CN106478325B - 一种合成α-烷基酮的方法 - Google Patents
一种合成α-烷基酮的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title description 6
- 230000015572 biosynthetic process Effects 0.000 title description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims abstract description 95
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- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 10
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- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 3
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- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 31
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种合成α‑烷基酮的方法,具体包括如下步骤：在反应容器中，加入仲醇，过渡金属催化剂，溶剂叔戊醇；反应混合物在油浴中加热回流，反应数小时后，冷却到室温；再加入伯醇，碱，反应混合物在油浴中加热回流，反应数小时后，然后通过柱分离，得到目标化合物。本发明从伯醇和仲醇出发，在过渡金属催化剂的参与下,经串联的仲醇的无受体脱氢氧化反应/酮的α‑烷基化反应生成α‑烷基酮，反应展现出三个显著的优点：1)使用近于无毒的醇为起始原料；2)反应只生成氢气和水为副产物，无环境危害；3)反应原子经济性高；4)反应只需要0.1当量的碳酸盐参与，反应只需要3‑6个小时。所以，该反应符合绿色化学的要求，具有广阔的发展前景。
Description
技术领域
本发明属有机合成化学技术领域，具体涉及一种合成α-烷基酮的方法。
背景技术
α-烷基酮是一类重要的化合物，不仅是重要的中间体，而且还有广泛的生理和药理活性。例如，这类化合物被使用作为脂肪酸酰胺水解酶的可逆酮杂环抑制剂(OL-135)、甲状腺受体共激活剂绑定抑制剂、口服生物可利用二氮杂萘酮缓激肽B1受体拮抗剂和5-HT7受体配体等等。(a)D.L.Boger,H.Miyauchi,W.Du,C.Hardouin,R.A.Fecik,H.Cheng,I.Hwang,M.P.Hedrick,D.Leung,O.Acevedo,C.R.W.W.L.Jorgensen,B.F.Cravatt,J.Med.Chem.2005,48,1849-1856；(b)J.Y.Hwang,L.A.Arnold,F.Zhu,A.Kosinski,T.J.Mangano,V.Setola,B.L.Roth,R.K.Guy,J.Med.Chem.2009,52,3892-3901；(c)K.Biswas,T.A.N.Peterkin,M.C.Bryan,L.Arik,S.G.Lehto,H.Sun,F.Hsieh,C.Xu,R.T.Fremeau,J.R.Allen,J.Med.Chem.2011,54,7232-7246；(d)R.Perrone,F.Berardi,N.A.Colabufo,E.Lacivita,M.Leopoldo,V.Tortorella,J.Med.Chem.2003,46,646-649；(e)C.Baskakis,V.Magrioti,N.Cotton,D.Stephens,V.Constantinou-Kokotou,E.A.Dennis,G.Kokotos,J.Med.Chem.2008,51,8027-8037；(f)S.R.Chhabra,C.Harty,D.S.W.Hooi,M.Daykin,P.Williams,G.Telford,D.I.Pritchard,B.W.Bycroft,J.Med.Chem.2003,46,97-104.)
近几年来，用醇替代卤代烃作为环境友好的烷基化试剂受到了许多关注，这种方法是以氢转移(或者借氢)过程为基础的，用钌、铱、钯以及其它过渡金属络合物作为催化剂(a)G.Guillena,D.J.Ramon,M.Yus,Angew.Chem.Int.Ed.2007,46,2358-2364；d)G.E.Dobereiner,R.H.Grabtree,Chem.Rev.2010,110,681-703)
最近，使用环境友好的仲醇和伯醇作为起始原料来合成α-烷基酮也获得发展，反应需要均相的或非均相的催化剂才实现。((g)K.Shimizu,R.Sato,A.Satsuma,Angew.Chem.2009,121,4042–4046；(h)K.Shimizu,R.Sato,A.SatsumaAngew.Chem.Int.Ed.2009,48,3982–3986；(i)S.Musa,L.Ackermann,D.Gelmana,Adv.Synth.Catal.2013,355,3077-3080.)
但是，使用这些催化剂，反应需要长的反应时间(48h)或者当量碱的参与。而且，由于氢自动转移，反应也不可避免的生成仲醇的β-烷基化产物。
因此，从有机合成的角度，发展一类新的有机金属催化剂，通过使用环境友好的仲醇和伯醇作为原料，能够在更环境友好和温和的状态下来催化这类反应有重要的意义。
发明内容
本发明的目的在于提供一种合成α-烷基酮的新方法。
本发明通过下述技术方案实现：合成α-烷基酮(式Ⅰ)
其包含仲醇(式Ⅱ)
经脱氢成(式IV)
与伯醇(式III)反应
反应是在过渡金属催化剂和碱的存在下发生，其反应通式为
其中，R1选自C1-C4烷基、甲基苯基、乙基苯基、甲氧基苯基、三氟甲基苯基、卤代
苯基、萘基、噻酚基。
R2选自C4-C7烷基、甲基苯基、甲氧基苯基、三氟甲基苯基、三氟甲氧基苯基、
卤代苯基、呋喃基、萘基。
本发明合成α-烷基酮是通过下述具体步骤实现：
步骤1、在反应容器中，加入仲醇，过渡金属催化剂，溶剂叔戊醇；反应混合物在油浴中加热回流，反应数小时后，冷却到室温；
步骤2、再加入伯醇，碱，反应混合物在油浴中加热回流，反应数小时后，然后通过柱分离，得到目标化合物。
步骤1中，所述的过渡金属催化剂为金属铱络合物[Cp*Ir(2,2’-bpyO)(H2O)]，结构如下：
过渡金属催化剂用量为仲醇的1mol％；所述的反应时间为3-6小时。
步骤2中，所述的碱为碳酸铯；所述的碱的摩尔量为仲醇摩尔量的0.1equiv.；所述的伯醇的摩尔量为仲醇摩尔量的1.1-2equiv.；所述的反应时间为3-6小时。
其反应机理如下式所示：
同现有技术相比，本发明从伯醇和仲醇出发，在过渡金属催化剂的参与下,经串联的仲醇的无受体脱氢氧化反应/酮的α-烷基化反应生成α-烷基酮，反应展现出三个显著的优点：1)使用近于无毒的醇为起始原料；2)反应只生成氢气和水为副产物，无环境危害；3)反应原子经济性高；4)反应只需要0.1当量的碳酸盐参与，反应只需要3-6个小时。所以，该反应符合绿色化学的要求，具有广阔的发展前景。
具体实施方式
展示一下实例来说明本发明的某些实施例，且不应解释为限制本发明的范围。对本发明公开的内容可以同时从材料，方法和反应条件上进行许多改进，变化和改变。所有这些改进，变化和改变均确定地落入本发明的精神和范围之内。
实施例1:1,3-二苯基-1-丙酮
1,3-diphenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开 剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：90％
1H NMR(500MHz,CDCl3)δ7.97(d,J＝7.2Hz,2H),7.56(t,J＝6.9Hz,1H),7.46(t,J＝6.9Hz,2H),7.32-7.26(m,4H),7.21(t,J＝7.2Hz,1H),3.31(t,J＝7.3Hz,2H),3.07(t,J＝7.3Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ199.2,141.2,136.8,133.0,128.6,128.5,128.4,128.0,126.1,40.4,30.1.
实施例2:3-(2-甲基苯基)-1-苯基-1-丙酮
1-phenyl-3-o-tolylpropan-1-one
将DL-1-苯乙醇(12 2mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和邻甲基苄醇(134mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：86％
1H NMR(500MHz,CDCl3)δ7.98-7.96(m,2H),7.56(t,J＝6.8Hz,1H),7.46(t,J＝7.7Hz,2H),7.20-7.14(m,4H),3.26(t,J＝7.9Hz,2H),3.06(t,J＝7.9Hz,2H),2.35(s,3H)；13C{1H}NMR(125MHz,CDCl3)δ199.4,139.4,136.8,136.0,133.1,130.3,128.7,128.6,128.0,126.3,126.2,39.1,27.5,19.3.
实施例3:3-(3,4-二甲基苯基)-1-苯基-1-丙酮
3-(3,4-dimethylphenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和3,4-二甲基苄醇(150mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：85％
1H NMR(500MHz,CDCl3)δ7.97(d,J＝7.8Hz,2H),7.55(t,J＝7.2Hz,1H),7.45(t,J＝7.6 Hz,2H),7.08-6.99(m,3H),3.28(t,J＝7.8Hz,2H),3.00(t,J＝7.8Hz,2H),2.25(s,3H),2.23(s,3H)；13C{1H}NMR(125MHz,CDCl3)δ199.4,138.7,136.9,136.6,134.3,133.0,129.8,128.6,128.0,125.7,40.7,29.7,19.7,19.3.
实施例4:3-(4-甲氧基苯基)-1-苯基-1-丙酮
3-(4-methoxyphenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-甲氧基苄醇(152mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：89％
1H NMR(500MHz,CDCl3)δ7.96(d,J＝7.5Hz,2H),7.56(t,J＝7.3Hz,1H),7.45(t,J＝7.6Hz,2H),7.18(d,J＝8.5Hz,2H),6.85(d,J＝8.5Hz,2H),3.79(s,3H),3.27(t,J＝7.4Hz,2H),3.01(t,J＝7.4Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ199.3,158.0,136.9,133.3,133.0,129.3,128.6,128.0,113.9,55.2,40.7,29.3.
实施例5:3-(4-异丙基苯基)-1-苯基-1-丙酮
3-(4-isopropylphenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-异丙基苄醇(165mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：87％
1H NMR(500MHz,CDCl3)δ7.97(d,J＝7.6Hz,2H),7.55(t,J＝7.3Hz,1H),7.45(t,J＝7.6Hz,2H),7.20-7.16(m,4H),3.30(t,J＝7.8Hz,2H),3.04(t,J＝7.8Hz,2H),2.91-2.86(m, 1H),1.25(d,J＝6.9Hz,6H)；13C{1H}NMR(125MHz,CDCl3)δ199.4,146.7,138.5,136.9,133.0,128.6,128.3,128.0,126.5,40.5,33.7,29.7,24.0.
实施例6:3-(4-氟苯基)-1-苯基-1-丙酮
3-(4-fluorophenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-氟苄醇(139mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：85％
1H NMR(500MHz,CDCl3)δ7.96(d,J＝7.2Hz,2H),7.56(t,J＝7.4Hz,1H),7.46(t,J＝7.5Hz,2H),7.22-7.19(m,2H),6.98(t,J＝8.7Hz,2H),3.28(t,J＝7.5Hz,2H),3.05(t,J＝7.5Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ199.0,162.3,160.4,136.9,133.1,129.8(d,JC-F＝6.4Hz),128.6,128.0,115.3(d,JC-F＝19.9Hz),40.4,29.2.
实施例7:3-(4-氯苯基)-1-苯基-1-丙酮
3-(4-chlorophenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-氯苄醇(157mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：88％
1H NMR(500MHz,CDCl3)δ7.96(d,J＝7.2Hz,2H),7.56(t,J＝7.4Hz,1H),7.46(t,J＝7.7Hz,2H),7.26(d,J＝4.2Hz,2H),7.19(d,J＝8.4Hz,2H),3.28(t,J＝7.5Hz,2H),3.04(t,J＝ 7.5Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.8,139.7,136.7,133.1,131.8,129.8,128.6,128.6,127.8,40.1,29.3.
实施例8:3-(2,4-二氯苯基)-1-苯基-1-丙酮
3-(2,4-dichlorophenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和2,4-二氯苄醇(195mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：90％
1H NMR(500MHz,CDCl3)δ7.96(d,J＝7.1Hz,2H),7.56(t,J＝7.4Hz,1H),7.45(t,J＝7.7Hz,2H),7.37(d,J＝2.1Hz,1H),7.26(d,J＝8.2Hz,1H),7.18(dd,J＝8.2and 2.1Hz,1H),3.31(t,J＝7.6Hz,2H),3.15(t,J＝7.5Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.6,137.4,136.6,134.5,133.2,132.6,131.6,129.3,128.6,128.0,127.2,38.1,27.6.
实施例9:3-(4-溴苯基)-1-苯基-1-丙酮
3-(4-bromophenyl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-溴苄醇(206mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：89％
1H NMR(500MHz,CDCl3)δ7.96(d,J＝7.2Hz,2H),7.56(t,J＝7.4Hz,1H),7.46(t,J＝7.7Hz,2H),7.42(d,J＝8.3Hz,2H),7.14(d,J＝8.3Hz,2H),3.28(t,J＝7.5Hz,2H),3.03(t,J＝ 7.5Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.8,140.2,136.7,133.2,131.2,130.2,128.6,128.0,119.9,40.0,29.4.
实施例10:1-苯基-3-(4-三氟甲基苯基)-1-丙酮
1-phenyl-3-(4-(trifluoromethyl)phenyl)propan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-三氟甲基苄醇(194mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：83％
1H NMR(500MHz,CDCl3)δ7.96-7.94(m,2H),7.58-7.54(m,3H),7.46(t,J＝7.7Hz,2H),7.38(d,J＝8.0Hz,2H),3.32(t,J＝7.5Hz,2H),3.13(t,J＝7.5Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.5,145.5,136.7,133.2,128.8,128.7,128.2(q,JC-F＝31.6Hz),128.0,125.4(q,JC-F＝2.7Hz),123.2(q,JC-F＝270.9Hz),39.8,29.8.
实施例11:1-苯基-3-(4-三氟甲氧基苯基)-1-丙酮
1-phenyl-3-(4-(trifluoromethoxy)phenyl)propan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和4-三氟甲氧基苄醇(211mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：80％
1H NMR(500MHz,CDCl3)δ7.96-7.94(m,2H),7.55(t,J＝7.3Hz,1H),7.45(t,J＝7.8Hz,2H),7.27(d,J＝8.5Hz,2H),7.14(d,J＝8.2Hz,2H),3.29(t,J＝7.5Hz,2H),3.07(t,J＝7.5 Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.7,147.6,140.1,136.7,133.2,130.0,128.6,128.0,121.1,119.5(q,JC-F＝255.3Hz),40.1,29.3.
实施例12:3-(1-萘基)-1-苯基-1-丙酮
3-(naphthalen-1-yl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和1-奈甲醇(174mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：84％
1H NMR(500MHz,CDCl3)δ8.07(d,J＝8.2Hz,1H),7.95(d,J＝7.1Hz,2H),7.89(d,J＝7.7Hz,1H),7.75(t,J＝4.4Hz,1H),7.57-7.48(m,3H),7.46-7.41(m,4H),3.55(t,J＝7.4Hz,2H),3.43(t,J＝7.4Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ199.3,137.4,136.8,133.9,133.1,131.7,128.9,128.6,128.0,127.0,126.1,126.1,125.6,125.6,123.5,39.7,27.2.
实施例13:3-(2-呋喃基)-1-苯基-1-丙酮
3-(furan-2-yl)-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和糠醇(108mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：83％
1H NMR(500MHz,CDCl3)δ7.98(d,J＝7.1Hz,2H),7.56(t,J＝7.4Hz,1H),7.45(t,J＝7.8Hz,2H),7.31(s,1H),6.28-6.27(m,1H),6.05-6.04(m,1H),3.33(t,J＝7.2Hz,2H),3.09(t,J＝7.2Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.6,154.7,141.1,136.7,133.1,128.6, 128.0,110.2,105.3,36.9,22.5.
实施例14:1-苯基-1-辛酮
1-phenyloctan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和正己醇(112mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：79％
1H NMR(500MHz,CDCl3)δ7.97(d,J＝7.1Hz,2H),7.55(t,J＝7.4Hz,1H),7.46(t,J＝7.6Hz,2H),2.96(t,J＝7.4Hz,2H),1.77-1.71(m,2H),1.36-1.25(m,8H),0.88(t,J＝6.8Hz,3H)；13C{1H}NMR(125MHz,CDCl3)δ200.6,137.1,132.8,128.5,128.0,38.6,31.7,29.3,29.1,24.4,22.6,14.0.
实施例15:3-环己基-1-苯基-1-丙酮
3-cyclohexyl-1-phenylpropan-1-one
将DL-1-苯乙醇(122mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和环己基甲醇(126mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：86％
1H NMR(500MHz,CDCl3)δ7.97(d,J＝7.2Hz,2H),7.55(t,J＝7.4Hz,1H),7.46(t,J＝7.6Hz,2H),2.98(t,J＝7.7Hz,2H),1.78-1.69(m,4H),1.65-1.61(m,3H),1.32-1.27(m,1H),1.25-1.14(m,3H),0,98-0.91(m,2H)；13C{1H}NMR(125MHz,CDCl3)δ200.9,137.1,132.8,128.5,128.0,37.4,36.1,33.2,31.8,26.5,26.3.
实施例16:3-苯基-1-(3-甲基苯基)-1-丙酮
3-phenyl-1-m-tolylpropan-1-one
将1-(3-甲基苯基)乙醇(136mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：88％
1H NMR(500MHz,CDCl3)δ7.77-7.74(m,2H),7.36-7.33(m,2H),7.30(t,J＝7.4Hz,2H),7.26-7.24(m,2H),7.20(t,J＝7.1Hz,1H),3.28(t,J＝7.8Hz,2H),3.06(t,J＝7.8Hz,2H),2.39(s,3H)；13C{1H}NMR(125MHz,CDCl3)δ199.4,141.3,138.4,136.9,133.8,128.6,128.5,128.4,128.4,126.1,125.2,40.5,30.2,21.3.
实施例17:3-苯基-1-(4-甲基苯基)-1-丙酮
3-phenyl-1-p-tolylpropan-1-one
将1-(4-甲基苯基)乙醇(136mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：82％
1H NMR(500MHz,CDCl3)δ7.87(d,J＝8.2Hz,2H),7.30(t,J＝7.4Hz,2H),7.26-7.24(m,4H),7.20(t,J＝7.1Hz,1H),3.28(t,J＝7.8Hz,2H),3.06(t,J＝7.8Hz,2H),2.40(s,3H)； 13C{1H}NMR(125MHz,CDCl3)δ198.9,143.8,141.4,134.4,129.3,128.5,128.4,128.1,126.1,40.3,30.2,21.6.
实施例18:1-(4-乙基苯基)-3-苯基-1-丙酮
1-(4-ethylphenyl)-3-phenylpropan-1-one
将1-(4-乙基苯基)乙醇(150mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：87％
1H NMR(500MHz,CDCl3)δ7.90(d,J＝8.2Hz,2H),7.32-7.25(m,6H),7.21(t,J＝7.1Hz,1H),3.28(t,J＝7.7Hz,2H),3.06(t,J＝7.7Hz,2H),2.71(q,J＝7.6Hz,2H),1.25(t,J＝7.6Hz,3H)；13C{1H}NMR(125MHz,CDCl3)δ198.9,150.0,141.4,134.6,128.5,128.4,128.2,128.1,126.1,40.3,30.2,28.9,15.2.
实施例19:1-(4-甲氧基苯基)-3-苯基-1-丙酮
1-(4-methoxyphenyl)-3-phenylpropan-1-one
将1-(4-甲氧基苯基)乙醇(152mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：88％
1H NMR(500MHz,CDCl3)δ7.95(d,J＝8.9Hz,2H),7.30(t,J＝7.4Hz,2H),7.26(d,J＝6.8Hz,2H),7.21(t,J＝7.1Hz,1H),6.93(d,J＝8.9Hz,2H),3.87(s,3H),3.25(t,J＝7.8Hz,2H),3.06(t,J＝7.8Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ197.8,163.4,141.4,130.2,129.9,128.5,128.4,126.1,113.7,55.4,40.1,30.3.
实施例20:1-(3-氟苯基)-3-苯基-1-丙酮
1-(3-fluorophenyl)-3-phenylpropan-1-one
将1-(3-氟苯基)乙醇(140mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：79％
1H NMR(500MHz,CDCl3)δ7.73(d,J＝7.8Hz,1H),7.64-7.61(m,1H),7.43-7.39(m,1H),7.31(t,J＝7.5Hz,2H),7.26-7.19(m,4H),3.28(t,J＝7.6Hz,2H),3.08(t,J＝7.6Hz,2H)； 13C{1H}NMR(125MHz,CDCl3)δ197.9(d,JC-F＝1.6Hz),163.8(d,JC-F＝246.6Hz),141.0,139.0(d,JC-F＝5.9Hz),130.0(d,JC-F＝6.9Hz),128.6,128.4,126.2,123.8(d,JC-F＝2.0Hz),120.1(d,JC-F＝21.1Hz),114.8(d,JC-F＝21.8Hz),40.6,30.0.
实施例21:1-(3-氯苯基)-3-苯基-1-丙酮
1-(4-chlorophenyl)-3-phenylpropan-1-one
将1-(3-氯苯基)乙醇(157mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：83％
1H NMR(500MHz,CDCl3)δ7.91-7.90(m,1H),7.81(d,J＝7.8Hz,1H),7.51-7.49(m,1H),7.37(t,J＝7.9Hz,1H),7.29(t,J＝7.5Hz,2H),7.24-7.19(m,3H),3.26(t,J＝7.7Hz,2H),3.05(t,J＝7.7Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ197.8,141.0,138.4,134.9,133.0,129.9,128.6,128.4,128.2,126.2,126.1,40.5,29.9.
实施例22:1-(4-氯苯基)-3-苯基-1-丙酮
1-(4-chlorophenyl)-3-phenylpropan-1-one
将1-(4-氯苯基)乙醇(157mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：82％
1H NMR(500MHz,CDCl3)δ7.90(d,J＝8.6Hz,2H),7.43(d,J＝8.6Hz,2H),7.30(t,J＝7.4Hz,2H),7.26-7.20(m,3H),3.27(t,J＝7.7Hz,2H),3.06(t,J＝7.7Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ197.9,141.0,139.5,135.1,129.4,128.9,128.5,128.4,126.2,40.4,30.0.
实施例23:1-(4-溴苯基)-3-苯基-1-丙酮
1-(4-bromophenyl)-3-phenylpropan-1-one
将1-(4-溴苯基)乙醇(201mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：89％
1H NMR(500MHz,CDCl3)δ7.82(d,J＝8.6Hz,2H),7.60(d,J＝8.6Hz,2H),7.31-7.19(m,5H),3.26(t,J＝7.7Hz,2H),3.06(t,J＝7.7Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ192.8,141.0,135.6,131.9,129.6,128.6,128.4,128.2,126.2,40.4,30.0.
实施例24:3-苯基-1-(4-三氟甲基苯基)-1-丙酮
3-phenyl-1-(4-(trifluoromethyl)phenyl)propan-1-one
将1-(4-三氟甲基苯基)乙醇(190mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：81％
1H NMR(500MHz,CDCl3)δ8.06(d,J＝8.1Hz,2H),7.73(d,J＝8.2Hz,2H),7.31(t,J＝7.4Hz,2H),7.24(m,3H),3.33(t,J＝7.6Hz,2H),3.08(t,J＝7.6Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ198.2,140.8,139.5,134.7(q,JC-F＝32.5Hz),128.6,128.4,128.3,126.3,125.7,125.6,40.7,29.9.
实施例25:1-(2-萘基)-3-苯基-1-丙酮
1-(naphthalen-2-yl)-3-phenylpropan-1-one
将2-奈乙醇(172mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：84％
1H NMR(500MHz,CDCl3)δ8.46(s,1H),8.05(dd,J＝8.6and 1.7Hz,1H),7.94(d,J＝8.1Hz,1H),7.88(t,J＝8.9Hz,2H),7.60(t,J＝6.8Hz,1H),7.55(t,J＝6.9Hz,1H),7.34-7.29(m,4H),7.22(t,J＝5.8Hz,1H),3.45(t,J＝7.8Hz,2H),3.13(t,J＝7.8Hz,2H)；13C{1H}NMR(125MHz,CDCl3)δ199.1,141.4,135.6,134.2,132.5,129.7,129.5,128.6,128.5,127.8,126.8,126.2,123.8,40.6,30.3.
实施例26:2-苄基-1-茚酮
2-benzyl-2,3-dihydroinden-1-one
将1-茚醇(134mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：82％
1H NMR(500MHz,CDCl3)δ7.78(d,J＝7.6Hz,1H),7.56(t,J＝7.4Hz,1H),7.38(t,J＝6.1Hz,1H),7.36(d,J＝7.4Hz,1H),7.29(t,J＝7.4Hz,2H),7.24-7.19(m,3H),3.40(dd,J＝14.0and 4.3Hz,1H),3.16(dd,J＝17.2and 7.8Hz,1H),3.01-2.97(m,1H),2.86(dd,J＝17.2and 4.0Hz,1H)；13C{1H}NMR(125MHz,CDCl3)δ207.8,153.6,139.6,136.5,134.8,128.9,128.5,127.4,126.6,126.3,124.0,48.9,37.0,32.2.
实施例27:2-苄基-1-四氢萘酮
2-benzyl-3,4-dihydronaphthalen-1-one
将α-四氢萘醇(148mg,1.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(119mg,1.1mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：80％
1H NMR(500MHz,CDCl3)δ8.08(d,J＝7.8Hz,1H),7.48-7.45(m,1H),7.33-7.29(m,3H),7.24-7.21(m,4H),3.50(dd,J＝4.0and 4.0Hz,1H),2.95-2.91(m,2H),2.77-2.72(m,1H),2.67-2.62(m,1H),2.13-2.09(m,1H),1.83-1.76(m,1H)；13C{1H}NMR(125MHz,CDCl3)δ199.4,144.0,140.0,133.2,132.5,129.2,128.7,128.4,127.5,126.6,126.1,49.4,35.6,28.6,27.6.
实施例28:1-环丙基-3-苯基-1-丙酮
1-cyclopropyl-3-phenylpropan-1-one
将环丙甲基酮(168mg,2.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(108mg,1.0mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：84％
1H NMR(500MHz,CDCl3)δ7.29-7.24(m,2H),7.20-7.17(m,3H),2.92-2.87(m,4H),1.91-1.88(m,1H),1.02-1.00(m,2H),0.86-0.83(m,2H)；13C{1H}NMR(125MHz,CDCl3)δ209.9,141.2,128.4,128.3,126.0,44.9,29.9,20.5,10.7.
实施例29:4-甲基-1-苯基-3-戊酮
4-methyl-1-phenylpentan-3-one
将3-甲基-2-丁醇(176mg,2.0mmol)、cat.[Ir](5.3mg,0.01mmol,1mol％)和叔戊醇(1mL)依次加入到5mL圆底烧瓶中。反应混合物在空气中回流反应6小时后，冷却到室温。然后加入碳酸铯(33mg,0.1mmol,0.1equiv.)和苄醇(108mg,1.0mmol)，在空气中回流6小时后，冷却到室温。旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：82％
1H NMR(500MHz,CDCl3)δ7.29-7.25(m,2H),7.19-7.17(m,3H),2.89(t,J＝7.6Hz,2H),2.76(t,J＝7.6Hz,2H),2.57-2.55(m,1H),1.07(d,J＝7.0Hz,6H)；13C{1H}NMR(125MHz,CDCl3)δ213.7,141.3,128.4,128.3,126.0,41.9,41.0,29.8,18.1.
实施例30:
除步骤1中反应时间为3小时，其它反应原料，条件和产物同实施例1，产率：75％。
实施例31:
除步骤2中反应时间为3小时，其它反应原料，条件和产物同实施例1，产率：71％。
Claims (7)
1.一种合成α-烷基酮的方法，其特征是，所述的α-烷基酮Ⅰ
是通过仲醇Ⅱ
脱氢成IV后
与伯醇III反应
反应是在过渡金属催化剂和碱的存在下发生，
其中，R1选自C1-C4烷基、甲基苯基、乙基苯基、甲氧基苯基、三氟甲基苯基、卤代苯基、萘基或噻酚基；
R2选自C4-C7烷基、甲基苯基、甲氧基苯基、三氟甲基苯基、三氟甲氧基苯基、卤代苯基、呋喃基或萘基；
具体包括如下步骤：
步骤1，在反应容器中，加入仲醇，过渡金属催化剂，溶剂叔戊醇，反应混合物在油浴中加热回流反应后，冷却到室温；
步骤2，再加入伯醇，碱，反应混合物在油浴中加热回流反应后，然后通过柱分离，得到目标化合物；
其中，过渡金属催化剂为金属铱络合物[Cp*Ir(2,2’-bpyO)(H2O)]，其结构如下：
2.如权利要求1所述的合成α-烷基酮的方法，其特征是，步骤1中，过渡金属催化剂用量为仲醇的1mol％。
3.如权利要求1所述的合成α-烷基酮的方法，其特征是，步骤1中，反应时间为3-6小时。
4.如权利要求1所述的合成α-烷基酮的方法，其特征是，步骤2中，碱为碳酸铯。
5.如权利要求1所述的合成α-烷基酮的方法，其特征是，步骤2中，碱的摩尔量为仲醇摩尔量的0.1当量。
6.如权利要求1所述的合成α-烷基酮的方法，其特征是，步骤2中，伯醇的摩尔量为仲醇摩尔量的1.1-2当量。
7.如权利要求1所述的合成α-烷基酮的方法，其特征是，步骤2中，反应时间为3-6小时。
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| CN1289753A (zh) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | 一种仲醇脱氢制备酮的工艺方法 |
| CN1289752A (zh) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | 醇类脱氢制备醛、酮的方法 |
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| CN1289752A (zh) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | 醇类脱氢制备醛、酮的方法 |
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| Title |
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| fengli等.α‑Alkylation of Ketones with Primary Alcohols Catalyzed by a Cp*Ir Complex Bearing a Functional Bipyridonate Ligand.《The Journal of Organic Chemistry》.2014,第79卷第10447-10455页. |
| One-Pot Sequential Catalytic Hydration of Alkynes and a-Alkylation with Alcohols for the Synthesis of a-Alkylated Ketones;J.Ma等;《Asian journal of organic chemistry》;20141231;第940-947页 |
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