CN107353245B - 一种喹啉类化合物的合成方法 - Google Patents
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- 229940111121 antirheumatic drug quinolines Drugs 0.000 title claims abstract description 19
- 238000010189 synthetic method Methods 0.000 title claims abstract description 18
- 150000003248 quinolines Chemical class 0.000 title abstract description 11
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
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- 235000019441 ethanol Nutrition 0.000 claims description 7
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- -1 methoxyl group Chemical group 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003480 eluent Substances 0.000 claims 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 239000002322 conducting polymer Substances 0.000 abstract 1
- 229920001940 conductive polymer Polymers 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 13
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- JZICUKPOZUKZLL-UHFFFAOYSA-N 2-methyl-1,2,3,4-tetrahydroquinoline Chemical class C1=CC=C2NC(C)CCC2=C1 JZICUKPOZUKZLL-UHFFFAOYSA-N 0.000 description 1
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical class C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 description 1
- CEIXWJHURKEBMQ-UHFFFAOYSA-N Heliamine Chemical class C1CNCC2=C1C=C(OC)C(OC)=C2 CEIXWJHURKEBMQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/18—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种喹啉类化合物的合成方法，以四氢喹啉类化合物：为原料，以硼氮碳为光催化剂，加入溶剂、氧化剂以及碱，在室温下可见光光照条件下反应，反应液经纯化后得到喹啉类化合物；硼氮碳(h‑BCNx)是一种可见光响应的不含金属元素的半导体聚合物光催化剂,具有廉价易得、化学稳定性好、无毒无害以及合适的禁带宽度和能带位置等优点，将该催化剂用于有机合成中，反应过程操作简单，条件温和，催化效果好，转化率能达到90%以上，对于目标产物的产率可达95%。本发明工艺简单，成本低，符合实际生产需要，具有较大的应用潜力。
Description
技术领域
本发明属于光催化有机合成技术领域，具体涉及一种一种喹啉类化合物的合成方法。
背景技术
喹啉化合物能用于制造药物和高效杀虫剂，氧化后可制成吡啶羧酸，它的衍生物可用于制造彩色影片与染料。用作合成药物、染料、杀虫剂的中间体及气相色谱固定液，同时也是一种具有生物活性的天然产物，同时还被作为市场药物或者是药物候选物应用于疟疾治疗。
传统的Skraup合成法由苯胺（或其他芳胺）、甘油、硫酸和硝基苯（相应于所用芳胺）、五氧化二砷（As2O5）或三氯化铁等氧化剂或者氢受体一起反应，生成喹啉。该合成法是合成喹啉及其衍生物最重要的合成法(Z. H. Skraup, Ber.1880, 13, 2086.)。近年来，发展了一些贵重金属催化剂通过热催化或者电催化四氢喹啉的脱氢方法。然而，过渡金属（Ru、Co、Ni）等催化剂的使用存在化学毒性和高成本等潜在问题，导致这些合成方法缺少经济效益，不符合绿色化学的要求(R. Yamaguchi, C. Ikeda, Y. Takahashi, K.-I.Fujita, J. Am. Chem. Soc.2009, 131, 8410； J. Wu, D. Talwar, S. Johnston, M.Yan, J. Xiao, Angew. Chem. Int. Ed. 2013, 52, 6983; K.-I. Fujita, Y. Tanaka,M. Kobayashi, R. Yamaguchi, J. Am. Chem. Soc.2014, 136, 4829; M. G. Manas, L.S. Sharninghausen, E. Lin, R. H. Crabtree, J. Organomet. Chem. 2015, 792, 184; M. Kojima, M. Kanai, Angew. Chem. Int. Ed.2016, 55, 12224.)。因此，开发简单、高效，便捷、实惠，底物范围广的喹啉骨架的合成策略，依然是该领域的研究热点。而通过光催化反应，使用可回收的非金属硼氮碳催化剂在可见光下将四氢喹啉脱氢合成喹啉类化合物，这样的例子尚未见报道。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的目的在于提供一种喹啉类化合物的合成方法。以硼氮碳为光催化剂，将该催化剂用于有机合成中，反应过程操作简单，条件温和，催化效果好，转化率能达到90%以上，对于目标产物的产率可达95%。本发明工艺简单，成本低，符合实际生产需要，具有较大的应用潜力。
本发明目的通过以下技术方案实现。
一种喹啉类化合物的合成方法：以四氢喹啉类化合物：为原料，以硼氮碳为光催化剂，加入溶剂、氧化剂以及碱，在室温下可见光光照条件下反应，反应液经纯化后得到喹啉类化合物：；所述的R1和R2包括甲基、甲氧基和硝基中的一种；硼氮碳与四氢喹啉类化合物的质量比为0.2:1；所述的溶剂为乙醇或水；所述的氧化剂为双氧水、氧气或过硫酸钠；所述的碱为碳酸钾或氟化铯，碱的加入量为调控初始反应液pH值为8-10。
所述的硼氮碳化学式为h-BCNx，类石墨结构，比表面积为10-200 m2/g，吸收带边在400-600nm。
所述的硼氮碳的制备方法为：
（1）将前驱体葡萄糖、尿素以及硼酸研磨混合均匀；
（2）将步骤（1）得到的固体粉末在氨气气氛下1000~1200℃煅烧，得到硼氮碳。
所述的纯化为反应结束后用乙酸乙酯萃取，合并有机相，干燥，过滤，减压蒸去溶剂得粗产物，经柱层析提纯得到喹啉类化合物。
所述的柱层析提纯是以石油醚与乙酸乙酯的体积比为2~20:1的混合溶剂为洗脱液的柱层析提纯。
本发明的原理为：在可见光照下，以四氢喹啉为原料，在光催化剂、氧化剂及碱的共同作用下，经历两分子脱氢过程一锅法合成喹啉类化合物。
本发明的制备方法具有如下优点及有益效果：
（1）本发明的合成方法避免了强氧化剂以及贵重金属的使用，减少了其所带来的副产物，方法简单易行，条件温和，操作安全；
（2）本发明的合成方法无需加热，在室温可见光照下就能得到较高的收率，节能环保；
（3）本发明的合成方法原子经济性高，高化学值得氢气为唯一副产物，对功能团适应性好，对底物适应性广，环境友好，具有良好的工业应用前景。
图1 喹啉类化合物的合成路线图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
在反应器中，加入100mg 1,2,3,4-四氢喹啉，10mg硼氮碳光催化剂，3ml的乙醇及1.2当量的碳酸钾，室温下光照搅拌反应24h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压蒸去溶剂得粗产物，所用的柱层析洗脱液为体积比为5:1的石油醚:乙酸乙酯混合溶剂，产率89%。
本实施例所得产物的结构表征数据如下：1H NMR (400 MHz, CDCl3) δ = 8.95-8.83 (m, 1H), 8.10 (t, J=9.7, 2H), 7.76 (d, J=8.1, 1H), 7.68 (t, J=7.7, 1H),7.50 (t, J=7.5, 1H), 7.33 (dd, J=8.1, 4.1, 1H). 13C NMR (101 MHz, CDCl3) δ =150.37, 148.26, 135.99, 129.42, 129.41, 128.24, 127.76, 126.50, 121.03. IR(KBr, cm-1) ν 2361, 2159, 2028.
根据以上数据推断所得产物的结构如下所示：
。
实施例2
在反应器中，加入100mg底物7-硝基-1,2,3,4-四氢喹啉，10mg硼氮碳光催化剂，3ml的水及1.2当量的氟化铯，室温下光照搅拌反应24h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压蒸去溶剂得粗产物，所用的柱层析洗脱液为体积比为1:1的石油醚:乙酸乙酯混合溶剂，产率91%。
本实施例所得产物的结构表征数据如下：1H NMR (400 MHz, CDCl3) δ = 9.10(d, J=4.1, 1H), 9.02 (s, 1H), 8.40-8.24 (m, 2H), 8.00 (d, J=9.0, 1H), 7.62(dd, J=8.4, 4.2, 1H). 13C NMR (101 MHz, CDCl3) δ = 152.69, 148.08, 147.13,135.93, 131.37, 129.49, 125.82, 123.94, 120.09. IR (KBr, cm-1) ν1741, 1244,872, 788, 752, 695, 608.
根据以上数据推断所得产物的结构如下所示：
。
实施例3
在反应器中，加入100mg底物2-甲基-1,2,3,4-四氢喹啉，10mg硼氮碳光催化剂，3ml的乙醇及1.2当量的氟化铯，室温下光照搅拌反应24h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压蒸去溶剂得粗产物，所用的柱层析洗脱液为体积比为3:1的石油醚:乙酸乙酯混合溶剂，产率95%。
本实施例所得产物的结构表征数据如下：1H NMR (400 MHz, CDCl3) δ = 8.06(t, J=8.9, 2H), 7.79 (d, J=8.1, 1H), 7.70 (t, J=7.7, 1H), 7.50 (t, J=7.5,1H), 7.34-7.29 (m, 1H), 2.75 (d, J=20.6, 3H). 13C NMR (101 MHz, CDCl3) δ=158.99, 147.82, 136.21, 129.44, 128.57, 127.48, 126.49, 125.68, 122.01,25.35. IR (KBr, cm-1) ν 1743, 1601, 1505, 1252, 1220, 819, 782, 745.
根据以上数据推断所得产物的结构如下所示：
。
实施例4
在反应器中，加入100mg底物6,7-二甲氧基-1,2,3,4-四氢异喹啉，10mg硼氮碳光催化剂，3ml的乙醇及1.2当量的碳酸钾，室温下光照搅拌反应18h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压蒸去溶剂得粗产物，所用的柱层析洗脱液为体积比为3:1的石油醚:乙酸乙酯混合溶剂，产率82%。
本实施例所得产物的结构表征数据如下：1H NMR (400 MHz, CDCl3) δ = 9.05(s, 1H), 8.39 (d, J=5.6, 1H), 7.52 (d, J=5.6, 1H), 7.21 (s, 1H), 7.08 (s,1H), 4.05 (s, 6H). 13C NMR (101 MHz, CDCl3) δ = 153.04, 150.33, 149.86,141.85, 132.57, 124.75, 119.29, 105.30, 104.54, 56.11, 56.05. IR (KBr, cm-1) ν1505, 1479, 1416, 1249, 1208, 1141, 1003, 853, 756, 635.
根据以上数据推断所得产物的结构如下所示：
。
实施例5
在反应器中，加入100mg底物7-甲氧基-1,2,3,4-四氢喹啉，10mg硼氮碳光催化剂，3ml的乙醇及1.2当量的碳酸钾，室温下光照搅拌反应24h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压蒸去溶剂得粗产物，所用的柱层析洗脱液为体积比为3:1的石油醚:乙酸乙酯混合溶剂，产率89%。
本实施例所得产物的结构表征数据如下：1H NMR (400 MHz, CDCl3) δ = 8.86(dd, J=4.2, 1.6, 1H), 8.07 (d, J=8.2, 1H), 8.02 (d, J=8.5, 1H), 7.56 (dd, J=11.4, 2.9, 2H), 7.37 (dd, J=8.3, 4.2, 1H), 2.55 (s, 3H).13C NMR (101 MHz,CDCl3) δ = 149.50, 146.84, 136.40, 135.41, 131.76, 129.05, 128.32, 126.59,121.07, 21.58. IR (KBr, cm-1) ν 1622, 1595, 1500, 1378, 1323, 1226, 1162,1114, 1024, 831, 710.
根据以上数据推断所得产物的结构如下所示:
。
实施例6
在反应器中，加入100mg底物7-甲基1,2,3,4-四氢喹啉，10mg硼氮碳光催化剂，3ml的乙醇及1.2当量的碳酸钾，室温下光照搅拌反应18h，反应结束后用乙酸乙酯萃取，合并有机相干燥，过滤，减压蒸去溶剂得粗产物，所用的柱层析洗脱液为体积比为3:1的石油醚:乙酸乙酯混合溶剂，产率90%。
本实施例所得产物的结构表征数据如下：1H NMR (400 MHz, CDCl3) δ = 8.05(dd, J=8.4, 3.9, 2H), 7.78 (d, J=8.1, 1H), 7.69 (q, 1H), 7.49 (t, J=7.5, 1H),7.31 – 7.28 (m, 1H), 2.76 (s, 3H). 13C NMR (101 MHz, CDCl3) δ = 158.98,147.80, 136.21, 129.44, 128.55, 127.48, 126.48, 125.68, 122.01, 25.33. IR(KBr, cm-1) ν 1594, 1570, 1500, 1373, 1323, 1119, 827, 796, 764, 614.
根据以上数据推断所得产物的结构如下所示：
。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (6)
1.一种喹啉类化合物的合成方法，其特征在于：以四氢喹啉类化合物：为原料，以硼氮碳为光催化剂，加入溶剂、氧化剂以及碱，在室温下可见光光照条件下反应，反应液经纯化后得到喹啉类化合物：；所述的R1和R2包括甲基、甲氧基和硝基中的一种；所述的硼氮碳化学式为h-BCNx，类石墨结构，比表面积为10-200 m2/g，吸收带边在400-600nm。
2.根据权利要求1所述的喹啉类化合物的合成方法，其特征在于：所述的硼氮碳的制备方法为：
（1）将前驱体葡萄糖、尿素以及硼酸研磨混合均匀；
（2）将步骤（1）得到的固体粉末在氨气气氛下1000~1200℃煅烧，得到硼氮碳。
3.根据权利要求1所述的喹啉类化合物的合成方法，其特征在于：硼氮碳与四氢喹啉类化合物的质量比为0.2:1。
4.根据权利要求1所述的喹啉类化合物的合成方法，其特征在于：所述的溶剂为乙醇或水；所述的氧化剂为双氧水、氧气或过硫酸钠；所述的碱为碳酸钾或氟化铯，碱的加入量为调控初始反应液pH值为8-10。
5.根据权利要求1所述的喹啉类化合物的合成方法，其特征在于：所述的纯化为反应结束后用乙酸乙酯萃取，合并有机相，干燥，过滤，减压蒸去溶剂得粗产物，经柱层析提纯得到喹啉类化合物。
6.根据权利要求5所述的喹啉类化合物的合成方法，其特征在于：所述的柱层析提纯是以石油醚与乙酸乙酯的体积比为2~20:1的混合溶剂为洗脱液的柱层析提纯。
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