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CN105753838A - Novel high-regioselectivity amination method of quinoline derivatives - Google Patents

Novel high-regioselectivity amination method of quinoline derivatives Download PDF

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CN105753838A
CN105753838A CN201610086051.XA CN201610086051A CN105753838A CN 105753838 A CN105753838 A CN 105753838A CN 201610086051 A CN201610086051 A CN 201610086051A CN 105753838 A CN105753838 A CN 105753838A
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quinoline
copper
gram
compound
times amount
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孙凯
王薪
赵丰
吕允贺
李刚
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Anyang Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明属于有机合成化学技术领域，发明了一种金属盐催化喹啉衍生物与多种氮源生成2?胺基喹啉衍生物的新方法。本发明克服了目前已经报道的喹啉胺化需要提前活化的卤代喹啉或者氧化喹啉作为反应前体的限制，高区域选择性的实现了喹啉C2位的胺化反应。本发明所实现的胺化反应具有步骤简洁，操作简单，原料、试剂和催化剂易得等特点，适用于合成各种2?胺基喹啉衍生物，并且适用于大规模的工业生产。The invention belongs to the technical field of organic synthesis chemistry, and discloses a new method for producing 2?aminoquinoline derivatives from quinoline derivatives catalyzed by metal salts and various nitrogen sources. The present invention overcomes the restriction that quinoline amination needs to be activated in advance as a reaction precursor, and realizes the amination reaction of quinoline at the C2 position with high regioselectivity. The amination reaction realized by the present invention has the characteristics of simple steps, simple operation, easy availability of raw materials, reagents and catalysts, etc., and is suitable for synthesizing various 2?aminoquinoline derivatives and for large-scale industrial production.

Description

Quinoline high regioselectivity amination new method
Technical field:
The invention belongs to technical field of organic synthetic chemistry, invent a kind of method that metal salt catalyst quinoline generates 2-amido quinoline with multiple nitrogen source.
Background technology:
Nitrogen-containing heterocycle compound is widely present in the middle of natural products and drug molecule, and play an important role in terms of medicine and pesticide synthesis ((a) Hili, R.；Yudin, A.K.Nat.Chem.Biol., 2006,2,284. (b) Ricci, A.Amino Group Chemistry:From Synthesis to the Life Sciences, lst ed.；Wiley-VCH:Weinheim, 2007).Wherein, many quinoline heterocyclic compounds have antibacterial, anti-inflammatory analgesic, the pharmacologically active such as antitumor and antiviral, by more concern in drug research, synthesized in a large number by chemist and studied ((a) Michael, J.P.Nat.Prod.Rep., 2008,25,166. (b) Solomon, V.R.；Lee, H.Curr.Med.Chem., 2011,18,1488).Quinoline containing 2-amido quinoline molecular skeleton is proved to have all multiple biologically actives, such as: resists disease, antibacterial, protease inhibitors, anti-induced mutation activity, the most also finds that some are antitumor, anticancer (Yamato, M.；Takeuchi, Y.J.Med.Chem., 1989,32,1295), oxidation resistant character (Korrichi, L.；Dalila, B.；Dalila, S.European J.of Bio.Sci., 2009,1,32.).Therefore, development environmental protection, the method particular importance of new and effective nitrogenous quinoline.
Synthesis 2-amido quinoline needs complex precursor before this, and reactions steps is loaded down with trivial details, and transformation efficiency is low, and accessory substance is more, and the most this method also faces the puzzlement that substrate spectrum is the most wide in range.((a) Toma, G.；Fujita, K.；Yamaguchi, R.Eur.J.Org.Chem., 2009,27,4586. (b) Fan, X.H.；Li, G.；Yang, L.M.J.Org.Chem., 2011,696,2482. (c) Appukkuttan, P.；Van der Eycken, E.Eur.J.Org.Chem., 2008,7,1133. (d) Poola, B.；Choung, W.；Nantz, M.H.Tetrahedron., 2008,64,10798).((a) Li, C.-J.Acc.Chem.Res., 2009,42,335. (b) Li Z. is developed rapidly along with in recent years intersect dehydrogenation coupling strategies；Li, C.-J.J.Am.Chem.Soc., 2005,127,3672), utilize simple raw material, experience shorter synthetic route and higher atom utilization ratio, the organic molecule of series of complex can be synthesized.Such as: utilize quinoline N-O activation strategy, series 2-amido quinoline can be synthesized by intersection dehydrogenation coupling, but this approach faces problem ((a) Li, the G. that substrate needs to prepare in advance equally；Jia, C.-Q.；Sun, K.Org.Lett., 2013,15,5198. (b) Zhu, C.-W.；Yi, M.-L.；Wei, D.-F.；Chen, X.；Wu, Y.-J.；Cui, X.-L.Org.Lett., 2014,16,1840).Therefore, utilizing the catalyst system and catalyzing of novel and high-efficiency, the method that 2-amido quinoline is prepared in development is of crucial importance.
Documents:
1. publication number: CN1213048C title: a kind of heterocyclic compound-2-amido imidazo pyrroles's-6-ketone and preparation method thereof and purposes
2. the patent No.: CN1890213 title: the method preparing the substituted heterocyclic compound of N-amino
3. Li, Gang et al.Copper-Catalyzed Intermolecular Dehydrogenative Amidation/Amination of Quinoline N-oxides with Lactams/Cyclamines<<Organic Letter>>2013,15 (20), pp 5198-201.
Summary of the invention:
Instant invention overcomes at present it has been reported that quinoline aminating reaction need the halogenated quinoline activated in advance or oxidation quinoline as the restriction of reacting precursor, utilize metal salt catalyst, be prepared for high regioselectivity serial 2-amido quinoline.
Its reaction equation is as follows:
In figure, compound 1 can be quinoline, isoquinolin, quinoxaline, quinazoline, 3-methylquinoline, 3-chloroquinoline, 4-methylquinoline, 4-fluorine quinoline, 4-bromoquinoline, 5-methoxy quinoline, 5-nitroquinoline, 6-fluorine quinoline, 6-bromoquinoline, 6-nitroquinoline, 7-methylquinoline, 8-methylquinoline, 8-methoxy quinoline, 8-fluorine quinoline, 8-chloroquinoline, 8-bromoquinoline, 8-nitroquinoline, 5-bromo-isoquinoline etc..Compound 2 can be saccharin and derivative, BTA, 1,2,4-triazoles, pyrazoles, benzopyrazoles, imidazoles, purine, 6-chloropurine etc..In reaction condition, slaine is the various salt compounds of copper, palladium, ruthenium, such as: copper acetate, copper sulphate, copper trifluoromethanesulfcomposite, bifluoride copper, stannous chloride, cuprous bromide, palladium, palladium trifluoroacetate, ruthenium trichloride, ruthenous chloride；Oxidant is selectfluor；Solvent is nitromethane (CH3NO2), nitroethane (C2H5NO2), dichloroethanes (DCE).
Technical solution of the present invention is as follows:
With quinoline, isoquinolin, quinoxaline and derivative thereof as raw material；In reaction, nitrogen source used is BTA, 1,2,4-triazoles, pyrazoles, benzopyrazoles, imidazoles, purine, 6-chloropurine, saccharin and derivative thereof etc.；Catalyst is copper acetate, copper sulphate, copper trifluoromethanesulfcomposite, bifluoride copper, stannous chloride, cuprous bromide, palladium, palladium trifluoroacetate, ruthenium trichloride, ruthenous chloride；Oxidant is selectfluor.To organic solvent nitromethane (CH3NO2), nitroethane (C2H5NO2) or dichloroethanes (DCE) 3.0～5.0 milliliters in add 1.0 mMs of above-mentioned heterocyclic compounds and 1.0 mMs of nitrogen sources.Add above-mentioned 0.1 mM of metallic catalyst, 2.0 mMs of oxidants finish, oil bath 120 degrees Celsius, stir 5～12 hours, post-treated isolated 2-amido quinoline compound, productivity depending on differential responses between 69%～94% (above quantity can scale up).Refer to the embodiment in detailed description of the invention.
Figure of description
Fig. 1 to Fig. 6 is representative 2-amido quinoline1H NMR spectra
Detailed description of the invention
Embodiment 1:
In 50 milliliters of round-bottomed flasks, add 0.1290 (1.0 mMs) quinoline, 0.1190 gram of (1.0 mMs) BTA, 0.0182 gram of (0.1 mM) copper acetate, 0.7080 gram of (2.0 mMs) selectfluor, 0.2764 gram of (2.0 mMs) potassium carbonate, 6.0 milliliters of nitromethane (CH3NO2), heat 120 DEG C, react 3 hours to quinoline reaction completely (thin-layer chromatography TLC monitoring).Reactant mixture is poured in 20 milliliters of water, extracts (10 milliliters × 3) with ethyl acetate.Merge organic phase, be dried with anhydrous sodium sulfate.After solvent is evaporated off, it is 0.2190 gram that residue separate (eluent: petrol ether/ethyl acetate=6/1) to obtain white solid through silica gel column chromatography, productivity 89%.Reaction sees below formula:
Know figure well and resolve data
White solid.Mp:137-139 DEG C.1H NMR(400MHz；CDCl3): δ=7.50-7.66 (m, 2H), 7.66 (d, J=7.2Hz, 1H), 7.77 (d, J=6.8Hz, 1H), 7.87 (d, J=8.4Hz, 1H), 8.15 (d, J=8.8Hz, 2H), 8.35 (d, J=8.8Hz, 1H), 8.47 (d, J=9.2Hz, 1H), 8.95 (d, J=8.4Hz, 1H).
Embodiment 2:
In 50 milliliters of round-bottomed flasks, add 0.1290 (1.0 mMs) isoquinolin, 0.1190 gram of (1.0 mMs) BTA, 0.0182 gram of (0.1 mM) copper acetate, 0.7080 gram of (2.0 mMs) selectfluor, 0.2764 gram of (2.0 mMs) potassium carbonate, 6.0 milliliters of nitromethane (CH3NO2), heat 120 DEG C, react 3 hours to quinoline reaction completely (thin-layer chromatography TLC monitoring).Reactant mixture is poured in 20 milliliters of water, extracts (10 milliliters × 3) with ethyl acetate.Merge organic phase, be dried with anhydrous sodium sulfate.After solvent is evaporated off, it is 0.2229 gram that residue separate (eluent: petrol ether/ethyl acetate=6/1) to obtain white solid through silica gel column chromatography, productivity 91%.Reaction sees below formula:
Know figure well and resolve data
White solid.Mp:126-127 DEG C.1H NMR(400MHz；CDCl3): δ=7.59 (d, J=7.6Hz, 1H), 7.64 (d, J=8.4Hz, 2H), 7.80 (d, J=7.2Hz, 1H), 8.01 (d, J=8.4Hz, 1H), 8.08 (d, J=8.0Hz, 1H), 8.16 (d, J=8.4Hz, 1H), 8.62 (s, 1H), 8.70 (d, J=8.4Hz, 1H), 9.32 (s, 1H).
Embodiment 3
In 50 milliliters of round-bottomed flasks, add 0.1310 (1.0 mMs) quinoxaline, 0.1190 gram of (1.0 mMs) BTA, 0.0182 gram of (0.1 mM) copper acetate, 0.7080 gram of (2.0 mMs) selectfluor, 0.2764 gram of (2.0 mMs) potassium carbonate, 6.0 milliliters of nitromethane (CH3NO2), heat 120 DEG C, react 3 hours to quinoline reaction completely (thin-layer chromatography TLC monitoring).Reactant mixture is poured in 20 milliliters of water, extracts (10 milliliters × 3) with ethyl acetate.Merge organic phase, be dried with anhydrous sodium sulfate.After solvent is evaporated off, it is 0.2606 gram that residue separate (eluent: petrol ether/ethyl acetate=6/1) to obtain white solid through silica gel column chromatography, productivity 73%.Reaction sees below formula:
Spectrum elucidation data
White solid.Mp:154-155 DEG C.1H NMR(400MHz；CDCl3): δ=7.57 (d, J=7.6Hz, 1H), 7.82-7.88 (m, 3H), 7.20-7.23 (m, 3H), 8.87 (d, J=8.4Hz, 1H), 10.00 (s, 1H).
Embodiment 4
In 50 milliliters of round-bottomed flasks, add 0.1290 (1.0 mMs) isoquinolin, 0.1190 gram of (1.0 mMs) BTA, 0.0182 gram of (0.1 mM) copper acetate, 0.7080 gram of (2.0 mMs) selectfluor, 0.2764 gram of (2.0 mMs) potassium carbonate, 6.0 milliliters of nitromethane (CH3NO2), heat 120 DEG C, react 3 hours to quinoline reaction completely (thin-layer chromatography TLC monitoring).Reactant mixture is poured in 20 milliliters of water, extracts (10 milliliters × 3) with ethyl acetate.Merge organic phase, be dried with anhydrous sodium sulfate.After solvent is evaporated off, it is 0.1385 gram that residue separate (eluent: petrol ether/ethyl acetate=6/1) to obtain white solid through silica gel column chromatography, productivity 71%.Reaction sees below formula:
Spectrum elucidation data
White solid.Mp:138-139 DEG C.1H NMR(400MHz；CDCl3): δ=6.53 (d, J=1.6Hz, 1H), 7.52 (d, J=7.2Hz, 1H), 7.71 (d, J=8.4Hz, 1H), 7.82 (d, J=8.4Hz, 2H), 8.02 (d, J=8.4Hz, 1H), 8.24 (d, J=10.8Hz, 2H), 8.81 (d, J=2.0Hz, 1H).
Embodiment 5:
In 50 milliliters of round-bottomed flasks, add 0.1290 (1.0 mMs) isoquinolin, 0.1190 gram of (1.0 mMs) BTA, 0.0182 gram of (0.1 mM) copper acetate, 0.7080 gram of (2.0 mMs) selectfluor, 0.2764 gram of (2.0 mMs) potassium carbonate, 6.0 milliliters of nitromethane (CH3NO2), heat 120 DEG C, react 3 hours to quinoline reaction completely (thin-layer chromatography TLC monitoring).Reactant mixture is poured in 20 milliliters of water, extracts (10 milliliters × 3) with ethyl acetate.Merge organic phase, be dried with anhydrous sodium sulfate.After solvent is evaporated off, it is 0.1695 gram that residue separate (eluent: petrol ether/ethyl acetate=6/1) to obtain white solid through silica gel column chromatography, productivity 74%.Reaction sees below formula:
Spectrum elucidation data
White solid；Mp:133-134 DEG C.1H NMR(400MHz；CDCl3): δ=7.54 (t, J=7.2Hz, 1H), 7.71-7.86 (m, 3H), 8.00 (d, J=8.4Hz, 1H), 8.16 (d, J=8.8Hz, 1H), 8.29 (d, J=8.4Hz, 1H), 8.79 (s, 1H).
Embodiment 6:
In 50 milliliters of round-bottomed flasks, add 0.1290 (1.0 mMs) isoquinolin, 0.1190 gram of (1.0 mMs) BTA, 0.0182 gram of (0.1 mM) copper acetate, 0.7080 gram of (2.0 mMs) selectfluor, 0.2764 gram of (2.0 mMs) potassium carbonate, 6.0 milliliters of nitromethane (CH3NO2), heat 120 DEG C, react 3 hours to quinoline reaction completely (thin-layer chromatography TLC monitoring).Reactant mixture is poured in 20 milliliters of water, extracts (10 milliliters × 3) with ethyl acetate.Merge organic phase, be dried with anhydrous sodium sulfate.After solvent is evaporated off, it is 0.1985 gram that residue separate (eluent: petrol ether/ethyl acetate=6/1) to obtain white solid through silica gel column chromatography, productivity 81%.Reaction sees below formula:
Spectrum elucidation data
White solid；Mp:105-107 DEG C.1H NMR(400MHz；CDCl3): δ=7.41-7.46 (m, 2H), 7.61 (d, J=7.2Hz, 1H), 7.72-7.83 (m, 4H), 7.91 (t, J=4.4Hz, 1H), 8.15 (d, J=8.4Hz, 2H), 8.40 (q, J=8.4Hz, 1H).

Claims (6)

1. metal salt catalyst quinoline and a multiple nitrogen source high regioselectivity C2 amination method, its feature comprises the following steps: First in the pressure pipe of organic solvent, add 1.0 times amount quinolines, then in above-mentioned solution, add 1.0 times amount nitrogen sources respectively, The catalyst of 0.1 times amount, the oxidant of 2.0 times amount, the alkali of 2.0 times amount, the pressure mouth of pipe is closed, oil bath 120 degrees Celsius, stir Mix 5～12 hours to reacting complete, ethyl acetate or dichloromethane extraction, be dried, column chromatography, isolated 2-amido quinoline Compound.
2. in figure, compound 1 can be quinoline, isoquinolin, quinoxaline, quinazoline, 3-methylquinoline, 3-chloroquinoline, 4-first Base quinoline, 4-fluorine quinoline, 4-bromoquinoline, 5-methoxy quinoline, 5-nitroquinoline, 6-fluorine quinoline, 6-bromoquinoline, 6-nitro quinoline Quinoline, 7-methylquinoline, 8-methylquinoline, 8-methoxy quinoline, 8-fluorine quinoline, 8-chloroquinoline, 8-bromoquinoline, 8-nitroquinoline, 5-bromo-isoquinoline etc..Compound 2 can be saccharin and derivative, BTA, 1,2,4-triazoles, pyrazoles, benzo pyrrole Azoles, imidazoles, purine, 6-chloropurine etc..
3. the slaine in claim 1 is the various salt compounds of copper, palladium, ruthenium, such as: copper acetate, copper sulphate, fluoroform sulphur Acid copper, bifluoride copper, stannous chloride, cuprous bromide, palladium, palladium trifluoroacetate, ruthenium trichloride, ruthenous chloride.Catalysis Agent is 0.1～0.2: 1 with the amount ratio of heterocyclic compound in claim 1.
4. in claim 1, oxidant is selectfluor, and oxidant is 1.1～2: 1 with the amount ratio of heterocyclic compound in claim 1.
5. in claim 1, solvent is nitromethane (CH3NO2), nitroethane (C2H5NO2), dichloroethanes (DCE).
6. in claim 1, temperature controls at 120 DEG C.
CN201610086051.XA 2016-02-11 2016-02-11 Novel high-regioselectivity amination method of quinoline derivatives Pending CN105753838A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110156760A (en) * 2019-05-17 2019-08-23 济南大学 A kind of preparation method of 4-(1,4-dioxan-2-yl)quinoline-2-carboxylic acid methyl ester derivative

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110156760A (en) * 2019-05-17 2019-08-23 济南大学 A kind of preparation method of 4-(1,4-dioxan-2-yl)quinoline-2-carboxylic acid methyl ester derivative
CN110156760B (en) * 2019-05-17 2022-09-30 济南大学 Preparation method of 4- (1, 4-dioxane-2-yl) quinoline-2-methyl formate derivative

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