CN114773385B - Biphosphine-containing ortho-carborane bivalent copper complex and preparation and application thereof - Google Patents

Biphosphine-containing ortho-carborane bivalent copper complex and preparation and application thereof Download PDF

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CN114773385B
CN114773385B CN202210230764.4A CN202210230764A CN114773385B CN 114773385 B CN114773385 B CN 114773385B CN 202210230764 A CN202210230764 A CN 202210230764A CN 114773385 B CN114773385 B CN 114773385B
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姚子健
张方磊
卞明
高永红
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Shanghai Institute of Technology
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    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • 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
    • B01J31/2414—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 comprising aliphatic or saturated rings
    • 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
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/50—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 4
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
    • 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
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a biphosphine-containing ortho-carborane bivalent copper complex, a preparation method and an application thereof, wherein ortho-carborane is used as a raw material, and n-butyllithium is used as a catalyst n Reacting with halogenated phosphine under BuLi action to generate biphosphine ortho-carborane ligand, and then adding copper bromide CuBr 2 The bivalent copper complex containing the biphosphine ortho-carborane ligand is obtained by adding a reaction system and a one-pot method. The copper complex can catalyze the multicomponent reaction of aromatic amine, glyoxylate and pyruvic acid ester under the condition of taking air as an oxidant to synthesize quinoline-2, 4-dicarboxyl derivatives at room temperature, the catalyst dosage is low, the reaction condition is mild, and the product yield is higher.

Description

Biphosphine-containing ortho-carborane bivalent copper complex and preparation and application thereof
Technical Field
The invention belongs to the technical field of synthetic chemistry, and relates to a biphosphine-containing ortho-carborane bivalent copper complex, and preparation and application thereof.
Background
Quinoline compounds are very important compounds in nitrogen heterocycles, have various biological activities such as antimalarial, antitumor, antihypertensive, hypoglycemic, anti-inflammatory and the like, and have wide application and development prospects in the aspects of medical care and plant protection. Among them, quinoline-2, 4-dicarboxylic derivatives play an important role in pharmaceutical chemistry and organic synthesis, and carboxyl fragments endow quinoline compounds with more unique biological activities, for example, substituted quinoline-2, 4-dicarboxylic acids are vesicle glutamate transporter (VGLUT) inhibitors synthesized for the first time, and some quinoline-2, 4-dicarboxylic derivatives can be used as fluorescent probes for detecting biomolecules. In addition, the derivatives are also important synthons, and various compounds with obvious biological activity can be synthesized by taking 2, 4-dicarboxyquinoline as a basic parent nucleus (J.Med. Chem.1992,35,1942). Therefore, a simple and efficient method for synthesizing the quinoline-2, 4-dicarboxy derivative is sought, and the method has important significance for enriching the synthesis method of the compound and carrying out more extensive biological activity research in future.
At present, the synthesis of the compound generally uses isatoic acid as a raw material, but the isatoic acid is not easy to obtain, the reaction condition is harsh, and the whole reaction applicability is poor (Chin.Chem.Lett.2010, 21,35;J.Heterocycl.Chem.2012,49,789). The modified Doebner reaction mostly utilizes acid catalyzed initiation of substituted aniline to react with alpha-ketoglutarate to produce quinoline-2, 4-dicarboxylic acid, however, alpha-ketoglutarate needs to be synthesized by multi-step reaction, and the final yield of the whole reaction is not high (J.Org.Chem.1992, 57,4452;J.Med.Chem.2002,45,2260). CuBr in 2014 2 The synthesis of this class of compounds was achieved by catalyzed three component reactions of aromatic amines, glyoxylates and pyruvates (chi.j. Org. Chem.2014,34,1437), but the reaction also requires higher temperatures and a pure oxygen environment.
Disclosure of Invention
The invention aims to provide a biphosphine-containing ortho-carborane bivalent copper complex, and preparation and application thereof.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a biphosphine-containing ortho-carborane bivalent copper complex, which has the following chemical structural formula:
wherein "·" is a boron hydrogen bond, R is any one of the following groups:
the second technical proposal of the invention provides a preparation method of the bivalent copper complex containing biphosphine ortho-carborane, which comprises the steps of dripping n-hexane solution of n-BuLi into the bivalent copper complex containing ortho-carborane (o-C) at the temperature of 0 DEG C 2 B 10 H 12 ) In diethyl ether solution (C), stirring after dripping, cooling to room temperature, reacting once, and adding halogenatedPhosphine is continuously reacted for the second time at room temperature, then copper bromide is added into a reaction system to continuously react for the third time at room temperature, after the reaction is finished, the solvent is pumped out under reduced pressure, and the obtained crude product is washed by diethyl ether and pumped out to obtain the target product.
The reaction formula of the invention is as follows:
further, the molar ratio of n-BuLi, phosphine halide and copper bromide is 1.0: (2.2-2.5): (2.2-3.0): 1.0.
further, the halogenated phosphine is ClPPh 2 、ClP(4-MeO-C 6 H 4 ) 2 、ClP(4-NO 2 -C 6 H 4 ) 2 Or ClPCy 2 。
Further, the stirring is continued for 20-40 min, preferably 30min; the time of one reaction is 20-40 min, preferably 30min; the time of the secondary reaction is 1-3 h, preferably 2h; the time of the three reactions is 3-6 h.
The third technical scheme of the invention provides application of a biphosphine-containing ortho-carborane bivalent copper complex, wherein the copper complex is used for catalyzing reaction of arylamine, glyoxylate and pyruvic acid ester in an organic solvent system under the condition of taking air as an oxidant to synthesize the quinoline-2, 4-dicarboxyl derivative.
Further, in the process of synthesizing the quinoline-2, 4-dicarboxylic derivative, the molar ratio of the copper complex, the aromatic amine, the glyoxylate and the pyruvic acid ester is 0.005-0.01: 1.0:1.0:1.0.
further, the aromatic amine is at least one of aniline, 2-methylaniline, 3-methylaniline, 4-methoxyaniline, 4-chloroaniline and 4-nitroaniline.
Further, the glyoxylate is at least one of methyl glyoxylate and ethyl glyoxylate;
the pyruvic acid ester is at least one of methyl pyruvic acid ester and phenyl pyruvic acid ester.
Further, the organic solvent is toluene.
Compared with the prior art, the invention has the following advantages:
(1) The bivalent copper complex containing the biphosphine ortho-carborane ligand has the advantages of simple preparation method, high yield and high stability, and can be prepared in one-pot reaction and stably exist in the air.
(2) The copper complex can efficiently catalyze the multicomponent reaction of the arylamine, the glyoxylate and the pyruvic acid ester to synthesize the quinoline-2, 4-dicarboxylic derivative, has good reaction selectivity, low catalyst consumption, mild reaction conditions, high reaction rate, high yield and wide substrate range, takes air as an oxidant, and has wide application prospect in industry.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise indicated, the starting materials or processing techniques are all conventional commercial products or conventional processing techniques in the art.
Example 1:
example 1:
synthesis of cupric Complex 1 containing biphosphine ortho-carborane ligand
At 0℃n-BuLi (2.2 mmol) in n-hexane was added dropwise to the solution containing ortho-carborane o-C 2 B 10 H 12 (1.0 mmol) in diethyl ether, stirring for 30min after the dripping, slowly heating to room temperature, reacting for 30min, and adding halophosphine ClPPh 2 (2.2 mmol) was continued at room temperature for 2 hours, then CuBr was added 2 (1.0 mmol) was added to the reaction system and the reaction was continued at room temperature for 3 hours, after the completion of the reaction, the mixture was allowed to stand still and filtered, and the solvent was drained under reduced pressure to give a crude productThe product was washed with diethyl ether and dried by suction to give the desired product 1 (yield 85%). The product was paramagnetic and therefore free of nuclear magnetic data. Theoretical value of elemental analysis C 26 B 10 H 30 Br 2 P 2 Cu: c42.43, h 4.11; experimental values: c42.50, h 4.16.
Example 2:
synthesis of cupric Complex 2 containing biphosphine ortho-carborane ligand
At 0℃n-BuLi (2.5 mmol) in n-hexane was added dropwise to the solution containing ortho-carborane o-C 2 B 10 H 12 (1.0 mmol) in diethyl ether, stirring for 30min after the addition, slowly heating to room temperature, reacting for 30min, and adding halophosphine ClP (4-MeO-C) 6 H 4 ) 2 (2.5 mmol) was continued at room temperature for 2 hours, then CuBr was added 2 (1.0 mmol) was added to the reaction system at room temperature for further reaction for 5 hours, after the reaction was completed, the mixture was allowed to stand and filtered, the solvent was drained under reduced pressure, and the obtained crude product was washed with diethyl ether and drained to give the objective product 2 (yield 82%). The product was paramagnetic and therefore free of nuclear magnetic data. Theoretical value of elemental analysis C 30 B 10 H 38 O 4 Br 2 P 2 Cu: c42.09, h 4.47; experimental values: c42.15, h 4.42.
Example 3:
synthesis of cupric Complex 3 containing biphosphine ortho-carborane ligand
At 0℃n-BuLi (2.3 mmol) in n-hexane was added dropwise to the solution containing ortho-carborane o-C 2 B 10 H 12 (1.0 mmol) in diethyl ether, stirring for 30min after the addition, slowly heating to room temperature, reacting for 30min, and adding halophosphine ClP (4-NO) 2 -C 6 H 4 ) 2 (3.0mmol)，The reaction was continued at room temperature for 2 hours, then CuBr was added 2 (1.0 mmol) was added to the reaction system and the reaction was continued at room temperature for 4 hours, after the completion of the reaction, the mixture was allowed to stand still, filtered, the solvent was drained under reduced pressure, and the obtained crude product was washed with diethyl ether and drained to give the objective product 3 (yield 78%). The product was paramagnetic and therefore free of nuclear magnetic data. Theoretical value of elemental analysis C 26 B 10 H 26 N 4 O 8 Br 2 P 2 Cu: C34.09,H 2.86,N 6.12; experimental values: and C34.15,H 2.92,N 6.05.
Example 4:
synthesis of cupric Complex 4 containing biphosphine ortho-carborane ligand
At 0℃n-BuLi (2.4 mmol) in n-hexane was added dropwise to the solution containing ortho-carborane o-C 2 B 10 H 12 (1.0 mmol) in diethyl ether, stirring for 30min after the addition, slowly heating to room temperature, reacting for 30min, and adding halophosphine ClPCy 2 (2.6 mmol) was continued at room temperature for 2 hours, then CuBr was added 2 (1.0 mmol) was added to the reaction system and the reaction was continued at room temperature for 5 hours, after the completion of the reaction, the mixture was allowed to stand still, filtered, the solvent was drained under reduced pressure, and the obtained crude product was washed with diethyl ether and drained to give the objective product 4 (yield 76%). The product was paramagnetic and therefore free of nuclear magnetic data. Theoretical value of elemental analysis C 26 B 10 H 54 Br 2 P 2 Cu: c41.08, h 7.16; experimental values: c41.00, h 7.21.
Example 5:
synthesis of quinoline-2, 4-dicarboxyl derivative by catalyzing multicomponent reaction of aniline, methyl glyoxylate and methyl pyruvate with bivalent copper complex 1-4
An amount of cupric complex, aniline (1.0 mmol) and ethyl glyoxylate (1.0 mmol) are put into a reaction tubeAnd methyl pyruvate (1.0 mmol)/(S)>Dissolving in toluene, reacting at room temperature for 5-8 hours, concentrating the reaction liquid after the reaction is finished, separating and purifying the crude product by column chromatography, wherein the eluent is petroleum ether: ethyl acetate=3:1 to obtain quinoline-2, 4-dicarboxy derivative +.>The specific results are shown in Table 1.
TABLE 1
Sequence number Catalyst Catalyst amount (mmol) Reaction time (h) Yield (%)
1 1 0.005 5 68
2 1 0.007 5 83
3 1 0.009 5 86
4 1 0.01 5 86
5 1 0.009 6 93
6 1 0.009 8 92
7 2 0.009 6 89
8 3 0.009 6 91
9 4 0.009 6 90
Example 6:
synthesis of quinoline-2, 4-dicarboxyl derivative by catalyzing multicomponent reaction of aniline, glyoxylate and pyruvic acid ester with bivalent copper complex 1-4
Cupric complex 1 (0.009 mmol), aromatic amine (1.0 mmol), glyoxylate (1.0 mmol) and pyruvic acid ester (1.0 mmol) were dissolved in toluene in a reaction tube, reacted at room temperature for 6 hours, the reaction solution was concentrated after the reaction was completed, the crude product was separated and purified by column chromatography, and the eluent was petroleum ether: ethyl acetate=3:1 to give quinoline-2, 4-dicarboxy derivatives, the specific results are shown in table 2.
TABLE 2
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (6)

1. The biphosphine-containing ortho-carborane bivalent copper complex is characterized by having the following chemical structural formula:
wherein "·" is a boron hydrogen bond, R is any one of the following groups:
2. the method for preparing the biphosphine-containing ortho-carborane bivalent copper complex, as claimed in claim 1, wherein n-BuLi n-hexane solution is dripped into ortho-carborane-containing diethyl ether solution at 0 ℃, stirring is continued after dripping is finished, the reaction is carried out once again after the reaction is carried out at room temperature, halogenated phosphine is added, the reaction is continued at room temperature for a second time, copper bromide is added into a reaction system for a third time at room temperature, after the reaction is finished, the solvent is pumped out under reduced pressure, and the obtained crude product is washed by diethyl ether and pumped out to obtain the target product.
3. The method for preparing the biphosphine-containing ortho-carborane divalent copper complex as recited in claim 2, wherein the molar ratio of ortho-carborane, n-BuLi, phosphine halide and copper bromide is 1.0: (2.2-2.5): (2.2-3.0): 1.0.
4. the method for preparing a biphosphine-containing ortho-carborane bivalent copper complex according to claim 2, wherein the halogenated phosphine is ClPPh 2 、ClP(4-MeO-C 6 H 4 ) 2 、ClP(4-NO 2 -C 6 H 4 ) 2 Or ClPCy 2 。
5. The method for preparing a biphosphine-containing ortho-carborane divalent copper complex as recited in claim 2, wherein the stirring is continued for 20-40 min; the time of one-time reaction is 20-40 min; the time of the secondary reaction is 1-3 h; the time of the three reactions is 3-6 h.
6. The use of a biphosphine-containing ortho-carborane divalent copper complex according to claim 1, wherein the copper complex is used for catalyzing the reaction of an aromatic amine, glyoxylate and pyruvic acid ester in an organic solvent system with air as an oxidant to synthesize a quinoline-2, 4-dicarboxyl derivative;
in the process of synthesizing the quinoline-2, 4-dicarboxylic derivative, the molar ratio of the copper complex, the aromatic amine, the glyoxylate to the pyruvate is 0.005-0.01: 1.0:1.0:1.0;
the aromatic amine is at least one of aniline, 2-methylaniline, 3-methylaniline, 4-methoxyaniline, 4-chloroaniline and 4-nitroaniline;
the glyoxylate is at least one of methyl glyoxylate and ethyl glyoxylate;
the pyruvic acid ester is at least one of methyl pyruvic acid ester and phenyl pyruvic acid ester;
the organic solvent is toluene.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
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CN111393480A (en) * 2020-04-07 2020-07-10 上海应用技术大学 Gold complex containing diphosphine o-carborane ligand and preparation method and application thereof
CN111635435A (en) * 2020-05-22 2020-09-08 上海应用技术大学 Bivalent copper complex containing diphosphine o-carborane ligand and preparation method and application thereof

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CN111039980A (en) * 2019-12-05 2020-04-21 上海应用技术大学 Cuprous complex containing diphosphine o-carborane ligand and preparation and application thereof
CN111393480A (en) * 2020-04-07 2020-07-10 上海应用技术大学 Gold complex containing diphosphine o-carborane ligand and preparation method and application thereof
CN111635435A (en) * 2020-05-22 2020-09-08 上海应用技术大学 Bivalent copper complex containing diphosphine o-carborane ligand and preparation method and application thereof

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