CN106432072A - Preparation method of substituted 1,2,3,4-tetrahydroquinoline - Google Patents
Preparation method of substituted 1,2,3,4-tetrahydroquinoline Download PDFInfo
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- CN106432072A CN106432072A CN201610844274.8A CN201610844274A CN106432072A CN 106432072 A CN106432072 A CN 106432072A CN 201610844274 A CN201610844274 A CN 201610844274A CN 106432072 A CN106432072 A CN 106432072A
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- tetrahydroquinoline
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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 the technical field of medical and natural compound chemical intermediates and relevant chemicals and relates to a preparation method of substituted 1,2,3,4-tetrahydroquinoline. The preparation method of the substituted 1,2,3,4-tetrahydroquinoline is characterized by taking quinoline and derivatives thereof as raw materials, taking a nano porous palladium catalyst as a catalyst, taking hydrogen as a hydrogen source, and carrying out selective hydrogenation to prepare 1,2,3,4-tetrahydroquinoline, wherein the pressure of hydrogen is 0.1-20.0MPa; the molar concentration of quinoline and derivatives thereof in a solvent is 0.01-2mmol/mL; the catalyst porous framework size is 1-50nm; the mole ratio of quinoline and derivatives thereof to the catalyst is (1 to 0.01)-(1 to 0.5). The preparation method of substituted 1,2,3,4-tetrahydroquinoline has the beneficial effects that the product selectivity is high, the reaction condition is extremely mild, operation and post-treatment are simple, the catalyst reproducibility is high, the catalysis effect is not obviously reduced after being repeatedly used, and the possibility is provided for implementation of industrialization.
Description
Technical field
The invention belongs to medicine and native compound chemical intermediate and related chemistry technical field, are related to a kind of replacement 1,
The preparation method of 2,3,4- tetrahydroquinoline.
Background technology
Quinoline selective reduction is a critically important step for 1,2,3,4- tetrahydroquinoline (py-THQ) in organic synthesiss
Suddenly, (such as bioactive molecule, natural product and other are important particularly in some important high value compound synthesis
The industrial materials of natural product), the synthesis of high-purity py-THQ is committed step.
The catalyst that tradition prepares py-THQ by quinoline selective reduction is broadly divided into two big class, one be by Ru, Rh, Ir with
And the homogeneous catalyst of other transition metal and ligand binding, such catalyst has high activity and a high selectivity, but 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.]；Two is that research is more heterogeneous urges
Agent, such catalyst includes to load Ru, Pd-BT-CF and Au/HAS-TiO2Deng, but generally existing temperature is higher, hydrogen pressure
Power is higher, the shortcomings of regioselectivity is poor, limits industrial applications.Additionally, quinoline and its reduzate are in heterogeneous catalysiss
Strong absorption in agent also have impact on catalysis 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 class novel nano structure is urged
Agent, which is made up of the pore of nanoscale and ligament, with great specific surface area compared with most metals, excellent is led
The hot and nontoxic performance of conductance, can show and the diverse physicochemical properties in reguline metal, be received in catalyticing research field
To extensive concern.Nanoporous palladium catalyst (PdNPore) have the advantages that catalysis activity high, stable, recycle convenient
[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.].
Content of the invention
The invention provides a kind of preparation method of replacement py-THQ, the method reaction condition as mild as a dove, regional choice
Property reach 100%, the advantages of selected catalyst active high, good stability, recycling repeatedly has not yet to see catalysis activity
Substantially reduce.
The present invention is that nanoporous palladium catalyst (PdNPore) is catalyst, hydrogen with quinoline and its derivates as raw material
For hydrogen source, selective hydrogenation preparation replacement py-THQ, synthetic route is as follows：
Reaction temperature is -50 DEG C～150 DEG C, and the response time is 12h～36h；
R1One kind in hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R2One kind in hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R1With R2Identical or different；
Wherein, the catalyst for being adopted is nanoporous palladium catalyst (PdNPore), and hole on framework size is 1nm～50nm
Between, quinoline and its derivates are 1 with used catalyst mol ratio:0.01～0.5.
The pressure of hydrogen is 0.1～20.0MPa.
Quinoline and its derivates molar concentration in a solvent is 0.01～2mmol/mL.
Solvent be ether, acetonitrile, dimethyl sulfoxide, dioxane, triethylamine, tetrahydrofuran, toluene, ethanol, isopropanol,
One or more mixing in chloroform, dichloromethane, acetone, N,N-dimethylformamide, water.
Separation method includes：Recrystallization, column chromatography etc..The solvent that recrystallization method is used such as, chloroform, hexamethylene, dioxy
Six rings, benzene, toluene, ethanol, petroleum ether, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate；Use column chromatography side
Method, it is possible to use silica gel or alkali alumina are used as fixing phase, and developing 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 invention has the beneficial effects as follows the condition of the reaction is as mild as a dove, and selectivity of product height, operation is simple with post processing,
Catalyst favorable reproducibility, and reuse multiple catalytic effect and substantially do not reduce, be its realize that industrialization provides may.
Description of the drawings
Fig. 1 is embodiment 1,2- methyl isophthalic acid in 2,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 2 is embodiment 3,3- methyl isophthalic acid in 4,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 3 is embodiment 5,8- methyl isophthalic acid in 6,2,3,4- tetrahydroquinolines1H nuclear magnetic spectrogram.
Fig. 4 is embodiment 7, chloro- 1,2,3, the 4- tetrahydroquinoline of 6- in 81H nuclear magnetic spectrogram.
Fig. 5 is embodiment 9,1,2,3,4- tetrahydroquinolines in 101H nuclear magnetic spectrogram.
Specific embodiment
The preparation method of replacement py-THQ of the present invention, highest selectivity and reaction yield respectively reach 100% He
95%, favorable reproducibility is reacted from catalyst, operation and post processing are simple, and it is not bright to reuse multiple catalytic effect
Aobvious reduction, is that its industrialized production provides advantage.
With reference to specific embodiment, the present invention is expanded on further.Technical staff in the art is done to the present invention
Simple replacement or improve belong within the technical scheme protected by the present invention.
Embodiment 1：2- methyl isophthalic acid, the synthesis of 2,3,4- tetrahydroquinoline
To in 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 apparatuss at 80 DEG C and react 16h, column chromatography (silica gel,
200-300 mesh；Developing solvent, petroleum ether, ethyl acetate) obtain 2- methyl isophthalic acid, 2,3,4- tetrahydroquinoline 58.89mg, yield 80%.
2- methyl isophthalic acid, 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 isophthalic acid, the synthesis of 2,3,4- tetrahydroquinoline
To in DMF (3mL) solvent added with PdNPore (5.4mg, 10mol%) catalyst, add
Substrate 2- methylquinoline (42.96mg, 0.3mmol), hydrogen (5bar), are placed on magnetic stirring apparatuss reaction 20h, post layer at 30 DEG C
Analysis (silica gel, 200-300 mesh；Developing solvent, petroleum ether, ethyl acetate) obtain 2- methyl isophthalic acid, 2,3,4- tetrahydroquinoline 30.92mg,
Yield 70%.
2- methyl isophthalic acid, 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 isophthalic acid, the synthesis of 2,3,4- tetrahydroquinoline
To in ethanol (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 apparatuss reaction 12h, column chromatography (silica gel, 200-300 at 60 DEG C
Mesh；Developing solvent, petroleum ether, ethyl acetate) obtain 3- methyl isophthalic acid, 2,3,4- tetrahydroquinoline 47.85mg, yield 65%.
3- methyl isophthalic acid, 2,3,4- tetrahydroquinoline
1H NMR(CDCl3,400MHz)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 isophthalic acid, the synthesis of 2,3,4- tetrahydroquinoline
To in 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 apparatuss reaction 24h, column chromatography (silica gel, 200-300 at 50 DEG C
Mesh；Developing solvent, petroleum ether, ethyl acetate) obtain 3- methyl isophthalic acid, 2,3,4- tetrahydroquinoline 61.1mg, yield 83%.
3- methyl isophthalic acid, 2,3,4- tetrahydroquinoline
1H NMR(CDCl3,400MHz)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 isophthalic acid, the synthesis of 2,3,4- tetrahydroquinoline
To in 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 apparatuss reaction 15h, column chromatography (silica gel, 200- at 50 DEG C
300 mesh；Developing solvent, petroleum ether, ethyl acetate) obtain 8- methyl isophthalic acid, 2,3,4- tetrahydroquinoline 104.53mg, yield 71%.
8- methyl isophthalic acid, 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 isophthalic acid, the synthesis of 2,3,4- tetrahydroquinoline
To in ethanol (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 apparatuss reaction 19h, column chromatography (silica gel, 200-300 at 70 DEG C
Mesh；Developing solvent, petroleum ether, ethyl acetate) obtain 8- methyl isophthalic acid, 2,3,4- tetrahydroquinoline 58.89mg, yield 80%.
8- methyl isophthalic acid, 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 7：The synthesis of the chloro- 1,2,3,4- tetrahydroquinoline of 6-
To in 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 apparatuss reaction 28h, column chromatography (silica gel, 200- at 50 DEG C
300 mesh；Developing solvent, petroleum ether, ethyl acetate) obtain chloro- 1,2,3, the 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).
Embodiment 8：The synthesis of the chloro- 1,2,3,4- tetrahydroquinoline of 6-
To in 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 apparatuss reaction 16h, column chromatography (silica gel, 200-300 at 30 DEG C
Mesh；Developing solvent, petroleum ether, ethyl acetate) obtain chloro- 1,2,3, the 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).
Embodiment 9：The synthesis of 1,2,3,4- tetrahydroquinoline
To in triethylamine (6mL) solvent added with PdNPore (1.1mg, 2mol%) catalyst, substrate quinoline is added
(129.16mg, 1mmol), hydrogen (3bar), is placed on magnetic stirring apparatuss reaction 20h, column chromatography (silica gel, 200-300 at 50 DEG C
Mesh；Developing 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).
Embodiment 10：The synthesis of 1,2,3,4- tetrahydroquinoline
To in ethanol (3mL) solvent added with PdNPore (2.7mg, 5mol%) catalyst, substrate quinoline is added
(64.58mg, 0.5mmol), hydrogen (6bar), is placed on magnetic stirring apparatuss reaction 24h, column chromatography (silica gel, 200- at 80 DEG C
300 mesh；Developing 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 (3)
1. one kind replaces the preparation method of 1,2,3,4- tetrahydroquinolines, it is characterised in that with quinoline and its derivates as raw material, receive
Rice porous palladium (PdNPore) is catalyst, H2For hydrogen source, selective hydrogenation is prepared and replaces 1,2,3,4- tetrahydroquinolines, synthesizes road
Line is as follows：
Reaction temperature is -50 DEG C～150 DEG C, and the response time is 12h～36h；
R1One kind in hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R2One kind in hydrogen, alkyl, methoxyl group, aldehyde radical, halogen, hydroxyl, ester group；
R1With R2Identical or different；
Wherein, quinoline and its derivates molar concentration in a solvent be 0.01～2mmol/mL, quinoline and its derivates with urge
Agent mol ratio is 1:0.01～1：0.5；
Described solvent is selected from ether, acetonitrile, dimethyl sulfoxide, dioxane, triethylamine, tetrahydrofuran, toluene, ethanol, different
One or more mixing in propanol, chloroform, dichloromethane, acetone, N,N-dimethylformamide, water.
2. preparation method according to claim 1, it is characterised in that the hole bone of described nano porous palladium (PdNPore)
Frame size is 1nm～50nm.
3. preparation method according to claim 1 and 2, it is characterised in that the pressure of described 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 |
| CN110066244A (en) * | 2019-05-31 | 2019-07-30 | 上海泰坦科技股份有限公司 | A method of utilizing saturated aldehyde synthesis of chiral tetrahydroquinoline |
| CN110606829A (en) * | 2019-09-26 | 2019-12-24 | 上海城建职业学院 | Method for synthesizing 4-substituted quinoline derivative under 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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| 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 |
| WO2020057274A1 (en) * | 2018-09-20 | 2020-03-26 | 大连理工大学 | Method for preparing substituted primary amine |
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| CN110606829A (en) * | 2019-09-26 | 2019-12-24 | 上海城建职业学院 | Method for synthesizing 4-substituted quinoline derivative under 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 |
| CN110918091A (en) * | 2019-12-10 | 2020-03-27 | 中国科学技术大学 | Application of RuSn alloy cluster composite material |
| CN110918091B (en) * | 2019-12-10 | 2021-04-23 | 中国科学技术大学 | Application of RuSn alloy cluster composite material |
| 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 |
| CN114130389A (en) * | 2021-08-31 | 2022-03-04 | 浙江工业大学 | Supported catalyst, preparation thereof and application thereof in selective hydrogenation of nitrogen-containing heterocyclic compound |
| 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 |
| CN113735767A (en) * | 2021-09-27 | 2021-12-03 | 广东工业大学 | Synthesis method of tetrahydroquinoline |
| CN113735767B (en) * | 2021-09-27 | 2023-12-05 | 广东工业大学 | Synthesis method of tetrahydroquinoline |
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