CN108276268B - Preparation method of 1, 3-diaryl propine ketone - Google Patents

Preparation method of 1, 3-diaryl propine ketone Download PDF

Info

Publication number
CN108276268B
CN108276268B CN201810051853.6A CN201810051853A CN108276268B CN 108276268 B CN108276268 B CN 108276268B CN 201810051853 A CN201810051853 A CN 201810051853A CN 108276268 B CN108276268 B CN 108276268B
Authority
CN
China
Prior art keywords
cdcl
nmr
mhz
hrms
found
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201810051853.6A
Other languages
Chinese (zh)
Other versions
CN108276268A (en
Inventor
程凯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Shaoxing
Original Assignee
University of Shaoxing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Shaoxing filed Critical University of Shaoxing
Priority to CN201810051853.6A priority Critical patent/CN108276268B/en
Publication of CN108276268A publication Critical patent/CN108276268A/en
Application granted granted Critical
Publication of CN108276268B publication Critical patent/CN108276268B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of 1, 3-diaryl propine ketone, which comprises the following steps: under the action of a silver catalyst and an oxidant, the alpha-keto acid and the aryl alkynoic acid are subjected to decarboxylation coupling reaction in a solvent, and after the reaction is finished, the 1, 3-diaryl alkynone is obtained through post-treatment. The method has the advantages of cheap and easily obtained reagents, mild reaction conditions, good compatibility of reaction functional groups, cheap and easily obtained catalyst and simple catalytic system.

Description

Preparation method of 1, 3-diaryl propine ketone
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of 1, 3-diaryl propine ketone.
Background
1, 3-diarylpropinones are of great interest to chemists because of their biomedical and material multifunctional properties and their widespread use in the synthesis of biologically active products. In the synthesis of natural products, 1, 3-diaryl propiophenone can be used as a precursor to construct various heterocyclic structural units, and various heterocyclic derivatives such as furan, flavone, benzodiazepine, pyrrole, pyrazole, pyrimidine and quinolone are synthesized and used for synthesizing natural products with different pharmacological properties. Due to the unique structural characteristics and biological activity, the synthesis strategy of the 1, 3-diaryl propargyl ketone becomes the research focus of organic chemists, and the synthesis method is continuously emerged. The traditional synthesis method of 1, 3-diaryl allene ketone relies on the coupling reaction of acyl halide catalyzed by transition metal and terminal alkyne or alkynyl organic metal reagent, however, the acyl halide has poor stability and harsh reaction conditions, which limits the applicable range of the substrate, and the Pd-Cu bimetallic system needs the high catalytic amount of expensive palladium salt and the catalysis of CuI. Another simpler method is the transition metal catalyzed Sonogashira reaction of aryl halides (or halogens) with terminal alkynes, however, the implementation of this method requires very high temperatures and requires gaseous carbon monoxide (carbon monoxide is odorless, tasteless, toxic and not easily handled), which greatly limits the application of this method and hinders the development of 1, 3-diarylpropiophenone Synthesis reactions (r.e. whitetater, a.dermenci, g.dong, Synthesis 2016,48, 161).
Transition metal catalyzed decarboxylative coupling reactions have been a powerful method of constructing a variety of carbon-carbon and carbon-heteroatom bonds in the past few years. (J.D. weaver, A.Recio, A.J.Grening, J.A.Tunge, chem.Rev.2011,111,1846) carboxylic acid is a cheap, low-toxicity and easily available raw material, and becomes an ideal complex molecular synthesis reagent. The decarboxylative alkynylation of (n.rodri guez, l.j.go β en, chem.soc.rev.2011,40,5030) carboxylic acids and their derivatives as radical precursors in a radical mechanism has recently been extensively developed and the construction of aryl, alkyl and silyl substituted alkynes by decarboxylative C-Csp coupling reactions has become a reality since 2015. Free radical decarboxylative alkylation reactions are of less interest than decarboxylative alkynylation reactions, which are nucleophilic or electrophilic reactions. Due to their excellent functional group compatibility and mild reaction conditions, the development of novel radical reaction strategies for more convenient and efficient C-Csp bond structures is essential. The main difficulty of the decarboxylation alkynylation reaction of the free radical type is the maintenance of carbon-carbon triple bonds, which are easy to undergo free radical addition reaction as a free radical acceptor, while the current solution mainly relies on the high-valence iodo (III) alkyne (1- (2-alkynyl) -1, 2-benziodox-3 (1H) -one) as an alkynylation reagent to solve, and the alkenyl radical intermediate eliminates the generated benzoxazolinone free radical in situ, thereby releasing the alkyne product. (a) (iv) f.l. valillant, j.w. chimia,2017,71, 226; (b) yang, j. -d.yang, y. -h.li, x.li, j. -p.cheng, j.org.chem.2016,81,12357; (c) -f.wang, y. -s.feng, z. -f.cheng, q. -m.wu, g. -y.wang, l.li, j. -j.dai, j.x, h.j.xu, j.org.chem.2015,80,9314; (d) x.li, s.li, s.sun, f.yang, w.zhu, y.zhu, y.wu, adv.synth.catal.2016,358, 1699; (e) l.l.valillant, t.c, j.waser, angelw.chem.int.ed.2015, 54,11200; (f) q. -q.zhou, w.guo, w.ding, x.wu, x.chen, l. -q.lu, w. -j.xiao, angelw.chem.int.ed.2015, 54,11196; (g) h.wang, l. -n.guo, s.wang, X-H Duan, org.lett.2015,17,3054; (h) h.tan, h.li, w.ji, l.wang.angelw.chem.int.ed.2015, 54,8374.
Another difficulty with free radical type decarboxylation alkynylation is the difficulty in directly generating free radicals by the decarboxylation reaction, which can be solved by reaction with a phthalimide-protected carboxylic acid (N- (formyloxy) phthalimide) to effect the decarboxylation process. (a) L.huang, a.m.olivares, d.j.weix, angelw.chem.int.ed.2017, 56,11901; (b) m.smith, t.qin, r.r.merchat, j.t.edwards, l.r.malins, z.liu, g.che, z.shen, s.a.shaw, m.d.eastgate, p.s.baran.angelw.chem.int.ed.2017, 56,11906; (c) h.zhang, p.zhang, m.jiang, h.yang, h.fu, org.lett.2017,19,1016; (d) yang, j.zhang, l.qi, c.hu, y.chen.chem.commun.2015,51,5275; (e) m. jiang, y.jin, h.yang, h.fu, sci.rep.2016,6,26161. free carboxylic acids are much cheaper and more readily available than N- (acyloxy) phthalimide and high cost iodonium (III) alkyne reagents, and therefore it is highly desirable to develop direct decarboxylative coupling reactions of free carboxylic acids.
In recent years, arylformylcarboxylic acids have begun to be used in organic synthesis as a new acylating agent. Compared with other acylation reagents, the silver-catalyzed acyl radical can participate in the reaction in the form of an acyl radical through the oxidative decarboxylation process catalyzed by silver, has the characteristics of high reaction activity and mild reaction conditions, and greatly expands the application range of the radical acylation reaction. Moreover, the operation and the treatment are relatively simple, and the byproduct of the decarboxylation process is only carbon dioxide and is easy to leave. The alkynyl carboxylic acid is used as an alkyne source through a decarboxylation process, and has the advantages of good stability, easiness in storage and treatment and the like, but the silver-catalyzed decarboxylation reaction of the alkynyl carboxylic acid still has great challenge.
Disclosure of Invention
The invention provides a preparation method of 1, 3-diaryl propine ketone, which has the advantages of cheap and easily obtained reagents, mild reaction conditions and high product yield.
A process for preparing a 1, 3-diarylpropiophenone comprising:
under the action of a silver catalyst and an oxidant, the alpha-keto acid and the aryl alkynoic acid are subjected to decarboxylation coupling reaction in a solvent, and after the reaction is finished, the 1, 3-diaryl alkynone is obtained through post-treatment;
the structure of the alpha-keto acid is shown as a formula (II):
Figure BDA0001552558910000031
the structure of the aryl alkynoic acid is shown as the formula (III):
Figure BDA0001552558910000032
the structure of the 1, 3-diaryl acetylene ketone is shown as the formula (I):
Figure BDA0001552558910000033
in the formulae (I) to (III), R1Is selected from R1Selected from H, C1～C5Alkyl radical, C1～C5Alkoxy, phenyl, halogen, CF3Nitro or C1～C5Alkoxycarbonyl, preferably H, methyl, methoxy, phenyl, F, Cl, CF3Nitro or methoxycarbonyl;
R2selected from H, C1～C5Alkyl, halogen or dimethylamino; preferably H, methyl, ethyl, tert-butyl, F, Cl, Br or dimethylamino.
Wherein R is1And R2May represent a plurality of substituents.
The invention develops decarboxylation alkynylation reaction of aryl formyl formic acid chemical selective free radical by introducing an activated carboxylic acid group on alkyne, taking aryl formyl formic acid potassium as an acylation reagent and using a catalytic amount of silver salt and a cheap inorganic oxidant, and provides a new synthesis method of 1, 3-diaryl propine ketone.
Preferably, the silver catalyst is AgOAc.
Preferably, the oxidant is (NH)4)2S2O8。
Preferably, the solvent is DMSO and H2Mixed solvent of O, DMSO and H2The volume ratio of O is 1: 0.5-1.5.
Preferably, the molar ratio of the aryl alkynoic acid, the alpha-keto acid, the silver catalyst and the oxidizing agent is 1: 1.0-1.1: 0.03-0.05: 1.5 to 2.0.
Preferably, the reaction temperature is 30-50 ℃ and the reaction time is 3-5 hours.
Preferably, the post-treatment comprises: adding ether for extraction, and then carrying out column chromatography to obtain the 1, 3-diaryl propargyl ketone.
The invention also provides another preparation method of the 1, 3-diaryl propiophenone, wherein the alpha-keto acid is replaced by the following compounds:
Figure BDA0001552558910000041
the invention also provides another preparation method of the 1, 3-diaryl alkynone, wherein the aryl alkynoic acid is replaced by the following compound:
Figure BDA0001552558910000042
compared with the prior art, the invention has the beneficial effects that:
the method has the advantages of cheap and easily obtained reagents, mild reaction conditions, good compatibility of reaction functional groups, cheap and easily obtained catalyst and simple catalytic system.
Detailed Description
The invention is further described with reference to specific examples.
Examples 1 to 14
Reacting an alpha-keto acid (1.1mmol, R)1H), arylalkynic acid (1mmol, R)2H), a silver catalyst (5 mol%), and an oxidizing agent (2mmol) were dispersed in a solvent, and then stirred at 50 ℃ for 3 hours under an air atmosphere. After the reaction is finished, Et is used2O (5mL) was extracted three times, the organic phases were combined and concentrated under reduced pressure. And carrying out column chromatography on the obtained crude product (silica gel with 300-400 meshes, and using petroleum ether and ethyl acetate as eluent) to obtain a target product. The silver catalyst, oxidant and solvent used and the reaction results are shown in table 1.
TABLE 1 reaction conditions and reaction results of examples 1 to 10
Figure BDA0001552558910000043
Figure BDA0001552558910000051
aThe total volume of solvent was kept at 2 mL.
Examples 14 to 29
Reacting alpha-keto acid (1.1mmol) and aryl alkynoic acid (1mmol, R)2H), AgOAc (5 mol%) and (NH)4)2S2O8(2mmol) in DMSO (1mL) and H2O (1mL) was added to the mixed solvent, followed by stirring at 50 ℃ for 3 hours under an air atmosphere. After the reaction is finished, Et is used2O (5mL) was extracted three times, the organic phases were combined and concentrated under reduced pressure. And carrying out column chromatography on the obtained crude product (silica gel with 300-400 meshes, and using petroleum ether and ethyl acetate as eluent) to obtain a target product. The substrates used and the reaction results are shown in Table 2.
TABLE 2 reaction substrates and results used in examples 14 to 29
Figure BDA0001552558910000052
Examples 30 to 41
Reacting an alpha-keto acid (1.1mmol, R)1＝H)Arylacetylenic acid (1mmol, R)2H), AgOAc (5 mol%) and (NH)4)2S2O8(2mmol) in DMSO (1mL) and H2O (1mL) was added to the mixed solvent, followed by stirring at 50 ℃ for 3 hours under an air atmosphere. After the reaction is finished, Et is used2O (5mL) was extracted three times, the organic phases were combined and concentrated under reduced pressure. And carrying out column chromatography on the obtained crude product (silica gel with 300-400 meshes, and using petroleum ether and ethyl acetate as eluent) to obtain a target product. The substrates used and the reaction results are shown in Table 3.
TABLE 3 reaction substrates and results used in examples 30 to 41
Figure BDA0001552558910000061
The characterization data for the partial products are as follows:
1,3-Diphenylprop-2-yn-1-one:White solid.1H NMR(400MHz,CDCl3)δ8.08(d,J＝7.2Hz,2H),7.54(d,J＝6.8Hz,2H),7.50–7.44(m,1H),7.38(t,J＝7.6Hz,2H),7.32(d,J＝7.2Hz,1H),7.28–7.26(m,2H).13C NMR(100MHz,CDCl3)δ178.0,136.9,134.2,133.1,130.9,129.6,128.7(d,J＝5.6Hz),120.1,93.2,86.9.HRMS(EI)Calcd for C15H11O[M+H]+,207.0804；found,207.0812.
1-(4-Methoxyphenyl)-3-phenylprop-2-yn-1-one(2a):White solid.1H NMR(400MHz,CDCl3)δ8.37(s,2H),7.66(d,J＝7.2Hz,2H),7.56–7.35(m,3H),6.99(d,J＝8.4Hz,2H),4.03–3.75(m,3H).13C NMR(100MHz,CDCl3)δ176.7,164.5,133.0,132.0,130.7,130.3,128.7,120.3,113.9,92.4,86.9,55.6.HRMS(EI)Calcd for C16H13O2[M+H]+,237.0910；found,237.0915.
3-Phenyl-1-(p-tolyl)prop-2-yn-1-one(2b):White solid.1H NMR(400MHz,CDCl3)δ8.16(d,J＝7.6Hz,2H),7.72(d,J＝7.6Hz,2H),7.47(dq,J＝14.8,7.2 Hz,3H),7.33(d,J＝7.8 Hz,2H),2.47(s,3H).13C NMR(100 MHz,CDCl3)δ177.8,145.3,134.6,133.1,129.8,129.3,120.2,92.7,87.0,21.9.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0954.
1-([1,1'-Biphenyl]-4-yl)-3-phenylprop-2-yn-1-one(2c):White solid.1H NMR(400 MHz,CDCl3)δ8.32(d,J＝8.4 Hz,2H),7.81–7.69(m,4H),7.67–7.61(m,2H),7.58–7.42(m,6H).13C NMR(100 MHz,CDCl3)δ177.6,146.9,139.7,135.8,133.2,130.9,130.3,130.1,129.1,128.8,127.4,127.3,120.2,93.2,87.1.HRMS(EI)Calcd for C21H15O[M+H]+,283.1117；found,283.1124.
1-(4-Fluorophenyl)-3-phenylprop-2-yn-1-one(2d):White solid.1H NMR(400 MHz,CDCl3)δ8.44–7.94(m,2H),7.57(d,J＝7.2 Hz,2H),7.43–7.35(m,1H),7.32(t,J＝7.2 Hz,2H),7.08(t,J＝8.4 Hz,2H).13C NMR(100 MHz,CDCl3)δ175.2,166.6,164.1,132.3,132.0,131.1(d,J＝9.6 Hz),129.9,127.7,118.8,114.8(d,J＝22.4 Hz),92.3,85.5.HRMS(EI)Calcd forC15H10FO[M+H]+,225.0710；found,225.0702.
1-(4-Chlorophenyl)-3-phenylprop-2-yn-1-one(2e):White solid.1H NMR(400 MHz,CDCl3)δ8.17(d,J＝8.4 Hz,2H),7.68(d,J＝7.6 Hz,2H),7.50(d,J＝8.0 Hz,3H),7.43(t,J＝7.6 Hz,2H).13C NMR(100 MHz,CDCl3)δ175.7,139.7,134.2,132.1,130.0,129.8,127.9,127.7,118.8,92.6,85.5.HRMS(EI)Calcd for C15H10ClO[M+H]+,241.0415；found,241.0408.
3-Phenyl-1-(4-(trifluoromethyl)phenyl)prop-2-yn-1-one(2f):White solid.1H NMR(400 MHz,CDCl3)δ8.32(d,J＝7.6 Hz,2H),7.78(d,J＝7.6Hz,2H),7.70(d,J＝7.6 Hz,2H),7.46(dt,J＝14.8,8.0 Hz,3H).13C NMR(100 MHz,CDCl3)δ176.8,139.4,133.2,131.3,129.8,128.8,125.8,125.7,119.7,94.5,86.6.HRMS(EI)Calcd for C16H10F3O[M+H]+,275.0678；found,275.0682.
4-(3-Phenylpropioloyl)benzonitrile(2g):White solid.1H NMR(400MHz,CDCl3)δ8.23(d,J＝8.4 Hz,2H),7.75(d,J＝8.4 Hz,2H),7.64–7.57(m,2H),7.45(dd,J＝10.8,4.4 Hz,1H),7.37(t,J＝7.6 Hz,2H).13C NMR(100 MHz,CDCl3)δ176.1,139.4,133.2,132.4,131.3,129.7,128.7,119.3,117.8,117.0,95.0,86.3.HRMS(EI)Calcd for C16H10NO[M+H]+,232.0757；found,232.0749.
Methyl 4-(3-phenylpropioloyl)benzoate(2h):White solid.1H NMR(400MHz,CDCl3)δ8.34–8.17(m,2H),8.19–8.08(m,2H),7.67(dd,J＝8.4,1.2Hz,2H),7.52–7.46(m,1H),7.45–7.37(m,2H),3.93(s,3H).13C NMR(100MHz,CDCl3)δ177.2,166.1,139.99,134.7,133.1,129.8,129.4,129.4,128.7,119.8,94.2,86.8,52.5.HRMS(EI)Calcd for C17H13O3[M+H]+,265.0859；found,265.0848.
1-(3-Fluorophenyl)-3-phenylprop-2-yn-1-one(2i):White solid.1H NMR(400 MHz,CDCl3)δ8.04(dt,J＝7.6,1.2 Hz,1H),7.87(dt,J＝9.2,2.0Hz,1H),7.72–7.66(m,2H),7.54–7.49(m,2H),7.47–7.41(m,2H),7.37-7.31(m,1H).13C NMR(100 MHz,CDCl3)δ176.6,164.0,161.5,139.0,138.9,133.2,131.1,130.4,130.3,128.8,125.5,125.4,121.3,121.1,119.8,116.1,115.9,93.8,86.6.HRMS(EI)Calcd for C15H10FO[M+H]+,225.0710；found,225.0715.
1-(3-Chlorophenyl)-3-phenylprop-2-yn-1-one(2j):White solid.1H NMR(400 MHz,CDCl3)δ8.16(d,J＝1.6 Hz,1H),8.10(d,J＝7.6 Hz,1H),7.72–7.64(m,2H),7.59(dd,J＝8.0,0.8 Hz,1H),7.45(dq,J＝12.0,7.2 Hz,4H).13C NMR(100 MHz,CDCl3)δ176.6,138.4,135.0,134.1,133.2,131.1,130.0,129.4,128.8,127.7,119.8,94.0,86.5.HRMS(EI)Calcd forC15H10ClO[M+H]+,241.0415；found,241.0411.
1-(3-Nitrophenyl)-3-phenylprop-2-yn-1-one(2k):Yellow solid.1H NMR(400 MHz,CDCl3)δ9.03(t,J＝2.0 Hz,1H),8.54–8.46(m,2H),7.80–7.72(m,3H),7.56–7.44(m,3H).13C NMR(100 MHz,CDCl3)δ175.5,148.5,138.1,134.6,133.3,131.5,129.9,128.2,124.6,119.4,95.4,86.2.HRMS(EI)Calcd for C15H10NO3[M+H]+,252.0655；found,252.0647.
1-(2-Chlorophenyl)-3-phenylprop-2-yn-1-one(2l):White solid.1H NMR(400 MHz,CDCl3)δ8.06(d,J＝7.6 Hz,1H),7.63(d,J＝7.6 Hz,2H),7.49–7.42(m,3H),7.39(t,J＝6.8 Hz,3H).13C NMR(100 MHz,CDCl3)δ176.7,135.8,133.5,133.3,133.0,132.5,131.5,130.9,128.6,126.7,119.9,93.9,88.2.HRMS(EI)Calcd for C15H10ClO[M+H]+,241.0415；found,241.0411.
1-(2-Methoxyphenyl)-3-phenylprop-2-yn-1-one(2m):White solid.1H NMR(400 MHz,CDCl3)δ8.08(dd,J＝7.6,2.0 Hz,1H),7.63(dt,J＝7.2,1.6Hz,2H),7.52(t,J＝8.0 Hz,1H),7.46–7.34(m,3H),7.10–6.96(m,2H),3.94(s,3H).13C NMR(100 MHz,CDCl3)δ176.7,159.7,134.9,132.9,132.6,130.4,128.5,126.6,120.6,120.2,112.1,91.5,89.1,55.9.HRMS(EI)Calcdfor C16H13O2[M+H]+,237.0910；found,237.0904.
1-(3,5-Difluorophenyl)-3-phenylprop-2-yn-1-one(2n):White solid.1H NMR(400 MHz,CDCl3)δ8.15(dd,J＝15.2,8.4 Hz,1H),7.64(d,J＝7.2 Hz,2H),7.53–7.44(m,1H),7.40(dd,J＝15.6,8.4 Hz,2H),7.00(t,J＝8.0 Hz,1H),6.95–6.86(m,1H).13C NMR(100 MHz,CDCl3)δ172.7,133.8,133.7,133.2,131.0,128.7,119.9,112.0,111.8,105.6,105.3,105.1,99.9,93.3,88.2.HRMS(EI)Calcd for C15H9F2O[M+H]+,243.0616；found,243.0625.
1-(Naphthalen-1-yl)-3-phenylprop-2-yn-1-one(2o):White solid.1H NMR(400 MHz,CDCl3)δ9.24(d,J＝8.4 Hz,1H),8.63(d,J＝8.0 Hz,1H),8.05(d,J＝8.0 Hz,1H),7.88(d,J＝8.4 Hz,1H),7.66(t,J＝7.6 Hz,4H),7.55(q,J＝7.2 Hz,3H),7.43(ddd,J＝14.8,8.0,6.4 Hz,2H).13C NMR(100 MHz,CDCl3)δ179.6,135.2,134.4,133.8,132.9,132.9,130.7,130.7,128.9,128.6,128.5,126.7,125.8,124.4,120.4,91.7,88.3.HRMS(EI)Calcd forC19H13O[M+H]+,257.0961；found,257.0955.
3-Phenyl-1-(quinolin-6-yl)prop-2-yn-1-one(2p):White solid.1H NMR(400 MHz,CDCl3)δ8.93(dd,J＝4.0,1.6 Hz,1H),8.62(d,J＝1.6 Hz,1H),8.35(dd,J＝8.8,2.0 Hz,1H),8.22(d,J＝8.4 Hz,1H),8.08(d,J＝8.8 Hz,1H),7.66–7.60(m,2H),7.40(dd,J＝7.6,3.6 Hz,2H),7.34(t,J＝7.2 Hz,2H).13C NMR(100 MHz,CDCl3)δ177.1,153.0,150.5,137.8,134.6,133.1,132.0,131.0,130.1,128.8,127.8,127.3,122.1,119.8,93.8,86.9；HRMS(EI)Calcd for C18H12NO[M+H]+,258.0913；found,258.0917.
3-(4-Methoxyphenyl)-1-phenylprop-2-yn-1-one(3a):White solid.1H NMR(400 MHz,CDCl3)δ8.23–8.11(m,2H),7.62–7.51(m,3H),7.46(t,J＝7.6 Hz,2H),6.86(d,J＝8.8 Hz,2H),3.78(s,3H).13C NMR(100 MHz,CDCl3)δ177.7,161.5,136.8,134.9,133.7,129.2,128.4,114.2,111.5,94.2,86.7,55.2.HRMS(EI)Calcd for C16H13O2[M+H]+,237.0910；found,237.0912.
1-(4-Methylphenyl)-1-phenylprop-2-yn-1-one(3b):White solid.1H NMR(400 MHz,CDCl3)δ8.27–8.18(m,2H),7.67–7.56(m,3H),7.51(t,J＝7.6 Hz,2H),7.24(d,J＝8.0 Hz,2H),2.41(s,3H).13C NMR(100 MHz,CDCl3)δ178.1,141.5,136.9,134.0,133.2,133.0,129.5,128.5,116.9,93.8,86.7,21.7.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0965.
1-(4-Ethylphenyl)-1-phenylprop-2-yn-1-one(3c):White solid.1H NMR(400 MHz,CDCl3)δ8.14(d,J＝8.0 Hz,2H),7.71(s,2H),7.54–7.26(m,5H),2.75(s,2H),1.28(d,J＝7.2 Hz,3H).13C NMR(100 MHz,CDCl3)δ176.7,150.4,133.7,132.0,129.7,128.8,127.6,127.1,119.2,91.6,85.9,28.1,14.1.HRMS(EI)Calcd for C17H15O[M+H]+,235.1117；found,235.1122.
3-(4-(tert-Butyl)phenyl)-1-phenylprop-2-yn-1-one(3d):White solid.1H NMR(400 MHz,CDCl3)δ8.27–8.18(m,2H),7.64–7.57(m,3H),7.49(dd,J＝10.4,4.8 Hz,2H),7.45–7.38(m,2H),1.32(s,9H).13C NMR(100 MHz,CDCl3)δ177.7,154.3,136.7,133.8,132.8,129.3,128.4,125.5,116.7,93.6,86.6,34.8,30.8.HRMS(EI)Calcd for C19H19O[M+H]+,235.1117；found,235.1122.
3-(4-Fluorophenyl)-1-phenylprop-2-yn-1-one(3e):White solid.1H NMR(400 MHz,CDCl3)δ8.10(d,J＝7.6 Hz,2H),7.62–7.55(m,2H),7.52(t,J＝7.6 Hz,1H),7.42(t,J＝7.6 Hz,2H),7.00(t,J＝8.4 Hz,2H).13C NMR(100 MHz,CDCl3)δ177.9,164.3,136.8,135.4,134.2,129.6,128.7,116.3,116.2,92.0,86.8；HRMS(EI)Calcd for C15H10FO[M+H]+,225.0710；found,225.0704.
3-(4-Chlorophenyl)-1-phenylprop-2-yn-1-one(3f):White solid.1H NMR(400 MHz,CDCl3)δ8.22(d,J＝8.0 Hz,2H),7.61(t,J＝7.2 Hz,3H),7.53(t,J＝7.6 Hz,2H),7.41(d,J＝8.0 Hz,2H).13C NMR(100 MHz,CDCl3)δ177.7,137.1,136.6,134.3,134.1,129.5,129.0,128.5,118.5,91.6,87.5；HRMS(EI)Calcd for C15H10ClO[M+H]+,241.0415；found,241.0418.
3-(4-Bromophenyl)-1-phenylprop-2-yn-1-one(3g):White solid.1H NMR(400 MHz,CDCl3)δ8.18(d,J＝7.6 Hz,2H),7.61(t,J＝7.2 Hz,1H),7.56–7.47(m,6H).13C NMR(100 MHz,CDCl3)δ177.7,136.5,134.2,134.2,131.9,129.5,128.6,125.5,118.9,91.5,87.6.HRMS(EI)Calcd forC15H10BrO[M+H]+,284.9910；found,284.9896.
3-(4-(Dimethylamino)phenyl)-1-phenylprop-2-yn-1-one(3h):White solid.1H NMR(400 MHz,CDCl3)δ8.21(d,J＝7.6 Hz,2H),7.62–7.40(m,5H),6.63(d,J＝8.8 Hz,2H),3.02(s,6H).13C NMR(100 MHz,CDCl3)δ177.9,151.6,137.3,135.2,133.4,129.4,128.4,111.6,105.5,97.6,87.7,39.9.HRMS(EI)Calcd for C17H16NO[M+H]+,250.1226；found,250.1219.
1-Phenyl-3-(m-tolyl)prop-2-yn-1-one(3i):White solid.1H NMR(400MHz,CDCl3)δ8.08(d,J＝7.2 Hz,2H),7.44(t,J＝7.2 Hz,1H),7.32(dd,J＝15.6,8.0 Hz,4H),7.11(t,J＝7.2 Hz,2H),2.17(s,3H).13C NMR(100 MHz,CDCl3)δ178.0,138.5,136.9,134.2,133.6,133.6,131.9,130.3,129.6,128.7,119.9,93.6,86.7,21.2.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0957.
1-Phenyl-3-(o-tolyl)prop-2-yn-1-one(3j):White solid.1H NMR(400MHz,CDCl3)δ8.25–7.94(m,2H),7.55–7.42(m,2H),7.35(t,J＝7.6 Hz,2H),7.22(td,J＝7.6,1.2 Hz,1H),7.14–7.04(m,2H),2.43(s,3H).13C NMR(100 MHz,CDCl3)δ178.0,142.2,137.0,134.1,133.7,130.9,129.9,129.6,128.7,126.0,120.0,92.2,90.8,20.9.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0969.
3-(Cyclohex-1-en-1-yl)-1-phenylprop-2-yn-1-one(3k):White solid.1H NMR(400 MHz,CDCl3)δ8.09(dd,J＝8.4,1.2 Hz,2H),7.55–7.51(m,1H),7.41(t,J＝7.6 Hz,2H),6.50(s,1H),2.25–2.18(m,2H),2.15–2.10(m,2H),1.66–1.53(m,4H).13C NMR(100 MHz,CDCl3)δ177.8,142.5,136.7,133.6,129.1,128.2,118.8,95.5,84.9,28.1,25.9,21.7,20.8.HRMS(EI)Calcd forC15H15O[M+H]+,211.1117；found,211.1125.
1-Phenyl-3-(thiophen-2-yl)prop-2-yn-1-one(3l):Pale yellow solid.1H NMR(400 MHz,CDCl3)δ8.18(d,J＝8.4 Hz,2H),7.67–7.62(m,1H),7.60–7.57(m,1H),7.55–7.49(m,3H),7.14–7.07(m,1H).13C NMR(100 MHz,CDCl3)δ177.5,136.7,136.6,134.1,131.7,129.4,128.6,127.7,119.8,91.6,87.0.HRMS(EI)Calcd for C13H9OS[M+H]+,213.0369；found,213.0361.
1,3-Diphenylprop-2-yn-1-one:White solid.1H NMR(400 MHz,CDCl3)δ8.08(d,J＝7.2 Hz,2H),7.54(d,J＝6.8 Hz,2H),7.50–7.44(m,1H),7.38(t,J＝7.6 Hz,2H),7.32(d,J＝7.2 Hz,1H),7.28–7.26(m,2H).13C NMR(100 MHz,CDCl3)δ178.0,136.9,134.2,133.1,130.9,129.6,128.7(d,J＝5.6Hz),120.1,93.2,86.9.HRMS(EI)Calcd for C15H11O[M+H]+,207.0804；found,207.0812.
1-(4-Methoxyphenyl)-3-phenylprop-2-yn-1-one(2a):White solid.1H NMR(400 MHz,CDCl3)δ8.37(s,2H),7.66(d,J＝7.2 Hz,2H),7.56–7.35(m,3H),6.99(d,J＝8.4 Hz,2H),4.03–3.75(m,3H).13C NMR(100 MHz,CDCl3)δ176.7,164.5,133.0,132.0,130.7,130.3,128.7,120.3,113.9,92.4,86.9,55.6.HRMS(EI)Calcd for C16H13O2[M+H]+,237.0910；found,237.0915.
3-Phenyl-1-(p-tolyl)prop-2-yn-1-one(2b):White solid.1H NMR(400MHz,CDCl3)δ8.16(d,J＝7.6 Hz,2H),7.72(d,J＝7.6 Hz,2H),7.47(dq,J＝14.8,7.2 Hz,3H),7.33(d,J＝7.8 Hz,2H),2.47(s,3H).13C NMR(100 MHz,CDCl3)δ177.8,145.3,134.6,133.1,129.8,129.3,120.2,92.7,87.0,21.9.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0954.
1-([1,1'-Biphenyl]-4-yl)-3-phenylprop-2-yn-1-one(2c):White solid.1H NMR(400 MHz,CDCl3)δ8.32(d,J＝8.4 Hz,2H),7.81–7.69(m,4H),7.67–7.61(m,2H),7.58–7.42(m,6H).13C NMR(100 MHz,CDCl3)δ177.6,146.9,139.7,135.8,133.2,130.9,130.3,130.1,129.1,128.8,127.4,127.3,120.2,93.2,87.1.HRMS(EI)Calcd for C21H15O[M+H]+,283.1117；found,283.1124.
1-(4-Fluorophenyl)-3-phenylprop-2-yn-1-one(2d):White solid.1H NMR(400 MHz,CDCl3)δ8.44–7.94(m,2H),7.57(d,J＝7.2 Hz,2H),7.43–7.35(m,1H),7.32(t,J＝7.2 Hz,2H),7.08(t,J＝8.4 Hz,2H).13C NMR(100 MHz,CDCl3)δ175.2,166.6,164.1,132.3,132.0,131.1(d,J＝9.6 Hz),129.9,127.7,118.8,114.8(d,J＝22.4 Hz),92.3,85.5.HRMS(EI)Calcd forC15H10FO[M+H]+,225.0710；found,225.0702.
1-(4-Chlorophenyl)-3-phenylprop-2-yn-1-one(2e):White solid.1H NMR(400 MHz,CDCl3)δ8.17(d,J＝8.4 Hz,2H),7.68(d,J＝7.6 Hz,2H),7.50(d,J＝8.0 Hz,3H),7.43(t,J＝7.6 Hz,2H).13C NMR(100 MHz,CDCl3)δ175.7,139.7,134.2,132.1,130.0,129.8,127.9,127.7,118.8,92.6,85.5.HRMS(EI)Calcd for C15H10ClO[M+H]+,241.0415；found,241.0408.
3-Phenyl-1-(4-(trifluoromethyl)phenyl)prop-2-yn-1-one(2f):White solid.1H NMR(400 MHz,CDCl3)δ8.32(d,J＝7.6 Hz,2H),7.78(d,J＝7.6Hz,2H),7.70(d,J＝7.6 Hz,2H),7.46(dt,J＝14.8,8.0 Hz,3H).13C NMR(100 MHz,CDCl3)δ176.8,139.4,133.2,131.3,129.8,128.8,125.8,125.7,119.7,94.5,86.6.HRMS(EI)Calcd for C16H10F3O[M+H]+,275.0678；found,275.0682.
4-(3-Phenylpropioloyl)benzonitrile(2g):White solid.1H NMR(400MHz,CDCl3)δ8.23(d,J＝8.4 Hz,2H),7.75(d,J＝8.4 Hz,2H),7.64–7.57(m,2H),7.45(dd,J＝10.8,4.4 Hz,1H),7.37(t,J＝7.6 Hz,2H).13C NMR(100 MHz,CDCl3)δ176.1,139.4,133.2,132.4,131.3,129.7,128.7,119.3,117.8,117.0,95.0,86.3.HRMS(EI)Calcd for C16H10NO[M+H]+,232.0757；found,232.0749.
Methyl 4-(3-phenylpropioloyl)benzoate(2h):White solid.1H NMR(400MHz,CDCl3)δ8.34–8.17(m,2H),8.19–8.08(m,2H),7.67(dd,J＝8.4,1.2Hz,2H),7.52–7.46(m,1H),7.45–7.37(m,2H),3.93(s,3H).13C NMR(100MHz,CDCl3)δ177.2,166.1,139.99,134.7,133.1,129.8,129.4,129.4,128.7,119.8,94.2,86.8,52.5.HRMS(EI)Calcd for C17H13O3[M+H]+,265.0859；found,265.0848.
1-(3-Fluorophenyl)-3-phenylprop-2-yn-1-one(2i):White solid.1H NMR(400 MHz,CDCl3)δ8.04(dt,J＝7.6,1.2 Hz,1H),7.87(dt,J＝9.2,2.0Hz,1H),7.72–7.66(m,2H),7.54–7.49(m,2H),7.47–7.41(m,2H),7.37-7.31(m,1H).13C NMR(100 MHz,CDCl3)δ176.6,164.0,161.5,139.0,138.9,133.2,131.1,130.4,130.3,128.8,125.5,125.4,121.3,121.1,119.8,116.1,115.9,93.8,86.6.HRMS(EI)Calcd for C15H10FO[M+H]+,225.0710；found,225.0715.
1-(3-Chlorophenyl)-3-phenylprop-2-yn-1-one(2j):White solid.1H NMR(400 MHz,CDCl3)δ8.16(d,J＝1.6 Hz,1H),8.10(d,J＝7.6 Hz,1H),7.72–7.64(m,2H),7.59(dd,J＝8.0,0.8 Hz,1H),7.45(dq,J＝12.0,7.2 Hz,4H).13C NMR(100 MHz,CDCl3)δ176.6,138.4,135.0,134.1,133.2,131.1,130.0,129.4,128.8,127.7,119.8,94.0,86.5.HRMS(EI)Calcd forC15H10ClO[M+H]+,241.0415；found,241.0411.
1-(3-Nitrophenyl)-3-phenylprop-2-yn-1-one(2k):Yellow solid.1H NMR(400 MHz,CDCl3)δ9.03(t,J＝2.0 Hz,1H),8.54–8.46(m,2H),7.80–7.72(m,3H),7.56–7.44(m,3H).13C NMR(100 MHz,CDCl3)δ175.5,148.5,138.1,134.6,133.3,131.5,129.9,128.2,124.6,119.4,95.4,86.2.HRMS(EI)Calcd for C15H10NO3[M+H]+,252.0655；found,252.0647.
1-(2-Chlorophenyl)-3-phenylprop-2-yn-1-one(2l):White solid.1H NMR(400 MHz,CDCl3)δ8.06(d,J＝7.6 Hz,1H),7.63(d,J＝7.6 Hz,2H),7.49–7.42(m,3H),7.39(t,J＝6.8 Hz,3H).13C NMR(100 MHz,CDCl3)δ176.7,135.8,133.5,133.3,133.0,132.5,131.5,130.9,128.6,126.7,119.9,93.9,88.2.HRMS(EI)Calcd for C15H10ClO[M+H]+,241.0415；found,241.0411.
1-(2-Methoxyphenyl)-3-phenylprop-2-yn-1-one(2m):White solid.1H NMR(400 MHz,CDCl3)δ8.08(dd,J＝7.6,2.0 Hz,1H),7.63(dt,J＝7.2,1.6Hz,2H),7.52(t,J＝8.0 Hz,1H),7.46–7.34(m,3H),7.10–6.96(m,2H),3.94(s,3H).13C NMR(100 MHz,CDCl3)δ176.7,159.7,134.9,132.9,132.6,130.4,128.5,126.6,120.6,120.2,112.1,91.5,89.1,55.9.HRMS(EI)Calcdfor C16H13O2[M+H]+,237.0910；found,237.0904.
1-(3,5-Difluorophenyl)-3-phenylprop-2-yn-1-one(2n):White solid.1H NMR(400 MHz,CDCl3)δ8.15(dd,J＝15.2,8.4 Hz,1H),7.64(d,J＝7.2 Hz,2H),7.53–7.44(m,1H),7.40(dd,J＝15.6,8.4 Hz,2H),7.00(t,J＝8.0 Hz,1H),6.95–6.86(m,1H).13C NMR(100 MHz,CDCl3)δ172.7,133.8,133.7,133.2,131.0,128.7,119.9,112.0,111.8,105.6,105.3,105.1,99.9,93.3,88.2.HRMS(EI)Calcd for C15H9F2O[M+H]+,243.0616；found,243.0625.
1-(Naphthalen-1-yl)-3-phenylprop-2-yn-1-one(2o):White solid.1H NMR(400 MHz,CDCl3)δ9.24(d,J＝8.4 Hz,1H),8.63(d,J＝8.0 Hz,1H),8.05(d,J＝8.0 Hz,1H),7.88(d,J＝8.4 Hz,1H),7.66(t,J＝7.6 Hz,4H),7.55(q,J＝7.2 Hz,3H),7.43(ddd,J＝14.8,8.0,6.4 Hz,2H).13C NMR(100 MHz,CDCl3)δ179.6,135.2,134.4,133.8,132.9,132.9,130.7,130.7,128.9,128.6,128.5,126.7,125.8,124.4,120.4,91.7,88.3.HRMS(EI)Calcd forC19H13O[M+H]+,257.0961；found,257.0955.
3-Phenyl-1-(quinolin-6-yl)prop-2-yn-1-one(2p):White solid.1H NMR(400 MHz,CDCl3)δ8.93(dd,J＝4.0,1.6 Hz,1H),8.62(d,J＝1.6 Hz,1H),8.35(dd,J＝8.8,2.0 Hz,1H),8.22(d,J＝8.4 Hz,1H),8.08(d,J＝8.8 Hz,1H),7.66–7.60(m,2H),7.40(dd,J＝7.6,3.6 Hz,2H),7.34(t,J＝7.2 Hz,2H).13C NMR(100 MHz,CDCl3)δ177.1,153.0,150.5,137.8,134.6,133.1,132.0,131.0,130.1,128.8,127.8,127.3,122.1,119.8,93.8,86.9；HRMS(EI)Calcd for C18H12NO[M+H]+,258.0913；found,258.0917.
3-(4-Methoxyphenyl)-1-phenylprop-2-yn-1-one(3a):White solid.1H NMR(400 MHz,CDCl3)δ8.23–8.11(m,2H),7.62–7.51(m,3H),7.46(t,J＝7.6 Hz,2H),6.86(d,J＝8.8 Hz,2H),3.78(s,3H).13C NMR(100 MHz,CDCl3)δ177.7,161.5,136.8,134.9,133.7,129.2,128.4,114.2,111.5,94.2,86.7,55.2.HRMS(EI)Calcd for C16H13O2[M+H]+,237.0910；found,237.0912.
1-(4-Methylphenyl)-1-phenylprop-2-yn-1-one(3b):White solid.1H NMR(400 MHz,CDCl3)δ8.27–8.18(m,2H),7.67–7.56(m,3H),7.51(t,J＝7.6 Hz,2H),7.24(d,J＝8.0 Hz,2H),2.41(s,3H).13C NMR(100 MHz,CDCl3)δ178.1,141.5,136.9,134.0,133.2,133.0,129.5,128.5,116.9,93.8,86.7,21.7.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0965.
1-(4-Ethylphenyl)-1-phenylprop-2-yn-1-one(3c):White solid.1H NMR(400 MHz,CDCl3)δ8.14(d,J＝8.0 Hz,2H),7.71(s,2H),7.54–7.26(m,5H),2.75(s,2H),1.28(d,J＝7.2 Hz,3H).13C NMR(100 MHz,CDCl3)δ176.7,150.4,133.7,132.0,129.7,128.8,127.6,127.1,119.2,91.6,85.9,28.1,14.1.HRMS(EI)Calcd for C17H15O[M+H]+,235.1117；found,235.1122.
3-(4-(tert-Butyl)phenyl)-1-phenylprop-2-yn-1-one(3d):White solid.1H NMR(400 MHz,CDCl3)δ8.27–8.18(m,2H),7.64–7.57(m,3H),7.49(dd,J＝10.4,4.8 Hz,2H),7.45–7.38(m,2H),1.32(s,9H).13C NMR(100 MHz,CDCl3)δ177.7,154.3,136.7,133.8,132.8,129.3,128.4,125.5,116.7,93.6,86.6,34.8,30.8.HRMS(EI)Calcd for C19H19O[M+H]+,235.1117；found,235.1122.
3-(4-Fluorophenyl)-1-phenylprop-2-yn-1-one(3e):White solid.1H NMR(400 MHz,CDCl3)δ8.10(d,J＝7.6 Hz,2H),7.62–7.55(m,2H),7.52(t,J＝7.6 Hz,1H),7.42(t,J＝7.6 Hz,2H),7.00(t,J＝8.4 Hz,2H).13C NMR(100 MHz,CDCl3)δ177.9,164.3,136.8,135.4,134.2,129.6,128.7,116.3,116.2,92.0,86.8；HRMS(EI)Calcd for C15H10FO[M+H]+,225.0710；found,225.0704.
3-(4-Chlorophenyl)-1-phenylprop-2-yn-1-one(3f):White solid.1H NMR(400 MHz,CDCl3)δ8.22(d,J＝8.0 Hz,2H),7.61(t,J＝7.2 Hz,3H),7.53(t,J＝7.6 Hz,2H),7.41(d,J＝8.0 Hz,2H).13C NMR(100 MHz,CDCl3)δ177.7,137.1,136.6,134.3,134.1,129.5,129.0,128.5,118.5,91.6,87.5；HRMS(EI)Calcd for C15H10ClO[M+H]+,241.0415；found,241.0418.
3-(4-Bromophenyl)-1-phenylprop-2-yn-1-one(3g):White solid.1H NMR(400 MHz,CDCl3)δ8.18(d,J＝7.6 Hz,2H),7.61(t,J＝7.2 Hz,1H),7.56–7.47(m,6H).13C NMR(100 MHz,CDCl3)δ177.7,136.5,134.2,134.2,131.9,129.5,128.6,125.5,118.9,91.5,87.6.HRMS(EI)Calcd forC15H10BrO[M+H]+,284.9910；found,284.9896.
3-(4-(Dimethylamino)phenyl)-1-phenylprop-2-yn-1-one(3h):White solid.1H NMR(400 MHz,CDCl3)δ8.21(d,J＝7.6 Hz,2H),7.62–7.40(m,5H),6.63(d,J＝8.8 Hz,2H),3.02(s,6H).13C NMR(100 MHz,CDCl3)δ177.9,151.6,137.3,135.2,133.4,129.4,128.4,111.6,105.5,97.6,87.7,39.9.HRMS(EI)Calcd for C17H16NO[M+H]+,250.1226；found,250.1219.
1-Phenyl-3-(m-tolyl)prop-2-yn-1-one(3i):White solid.1H NMR(400MHz,CDCl3)δ8.08(d,J＝7.2 Hz,2H),7.44(t,J＝7.2 Hz,1H),7.32(dd,J＝15.6,8.0 Hz,4H),7.11(t,J＝7.2 Hz,2H),2.17(s,3H).13C NMR(100 MHz,CDCl3)δ178.0,138.5,136.9,134.2,133.6,133.6,131.9,130.3,129.6,128.7,119.9,93.6,86.7,21.2.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0957.
1-Phenyl-3-(o-tolyl)prop-2-yn-1-one(3j):White solid.1H NMR(400MHz,CDCl3)δ8.25–7.94(m,2H),7.55–7.42(m,2H),7.35(t,J＝7.6 Hz,2H),7.22(td,J＝7.6,1.2 Hz,1H),7.14–7.04(m,2H),2.43(s,3H).13C NMR(100 MHz,CDCl3)δ178.0,142.2,137.0,134.1,133.7,130.9,129.9,129.6,128.7,126.0,120.0,92.2,90.8,20.9.HRMS(EI)Calcd for C16H13O[M+H]+,221.0961；found,221.0969.
3-(Cyclohex-1-en-1-yl)-1-phenylprop-2-yn-1-one(3k):White solid.1H NMR(400 MHz,CDCl3)δ8.09(dd,J＝8.4,1.2 Hz,2H),7.55–7.51(m,1H),7.41(t,J＝7.6 Hz,2H),6.50(s,1H),2.25–2.18(m,2H),2.15–2.10(m,2H),1.66–1.53(m,4H).13C NMR(100 MHz,CDCl3)δ177.8,142.5,136.7,133.6,129.1,128.2,118.8,95.5,84.9,28.1,25.9,21.7,20.8.HRMS(EI)Calcd forC15H15O[M+H]+,211.1117；found,211.1125.
1-Phenyl-3-(thiophen-2-yl)prop-2-yn-1-one(3l):Pale yellow solid.1H NMR(400 MHz,CDCl3)δ8.18(d,J＝8.4 Hz,2H),7.67–7.62(m,1H),7.60–7.57(m,1H),7.55–7.49(m,3H),7.14–7.07(m,1H).13C NMR(100 MHz,CDCl3)δ177.5,136.7,136.6,134.1,131.7,129.4,128.6,127.7,119.8,91.6,87.0.HRMS(EI)Calcd for C13H9OS[M+H]+,213.0369；found,213.0361。

Claims (6)

1. a method for preparing 1, 3-diaryl acetylene ketone is characterized by comprising the following steps:
under the action of a silver catalyst and an oxidant, the alpha-keto acid and the aryl alkynoic acid are subjected to decarboxylation coupling reaction in a solvent, and after the reaction is finished, the 1, 3-diaryl alkynone is obtained through post-treatment;
the structure of the alpha-keto acid is shown as a formula (II):
Figure FDA0002820201550000011
the structure of the aryl alkynoic acid is shown as the formula (III):
Figure FDA0002820201550000012
the structure of the 1, 3-diaryl acetylene ketone is shown as the formula (I):
Figure FDA0002820201550000013
in the formulae (I) to (III), R1Selected from H, C1～C5Alkyl radical, C1～C5Alkoxy, phenyl, halogen, CF3Nitro or C1～C5An alkoxycarbonyl group;
R2selected from H, C1～C5Alkyl, halogen or dimethylamino;
the silver catalyst is AgOAc;
the oxidant is (NH)4)2S2O8；
The solvent is DMSO and H2Mixed solvent of O, DMSO and H2The volume ratio of O is 1: 0.5-1.5.
2. The method according to claim 1, wherein the molar ratio of the arylacetylenic acid, the α -keto acid, the silver catalyst, and the oxidizing agent is 1: 1.0-1.1: 0.03-0.05: 1.5 to 2.0.
3. The method for preparing 1, 3-diarylpropiophenone according to claim 1, wherein the reaction temperature is 30 to 50 ℃ and the reaction time is 3 to 5 hours.
4. The process for preparing 1, 3-diarylalkynones according to claim 1, characterized in that the post-treatment comprises: adding ether for extraction, and then carrying out column chromatography to obtain the 1, 3-diaryl propargyl ketone.
5. A process for the preparation of 1, 3-diarylalkynones according to any one of claims 1 to 4, characterized in that the α -keto acids are replaced with:
Figure FDA0002820201550000021
6. a process for the preparation of 1, 3-diarylalkynones according to any one of claims 1 to 4, characterized in that the arylalkynoic acids are replaced with the following compounds:
Figure FDA0002820201550000022
CN201810051853.6A 2018-01-19 2018-01-19 Preparation method of 1, 3-diaryl propine ketone Expired - Fee Related CN108276268B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810051853.6A CN108276268B (en) 2018-01-19 2018-01-19 Preparation method of 1, 3-diaryl propine ketone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810051853.6A CN108276268B (en) 2018-01-19 2018-01-19 Preparation method of 1, 3-diaryl propine ketone

Publications (2)

Publication Number Publication Date
CN108276268A CN108276268A (en) 2018-07-13
CN108276268B true CN108276268B (en) 2021-06-18

Family

ID=62804009

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810051853.6A Expired - Fee Related CN108276268B (en) 2018-01-19 2018-01-19 Preparation method of 1, 3-diaryl propine ketone

Country Status (1)

Country Link
CN (1) CN108276268B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110683949B (en) * 2019-10-08 2022-02-22 安徽理工大学 Method for preparing 9, 10-phenanthrene dicarboxylic ester compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Dual Hypervalent Iodine(III) Reagents and Photoredox Catalysis Enable Decarboxylative Ynonylation under Mild Conditions;Hanchu Huang等;《Angew. Chem. Int. Ed.》;20151231(第54期);7872-7876 *

Also Published As

Publication number Publication date
CN108276268A (en) 2018-07-13

Similar Documents

Publication Publication Date Title
CN107141248B (en) A kind of method of visible light catalytic synthesis three ketene compound of 3- sulfuryl loop coil
CN107805232B (en) Synthetic method of derivative containing methylthio furan
Desai et al. Recent advances in directed sp 2 C–H functionalization towards the synthesis of N-heterocycles and O-heterocycles
Arshadi et al. Cross-dehydrogenative coupling reactions between arenes (C–H) and carboxylic acids (O–H): a straightforward and environmentally benign access to O-aryl esters
CN108250229B (en) Method for synthesizing axial chiral biaryl compound by palladium-catalyzed asymmetric alkynylation
Wang et al. Deep eutectic solvents to organic synthesis
Sato et al. Synthesis of Biaryls via Palladium‐Catalyzed [2+ 2+ 2] Cocyclization of Arynes and Diynes: Application to the Synthesis of Arylnaphthalene Lignans
JP2017533234A (en) Method for producing biphenylamines from azobenzoles by ruthenium catalysis
Ramakrishna et al. Brønsted acid mediated N–O bond cleavage for α-amination of ketones through the aromatic nitroso aldol reaction
CN110981877B (en) Synthesis method of indolo [1,2-a ] quinoxaline derivative
CN108276268B (en) Preparation method of 1, 3-diaryl propine ketone
CN107629028A (en) A kind of method based on intermolecular ring-closure reaction synthesis furan derivatives
Xiao et al. Copper-catalyzed acylation of pyrazolones with aldehydes to afford 4-acylpyrazolones
CN100376555C (en) Process for preparing diindolylmethane derivatives
CN108864164B (en) Synthesis method of primary amine-guided 2-alkynyl indole compound
CN113651788B (en) 3-aminoalkylchromone compound and preparation method thereof
CN102093355A (en) C-3 acylated indolizine compound and preparation method thereof
CN105646326B (en) A kind of preparation method of the ketone compounds of polysubstituted indoles 2
CN111978167B (en) One-step synthesis method of polysubstituted cyclohex-2-enone
CN113880781A (en) Method for synthesizing 3-trifluoromethyl substituted 1,2, 4-triazole compound by taking glucose as carbon source
Zang et al. An efficient one‐pot synthesis of pyrazolone derivatives promoted by acidic ionic liquid
CN107954960B (en) Synthetic method of 1,3-dihydroisobenzofuran compound
CN110590636A (en) 4-sulfonyl pyrrolidone compound and synthesis method thereof
CN106083690A (en) A kind of preparation method of polysubstituted 3 methylene indolones
Cao et al. Catalyst-free, Solvent-promoted and Scalable Multicomponent Synthesis of 3-Aminoalkylated Indoles via a Mannich-type Reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210618

Termination date: 20220119