documents

Publication Publication Date Title
CN105732725B (en) A kind of application of chiral tridentate nitrogen phosphine oxygen ligand and its associated ligands in asymmetric catalysis
JP5214609B2 (en) Recovery of bis (diarylphenol) ligands during the production of isopulegol
CN110590658B (en) Method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compound
CN108329194A (en) A kind of citronellal prepares the method for isopulegol and its recovery method of catalyst
CN104610256A (en) Method for preparing tetrahydro-1,5-naphthyridine compound and prepared chiral product thereof
CN102321104B (en) Alkyl-bridged N-heterocyclic dicarbene metal complex as well as preparation method and application thereof
CA2905638C (en) Complex catalysts based on amino-phosphine ligands for hydrogenation and dehydrogenation processes
CN110615811B (en) Method for preparing chiral sulfinamide monophosphine ligand in large scale
WO2021253868A1 (en) Method for hydroboration of carbonate
Tu et al. Ligand electronic effects in the palladium catalyzed asymmetric allylic alkylation reaction with planar chiral diphosphine-oxazoline ferrocenyl ligands
CN113004326A (en) Phosphine ligand for butadiene hydroformylation reaction and preparation method thereof
CN106242996B (en) A kind of schiff bases magnesium metallo-organic compound and its preparation method and application
CN110437277B (en) Synthetic method of phosphoalkenyl ester compound
CN111217809B (en) Chiral nitrogen-containing diene ligand and preparation method and application thereof
CN103012422A (en) Preparation and application of 5,11-methylenemorphanthridine compound
CN111039767B (en) Method for preparing deuterated aldehyde by using triazole carbene as catalyst
Sun et al. Synthesis of new Schiff base-camphorsulfonyl amide ligands and in situ screening in the asymmetric additions of organozinc reagents to aldehydes
CN107935803B (en) Synthetic method of 1, 2-diketone compound
CN102040594A (en) C2 axisymmetric chiral bisoxazoline ligand compound containing imidazole salt ion pair group, and preparation and application thereof
CN104437642B (en) It is a kind of for catalyst of olefin metathesis reaction and preparation method thereof
CN111690009A (en) Phosphine pyridine oxazoline compound, metal complex, preparation method and application thereof
CN109232187A (en) A kind of chirality hair fastener woods alcohol analog and its synthetic method and application
CN107033342B (en) A kind of preparation method of the immobilized chiral double oxazoline ligands of PEG
CN104513274A (en) P chiral pincer compound and palladium coordination compound thereof
CN110483502B (en) Pyrido [1,2-a ] [1,2,4] triazole carbene ligand and synthetic method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant