本发明属于有机合成领域，具体涉及一种1,3-二芳基丙炔酮的制备方法。
背景技术：
1,3-二芳基丙炔酮因其生物医学和材料的多功能特性以及在生物活性产物合成中的广泛应用而备受化学家关注。在天然产物合成中，1,3-二芳基丙炔酮可以作为前体构筑各类杂环结构单元，合成了呋喃、黄酮、苯二氮卓、吡咯、吡唑、嘧啶和喹诺酮等多种杂环衍生物，并用于具有不同药理学性质天然产物的合成。由于其独特的结构特征和生物活性，1,3-二芳基丙炔酮的合成策略成为了有机化学家的研究焦点，其合成的方法不断涌现。传统的1,3-二芳基丙炔酮的合成方法依赖于过渡金属催化的酰基卤化物与端炔或炔基有机金属试剂的偶联反应，然而酰基卤化物稳定性差，反应条件比较苛刻，限制了底物适用的范围，而且pd-cu双金属体系需要高催化量的昂贵钯盐和cui的助催化。另一种更简单的方法则是过渡金属催化的芳基卤化物(或类卤素)与末端炔烃的插羰sonogashira反应，然而，该方法的实现需要很高的温度，并且需要气态的一氧化碳(一氧化碳无嗅无味，毒性高，不容易处理)，这些都大大限制了该方法的应用，阻碍了1,3-二芳基丙炔酮合成反应的发展(r.e.whittaker,a.dermenci,g.dong,synthesis2016,48,161)。
过去几年中，过渡金属催化的脱羧性偶联反应是构建各种碳—碳键和碳—杂原子键的有力方法。(j.d.weaver,a.recio,a.j.grenning,j.a.tunge,chem.rev.2011,111,1846)羧酸作为一种廉价、低毒和易得的原料，成为理想的复杂分子的合成试剂。(n.rodríguez,l.j.gooβen,chem.soc.rev.2011,40,5030)羧酸及其衍生物作为自由基前体参与的自由基机理的脱羧性炔基化反应最近得到了广泛的发展，自2015起通过脱羧性c-csp偶联反应来构建芳基、烷基和甲硅烷基取代的炔烃已成为现实。相比于亲核或者亲电反应的脱羧炔基化反应、自由基脱羧烷基化反应受到的关注较少。由于其极好的官能团相容性和温和的反应条件，发展更方便有效的c-csp键结构的新颖的自由基反应策略是十分必要的。自由基类型的脱羧炔基化反应的主要难点是碳碳三键的保持，其作为自由基受体很容易发生自由基加成反应，而目前的解决方法主要依赖于高价碘(iii)炔(1-(2-炔基)-1,2-苯并碘噁-3(1h)-酮)作为炔基化试剂来解决,烯基自由基中间体原位消除生成的苯唑啉酮自由基，从而释放炔烃产物。(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-hduan,org.lett.2015,17,3054；(h)h.tan,h.li,w.ji,l.wang.angew.chem.int.ed.2015,54,8374.
自由基类型的脱羧炔基化反应的另一个难点在于脱羧反应直接生成自由基的难度，可以通过与邻苯二甲酰亚胺保护的羧酸(n-(甲酰氧基)邻苯二甲酰亚胺)的反应，实现脱羧过程来解决。(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.与n-(酰氧基)邻苯二甲酰亚胺和高价碘(iii)炔试剂相比，自由羧酸更价廉易得，因此发展自由羧酸的直接脱羧偶联反应是非常必要的。
近几年，芳基甲酰甲酸开始作为一种新的酰基化试剂应用于有机合成中。与其他酰基化试剂相比，其可以通过银催化的氧化性脱羧过程以酰基自由基的形式参与反应，具有反应活性高、反应条件温和的特点，大大拓展了自由基酰基化反应的应用范围。而且它的操作和处理相对简便，且脱羧过程的副产物只有二氧化碳，易于离去。而炔基羧酸通过脱羧过程作为炔烃来源，同样具有稳定性好，易于储存和处理等优点，然而银催化的炔基羧酸的脱羧反应仍然具有很大的挑战性。
技术实现要素：
本发明提供了一种1,3-二芳基丙炔酮的制备方法，该制备方法试剂价廉易得，反应条件温和，并且产物收率高。
一种1,3-二芳基丙炔酮的制备方法，包括：
在银催化剂和氧化剂的作用下，α-酮酸和芳基炔酸在溶剂中发生脱羧偶联反应，反应结束后经过后处理得到所述的1,3-二芳基丙炔酮；
所述α-酮酸的结构如式(ii)所示：
所述的芳基炔酸的结构如式(iii)所示：
所述的1,3-二芳基丙炔酮的结构如式(i)所示：
式(i)～(iii)中，r1选自r1选自h、c1～c5烷基、c1～c5烷氧基、苯基、卤素、cf3、硝基或者c1～c5烷氧羰基，优选为h、甲基、甲氧基、苯基、f、cl、cf3、硝基或者甲氧羰基；
r2选自h、c1～c5烷基、卤素或二甲氨基；优选为h、甲基、乙基、叔丁基、f、cl、br或二甲氨基。
其中，r1和r2可以代表多个取代基。
本发明通过在炔烃上引入一个活化羧酸基团，以芳基甲酰甲酸钾为酰基化试剂，使用催化量的银盐和廉价的无机氧化剂，发展了芳基甲酰甲酸化学选择性自由基的脱羧炔基化反应，提供了1,3-二芳基丙炔酮的新合成方法。
作为优选，所述的银催化剂为agoac。
作为优选，所述的氧化剂为(nh4)2s2o8。
作为优选，所述的溶剂为dmso和h2o的混合溶剂，dmso和h2o的体积比为1:0.5～1.5。
作为优选，所述的芳基炔酸、α-酮酸、银催化剂、氧化剂的摩尔比为1：1.0～1.1：0.03～0.05：1.5～2.0。
作为优选，反应温度为30～50℃，反应时间为3～5小时。
作为优选，所述的后处理包括：加入乙醚进行萃取，然后进行柱层析得到所述1,3-二芳基丙炔酮。
本发明还提供了另一种所述的1,3-二芳基丙炔酮的制备方法，所述的α-酮酸的用以下化合物进行替换：
本发明还提供了另一种所述的1,3-二芳基丙炔酮的制备方法，所述的芳基炔酸用以下化合物进行替换：
同现有技术相比，本发明的有益效果体现在：
本发明的方法试剂价廉易得，反应条件温和，反应官能团兼容性好，催化剂价廉易得，催化体系简单。
具体实施方式
下面结合具体实施例对本发明做进一步的描述。
实施例1～14
将α-酮酸(1.1mmol，r1＝h)、芳基炔酸(1mmol，r2＝h)、银催化剂(5mol％)和氧化剂(2mmol)分散于溶剂中，然后于空气氛围下，50℃搅拌3小时。反应结束后，用et2o(5ml)萃取三次，合并有机相，减压浓缩。得到的粗产物进行柱层析(300～400目硅胶，石油醚和乙酸乙酯作为淋洗剂)，得到目标产物。所用的银催化剂、氧化剂和溶剂以及反应结果见表1。
表1实施例1～10的反应条件和反应结果
a溶剂的总体积保持在2ml。
实施例14～29
将α-酮酸(1.1mmol)、芳基炔酸(1mmol，r2＝h)、agoac(5mol％)和(nh4)2s2o8(2mmol)分散于dmso(1ml)和h2o(1ml)的混合溶剂中，然后于空气氛围下，50℃搅拌3小时。反应结束后，用et2o(5ml)萃取三次，合并有机相，减压浓缩。得到的粗产物进行柱层析(300～400目硅胶，石油醚和乙酸乙酯作为淋洗剂)，得到目标产物。所用的底物及反应结果见表2。
表2实施例14～29所用的反应底物及结果
实施例30～41
将α-酮酸(1.1mmol，r1＝h)、芳基炔酸(1mmol，r2＝h)、agoac(5mol％)和(nh4)2s2o8(2mmol)分散于dmso(1ml)和h2o(1ml)的混合溶剂中，然后于空气氛围下，50℃搅拌3小时。反应结束后，用et2o(5ml)萃取三次，合并有机相，减压浓缩。得到的粗产物进行柱层析(300～400目硅胶，石油醚和乙酸乙酯作为淋洗剂)，得到目标产物。所用的底物及反应结果见表3。
表3实施例30～41所用的反应底物及结果
部分产物的表征数据如下：
1,3-diphenylprop-2-yn-1-one:whitesolid.1hnmr(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).13cnmr(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)calcdforc15h11o[m+h]+,207.0804；found,207.0812.
1-(4-methoxyphenyl)-3-phenylprop-2-yn-1-one(2a):whitesolid.1hnmr(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).13cnmr(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)calcdforc16h13o2[m+h]+,237.0910；found,237.0915.
3-phenyl-1-(p-tolyl)prop-2-yn-1-one(2b):whitesolid.1hnmr(400mhz,cdcl3)δ8.16(d,j＝7.6hz,2h),7.72(d,j＝7.6hz,2h),7.47(dq,j＝14.8,7.2hz,3h),7.33(d,j＝7.8hz,2h),2.47(s,3h).13cnmr(100mhz,cdcl3)δ177.8,145.3,134.6,133.1,129.8,129.3,120.2,92.7,87.0,21.9.hrms(ei)calcdforc16h13o[m+h]+,221.0961；found,221.0954.
1-([1,1'-biphenyl]-4-yl)-3-phenylprop-2-yn-1-one(2c):whitesolid.1hnmr(400mhz,cdcl3)δ8.32(d,j＝8.4hz,2h),7.81–7.69(m,4h),7.67–7.61(m,2h),7.58–7.42(m,6h).13cnmr(100mhz,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)calcdforc21h15o[m+h]+,283.1117；found,283.1124.
1-(4-fluorophenyl)-3-phenylprop-2-yn-1-one(2d):whitesolid.1hnmr(400mhz,cdcl3)δ8.44–7.94(m,2h),7.57(d,j＝7.2hz,2h),7.43–7.35(m,1h),7.32(t,j＝7.2hz,2h),7.08(t,j＝8.4hz,2h).13cnmr(100mhz,cdcl3)δ175.2,166.6,164.1,132.3,132.0,131.1(d,j＝9.6hz),129.9,127.7,118.8,114.8(d,j＝22.4hz),92.3,85.5.hrms(ei)calcdforc15h10fo[m+h]+,225.0710；found,225.0702.
1-(4-chlorophenyl)-3-phenylprop-2-yn-1-one(2e):whitesolid.1hnmr(400mhz,cdcl3)δ8.17(d,j＝8.4hz,2h),7.68(d,j＝7.6hz,2h),7.50(d,j＝8.0hz,3h),7.43(t,j＝7.6hz,2h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0408.
3-phenyl-1-(4-(trifluoromethyl)phenyl)prop-2-yn-1-one(2f):whitesolid.1hnmr(400mhz,cdcl3)δ8.32(d,j＝7.6hz,2h),7.78(d,j＝7.6hz,2h),7.70(d,j＝7.6hz,2h),7.46(dt,j＝14.8,8.0hz,3h).13cnmr(100mhz,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)calcdforc16h10f3o[m+h]+,275.0678；found,275.0682.
4-(3-phenylpropioloyl)benzonitrile(2g):whitesolid.1hnmr(400mhz,cdcl3)δ8.23(d,j＝8.4hz,2h),7.75(d,j＝8.4hz,2h),7.64–7.57(m,2h),7.45(dd,j＝10.8,4.4hz,1h),7.37(t,j＝7.6hz,2h).13cnmr(100mhz,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)calcdforc16h10no[m+h]+,232.0757；found,232.0749.
methyl4-(3-phenylpropioloyl)benzoate(2h):whitesolid.1hnmr(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).13cnmr(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)calcdforc17h13o3[m+h]+,265.0859；found,265.0848.
1-(3-fluorophenyl)-3-phenylprop-2-yn-1-one(2i):whitesolid.1hnmr(400mhz,cdcl3)δ8.04(dt,j＝7.6,1.2hz,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).13cnmr(100mhz,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)calcdforc15h10fo[m+h]+,225.0710；found,225.0715.
1-(3-chlorophenyl)-3-phenylprop-2-yn-1-one(2j):whitesolid.1hnmr(400mhz,cdcl3)δ8.16(d,j＝1.6hz,1h),8.10(d,j＝7.6hz,1h),7.72–7.64(m,2h),7.59(dd,j＝8.0,0.8hz,1h),7.45(dq,j＝12.0,7.2hz,4h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0411.
1-(3-nitrophenyl)-3-phenylprop-2-yn-1-one(2k):yellowsolid.1hnmr(400mhz,cdcl3)δ9.03(t,j＝2.0hz,1h),8.54–8.46(m,2h),7.80–7.72(m,3h),7.56–7.44(m,3h).13cnmr(100mhz,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)calcdforc15h10no3[m+h]+,252.0655；found,252.0647.
1-(2-chlorophenyl)-3-phenylprop-2-yn-1-one(2l):whitesolid.1hnmr(400mhz,cdcl3)δ8.06(d,j＝7.6hz,1h),7.63(d,j＝7.6hz,2h),7.49–7.42(m,3h),7.39(t,j＝6.8hz,3h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0411.
1-(2-methoxyphenyl)-3-phenylprop-2-yn-1-one(2m):whitesolid.1hnmr(400mhz,cdcl3)δ8.08(dd,j＝7.6,2.0hz,1h),7.63(dt,j＝7.2,1.6hz,2h),7.52(t,j＝8.0hz,1h),7.46–7.34(m,3h),7.10–6.96(m,2h),3.94(s,3h).13cnmr(100mhz,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)calcdforc16h13o2[m+h]+,237.0910；found,237.0904.
1-(3,5-difluorophenyl)-3-phenylprop-2-yn-1-one(2n):whitesolid.1hnmr(400mhz,cdcl3)δ8.15(dd,j＝15.2,8.4hz,1h),7.64(d,j＝7.2hz,2h),7.53–7.44(m,1h),7.40(dd,j＝15.6,8.4hz,2h),7.00(t,j＝8.0hz,1h),6.95–6.86(m,1h).13cnmr(100mhz,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)calcdforc15h9f2o[m+h]+,243.0616；found,243.0625.
1-(naphthalen-1-yl)-3-phenylprop-2-yn-1-one(2o):whitesolid.1hnmr(400mhz,cdcl3)δ9.24(d,j＝8.4hz,1h),8.63(d,j＝8.0hz,1h),8.05(d,j＝8.0hz,1h),7.88(d,j＝8.4hz,1h),7.66(t,j＝7.6hz,4h),7.55(q,j＝7.2hz,3h),7.43(ddd,j＝14.8,8.0,6.4hz,2h).13cnmr(100mhz,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)calcdforc19h13o[m+h]+,257.0961；found,257.0955.
3-phenyl-1-(quinolin-6-yl)prop-2-yn-1-one(2p):whitesolid.1hnmr(400mhz,cdcl3)δ8.93(dd,j＝4.0,1.6hz,1h),8.62(d,j＝1.6hz,1h),8.35(dd,j＝8.8,2.0hz,1h),8.22(d,j＝8.4hz,1h),8.08(d,j＝8.8hz,1h),7.66–7.60(m,2h),7.40(dd,j＝7.6,3.6hz,2h),7.34(t,j＝7.2hz,2h).13cnmr(100mhz,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)calcdforc18h12no[m+h]+,258.0913；found,258.0917.
3-(4-methoxyphenyl)-1-phenylprop-2-yn-1-one(3a):whitesolid.1hnmr(400mhz,cdcl3)δ8.23–8.11(m,2h),7.62–7.51(m,3h),7.46(t,j＝7.6hz,2h),6.86(d,j＝8.8hz,2h),3.78(s,3h).13cnmr(100mhz,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)calcdforc16h13o2[m+h]+,237.0910；found,237.0912.
1-(4-methylphenyl)-1-phenylprop-2-yn-1-one(3b):whitesolid.1hnmr(400mhz,cdcl3)δ8.27–8.18(m,2h),7.67–7.56(m,3h),7.51(t,j＝7.6hz,2h),7.24(d,j＝8.0hz,2h),2.41(s,3h).13cnmr(100mhz,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)calcdforc16h13o[m+h]+,221.0961；found,221.0965.
1-(4-ethylphenyl)-1-phenylprop-2-yn-1-one(3c):whitesolid.1hnmr(400mhz,cdcl3)δ8.14(d,j＝8.0hz,2h),7.71(s,2h),7.54–7.26(m,5h),2.75(s,2h),1.28(d,j＝7.2hz,3h).13cnmr(100mhz,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)calcdforc17h15o[m+h]+,235.1117；found,235.1122.
3-(4-(tert-butyl)phenyl)-1-phenylprop-2-yn-1-one(3d):whitesolid.1hnmr(400mhz,cdcl3)δ8.27–8.18(m,2h),7.64–7.57(m,3h),7.49(dd,j＝10.4,4.8hz,2h),7.45–7.38(m,2h),1.32(s,9h).13cnmr(100mhz,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)calcdforc19h19o[m+h]+,235.1117；found,235.1122.
3-(4-fluorophenyl)-1-phenylprop-2-yn-1-one(3e):whitesolid.1hnmr(400mhz,cdcl3)δ8.10(d,j＝7.6hz,2h),7.62–7.55(m,2h),7.52(t,j＝7.6hz,1h),7.42(t,j＝7.6hz,2h),7.00(t,j＝8.4hz,2h).13cnmr(100mhz,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)calcdforc15h10fo[m+h]+,225.0710；found,225.0704.
3-(4-chlorophenyl)-1-phenylprop-2-yn-1-one(3f):whitesolid.1hnmr(400mhz,cdcl3)δ8.22(d,j＝8.0hz,2h),7.61(t,j＝7.2hz,3h),7.53(t,j＝7.6hz,2h),7.41(d,j＝8.0hz,2h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0418.
3-(4-bromophenyl)-1-phenylprop-2-yn-1-one(3g):whitesolid.1hnmr(400mhz,cdcl3)δ8.18(d,j＝7.6hz,2h),7.61(t,j＝7.2hz,1h),7.56–7.47(m,6h).13cnmr(100mhz,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)calcdforc15h10bro[m+h]+,284.9910；found,284.9896.
3-(4-(dimethylamino)phenyl)-1-phenylprop-2-yn-1-one(3h):whitesolid.1hnmr(400mhz,cdcl3)δ8.21(d,j＝7.6hz,2h),7.62–7.40(m,5h),6.63(d,j＝8.8hz,2h),3.02(s,6h).13cnmr(100mhz,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)calcdforc17h16no[m+h]+,250.1226；found,250.1219.
1-phenyl-3-(m-tolyl)prop-2-yn-1-one(3i):whitesolid.1hnmr(400mhz,cdcl3)δ8.08(d,j＝7.2hz,2h),7.44(t,j＝7.2hz,1h),7.32(dd,j＝15.6,8.0hz,4h),7.11(t,j＝7.2hz,2h),2.17(s,3h).13cnmr(100mhz,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)calcdforc16h13o[m+h]+,221.0961；found,221.0957.
1-phenyl-3-(o-tolyl)prop-2-yn-1-one(3j):whitesolid.1hnmr(400mhz,cdcl3)δ8.25–7.94(m,2h),7.55–7.42(m,2h),7.35(t,j＝7.6hz,2h),7.22(td,j＝7.6,1.2hz,1h),7.14–7.04(m,2h),2.43(s,3h).13cnmr(100mhz,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)calcdforc16h13o[m+h]+,221.0961；found,221.0969.
3-(cyclohex-1-en-1-yl)-1-phenylprop-2-yn-1-one(3k):whitesolid.1hnmr(400mhz,cdcl3)δ8.09(dd,j＝8.4,1.2hz,2h),7.55–7.51(m,1h),7.41(t,j＝7.6hz,2h),6.50(s,1h),2.25–2.18(m,2h),2.15–2.10(m,2h),1.66–1.53(m,4h).13cnmr(100mhz,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)calcdforc15h15o[m+h]+,211.1117；found,211.1125.
1-phenyl-3-(thiophen-2-yl)prop-2-yn-1-one(3l):paleyellowsolid.1hnmr(400mhz,cdcl3)δ8.18(d,j＝8.4hz,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).13cnmr(100mhz,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)calcdforc13h9os[m+h]+,213.0369；found,213.0361.
1,3-diphenylprop-2-yn-1-one:whitesolid.1hnmr(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).13cnmr(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)calcdforc15h11o[m+h]+,207.0804；found,207.0812.
1-(4-methoxyphenyl)-3-phenylprop-2-yn-1-one(2a):whitesolid.1hnmr(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).13cnmr(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)calcdforc16h13o2[m+h]+,237.0910；found,237.0915.
3-phenyl-1-(p-tolyl)prop-2-yn-1-one(2b):whitesolid.1hnmr(400mhz,cdcl3)δ8.16(d,j＝7.6hz,2h),7.72(d,j＝7.6hz,2h),7.47(dq,j＝14.8,7.2hz,3h),7.33(d,j＝7.8hz,2h),2.47(s,3h).13cnmr(100mhz,cdcl3)δ177.8,145.3,134.6,133.1,129.8,129.3,120.2,92.7,87.0,21.9.hrms(ei)calcdforc16h13o[m+h]+,221.0961；found,221.0954.
1-([1,1'-biphenyl]-4-yl)-3-phenylprop-2-yn-1-one(2c):whitesolid.1hnmr(400mhz,cdcl3)δ8.32(d,j＝8.4hz,2h),7.81–7.69(m,4h),7.67–7.61(m,2h),7.58–7.42(m,6h).13cnmr(100mhz,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)calcdforc21h15o[m+h]+,283.1117；found,283.1124.
1-(4-fluorophenyl)-3-phenylprop-2-yn-1-one(2d):whitesolid.1hnmr(400mhz,cdcl3)δ8.44–7.94(m,2h),7.57(d,j＝7.2hz,2h),7.43–7.35(m,1h),7.32(t,j＝7.2hz,2h),7.08(t,j＝8.4hz,2h).13cnmr(100mhz,cdcl3)δ175.2,166.6,164.1,132.3,132.0,131.1(d,j＝9.6hz),129.9,127.7,118.8,114.8(d,j＝22.4hz),92.3,85.5.hrms(ei)calcdforc15h10fo[m+h]+,225.0710；found,225.0702.
1-(4-chlorophenyl)-3-phenylprop-2-yn-1-one(2e):whitesolid.1hnmr(400mhz,cdcl3)δ8.17(d,j＝8.4hz,2h),7.68(d,j＝7.6hz,2h),7.50(d,j＝8.0hz,3h),7.43(t,j＝7.6hz,2h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0408.
3-phenyl-1-(4-(trifluoromethyl)phenyl)prop-2-yn-1-one(2f):whitesolid.1hnmr(400mhz,cdcl3)δ8.32(d,j＝7.6hz,2h),7.78(d,j＝7.6hz,2h),7.70(d,j＝7.6hz,2h),7.46(dt,j＝14.8,8.0hz,3h).13cnmr(100mhz,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)calcdforc16h10f3o[m+h]+,275.0678；found,275.0682.
4-(3-phenylpropioloyl)benzonitrile(2g):whitesolid.1hnmr(400mhz,cdcl3)δ8.23(d,j＝8.4hz,2h),7.75(d,j＝8.4hz,2h),7.64–7.57(m,2h),7.45(dd,j＝10.8,4.4hz,1h),7.37(t,j＝7.6hz,2h).13cnmr(100mhz,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)calcdforc16h10no[m+h]+,232.0757；found,232.0749.
methyl4-(3-phenylpropioloyl)benzoate(2h):whitesolid.1hnmr(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).13cnmr(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)calcdforc17h13o3[m+h]+,265.0859；found,265.0848.
1-(3-fluorophenyl)-3-phenylprop-2-yn-1-one(2i):whitesolid.1hnmr(400mhz,cdcl3)δ8.04(dt,j＝7.6,1.2hz,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).13cnmr(100mhz,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)calcdforc15h10fo[m+h]+,225.0710；found,225.0715.
1-(3-chlorophenyl)-3-phenylprop-2-yn-1-one(2j):whitesolid.1hnmr(400mhz,cdcl3)δ8.16(d,j＝1.6hz,1h),8.10(d,j＝7.6hz,1h),7.72–7.64(m,2h),7.59(dd,j＝8.0,0.8hz,1h),7.45(dq,j＝12.0,7.2hz,4h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0411.
1-(3-nitrophenyl)-3-phenylprop-2-yn-1-one(2k):yellowsolid.1hnmr(400mhz,cdcl3)δ9.03(t,j＝2.0hz,1h),8.54–8.46(m,2h),7.80–7.72(m,3h),7.56–7.44(m,3h).13cnmr(100mhz,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)calcdforc15h10no3[m+h]+,252.0655；found,252.0647.
1-(2-chlorophenyl)-3-phenylprop-2-yn-1-one(2l):whitesolid.1hnmr(400mhz,cdcl3)δ8.06(d,j＝7.6hz,1h),7.63(d,j＝7.6hz,2h),7.49–7.42(m,3h),7.39(t,j＝6.8hz,3h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0411.
1-(2-methoxyphenyl)-3-phenylprop-2-yn-1-one(2m):whitesolid.1hnmr(400mhz,cdcl3)δ8.08(dd,j＝7.6,2.0hz,1h),7.63(dt,j＝7.2,1.6hz,2h),7.52(t,j＝8.0hz,1h),7.46–7.34(m,3h),7.10–6.96(m,2h),3.94(s,3h).13cnmr(100mhz,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)calcdforc16h13o2[m+h]+,237.0910；found,237.0904.
1-(3,5-difluorophenyl)-3-phenylprop-2-yn-1-one(2n):whitesolid.1hnmr(400mhz,cdcl3)δ8.15(dd,j＝15.2,8.4hz,1h),7.64(d,j＝7.2hz,2h),7.53–7.44(m,1h),7.40(dd,j＝15.6,8.4hz,2h),7.00(t,j＝8.0hz,1h),6.95–6.86(m,1h).13cnmr(100mhz,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)calcdforc15h9f2o[m+h]+,243.0616；found,243.0625.
1-(naphthalen-1-yl)-3-phenylprop-2-yn-1-one(2o):whitesolid.1hnmr(400mhz,cdcl3)δ9.24(d,j＝8.4hz,1h),8.63(d,j＝8.0hz,1h),8.05(d,j＝8.0hz,1h),7.88(d,j＝8.4hz,1h),7.66(t,j＝7.6hz,4h),7.55(q,j＝7.2hz,3h),7.43(ddd,j＝14.8,8.0,6.4hz,2h).13cnmr(100mhz,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)calcdforc19h13o[m+h]+,257.0961；found,257.0955.
3-phenyl-1-(quinolin-6-yl)prop-2-yn-1-one(2p):whitesolid.1hnmr(400mhz,cdcl3)δ8.93(dd,j＝4.0,1.6hz,1h),8.62(d,j＝1.6hz,1h),8.35(dd,j＝8.8,2.0hz,1h),8.22(d,j＝8.4hz,1h),8.08(d,j＝8.8hz,1h),7.66–7.60(m,2h),7.40(dd,j＝7.6,3.6hz,2h),7.34(t,j＝7.2hz,2h).13cnmr(100mhz,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)calcdforc18h12no[m+h]+,258.0913；found,258.0917.
3-(4-methoxyphenyl)-1-phenylprop-2-yn-1-one(3a):whitesolid.1hnmr(400mhz,cdcl3)δ8.23–8.11(m,2h),7.62–7.51(m,3h),7.46(t,j＝7.6hz,2h),6.86(d,j＝8.8hz,2h),3.78(s,3h).13cnmr(100mhz,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)calcdforc16h13o2[m+h]+,237.0910；found,237.0912.
1-(4-methylphenyl)-1-phenylprop-2-yn-1-one(3b):whitesolid.1hnmr(400mhz,cdcl3)δ8.27–8.18(m,2h),7.67–7.56(m,3h),7.51(t,j＝7.6hz,2h),7.24(d,j＝8.0hz,2h),2.41(s,3h).13cnmr(100mhz,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)calcdforc16h13o[m+h]+,221.0961；found,221.0965.
1-(4-ethylphenyl)-1-phenylprop-2-yn-1-one(3c):whitesolid.1hnmr(400mhz,cdcl3)δ8.14(d,j＝8.0hz,2h),7.71(s,2h),7.54–7.26(m,5h),2.75(s,2h),1.28(d,j＝7.2hz,3h).13cnmr(100mhz,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)calcdforc17h15o[m+h]+,235.1117；found,235.1122.
3-(4-(tert-butyl)phenyl)-1-phenylprop-2-yn-1-one(3d):whitesolid.1hnmr(400mhz,cdcl3)δ8.27–8.18(m,2h),7.64–7.57(m,3h),7.49(dd,j＝10.4,4.8hz,2h),7.45–7.38(m,2h),1.32(s,9h).13cnmr(100mhz,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)calcdforc19h19o[m+h]+,235.1117；found,235.1122.
3-(4-fluorophenyl)-1-phenylprop-2-yn-1-one(3e):whitesolid.1hnmr(400mhz,cdcl3)δ8.10(d,j＝7.6hz,2h),7.62–7.55(m,2h),7.52(t,j＝7.6hz,1h),7.42(t,j＝7.6hz,2h),7.00(t,j＝8.4hz,2h).13cnmr(100mhz,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)calcdforc15h10fo[m+h]+,225.0710；found,225.0704.
3-(4-chlorophenyl)-1-phenylprop-2-yn-1-one(3f):whitesolid.1hnmr(400mhz,cdcl3)δ8.22(d,j＝8.0hz,2h),7.61(t,j＝7.2hz,3h),7.53(t,j＝7.6hz,2h),7.41(d,j＝8.0hz,2h).13cnmr(100mhz,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)calcdforc15h10clo[m+h]+,241.0415；found,241.0418.
3-(4-bromophenyl)-1-phenylprop-2-yn-1-one(3g):whitesolid.1hnmr(400mhz,cdcl3)δ8.18(d,j＝7.6hz,2h),7.61(t,j＝7.2hz,1h),7.56–7.47(m,6h).13cnmr(100mhz,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)calcdforc15h10bro[m+h]+,284.9910；found,284.9896.
3-(4-(dimethylamino)phenyl)-1-phenylprop-2-yn-1-one(3h):whitesolid.1hnmr(400mhz,cdcl3)δ8.21(d,j＝7.6hz,2h),7.62–7.40(m,5h),6.63(d,j＝8.8hz,2h),3.02(s,6h).13cnmr(100mhz,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)calcdforc17h16no[m+h]+,250.1226；found,250.1219.
1-phenyl-3-(m-tolyl)prop-2-yn-1-one(3i):whitesolid.1hnmr(400mhz,cdcl3)δ8.08(d,j＝7.2hz,2h),7.44(t,j＝7.2hz,1h),7.32(dd,j＝15.6,8.0hz,4h),7.11(t,j＝7.2hz,2h),2.17(s,3h).13cnmr(100mhz,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)calcdforc16h13o[m+h]+,221.0961；found,221.0957.
1-phenyl-3-(o-tolyl)prop-2-yn-1-one(3j):whitesolid.1hnmr(400mhz,cdcl3)δ8.25–7.94(m,2h),7.55–7.42(m,2h),7.35(t,j＝7.6hz,2h),7.22(td,j＝7.6,1.2hz,1h),7.14–7.04(m,2h),2.43(s,3h).13cnmr(100mhz,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)calcdforc16h13o[m+h]+,221.0961；found,221.0969.
3-(cyclohex-1-en-1-yl)-1-phenylprop-2-yn-1-one(3k):whitesolid.1hnmr(400mhz,cdcl3)δ8.09(dd,j＝8.4,1.2hz,2h),7.55–7.51(m,1h),7.41(t,j＝7.6hz,2h),6.50(s,1h),2.25–2.18(m,2h),2.15–2.10(m,2h),1.66–1.53(m,4h).13cnmr(100mhz,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)calcdforc15h15o[m+h]+,211.1117；found,211.1125.
1-phenyl-3-(thiophen-2-yl)prop-2-yn-1-one(3l):paleyellowsolid.1hnmr(400mhz,cdcl3)δ8.18(d,j＝8.4hz,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).13cnmr(100mhz,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)calcdforc13h9os[m+h]+,213.0369；found,213.0361。