CN111689883A - Synthetic method of diaryl sulfone compound - Google Patents
Synthetic method of diaryl sulfone compound Download PDFInfo
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- CN111689883A CN111689883A CN202010444190.1A CN202010444190A CN111689883A CN 111689883 A CN111689883 A CN 111689883A CN 202010444190 A CN202010444190 A CN 202010444190A CN 111689883 A CN111689883 A CN 111689883A
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- diaryl sulfone
- hydrazide
- sulfone compound
- copper complex
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- -1 diaryl sulfone compound Chemical class 0.000 title claims abstract description 49
- 238000010189 synthetic method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 150000004699 copper complex Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 150000003003 phosphines Chemical class 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- AKJFBIZAEPTXIL-UHFFFAOYSA-N chloro(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(Cl)C1CCCCC1 AKJFBIZAEPTXIL-UHFFFAOYSA-N 0.000 claims description 3
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 3
- UIWFWZLAICURGT-UHFFFAOYSA-N 4-Methoxybenzenesulfonohydrazide Chemical compound COC1=CC=C(S(=O)(=O)NN)C=C1 UIWFWZLAICURGT-UHFFFAOYSA-N 0.000 claims description 2
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 8
- 238000005086 pumping Methods 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 101900297506 Human immunodeficiency virus type 1 group M subtype B Reverse transcriptase/ribonuclease H Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 150000003833 nucleoside derivatives Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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:
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 temperature2B10H12Solutions ofStirring;
(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:
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:
TABLE 1
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:
theoretical value of elemental analysis C34B10H44O8P2Cu: c50.15, 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:
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:
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:
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 (10)
1. A synthetic method of diaryl sulfone compounds is characterized in that the method 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.
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.
5. 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)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.
6. The method for synthesizing diaryl sulfone compound according to claim 5, 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).
7. The method for synthesizing diaryl sulfone compounds according to claim 5, 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 into a reaction system for reaction, decompressing and pumping out the solvent after the reaction is finished, washing and pumping out the obtained crude product to obtain the product containingCopper complexes of diphosphine orthocarborane ligands.
8. The method for synthesizing the diaryl sulfone compound according to claim 7, 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.
9. The method for synthesizing diaryl sulfone compound according to claim 7, 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.
10. The method for synthesizing diaryl sulfone compound according to claim 7, 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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