CN107353245A - A kind of synthetic method of quinolines - Google Patents
A kind of synthetic method of quinolines Download PDFInfo
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- CN107353245A CN107353245A CN201710732718.3A CN201710732718A CN107353245A CN 107353245 A CN107353245 A CN 107353245A CN 201710732718 A CN201710732718 A CN 201710732718A CN 107353245 A CN107353245 A CN 107353245A
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- Prior art keywords
- quinolines
- synthetic method
- nitrogen carbon
- boron nitrogen
- solvent
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- 229940111121 antirheumatic drug quinolines Drugs 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims abstract description 19
- 150000003248 quinolines Chemical class 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 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
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052796 boron Inorganic materials 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000004440 column chromatography Methods 0.000 claims description 12
- 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 10
- 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
- 230000006837 decompression Effects 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- -1 methoxyl group Chemical group 0.000 claims description 4
- 239000012074 organic phase Substances 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
- 239000007788 liquid Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 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
- 150000001875 compounds Chemical class 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
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 8
- 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
- 238000003756 stirring 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
- 230000015572 biosynthetic process Effects 0.000 description 4
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 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
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-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
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 229940081066 picolinic acid Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003530 tetrahydroquinolines Chemical class 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
-
- B01J35/39—
-
- 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
Abstract
The invention discloses a kind of synthetic method of quinolines, with Tetrahydroquinolinesas：For raw material, using boron nitrogen carbon as photochemical catalyst, solvent, oxidant and alkali are added, is reacted at room temperature under visible ray illumination condition, quinolines is obtained after reaction solution is purified；Boron nitrogen carbon (h‑BCNx) it is a kind of visible light-responded semi-conducting polymer photochemical catalyst without metallic element, have the advantages that cheap and easy to get, chemical stability is good, nontoxic and suitable energy gap and position of energy band, the catalyst is used in organic synthesis, course of reaction is simple to operate, mild condition, excellent catalytic effect, conversion ratio can reach more than 90%, for target product yield up to 95%.Present invention process is simple, and cost is low, meets needs of production, has larger application potential.
Description
Technical field
The invention belongs to photocatalysis technical field of organic synthesis, and in particular to a kind of synthesis side of quinolines
Method.
Background technology
Quinoline compound can be used to manufacture medicine and efficient pesticides, can be made into picolinic acid after oxidation, its derivative
Available for manufacture colour motion picture films and dyestuff.As synthetic drug, dyestuff, insecticide intermediate and GC stationary liquid, together
When be also a kind of natural products with bioactivity, while also by as market medicine either drug candidates be applied to malaria
Disease is treated.
Traditional Skraup synthetic methods are by aniline（Or other arylamine）, glycerine, sulfuric acid and nitrobenzene（Corresponding to virtue used
Amine）, diarsenic pentoxide（As2O5）Or the oxidant such as ferric trichloride or hydrogen acceptor one react, quinoline is generated.The synthetic method is
Synthesis of quinoline and its most important synthetic method of derivative (Z. H. Skraup,Ber.1880, 13, 2086.).In recent years, send out
Open up some precious metal catalysts and pass through thermocatalytic or the method for dehydrogenating of electro-catalysis tetrahydroquinoline.However, transition metal
（Ru、Co、Ni）The potential problems such as chemical toxicity and high cost be present in the use Deng catalyst, cause these synthetic methods lack through
Ji benefit, requirement (R. Yamaguchi, C. Ikeda, the Y. Takahashi, K.-I. of Green Chemistry are not met
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.).Therefore, exploitation letter
List, efficient, convenient, economical, the synthesis strategy of the wide chinoline backbone of substrate spectrum, it is still the study hotspot in the field.And lead to
Light-catalyzed reaction is crossed, using recyclable nonmetallic boron nitrogen C catalyst under visible light by tetrahydroquinoline dehydrogenation synthesis of quinoline class
Compound, there is not been reported for such example.
The content of the invention
In order to solve the shortcomings that above prior art and weak point, it is an object of the invention to provide a kind of quinolines
The synthetic method of compound.Using boron nitrogen carbon as photochemical catalyst, the catalyst is used in organic synthesis, course of reaction is simple to operate,
Mild condition, excellent catalytic effect, conversion ratio can reach more than 90%, for target product yield up to 95%.Present invention process
Simply, cost is low, meets needs of production, has larger application potential.
The object of the invention is achieved through the following technical solutions.
A kind of synthetic method of quinolines：With Tetrahydroquinolinesas：For raw material, with
Boron nitrogen carbon is photochemical catalyst, adds solvent, oxidant and alkali, is reacted at room temperature under visible ray illumination condition, reaction solution warp
Quinolines are obtained after purification：；Described R1And R2Including one kind in methyl, methoxyl group and nitro；
The mass ratio of boron nitrogen carbon and Tetrahydroquinolinesas is 0.2:1；Described solvent is ethanol or water；Described oxidant is double
Oxygen water, oxygen or sodium peroxydisulfate；Described alkali is potassium carbonate or cesium fluoride, and the addition of alkali is that regulation and control initial reaction liquid pH value is
8-10。
Described boron nitrogen carbon geochemistry formula is h-BCNx, graphite-like structure, specific surface area is 10-200 m2/ g, absorb band edge and exist
400-600nm。
The preparation method of described boron nitrogen carbon is：
（1）Presoma glucose, urea and boric acid ground and mixed is uniform；
（2）By step（1）1000 ~ 1200 DEG C of calcinings under ammonia atmosphere of obtained solid powder, obtain boron nitrogen carbon.
Described purifying is to be extracted with ethyl acetate after reaction terminates, and merges organic phase, dries, filtering, decompression boils off molten
Agent obtains crude product, purifies to obtain quinolines through column chromatography.
Described column chromatography purification is using the volume ratio of petroleum ether and ethyl acetate as 2 ~ 20:1 mixed solvent is elution
The column chromatography purification of liquid.
The present invention principle be：Under visible ray photograph, using tetrahydroquinoline as raw material, in photochemical catalyst, oxidant and alkali
Under collective effect, two molecule certain embodiments one pot process quinolines are undergone.
The preparation method of the present invention has the following advantages that and beneficial effect：
（1）The synthetic method of the present invention avoids the use of strong oxidizer and precious metal, reduces its caused by-product
Thing, method is simple and easy, mild condition, safe operation；
（2）The synthetic method of the present invention is without heating, with regard to that can obtain higher yield, energy-conserving and environment-protective under room temperature visible ray photograph；
（3）The synthetic method Atom economy of the present invention is high, and it is unique accessory substance that high chemical score, which obtains hydrogen, to functional group adaptability
It is good, it is environment-friendly to substrate wide adaptability, there is good prospects for commercial application.
The synthetic route chart of Fig. 1 quinolines.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
In the reactor, add the tetrahydroquinolines of 100mg 1,2,3,4-, 10mg boron nitrogen carbon photochemical catalysts, 3ml ethanol and 1.2 work as
The potassium carbonate of amount, at room temperature illumination stirring reaction 24h, reaction are extracted with ethyl acetate after terminating, and merge organic dry, mistake that is concerned with
Filter, decompression boil off solvent and obtain crude product, and column chromatography eluent used is that volume ratio is 5:1 petroleum ether:Ethyl acetate mixes
Solvent, yield 89%.
The structural characterization data of the present embodiment products therefrom are as follows：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.
Infer that the structure of products therefrom is as follows according to data above：
。
Embodiment 2
In the reactor, addition 100mg substrate 7- nitros -1,2,3,4- tetrahydroquinolines, 10mg boron nitrogen carbon photochemical catalysts, 3ml's
The cesium fluoride of water and 1.2 equivalents, at room temperature illumination stirring reaction 24h, reaction are extracted with ethyl acetate after terminating, and merge organic phase
Dry, filtering, decompression boils off solvent and obtains crude product, and column chromatography eluent used is that volume ratio is 1:1 petroleum ether:Acetic acid second
Ester mixed solvent, yield 91%.
The structural characterization data of the present embodiment products therefrom are as follows：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.
Infer that the structure of products therefrom is as follows according to data above：
。
Embodiment 3
In the reactor, addition 100mg substrate 2- methyl isophthalic acids, 2,3,4- tetrahydroquinolines, 10mg boron nitrogen carbon photochemical catalysts, 3ml's
The cesium fluoride of ethanol and 1.2 equivalents, at room temperature illumination stirring reaction 24h, reaction are extracted with ethyl acetate after terminating, merged organic
Mutually dry, filtering, decompression boils off solvent and obtains crude product, and column chromatography eluent used is that volume ratio is 3:1 petroleum ether:Acetic acid
Acetate mixed solvent, yield 95%.
The structural characterization data of the present embodiment products therefrom are as follows：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.
Infer that the structure of products therefrom is as follows according to data above：
。
Embodiment 4
In the reactor, 100mg substrates 6,7- dimethoxys -1,2,3,4- tetrahydroisoquinolines, 10mg boron nitrogen carbon photocatalysis are added
The potassium carbonate of agent, 3ml ethanol and 1.2 equivalents, at room temperature illumination stirring reaction 18h, reaction are extracted with ethyl acetate after terminating,
Merge organic relevant dry, filtering, decompression boils off solvent and obtains crude product, and column chromatography eluent used is that volume ratio is 3:1 stone
Oily ether:Ethyl acetate mixed solvent, yield 82%.
The structural characterization data of the present embodiment products therefrom are as follows：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) ν
1505, 1479, 1416, 1249, 1208, 1141, 1003, 853, 756, 635.
Infer that the structure of products therefrom is as follows according to data above：
。
Embodiment 5
In the reactor, 100mg substrate 7- methoxyl groups -1,2,3,4- tetrahydroquinolines, 10mg boron nitrogen carbon photochemical catalysts, 3ml are added
Ethanol and 1.2 equivalents potassium carbonate, illumination stirring reaction 24h at room temperature, reaction is extracted with ethyl acetate after terminating, is associated with
Machine is mutually dried, and filtering, decompression boils off solvent and obtains crude product, and column chromatography eluent used is that volume ratio is 3:1 petroleum ether:Second
Acetoacetic ester mixed solvent, yield 89%.
The structural characterization data of the present embodiment products therefrom are as follows：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.
Infer that the structure of products therefrom is as follows according to data above:
。
Embodiment 6
In the reactor, the tetrahydroquinoline of 100mg substrate 7- methyl 1,2,3,4-, 10mg boron nitrogen carbon photochemical catalysts, 3ml second are added
The potassium carbonate of alcohol and 1.2 equivalents, at room temperature illumination stirring reaction 18h, reaction are extracted with ethyl acetate after terminating, and merge organic phase
Dry, filtering, decompression boils off solvent and obtains crude product, and column chromatography eluent used is that volume ratio is 3:1 petroleum ether:Acetic acid second
Ester mixed solvent, yield 90%.
The structural characterization data of the present embodiment products therefrom are as follows：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.
Infer that the structure of products therefrom is as follows according to data above：
。
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
- A kind of 1. synthetic method of quinolines, it is characterised in that：With Tetrahydroquinolinesas：For Raw material, using boron nitrogen carbon as photochemical catalyst, solvent, oxidant and alkali are added, is reacted at room temperature under visible ray illumination condition, instead Quinolines are obtained after answering liquid purified：；Described R1And R2Including in methyl, methoxyl group and nitro One kind.
- 2. the synthetic method of quinolines according to claim 1, it is characterised in that：Described boron nitrogen carbon geochemistry formula For h-BCNx, graphite-like structure, specific surface area is 10-200 m2/ g, band edge is absorbed in 400-600nm.
- 3. the synthetic method of quinolines according to claim 1, it is characterised in that：The preparation of described boron nitrogen carbon Method is：（1）Presoma glucose, urea and boric acid ground and mixed is uniform；（2）By step（1）1000 ~ 1200 DEG C of calcinings under ammonia atmosphere of obtained solid powder, obtain boron nitrogen carbon.
- 4. the synthetic method of quinolines according to claim 1, it is characterised in that：Boron nitrogen carbon and tetrahydro chinolines The mass ratio of compound is 0.2:1.
- 5. the synthetic method of quinolines according to claim 1, it is characterised in that：Described solvent be ethanol or Water；Described oxidant is hydrogen peroxide, oxygen or sodium peroxydisulfate；Described alkali is potassium carbonate or cesium fluoride, and the addition of alkali is It is 8-10 to regulate and control initial reaction liquid pH value.
- 6. the synthetic method of quinolines according to claim 1, it is characterised in that：Described purifying is tied for reaction It is extracted with ethyl acetate after beam, merges organic phase, dried, filtering, decompression boils off solvent and obtains crude product, purifies to obtain through column chromatography Quinolines.
- 7. the synthetic method of quinolines according to claim 6, it is characterised in that：Described column chromatography purifies Using the volume ratio of petroleum ether and ethyl acetate as 2 ~ 20:1 mixed solvent purifies for the column chromatography of eluent.
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| CN108017579A (en) * | 2017-11-22 | 2018-05-11 | 河南大学 | A kind of method of visible ray concerted catalysis Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound |
| CN108440236A (en) * | 2018-05-09 | 2018-08-24 | 福州大学 | A method of utilizing conductor photocatalysis hydrogenating reduction organohalogen compounds |
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| CN106831563A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of method that carbon-nitrogen material catalysis nitrogen heterocyclic ring oxidative dehydrogenation prepares quinoline |
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| CN103721737A (en) * | 2014-01-07 | 2014-04-16 | 福州大学 | Non-metallic material for driving photocatalytic decomposition of water by using efficient visible light |
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| CN108017579A (en) * | 2017-11-22 | 2018-05-11 | 河南大学 | A kind of method of visible ray concerted catalysis Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound |
| CN108017579B (en) * | 2017-11-22 | 2021-01-29 | 河南大学 | Method for synthesizing quinoline compound by oxidative dehydrogenation of tetrahydroquinoline compound under synergistic catalysis of visible light |
| CN108440236A (en) * | 2018-05-09 | 2018-08-24 | 福州大学 | A method of utilizing conductor photocatalysis hydrogenating reduction organohalogen compounds |
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