CN109988113A - 一种[60]富勒烯四氢喹啉衍生物的合成方法 - Google Patents
一种[60]富勒烯四氢喹啉衍生物的合成方法 Download PDFInfo
- Publication number
- CN109988113A CN109988113A CN201910398015.0A CN201910398015A CN109988113A CN 109988113 A CN109988113 A CN 109988113A CN 201910398015 A CN201910398015 A CN 201910398015A CN 109988113 A CN109988113 A CN 109988113A
- Authority
- CN
- China
- Prior art keywords
- fullerene
- tetrahydroquinoline derivative
- sulfonyl
- synthetic method
- copper chloride
- 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
- -1 [60] fullerene tetrahydroquinoline derivative Chemical class 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 8
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical compound O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002904 solvent 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 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 229910052799 carbon Inorganic materials 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 229910003472 fullerene Inorganic materials 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 10
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 9
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VPMIAOSOTOODMY-KJAPKAAFSA-N (4r)-6-[(e)-2-[6-tert-butyl-4-(4-fluorophenyl)-2-propan-2-ylpyridin-3-yl]ethenyl]-4-hydroxyoxan-2-one Chemical compound C([C@H](O)C1)C(=O)OC1/C=C/C=1C(C(C)C)=NC(C(C)(C)C)=CC=1C1=CC=C(F)C=C1 VPMIAOSOTOODMY-KJAPKAAFSA-N 0.000 description 1
- QRDAPCMJAOQZSU-KQQUZDAGSA-N (e)-3-[4-[(e)-3-(3-fluorophenyl)-3-oxoprop-1-enyl]-1-methylpyrrol-2-yl]-n-hydroxyprop-2-enamide Chemical compound C1=C(\C=C\C(=O)NO)N(C)C=C1\C=C\C(=O)C1=CC=CC(F)=C1 QRDAPCMJAOQZSU-KQQUZDAGSA-N 0.000 description 1
- 238000007115 1,4-cycloaddition reaction Methods 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BJTQKRCFMBXXIJ-UHFFFAOYSA-N 2-(chloromethyl)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1CCl BJTQKRCFMBXXIJ-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- WEQPBCSPRXFQQS-UHFFFAOYSA-N 4,5-dihydro-1,2-oxazole Chemical compound C1CC=NO1 WEQPBCSPRXFQQS-UHFFFAOYSA-N 0.000 description 1
- REDUQXCPUSNJOL-UHFFFAOYSA-N C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O Chemical compound C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O REDUQXCPUSNJOL-UHFFFAOYSA-N 0.000 description 1
- CYSWUSAYJNCAKA-FYJFLYSWSA-N ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O Chemical compound ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O CYSWUSAYJNCAKA-FYJFLYSWSA-N 0.000 description 1
- QBXVXKRWOVBUDB-GRKNLSHJSA-N ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C Chemical compound ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C QBXVXKRWOVBUDB-GRKNLSHJSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- JEYWNNAZDLFBFF-UHFFFAOYSA-N Nafoxidine Chemical compound C1CC2=CC(OC)=CC=C2C(C=2C=CC(OCCN3CCCC3)=CC=2)=C1C1=CC=CC=C1 JEYWNNAZDLFBFF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KSCRVOKQPYZBHZ-IXPOFIJOSA-N benzyl n-[(2s)-1-[[(2s)-1-[[(2s)-1-(1,3-benzothiazol-2-yl)-1-oxo-3-[(3s)-2-oxopyrrolidin-3-yl]propan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-methyl-1-oxobutan-2-yl]carbamate Chemical compound N([C@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C[C@H]1C(NCC1)=O)C(=O)C=1SC2=CC=CC=C2N=1)C(C)C)C(=O)OCC1=CC=CC=C1 KSCRVOKQPYZBHZ-IXPOFIJOSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 1
- 229950002366 nafoxidine Drugs 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种[60]富勒烯四氢喹啉衍生物的合成方法,以富勒烯C60与取代的N‑磺酰基邻氨基苯丙二酸二甲酯为原料,以氯化铜和水合乙酸锰为催化剂,以碳酸铯为无机碱,以邻二氯苯和乙腈的混合溶液为溶剂,在氮气氛围下于120‑140℃反应制得目标产物[60]富勒烯四氢喹啉衍生物。本发明的合成方法中反应步骤简单,在氯化铜和水合乙酸锰的联合催化下以较高的收率获得了富勒烯四氢喹啉类化合物,催化剂价廉易得,实验方法简单,原子经济性高。
Description
技术领域
本发明属于富勒烯衍生物的合成技术领域,具体涉及一种[60]富勒烯四氢喹啉衍生物的合成方法。
背景技术
杂环结构在光电材料、天然产物及生物分子中经常出现,在富勒烯中引入含有氧或氮的杂环结构,有利于增强富勒烯杂环衍生物的电子接受能力,扩宽其在光电材料领域的应用。富勒烯杂环化合物的构建通常是通过1,3-偶极环加成反应形成碳-杂原子键,一系列富勒烯杂环衍生物如富勒烯四氢吡咯、吡唑啉、三唑啉、噁唑啉、异噁唑啉、呋喃、吡咯和噻唑类衍生物被合成出来,并且在材料化学、有机光电和医学等领域得到了较为广泛地应用。而对于含杂原子的富勒烯四氢喹啉类化合物的构建,目前已经报道的方法有限。在仅有的方法中,Martín在1998年报道了富勒烯C60与N-甲基苯胺基氯代苯硼烷、醛在回流的条件下反应,仅仅合成了三个富勒烯四氢喹啉类化合物(J.Org.Chem.1998,63,8074-8076)。此外,在2018年,富勒烯C60与2-氯甲基苯磺酰胺发生的[4+2]环加成反应合成富勒烯四氢喹啉类化合物的反应也被报道(J.Org.Chem.2018,83,1959-1968)。以上是仅有的报道合成富勒烯四氢喹啉类化合物的方法,在原料合成、底物适用范围和产物结构多样性等方面均存在不同的局限性。
发明内容
本发明解决的技术问题是提供了一种更加简便且适用范围广的[60]富勒烯四氢喹啉衍生物的合成方法。
本发明为解决上述技术问题采用如下技术方案,一种[60]富勒烯四氢喹啉衍生物的合成方法,其特征在于具体过程为:以富勒烯C60与取代的N-磺酰基邻氨基苯丙二酸二甲酯为原料,以氯化铜和水合乙酸锰为催化剂,以碳酸铯为无机碱,以邻二氯苯和乙腈的混合溶液为溶剂,在氮气氛围下于120-140℃反应制得目标产物[60]富勒烯四氢喹啉衍生物,合成过程中的反应方程式为:
其中取代基R选自C1-4烷基或芳基;取代基R1选自氢、甲基、卤素、甲氧基或三氟甲基;取代基R2选自对甲苯磺酰基、苯磺酰基、对甲氧基苯基磺酰基、对硝基苯基磺酰基、萘磺酰基或2-噻吩磺酰基。
优选的,所述的富勒烯C60、取代的N-磺酰基邻氨基苯丙二酸二甲酯、氯化铜、水合乙酸锰与碳酸铯的投料摩尔比为1:3:2:2:1。
优选的,所述的溶剂为体积比7:1的邻二氯苯和乙腈的混合溶液。
优选的,所述的[60]富勒烯四氢喹啉衍生物包括以下化合物:
本发明具有以下有益效果:本发明的合成方法中反应步骤简单,在氯化铜和水合乙酸锰的联合催化下以较高的收率获得了富勒烯四氢喹啉类化合物,催化剂价廉易得,实验方法简单,原子经济性高。同时具有广泛的底物使用范围和良好的官能团耐受性,为富勒烯四氢喹啉类化合物的制备和应用提供了一种更加简便的方法。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例
在Shrek tube中加入富勒烯C60(36.0mg,0.05mmol)、各种取代的N-磺酰基邻氨基苯丙二酸二酯(1a-1k,0.15mmol)、氯化铜(13.4mg,0.1mmol)、水合乙酸锰(26.8mg,0.1mmol)和碳酸铯(16.3mg,0.05mol),加入无水邻二氯苯(7mL)和无水乙腈(1mL),在超声波中超声使其溶解,然后在真空线上进行三次抽气和换气,使反应容器中充满氮气,再将Shrek tube置于130℃油浴中进行反应3h。
反应结束后,将体系冷却至室温,使用短的硅胶柱过滤不溶性的杂质。减压条件下除去溶剂后,采用柱层析的方法分离。首先用二硫化碳作为洗脱剂回收未反应的富勒烯C60,然后采用二硫化碳/二氯甲烷体系,即可分离得到目标产物富勒烯四氢喹啉类化合物2a-2k。并对目标产物进行了1H NMR、13C NMR、HRMS、IR和UV表征,确认了该类化合物为富勒烯四氢喹啉类化合物。
Compound 2a.Yield 19.7mg,36%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.21-8.19(m,1H),8.02(d,J=8.4Hz,2H),7.69-7.66(m,1H),7.63-7.59(m,2H),7.29(d,J=8.0Hz,2H),4.12(br,3H),3.88(s,3H),2.41(s,3H).13C{1H}NMR(100MHz,CDCl3,all 1C unless indicated)δ169.1,167.7,152.4,151.2,148.3,147.9,147.8,146.8,146.7(2C),146.6,146.3,146.28,146.26,146.2,146.1,146.0,145.9,145.7,145.6,145.58,145.56(2C),145.5,145.45,145.4,145.35,145.1,144.8,144.7(2C),144.6,144.5,144.41,143.40,143.3,143.1,142.9,142.88,142.8(2C),142.75,142.7,142.5,142.3,142.1,141.84,141.83,141.6,141.59,141.45,141.41,141.12,139.1,139.06(2C),139.0,138.2,137.6,135.2,134.9,134.87,129.9(3C),129.5,129.2(3C),129.1,128.1,126.1,82.9,76.2,54.3,53.8,21.8;FT-IRν/cm-1(KBr)2952(CH3),1738(C=O),1462,1432,1359(S=O),1235(C-O-C),1167(S=O),1086(C-O-C),1034(C-O-C),753,664,566,527;λmax/nm(CHCl3)258,318,415,694;MALDI-FT MS m/z calcd for C78H17NO6S[M]+1095.0771,found 1095.0778。
Compound 2b.Yield 19.4mg,36%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.21-8.19(m,1H),8.15(d,J=8.0Hz,2H),7.70-7.68(m,1H),7.63-7.61(m,2H),7.57(d,J=7.6Hz,1H),7.52-7.48(m,2H),4.13(s,3H),3.88(s,3H);13C{1H}NMR(100MHz,CDCl3,all 1C unless indicated)δ169.1,167.7,152.4,151.0,148.3,147.9,147.5,146.8,146.7(2C),146.6,146.3,146.27(2C),146.2,146.1,146.0,145.9,145.7,145.6,145.56(2C),145.55,145.5,145.46,145.3(2C),145.1,144.8,144.6,144.55,144.4,143.4,143.2,143.1,143.07,142.9,142.88,142.82,142.80,142.7(2C),142.5,142.3,142.1,142.0,141.83,141.81,141.6(2C),141.43,141.41,141.1,139.1,139.0,138.9,138.2,137.6,135.2,135.0,134.8,133.7,129.6,129.3(3C),129.2,129.1(3C),128.2,126.1,82.9,76.2,54.3,53.9;FT-IRν/cm-1(KBr)2949(CH3),1738(C=O),1512,1481,1432,1361(S=O),1234(C-O-C),1169(S=O),1086(C-O-C),1034(C-O-C),753,688,569,527;λmax/nm(CHCl3)258,318,416,694;MALDI-FT MS m/z calcd for C77H15NO6S[M]+1081.0615,found 1081.0609。
Compound 2c.Yield 18.7mg,34%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.20-8.18(m,1H),8.06(d,J=8.8Hz,2H),7.75-7.73(m,1H),7.62-7.60(m,2H),6.94(d,J=9.2Hz,2H),4.12(br,3H),3.88(s,3H),3.85(s,3H);13C{1H}NMR(150MHz,CDCl3,all 1C unless indicated)δ169.0,167.5,163.5,152.2,151.0,148.1,147.7,147.5,146.7,146.5(2C),146.4,146.2,146.1(2C),146.06,145.9(2C),145.7,145.5,145.42(3C),145.4,145.34,145.3,145.27,145.2,144.9,144.6,144.4,144.37,144.2,143.2,143.1,142.9,142.8,142.7,142.6(2C),142.57,142.5,142.3,142.2,141.9,141.7,141.6,141.5,141.4,141.3,141.26,141.0,139.0,138.95,138.8,138.0,137.4,134.9,134.8,134.7,133.1,131.4(3C),129.4,128.9,127.8,125.9,114.2(2C),82.7,76.1,55.8,54.1,53.7;FT-IRν/cm-1(KBr)2944(CH3),1740(C=O),1593,1496,1311(S=O),1263(C-O-C),1157(S=O),1089(C-O-C),1025(C-O-C),833,584,551,528;λmax/nm(CHCl3)258,318,417,694;MALDI-FT MS m/z calcd for C78H17NO7S[M]+1111.0720,found 1111.0728。
Compound 2d.Yield 15.2mg,27%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.36(s,4H),8.27(dd,J=7.6,1.2Hz,1H),7.69-7.59(m,2H),7.49(d,J=7.2Hz,1H),4.12(br,3H),3.88(s,3H);13C{1H}NMR(100MHz,CDCl3,all 1C unless indicated)δ169.0,167.5,152.0,150.6,150.4,148.4,148.0,147.7,147.2,146.9,146.7(2C),146.66,146.4,146.35(2C),146.3,146.0(2C),145.8,145.7,145.65,145.63,145.6(2C),145.5,145.49,145.4,145.1,144.8,144.62,144.6,144.57,144.3,143.5,143.25,143.2,143.0,142.99,142.93,142.9,142.8,142.7,142.6,142.5,142.3,142.0,141.9,141.8,141.78,141.6,141.5,141.45,141.1,139.3,139.2,138.6,138.2,137.8,135.3,135.2,134.7,130.3(3C),129.8,129.7,128.8,125.7,124.5(3C),83.3,75.8,54.4,53.9;FT-IRν/cm-1(KBr)2945(CH3),1738(C=O),1529(N=O),1370(S=O),1346(N=O),1105(C-O-C),798,736,683,587,553,526;λmax/nm(CHCl3)258,318,416,692;MALDI-FT MS m/z calcd forC77H14N2O8S[M]+1126.0465,found 1126.0455。
Compound 2e.Yield 15.8mg,28%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.66(s,1H),8.22-8.16(m,2H),7.98(d,J=8.8Hz,1H),7.89(d,J=8.4Hz,1H),7.82(d,J=8.4Hz,1H),7.66-7.56(m,5H),4.14(br,3H),3.89(s,3H);13C{1H}NMR(100MHz,CDCl3/CS2,all 1C unless indicated)δ168.9,167.5,152.2,151.0,148.2,147.7,147.6,146.7,146.6,146.52,146.5,146.2,146.17,146.14,146.1,146.0,145.9,145.8,145.52,145.5,145.45(2C),145.43(2C),145.4(2C),145.23,145.2,145.0,144.7,144.45,144.43,144.3,143.3,143.1,143.0,142.9,142.84,142.8,142.7,142.68,142.66,142.6,142.4,142.2,142.0,141.7,141.67,141.5,141.4,141.34,141.3,141.0,139.0,138.8(3C),138.7,138.0,137.5,135.2,135.0,134.8,134.78,132.0,131.2,129.5,129.49,129.47,129.4,129.1,128.04,128.0,127.95,125.9,123.4,82.9,76.1,54.2,53.7,53.6;FT-IRν/cm-1(KBr)2948(CH3),1761,1742(C=O),1432,1358(S=O),1224(C-O-C),1165(S=O),1070(C-O-C),1034(C-O-C),860,745,663,615,557,527;λmax/nm(CHCl3)258,318,415,694;MALDI-FT MS m/z calcd for C81H17NO6S[M]+1131.0771,found 1131.0767。
Compound 2f.Yield 21.5mg,40%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.17(d,J=7.6Hz,1H),7.91(d,J=7.2Hz,1H),7.80(dd,J=3.6,1.2Hz,1H),7.70-7.62(m,3H),7.00-6.99(m,1H),4.11(br,3H),3.89(s,3H);13C{1H}NMR(100MHz,CDCl3,all1C unless indicated)δ169.2,167.6,152.2,150.4,148.3,147.8,147.1,146.8,146.7,146.66,146.6,146.3,146.27,146.26,146.2(2C),146.0,145.9,145.7,145.6,145.5(4C),145.5,145.46(2C),145.3,145.0,144.7,144.6,144.5,144.4,143.4,143.1,143.0,142.97,142.9,142.85,142.8,142.78,142.7(2C),142.5,142.3,142.0,141.8(2C),141.6,141.5,141.4(2C),141.1,139.2,139.0,138.7,137.7,137.6,136.1(2C),135.1,135.0,134.8,133.7(2C),129.7,128.9,128.1,127.1,126.1,82.9,76.4,54.3,53.9,53.6;FT-IRν/cm-1(KBr)2947(CH3),1740(C=O),1513,1482,1429,1356(S=O),1242(C-O-C),1169(S=O),1091(C-O-C),1014(C-O-C),927,726,671,570,526;λmax/nm(CHCl3)258,318,416,694;MALDI-FT MS m/z calcd for C75H13NO6S2[M]+1087.0179,found 1087.0184。
Compound 2g.Yield 20.5mg,37%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.06(d,J=8.0Hz,1H),8.01(d,J=8.4Hz,2H),7.45(s,1H),7.40(d,J=8.0Hz,1H),7.29(d,J=8.0Hz,2H),4.12(br,3H),3.86(s,3H),2.49(s,3H),2.41(s,3H);13C{1H}NMR(100MHz,CDCl3,all 1C unless indicated)δ169.3,167.8,152.6,151.3,148.3,147.9,146.8,146.7(2C),146.6,146.3,146.26,146.24,146.2,146.1,146.0,145.8,145.6,145.57,145.55,145.54(2C),145.48,145.42,145.4,145.3,145.0,144.8,144.7(2C),144.6,144.5,144.4,143.4,143.3,143.2(3C),143.0,142.9,142.86,142.8(2C),142.74,142.7,142.5,142.3,142.1,141.8(2C),141.63,141.62,141.4,141.39,141.2,139.6(2C),139.1,139.06,139.0,138.8,138.2,137.6,135.0,134.9,129.8(2C),129.2(2C),128.9,128.8,126.5,82.9,76.1,54.3,53.8,21.8(2C);FT-IRν/cm-1(KBr)2945(CH3),1737(C=O),1497,1429,1357(S=O),1246(C-O-C),1164(S=O),1085(C-O-C),1042(C-O-C),822,773,727,678,650,559,526;λmax/nm(CHCl3)258,318,415,694;MALDI-FT MS m/zcalcd for C79H19NO6S[M]+1109.0928,found1109.0926。
Compound 2h.Yield 21.6mg,39%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.01(d,J=8.4Hz,2H),7.96(s,1H),7.51(d,J=8.0Hz,1H),7.38(d,J=7.2Hz,1H),7.28(d,J=8.4Hz,2H),4.12(br,3H),3.88(s,3H),2.57(s,3H),2.40(s,3H);13C{1H}NMR(100MHz,CDCl3,all 1C unless indicated)δ169.2,167.7,152.4,151.3,148.3,147.9,146.8,146.7,146.6,146.58,146.3,146.25,146.23,146.2,146.1,146.06,145.8,145.6(2C),145.57,145.5(2C),145.47,145.4,145.38,145.3,145.0,144.8,144.6,144.57(2C),144.5,144.4,143.4,143.3,143.2,143.0,142.9,142.8,142.78(2C),142.7,142.69,142.5,142.3,142.1,141.8(3C),141.6,141.58,141.4(3C),141.1,139.2,139.1,139.0,138.2,138.1(2C),137.5,136.2,135.0,134.93,134.9,130.3,129.9(2C),129.7,129.1(2C),125.6,82.9,76.1,54.3,53.8,22.1,21.8;FT-IRν/cm-1(KBr)2949(CH3),1734(C=O),1653,1559,1507,1490,1457,1431,1361(S=O),1242(C-O-C),1167(S=O),1085(C-O-C),1036(C-O-C),811,706,660,577,526;λmax/nm(CHCl3)258,318,416,694;MALDI-FT MS m/zcalcd for C79H19NO6S[M]+1109.0928,found1109.0933。
Compound 2i.Yield 13.5mg,24%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.13(d,J=8.4Hz,1H),8.03(d,J=8.4Hz,2H),7.29(d,J=8.4Hz,2H),7.14-7.10(m,2H),4.11(br,3H),3.87(s,3H),3.86(s,3H),2.41(s,3H);13C{1H}NMR(150MHz,CDCl3,all 1C unless indicated)δ169.3,167.9,160.2,152.7,151.2,148.3,147.9,146.8,146.7(2C),146.6,146.3,146.29,146.25,146.2,146.1,145.8(2C),145.6,145.57(3C),145.56(3C),145.5,145.4,145.37,145.3,145.1,144.8,144.7,144.6,144.55,144.5,143.4,143.3,143.1,142.9,142.88,142.83,142.82,142.8,142.7,142.5,142.3,142.1,141.9,141.86,141.7,141.66,141.5,141.4,141.2,140.0,139.2,139.1(2C),138.4,137.7,135.1,135.0,130.0,129.9(3C),129.1(3C),113.1,112.4(2C),83.0,76.3,55.7,54.3,53.8,21.8;FT-IRν/cm-1(KBr)2944(CH3),1739(C=O),1610,1500,1427,1315(S=O),1278(C-O-C),1249(C-O-C),1199(S=O),1131(C-O-C),986,822,648,585,526;λmax/nm(CHCl3)258,319,416,693;MALDI-FT MS m/z calcd for C79H19NO7S[M]+1125.0877,found1125.0866。
Compound 2j.Yield 16.7mg,29%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.37(d,J=8.8Hz,1H),7.98(d,J=8.4Hz,2H),7.82(br,2H),7.33(d,J=8.4Hz,2H),4.07(br,3H),3.88(s,3H),2.47(s,3H);13C{1H}NMR(100MHz,CDCl3/CS2,all 1C unlessindicated)δ167.7,167.0,151.6,150.5,148.1,147.7,146.7,146.6,146.5,146.47,146.2,146.12,146.11,146.1,145.9,145.7,145.6,145.5,145.47,145.4,145.38,145.3(3C),145.2,144.9,144.89,144.86,144.7,144.4,144.3,144.0,143.3,143.1(4C),143.0,142.84,142.8,142.7,142.66(2C),142.6,142.5,142.3,142.2,141.8,141.75,141.53,141.50,141.33,141.3,141.2,141.0,139.6,139.1,138.9,138.7,138.6,138.3,137.6,134.7,134.5,131.4(JC-F=32.9Hz),129.8(3C),129.0(2C),124.3(JC-F=3.6Hz),123.4(JC-F=271.4Hz),122.5(JC-F=3.7Hz),82.5,75.6,54.1,53.5,21.7;FT-IRν/cm-1(KBr)2944(CH3),1742(C=O),1422,1369(S=O),1328,1223(C-O-C),1170(S=O),1129(C-O-C),1081(C-O-C),834,649,592,559,526;λmax/nm(CHCl3)258,319,418,692;MALDI-FT MS m/zcalcd for C79H16F3NO6S[M]+1163.0645,found 1163.0644.
Compound 2k.Yield 17.4mg,31%;brown solid;mp>300℃;1H NMR(400MHz,CDCl3)δ8.21(s,1H),8.02(d,J=8.0Hz,2H),7.73-7.71(m,1H),7.61-7.59(m,2H),7.28(d,J=8.4Hz,2H),4.97-4.79(m,1H),4.44-4.38(m,2H),4.27-4.19(m,1H),2.40(s,3H),1.39(br,3H),1.28(t,J=7.2Hz,3H);13C{1H}NMR(150MHz,CDCl3,all 1C unless indicated)δ168.3,167.1,152.5,151.1,148.1,147.7,146.7,146.52,146.51,146.4,146.2,146.1(2C),146.06,146.0,145.9,145.7,145.5,145.45(2C),145.4(2C),145.35,145.32,145.2,145.18,144.9,144.6,144.59,144.5,144.4,144.38,143.3,143.2,142.9,142.8,142.7,142.6(2C),142.58,142.5,142.3,142.2,141.7,141.5,141.46,141.3(2C),141.0,139.9,139.0(2C),138.8,138.7,138.0,137.4,135.0,134.8,134.7,129.7(3C),129.2,129.1(4C),129.0,127.7,126.0,82.8,76.0,63.0(2C),21.6,14.0,13.9;FT-IRν/cm-1(KBr)2929(CH3),1735(C=O),1437,1364(S=O),1232(C-O-C),1167(S=O),1086(C-O-C),1034(C-O-C),908,814,744,707,664,566,526;λmax/nm(CHCl3)258,318,417,694;MALDI-FT MS m/zcalcd for C80H21NO6S[M]+1123.1084,found 1123.1091。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (4)
1.一种[60]富勒烯四氢喹啉衍生物的合成方法,其特征在于具体过程为:以富勒烯C60与取代的N-磺酰基邻氨基苯丙二酸二甲酯为原料,以氯化铜和水合乙酸锰为催化剂,以碳酸铯为无机碱,以邻二氯苯和乙腈的混合溶液为溶剂,在氮气氛围下于120-140℃反应制得目标产物[60]富勒烯四氢喹啉衍生物,合成过程中的反应方程式为:
其中取代基R选自C1-4烷基或芳基;取代基R1选自氢、甲基、卤素、甲氧基或三氟甲基;取代基R2选自对甲苯磺酰基、苯磺酰基、对甲氧基苯基磺酰基、对硝基苯基磺酰基、萘磺酰基或2-噻吩磺酰基。
2.根据权利要求1所述的[60]富勒烯四氢喹啉衍生物的合成方法,其特征在于:所述的富勒烯C60、取代的N-磺酰基邻氨基苯丙二酸二甲酯、氯化铜、水合乙酸锰与碳酸铯的投料摩尔比为1:3:2:2:1。
3.根据权利要求1所述的[60]富勒烯四氢喹啉衍生物的合成方法,其特征在于:所述的溶剂为体积比7:1的邻二氯苯和乙腈的混合溶液。
4.根据权利要求1所述的[60]富勒烯四氢喹啉衍生物的合成方法,其特征在于:所述的[60]富勒烯四氢喹啉衍生物包括以下化合物:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910398015.0A CN109988113B (zh) | 2019-05-14 | 2019-05-14 | 一种[60]富勒烯四氢喹啉衍生物的合成方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910398015.0A CN109988113B (zh) | 2019-05-14 | 2019-05-14 | 一种[60]富勒烯四氢喹啉衍生物的合成方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109988113A true CN109988113A (zh) | 2019-07-09 |
CN109988113B CN109988113B (zh) | 2022-04-12 |
Family
ID=67136500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910398015.0A Expired - Fee Related CN109988113B (zh) | 2019-05-14 | 2019-05-14 | 一种[60]富勒烯四氢喹啉衍生物的合成方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109988113B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113024464A (zh) * | 2021-03-05 | 2021-06-25 | 湖北大学 | 一种基于三氟甲磺酸/对甲苯磺酸催化制备[60]富勒烯四氢喹啉衍生物的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2565782C1 (ru) * | 2014-05-08 | 2015-10-20 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Способ получения 6-алкил(арил)-2,3-(с60-ih)[5,6]фуллеро-2,3,4,5-тетрагидропиридинов |
CN107118150A (zh) * | 2017-05-19 | 2017-09-01 | 河南师范大学 | 一种[60]富勒烯二氢吡咯衍生物的合成方法 |
-
2019
- 2019-05-14 CN CN201910398015.0A patent/CN109988113B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2565782C1 (ru) * | 2014-05-08 | 2015-10-20 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Способ получения 6-алкил(арил)-2,3-(с60-ih)[5,6]фуллеро-2,3,4,5-тетрагидропиридинов |
CN107118150A (zh) * | 2017-05-19 | 2017-09-01 | 河南师范大学 | 一种[60]富勒烯二氢吡咯衍生物的合成方法 |
Non-Patent Citations (4)
Title |
---|
GEORG SCHICK等: "Formation of an Effective Opening within the Fullerene Core of C60 by an Unusual Reaction Sequence", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
NAZARIO MARTIN等: "The First Hetero-Diels-Alder Reaction of C60 with 1-Azadienes. Synthesis of Tetrahydropyrido[2,3:1,2][60]fullerene Derivatives", 《J. ORG. CHEM.》 * |
SHENG-PENG JIANG等: "Synthesis of Fullerotetrahydroquinolines via [4+2] Cycloaddition Reaction of [60]Fullerene with in Situ Generated Aza-o-quinone Methides", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
TONG-XIN LIU等: "Synthesis of [60]Fullerene-Fused Tetrahydroazepinones and Azepinonimines via Cu(OAc)2‑Promoted N‑Heteroannulation Reaction", 《ORGANIC LETTERS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113024464A (zh) * | 2021-03-05 | 2021-06-25 | 湖北大学 | 一种基于三氟甲磺酸/对甲苯磺酸催化制备[60]富勒烯四氢喹啉衍生物的方法 |
CN113024464B (zh) * | 2021-03-05 | 2022-05-13 | 湖北大学 | 一种基于三氟甲磺酸/对甲苯磺酸催化制备[60]富勒烯四氢喹啉衍生物的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN109988113B (zh) | 2022-04-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110204486B (zh) | 一种喹啉衍生物的合成方法 | |
CN108484477A (zh) | 一种5-酰基苯并[a]咔唑类化合物的合成方法 | |
JP5171640B2 (ja) | 2,2’,6,6’−テトラオキサゾリンビフェニル配位子およびその調製方法 | |
CN109988113A (zh) | 一种[60]富勒烯四氢喹啉衍生物的合成方法 | |
CN108689901A (zh) | 一种氮杂环丙烯类化合物的合成方法 | |
CN107513056B (zh) | 一种含四氢呋喃基团的喹啉类化合物的合成方法 | |
CN114014805B (zh) | 三氟甲基化2,4-喹啉二酮类化合物的制备方法 | |
CN110407830B (zh) | 一种合成n-芳基吩噻嗪类化合物的方法 | |
CN105646326B (zh) | 一种多取代的吲哚‑2‑酮类化合物的制备方法 | |
CN109824530B (zh) | 一种由芳香羧酸合成邻氨基芳香酮的方法 | |
TW202200546A (zh) | 芳香醚類化合物的製備方法 | |
CN107619386A (zh) | 一种芳环并[c]咔唑类衍生物及其合成方法 | |
CN106883229A (zh) | 一种3‑羟基咪唑并[1,2‑a]吡啶衍生物的制备方法 | |
CN106632213B (zh) | 一种二苯并吡喃偶联化合物的合成方法 | |
CN102718694B (zh) | 3-氰基取代吲哚化合物及其合成方法 | |
CN107935913B (zh) | 咔唑类化合物及其合成方法和应用 | |
Ji et al. | Copper-catalyzed cyclization reaction: synthesis of trifluoromethylated indolinyl ketones | |
CN110563721A (zh) | 一种新的盐酸阿扎司琼的制备方法 | |
CN113278007B (zh) | 一种2-羟基-吲哚-3-酮类化合物的合成方法 | |
CN108727323A (zh) | 一种氮杂环卡宾催化合成三氟甲基取代高异黄酮类化合物的方法 | |
JPH061776A (ja) | 置換ピラジンカルボニトリルの製造方法 | |
CN113845481B (zh) | 一种4,4-二甲基-4,5-二氢哒嗪-3-酮的合成方法 | |
CN111574448B (zh) | 一种苯基四氢异喹啉的制备方法 | |
CN108218762A (zh) | 一种2位季碳吲哚-3-酮类化合物的合成方法 | |
CN111196786B (zh) | 三氟甲磺酰基取代异噁唑类化合物及其合成方法 |
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: 20220412 |