CN111689883B - Synthetic method of diaryl sulfone compound - Google Patents

Synthetic method of diaryl sulfone compound Download PDF

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CN111689883B
CN111689883B CN202010444190.1A CN202010444190A CN111689883B CN 111689883 B CN111689883 B CN 111689883B CN 202010444190 A CN202010444190 A CN 202010444190A CN 111689883 B CN111689883 B CN 111689883B
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diaryl sulfone
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姚子健
邓维
高永红
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • 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
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4294—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using S nucleophiles, e.g. thiols
    • 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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Abstract

The invention relates to a synthesis method of diaryl sulfone compounds, which is characterized by comprising the following steps: dissolving the copper complex and the aryl sulfonyl hydrazide in an organic solvent, reacting at room temperature by taking air as an oxidant, separating and purifying to obtain the corresponding diaryl sulfone compound, wherein the molar ratio of the copper complex to the aryl sulfonyl hydrazide is (0.01-0.03):1.0, and the reaction time is 2-5 h. Compared with the prior art, the synthesis process has excellent selectivity and higher yield, the catalyst copper complex in the reaction can catalyze the self-coupling synthesis of the diaryl sulfone compound by the aryl sulfonyl hydrazide at room temperature, and the reaction has the characteristics of mild and simple conditions, wide substrate range, convenient product separation, high reaction efficiency and the like.

Description

Synthetic method of diaryl sulfone compound
Technical Field
The invention relates to the field of synthesis of sulfone compounds, in particular to a synthesis method of diaryl sulfone compounds.
Background
The diaryl sulfone compound is used as a medicine and pesticide intermediate commonly used in organic synthesis and shows good biological activity. For example, diaryl sulfones have been shown to have antifungal, antibacterial, antitumor activity; and diaryl sulfones and aryl heterocyclic sulfones have been shown to inhibit HIV-1 reverse transcriptase, represent an emerging class of substances that can address the problems of drug residual toxicity and drug resistance of nucleoside inhibitors.
Conventional diaryl sulfone syntheses often require strongly acidic conditions and high temperatures above 200 ℃. The preparation of diaryl sulfone by Friedel-crafts reaction of aryl sulfonyl chloride and aromatic hydrocarbon has the defects that the diaryl sulfone can only occur on an electron-rich aromatic ring, and the substitution position is influenced by the positioning effect of a substituent group, so that the application range of a substrate is greatly limited.
In recent years, the synthesis of diaryl sulfones by transition metal catalyzed cross-coupling strategies has received a great deal of attention from chemists, and most of these methods are used to synthesize asymmetric diaryl sulfone derivatives. Sodium arylsulfinate is most commonly used to provide SO2The electrophile of the group can be reacted with an arylboronic acid, a haloarene to produce a diaryl sulfone. However, the preparation of sodium arylsulfinate and halogenated aromatic hydrocarbons requiring the same substituent by cross-coupling of symmetrical diaryl sulfone compounds (such as bisphenol S) used in industry increases the reaction cost and the difficulty of conversion.
A more economical method is to prepare symmetric diphenyl sulfone directly by self-coupling of sulfonyl substrates; for example, sodium arylsulfinate can be used to provide arylating agents in coupling reactions, C-H activation reactions by Pd-catalyzed desulfurization, such as the Mizoroki-Heck reaction in which arylsulfonylhydrazide participates in palladium catalysis with oxygen as an oxidant and the C-H direct arylation reaction of heterocyclic compounds in which arylsulfonylhydrazide participates in palladium-copper co-catalysis, in which the role of the noble metal palladium is important. In addition, the aryl sulfonyl hydrazide can obtain the diaryl sulfone compound with high selectivity and high yield under the action of copper acetate without nitrogen protection, but the reaction needs a high equivalent catalyst and has higher reaction temperature.
Therefore, the development of a novel efficient catalyst has very important practical significance for realizing the reaction under mild conditions.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a synthetic method of diaryl sulfone compounds, which has the advantages of simple synthetic method, good effect of used catalyst, mild and simple condition, wide range of substrate, convenient product separation and high reaction efficiency.
The purpose of the invention can be realized by the following technical scheme:
a synthetic method of diaryl sulfone compounds comprises the following steps: dissolving the copper complex and the aryl sulfonyl hydrazide in an organic solvent, reacting at room temperature by taking air as an oxidant, and separating and purifying to obtain the corresponding diaryl sulfone compound.
Further, the aryl sulfonyl hydrazide comprises one or more of benzenesulfonyl hydrazide, 4-methylbenzenesulfonyl hydrazide, 4-methoxybenzenesulfonyl hydrazide, 4-nitrobenzenesulfonyl hydrazide, 4-chlorobenzenesulfonyl hydrazide, 2-methylbenzenesulfonyl hydrazide, 3-methylbenzenesulfonyl hydrazide or 2, 6-dimethylbenzenesulfonyl hydrazide, and the organic solvent is one or more of toluene, methanol or dichloromethane.
Furthermore, the molar ratio of the copper complex to the aryl sulfonyl hydrazide is (0.01-0.03):1.0, and the reaction time is 2-5 h.
Further, the structural formula of the copper complex is shown as follows:
Figure BDA0002505153950000021
wherein R is-Ph, 4-MeO-C6H4-、4-NO2-C6H4-or-Cy, "·" is a boron hydrogen bond.
Further, the copper complex is prepared by adopting the following method: 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.
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 time for continuous reaction is 1-3 h.
Further, the time for the subsequent reaction in the step (4) is 3-6h, and the washing is carried out by using diethyl ether as a detergent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the monovalent copper complex containing the diphosphine o-carborane ligand is simple, the monovalent copper complex can be prepared in high yield through one-pot reaction, and the monovalent copper complex has high stability and can stably exist in air;
(2) the copper complex can efficiently catalyze the self-coupling reaction of aryl sulfonyl hydrazide to synthesize the diaryl sulfone compound. Mild and simple conditions, wide substrate range, convenient product separation, high reaction efficiency and the like, 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 diaryl sulfone compound
n-BuLi (2.2mmol) 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 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 (the yield is 79 percent), wherein the reaction formula is as follows:
Figure BDA0002505153950000041
theoretical value of elemental analysis C30B10H36P2O4Cu: c51.90, H5.23; experimental values: c51.96, H5.15.
Dissolving copper complex 1(0.02mmol) and aryl sulfonyl hydrazide (1.0mmol) in toluene (2mL) in a reaction tube, reacting for 3 hours at room temperature by using air as an oxidant, concentrating a reaction solution after the reaction is finished, separating and purifying a crude product by column chromatography, wherein an eluent is petroleum ether: and (3) obtaining the corresponding diaryl sulfone compound by taking dichloromethane as 6:1, wherein the specific result is shown in table 1, and the reaction formula is as follows:
Figure BDA0002505153950000042
TABLE 1
Figure BDA0002505153950000043
Figure BDA0002505153950000051
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, stirring for 30 min after dropping, slowly raising the temperature to room temperature, reacting for 30 min, and adding halogenated phosphine ClP (4-MeO-C)6H4)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 (yield 81 percent), wherein the reaction formula is as follows:
Figure BDA0002505153950000052
theoretical value of elemental analysis C34B10H44O8P2Cu：C 50.15,H5.45；Experimental values: c50.08, H5.42.
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 (the yield is 86 percent), and the reaction formula is as follows:
Figure BDA0002505153950000061
theoretical value of elemental analysis C30B10H32N4O12P2Cu: c41.22, H3.69, N6.41; experimental values: c41.18, H3.75, N6.50.
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 BDA0002505153950000062
theoretical value of elemental analysis C30B10H60O4P2Cu: c50.16, H8.42; experimental values: c50.22, H8.49.
Example 5
The copper complex 1-4 is used for catalyzing the self-coupling of benzenesulfonyl hydrazide, and the specific steps are as follows:
dissolving a copper complex and benzenesulfonyl hydrazide (1.0mmol) in an organic solvent (2mL) in a reaction tube, reacting for 2-5 hours at room temperature by taking air as an oxidant, concentrating a reaction solution after the reaction is finished, separating and purifying a crude product by column chromatography, wherein an eluent is petroleum ether: and (3) obtaining the corresponding diaryl sulfone compound by taking dichloromethane as 6:1, wherein the specific result is shown in table 2, and the reaction formula is as follows:
Figure BDA0002505153950000071
TABLE 2
Serial number Catalyst and process for preparing same Amount of catalyst (mmol) Solvent(s) Reaction time (h) Yield (%)
1 Example 1 0.01 Toluene 2 67
2 Example 1 0.01 Toluene 3 82
3 Example 1 0.01 Toluene 5 83
4 Example 1 0.02 Toluene 3 92
5 Example 1 0.03 Toluene 3 92
6 Example 1 0.02 CH3OH 3 72
7 Example 1 0.02 CH2Cl2 3 48
8 Example 2 0.02 Toluene 3 88
9 Example 3 0.02 Toluene 3 91
10 Example 4 0.02 Toluene 3 92
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 (9)

1. A synthetic method of diaryl sulfone compounds is characterized in that the method comprises the following steps: dissolving a copper complex and aryl sulfonyl hydrazide in an organic solvent, reacting at room temperature by taking air as an oxidant, and separating and purifying to obtain a corresponding diaryl sulfone compound;
the structural formula of the copper complex is shown as follows:
Figure FDA0003335982110000011
wherein R is-Ph, 4-MeO-C6H4-、4-NO2-C6H4-or-Cy, "·" is a boron hydrogen bond.
2. The method for synthesizing diaryl sulfone compounds according to claim 1, wherein the aryl sulfonyl hydrazide comprises one or more of benzenesulfonyl hydrazide, 4-methylbenzenesulfonyl hydrazide, 4-methoxybenzenesulfonyl hydrazide, 4-nitrobenzenesulfonyl hydrazide, 4-chlorobenzenesulfonyl hydrazide, 2-methylbenzenesulfonyl hydrazide, 3-methylbenzenesulfonyl hydrazide or 2, 6-dimethylbenzenesulfonyl hydrazide, and the organic solvent is one or more of toluene, methanol or dichloromethane.
3. The synthesis method of the diaryl sulfone compound according to claim 1, wherein the molar ratio of the copper complex to the aryl sulfonyl hydrazide is (0.01-0.03):1.0, and the reaction time is 2-5 h.
4. The method for synthesizing the diaryl sulfone compound according to claim 1, wherein the copper complex is prepared by the following method: reacting n-BuLi with o-carborane o-C2B10H12Reacting, adding halogenated phosphine, continuing the reaction, and adding copper acetate Cu (OAc)2Is added into the reaction systemThen reacting, and separating after the reaction is finished to obtain the copper complex containing the diphosphine o-carborane ligand.
5. The method for synthesizing diaryl sulfone compound according to claim 4, wherein 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).
6. The method for synthesizing diaryl sulfone compounds according to claim 4, 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.
7. The method for synthesizing the diaryl sulfone compound according to claim 6, 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.
8. The method for synthesizing diaryl sulfone compound according to claim 6, wherein the halogenated phosphine in step (3) comprises ClPPh2、ClP(4-MeO-C6H4)2、ClP(4-NO2-C6H4)2Or ClPCy2(ii) a The time for continuous reaction is 1-3 h.
9. The method for synthesizing diaryl sulfone compound according to claim 6, wherein the subsequent reaction time in step (4) is 3-6h, and the washing is carried out by using diethyl ether as a detergent.
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