CN114835599B - Preparation method of o-aryl benzamide compound - Google Patents
Preparation method of o-aryl benzamide compound Download PDFInfo
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- CN114835599B CN114835599B CN202210449632.0A CN202210449632A CN114835599B CN 114835599 B CN114835599 B CN 114835599B CN 202210449632 A CN202210449632 A CN 202210449632A CN 114835599 B CN114835599 B CN 114835599B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- RRSIMIHTHWYRRA-UHFFFAOYSA-L dibromonickel;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound Br[Ni]Br.COCCOCCOC RRSIMIHTHWYRRA-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 150000001499 aryl bromides Chemical class 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 52
- 238000001228 spectrum Methods 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- UERSZVOVPLBEHC-UHFFFAOYSA-N n-methyl-2-phenylbenzamide Chemical compound CNC(=O)C1=CC=CC=C1C1=CC=CC=C1 UERSZVOVPLBEHC-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 238000010791 quenching Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical compound O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical group [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 2
- DMSSTTLDFWKBSX-UHFFFAOYSA-N 1h-1,2,3-benzotriazin-4-one Chemical compound C1=CC=C2C(=O)N=NNC2=C1 DMSSTTLDFWKBSX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- XHCAGOVGSDHHNP-UHFFFAOYSA-N 1-bromo-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(Br)C=C1 XHCAGOVGSDHHNP-UHFFFAOYSA-N 0.000 description 1
- LKDMZYWGTNDILK-UHFFFAOYSA-N 2-(4-methoxyphenyl)-N-methylbenzamide Chemical compound COC1=CC=C(C=C1)C1=C(C(=O)NC)C=CC=C1 LKDMZYWGTNDILK-UHFFFAOYSA-N 0.000 description 1
- OTKMYOUJGFPIHL-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-N-methylbenzamide Chemical compound CNC(=O)C1=CC=CC=C1C1=CC=C(C(C)(C)C)C=C1 OTKMYOUJGFPIHL-UHFFFAOYSA-N 0.000 description 1
- NAWSYQWIQGAWMC-UHFFFAOYSA-N 3-butyl-1,2,3-benzotriazin-4-one Chemical compound C1=CC=C2C(=O)N(CCCC)N=NC2=C1 NAWSYQWIQGAWMC-UHFFFAOYSA-N 0.000 description 1
- OSZDOFKUFXEPNC-UHFFFAOYSA-N 3-phenyl-1,2,3-benzotriazin-4-one Chemical compound N1=NC2=CC=CC=C2C(=O)N1C1=CC=CC=C1 OSZDOFKUFXEPNC-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- LFGLPAHKPKIRIN-UHFFFAOYSA-N CNC(=O)C1=CC=CC=C1C1=CC=CC=C1C Chemical compound CNC(=O)C1=CC=CC=C1C1=CC=CC=C1C LFGLPAHKPKIRIN-UHFFFAOYSA-N 0.000 description 1
- AMAYIGUKJRERNM-UHFFFAOYSA-N CNC(=O)C=1C(=CC=CC=1)C1=CC(=CC=C1)C Chemical compound CNC(=O)C=1C(=CC=CC=1)C1=CC(=CC=C1)C AMAYIGUKJRERNM-UHFFFAOYSA-N 0.000 description 1
- PPHYQHRTZDFNPT-UHFFFAOYSA-N CNC(C1=CC=CC=C1C1=CC=C(C=C)C=C1)=O Chemical compound CNC(C1=CC=CC=C1C1=CC=C(C=C)C=C1)=O PPHYQHRTZDFNPT-UHFFFAOYSA-N 0.000 description 1
- RDJSXICLTVOYFP-UHFFFAOYSA-N ClC1=CC=C(C=C1)C1=C(C(=O)NC)C=CC=C1 Chemical compound ClC1=CC=C(C=C1)C1=C(C(=O)NC)C=CC=C1 RDJSXICLTVOYFP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940054066 benzamide antipsychotics Drugs 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JVRMUFJCFLXSMJ-UHFFFAOYSA-N n,2-diphenylbenzamide Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1C(=O)NC1=CC=CC=C1 JVRMUFJCFLXSMJ-UHFFFAOYSA-N 0.000 description 1
- MCWSSHGOLQOLKX-UHFFFAOYSA-N n-(4-fluorophenyl)-2-phenylbenzamide Chemical compound C1=CC(F)=CC=C1NC(=O)C1=CC=CC=C1C1=CC=CC=C1 MCWSSHGOLQOLKX-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an o-aryl benzamide compound, which comprises the steps of mixing a1, 2, 3-benzotriazine-4- (3H) -ketone compound and an aryl bromide with an organic solvent under the action of a transition metal catalyst and a reducing agent, and carrying out reduction cross-coupling reaction to obtain the o-aryl benzamide compound. The invention uses 1,2, 3-benzotriazine-4- (3H) -ketone compounds and aryl bromides as raw materials, zinc powder as a reducing agent and nickel bromide diethylene glycol dimethyl ether as a catalyst, so as to prepare a series of o-aryl benzamide compounds.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of an o-aryl benzamide compound.
Background
The reduction cross-coupling reaction catalyzed by transition metal is one of important means for constructing carbon-carbon bonds and carbon-hetero bonds, and has wide application in the synthesis of drug molecules and natural products.
The reduction cross-coupling reaction between two different electrophiles catalyzed by transition metal has good functional group tolerance, can avoid the use of organic metal reagents sensitive to water and air, and simplifies the traditional process.
The o-arylbenzamide compounds are important organic synthesis reagents, and most routes in the prior art require the use of pre-prepared organometallic reagents (organozinc reagents, organomagnesium reagents, organoboron reagents, etc.), which are extremely inconvenient to use and operate.
Therefore, there is a need in the art for a simple and efficient synthetic method for preparing ortho-aryl benzamides.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of an o-aryl benzamide compound.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing an o-aryl benzamide compound comprises the following steps,
Mixing 1,2, 3-benzotriazine-4- (3H) -ketone compounds and aryl bromides with an organic solvent under the action of a transition metal catalyst and a reducing agent, and carrying out reduction cross-coupling reaction to obtain o-aryl benzamide compounds; wherein,
The structural formula of the 1,2, 3-benzotriazine-4- (3H) -ketone compound is shown as the following I:
the structural formula of the aryl bromide is shown as the following II:
The structural formula of the o-arylbenzamide compound is shown as the following III:
Wherein R 1 is selected from methyl, butyl, phenyl or substituted phenyl; r 2 is selected from hydrogen, 4-tert-butyl, 4-methoxy, 4-halo, 2-methyl, 3-methyl or 4-vinyl.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the reaction is carried out under the protection of inert gas, and the inert gas is nitrogen or argon.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the transition metal catalyst comprises a nickel catalyst.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the nickel catalyst is bis- (1, 5-cyclooctadiene) nickel, nickel chloride, nickel bromide or nickel bromide diethylene glycol dimethyl ether.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the reducing agent is zinc powder or manganese powder.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the organic solvent is N, N-dimethylacetamide, N-dimethylformamide or tetrahydrofuran.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the molar ratio of the 1,2, 3-benzotriazine-4- (3H) -ketone compound to the aryl bromide to the reducing agent to the catalyst is 1-2: 1-2: 1-2: 0.05 to 0.2.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the molar ratio of the 1,2, 3-benzotriazine-4- (3H) -ketone compound to the aryl bromide to the reducing agent to the catalyst is 1:2:2:0.01.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the reaction temperature is 40-120 ℃ and the reaction time is 12-14 h.
As a preferable mode of the preparation method of the o-arylbenzamide compound of the invention, wherein: the temperature is 60-100 ℃.
The invention has the beneficial effects that:
(1) The invention provides a synthesis method of a preparation method of an o-aryl benzamide compound, which adopts cheap and easily available raw materials and is environment-friendly; the invention adopts a one-pot synthesis method, reduces the loss of raw materials due to fewer reaction steps, and improves the yield of the product;
(2) The method has the advantages that the required operation steps are simple and convenient, the reaction can be carried out only under normal pressure without extreme temperature rise or temperature reduction, and the method is safe and convenient; the method has wider applicability and can synthesize various o-aryl benzamide compounds.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 1 of the present invention;
FIG. 2 is a chart showing the carbon spectrum of the product obtained in example 1 of the present invention;
FIG. 3 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 2 of the present invention;
FIG. 4 is a chart showing the carbon spectrum of the product obtained in example 2 of the present invention;
FIG. 5 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 3 of the present invention;
FIG. 6 is a chart showing the carbon spectrum of the product obtained in example 3 of the present invention;
FIG. 7 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 4 of the present invention;
FIG. 8 is a chart showing the carbon spectrum of the product obtained in example 4 of the present invention;
FIG. 9 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 5 of the present invention;
FIG. 10 is a chart showing the carbon spectrum of the product obtained in example 5 of the present invention;
FIG. 11 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 6 of the present invention;
FIG. 12 is a carbon spectrum of the product obtained in example 6 of the present invention;
FIG. 13 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 7 of the present invention;
FIG. 14 is a carbon spectrum of the product obtained in example 7 of the present invention;
FIG. 15 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 8 of the present invention;
FIG. 16 is a carbon spectrum of the product obtained in example 8 of the present invention;
FIG. 17 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 9 of the present invention;
FIG. 18 is a chart showing the carbon spectrum of the product obtained in example 9 of the present invention;
FIG. 19 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 10 of the present invention;
FIG. 20 is a chart showing the nuclear magnetic resonance spectrum of the product obtained in example 10 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The various materials referred to in the specification are all purchased from the market, or through simple synthesis, other medicines and the like are purchased from Sigma-Aldrich, acros, ALFA AESAR, TCI China, adamas-beta or J & K, and the model of the nuclear magnetic resonance spectrometer is Bruck 400 megabits.
The invention provides a transition metal catalyzed reduction cross-coupling reaction of 1,2, 3-benzotriazine-4- (3H) -ketone compounds and aryl bromides, and can obtain various o-aryl benzamide compounds with bioactivity and medicinal value. The synthesis method is simple, economical, environment-friendly, more widely applicable and suitable for large-scale production. The specific scheme is as follows:
R 1 is selected from methyl, butyl, phenyl or substituted phenyl; r 2 is selected from hydrogen, 4-tert-butyl, 4-methoxy, 4-halo, 2-methyl, 3-methyl or 4-vinyl.
Example 1
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), bromobenzene (21. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy2,2' -bipyridine (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to the microwave tube in a glove box, followed by 0.2mL of N, N-dimethylacetamide, and taken out of the glove box with a cap.
Then reflux is carried out for 12 hours at 80 ℃, cooling is carried out to room temperature, cover opening is carried out, three drops of water are added for quenching reaction, the solvent is removed under reduced pressure, and the crude product is separated by column chromatography (petroleum ether: ethyl acetate=5:1), thus obtaining N-methyl- [1,1' -biphenyl ] -2-formamide (18.4 mg,87% yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in figure 1 and figure 2, and the spectrum data are ：1H NMR(400MHz,CDCl3)δ:7.66(d,J＝8.1Hz,1H),7.49–7.45(m,1H),7.42–7.36(m,5H),7.38–7.35(m,2H),5.30(s,1H),2.66(d,J＝4.9Hz,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:170.3,140.1,139.3,135.7,130.1,130.0,128.7,128.54,128.52,127.7,127.5,26.6ppm.
Example 2
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), 4-tert-butylbromobenzene (35. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, and removed from the glove box with a cap.
Then reflux at 80 ℃ for 12 hours, cool to room temperature, open the cap and add three drops of water to quench the reaction, remove the solvent under reduced pressure, and separate the crude product by column chromatography (petroleum ether: ethyl acetate=5:1) to obtain 4'- (tert-butyl) -N-methyl- [1,1' -biphenyl ] -2-carboxamide (24.1 mg,90% yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in fig. 3 and 4, and the spectrum data are ：1H NMR(400MHz,CDCl3)δ:7.69-7.67(m,1H),7.47–7.42(m,3H),7.40–7.33(m,4H),5.22(s,1H),2.67(d,J＝4.9Hz,3H),1.35(s,9H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:170.4,150.7,139.2,137.0,135.5,130.09,130.07,128.8,128.3,127.4,125.5,34.6,31.3,26.6ppm.
Example 3
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), 4-methoxybromobenzene (25. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, capped and removed from the glove box.
Then reflux at 80 ℃ for 12 hours, cool to room temperature, open the cap and add three drops of water to quench the reaction, remove the solvent under reduced pressure, and separate the crude product by column chromatography (petroleum ether: ethyl acetate=5:1) to obtain 4'- (methoxy) -N-methyl- [1,1' -biphenyl ] -2-carboxamide (22.0 mg,91% yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in fig. 5 and 6, and the spectrum data are ：7.68–7.63(m,1H),7.46–7.42(m,1H),7.38–7.31(m,4H),6.97–6.93(m,2H),5.29(s,1H),3.84(s,3H),2.70(d,J＝4.9Hz,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:170.5,159.3,138.9,135.5,132.4,130.06,130.04,129.8,128.8,127.2,113.9,55.3,26.6ppm.
Example 4
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), 4-chlorobromobenzene (23. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, capped and taken out of the glove box.
Then reflux-extracting at 80deg.C for 12 hr, cooling to room temperature, opening the cover, adding three drops of water for quenching reaction, removing solvent under reduced pressure, and separating crude product by column chromatography (petroleum ether: ethyl acetate=5:1) to obtain 4 '-chloro-N-methyl- [1,1' -biphenyl ] -2-carboxamide (20.6 mg,84% yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in fig. 7 and 8, and the spectrum data are ：1H NMR(400MHz,CDCl3)δ:7.64–7.62(m,1H),7.50-7.46(m,1H),7.44–7.39(m,2H),7.36-7.33(m,4H),5.32(s,1H),2.73(d,J＝4.9Hz,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:170.2,138.5,138.0,135.8,133.9,130.2,130.0,129.7,128.7,128.6,127.9,26.7ppm.
Example 5
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), 2-methyl bromobenzene (24. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, capped and taken out of the glove box.
Then reflux is carried out for 12 hours at 80 ℃, cooling is carried out to room temperature, cover opening is carried out, three drops of water are added for quenching reaction, the solvent is removed under reduced pressure, and the crude product is separated by column chromatography (petroleum ether: ethyl acetate=5:1), thus obtaining N, 2 '-dimethyl- [1,1' -biphenyl ] -2-formamide (21.0 mg,93 percent yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in fig. 9 and 10, and the spectrum data are ：1H NMR(400MHz,CDCl3)δ:7.93-7.91(m,1H),7.46-7.43(m,2H),7.31–7.26(m,3H),7.21–7.17(m,2H),5.26(s,1H),2.62(d,J＝4.8Hz,3H),2.11(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:168.9,140.1,139.0,136.1,134.8,130.4,130.32,130.29,129.2,129.1,128.2,127.6,126.1,26.7,19.9ppm.
Example 6
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), 3-methyl bromobenzene (24. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, capped and taken out of the glove box.
Then reflux is carried out for 12 hours at 80 ℃, cooling is carried out to room temperature, cover opening is carried out, three drops of water are added for quenching reaction, the solvent is removed under reduced pressure, and the crude product is separated by column chromatography (petroleum ether: ethyl acetate=5:1), thus obtaining N, 3 '-dimethyl- [1,1' -biphenyl ] -2-formamide (20.5 mg,91 percent yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in FIG. 11 and FIG. 12, and the spectrum data are that ：1H NMR(400MHz,CDCl3)δ:7.71–7.69(m,1H),7.48–7.44(m,1H),7.41–7.35(m,2H),7.33–7.26(m,1H),7.23–7.17(m,3H),5.21(s,1H),2.68(d,J＝4.9Hz,3H),2.39(s,3H)ppm.13C NMR(101MHz,Chloroform-d)δ：170.3,140.1,139.4,138.3,135.5,130.09,130.05,129.3,128.8,128.51,128.45,127.5,125.7,26.6,21.4ppm.
Example 7
3-Toluo [ d ] [1,2,3] triazin-4 (3H) -one (16.1 mg,0.10 mmol), 4-vinylbromobenzene (33. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were charged into a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, capped and taken out of the glove box.
Then reflux is carried out for 12 hours at 80 ℃, cooling is carried out to room temperature, cover opening is carried out, three drops of water are added for quenching reaction, the solvent is removed under reduced pressure, and the crude product is separated by column chromatography (petroleum ether: ethyl acetate=5:1), thus obtaining N-methyl-4 '-vinyl- [1,1' -biphenyl ] -2-formamide (15.9 mg,67 percent yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in fig. 13 and 14, and the spectrum data are that ：1H NMR(400MHz,CDCl3)δ:7.69-7.66(m,1H),7.49–7.45(m,3H),7.42–7.36(m,4H),6.75(dd,J＝17.6,10.9Hz,1H),5.81(dd,J＝17.6,0.8Hz,1H),5.31(dd,J＝10.9,0.8Hz,1H),5.25(s,1H),2.70(d,J＝5.0Hz,3H)ppm.13C NMR(101MHz,Chloroform-d)δ：170.3,139.5,138.8,136.9,136.2,135.6,130.1,130.0,128.8,127.6,126.4,114.4,26.7ppm.
Example 8
3-Butylbenzo [ d ] [1,2,3] triazin-4 (3H) -one (20.3 mg,0.10 mmol), bromobenzene (21. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mL of N, N-dimethylacetamide, capped and removed from the glove box.
Then reflux is carried out for 12 hours at 80 ℃, cooling is carried out to room temperature, cover opening is carried out, three drops of water are added for quenching reaction, the solvent is removed under reduced pressure, and the crude product is separated by column chromatography (petroleum ether: ethyl acetate=5:1), thus obtaining N-N-butyl- [1,1' -biphenyl ] -2-formamide (22.0 mg,87 percent yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in fig. 15 and 16, and the spectrum data are that ：1H NMR(400MHz,CDCl3)δ:7.71(d,J＝7.5Hz,1H),7.48–7.45(m,1H),7.43–7.36(m,7H),5.19(s,1H),3.17–3.12(m,2H),1.18-1.05(m,2H),1.03–0.97(m,2H),0.77(t,J＝7.2Hz,3H)ppm.13C NMR(101MHz,Chloroform-d)δ：169.4,140.2,139.3,135.9,130.1,129.9,128.8,128.7,128.6,127.7,127.6,39.5,30.8,19.8,13.7ppm.
Example 9
3-Phenylbenzo [ d ] [1,2,3] triazin-4 (3H) -one (22.3 mg,0.10 mmol), bromobenzene (21. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc powder (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mL of N, N-dimethylacetamide, capped and removed from the glove box.
Then reflux at 80 ℃ for 12 hours, cool to room temperature, open the cover and add three drops of water to quench the reaction, decompress and remove the solvent, and separate the crude product by column chromatography (petroleum ether: ethyl acetate=5:1) to obtain N-phenyl- [1,1' -biphenyl ] -2-carboxamide (23.8 mg,87% yield).
The hydrogen spectrum and carbon spectrum nuclear magnetic resonance spectrum of the product are respectively shown in figure 17 and figure 18, and the spectrum data are that ：1H NMR(400MHz,CDCl3)δ:7.87-7.84(m,2H),7.53–7.40(m,7H),7.24-7.19(m,2H),7.11-7.09(m,2H),7.06-7.02(m,1H),6.96(s,1H)ppm.13C NMR(101MHz,Chloroform-d)δ：167.1,139.9,139.5,137.5,135.2,130.6,130.3,129.5,128.9,128.8,128.1,127.8,127.0,124.4,119.9ppm.
Example 10
3- (4-Fluorophenyl) benzo [ d ] [1,2,3] triazin-4 (3H) -one (24.1 mg,0.10 mmol), bromobenzene (21. Mu.L, 0.2 mmol), nickel bromide diethylene glycol dimethyl ether (3.5 mg,0.001 mmol), bipy (2.3 mg,0.0015 mmol) and zinc dust (1.31 g,0.2 mmol) were added to a microwave tube in a glove box, followed by 0.2mLN, N-dimethylacetamide, capped and removed from the glove box.
Then reflux is carried out for 12 hours at 80 ℃, cooling is carried out to room temperature, cover opening is carried out, three drops of water are added for quenching reaction, the solvent is removed under reduced pressure, and the crude product is separated by column chromatography (petroleum ether: ethyl acetate=5:1), thus obtaining N- (4-fluorophenyl) - [1,1' -biphenyl ] -2-carboxamide (25.1 mg,86% yield).
The hydrogen spectrum and carbon spectrum of the product are shown in FIG. 19 and FIG. 20, respectively, and the spectrum data are ：1H NMR(400MHz,CDCl3)δ:7.85-7.83(m,1H),7.61–7.47(m,2H),7.48–7.38(m,6H),7.05-7.00(m,2H),6.93(s,1H),6.94–6.86(m,2H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:167.2,159.3(JC-F＝242Hz),139.9,139.5,135.0,133.5(JC-F＝2.7Hz),130.6,129.8,128.9,128.8,128.1,127.9,127.0,121.7(JC-F＝7.9Hz),115.3(JC-F＝22Hz)ppm.
The structural formulas of the products in each of examples 1 to 10 are shown in Table 1, and in the first 10 examples, the types of the 1,2, 3-benzotriazine-4- (3H) -one compounds and aryl bromides which are used only are different, other raw materials, the use amounts, the conditions and the like are kept consistent, and the yields of the products in each example are shown in the last column.
TABLE 1
Example 11
The catalyst of example 1 was converted from nickel bromide diethylene glycol dimethyl ether to bis- (1, 5-cyclooctadiene) nickel, and the conditions of the starting materials and amounts used in the other steps were maintained, to give N-methyl- [1,1' -biphenyl ] -2-carboxamide (13.3 mg,63% yield).
Example 12
The catalyst in example 1 was changed from nickel bromide diethylene glycol dimethyl ether to nickel chloride, and the conditions such as raw materials and the amount in other steps were kept unchanged, so that N-methyl- [1,1' -biphenyl ] -2-carboxamide (a small amount, < 5% yield) was finally obtained, wherein a small amount means that after the reaction was completed, the formation of a product was detected through a dot plate, but the product was few, and the yield was less than five percent.
Example 13
The catalyst in example 1 was changed from nickel bromide diethylene glycol dimethyl ether to nickel bromide, and the conditions such as raw materials and the amount in other steps were kept unchanged, so that N-methyl- [1,1' -biphenyl ] -2-carboxamide (a small amount, < 5% yield) was finally obtained, wherein a small amount means that after the reaction was completed, the formation of a product was detected through a dot plate, but the product was few, and the yield was less than five percent.
Example 14
The amount of 3-toluo [ d ] [1,2,3] triazin-4 (3H) -one in example 1 was changed from 1 equivalent to 2 equivalents, and the other conditions were unchanged, to obtain the product N-methyl- [1,1' -biphenyl ] -2-carboxamide in 53% yield.
Example 15
The amount of bromobenzene used in example 1 was changed from 2 equivalents to 1 equivalent, and the other conditions were unchanged, to give the product N-methyl- [1,1' -biphenyl ] -2-carboxamide in 49% yield.
Example 16
The amount of nickel bromide diethylene glycol dimethyl ether in example 1 was changed from 0.1 equivalent to 0.05 equivalent, and the other conditions were unchanged, to give the product N-methyl- [1,1' -biphenyl ] -2-carboxamide in 26% yield.
Example 17
The amount of nickel bromide diethylene glycol dimethyl ether in example 1 was changed from 0.1 equivalent to 0.2 equivalent, and the other conditions were unchanged, to obtain the product N-methyl- [1,1' -biphenyl ] -2-carboxamide in 77% yield.
Example 18
The reaction temperature in example 1 was changed to 40℃and the other conditions were unchanged, to give a small amount of N-methyl- [1,1' -biphenyl ] -2-carboxamide, and the formation of the product was detected by dot-plating, but the product was few, and the yield was less than five percent.
Example 19
The reaction temperature in example 1 was changed to 60℃and other conditions were unchanged, to obtain N-methyl- [1,1' -biphenyl ] -2-carboxamide as a product in 67% yield.
Example 20
The reaction temperature in example 1 was changed to 100℃and the other conditions were unchanged, to obtain N-methyl- [1,1' -biphenyl ] -2-carboxamide as a product in 56% yield.
Example 21
The reaction temperature in example 1 was changed to 120℃and other conditions were unchanged, to give the product N-methyl- [1,1' -biphenyl ] -2-carboxamide in 33% yield.
Example 22
The reducing agent of example 1 was converted to manganese powder under otherwise unchanged conditions to give the product N-methyl- [1,1' -biphenyl ] -2-carboxamide in small amounts, which was detectable by dot-panel, but in very few products in less than five percent yield.
Example 23
The solvent of example 1 was changed to tetrahydrofuran, and the other conditions were unchanged to give a small amount of N-methyl- [1,1' -biphenyl ] -2-carboxamide, and the formation of the product was detected by dot-plating, but the product was few, and the yield was less than five percent.
Example 24
The solvent in example 1 was changed to N, N-dimethylformamide, and other conditions were unchanged, to obtain N-methyl- [1,1' -biphenyl ] -2-carboxamide as a product in 62% yield.
In conclusion, the invention provides a synthesis method of the preparation method of the o-aryl benzamide compound, which adopts cheap and easily available raw materials and is environment-friendly; the invention adopts a one-pot synthesis method, reduces the loss of raw materials due to fewer reaction steps, and improves the yield of the product; the method has the advantages that the required operation steps are simple and convenient, the reaction can be carried out only under normal pressure without extreme temperature rise or temperature reduction, and the method is safe and convenient; the method has wider applicability and can synthesize various o-aryl benzamide compounds.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (7)
1. A preparation method of an o-aryl benzamide compound is characterized by comprising the following steps of: comprising the steps of (a) a step of,
Mixing 1,2, 3-benzotriazine-4- (3H) -ketone compounds and aryl bromides with an organic solvent under the action of a transition metal catalyst and a reducing agent, and carrying out reduction cross-coupling reaction to obtain o-aryl benzamide compounds; wherein,
The structural formula of the 1,2, 3-benzotriazine-4- (3H) -ketone compound is shown as the following I:
Ⅰ
the structural formula of the aryl bromide is shown as the following II:
Ⅱ
The structural formula of the o-arylbenzamide compound is shown as the following III:
Ⅲ
Wherein R 1 is selected from methyl, butyl, phenyl or substituted phenyl; r 2 is selected from hydrogen, 4-tert-butyl, 4-methoxy, 4-halo, 2-methyl, 3-methyl or 4-vinyl;
Wherein the transition metal catalyst is nickel bromide diethylene glycol dimethyl ether, and the reducing agent is manganese powder.
2. The method for producing an o-arylbenzamide compound according to claim 1, characterized in that: the reaction is carried out under the protection of inert gas, and the inert gas is nitrogen or argon.
3. The method for producing an o-arylbenzamide compound according to claim 1, characterized in that: the organic solvent is N, N-dimethylacetamide, N-dimethylformamide or tetrahydrofuran.
4. The method for producing an o-arylbenzamide compound according to claim 1, characterized in that: the molar ratio of the 1,2, 3-benzotriazine-4- (3H) -ketone compound to the aryl bromide to the reducer to the transition metal catalyst is 1-2: 1-2: 1-2: 0.05 to 0.2.
5. The method for producing an o-arylbenzamide compound according to claim 1, characterized in that: the molar ratio of the 1,2, 3-benzotriazine-4- (3H) -ketone compound to the aryl bromide to the reducing agent to the transition metal catalyst is 1:2:2:0.01.
6. The method for producing an o-arylbenzamide compound according to claim 1, characterized in that: the reaction temperature is 40-120 ℃ and the reaction time is 12-14 h.
7. The method for producing an o-arylbenzamide compound according to claim 6, wherein: the temperature is 60-100 ℃.
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| Madasamy Hari Balakrishnan et al.Nickel-Catalyzed Denitrogenative Cross-Coupling Reaction of 1,2,3- Benzotriazin-4(3H)‑ones with Organoboronic Acids: An Easy Access to Ortho-Arylated and Alkenylated Benzamides.Org. Lett..2018,第2018卷(第20期),3815-3818. * |
| Nickel-Catalyzed Denitrogenative ortho-Arylation of Benzotriazinones with Organic Boronic Acids: an Efficient Route to Losartan and Irbesartan Drug Molecules;Vijaykumar H. Thorat et al.;Adv. Synth. Catal;第2018卷(第360期);4784-4789 * |
| Replacing Conventional Carbon Nucleophiles with Electrophiles: Nickel-Catalyzed Reductive Alkylation of Aryl Bromides and Chlorides;Daniel A. Everson;J. Am. Chem. Soc.;第2012卷(第134期);6146-6159 * |
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