CN108276268A - A kind of preparation method of 1,3- diaryl propine ketone - Google Patents

A kind of preparation method of 1,3- diaryl propine ketone Download PDF

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CN108276268A
CN108276268A CN201810051853.6A CN201810051853A CN108276268A CN 108276268 A CN108276268 A CN 108276268A CN 201810051853 A CN201810051853 A CN 201810051853A CN 108276268 A CN108276268 A CN 108276268A
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程凯
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University of Shaoxing
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    • 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
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • 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
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    • 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
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    • 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
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Abstract

The invention discloses a kind of preparation methods of 1,3 diaryl propine ketone, including：Under the action of silver catalyst and oxidant, decarboxylation coupling reaction occurs in a solvent for α ketone acids and aryl acetylenic acid, passes through post-processing after reaction and obtains 1, the 3 diaryl propine ketone.This method reagent is cheap and easy to get, and reaction condition is mild, and reactive functionality good compatibility, catalyst is cheap and easy to get, and catalyst system and catalyzing is simple.

Description

A kind of preparation method of 1,3- diaryl propine ketone
Technical field
The invention belongs to organic synthesis fields, and in particular to the preparation method of one kind 1,3- diaryl propine ketone.
Background technology
1,3- diaryl propine ketone is synthesized because of its biomedical and material multi-functional characteristic and in bioactive product In extensive use and receive chemist concern.In natural products synthesis, 1,3- diaryl propine ketone can be used as precursor structure All kinds of heterocycle structure units are built, the multiple heterocycles such as furans, flavones, Benzodiazepine, pyrroles, pyrazoles, pyrimidine and quinolone have been synthesized Derivative, and for the synthesis with different pharmacological property natural products.Due to its unique structure feature and bioactivity, The synthesis strategy of 1,3- diaryl propine ketone becomes the research focus of organic chemist, and synthetic method continues to bring out.It passes The synthetic method of the 1,3- diaryl propine ketone of system is organic dependent on transition metal-catalyzed acyl halide and Terminal Acetylenes or alkynyl The coupling reaction of metal reagent, however acyl halide stability is poor, reaction condition is harsher, limits the applicable model of substrate It encloses, and Pd-Cu bimetallic systems need the expensive palladium salt of high catalytic amount and the co-catalysis of CuI.Another simpler method It is then that transition metal-catalyzed aryl halide (or class halogen) is reacted with the slotting carbonyl Sonogashira of terminal alkyne, however, should The realization of method needs very high temperature, and needs gaseous carbon monoxide (carbon monoxide is odorless tasteless, and toxicity is high, does not allow It is disposable), these all greatly limit the application of this method, hinder the development of 1,3- diaryl propine ketone synthetic reactions (R.E.Whittaker,A.Dermenci,G.Dong,Synthesis 2016,48,161)。
In past few years, transition metal-catalyzed decarboxylation coupling reaction is the various carbon-carbon keys of structure and carbon-hetero atom The powerful approach of key.(J.D.Weaver,A.Recio,A.J.Grenning,J.A.Tunge,Chem.Rev.2011,111, 1846) carboxylic acid becomes the synthetic agent of ideal complicated molecule as a kind of cheap, low toxicity and the raw material being easy to get.(N.Rodrí Guez, L.J.Goo β en, Chem.Soc.Rev.2011,40,5030) carboxylic acid and its derivative participate in as free based precursor The decarboxylation alkynylation reaction of free radical mechanism has obtained extensive development recently, is coupled by decarboxylation C-Csp from 2015 It reacts and has become reality to build the alkynes of aryl, alkyl and silicyl substitution.It is de- compared to nucleophilic or electrophilic reaction The concern that carboxylic alkynylation reaction, free radical decarboxylation alkylated reaction are subject to is less.Due to its fabulous functional group's compatibility and temperature The reaction condition of sum, it is very necessary to develop the novel radical reaction strategy of more convenient effective C-Csp bond structures.From Major Difficulties by the decarboxylation alkynylation reaction of base type are the holdings of triple carbon-carbon bonds, are easy to occur as free radical aceeptor Radical Addition, and current solution depends on high price iodine (III) alkynes (1- (2- alkynyls) -1,2- benzo iodine Evil -3 (1H) -one) it is solved as alkynyl reagent, it is free that alkenyl radical intermediate eliminates the Tolazoline ketone generated in situ Base, to discharge alkynes product.(a)F.L.Vaillant,J.W.Chimia,2017,71,226；(b)C.Yang,J.- D.Yang,Y.-H.Li,X.Li,J.-P.Cheng,J.Org.Chem.2016,81,12357；(c)P.-F.Wang,Y.- S.Feng,Z.-F.Cheng,Q.-M.Wu,G.-Y.Wang,L.-L.Liu,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,Y.Wu, Adv.Synth.Catal.2016,358,1699；(e)F.L.Vaillant,T.C,J.Waser, Angew.Chem.Int.Ed.2015,54,11200；(f)Q.-Q.Zhou,W.Guo,W.Ding,X.Wu,X.Chen,L.- Q.Lu,W.-J.Xiao,Angew.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.Angew.Chem.Int.Ed.2015, 54,8374.
Another difficult point of the decarboxylation alkynylation reaction of free radical type is that decarboxylic reaction directly generates the difficulty of free radical Degree, can reacting by carboxylic acid (N- (formyloxy) phthalimide) protected with phthalimide, realize Decarboxylation procedure solves.(a)L.Huang,A.M.Olivares,D.J.Weix,Angew.Chem.Int.Ed.2017,56, 11901；(b)J.M.Smith,T.Qin,R.R.Merchant,J.T.Edwards,L.R.Malins,Z.Liu,G.Che, Z.Shen,S.A.Shaw,M.D.Eastgate,P.S.Baran.Angew.Chem.Int.Ed.2017,56,11906；(c) H.Zhang,P.Zhang,M.Jiang,H.Yang,H.Fu,Org.Lett.2017,19,1016；(d)J.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. compared with N- (acyloxy) phthalimides and high price iodine (III) alkynes reagent, free carboxylic Acid is more cheap and easy to get, therefore the direct decarboxylation coupling reaction for developing free carboxylic acid is very important.
In recent years, aryl formic acid was applied to initially as a kind of new acylting agent in organic synthesis.With other Acylting agent is compared, and reaction, tool can be participated in the form of acyl group free radical by the oxidative decarboxylation process of silver catalysis Have the characteristics that reactivity is high, reaction condition is mild, has expanded the application range of free radical acylation reaction significantly.And it Operation and processing relative ease, and the by-product of decarboxylation procedure only has carbon dioxide, is easy to leave away.And alkynyl carboxylic acid passes through decarboxylation Process equally has many advantages, such as that stability is good as alkynes source, easily stored and processing, however the alkynyl carboxylic acid of silver catalysis Decarboxylic reaction still has prodigious challenge.
Invention content
The present invention provides the preparation methods of one kind 1,3- diaryl propine ketone, and the preparation method reagent is cheap and easy to get, instead Answer mild condition, and product yield high.
The preparation method of one kind 1,3- diaryl propine ketone, including：
Under the action of silver catalyst and oxidant, decarboxylation coupling reaction occurs in a solvent for 2-ketoacid and aryl acetylenic acid, Pass through post-processing after reaction and obtains the 1,3- diaryl propine ketone；
Shown in the structure of the 2-ketoacid such as formula (II)：
Shown in the structure such as formula (III) of the aryl acetylenic acid：
Shown in the structure such as formula (I) of the 1,3- diaryl propine ketone：
In formula (I)~(III), R1Selected from R1Selected from H, C1~C5Alkyl, C1~C5Alkoxy, phenyl, halogen, CF3, nitro Or C1~C5Alkoxy carbonyl group, preferably H, methyl, methoxyl group, phenyl, F, Cl, CF3, nitro or methoxycarbonyl group；
R2Selected from H, C1~C5Alkyl, halogen or dimethylamino；Preferably H, methyl, ethyl, tertiary butyl, F, Cl, Br or two Methylamino.
Wherein, R1And R2Multiple substituent groups can be represented.
The present invention on alkynes by introducing activating carboxy acid's group, using aryl formic acid potassium as acylting agent, Silver salt using catalytic amount and cheap inorganic oxidizer have developed the decarboxylation alkynes of aryl formic acid chemo-selective free radical Glycosylation reaction provides the novel synthesis of 1,3- diaryl propine ketone.
Preferably, the silver catalyst is AgOAc.
Preferably, the oxidant is (NH4)2S2O8。
Preferably, the solvent is DMSO and H2The mixed solvent of O, DMSO and H2The volume ratio of O is 1:0.5~ 1.5。
Preferably, the molar ratio of the aryl acetylenic acid, 2-ketoacid, silver catalyst, oxidant is 1：1.0~1.1： 0.03~0.05：1.5~2.0.
Preferably, reaction temperature is 30~50 DEG C, the reaction time is 3~5 hours.
Preferably, the post-processing includes：Ether is added to be extracted, then carries out column chromatography and obtains described 1,3- Diaryl propine ketone.
The present invention also provides the preparation method of 1, the 3- diaryl propine ketone described in another kind, the use of the 2-ketoacid Following compound is replaced：
The present invention also provides the preparation method of 1, the 3- diaryl propine ketone described in another kind, the aryl acetylenic acid is used Following compound is replaced：
Compared with the existing technology, beneficial effects of the present invention are embodied in：
The method reagent of the present invention is cheap and easy to get, and reaction condition is mild, reactive functionality good compatibility, and catalyst is inexpensive easily , catalyst system and catalyzing is simple.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.
Embodiment 1~14
By 2-ketoacid (1.1mmol, R1=H), aryl acetylenic acid (1mmol, R2=H), silver catalyst (5mol%) and oxidant (2mmol) is scattered in solvent, and then under air atmosphere, 50 DEG C are stirred 3 hours.After reaction, Et is used2O (5mL) is extracted Three times, merge organic phase, be concentrated under reduced pressure.Obtained crude product carries out column chromatography (300~400 mesh silica gel, petroleum ether and acetic acid second Ester is as eluent), obtain target product.Silver catalyst, oxidant and solvent used and reaction result are shown in Table 1.
The reaction condition and reaction result of 1 Examples 1 to 10 of table
aThe total volume of solvent is maintained at 2mL.
Embodiment 14~29
By 2-ketoacid (1.1mmol), aryl acetylenic acid (1mmol, R2=H), AgOAc (5mol%) and (NH4)2S2O8 (2mmol) is scattered in DMSO (1mL) and H2The in the mixed solvent of O (1mL), then under air atmosphere, 50 DEG C are stirred 3 hours. After reaction, Et is used2O (5mL) is extracted three times, merges organic phase, is concentrated under reduced pressure.Obtained crude product carries out column chromatography (300 ~400 mesh silica gel, petroleum ether and ethyl acetate are as eluent), obtain target product.Substrate and reaction result used is shown in Table 2。
Reaction substrate used in 2 embodiment 14~29 of table and result
Embodiment 30~41
By 2-ketoacid (1.1mmol, R1=H), aryl acetylenic acid (1mmol, R2=H), AgOAc (5mol%) and (NH4)2S2O8 (2mmol) is scattered in DMSO (1mL) and H2The in the mixed solvent of O (1mL), then under air atmosphere, 50 DEG C are stirred 3 hours. After reaction, Et is used2O (5mL) is extracted three times, merges organic phase, is concentrated under reduced pressure.Obtained crude product carries out column chromatography (300 ~400 mesh silica gel, petroleum ether and ethyl acetate are as eluent), obtain target product.Substrate and reaction result used is shown in Table 3。
Reaction substrate used in 3 embodiment 30~41 of table and result
The characterize data of portion of product is 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) δ 8.37 (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) δ 8.16 (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) δ 8.32 (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) δ 8.44-7.94 (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) δ 8.17 (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) δ 8.32 (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) δ 8.23 (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) δ 8.34-8.17 (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) δ 8.04 (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)δ 176.6,164.0,161.5,139.0,138.9,133.2,131.1,130.4,130.3,128.8,125.5,125.4, 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) δ 8.16 (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) δ 9.03 (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) δ 8.06 (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) δ 8.08 (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)δ 176.7,159.7,134.9,132.9,132.6,130.4,128.5,126.6,120.6,120.2,112.1,91.5,89.1, 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) δ 8.15 (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) δ 9.24 (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) δ 8.93 (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) δ 8.23-8.11 (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) δ 8.27-8.18 (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) δ 8.14 (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) δ 8.27-8.18 (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) δ 8.10 (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) δ 8.22 (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) δ 8.18 (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) δ 8.21 (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) δ 8.08 (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) δ 8.25-7.94 (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) δ 8.09 (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) δ 8.18 (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) δ 8.37 (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) δ 8.16 (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) δ 8.32 (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) δ 8.44-7.94 (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) δ 8.17 (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) δ 8.32 (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) δ 8.23 (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) δ 8.34-8.17 (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) δ 8.04 (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)δ 176.6,164.0,161.5,139.0,138.9,133.2,131.1,130.4,130.3,128.8,125.5,125.4, 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) δ 8.16 (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) δ 9.03 (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) δ 8.06 (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) δ 8.08 (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)δ 176.7,159.7,134.9,132.9,132.6,130.4,128.5,126.6,120.6,120.2,112.1,91.5,89.1, 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) δ 8.15 (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) δ 9.24 (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) δ 8.93 (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) δ 8.23-8.11 (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) δ 8.27-8.18 (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) δ 8.14 (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) δ 8.27-8.18 (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) δ 8.10 (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) δ 8.22 (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) δ 8.18 (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) δ 8.21 (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) δ 8.08 (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) δ 8.25-7.94 (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) δ 8.09 (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) δ 8.18 (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 (9)

1. one kind 1, the preparation method of 3- diaryl propine ketone, which is characterized in that including：
Under the action of silver catalyst and oxidant, decarboxylation coupling reaction occurs in a solvent for 2-ketoacid and aryl acetylenic acid, reaction After by post-processing obtain the 1,3- diaryl propine ketone；
Shown in the structure of the 2-ketoacid such as formula (II)：
Shown in the structure such as formula (III) of the aryl acetylenic acid：
Shown in the structure such as formula (I) of the 1,3- diaryl propine ketone：
In formula (I)~(III), R1Selected from H, C1~C5Alkyl, C1~C5Alkoxy, phenyl, halogen, CF3, nitro or C1~C5 Alkoxy carbonyl group；
R2Selected from H, C1~C5Alkyl, halogen or dimethylamino.
2. the preparation method of 1,3- diaryl propine ketone according to claim 1, which is characterized in that the silver catalyst For AgOAc.
3. the preparation method of 1,3- diaryl propine ketone according to claim 1, which is characterized in that the oxidant is (NH4)2S2O8。
4. the preparation method of 1,3- diaryl propine ketone according to claim 1, which is characterized in that the solvent is DMSO and H2The mixed solvent of O, DMSO and H2The volume ratio of O is 1:0.5~1.5.
5. the preparation method of 1,3- diaryl propine ketone according to claim 1, which is characterized in that the arylalkyne Acid, 2-ketoacid, silver catalyst, oxidant molar ratio be 1：1.0~1.1：0.03~0.05：1.5~2.0.
6. the preparation method of 1,3- diaryl propine ketone according to claim 1, which is characterized in that reaction temperature be 30~ 50 DEG C, the reaction time is 3~5 hours.
7. the preparation method of 1,3- diaryl propine ketone according to claim 1, which is characterized in that the post-processing packet It includes：Ether is added to be extracted, then carries out column chromatography and obtains 1, the 3- diaryl propine ketone.
8. a kind of such as claim 1~7 any one of them 1, the preparation method of 3- diaryl propine ketone, which is characterized in that institute The 2-ketoacid stated is replaced with following compound：
9. a kind of such as claim 1~7 any one of them 1, the preparation method of 3- diaryl propine ketone, which is characterized in that institute The aryl acetylenic acid stated is replaced with following compound：
CN201810051853.6A 2018-01-19 2018-01-19 Preparation method of 1, 3-diaryl propine ketone Expired - Fee Related CN108276268B (en)

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Publication number Priority date Publication date Assignee Title
CN110683949A (en) * 2019-10-08 2020-01-14 安徽理工大学 Method for preparing 9, 10-phenanthrene dicarboxylic ester compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110683949A (en) * 2019-10-08 2020-01-14 安徽理工大学 Method for preparing 9, 10-phenanthrene dicarboxylic ester compound
CN110683949B (en) * 2019-10-08 2022-02-22 安徽理工大学 Method for preparing 9, 10-phenanthrene dicarboxylic ester compound

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