CN108794385A - 一种合成苯乙炔基吡啶衍生物的方法 - Google Patents
一种合成苯乙炔基吡啶衍生物的方法 Download PDFInfo
- Publication number
- CN108794385A CN108794385A CN201810814501.1A CN201810814501A CN108794385A CN 108794385 A CN108794385 A CN 108794385A CN 201810814501 A CN201810814501 A CN 201810814501A CN 108794385 A CN108794385 A CN 108794385A
- Authority
- CN
- China
- Prior art keywords
- phenylethynylpyridin
- synthesis
- derivative
- phenylacetylene
- iodo
- 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.)
- Granted
Links
- RODTWUBQTXSTLJ-UHFFFAOYSA-N 2-(2-phenylethynyl)pyridine Chemical class C1=CC=CC=C1C#CC1=CC=CC=N1 RODTWUBQTXSTLJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 phenylacetylene class compound Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- CCZWSTFVHJPCEM-UHFFFAOYSA-N 2-iodopyridine Chemical compound IC1=CC=CC=N1 CCZWSTFVHJPCEM-UHFFFAOYSA-N 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- NEBFBVFMEJNMTO-UHFFFAOYSA-N acetylene;benzene Chemical group C#C.C1=CC=CC=C1 NEBFBVFMEJNMTO-UHFFFAOYSA-N 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 2
- PUDXEETWGICZTG-UHFFFAOYSA-N 2-[2-(2-methylphenyl)ethynyl]pyridine Chemical compound CC1=CC=CC=C1C#CC1=CC=CC=N1 PUDXEETWGICZTG-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 0 C=C(C=C=CCN)C#CC1=CCC*=C=C1 Chemical compound C=C(C=C=CCN)C#CC1=CCC*=C=C1 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- DGLHLIWXYSGYBI-UHFFFAOYSA-N 1-chloro-2-ethynylbenzene Chemical class ClC1=CC=CC=C1C#C DGLHLIWXYSGYBI-UHFFFAOYSA-N 0.000 description 1
- MYBSUWNEMXUTAX-UHFFFAOYSA-N 1-ethynyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C#C MYBSUWNEMXUTAX-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical class COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012918 MOF catalyst Substances 0.000 description 1
- MJPDNAAYVFLXBK-UHFFFAOYSA-N N1=CC=CC=C1.C1(=CC=CC=C1)C#C Chemical class N1=CC=CC=C1.C1(=CC=CC=C1)C#C MJPDNAAYVFLXBK-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- UISZKHSCSVDZMV-UHFFFAOYSA-N acetylene nitrobenzene Chemical class C#C.[N+](=O)([O-])C1=CC=CC=C1 UISZKHSCSVDZMV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种合成苯乙炔基吡啶衍生物的方法,该方法以醋酸钯为催化剂,以4,5‑双二苯基膦‑9,9‑二甲氧基杂蒽为配体,甲醇为溶剂,在碳酸铯碱性条件下,将2‑碘代吡啶与苯乙炔类化合物偶联制得苯乙炔基吡啶衍生物。本发明操作简单,反应高效、条件温和,底物适用性好,可广泛用于苯乙炔基吡啶衍生物的制备。
Description
技术领域
本发明涉及一种以碘代吡啶和苯乙炔类化合物为底物,醋酸钯作为催化剂,4,5-双二苯基膦-9,9-二甲基氧杂蒽(Xantphos)为配体,在CsCO3碱性条件下合成苯乙炔基吡啶衍生物的方法。
背景技术
Sonogashira反应是一种由金属钯化合物催化的末端炔烃与sp2型碳的交叉耦联反应,这一反应为合成芳基炔烃衍生物提供了一种行之有效的反应路线。
苯乙炔基吡啶衍生物具有多种生理活性,是构筑杂环类结构的重要小分子,近来引起了研究者的关注,其在有机合成、分子电子学、天然产物活性分子、纳米结构、农药、染料、日用化学品合成、共聚物以及材料等领域有着广泛的用途,因此研究高效合成苯乙炔基吡啶衍生物的方法非常重要。
2010年Saisuree Prateeptongkum报道了利用K2PdCl4催化剂(0.5mol%),CuI(1mol%)做助催化剂,四甲基乙二胺(TMEDA)作溶剂,氩气保护下80℃下反应20h,可以高收率的合成多种苯乙炔基吡啶衍生物。2013年Rafique Ul Islam合成了用于Sonogashira偶联反应的钯-聚合物超分子催化剂,在无铜盐助催化剂和无配体条件下该催化反应转换频率(TOF)值较高。2014年Christopher W.D.Gallop提出了使用(N-杂环卡宾)-Cu和(N-杂环卡宾)-Pd配合物的100:1组合的Sonogashira反应催化剂体系。使用1mol%(NHC)-Cu和0.01mol%(NHC)-Pd的催化剂体系可以使芳基溴化物和芳基炔烃在空气和非无水溶剂中发生偶联,且收率较高。2016年Chizoba I.Ezugwu合成了非均相的N-杂环卡宾基MOF催化剂(1-Pd),它对于Sonogashira交叉偶联反应非常有效。2016年Monica Dell'Acqua以PdCl2(PPh3)2为催化剂,CuI做助催化剂,无水TEA作溶剂,在氮气保护下可以高收率的合成苯乙炔基吡啶衍生物。
目前,报道的这些反应虽然可以高产率的得到苯乙炔基吡啶衍生物,但是大部分反应中要加入铜盐助催化剂。而且这些反应要对溶剂进行严格的除水除氧,反应过程需要氮气或氩气保护,或者要先合成复杂的催化剂体系,这就造成合成苯乙炔基吡啶衍生物的方法和过程复杂,成本高,不利于苯乙炔基吡啶衍生物的放大合成。
发明内容
本发明所要解决的技术问题在于克服现有苯乙炔基吡啶衍生物制备方法对水、氧敏感需要氮气或氩气保护,溶剂需要严格的除水除氧,反应温度高,需要的有机碱含量高,且在Sonogashira反应中,需要加入铜盐作为助催化剂等缺点,提供一种操作简单、反应温和、反应速度快、高效安全的合成苯乙炔基吡啶衍生物的方法。
解决上述技术问题所采用的技术方案是:以甲醇为溶剂、醋酸钯为催化剂,Xantphos为配体,CsCO3提供碱性环境,将2-碘代吡啶和苯乙炔类化合物在50~60℃下反应,得到苯乙炔基吡啶衍生物,反应方程式如下所示:
式中R1代表H、NO2、卤素、C1~C4烷基、C1~C4烷氧基中任意一种。
上述合成方法中,所述2-碘代吡啶和苯乙炔类化合物的摩尔比为1:1.0~1.3,醋酸钯的加入量为2-碘代吡啶摩尔量的4%~8%,Xantphos的加入量为2-碘代吡啶摩尔量的8%~12%,CsCO3的加入量为2-碘代吡啶摩尔量的1~3倍。
上述Xantphos的结构式为
本发明以甲醇为溶剂、醋酸钯为催化剂,Xantphos为配体,碱性条件下,将2-碘代吡啶和苯乙炔类化合物进行Sonogashira偶联制得苯乙炔基吡啶衍生物。本发明操作简单,无需铜盐助催化剂,反应在空气中进行,所用得溶剂甲醇不用除水除氧,对设备要求低,反应高效、条件温和,底物适用性好,可广泛用于苯乙炔基吡啶衍生物的制备。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
合成结构式如下的2-(2-苯基乙炔基)吡啶
称取0.0112g(0.05mmol)醋酸钯、0.0579g(0.10mmol)Xantphos、0.6516g(2.00mmol)碳酸铯于反应瓶中,并加入5mL甲醇、106.2μL(1.00mmol)2-碘吡啶、131.8μL(1.00mmol)苯乙炔,在55℃下反应6h,停止反应,自然降至室温,柱色谱分离,得到棕色液体2-(2-苯基乙炔基)吡啶,产率为96%,结构表征数据为:1H NMR(400MHz,CDCl3):δ8.63-8.62(d,1H),7.70-7.66(dt,1H),7.62-7.59(m,2H),7.52(d,1H),7.37-7.36(m,3H),7.24-7.23(m,1H);13C NMR(100MHz,CDCl3):δ150.05,143.44,136.17,132.04,128.99,128.40,127.16,122.76,122.26,89.23,88.64.
实施例2
合成结构式如下的2-((4-甲氧基苯基)乙炔基)吡啶
本实施例中,用等摩尔4-甲氧基苯乙炔替换实施例1中的苯乙炔,反应时间延长至10h,其他步骤与实施例1相同,得到棕红色液体2-((4-甲氧基苯基)乙炔基)吡啶,产率为96%,结构表征数据为:1H NMR(400MHz,CDCl3):δ8.60-8.59(d,1H),7.67-7.63(dt,1H),7.55-7.52(d,2H),7.50-7.48(d,1H),7.22-7.19(dq,1H),6.89-6.77(d,2H),3.83(s,3H);13C NMR(100MHz,CDCl3):δ160.26,149.73,143.78,136.20,133.59,126.95,122.47,114.30,114.01,89.32,87.41,55.16.
实施例3
合成结构式如下的2-((4-硝基苯基)乙炔基)吡啶
本实施例中,用等摩尔4-硝基苯乙炔替换实施例1中的苯乙炔,反应时间延长至10h,其他步骤与实施例1相同,得到微黄色固体2-((4-硝基苯基)乙炔基)吡啶,产率为90%,结构表征数据为:1H NMR(400MHz,CDCl3):δ8.68(d,1H),8.26(d,2H),7.76-7.72(dd,3H),7.59(d,1H),7.34(dt,1H);13C NMR(100MHz,CDCl3):δ151.79,148.94,143.89,137.78,134.20,130.55,128.95,125.09,125.02,94.59,88.15.
实施例4
合成结构式如下的2-(邻甲苯基乙炔基)吡啶
本实施例中,用等摩尔2-乙炔基甲苯替换实施例1中的苯乙炔,反应时间延长至10h,其他步骤与实施例1相同,得到棕色液体2-(邻甲苯基乙炔基)吡啶,产率为95%、结构表征数据为:1H NMR(400MHz,CDCl3):δ8.63-8.62(d,1H),7.70-7.66(dt,1H),7.58-7.56(d,1H),7.54-7.52(d,1H),7.29-7.16(m,4H),2.55(s,3H);13C NMR(100MHz,CDCl3):δ150.08,143.70,140.75,136.13,132.40,129.53,129.03,127.19,125.65,122.67,122.04,92.54,88.23,20.78.
实施例5
合成结构式如下的2-(邻氯苯基乙炔基)吡啶
本实施例中,用等摩尔1-氯-2-乙炔基苯替换实施例1中的苯乙炔,反应时间延长至10h,其他步骤与实施例1相同,得到棕色液体2-(邻氯苯基乙炔基)吡啶,产率为98%,结构表征数据为:1H NMR(400MHz,CDCl3):δ8.65-8.64(d,1H),7.72-7.68(t,1H),7.65-7.63(d,1H),7.59-7.57(d,1H),7.43-7.45(d,1H),7.31-7.24(m,3H);13C NMR(100MHz,CDCl3):δ150.15,143.14,136.33,136.18,133.73,130.01,129.35,127.53,126.55,123.08,122.29,93.42,85.80.
Claims (6)
1.一种合成苯乙炔基吡啶衍生物的方法,其特征在于:以甲醇为溶剂、醋酸钯为催化剂,4,5-双二苯基膦-9,9-二甲基氧杂蒽为配体,碳酸铯提供碱性环境,将2-碘代吡啶和苯乙炔类化合物在50~60℃下反应,得到苯乙炔基吡啶衍生物。
2.根据权利要求1所述的合成苯乙炔基吡啶衍生物的方法,其特征在于:所述苯乙炔类化合物为苯乙炔、硝基取代苯乙炔、卤代苯乙炔、C1~C4烷基取代苯乙炔、C1~C4烷氧基取代苯乙炔中任意一种。
3.根据权利要求1或2所述的合成苯乙炔基吡啶衍生物的方法,其特征在于:所述2-碘代吡啶和苯乙炔类化合物的摩尔比为1:1.0~1.3。
4.根据权利要求1或2所述的合成苯乙炔基吡啶衍生物的方法,其特征在于:所述醋酸钯的加入量为2-碘代吡啶摩尔量的4%~8%。
5.根据权利要求1或2所述的合成苯乙炔基吡啶衍生物的方法,其特征在于:所述4,5-双二苯基膦-9,9-二甲基氧杂蒽的加入量为2-碘代吡啶摩尔量的8%~12%。
6.根据权利要求1或2所述的合成苯乙炔基吡啶衍生物的方法,其特征在于:所述碳酸铯的加入量为2-碘代吡啶摩尔量的1~3倍。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810814501.1A CN108794385B (zh) | 2018-07-23 | 2018-07-23 | 一种合成苯乙炔基吡啶衍生物的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810814501.1A CN108794385B (zh) | 2018-07-23 | 2018-07-23 | 一种合成苯乙炔基吡啶衍生物的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108794385A true CN108794385A (zh) | 2018-11-13 |
CN108794385B CN108794385B (zh) | 2021-09-21 |
Family
ID=64077768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810814501.1A Expired - Fee Related CN108794385B (zh) | 2018-07-23 | 2018-07-23 | 一种合成苯乙炔基吡啶衍生物的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108794385B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114702437A (zh) * | 2022-04-15 | 2022-07-05 | 南京工业大学 | 一种杂芳基鏻盐与末端炔烃的Sonogashira偶联方法 |
CN114950569A (zh) * | 2022-06-30 | 2022-08-30 | 齐鲁工业大学 | 一种催化芳基卤化物与末端炔烃反应的催化剂及反应方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060652A (zh) * | 2010-12-20 | 2011-05-18 | 四川大学 | 用水作反应溶剂制备多苯乙炔基苯类化合物的方法 |
-
2018
- 2018-07-23 CN CN201810814501.1A patent/CN108794385B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060652A (zh) * | 2010-12-20 | 2011-05-18 | 四川大学 | 用水作反应溶剂制备多苯乙炔基苯类化合物的方法 |
Non-Patent Citations (5)
Title |
---|
ALAVALA GOPI KRISHNA REDDY ET AL.: "Palladium-Catalyzed Copper-Free Sonogashira Coupling of 2-Bromoarylcarbonyls: Synthesis of Isobenzofurans via One-Pot Reductive Cyclization", 《SYNTHESIS》 * |
FELIX N. NGASSA ET AL.: "The first Cu- and amine-free Sonogashira-type cross-coupling in the C-6-alkynylation of protected 2’-deoxyadenosine", 《TETRAHEDRON》 * |
MEILIN LIU ET AL.: "Sonogashira coupling catalyzed by the Cu(Xantphos)I-Pd(OAc)2 system", 《TETRAHEDRON LETTERS》 * |
TAO YI ET AL.: "Highly Efficient Pd/Tetraphosphine Catalytic System for Copper-Free Sonogashira Reactions of Aryl Bromides with Terminal Alkynes", 《CATAL LETT》 * |
美国化学会: "RN:13141-42-9、16344-79-9、16344-81-3、1092378-39-6、1072190-52-3", 《STN ON THE WEB》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114702437A (zh) * | 2022-04-15 | 2022-07-05 | 南京工业大学 | 一种杂芳基鏻盐与末端炔烃的Sonogashira偶联方法 |
CN114950569A (zh) * | 2022-06-30 | 2022-08-30 | 齐鲁工业大学 | 一种催化芳基卤化物与末端炔烃反应的催化剂及反应方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108794385B (zh) | 2021-09-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Patel et al. | Copper-catalyzed highly efficient oxidative amidation of aldehydes with 2-aminopyridines in an aqueous micellar system | |
CN108794385A (zh) | 一种合成苯乙炔基吡啶衍生物的方法 | |
CN107382884A (zh) | 一种β‑碘代‑N‑烷氧基苯并三氮唑类化合物的合成方法 | |
Zhang et al. | Pd (II)-catalyzed selective sulfenylation of arene C–H bonds using N-arylthiobenzamides as thiolation reagent and oxidant | |
Huynh et al. | Rotamers of palladium complexes bearing IR active N-heterocyclic carbene ligands: Synthesis, structural characterization and catalytic activities | |
EP3245191A1 (en) | Quinolines and process for the preparation thereof | |
CN102391059A (zh) | 环丙烷基芳香化合物的合成方法 | |
Chen et al. | Copper-catalyzed redox neutral ketoalkylation of Csp 2–H bonds via C–C bond cleavage | |
Das et al. | Organocatalytic synthesis of (Het) biaryl scaffolds via photoinduced intra/intermolecular C (sp 2)–H arylation by 2-pyridone derivatives | |
CN107011275A (zh) | 一种1,4,5‑三取代‑1,2,3‑三氮唑类化合物的合成方法 | |
CN109232364A (zh) | 一种烷基化羟吲哚的制备方法 | |
Shen et al. | Selective aerobic oxidation of benzylic amines to aryl nitriles catalyzed by CuBr2/N-methyl imidazole | |
Zhao et al. | Urea-based organocatalyst catalyzed direct CH bond arylations of unactivated arenes | |
EP2487179A1 (en) | Metal complex, pyridylphosphine compound, and method for producing alkyl methacrylate | |
Nishiura et al. | N‐Arylation of Benzimidazole with Arylboronate, Boroxine and Boronic Acids. Acceleration with an Optimal Amount of Water | |
CN102863399A (zh) | 一种靛红酸酐衍生物的合成方法 | |
CN109438342A (zh) | 一种钯催化8-甲基喹啉衍生物与α-酮酸的脱氢偶联反应合成α-酮酸酯的方法 | |
JPWO2016125845A1 (ja) | クロスカップリング方法、及び該クロスカップリング方法を用いた有機化合物の製造方法 | |
CN109574818A (zh) | 一种多取代茚酮衍生物及其制备方法 | |
CN114478378A (zh) | 一种异喹啉类化合物的合成方法 | |
CN104860881A (zh) | 8-(硝基甲基)喹啉类化合物和8-甲氨基四氢喹啉类化合物的合成方法 | |
CN105669542A (zh) | 一种直接催化氧化法合成吡啶伯酰胺化合物的方法 | |
CN106588767B (zh) | 一种在水相中催化串联反应合成异喹啉酮衍生物的方法 | |
US6201131B1 (en) | Process for producing [2-(arylsulfonyl) ethenyl] benzene derivatives | |
CN114478379B (zh) | 一种利用卤化亚铜催化合成异喹啉氮氧化合物及其衍生物的合成方法 |
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 |
Granted publication date: 20210921 |
|
CF01 | Termination of patent right due to non-payment of annual fee |