CN114349612B - Preparation method of aryl ketone compound - Google Patents
Preparation method of aryl ketone compound Download PDFInfo
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- CN114349612B CN114349612B CN202210069536.3A CN202210069536A CN114349612B CN 114349612 B CN114349612 B CN 114349612B CN 202210069536 A CN202210069536 A CN 202210069536A CN 114349612 B CN114349612 B CN 114349612B
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- -1 aryl ketone compound Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical group [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 238000004809 thin layer chromatography Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 4
- QLLQUGHRMDUZCX-UHFFFAOYSA-N 1-hex-1-ynyl-4-methylbenzene Chemical compound CCCCC#CC1=CC=C(C)C=C1 QLLQUGHRMDUZCX-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- SICBLYCPRWNHHP-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1CC(=O)C1=CC=C(OC)C=C1 SICBLYCPRWNHHP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- PLALKSRAHVYFOH-UHFFFAOYSA-N 1-(4-methoxyphenyl)-2-phenylethanone Chemical compound C1=CC(OC)=CC=C1C(=O)CC1=CC=CC=C1 PLALKSRAHVYFOH-UHFFFAOYSA-N 0.000 description 1
- BCVCZJADTSTKNH-UHFFFAOYSA-N 1-(4-methylphenyl)pentan-1-one Chemical compound CCCCC(=O)C1=CC=C(C)C=C1 BCVCZJADTSTKNH-UHFFFAOYSA-N 0.000 description 1
- BXXYBNVPUWTQFR-UHFFFAOYSA-N 1-methoxy-4-(2-phenylethynyl)benzene Chemical compound C1=CC(OC)=CC=C1C#CC1=CC=CC=C1 BXXYBNVPUWTQFR-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical class [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000011924 stereoselective hydrogenation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/26—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydration of carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of aryl ketone compounds, and belongs to the technical field of compound synthesis. The method comprises the steps of reacting the aryl internal alkyne with the structure shown in the formula 1 in a solvent at 60-120 ℃ for 12-48 hours under the action of a silver catalyst and water, and separating and purifying the product after the reaction is finished to obtain the single aryl ketone compound with the structure shown in the formula I. The invention has the advantages of easily obtained raw materials, simple experimental operation, good yield of the prepared single aryl ketone compound and gram-scale experiment.
Description
Technical Field
The invention belongs to the technical field of compound synthesis, and particularly relates to a preparation method of aryl ketone compounds.
Background
As an essential component in organic synthesis, alkynes are widely used by organic chemists, biochemists and material scientists. Alkynes have prompted the development of various synthetic methods, and in these important applications, the hydration of alkynes is a simple, effective and practical strategy for the synthesis of carbonyl compounds (M.Rubina, M.Conley andV.Gevorgyan, J.Am.Chem.Soc.,2006,128,5818.). Conventional processes are usually carried out in aqueous sulfuric acid with the use of toxic mercury (II) salts as catalysts, and have limited application in the laboratory and industry (Kutscheroff, m.berg.dtsch.chem.ges., 1881,14,1540-1542.). Therefore, it is very feasible to develop alternative catalysts to overcome the toxicity of mercury salts.
Despite success in the regioselective hydration of terminal alkynes, the conversion of internal C-C triple bonds, and in particular of asymmetric internal alkynes, in a regiospecific manner has remained elusive to date, although in some notable precedents regioselectivity has been increased to about 90/10 (Rzhevskiy, s.a., philipopova, a.n., chesnokov, g.a., ageshina, a.a., minaaeva, l.i., topshiy, m.a., nechaev, m.s., asachenko, a.f., chemical communications.2021,57, 5686-5689). To address this problem, some precursor studies have employed additional directing groups, which impose additional synthetic routes and limit substrate scope.
However, from previous literature reports, acid additives are required for the preparation of aryl ketones by monometallic Ag-catalyzed hydration of the alkyne in the aryl group. The inventors utilized CO 2 Accelerated AgOAc catalyzed hydration of propargyl alcohol and utilization of AgNO 3 Catalytic hydration of alkynylphosphonates to aryl ketones (H.He, C.Qi, X.Hu, Y.Guana, H.Jianga, green chem.2014,16; xiang, N.Yi, R.Wang, L.Lu, H.Zou, Y.Pan, W.He, tetrahedron,2015,71, 694-699), but with the reaction system requiring additional additives and harsh reaction conditions.
Disclosure of Invention
The invention aims to solve the problems that an additional additive and regioselectivity are needed in the preparation of the existing aryl ketone compound preparation method, and provides a preparation method of the aryl ketone compound.
The invention provides a preparation method of aryl ketone compounds, which comprises the following steps:
under the action of a silver catalyst and water, reacting the aryl internal alkyne with the structure shown in the formula 1 in a solvent at 70-120 ℃ for 38-48 hours, and separating and purifying a product after the reaction is finished to obtain an aryl ketone compound with the structure shown in the formula I;
in the formula 1 and the formula I, R 1 Is naphthyl, thienyl, biphenyl, substituted or unsubstituted phenyl, wherein the substituent group is alkyl, alkoxy, amino or halogen;
R 2 is alkyl, hydrogen atom, substituted or unsubstituted phenyl, and the substituent group is alkyl, alkoxy, cyano or halogen.
Preferably, said R 1 Is p-methoxyphenyl, R 2 Is a hydrogen atom.
Preferably, said R 1 Is biphenyl, R 2 Is methyl.
Preferably, the silver catalyst is AgSbF 6 、AgOAc、AgBr、CF 3 COOAg or AgOTf.
Preferably, the molar ratio of the silver catalyst to the alkyne in the aryl group of formula 1 is preferably (0.05-0.2): 1.
Preferably, the water is fed in an equivalent of 1.0 to 6.0 equivalents.
Preferably, the solvent is dichloromethane, chlorobenzene, trichloromethane or 1, 2-dichloroethane.
Preferably, the reaction temperature is 70-120 ℃ and the reaction time is 12-48 hours.
Preferably, the separation and purification use column chromatography or thin layer chromatography, and the developing agent used for chromatography is a mixture of petroleum ether and ethyl acetate.
Preferably, the volume ratio of petroleum ether to diethyl ether is 100:1-10:1.
The beneficial effects of the invention are that
The invention provides a preparation method of aryl ketone compound, which utilizes silver-catalyzed hydration of alkyne in aryl to synthesize aryl ketone compound, the reaction principle is that silver ions attack triple bonds of alkyne and form Ag-complex B, and then the Ag-complex B and H 2 The O reaction gives intermediate C by nucleophilic attack of-OH and deprotonation to give more stable intermediate D, which is then protonated to form enol E, which undergoes keto-enol tautomerism to aryl ketones. The method is simple, raw materials are easy to obtain, no additional additive is needed in the reaction process, and the prepared product has high yield and is prepared in gram scale.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the product 1, 2-bis (4-methoxyphenyl) ethane-1-one prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the product 1, 2-bis (4-methoxyphenyl) ethane-1-one prepared in example 1 according to the present invention.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the product 1- (4-methoxyphenyl) -2-phenethyl-1-one prepared on a scale of 2 g in example of the present invention.
FIG. 4 is a nuclear magnetic resonance carbon spectrum of the product 1- (4-methoxyphenyl) -2-phenethyl-1-one prepared in a 2 g scale according to the present invention.
Detailed Description
The invention firstly provides a preparation method of aryl ketone compounds, which comprises the following steps:
under the action of a silver catalyst and water without using an additive, reacting the aryl internal alkyne with the structure shown in the formula 1 in a solvent at 70-120 ℃ for 12-48 hours, and separating and purifying a product after the reaction is finished to obtain an aryl ketone compound with the structure shown in the formula I;
r in formula 1 and formula I 1 Is naphthyl, thienyl, biphenyl, substituted or unsubstituted phenyl, wherein the substituent group is alkyl, alkoxy, amino or halogen; preferably p-tolyl, m-tolyl, p-methoxyphenyl, o-tolyl, p-aminophenyl, phenyl, p-fluorophenyl, p-bromophenyl or p-chlorophenyl,
R 2 alkyl, hydrogen atom, substituted or unsubstituted phenyl, said substituent being alkyl, alkoxy, cyano or halogen, preferably p-tolyl, p-methoxyphenyl, phenyl, p-cyanophenyl, t-butyl, methyl, ethyl, n-butyl or hydrogen.
Preferably, the formula I has the following structure:
according to the invention, the molar ratio of silver catalyst to alkyne in aryl of formula 1 is preferably (0.05-0.2): 1; the water is preferably added in an amount of 1.0 to 6.0 equivalents, more preferably 3.0 equivalents.
According to the invention, the silver catalyst is preferably AgSbF 6 AgOAc, agBr, CF3COOAg or AgOTf, more preferably AgSbF 6 Or AgOTf, most preferably AgOTf; the solvent is preferably dichloromethane, chlorobenzene, chloroform or 1, 2-dichloroethane, more preferably chlorobenzene.
According to the invention, the reaction temperature is 70-120 ℃, preferably 100 ℃; the reaction time is 12 to 48 hours, preferably 44 hours.
According to the invention, column chromatography or thin layer chromatography is used for separation and purification, and the developing agent used for chromatography is a mixture of petroleum ether and ethyl acetate, and the mixing volume ratio of petroleum ether to ethyl acetate is preferably 100:1-10:1, more preferably 30:1.
The reaction process route is as follows:
the following examples illustrate the invention in more detail, but do not limit it further.
The aryl alkyne starting materials used in the examples of the present invention can be prepared by methods commercially available or documented in the literature, specific references: (1) reference may be made to Liu, y; du, H.an. Alkene-protein bound-Catalyzed Highly Stereoselective Hydrogenation ofAlkynes to Give Z-and E-Alkenes. Chem. Eur. J.2015,21,3495-3501; li, K.Cobalt Catalyzed Stereodivergent semi-hydrogenation ofAlkynes using H 2 O as the Hydrogen Source.Chem.Commun.2019,55,5663-5666.
Example 1
1. The reaction formula:
2. the amounts and properties of the reaction materials are shown in Table 1:
TABLE 1
| Substance (B) | Molecular weight | Millimoles | Mass/mg | Volume of |
| 1-p-tolylhexane-1-yne | 158.24 | 0.3 | 47.5 | |
| H 2 O | 18 | 0.9 | 16.2 | |
| AgOTf | 256.94 | 0.03 | 7.70 | |
| PhCl | 112.56 | - | - | 2.0mL |
3. The preparation method comprises the following steps:
a magnetic stirrer, 1-p-tolylhexane-1-yne (47.5 mg,0.3 mmol), agOTf (7.70 mg,0.03 mmol), was added to the tube, and the system was argon-shielded. Water (0.9 mmol) was dissolved in 2mL of PhCl and the vial was quickly added with a 5mL syringe, after which the vial was sealed. The tube was placed in an oil bath on a magnetic stirrer with heating function, stirred at constant temperature of 100℃for 44 hours, and the reaction was monitored by thin layer chromatography. After cooling to room temperature, concentrating under reduced pressure, and separating by chromatography column chromatography to obtain product 1- (p-tolyl) pentane-1-one (42 mg,74% yield), and nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the product are shown in figures 1 and 2.
The nuclear magnetic resonance data of the product were: 1 H NMR(400MHz,CDCl3)δ7.86(d,J＝7.8Hz,2H),7.25(d,J＝7.8Hz,2H),2.93(t,J＝7.3Hz,2H),2.41(s,3H),1.73(s,2H),1.36(d,J＝2.9Hz,4H),0.91(s,3H). 13 C NMR(101MHz,CDCl 3 )δ200.3(s),143.5(s),134.7(s),129.2(s),128.2(s),38.5(s),31.6(s),24.2(s),22.5(s),21.6(s),13.9(s).
FIGS. 1 and 2 fully demonstrate the structure of the resulting product, which is the hydrogen spectrum 1, alkyl chain CH 3 Peak at 0.91ppm, CH on alkyl chain 2 Peaks at 1.36ppm,1.73ppm,2.91-2.94ppm, respectively, CH on aromatic ring 3 Peaks at 3.06ppm and aromatic ring hydrogens at 7.24-7.87ppm, consistent with structure. In the carbon spectrum 2, the carbon in the alkyl region was peaked at 38.5,31.6,24.2,22.5,21.6,13.9ppm, the aromatic carbon was peaked at 143.5,134.7,129.2,128.2ppm, and the carbonyl carbon was peaked at 200.3ppm, respectively, in accordance with the structure. Thus, the structure of the compound is clearly confirmed.
Example 2
1. The reaction formula:
2. the amounts and properties of the reaction materials are shown in Table 2:
TABLE 2
| Substance (B) | Molecular weight | Millimoles | Mass/g | Volume of |
| 1-methoxy-4- (phenylethynyl) benzene | 208.08 | 7 | 1.45 | |
| H 2 O | 18 | 8.4 | 0.152 | |
| AgOTf | 256.94 | 0.35 | 0.0899 | |
| PhCl | 112.56 | - | - | 10.0mL |
3. The preparation method comprises the following steps:
a magnetic stirrer, 1-p-tolylhexane-1-yne (1.45 g,7 mmol), agOTf (89.9 mg,0.35 mmol), was added to the tube, and the system was argon-shielded. Water (8.4 mmol) was dissolved in 10mL of PhCl and the vial was quickly added with a 20mL syringe, after which the vial was sealed. The tube was placed in an oil bath on a magnetic stirrer with heating function, stirred at constant temperature of 100℃for reaction for 46 hours, and the reaction was monitored by thin layer chromatography. After cooling to room temperature, concentrating under reduced pressure, and separating by chromatography column chromatography to obtain the product 1- (4-methoxyphenyl) -2-phenylethan-1-one (1 g,63% yield), wherein the nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the product are shown in figures 3 and 4.
The nuclear magnetic resonance data of the product were: 1H NMR (400 MHz, CDCl 3) delta 7.98 (d, J=8.6 Hz, 2H), 7.43-7.14 (m, 5H), 6.91 (d, J=8.6 Hz, 2H), 4.22 (s, 2H), 3.83 (s, 3H) 13C NMR (101 MHz, CDCl 3) delta 196.15,163.48,134.95,130.88,129.64,129.33,128.57,126.70,113.75,55.39,45.20.
FIGS. 3 and 4 fully demonstrate the structure of the resulting product, which has a hydrogen spectrum 3, alkoxy CH 3 Peak at 3.83ppm, CH of methylene 2 The peak at 4.22ppm and the peak at 6.91-7.98ppm of aromatic ring hydrogen are consistent with the structure. In the carbon spectrum 4, the carbon of the alkyl base region was peaked at 55.39 and 45.20ppm, the aromatic carbon was peaked at 163.48,134.95,130.88,129.64,129.33,128.57,126.70 and 113.75ppm, and the carbonyl carbon was peaked at 196.15ppm, respectively, which corresponds to the structure. Thus, the structure of the compound is clearly confirmed.
Example 3
1. The reaction formula:
2. r in the formula 1 、R 2 Aryl ketone compounds prepared by different substituents and the preparation method is the sameExample 1 was identical and the results are shown in Table 3:
TABLE 3 Table 3
The results show that: the method has wide application range, and a wider substrate range can be used for synthesizing corresponding compounds.
Example 4
The reaction procedure and conditions were the same as in example 1, except that the reaction solvents were varied, and the results are shown in Table 4:
TABLE 4 Table 4
| Solvent(s) | Dichloromethane (dichloromethane) | Chlorobenzene (Chlorobenzene) | Trichloromethane | 1, 2-dichloroethane |
| Product yield (%) | 25 | 83 | 20 | 53 |
Table 4 shows that the yields were highest using chlorobenzene under otherwise identical conditions.
Example 5
The reaction procedure and conditions were the same as in example 1, except that the catalysts were varied and the results are shown in Table 5:
TABLE 5
| Catalyst | AgSbF 6 | AgOAc | AgBr | CF 3 COOAg | AgOTf |
| Product yield (%) | 37 | 0 | 0 | 0 | 83 |
As can be seen from Table 5, other silver catalysts also catalyzed the reaction, but the AgOTf yield was highest.
Example 6
The reaction procedure and conditions were the same as in example 1, except that the equivalent of water was varied and the results are shown in Table 6:
TABLE 6
Table 6 shows that the water yield was highest using 3 equivalents under otherwise identical conditions.
Example 7
In order to select the appropriate developing agent for isolation of the product, a series of experiments were performed to determine the Rf values for the different developing agents, as shown in Table 7:
TABLE 7
| Petroleum ether/diethyl ether volume ratio | 100:1 | 50:1 | 30:1 | 20:1 |
| Rf | 0.1 | 0.5 | 0.7 | 0.9 |
As is clear from Table 7, the developing agent was suitable for column chromatography when the volume ratio of petroleum ether/diethyl ether was 3:1 to 50:1.
Claims (5)
1. A method for preparing an aryl ketone compound, comprising the steps of:
under the action of a silver catalyst and water, reacting the aryl internal alkyne with the structure shown in the formula 1 in a solvent at 70-120 ℃ for 38-48 hours, and separating and purifying a product after the reaction is finished to obtain an aryl ketone compound with the structure shown in the formula I;
in the formula 1 and the formula I, R 1 P-tolyl, m-tolyl, p-methoxyphenyl, o-tolyl, p-aminophenyl, phenyl, p-fluorophenyl, p-bromophenyl or p-chlorophenyl;
R 2 p-tolyl, p-methoxyphenyl, phenyl, p-cyanophenyl, t-butyl, methyl, ethyl or n-butyl;
the solvent is chlorobenzene;
the silver catalyst is AgOTf;
the water feed equivalent is 3.0equiv.
2. The method for preparing aryl ketone compound according to claim 1, wherein the molar ratio of silver catalyst to aryl internal alkyne of formula 1 is (0.05-0.2): 1.
3. The method for preparing aryl ketone compound according to claim 1, wherein the reaction temperature is 70-120 ℃ and the reaction time is 12-48 hours.
4. The method for preparing aryl ketone compound according to claim 1, wherein the separation and purification use column chromatography or thin layer chromatography, and the developing agent used for chromatography is a mixture of petroleum ether and ethyl acetate.
5. The method for preparing aryl ketone compound according to claim 4, wherein the volume ratio of petroleum ether to diethyl ether is 100:1-10:1.
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| Bhaskar Sarmah等.Highly Efficient Silver Nanoparticles Supported Nanocrystalline Zirconosilicate Catalyst for the Epoxidation and Hydration Reactions.《ChemistrySelect》.2016,第1047-1056页. * |
| Jose R. Cabrero-Antonino等.Bimetallic nanosized solids with acid and redox properties for catalytic activation of C–C and C–H bonds.《Chem. Sci.》.2017,第689-696页. * |
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