CN108558751B - Synthesis process of 3-nitroquinoline derivative - Google Patents
Synthesis process of 3-nitroquinoline derivative Download PDFInfo
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- CN108558751B CN108558751B CN201810758846.XA CN201810758846A CN108558751B CN 108558751 B CN108558751 B CN 108558751B CN 201810758846 A CN201810758846 A CN 201810758846A CN 108558751 B CN108558751 B CN 108558751B
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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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- 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
- C07D215/20—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention relates to a synthesis method of a 3-nitroquinoline derivative, under the action of a copper salt catalyst, nitroolefin and ortho-position aldehyde group substituted aryl azide generate [3+2] cycloaddition reaction in the presence of a solvent, wherein the nitroolefin is alkyl, substituted alkyl, aryl or substituted aryl substituted nitroolefin, and the aryl in the ortho-position aldehyde group substituted aryl azide is aryl or substituted aryl. The invention adopts cheap and easily available ortho-position aldehyde group substituted aryl azide as a raw material, and the aryl azide and nitroolefin undergo [3+2] cycloaddition under the catalysis of copper salt to obtain the 3-nitroquinoline compound, the reaction yield is high, the catalyst is low, reaction byproducts only contain nitrogen and water, the post-treatment is simple, and the synthesis method is environment-friendly.
Description
Technical Field
The invention relates to a synthetic method of a 3-nitroquinoline derivative, belonging to the technical field of organic and pharmaceutical synthesis.
Technical Field
Quinoline is an important nitrogen-containing heterocyclic compound in organic synthesis. Wherein, the quinoline substituted by the nitrogen atom at the 3-position widely exists in natural products, such as the chinoline quinoline alkali, has good antimalarial and anticancer activities, and in addition, some compounds containing the skeleton also have the characteristics of anticancer, antimalarial, antiasthmatic, antidiabetic, antibacterial, antitumor and the like. The 3-nitroquinoline compound as a precursor of the compound has the characteristics of stable property and easy derivatization, is concerned about organic synthesis, and has great potential in drug synthesis.
However, to date, the synthesis methods of 3-nitroquinoline compounds are very few, and there are three main methods: (1) the method has the advantages that the quinoline ring is directly nitrified, the selectivity is low, several position isomers are generated, the quinoline ring is oxidized to form quinoline oxynitride, and therefore, the direct nitration mode is rarely used for synthesizing the 3-nitroquinoline compound. (2) 2-aminobenzaldehyde and alpha-nitroketone compounds are condensed in alcohol solvents to obtain 3-nitroquinoline, but the ketone compounds are complicated in preparation and have strong limitation on substrates. (3) In 2004, the group of Yaoqing hair subjects reported that o-aminobenzaldehyde and nitroolefin were refluxed using benzene as a solvent under DABCO as an organic base to give 3-nitro-1, 2-dihydroquinoline, which was subsequently oxidized under DDQ or silica gel to give 3-nitroquinoline. This method is widely used, but has three problems, namely, benzene with high toxicity is used as a solvent in the first cycloaddition, anthranilic aldehyde is very easy to polymerize, the price is very high, the yield is low in practice, the reaction is carried out in two steps, a plurality of equivalents of alkali and oxidant are used, and the post-treatment is complicated.
Disclosure of Invention
In order to solve the defects of the prior art, the invention adopts cheap and easily obtained ortho-position aldehyde group substituted aryl azide as a raw material, and obtains the 3-nitroquinoline compound with nitroolefin under the catalysis of copper salt. The reaction by-products are only nitrogen and water, the post-treatment is simple, and the method is an environment-friendly synthesis method.
In order to achieve the purpose, the invention is realized by the following technical scheme: the synthesis process of the 3-nitroquinoline derivative is characterized by comprising the following steps: under the action of a copper salt catalyst, nitroolefin and aryl azide substituted by ortho aldehyde group undergo [3+2] cycloaddition reaction in the presence of a solvent, wherein the nitroolefin is alkyl, substituted alkyl, aryl or substituted aryl substituted nitroolefin, and the aryl in the aryl azide substituted by the ortho aldehyde group is aryl or substituted aryl.
The specific reaction formula is shown as formula I:
in the formula I, R1Is aryl or substituted aryl, alkyl or substituted alkyl, R is halogen,Methyl, methoxy, hydrogen or aryl.
According to the scheme, the copper salt catalyst is selected from CuI, CuCl, CuBr and Cu2O or Cu (OTf)2。
According to the scheme, the copper salt catalyst is CuI.
According to the scheme, the dosage of the copper salt catalyst is 0.01-0.2 times of the dosage of the nitroolefin according to the amount of the substance.
According to the scheme, the dosage of the copper salt catalyst is 0.01 time of that of the nitroolefin according to the amount of the substance.
According to the scheme, the solvent is any one or the mixture of DMSO, DMF, DMA, ethanol, toluene and acetonitrile.
According to the above scheme, the solvent used was DMF.
According to the above scheme, the reaction is carried out at a temperature ranging from 80 to 130 ℃.
According to the scheme, the reaction is carried out at 110 ℃.
According to the scheme, the reaction time is 8-15 hours.
The specific reaction formula of the catalyst CuI at 110 ℃ is as follows:
the specific reaction steps are as follows: nitroolefin, ortho-aldehyde group substituted aryl azide, CuI and a solvent are magnetically stirred to react for 8-15 hours under the heating condition, after the reaction is finished, ethyl acetate is used for dissolving, an organic layer is washed by saturated saline solution, anhydrous sodium sulfate is dried, the solvent is evaporated under reduced pressure to obtain a crude product, and the product, namely the 3-nitroquinoline compound, is obtained through column chromatography separation and purification.
The invention has the beneficial effects that: the invention adopts cheap and easily available ortho-position aldehyde group substituted aryl azide as a raw material, and the aryl azide and nitroolefin undergo [3+2] cycloaddition under the catalysis of copper salt to obtain the 3-nitroquinoline compound, the reaction yield is high, the catalyst is low, reaction byproducts only contain nitrogen and water, the post-treatment is simple, and the synthesis method is environment-friendly.
Drawings
In order to more clearly illustrate the technical solution of the embodiment of the present invention, the drawings of the embodiment are briefly introduced below.
FIG. 1 is a scheme showing the synthesis of 2-phenyl-3-nitroquinoline compound according to example 1 of the present invention1H NMR characterization spectrum;
FIG. 2 shows the synthesis of 2-phenyl-3-nitroquinoline compound according to example 1 of the present invention13C NMR characterization spectrum;
FIG. 3 is a scheme showing the synthesis of 2- (2-bromophenyl) -3-nitroquinoline compound of example 2 of the present invention1H NMR characterization spectrum;
FIG. 4 shows the synthesis of 2- (2-bromophenyl) -3-nitroquinoline compound of example 2 of the present invention13C NMR characterization spectrum;
FIG. 5 shows a scheme for synthesizing a 2-phenyl-3-nitro-7-fluoroquinoline compound according to example 3 of the present invention1H NMR characterization spectrum;
FIG. 6 shows a scheme for synthesizing a 2-phenyl-3-nitro-7-fluoroquinoline compound according to example 3 of the present invention13C NMR characterization spectrum;
FIG. 7 shows the synthesis of 2- (2-furyl) -3-nitroquinoline compound in example 4 of the present invention1H NMR characterization spectrum;
FIG. 8 shows the synthesis of 2- (2-furyl) -3-nitroquinoline according to example 4 of the present invention13C NMR characterization spectrum;
FIG. 9 shows a scheme for synthesizing a 2-phenyl-3-nitro-6, 7-dimethoxyquinoline compound according to example 5 of the present invention1H NMR characterization spectrum;
FIG. 10 shows a scheme for synthesizing a 2-phenyl-3-nitro-6, 7-dimethoxyquinoline compound according to example 5 of the present invention13C NMR characterization spectrum.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
the method comprises the following specific steps: adding nitrostyrene (1mmol), 2-azidobenzaldehyde (1.5mmol), CuI (0.01mmol) and DMF (2mL) into a round-bottom flask (50mL), reacting at 110 ℃ under magnetic stirring for 8 hours, dissolving with ethyl acetate, washing an organic layer with saturated saline solution, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a crude product, and performing column separation and purification on the crude product by using ethyl acetate/petroleum ether ═ 1:10(V/V) as a leacheate to obtain the required product 2-phenyl-3-nitroquinoline, wherein the yield is 85 percent.
As shown in fig. 1 and fig. 2, the nuclear magnetic hydrogen spectrum result of the obtained product is as follows:1H NMR(600MHz,DMSO-d6):8.60(s,1H),8.20(d,J＝8.4Hz,1H),7.90(d,J＝8.4Hz,1H),7.86(t,J＝7.8Hz,1H),7.63(t,J＝7.2Hz,1H),7.58(d,J＝7.8Hz,2H),7.30(d,J＝7.8Hz,2H),2.42(s,3H).13C NMR(100MHz,CDCl3,ppm)152.1,148.3,143.9,137.0,132.8,132.6,129.8,129.6,128.7,128.6,128.4,128.1,125.5.
example 2:
the method comprises the following specific steps: adding nitro o-bromostyrene (1mmol), 2-azidobenzaldehyde (1.5mmol), CuI (0.01mmol) and toluene (2mL) into a round-bottom flask (50mL), reacting for 12 hours under magnetic stirring at 110 ℃, dissolving with ethyl acetate, washing an organic layer with saturated saline solution, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a crude product, and performing column separation and purification on the crude product by using ethyl acetate/petroleum ether ═ 1:10(V/V) as a leacheate to obtain the required product 2- (2-bromophenyl) -3-nitroquinoline as a yellow solid with the yield of 78%.
As shown in fig. 3 and 4, the nuclear magnetic hydrogen spectrum results of the obtained product are as follows:1H NMR(600MHz,CDCl3,ppm)8.98(s,1H),8.25(d,J＝8.4Hz,1H),8.06(d,J＝7.8Hz,1H),7.95(t,J＝7.2Hz,1H),7.74(t,J＝7.2Hz,1H),7.65(d,J＝7.8Hz,1H),7.59-7.45(m,2H),7.34(t,J＝7.2Hz,1H).13C NMR(100MHz,CDCl3,ppm)152.2,148.5,143.0,139.4,133.4,133.3,132.4,130.3,130.1,129.8,129.0,128.9,127.7,126.0,121.8.
example 3:
the method comprises the following specific steps: to a round-bottomed flask (50mL) were added nitrostyrene (1mmol), 2-azido-4-fluorobenzaldehyde (1.5mmol), Cu2O (0.01mmol) and DMSO (2mL) are magnetically stirred to react for 15 hours at 100 ℃, then ethyl acetate is used for dissolving, an organic layer is washed by saturated saline solution, anhydrous sodium sulfate is dried, a solvent is evaporated under reduced pressure to obtain a crude product, the crude product is subjected to column separation and purification by using ethyl acetate/petroleum ether (1: 15(V/V) as eluent to obtain the required product 2-phenyl-3-nitro-7-fluoroquinoline, the product is yellow solid, and the yield is 72%.
As shown in fig. 5 and 6, the nuclear magnetic hydrogen spectrum results of the obtained product are as follows:1H NMR(600MHz,CDCl3,ppm)8.70(s,1H),8.03-7.97(m,1H),7.86(d,J＝9.6Hz,1H),7.65(s,2H),7.48-7.51(m,4H).13C NMR(150MHz,CDCl3,ppm)166.0,164.3,153.3,149.6(d,J＝13.4Hz),143.5,136.7,132.7,130.8(d,J＝10.4Hz),129.8,128.8,122.5,119.3(d,J＝25.9Hz),113.8(d,J＝21.0Hz).
example 4:
the method comprises the following specific steps: adding 2-nitrofuranstyrene (1mmol), 2-azidobenzaldehyde (1.5mmol) and CuCl (0.01mmol) into a round-bottom flask (50mL), magnetically stirring at 100 ℃ for reaction for 12 hours, dissolving with ethyl acetate, washing an organic layer with saturated saline solution, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a crude product, and performing column separation and purification on the crude product by using ethyl acetate/petroleum ether ═ 1:15(V/V) as a leacheate to obtain the required product 2- (2-furyl) -3-nitroquinoline, wherein the product is a yellow solid, and the yield is 69%.
As shown in fig. 7 and 8, the nuclear magnetic hydrogen spectrum results of the obtained product are as follows:1H NMR(400MHz,CDCl3,ppm)8.45(s,1H),8.16(d,J＝8.4Hz,1H),7.83-7.89(m,2H),7.65-7.60(m,2H),7.23(d,J＝3.6Hz,1H),6.59-6.60(m,1H).13C NMR(100MHz,CDCl3,ppm)149.7,148.1,145.2,142.3,140.6,132.6,131.7,129.6,128.4,128.4,125.3,113.1,112.3.
example 5:
the method comprises the following specific steps: adding nitrostyrene (1mmol), 2-azido-4, 5-dimethoxybenzaldehyde (1.5mmol), CuBr (0.01mmol) and DMF (2mL) into a round-bottom flask (50mL), magnetically stirring at 130 ℃ for reaction for 11 hours, dissolving with ethyl acetate, washing an organic layer with saturated saline solution, drying with anhydrous sodium sulfate, evaporating under reduced pressure to remove a solvent to obtain a crude product, and carrying out column separation and purification on the crude product by using ethyl acetate/petroleum ether ═ 1:2.5(V/V) as eluent to obtain the required product, namely the 2-phenyl-3-nitro-6, 7-dimethoxyquinoline, wherein the product is a yellow solid, and the yield is 78%.
As shown in fig. 9 and 10, the nuclear magnetic hydrogen spectrum results of the obtained product are as follows:1H NMR(600MHz,CDCl3,ppm)8.55(s,1H),7.60(d,J＝4.8Hz,2H),7.52-7.44(m,4H),7.15(s,1H),4.05(s,3H),4.04(s,3H).13C NMR(100MHz,CDCl3,ppm)155.3,151.4,150.3,146.1,142.5,137.6,130.9,129.1,128.6,128.0,121.4,108.1,105.2,56.5,56.3.
the invention adopts cheap and easily available CuI as a catalyst to catalyze the reaction of nitroolefin and 2-azidobenzaldehyde to synthesize the 3-nitro-substituted quinoline compound, compared with the prior method, the method has the advantages of cheap and easily available reaction raw materials, simple and convenient operation, high reaction yield, low catalyst cost, nitrogen and water as byproducts, good atom economy and potential application value.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent minor changes fall within the scope of the present invention.
Claims (10)
- The synthesis process of the 3-nitroquinoline derivative is characterized by comprising the following steps: under the action of a copper salt catalyst, nitroolefin 1 and ortho aldehyde group substituted aryl azide 2 undergo a [3+2] cycloaddition reaction in the presence of a solvent, the specific reaction equation is shown as a formula I,
in the formula I, R1Is aryl or substituted aryl, alkyl or substituted alkyl, and R is halogen, methyl, methoxy, hydrogen or aryl. - 2. The process of claim 1, wherein the reaction is carried out in the presence of a catalyst: the copper salt catalyst is selected from CuI, CuCl, CuBr or Cu (OTf)2。
- 3. The synthesis process according to claim 2, characterized in that: the copper salt catalyst is CuI.
- 4. A process according to any one of claims 1 to 3, characterized in that: the dosage of the copper salt catalyst is 0.01 to 0.2 time of the dosage of the nitroolefin according to the amount of the substance.
- 5. The process of synthesis according to claim 4, characterized in that: the dosage of the copper salt catalyst is 0.01 time of that of the nitroolefin according to the amount of the substance.
- 6. The process according to any one of claims 1 to 3, wherein the solvent is any one or a mixture of DMSO, DMF, DMA, ethanol, toluene and acetonitrile.
- 7. The process of claim 6, wherein the solvent used is DMF.
- 8. The process of synthesis according to claim 6, characterized in that: the reaction is carried out at a temperature in the range of 80 to 130 ℃.
- 9. The process of synthesis according to claim 8, wherein: the reaction was carried out at 110 ℃.
- 10. The process of synthesis according to claim 6, characterized in that: the reaction time is 8-15 hours.
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Non-Patent Citations (4)
| Title |
|---|
| An Investigation of the Reaction of 2-Aminobenzaldehyde Derivatives with Conjugated Nitro-olefins: An Easy and Efficient Synthesis of 3-Nitro-1,2-dihydroquinolines and 3-Nitroquinolines;Ming-Chung Yan，et al.;《J.Org.Chem.》;20040212;第69卷(第5期);1565-1570 * |
| Bifunctional acid-base ionic liquid for the one-pot synthesis of fine chemicals:Thioethers, 2H-chromenes and 2H-quinoline derivatives;Marial J. Climent，et al.;《Applied Catalyst A: General》;20140514;第481卷;27-38 * |
| ISOLATION, BIOLOGICAL ACTIVITIES AND SYNTHESIS OF INDOLOQUINOLINE ALKALOIDS: CRYPTOLEPINE, ISOCRYPTOLEPINE AND NEOCRYPTOLEPINE;Prakash T. Parvatkar，et al.;《Curr. Org. Chem》;20111231;第15卷(第7期);1036-1057 * |
| Synthesis of 3-Amino- and 3-Nitro-2-arylquinolines;HENRY E.BAUMGARTEN,et al.;《Journal of the American Chemical Society》;19570320;第79卷;1502-1505 * |
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