CN110759863B - Method for preparing quinoline derivative by one-pot two-step method - Google Patents

Method for preparing quinoline derivative by one-pot two-step method Download PDF

Info

Publication number
CN110759863B
CN110759863B CN201810840444.4A CN201810840444A CN110759863B CN 110759863 B CN110759863 B CN 110759863B CN 201810840444 A CN201810840444 A CN 201810840444A CN 110759863 B CN110759863 B CN 110759863B
Authority
CN
China
Prior art keywords
reaction
equal
nitro compound
aromatic nitro
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810840444.4A
Other languages
Chinese (zh)
Other versions
CN110759863A (en
Inventor
王峰
张超锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201810840444.4A priority Critical patent/CN110759863B/en
Publication of CN110759863A publication Critical patent/CN110759863A/en
Application granted granted Critical
Publication of CN110759863B publication Critical patent/CN110759863B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a method for preparing quinoline derivatives by a one-pot two-step method. The method comprises the steps of taking an aromatic nitro compound and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, firstly reacting for 2-10 hours under the conditions of hydrogen pressure of 0.3-3.0 MPa and temperature of 120-160 ℃, converting the aromatic nitro compound into aromatic amine, then replacing reaction atmosphere, reacting for 2-12 hours under the conditions of inert atmosphere or oxygen-containing atmosphere and temperature of 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating by using a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.

Description

Method for preparing quinoline derivative by one-pot two-step method
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing quinoline derivatives by a one-pot two-step method.
Background
Quinolines and their derivatives are an important class of organic compounds, which are widely used in the synthesis of functional drugs, pesticides, dyes, chemical agents, optical materials, functional polymers, and the like (Andries K et al science.2005; 307(5707): 223-27; Theraladanon C et al tetrahedron: asymmetry.2005; 16(4): 827-31; Roma G et al European Journal of medical chemistry.2000; 35(11): 1021-35; Zhang X J et al macromolecules.1999; 32(22): 7422-29). The synthesis methods have been receiving much attention, among which Skraup reaction (Organic reactions.1953; 7:59-98), Doebner reaction (J.chem.Soc.1934:1520-23), Doebner-Von Miller reaction (Berichte der deutschen chemischen Gesellschaft.1883; 6(2):2464-72), Combes reaction (J.chem.Soc.1927:1832-57), Conrad-Limpach reaction (chem.Rev.1942; 30(1):113-44),
Figure BDA0001745461800000011
reactions (chem. Rev.2009; 109(6):2652-71) and Pfitsinger reactions (J.Am. chem. Soc.1954; 76(18): 4580-84). However, the above methods mostly employ substituted anilines and carbonyl compounds to prepare quinoline compounds, and considering that substituted anilines must first be synthesized from nitroarenes by a multi-step process, and that carbonyl compounds from aliphatic alcohols are generally unstable (Catal today. 1997; 37(2):121-36), direct conversion of nitroarenes and aliphatic alcohols to quinoline by a single pot series reaction is more attractive than other synthetic strategies.
However, this strategy for the direct synthesis of quinolines has subsequently proved to be rather difficult, mainly due to the tandem connectionThe complexity of the reaction. So far, only a few have used homogeneous Ru (chem. Soc. Jpn.1984,57,435-438), Rh (Organometallics 1982,1,1003-1006) compounds and heterogeneous Ir/TiO2(Angew. chem. int. Ed.2011,50,10216-10220) and Pt-Sn/Al2O3Catalytic systems (Chin.J.Catal.2013,33, 1423-1426). And TiO2acidified-TiO2、N-doping TiO2And TiO2The noble metal supported photocatalytic system (Arab J Chem 2017,10, S28-S34, ACS Catal.2013,3, 565-. By way of analysis, one economically viable solution is to use a non-noble metal heterogeneous catalyst that is inexpensive, readily available, and stable to achieve the direct conversion process. Or the reaction is divided into two steps, under the condition that the catalyst and the solvent are not changed, the hydrogenation of the aromatic nitro compound is converted into the aromatic amine in the first step, the conversion of the aliphatic alcohol is realized by changing the reaction atmosphere in the second step, and meanwhile, the selective reaction of the aniline and the carbonyl compound intermediate generated in situ is realized to generate the quinoline compound.
The invention relates to a method for preparing quinoline derivatives by a one-pot two-step method. The method comprises the steps of taking an aromatic nitro compound and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, firstly reacting for 2-10 hours under the conditions of hydrogen pressure of 0.3-3.0 MPa and temperature of 120-160 ℃, converting the aromatic nitro compound into aromatic amine, then replacing reaction atmosphere, reacting for 2-12 hours under the conditions of inert atmosphere or oxygen-containing atmosphere and temperature of 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating by using a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.
Disclosure of Invention
The invention relates to a method for preparing quinoline derivatives by a one-pot two-step method. The method comprises the steps of taking an aromatic nitro compound and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, firstly reacting for 2-10 hours under the conditions of hydrogen pressure of 0.3-3.0 MPa and temperature of 120-160 ℃, converting the aromatic nitro compound into aromatic amine, then replacing reaction atmosphere, reacting for 2-12 hours under the conditions of inert atmosphere or oxygen-containing atmosphere and temperature of 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating by using a silica gel column to obtain the substituted quinoline compound.
For aromatic nitro compounds, it may be: (1) nitrobenzene and nitrobenzene substituent Rx-(C6H5-X)-NO2(x is 1-5), wherein R represents different substituents (R is H, F, Cl, Br, I, CH)3，OCH3，NH2，NO2CHO, Ph, etc.), X represents the number of substituents. When X is>1 is the same substituent that R may represent or different substituents; (2) nitro compounds with benzene rings substituted by other aromatic condensed rings, wherein the other aromatic condensed rings can be one or more of naphthalene rings, anthracene rings and the like; (3) the nitro compound with the benzene ring substituted by the aromatic heterocyclic ring can be one or more of a pyridine ring, a thiophene ring, a furan ring, an imidazole ring and the like.
For fatty alcohols, the fatty alcohol is H (CH)2)nCH2CH3One or more of OH (n is more than or equal to 0 and less than or equal to 6). When n is>2 is, in addition to a linear alkane substituent, a substituent having a branch.
The catalyst containing molybdenum disulfide oxide is MoS2-XOyBy controlling the sulfuration and reduction degree of the molybdate precursor, x is more than or equal to 0 and less than or equal to 0.4 and y is more than or equal to 0 and less than or equal to 0.2 in the obtained catalyst. Regarding the preparation method of the molybdenum sulfide catalyst: ammonium molybdate and/or sodium molybdate are/is taken as a precursor, thiourea and/or sodium sulfide is taken as a sulfur source, and the formula is shown in the specification(Mo):n(S)Dispersing the catalyst in an aqueous solution according to a molar ratio of 1: 3-1: 30, carrying out hydrothermal treatment at 160-240 ℃ for 6-72 h, filtering and washing to obtain the catalyst. Wherein, the effect of taking ammonium molybdate as a precursor is better than that of sodium molybdate, thiourea in the sulfur source is cheap and easy to control and decompose, and is more suitable in the process of preparing molybdenum sulfide materials, and the synthesis of the catalyst is optimized: according to n(Mo):n(S)The feeding is carried out at a molar ratio of 1: 6-1: 30, and the hydrothermal treatment is carried out at 160-220 ℃ for 12-48 h.
The solvent for the reaction may be one or more of toluene, p-xylene, m-xylene, mesitylene and dodecane.
Aiming at specific synthesis conditions, the concentration of the substrate aromatic nitro compound is 0.05-2 mol/L; the amount of the fatty alcohol substance is 10-30 times of that of the aromatic nitro compound; the dosage of the catalyst is 0.5-20 w% of the mass of the aromatic nitro compound substrate; the first step is carried out at the reaction temperature of 120-160 ℃ for 2-10 h; the reaction temperature of the second step is 120-200 ℃, and the reaction time is 2-12 h. Regarding atmosphere conversion mainly involved in a one-pot two-step method, the reaction atmosphere in the first step is hydrogen, and the pressure is 0.3-3.0 MPa; the second reaction atmosphere may be a pure inert atmosphere, N2Ar or the mixed gas of the Ar and the Ar, the pressure is 0.1-3 MPa, or the second step reaction is carried out in air or O2The reaction is carried out under the atmosphere, and the pressure is 0.1-1 MPa.
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a quinoline compound through oxidation-reduction integration.
Drawings
FIG. 1 commercial MoS2 (Black 2H-MoS)2) And MoS2-xOy(180-24h) (Red O-MoS)2) Raman mapping of (a). Contrast display MoS2-xOy(180-24h) obvious crystal lattice oxygen residue or doping.
FIG. 2.MoS2-xOy(180-24h) EDX elemental analysis, the catalyst after analysis being expressed in MoS form1.73O0.1(180-24h)。
FIG. 3 shows a reaction equation for preparing quinoline derivatives by a one-pot two-step method.
The specific implementation mode is as follows:
in order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
First, for the convenience of expressing the catalyst used, the relevant catalyst will be described. MoSxThe base catalyst is synthesized hydrothermally. Commercial ammonium molybdate and thiourea according to n(Mo):n(S)Adding the mixture into a 150mL stainless steel autoclave with a tetrafluoro lining in a ratio of 1: 3-1: 30, and adding 90mL of the mixture under the stirring condition to removeAnd (5) sub-water. And then the sealed stainless steel autoclave is placed in an oven at 160-250 ℃ for treatment for 12-48 h. After the treatment is finished, the reaction kettle is naturally cooled to room temperature, and the black solid is washed by deionized water and absolute ethyl alcohol. The catalyst obtained was named MoS2-xOy(m-nh), wherein m represents the temperature of the treatment and n represents the time of the treatment. In order to verify whether the catalyst contains lattice oxygen residues or incorporation, the resulting catalyst was first characterized using Raman spectroscopy, followed by characterization of the oxygen content in the catalyst using EDX electron microscopy characterization techniques. MoS2-xOy(m-n h), the correlation results are plotted for the x and y parameters of the catalyst. With MoS2-xOy(180-24h), the Raman spectrum diagram is shown in figure 1, and the element distribution diagram is shown in figure 2.
Example 1:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 150 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 95% and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 70%.
Example 2:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.1MPa Air gas, and reacting for 6h at 180 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 95% and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 55%.
Example 3:
mixing 0.5mmol nitrobenzene, 15mmol ethanol, 2.5mLToluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2The reaction was carried out at 160 ℃ for 8 hours. Cooling, replacing gas, charging Ar gas of 0.1MPa, and continuing to react for 6h at 180 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 90% and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 35%.
Example 4:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of p-xylene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging Ar gas of 0.1MPa, and continuing to react for 6h at 180 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 97%, and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 65%.
Example 5:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.85O0.02(200-24H), placing in a 25mL reaction kettle, replacing gas, charging 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging Ar gas of 0.1MPa, and continuing to react for 6h at 180 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 70% and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 25%.
Example 6:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.85O0.02(200-24H), placing in a 25mL reaction kettle, replacing gas, charging 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.1MPa Air gas, and continuing to react at 180 ℃ for 6 h. After the reaction is finished, useThe liquid phase samples were analyzed by GC, followed by concentration of the liquid phase components and isolation of the product using a silica gel column. The conversion of nitrobenzene was 75% and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 45%.
Example 7:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.99O0(200-48H), placing in a 25mL reaction kettle, replacing gas, filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging Ar gas of 0.1MPa, and continuing to react for 6h at 180 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 45% and the isolation yield of alkyl-substituted quinoline (2-methylquinoline) was 15%.
Example 8:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.99O0(200-48H), placing in a 25mL reaction kettle, replacing gas, filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 180 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 85% and the isolation yield of alkyl substituted quinolines was 45%.
Example 9:
0.5mmol of p-methylnitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging Ar gas of 0.1MPa, and continuing to react for 6h at 180 ℃. After the reaction was completed, a liquid phase sample was analyzed by GC, then the liquid phase component was concentrated, and the product was separated by silica gel column. The conversion of p-methylnitrobenzene was 90% and the isolation yield of alkyl-substituted quinolines was 35%.
Example 10:
adding 0.5mmol of p-tolueneNitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 140 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of p-methylnitrobenzene was 90% and the isolation yield of alkyl-substituted quinolines was 45%.
Example 11:
0.5mmol of p-chloronitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 170 ℃, for 10 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 160 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of p-chloronitrobenzene was 97% and the isolation yield of alkyl substituted quinolines was 55%.
Example 12:
0.5mmol of p-chloronitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 170 ℃, for 10 hours. Cooling, replacing gas, and flushing in 0.4MPa O2The reaction was continued at 160 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of p-chloronitrobenzene was 98% and the isolation yield of alkyl substituted quinolines was 45%.
Example 13:
0.5mmol of nitrobenzene, 15mmol of n-propanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, injecting 0.4MPa Air gas, and continuingReacting at 150 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene is>99% and the isolation yield of the alkyl-substituted quinoline was 75%.
Example 14:
0.5mmol of nitrobenzene, 15mmol of n-butanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, filling with 1.0MPa H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 150 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 97% and the isolation yield of alkyl substituted quinolines was 54%.
Example 15:
0.5mmol of nitrobenzene, 15mmol of n-pentanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 150 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 93% and the isolation yield of alkyl substituted quinoline was 49%.
Example 16:
0.5mmol of nitrobenzene, 15mmol of n-hexanol, 2.5mL of toluene and 25mg of catalyst MoS1.73O0.1(180-24H), placing in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and reacting for 6h at 150 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene is>99% and the isolation yield of the alkyl-substituted quinoline was 63%.
Example 17:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of catalyst MoO3Placing the mixture in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and reacting for 6h at 150 ℃. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 30% and the isolation yield of alkyl substituted quinolines was 15%.
Example 18:
0.5mmol of nitrobenzene, 15mmol of ethanol, 2.5mL of toluene and 25mg of commercial catalyst 2H-MoS2Placing the mixture in a 25mL reaction kettle, replacing gas, and filling 1.0MPa of H2Gas, at 160 ℃, for 8 hours. Cooling, replacing gas, charging 0.4MPa Air gas, and continuing to react at 150 ℃ for 6 h. After the reaction, a liquid phase sample was analyzed by GC, followed by concentration of the liquid phase components and isolation of the product by silica gel column. The conversion of nitrobenzene was 30% and the isolation yield of alkyl substituted quinolines was 9%.

Claims (9)

1. A method for preparing quinoline derivatives by a one-pot two-step method is characterized by comprising the following steps: taking an aromatic nitro compound and aliphatic alcohol as raw materials, taking oxygen-containing molybdenum disulfide as a catalyst, reacting for 2-10 h in an organic reaction solvent under the conditions of 0.3-3.0 MPa of hydrogen and 120-160 ℃, converting the aromatic nitro compound into aromatic amine, then replacing the reaction atmosphere, reacting for 2-12 h in an inert atmosphere or an oxygen-containing atmosphere at 120-200 ℃, separating liquid phase components after the reaction is finished, concentrating, and separating by a silica gel column to obtain a quinoline derivative;
wherein, the aromatic nitro compound is one or more than two of the following structures: nitrobenzene and nitrobenzene substituent Rx-(C6H5-X)-NO2X represents the number of substituents, x is 1-5, R is F, Cl, Br, I, CH3，OCH3When x is>1, R represents the same substituent or different substituents;
the fatty alcohol is H (CH)2)nCH2CH2One or more than two of OH, wherein n is more than or equal to 0 and less than or equal to 6;
the oxygen-containing molybdenum disulfide is MoS2-xOyWherein x is more than or equal to 0.001 and less than or equal to 0.4 and y is more than or equal to 0.001 and less than or equal to 0.2.
2. The method of claim 1, wherein: the aliphatic alcohol is H (CH)2)nCH2CH2One or more than two of OH, wherein n is more than or equal to 0 and less than or equal to 2.
3. The method of claim 1, wherein: the oxygen-containing molybdenum disulfide is MoS2-xOyWherein x is more than or equal to 0.002 and less than or equal to 0.1, and y is more than or equal to 0.002 and less than or equal to 0.1.
4. The process of claim 1, wherein the solvent for the reaction is one or more selected from toluene, p-xylene, m-xylene and mesitylene.
5. The method of claim 1, wherein: the concentration of the aromatic nitro compound in the organic reaction solvent is 0.05-2 mol/L; the amount of the fatty alcohol substance is 10-30 times of that of the aromatic nitro compound; the dosage of the catalyst is 0.5-30 wt% of the mass of the aromatic nitro compound.
6. The method of claim 1, wherein: the concentration of the aromatic nitro compound in the organic reaction solvent is 0.1-0.5 mol/L; the amount of the fatty alcohol substance is 15-30 times of that of the aromatic nitro compound; the amount of the catalyst is 5-20 wt% of the mass of the aromatic nitro compound; the first step is carried out at the reaction temperature of 120-160 ℃ for 4-10 h; the reaction temperature of the second step is 160-180 ℃, and the reaction time is 2-10 h.
7. The method of claim 1, wherein: the second reaction atmosphere is N2Ar or the mixed gas of the Ar and the Ar, the pressure is 0.1-3 MPa, or the second step reaction is carried out in air or O2Or bothThe reaction is carried out under the mixed gas, and the pressure is 0.1-1 MPa.
8. The method of claim 1, wherein: the first step is that the reaction atmosphere is hydrogen, and the pressure is 0.5-1.0 MPa; the second reaction atmosphere is N2Ar or the mixed gas of the Ar and the Ar, the pressure is 0.1-1.0 MPa, or the second step reaction is carried out in air or O2Or the mixture of the two gases under the pressure of 0.3-0.5 MPa.
9. The method of claim 1, wherein: the aromatic nitro compound is nitrobenzene and nitrobenzene substituent Rx-(C6H5-X)-NO2Wherein x is 1-2.
CN201810840444.4A 2018-07-27 2018-07-27 Method for preparing quinoline derivative by one-pot two-step method Active CN110759863B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810840444.4A CN110759863B (en) 2018-07-27 2018-07-27 Method for preparing quinoline derivative by one-pot two-step method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810840444.4A CN110759863B (en) 2018-07-27 2018-07-27 Method for preparing quinoline derivative by one-pot two-step method

Publications (2)

Publication Number Publication Date
CN110759863A CN110759863A (en) 2020-02-07
CN110759863B true CN110759863B (en) 2022-05-31

Family

ID=69326964

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810840444.4A Active CN110759863B (en) 2018-07-27 2018-07-27 Method for preparing quinoline derivative by one-pot two-step method

Country Status (1)

Country Link
CN (1) CN110759863B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805287B (en) * 2010-04-01 2012-06-27 浙江工业大学 Method for one-pot liquid phase synthesis of quinoline and derivative thereof
CN105669338B (en) * 2014-11-21 2017-09-15 中国科学院大连化学物理研究所 A kind of method that reduction of aromatic nitro-compounds by hydrazine hydrate prepares aromatic amine
CN105601458B (en) * 2014-11-21 2018-01-16 中国科学院大连化学物理研究所 A kind of method that aqueous phase reduction nitro substituted aromatic compound prepares aromatic amine
CN105175327B (en) * 2015-10-21 2017-07-14 南阳师范学院 A kind of synthetic method of quinoline
CN106543078B (en) * 2016-07-21 2019-01-11 中国科学院兰州化学物理研究所苏州研究院 A kind of preparation method of quinoline

Also Published As

Publication number Publication date
CN110759863A (en) 2020-02-07

Similar Documents

Publication Publication Date Title
Roy et al. A quick Chan–Lam C–N and C–S cross coupling at room temperature in the presence of square pyramidal [Cu (DMAP) 4 I] I as a catalyst
Cui et al. Au/Ag–Mo nano-rods catalyzed reductive coupling of nitrobenzenes and alcohols using glycerol as the hydrogen source
CN106925349B (en) A kind of solid supported type metal porphyrin catalyst and its application in terms of preparing maleic acid
Hsieh et al. Indole synthesis: palladium-catalyzed C–H bond amination via reduction of nitroalkenes with carbon monoxide
JP2015145375A (en) Method of producing 2-methoxymethyl-1,4-benzenediamine
Zhu et al. Pd/Cu cooperative catalysis: an efficient synthesis of (3-isoindazolyl) allenes via cross-coupling of 2-alkynyl azobenzenes and terminal alkynes
Xu et al. Stable Ni catalyst encapsulated in N-doped carbon nanotubes for one-pot reductive amination of nitroarenes with aldehydes
Romanowski et al. Synthesis, structure, spectroscopic characterization and catalytic activity of chiral dioxidomolybdenum (VI) Schiff base complexes derived from R (−)-2-amino-1-propanol
CN110759863B (en) Method for preparing quinoline derivative by one-pot two-step method
CN112500361B (en) Preparation method of (S) -4-phenyl-2-oxazolidinone
CN110759861B (en) Preparation method of quinoline derivative
Krafft et al. Catalyst precursors for the catalytic Pauson-Khand reaction
CN106732725B (en) The preparation and its application of the carbon-based transition-metal catalyst of MgO-Supported N doping
CN110256401B (en) Selenylation benzothiophene compound and synthetic method thereof
CN110759862B (en) Method for preparing quinoline compound by oxidation-reduction integration
CN107501338B (en) Preparation method of 2, 6-diaminopyridine condensed 4-carboxybenzaldehyde bis-Schiff base cobalt complex
CN110878104A (en) Preparation method of chiral 1, 2-bis (2, 5-diphenylphosphino) ethane
CN111704591B (en) Synthesis method of copper-catalyzed thionaphthothiazolone compound
CN113861119A (en) Method for synthesizing quinoline and quinazoline compounds under catalysis of cobalt
CN108558785A (en) A kind of 5- aryl -2- arylseleno -1,3- oxazole compounds and preparation method
CN107513078B (en) Preparation method of 2, 6-diaminopyridine condensed 3-carboxybenzaldehyde bis-Schiff base cobalt complex
CN103588599A (en) Method for preparing hydroxylamine through nitro-reduction
CN111377850B (en) Chiral N-substituted-3,3-difluoro-4-hydroxypiperidine derivative and preparation method thereof
Kang et al. One-pot solvent-free reductive amination with a solid ammonium carbamate salt from CO 2 and amine
Zerguini et al. Synthesis, crystal structure and Chan-Evans-Lam CN cross coupling catalysis of monohydrated tetrapyrazole copper (II) sulfate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant