Method for preparing quinoline compound by oxidation-reduction integration
阅读说明：本技术 一种氧化还原一体化制备喹啉化合物的方法 (Method for preparing quinoline compound by oxidation-reduction integration ) 是由 王峰 张超锋 高著衍 任濮宁 于 2018-07-27 设计创作，主要内容包括：本发明涉及一种氧化还原一体化制备喹啉化合物的方法。该方法以芳香硝基化合物和脂肪醇为原料,以含氧二硫化钼为催化剂,在惰性气氛或者在含氧的气氛,150～200℃条件下反应2～12h,反应完成后,分离液相成分,浓缩,经硅胶柱分离,得到取代喹啉化合物。该合成方法在喹啉化合物合成方面可能有重要的应用。(The invention relates to a method for preparing a quinoline compound by oxidation-reduction integration. 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, reacting for 2-12 hours at 150-200 ℃ in an inert atmosphere or an oxygen-containing atmosphere, separating liquid phase components after the reaction is finished, concentrating, and separating through a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.)
1. A method for preparing quinoline compound by oxidation-reduction integration is characterized in that: the method comprises the steps of taking an aromatic nitro compound and aliphatic alcohol as raw materials, taking molybdenum disulfide containing oxygen as a catalyst, reacting for 1-12 hours at 140-240 ℃ in an inert atmosphere or an oxygen-containing atmosphere, separating liquid phase components after the reaction is finished, concentrating, and separating through a silica gel column to obtain the substituted quinoline compound.
2. The method of claim 1, wherein:
the aromatic nitro compound is one or more than two of the following structures:
(1) nitrobenzene and nitrobenzene substituent Rx-(C6H5-X)-NO2(x＝1～5)，Wherein R represents different substituents (R ═ H, F, Cl, Br, I, CH3，OCH3，NH2，NO2One to five of CHO, Ph, etc.), X represents the number of substituents, when X represents the number of substituents>1, R may represent the same substituent or different substituents;
(2) the compound of aromatic condensed ring H is substituted by mononitro, wherein the aromatic condensed ring can be one or two of naphthalene ring and anthracene ring;
(3) the compound of the aromatic heterocyclic ring H substituted by the mononitro group, wherein the aromatic heterocyclic ring can be one or more of a pyridine ring, a thiophene ring, a furan ring and an imidazole ring.
3. The method of claim 1, wherein: the fatty alcohol is used as both solvent and reactant, and the fatty alcohol is H (CH)2)nCH2CH3One or more of OH (0. ltoreq. n.ltoreq.6, preferably 0. ltoreq. n.ltoreq.2).
4. The method of claim 1, wherein: the catalyst containing oxygen molybdenum disulfide is MoS2-xOy0.001. ltoreq. x.ltoreq.0.4 and 0.001. ltoreq. y.ltoreq.0.2, preferably 0.002. ltoreq. x.ltoreq.0.1 and 0.002. ltoreq. y.ltoreq.0.1, in the catalyst.
5. The method of claim 1, wherein: the aliphatic alcohol in claim 3 is used as a substrate and a reaction solvent at the same time, the concentration of the aromatic nitro compound substrate is 0.001-5 mol/L, the dosage of the catalyst is 0.5-20 w% of the mass of the aromatic nitro compound substrate, the reaction temperature is 140-220 ℃, and the reaction time is 1-12 h.
6. The method of claim 1, wherein: the aliphatic alcohol in claim 3 is used as a substrate and a reaction solvent at the same time, the concentration of the aromatic nitro compound substrate is 0.05-2 mol/L, the dosage of the catalyst is 0.5-20 w% of the mass of the aromatic nitro compound substrate, the reaction temperature is 140-200 ℃, and the reaction time is 2-12 h.
7. The method of claim 1, wherein: the reaction atmosphere may be a pure inert atmosphere, preferably N2Ar or a mixed gas of the Ar and the Ar, wherein the pressure is 0.1-3.0 MPa, preferably 0.1-1.0 MPa; or the reaction is carried out in an oxygen-containing atmosphere, preferably air or O2The pressure of the atmosphere or the mixed gas of the atmosphere and the mixed gas is 0.1-1 MPa and 0.3-0.5 MPa.
8. The method of claim 1, wherein: the aromatic nitro compound is preferably nitrobenzene and nitrobenzene substituent Rx-(C6H5-X)-NO2(x＝1～2)。
Technical Field
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.
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 method thereof has been widely noticed, wherein the Skraup reaction (Organ) is a reaction of multiple organic namesic reactions.1953; 7:59-98), the Doebner reaction (J.chem.Soc.1934:1520-23), the Doebner-Von Miller reaction (Berichtedder deutschen chemischen Gesellschaft.1883; 2464-72), the Combes reaction (J.chem.Soc.1927:1832-57), the Conrad-Limpach reaction (chem.Rev.1942; 30(1):113-44),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 for the preparation of quinoline compounds, and it is therefore more attractive to convert nitroarenes and fatty alcohols directly to quinoline by a one-pot cascade reaction than other synthetic strategies, considering that substituted anilines must first be synthesized from nitroarenes by a multi-step process, and that carbonyl compounds from fatty alcohols are generally unstable (Catal day. 1997; 37(2): 121-36).
However, this strategy for the direct synthesis of quinolines has subsequently proven to be rather difficult, mainly due to the complexity of the tandem 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.
The invention relates to a method for preparing a quinoline compound by oxidation-reduction integration. 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, reacting for 2-12 hours at 150-200 ℃ in an inert atmosphere or an oxygen-containing atmosphere, separating liquid phase components after the reaction is finished, concentrating, and separating through 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 a quinoline compound by oxidation-reduction integration. 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, reacting for 2-12 hours at 150-200 ℃ in an inert atmosphere or an oxygen-containing atmosphere, separating liquid phase components after the reaction is finished, concentrating, and separating through a silica gel column to obtain the substituted quinoline compound. The synthesis method can be applied to the synthesis of quinoline compounds.
For aromatic nitro compounds, it may be: (1) nitrobenzene and nitrobenzene substituent Rx-(C6H5-X)-NO2(x ═ 1 to 5), wherein R represents various substituents (R ═ H, F, Cl, Br, I, CH3，OCH3，NH2，NO2CHO, Ph, etc.), X represents the number of substituents. When X is present>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, it acts as both a solvent and a reactant in the process. The aliphatic 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)1:3 to 1:30Dispersing the mixture in a water solution according to a molar ratio, carrying out hydrothermal treatment for 6-72 h at 160-240 ℃, 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.
According to specific synthesis conditions, the aliphatic alcohol is used as a substrate and a reaction solvent at the same time, the concentration of the aromatic nitro compound substrate is 0.001-5 mol/L, the dosage of the catalyst is 0.5-20 w% of the mass of the aromatic nitro compound substrate, the reaction temperature is 140-220 ℃, and the reaction time is 1-12 h. The optimized conditions are that the concentration of the aromatic nitro compound substrate is 0.05-2 mol/L, the dosage of the catalyst is 0.5-20 w% of the mass of the aromatic nitro compound substrate, the reaction temperature is 140-200 ℃, and the reaction time is 2-12 h.
The reaction atmosphere may be a pure inert atmosphere, N, depending on the specific synthesis conditions2Ar or the mixed gas of the Ar and the Ar, wherein the pressure is 0.1-3 MPa; or the reaction is carried out in an oxygen-containing atmosphere, air or O2The atmosphere is under a pressure of 0.1 to 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)。
Detailed Description
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)The mixture was added to a 150mL stainless steel autoclave lined with tetrafluoro at 1:3 to 1:30, and 90mL deionized water was added with stirring. 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. In MoS2-xOy(180-24h), wherein FIG. 1 is a Raman spectrum diagram and FIG. 2 is an element distribution diagram.
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)
Example for the reaction:
the reaction equation is as follows:
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