CN111635435A - Bivalent copper complex containing diphosphine o-carborane ligand and preparation method and application thereof - Google Patents

Bivalent copper complex containing diphosphine o-carborane ligand and preparation method and application thereof Download PDF

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CN111635435A
CN111635435A CN202010443167.0A CN202010443167A CN111635435A CN 111635435 A CN111635435 A CN 111635435A CN 202010443167 A CN202010443167 A CN 202010443167A CN 111635435 A CN111635435 A CN 111635435A
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姚子健
邓维
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Shanghai Institute of Technology
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    • 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
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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Abstract

The invention relates to a bivalent copper complex containing diphosphine o-carborane ligand and a preparation method and application thereof, wherein the copper complex is prepared by the following steps: dropwise addition of n-BuLi solution to ortho-carborane o-C2B10H12Stirring the solution for reaction, adding the halogenated phosphine for continuous reaction, and adding copper acetate Cu (OAc)2The copper complex containing diphosphine o-carborane ligand is obtained after the reaction is finished and separated, and is applied to catalytic synthesis of β -carbonyl phosphine oxide.

Description

Bivalent copper complex containing diphosphine o-carborane ligand and preparation method and application thereof
Technical Field
The invention relates to the field of complex synthesis, in particular to a bivalent copper complex containing diphosphine o-carborane ligand and a preparation method and application thereof.
Background
The beta-phosphine oxide carbonyl compound as an important phosphorus-containing organic compound has wide application in various fields of organic chemistry, coordination chemistry, biochemistry and the like. For example, the compounds are important ligands in coordination chemistry; the method is used for preparing various compounds such as beta-aminophosphonic acid, chiral beta-hydroxyphosphonic acid and the like in organic synthesis; in addition, the beta-carbonylphosphinyl derivatives also have a wide range of biological activities, such as anticancer effects, promotion of bone metabolism, and inhibition of beta-lactamase activity.
The traditional synthesis method of the beta-carbonyl phosphine oxide compound mainly comprises Arbuzov reaction, acylation reaction of alkyl phosphonate ester under strong acid or strong alkali condition and the like, but the reaction condition is harsh and difficult to control. In recent years, addition reactions and hydration reactions of phosphorus-centered radicals have been developed to prepare such compounds, but such reactions usually involve two steps (addition and hydration), and expensive reagents such as alkynes and derivatives thereof, poly-substituted alkenes or allenes, etc. are used as reactants; meanwhile, the reaction also needs the participation of an oxidant and is complex.
Therefore, the development of a novel efficient catalyst has very important practical significance in one-step synthesis of the beta-phosphine oxide compound by using a cheap substrate under mild conditions.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a bivalent copper complex containing diphosphine o-carborane ligand, which has the advantages of simple preparation method, good catalytic effect and high stability, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a divalent copper complex comprising a bisphosphine orthocarborane ligand, the copper complex having the formula:
Figure BDA0002504886000000021
wherein R is-Ph, 4-MeO-C6H4-、4-NO2-C6H4-or-Cy, "·" is a boron hydrogen bond.
Preferably, the copper complex comprises a copper complex 1, a copper complex 2, a copper complex 3 and a copper complex 4, and the structural formula is as follows:
Figure BDA0002504886000000022
preparation method of bivalent copper complex containing diphosphine o-carborane ligandThe method comprises the following steps: dropwise addition of n-BuLi solution to ortho-carborane o-C2B10H12Stirring the solution for reaction, adding the halogenated phosphine for continuous reaction, and adding copper acetate Cu (OAc)2Adding the mixture into a reaction system for subsequent reaction, and separating after the reaction is finished to obtain the copper complex containing the diphosphine o-carborane ligand.
Further, the ortho-carborane, n-BuLi, phosphine halide and Cu (OAc)2The molar ratio of (1.0), (2.2-2.5), (2.2-3.0), (0.8-1.2).
Further, the method specifically comprises the following steps:
(1) dropwise addition of n-BuLi solution to ortho-carborane o-C at low temperature2B10H12Stirring in the solution;
(2) heating to room temperature, and reacting;
(3) adding halogenated phosphine, and continuing to react;
(4) mixing copper acetate Cu (OAc)2Adding the raw materials into a reaction system for reaction, decompressing and draining the solvent after the reaction is finished, and washing and draining the obtained crude product to obtain the copper complex containing the diphosphonic acid ortho-carborane ligand.
Further, the low temperature in the step (1) is-5 to 5 ℃; the n-BuLi solution is n-BuLi n-hexane solution, and the o-C solution is2B10H12The solution is o-C2B10H12Ether solution; the stirring time is 20-40 min; the re-reaction time in the step (2) is 20-40 min.
Further, the halogenated phosphine described in the step (3) includes ClPPh2、ClP(4-MeO-C6H4)2、ClP(4-NO2-C6H4)2Or ClPCy2(ii) a The continuous reaction time is 1-3 h; the time of the subsequent reaction in the step (4) is 3-6h, and the washing adopts diethyl ether as a detergent.
The application of the bivalent copper complex containing diphosphine o-carborane ligand, which is applied to catalytic synthesis of beta-carbonyl phosphine oxide, is described above.
Further, the specific application method comprises the following steps: dissolving the copper complex, alpha-halogenated ketone, phosphite ester and alkali in an organic solvent, reacting at room temperature, separating and purifying to obtain the corresponding beta-phosphine oxide compound.
Furthermore, the mole ratio of the divalent copper complex, the alpha-haloketone, the phosphite ester and the alkali is (0.005-0.01) to 1.0 (1.0-1.5) to (1.5-2), and the reaction time is 5-8 h.
Further, the α -halogenated ketone comprises one or more of α -bromoacetone, α -bromoacetophenone, α -bromo (4-methylphenyl) ethanone, α -chloro (4-methoxyphenyl) ethanone, α -chloro (2-methylphenyl) ethanone, α -bromo (4-chlorophenyl) ethanone, α -bromo (3-methylphenyl) ethanone or α -bromo (4-nitrophenyl) ethanone, the phosphite ester is diethyl phosphite or diphenyl phosphite, and the base is Na2CO3、K2CO3Or Cs2CO3One or more of (a).
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the bivalent copper complex containing the diphosphine o-carborane ligand is simple, the bivalent copper complex can be prepared in high yield through one-pot reaction, and the complex has high stability and can stably exist in air;
(2) the copper complex can efficiently catalyze the reaction of alpha-haloketone and phosphite ester to synthesize the beta-phosphine oxide compound, has good selectivity, low catalyst consumption, mild reaction conditions, no need of acid, alkali or oxidant, high reaction rate, high yield and wide substrate range, and has wide industrial application prospect.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1: synthesis of copper complex 1 and application thereof in catalytic synthesis of beta-phosphine oxide compound
0℃Next, n-BuLi (2.2mmol) in n-hexane was added dropwise to the o-C compound containing orthocarborane2B10H12(1.0mmol) of the obtained product in ether solution, continuously stirring for 30 minutes after dropwise adding, slowly raising the temperature to room temperature, continuously reacting for 30 minutes, and adding halogenated phosphine ClPPh2(2.2mmol) and continued reaction at room temperature for 2 hours, then Cu (OAc)2(1.0mmol) is added into a reaction system to continue reacting for 3 hours at room temperature, after the reaction is finished, standing and filtering are carried out, the solvent is pumped out under reduced pressure, the obtained crude product is washed by ether, and the crude product is pumped out to obtain a target product 1 (yield is 80 percent), wherein the reaction formula is as follows:
Figure BDA0002504886000000041
theoretical value of elemental analysis C30B10H36O4P2Cu: c51.90, H5.23; experimental values: c51.79, H5.26.
Dissolving divalent copper complex 1(0.005mmol), alpha-haloketone (1.0mmol) and phosphite ester (1.2mmol) in acetone in a reaction tube, reacting at room temperature for 7 hours, concentrating the reaction solution after the reaction is finished, and separating and purifying the crude product by column chromatography, wherein the eluent is petroleum ether: ethyl acetate 8:1, namely the beta-phosphine oxide compound is obtained, the specific result is shown in table 1, and the reaction formula is as follows:
Figure BDA0002504886000000042
TABLE 1
Figure BDA0002504886000000043
Figure BDA0002504886000000051
Example 2: synthesis of copper Complex 2
n-BuLi (2.5mmol) in n-hexane was added dropwise to the o-C orthocarborane at 0 deg.C2B10H12(1.0mmol) in diethyl ether and the addition is completeThen stirring is continued for 30 minutes, the temperature is slowly raised to room temperature, the reaction is continued for 30 minutes, and the halogenated phosphine ClP (4-MeO-C) is added6H4)2(2.5mmol) and continued reaction at room temperature for 2 hours, then Cu (OAc)2(1.0mmol) is added into a reaction system to continue reacting for 5 hours at room temperature, after the reaction is finished, standing and filtering are carried out, the solvent is pumped out under reduced pressure, the obtained crude product is washed by ether, and the crude product is pumped out to obtain a target product 2 (the yield is 86 percent), and the reaction formula is as follows:
Figure BDA0002504886000000061
theoretical value of elemental analysis C34B10H44O8P2Cu: c50.15, H5.45; experimental values: c50.23, H5.51.
Example 3: synthesis of copper Complex 3
n-BuLi (2.3mmol) in n-hexane was added dropwise to the o-C orthocarborane at 0 deg.C2B10H12(1.0mmol) in ether solution, stirring for 30 min after dropping, slowly raising the temperature to room temperature, reacting for 30 min, and adding halogenated phosphine ClP (4-NO)2-C6H4)2(3.0mmol) and continued reaction at room temperature for 2 hours, then Cu (OAc)2(1.0mmol) is added into a reaction system to continue reacting for 4 hours at room temperature, after the reaction is finished, standing and filtering are carried out, the solvent is pumped out under reduced pressure, the obtained crude product is washed by ether, and the crude product is pumped out to obtain a target product 3 (yield 81 percent), wherein the reaction formula is as follows:
Figure BDA0002504886000000062
the product was paramagnetic, so there was no nuclear magnetic data. Theoretical value of elemental analysis C30B10H32N4O12P2Cu: c41.22, H3.69, N6.41; experimental values: c41.29, H3.66, N6.43.
Example 4: synthesis of copper Complex 4
n-BuLi (2.4mmol) in n-hexane was added dropwise to the o-C orthocarborane at 0 deg.C2B10H12(1.0mmol) of the obtained product in ether solution, continuously stirring for 30 minutes after dropwise adding, slowly raising the temperature to room temperature, continuously reacting for 30 minutes, and adding halogenated phosphine ClPCy2(2.6mmol) and continued reaction at room temperature for 2 hours, then Cu (OAc)2(1.0mmol) is added into a reaction system to continue reacting for 5 hours at room temperature, after the reaction is finished, standing and filtering are carried out, the solvent is pumped out under reduced pressure, the obtained crude product is washed by ether, and the crude product is pumped out to obtain a target product 4 (the yield is 79 percent), and the reaction formula is as follows:
Figure BDA0002504886000000071
theoretical value of elemental analysis C30B10H60O4P2Cu: c50.16, H8.42; experimental values: c50.12 and H8.40.
The copper complex 1-4 is used for catalyzing the reaction of alpha-bromoacetone and diethyl phosphite ester, and the specific steps are as follows:
divalent copper complex, α -bromoacetone, are put into a reaction tube
Figure BDA0002504886000000072
(1.0mmol), diethyl phosphite
Figure BDA0002504886000000073
Dissolving alkali (1.8mmol) in tetrahydrofuran, reacting at room temperature for 5-8 hr, concentrating the reaction solution, purifying the crude product by column chromatography to obtain β -carbonylphosphine oxide
Figure BDA0002504886000000074
The specific results are shown in Table 2, and the reaction formula is:
Figure BDA0002504886000000075
TABLE 2
Figure BDA0002504886000000076
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should understand that they can make various modifications, changes, substitutions, combinations, and the like equivalent to the embodiments without departing from the scope of the present invention.

Claims (10)

1. A divalent copper complex containing a diphosphine ortho-carborane ligand, wherein the copper complex has the formula:
Figure FDA0002504885990000011
wherein R is-Ph, 4-MeO-C6H4-、4-NO2-C6H4-or-Cy, "·" is a boron hydrogen bond.
2. A process for the preparation of a divalent copper complex containing a bisphosphine orthocarborane ligand according to claim 1, comprising: reacting n-BuLi with o-carborane o-C2B10H12Reacting, adding halogenated phosphine, continuing the reaction, and adding copper acetate Cu (OAc)2Adding the mixture into a reaction system for subsequent reaction, and separating after the reaction is finished to obtain the copper complex containing the diphosphine o-carborane ligand.
3. The process according to claim 2, wherein the ortho-carborane, n-BuLi, phosphine halide and Cu (OAc) are selected from the group consisting of2The molar ratio of (1.0), (2.2-2.5), (2.2-3.0), (0.8-1.2).
4. The method for preparing the bivalent copper complex containing the diphosphine o-carborane ligand according to claim 2, which is characterized by comprising the following steps:
(1) dropwise addition of n-BuLi solution to ortho-carborane o-C at low temperature2B10H12Stirring in the solution;
(2) heating to room temperature, and reacting;
(3) adding halogenated phosphine, and continuing to react;
(4) mixing copper acetate Cu (OAc)2Adding the raw materials into a reaction system for reaction, decompressing and draining the solvent after the reaction is finished, and washing and draining the obtained crude product to obtain the copper complex containing the diphosphonic acid ortho-carborane ligand.
5. The method for preparing the bivalent copper complex containing diphosphine o-carborane ligand according to claim 4, wherein the low temperature in the step (1) is-5 to 5 ℃; the n-BuLi solution is n-BuLi n-hexane solution, and the o-C solution is2B10H12The solution is o-C2B10H12Ether solution; the stirring time is 20-40 min; the re-reaction time in the step (2) is 20-40 min.
6. The method for preparing a cupric complex with diphosphine carborane ligand according to claim 4, wherein said halophosphine in step (3) comprises ClPPh2、ClP(4-MeO-C6H4)2、ClP(4-NO2-C6H4)2Or ClPCy2(ii) a The continuous reaction time is 1-3 h; the time of the subsequent reaction in the step (4) is 3-6h, and the washing adopts diethyl ether as a detergent.
7. Use of a divalent copper complex containing a bisphosphine orthocarborane ligand according to claim 1, wherein the copper complex is used in the catalytic synthesis of a β -carbonylphosphine oxide compound.
8. The application of the bivalent copper complex containing diphosphine o-carborane ligand according to claim 7 is characterized in that the specific application method comprises the following steps: dissolving the copper complex, alpha-halogenated ketone, phosphite ester and alkali in an organic solvent, reacting at room temperature, separating and purifying to obtain the corresponding beta-phosphine oxide compound.
9. The use of a divalent copper complex containing a bisphosphine o-carborane ligand according to claim 8, wherein the molar ratio of the divalent copper complex, the α -haloketone, the phosphite, and the base is (0.005-0.01):1.0 (1.0-1.5): 1.5-2), and the reaction time is 5-8 hours.
10. The use of a divalent copper complex containing a bisphosphine orthocarborane ligand according to claim 8, wherein the α -haloketone comprises one or more of α -bromoacetone, α -bromoacetophenone, α -bromo (4-methylphenyl) ethanone, α -chloro (4-methoxyphenyl) ethanone, α -chloro (2-methylphenyl) ethanone, α -bromo (4-chlorophenyl) ethanone, α -bromo (3-methylphenyl) ethanone, or α -bromo (4-nitrophenyl) ethanone, the phosphite is diethyl phosphite or diphenyl phosphite, the base is Na, and the divalent copper complex contains a bisphosphine ligand2CO3、K2CO3Or Cs2CO3One or more of (a).
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185462A (en) * 2021-04-26 2021-07-30 上海应用技术大学 Method for catalyzing direct arylation of imidazole compounds by using palladium complex
CN113200921A (en) * 2021-04-26 2021-08-03 上海应用技术大学 Method for catalytic synthesis of phenylbenzimidazole compounds by using copper complexes
CN114773385A (en) * 2022-03-10 2022-07-22 上海应用技术大学 Diphosphine-containing o-carborane bivalent copper complex and preparation and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070073065A1 (en) * 2005-09-22 2007-03-29 Takasago International Corporation Substituted optically active disphosphine compound
JP2010053049A (en) * 2008-08-26 2010-03-11 Chiba Univ Diphosphine compound, its transition metal complex and catalyst containing the transition metal complex and phosphine oxide compound and diphosphine oxide compound
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070073065A1 (en) * 2005-09-22 2007-03-29 Takasago International Corporation Substituted optically active disphosphine compound
JP2010053049A (en) * 2008-08-26 2010-03-11 Chiba Univ Diphosphine compound, its transition metal complex and catalyst containing the transition metal complex and phosphine oxide compound and diphosphine oxide compound
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185462A (en) * 2021-04-26 2021-07-30 上海应用技术大学 Method for catalyzing direct arylation of imidazole compounds by using palladium complex
CN113200921A (en) * 2021-04-26 2021-08-03 上海应用技术大学 Method for catalytic synthesis of phenylbenzimidazole compounds by using copper complexes
CN113185462B (en) * 2021-04-26 2022-12-16 上海应用技术大学 Method for catalyzing direct arylation of imidazole compounds by using palladium complex
CN114773385A (en) * 2022-03-10 2022-07-22 上海应用技术大学 Diphosphine-containing o-carborane bivalent copper complex and preparation and application thereof
CN114773385B (en) * 2022-03-10 2023-09-26 上海应用技术大学 Biphosphine-containing ortho-carborane bivalent copper complex and preparation and application thereof

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