CN106432072B - A kind of preparation method replacing 1,2,3,4- tetrahydroquinoline - Google Patents
A kind of preparation method replacing 1,2,3,4- tetrahydroquinoline Download PDFInfo
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- CN106432072B CN106432072B CN201610844274.8A CN201610844274A CN106432072B CN 106432072 B CN106432072 B CN 106432072B CN 201610844274 A CN201610844274 A CN 201610844274A CN 106432072 B CN106432072 B CN 106432072B
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- 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
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- 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
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Abstract
The invention belongs to medicine and native compound chemical intermediate and related chemistry technical fields, are related to a kind of preparation method for replacing 1,2,3,4- tetrahydroquinolines.The present invention is using quinoline and its derivates as raw material, nanoporous palladium catalyst is catalyst, hydrogen is hydrogen source, and selective hydrogenation prepares 1,2,3,4- tetrahydroquinolines, and wherein the pressure of hydrogen is 0.1~20.0MPa；The molar concentration of quinoline and its derivates in a solvent is 0.01~2mmol/mL.For used catalyst pores skeleton size between 1nm~50nm, quinoline and its derivates and used catalyst molar ratio are 1:0.01~1:0.5.The beneficial effects of the invention are as follows selectivity of product height, as mild as a dove, operation and post-processing are simple, catalyst favorable reproducibility for reaction condition, and reuse multiple catalytic effect and be not substantially reduced, and realize that industrialization provides possibility for it.
Description
Technical field
The invention belongs to medicine and native compound chemical intermediate and related chemistry technical fields, are related to a kind of substitution 1,
The preparation method of 2,3,4- tetrahydroquinoline.
Background technique
Quinoline selective reduction is that 1,2,3,4- tetrahydroquinoline (py-THQ) is a critically important step in organic synthesis
Suddenly, (such as bioactive molecule, natural products and other are important especially in some important high value compound synthesis
The industrial materials of natural products), the synthesis of high-purity py-THQ is committed step.
Tradition is broadly divided into two major classes by the catalyst that quinoline selective reduction prepares py-THQ, first is that by Ru, Rh, Ir with
And the homogeneous catalyst of other transition metal and ligand binding, such catalyst have a high activity and highly selective, however these
Catalyst has the shortcomings that expensive, difficult separation and recycling, not reproducible use [ROSALES M, VALLEJO R, SOTO J
J,et al.Catal.Lett.2006,106,101–105.；DOBEREINER G E,NOVA A,SCHLEY N D,
CRABTREE R H,et al.J.Am.Chem.Soc.2011,133,7547–7562.；WANG T L,ZHUO L G,LI Z
W,CHAN A S C,et al.J.Am.Chem.Soc.2011,133,9878–9891.]；It heterogeneous is urged second is that research is more
Agent, such catalyst include load Ru, Pd-BT-CF and Au/HAS-TiO2Deng, but generally existing temperature is higher, hydrogen pressure
The disadvantages of power is higher, and regioselectivity is poor limits industrial applications.In addition, quinoline and its reduzate are in heterogeneous catalysis
Strong absorption in agent also affects catalytic activity and selectivity [MAO H, CHEN C, LIAO X P, SHI
B.J.Mol.Catal.A:Chem.2011,341,51-56；REN D,HE L,YU L,DING R S,CAO Y,et
al.J.Am.Chem.Soc.2012,134,17592–17598；ZHANG L,WANG X Y,XUE Y,LI R X,WANG S L,
et al.Catal.Sci.Technol.2014,4,1939–1948].Nano porous palladium material is that a kind of novel nano structure is urged
Agent is made of the pore of nanoscale and ligament, is had great specific surface area compared with most metals, excellent is led
Conductance heat and nontoxic performance can express physicochemical properties entirely different with reguline metal, catalyticing research field by
To extensive concern.Nanoporous palladium catalyst (PdNPore) has many advantages, such as that catalytic activity is high, stablizes, it is convenient to recycle
[TANAKA S,KANEKO T,ASAO N,YAMAMOTO Y,CHEN M-W,ZHANG W,INOUE A.Chem.Commun.,
2011,47,5985-5987；KANEKO T,TANAKA S,ASAO N,YAMAMOTO Y,et al.Adv.Synth.Catal.,
2011,353,2927–2932.]。
Summary of the invention
The present invention provides it is a kind of replace py-THQ preparation method, this method reaction condition as mild as a dove, regional choice
Property reach 100%, the advantages that selected catalyst is active high, stability is good, recycling repeatedly has not yet to see catalytic activity
It is substantially reduced.
The present invention is using quinoline and its derivates as raw material, and nanoporous palladium catalyst (PdNPore) is catalyst, hydrogen
For hydrogen source, selective hydrogenation preparation replaces py-THQ, and synthetic route is as follows:
Reaction temperature is -50 DEG C~150 DEG C, and the reaction time is 12h~36h；
R1Selected from one of hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R2Selected from one of hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R1With R2It is identical or different；
Wherein, used catalyst is nanoporous palladium catalyst (PdNPore), and hole on framework size is 1nm~50nm
Between, quinoline and its derivates and used catalyst molar ratio are 1:0.01~0.5.
The pressure of hydrogen is 0.1~20.0MPa.
The molar concentration of quinoline and its derivates in a solvent is 0.01~2mmol/mL.
Solvent be ether, acetonitrile, dimethyl sulfoxide, dioxane, triethylamine, tetrahydrofuran, toluene, ethyl alcohol, isopropanol,
The mixing of one or more of chloroform, methylene chloride, acetone, N,N-dimethylformamide, water.
Separation method includes: recrystallization, column chromatography etc..The solvent that recrystallization method uses such as, chloroform, hexamethylene, dioxy
Six rings, benzene, toluene, ethyl alcohol, petroleum ether, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate；With column chromatography side
Silica gel or alkali alumina can be used as stationary phase in method, and solvent is generally polarity and nonpolar mixed solvent, such as second
Acetoacetic ester-petroleum ether, ethyl acetate-hexane, dichloromethane-petroleum ether, methanol-petroleum ether.
The beneficial effects of the invention are as follows the conditions of the reaction as mild as a dove, and selectivity of product is high, and operation and post-processing are simple,
Catalyst favorable reproducibility, and reuse multiple catalytic effect and be not substantially reduced, realize that industrialization provides possibility for it.
Detailed description of the invention
Fig. 1 is 2- methyl-1 in embodiment 1,2,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 2 is 3- methyl-1 in embodiment 3,4,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 3 is 8- methyl-1 in embodiment 5,6,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 4 is 6- chloro- 1 in embodiment 7,8,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 5 is 1,2,3,4- tetrahydroquinolines in embodiment 9,101H nuclear magnetic spectrogram.
Specific embodiment
The preparation method of the present invention for replacing py-THQ, highest selectivity and reaction yield respectively reach 100% He
95%, select catalyst to react favorable reproducibility, operation and post-processing are simple, and it is not bright to reuse multiple catalytic effect
It is aobvious to reduce, advantage is provided for its industrialized production.
Present invention will be further explained below with reference to specific examples.Technical staff in the art is the present invention
Simple replacement or improvement belong within the technical solution protected of the present invention.
Embodiment 1:2- methyl-1, the synthesis of 2,3,4- tetrahydroquinoline
Into dioxane (5mL) solvent added with PdNPore (2.7mg, 5mol%) catalyst, substrate 2- methyl is added
Quinoline (71.6mg, 0.5mmol), hydrogen (8bar), are placed on magnetic stirring apparatus and react 16h at 80 DEG C, column chromatography (silica gel,
200-300 mesh；Solvent, petroleum ether, ethyl acetate) obtain 2- methyl-1,2,3,4- tetrahydroquinoline 58.89mg, yield 80%.
2- methyl-1,2,3,4- tetrahydroquinoline
1H NMR(400MHz,CDCl3) δ 6.98-6.92 (m, 2H), 6.62-6.55 (m, 1H), 6.45 (d, J=8.4Hz,
1H),3.66(br,1H),3.45-3.30(m,1H),2.89-2.65(m,2H),1.95-1.87(m,1H),1.63-1.50(m,
1H), 1.19 (d, J=6Hz, 3H)
Embodiment 2:2- methyl-1, the synthesis of 2,3,4- tetrahydroquinoline
Into n,N-Dimethylformamide (3mL) solvent added with PdNPore (5.4mg, 10mol%) catalyst, it is added
Substrate 2- methylquinoline (42.96mg, 0.3mmol), hydrogen (5bar), are placed on magnetic stirring apparatus and react 20h at 30 DEG C, column layer
Analyse (silica gel, 200-300 mesh；Solvent, petroleum ether, ethyl acetate) obtain 2- methyl-1,2,3,4- tetrahydroquinoline 30.92mg,
Yield 70%.
2- methyl-1,2,3,4- tetrahydroquinoline
1H NMR(400MHz,CDCl3) δ 6.98-6.92 (m, 2H), 6.62-6.55 (m, 1H), 6.45 (d, J=8.4Hz,
1H),3.66(br,1H),3.45-3.30(m,1H),2.89-2.65(m,2H),1.95-1.87(m,1H),1.63-1.50(m,
1H), 1.19 (d, J=6Hz, 3H)
Embodiment 3:3- methyl-1, the synthesis of 2,3,4- tetrahydroquinoline
Into ethyl alcohol (2mL) solvent added with PdNPore (3.2mg, 6mol%) catalyst, substrate 3- methylquinoline is added
(71.6mg, 0.5mmol), hydrogen (3bar), is placed on magnetic stirring apparatus and reacts 12h at 60 DEG C, and column chromatographs (silica gel, 200-300
Mesh；Solvent, petroleum ether, ethyl acetate) obtain 3- methyl-1,2,3,4- tetrahydroquinoline 47.85mg, yield 65%.
3- methyl-1,2,3,4- tetrahydroquinoline
1H NMR(CDCl3, 400MHz) and δ: 6.98-6.91 (m, 2H), 6.59 (t, J=7.2Hz, 1H), 6.45 (d, J=
8Hz, 1H), 3.77 (br, 1H), 3.23-3.21 (m, 1H), 2.87 (t, J=10.8Hz, 2H), 2.79-2.73 (m, 1H),
2.45-2.37 (m, 1H), 2.08-2.0 (m, 1H), 1.03 (d, J=6.4Hz, 3H)
Embodiment 4:3- methyl-1, the synthesis of 2,3,4- tetrahydroquinoline
Into acetonitrile (5mL) solvent added with PdNPore (1.1mg, 2mol%) catalyst, substrate 3- methylquinoline is added
(71.6mg, 0.5mmol), hydrogen (5bar), is placed on magnetic stirring apparatus and reacts for 24 hours at 50 DEG C, and column chromatographs (silica gel, 200-300
Mesh；Solvent, petroleum ether, ethyl acetate) obtain 3- methyl-1,2,3,4- tetrahydroquinoline 61.1mg, yield 83%.
3- methyl-1,2,3,4- tetrahydroquinoline
1H NMR(CDCl3, 400MHz) and δ: 6.98-6.91 (m, 2H), 6.59 (t, J=7.2Hz, 1H), 6.45 (d, J=
8Hz, 1H), 3.77 (br, 1H), 3.23-3.21 (m, 1H), 2.87 (t, J=10.8Hz, 2H), 2.79-2.73 (m, 1H),
2.45-2.37 (m, 1H), 2.08-2.0 (m, 1H), 1.03 (d, J=6.4Hz, 3H)
Embodiment 5:8- methyl-1, the synthesis of 2,3,4- tetrahydroquinoline
Into triethylamine (6mL) solvent added with PdNPore (1.6mg, 3mol%) catalyst, substrate 8- methyl quinoline is added
Quinoline (143.19mg, 1mmol), hydrogen (2bar), are placed on magnetic stirring apparatus and react 15h at 50 DEG C, and column chromatographs (silica gel, 200-
300 mesh；Solvent, petroleum ether, ethyl acetate) obtain 8- methyl-1,2,3,4- tetrahydroquinoline 104.53mg, yield 71%.
8- methyl-1,2,3,4- tetrahydroquinoline
1H NMR(400MHz,CDCl3) δ: 6.84 (dd, J=7.6Hz, 10.4Hz, 2H), 6.54 (t, J=7.2Hz, 1H),
(3.59 br, 1H), 3.34 (t, J=5.6Hz, 2H), 2.76 (t, J=6.4Hz, 2H), 2.05 (s, 3H), 1.95-1.85 (m,
2H).
Embodiment 6:8- methyl-1, the synthesis of 2,3,4- tetrahydroquinoline
Into ethyl alcohol (5mL) solvent added with PdNPore (2.7mg, 5mol%) catalyst, substrate 8- methylquinoline is added
(71.6mg, 0.5mmol), hydrogen (5bar), is placed on magnetic stirring apparatus and reacts 19h at 70 DEG C, and column chromatographs (silica gel, 200-300
Mesh；Solvent, petroleum ether, ethyl acetate) obtain 8- methyl-1,2,3,4- tetrahydroquinoline 58.89mg, yield 80%.
8- methyl-1,2,3,4- tetrahydroquinoline
1H NMR(400MHz,CDCl3) δ: 6.84 (dd, J=7.6Hz, 10.4Hz, 2H), 6.54 (t, J=7.2Hz, 1H),
3.59 (br, 1H), 3.34 (t, J=5.6Hz, 2H), 2.76 (t, J=6.4Hz, 2H), 2.05 (s, 3H), 1.95-1.85 (m,
2H).
The synthesis of the chloro- 1,2,3,4- tetrahydroquinoline of embodiment 7:6-
Into isopropanol (3mL) solvent added with PdNPore (5.4mg, 10mol%) catalyst, substrate 6- chloroquine is added
Quinoline (49.08mg, 0.3mmol), hydrogen (2bar), are placed on magnetic stirring apparatus and react 28h at 50 DEG C, and column chromatographs (silica gel, 200-
300 mesh；Solvent, petroleum ether, ethyl acetate) obtain chloro- 1,2,3,4- tetrahydroquinoline 36.21mg of 6-, yield 72%.
The chloro- 1,2,3,4- tetrahydroquinoline of 6-
1H NMR(400MHz,CDCl3) δ: 6.91-6.85 (m, 2H), 6.37 (d, J=8Hz, 1H), 3.80 (br, 1H),
3.28 (t, J=5.6Hz, 2H), 2.72 (t, J=6.4Hz, 2H), 1.95-1.85 (m, 2H)
The synthesis of the chloro- 1,2,3,4- tetrahydroquinoline of embodiment 8:6-
Into acetonitrile (5mL) solvent added with PdNPore (2.7mg, 5mol%) catalyst, substrate 6- chloroquinoline is added
(81.8mg, 0.5mmol), hydrogen (5bar), is placed on magnetic stirring apparatus and reacts 16h at 30 DEG C, and column chromatographs (silica gel, 200-300
Mesh；Solvent, petroleum ether, ethyl acetate) obtain chloro- 1,2,3,4- tetrahydroquinoline 69.57mg of 6-, yield 83%.
The chloro- 1,2,3,4- tetrahydroquinoline of 6-
1H NMR(400MHz,CDCl3) δ: 6.91-6.85 (m, 2H), 6.37 (d, J=8Hz, 1H), 3.80 (br, 1H),
3.28 (t, J=5.6Hz, 2H), 2.72 (t, J=6.4Hz, 2H), 1.95-1.85 (m, 2H)
The synthesis of embodiment 9:1,2,3,4- tetrahydroquinoline
Into triethylamine (6mL) solvent added with PdNPore (1.1mg, 2mol%) catalyst, substrate quinoline is added
(129.16mg, 1mmol), hydrogen (3bar), is placed on magnetic stirring apparatus and reacts 20h at 50 DEG C, and column chromatographs (silica gel, 200-300
Mesh；Solvent, petroleum ether, ethyl acetate) obtain 1,2,3,4- tetrahydroquinoline 99.89mg, yield 75%.
1,2,3,4- tetrahydroquinoline
1H NMR(400MHz,CDCl3) δ: 7.00-6.90 (m, 2H), 6.56 (t, J=7.2Hz, 1H), 6.44 (d, J=
7.6Hz, 1H), 3.74 (br, 1H), 3.27 (t, J=5.6Hz, 2H), 2.74 (t, J=6.4Hz, 2H), 1.96-1.88 (m,
2H).
The synthesis of embodiment 10:1,2,3,4- tetrahydroquinoline
Into ethyl alcohol (3mL) solvent added with PdNPore (2.7mg, 5mol%) catalyst, substrate quinoline is added
(64.58mg, 0.5mmol), hydrogen (6bar), is placed on magnetic stirring apparatus and reacts for 24 hours at 80 DEG C, and column chromatographs (silica gel, 200-
300 mesh；Solvent, petroleum ether, ethyl acetate) obtain 1,2,3,4- tetrahydroquinoline 57.27mg, yield 86%.
1,2,3,4- tetrahydroquinoline
1H NMR(400MHz,CDCl3) δ: 7.00-6.90 (m, 2H), 6.56 (t, J=7.2Hz, 1H), 6.44 (d, J=
7.6Hz, 1H), 3.74 (br, 1H), 3.27 (t, J=5.6Hz, 2H), 2.74 (t, J=6.4Hz, 2H), 1.96-1.88 (m,
2H)。
Claims (2)
1. a kind of preparation method for replacing 1,2,3,4- tetrahydroquinolines, which is characterized in that using quinoline and its derivates as raw material, receive
Rice porous palladium is catalyst, H2For hydrogen source, selective hydrogenation preparation replaces 1,2,3,4- tetrahydroquinolines, and synthetic route is as follows:
Reaction temperature is -50 DEG C~150 DEG C, and the reaction time is 12h~36h；
R1Selected from one of hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R2Selected from one of hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R1With R2It is identical or different；
Wherein, the molar concentration of quinoline and its derivates in a solvent be 0.01~2mmol/mL, quinoline and its derivates with urge
Agent molar ratio is 1:0.01~1:0.5；
The solvent is acetonitrile；
The hole on framework size of the nano porous palladium is 1nm~50nm.
2. preparation method according to claim 1, which is characterized in that the pressure of the hydrogen is 0.1~20.0MPa.
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| CN107098786A (en) * | 2017-05-15 | 2017-08-29 | 大连理工大学 | A kind of preparation method of aromatic amine compounds |
| CN109180498A (en) * | 2018-09-20 | 2019-01-11 | 大连理工大学 | A kind of preparation method replacing Armeen |
| CN110066244B (en) * | 2019-05-31 | 2022-06-28 | 上海泰坦科技股份有限公司 | Method for synthesizing chiral tetrahydroquinoline by using saturated aldehyde |
| CN110606829B (en) * | 2019-09-26 | 2023-04-28 | 上海城建职业学院 | Method for synthesizing 4-substituted quinoline derivative by palladium catalysis |
| CN110724032A (en) * | 2019-11-06 | 2020-01-24 | 大连理工大学 | Method for preparing alcohol compound by hydrogenation reduction of ketone and aldehyde |
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| US11446636B2 (en) | 2019-12-16 | 2022-09-20 | King Fahd University Of Petroleum And Minerals | Jute stem-supported palladium-NPS and use as dip-catalysts for aqueous transfer hydrogenation |
| CN114130389B (en) * | 2021-08-31 | 2023-11-17 | 浙江工业大学 | Supported catalyst, preparation thereof and application thereof in selective hydrogenation of nitrogen-containing heterocyclic compound |
| CN113735767B (en) * | 2021-09-27 | 2023-12-05 | 广东工业大学 | Synthesis method of tetrahydroquinoline |
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