CN106565603B - A kind of synthetic method of 5,7- dinitro -8- amide groups quinolines - Google Patents

A kind of synthetic method of 5,7- dinitro -8- amide groups quinolines Download PDF

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CN106565603B
CN106565603B CN201610926191.3A CN201610926191A CN106565603B CN 106565603 B CN106565603 B CN 106565603B CN 201610926191 A CN201610926191 A CN 201610926191A CN 106565603 B CN106565603 B CN 106565603B
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quinolines
amide groups
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nitrate
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CN106565603A (en
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范学森
何艳
张新迎
赵宁宁
邱丽琪
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Henan Normal University
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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
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention discloses the synthetic methods of one kind 5,7- dinitro -8- amide groups quinolines, belong to the synthesis technical field of quinolines.Technical solution of the present invention main points are as follows: 8- amide groups quinolines are dissolved in solvent, nitrate and catalyst is then added, is reacted in 80-120 DEG C and 5,7- dinitro -8- amide groups quinolines is made.The present invention selects inexpensive, non-toxic or low-toxic nitrate as nitrating agent, make nitrating agent and catalyst without using the corrosivity strong acid such as nitric acid and sulfuric acid, make synthesis process economy, efficient, green, environmental protection, a kind of economical and practical and environmentally protective new method is provided for the synthesis of 5,7- dinitro -8- amide groups quinolines.

Description

A kind of synthetic method of 5,7- dinitro -8- amide groups quinolines
Technical field
The invention belongs to the synthesis technical fields of quinolines, and in particular to one kind 5,7- dinitro -8- amide groups The synthetic method of quinolines.
Background technique
As a kind of important industrial chemicals, 5,7- dinitro -8- amide groups quinolines are in pharmacy and fining The fields such as work have a wide range of applications.Currently, the synthesis of such compound is mainly by using the mixed of excess nitrate and sulfuric acid It closes object or excessive nitration mixture is realized as nitrating agent.This method severe reaction conditions, to make the regioselectivity of reaction It is poor with the functional group compatibility of substrate, meanwhile, also environment is caused to seriously endanger because generating a large amount of spent acid, so the party The practicability of method is very limited.In view of this, further studying and developing from the raw material being easy to get, in mild reaction Under the conditions of synthesize 5,7- dinitro -8- amide groups quinolines efficient, green new method have great importance.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of synthesis of 5,7- dinitro -8- amide groups quinolines Method, this method is using 8- amide groups quinolines as raw material, is catalysis with transition metal salt using nitrate as nitrating agent Agent directly obtains 5,7- dinitro -8- amide groups quinolines by one pot reaction under the conditions of without existing for strong acid, This method is easy to operate, mild condition, and wide application range of substrates is environmental-friendly, is suitble to industrialized production.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, one kind 5,7- dinitro -8- amide groups quinoline The synthetic method of class compound, it is characterised in that: 8- amide groups quinolines are dissolved in solvent, nitrate is then added And catalyst, it is reacted in 80-120 DEG C and 5,7- dinitro -8- amide groups quinolines is made, the reaction in the synthetic method Equation are as follows:
Wherein R1For alkyl, 2- thienyl, phenyl or substituted-phenyl, the substituent group on the substituted-phenyl phenyl ring is fluorine, chlorine Or methyl, alkyl are tert-butyl, benzhydryl, adamantane -1- base, phenethyl, benzyl or substituted benzyl, the substituted benzyl phenyl ring On substituent group be fluorine, chlorine or methoxyl group, R2For hydrogen or methyl, nitrate is ferric nitrate, bismuth nitrate or cobalt nitrate, and catalyst is Copper bromide, copper chloride, trifluoromethanesulfonic acid ketone, copper acetate, palladium chloride or palladium acetate, solvent be dichloroethanes, Isosorbide-5-Nitrae-dioxane, Acetonitrile or trifluoroethanol.
It further limits, the ratio between amount for the substance that feeds intake of the 8- amide groups quinolines and nitrate is 1: The ratio between amount for the substance that feeds intake of 0.5-2, the 8- amide groups quinolines and catalyst is 1:0.05-0.2.
Compared with the prior art, the present invention has the following advantages: (1) select inexpensive, non-toxic or low-toxic nitrate as nitre Change reagent, make nitrating agent and catalyst without using the corrosivity strong acid such as nitric acid and sulfuric acid, make synthesis process economy, efficiently, Green, environmental protection；(2) raw material is easily prepared；(3) reaction is carried out at 120 DEG C or less, and mild condition is easy to operate；(4) substrate It is applied widely；(5) regioselectivity reacted is high.Therefore, the present invention 5,7- dinitro -8- amide groups quinolines Synthesis provide a kind of economical and practical and environmentally protective new method.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment 1
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).It is stirred to react 5 hours in 100 DEG C, so 10mL saturated sodium chloride solution quenching reaction is added afterwards, is extracted with ethyl acetate (10mL × 3), merges organic phase, anhydrous slufuric acid Sodium is dry.Filtering is spin-dried for, cross silica gel post separation (petrol ether/ethyl acetate=5:1) yellow solid product 2a (137mg, 86%).The characterize data of the compound is as follows:1H NMR(600MHz,CDCl3)δ1.44(s,9H),7.89(dd,J1= 9.0Hz,J2=4.2Hz, 1H), 8.98 (s, 1H), 9.07 (dd, J1=10.2Hz, J2=1.8Hz, 1H), 9.29 (dd, J1= 9.0Hz,J2=1.8Hz, 1H), 10.34 (br s, 1H)13C NMR(150MHz,CDCl3)δ27.0,40.4,122.1, 122.9,126.6,133.6,133.9,137.5,138.7,140.4,151.0,176.3.HRMS calcd for C14H15N4O5:319.1037[M+H]+,found:319.1044。
Embodiment 2
By method described in embodiment 1,1a (0.5mmol, 114mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.25mmol, 101mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and silica gel post separation (petrol ether/ethyl acetate=20:1) it is solid to obtain yellow excessively Body product 2a (32mg, 20%).
Embodiment 3
By method described in embodiment 1,1a (0.5mmol, 114mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (1mmol, 404mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 DEG C It is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=20:1) and is obtained yellow solid Product 2a (127mg, 80%).
Embodiment 4
By method described in embodiment 1,1a (0.5mmol, 114mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.025mmol,4mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and silica gel post separation (petrol ether/ethyl acetate=20:1) it is solid to obtain yellow excessively Body product 2a (80mg, 50%).
Embodiment 5
By method described in embodiment 1,1a (0.5mmol, 114mg) and trifluoroethanol are added in the seal pipe of 15mL Bi (NO is then added in (2.5mL)3)3·5H2O (0.5mmol, 243mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and silica gel post separation (petrol ether/ethyl acetate=20:1) it is solid to obtain yellow excessively Body product 2a (92mg, 58%).
Embodiment 6
By method described in embodiment 1,1a (0.5mmol, 114mg) and trifluoroethanol are added in the seal pipe of 15mL Co (NO is then added in (2.5mL)3)2·6H2O (0.75mmol, 218mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and silica gel post separation (petrol ether/ethyl acetate=20:1) it is solid to obtain yellow excessively Body product 2a (103mg, 65%).
Embodiment 7
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and CuBr2(0.1mmol,22mg).It is stirred to react in 100 DEG C 5 hours, is then added 10mL saturated sodium chloride solution quenching reaction, is extracted with ethyl acetate (10mL × 3), merges organic phase, and anhydrous sodium sulfate is dry. Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (87mg, 55%).
Embodiment 8
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and Cu (OTf)2(0.1mmol,36mg).It is stirred to react 5 hours in 100 DEG C, then 10mL saturated sodium chloride solution quenching reaction is added, is extracted with ethyl acetate (10mL × 3), merges organic phase, anhydrous sodium sulfate It is dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (83mg, 52%).
Embodiment 9
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and Cu (OAc)2(0.1mmol,18mg).It is stirred to react 5 hours in 100 DEG C, then 10mL saturated sodium chloride solution quenching reaction is added, is extracted with ethyl acetate (10mL × 3), merges organic phase, anhydrous sodium sulfate It is dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (99mg, 62%).
Embodiment 10
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and PdCl2(0.1mmol,18mg).It is stirred to react in 100 DEG C 5 hours, is then added 10mL saturated sodium chloride solution quenching reaction, is extracted with ethyl acetate (10mL × 3), merges organic phase, and anhydrous sodium sulfate is dry. Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (116mg, 73%).
Embodiment 11
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and Pd (OAc)2(0.1mmol,22mg).It is stirred to react 5 hours in 100 DEG C, then 10mL saturated sodium chloride solution quenching reaction is added, is extracted with ethyl acetate (10mL × 3), merges organic phase, anhydrous sodium sulfate It is dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (75mg, 47%).
Embodiment 12
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).It is stirred to react 5 hours in 80 DEG C, then 10mL saturated sodium chloride solution quenching reaction is added, is extracted with ethyl acetate (10mL × 3), merges organic phase, anhydrous sodium sulfate It is dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (111mg, 70%).
Embodiment 13
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is then added (NO3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).It is stirred to react 5 hours in 120 DEG C, so 10mL saturated sodium chloride solution quenching reaction is added afterwards, is extracted with ethyl acetate (10mL × 3), merges organic phase, anhydrous slufuric acid Sodium is dry.Filtering is spin-dried for, cross silica gel post separation (petrol ether/ethyl acetate=5:1) yellow solid product 2a (134mg, 84%).
Embodiment 14
1a (0.5mmol, 114mg) and acetonitrile (2.5mL) are added in the seal pipe of 15mL, Fe (NO is then added3)3· 9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).It is stirred to react in 100 DEG C 5 hours, is then added 10mL saturated sodium chloride solution quenching reaction, is extracted with ethyl acetate (10mL × 3), merges organic phase, and anhydrous sodium sulfate is dry. Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid product 2a (64mg, 40%).
Embodiment 15
By method described in embodiment 1,1b (0.5mmol, 138mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2b (131mg, 72%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ 2.97 (t, J= 8.0Hz, 2H), 3.13 (t, J=8.0Hz, 2H), 7.21-7.32 (m, 5H), 7.86 (dd, J1=8.8Hz, J2=4.0Hz, 1H), 8.98-8.99(m,2H),9.27(dd,J1=8.8Hz, J2=1.2Hz, 1H), 9.90 (br s, 1H)13C NMR(150MHz, CDCl3)δ30.8,39.1,122.1,122.9,126.6,128.4,128.7,133.1,133.5,137.7,139.0,139.9, 143.9,145.3,150.9,170.2.HRMS calcd for C18H15N4O5:367.1037[M+H]+,found: 367.1059。
Embodiment 16
By method described in embodiment 1,1c (0.5mmol, 140mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2c (148mg, 80%).The characterize data of the compound is as follows:1H NMR(600MHz,CDCl3)δ3.93(s,2H),7.13 (t, J=8.4Hz, 2H), 7.40 (t, J=7.2Hz, 2H), 7.84 (dd, J1=8.4Hz, J2=4.2Hz, 1H), 8.94-8.97 (m, 2H), 9.25 (d, J=9.0Hz, 1H), 9.97 (br s, 1H)13C NMR(150MHz,CDCl3)δ43.6,116.2(d,2JC-F=20.7Hz), 122.0,122.9,126.6,128.8 (d,4JC-F=3.3Hz), 131.3 (d,3JC-F=7.7Hz), 133.0,133.5,137.6,139.2,140.1,151.0,162.5(d,1JC-F=245.0Hz), 168.6.HRMS calcd for C17H12FN4O5:371.0786[M+H]+,found:371.0787。
Embodiment 17
By method described in embodiment 1,1d (0.5mmol, 148mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2d (162mg, 84%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ3.93(s,2H),7.36 (d, J=8.8Hz, 2H), 7.42 (d, J=8.4Hz, 2H), 7.85 (dd, J1=8.4Hz, J2=4.0Hz, 1H), 8.95 (dd, J1 =8.4Hz, J2=1.2Hz, 1H), 8.98 (s, 1H), 9.25 (dd, J1=8.8Hz, J2=1.2Hz, 1H), 9.96 (br s, 1H).13C NMR(150MHz,CDCl3)δ43.7,122.0,122.9,126.6,129.4,131.0,131.5,133.0, 133.6,134.1,137.7,140.1,144.5,151.0,168.3.HRMS calcd for C17H11ClN4O5Na: 409.0310[M+Na]+,found:409.0317。
Embodiment 18
By method described in embodiment 1,1e (0.5mmol, 146mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2e (151mg, 79%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ3.84(s,3H),3.89 (s, 2H), 6.97 (d, J=8.8Hz, 2H), 7.35 (d, J=8.4Hz, 2H), 7.81 (dd, J1=8.8Hz, J2=4.4Hz, 1H),8.91(dd,J1=8.0Hz, J2=1.2Hz, 1H), 8.97 (s, 1H), 9.24 (dd, J1=8.8Hz, J2=1.2Hz, 1H),9.98(br s,1H).13C NMR(150MHz,CDCl3)δ43.7,55.3,114.1,114.7,122.0,122.9, 125.0,125.4,126.5,130.4,130.8,133.4,150.9,158.9,159.4,169.3.HRMS calcd for C18H15N4O6:383.0986[M+H]+,found:383.0989。
Embodiment 19
By method described in embodiment 1,1f (0.5mmol, 124mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2f (149mg, 88%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ 7.58 (t, J= 8.0Hz, 2H), 7.68 (t, J=7.6Hz, 1H), 7.90 (dd, J1=8.8Hz, J2=4.0Hz, 1H), 8.10 (d, J=8.4Hz, 2H),9.05-9.07(m,2H),9.31(dd,J1=8.8Hz, J2=1.6Hz, 1H), 10.78 (br s, 1H)13C NMR (150MHz,CDCl3)δ122.2,123.0,126.7,128.3,129.1,132.4,133.5,133.7,134.0,137.4, 138.9,140.3,151.0,164.9.HRMS calcd for C16H11N4O5:339.0724[M+H]+,found: 339.0724。
Embodiment 20
By method described in embodiment 1,1g (0.5mmol, 138mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2g (128mg, 70%).The characterize data of the compound is as follows:1H NMR(600MHz,CDCl3)δ2.43(s,3H),2.84 (s, 3H), 7.27 (d, J=6.6Hz, 2H), 7.73 (d, J=9.0Hz, 1H), 7.98 (d, J=7.8Hz, 2H), 8.96 (s, 1H), 9.15 (d, J=9.0Hz, 1H), 10.77 (br s, 1H)13C NMR(100MHz,CDCl3)δ21.7,25.2,121.2, 122.2,126.7,127.7,128.27,128.31,129.2,129.9,130.2,133.4,134.8,144.6,160.9, 164.9.HRMS calcd for C18H15N4O5:367.1037[M+H]+,found:367.1042。
Embodiment 21
By method described in embodiment 1,1h (0.5mmol, 127mg) and trifluoroethanol are added in the seal pipe of 15mL Fe (NO is then added in (2.5mL)3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 It DEG C is stirred to react 5 hours, 10mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (10mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=5:1) and is obtained yellow solid Product 2h (112mg, 65%).The characterize data of the compound is as follows:1H NMR(600MHz,CDCl3)δ7.25(dd,J1= 4.8Hz,J2=4.2Hz, 1H), 7.73 (d, J=4.8Hz, 1H), 7.91 (dd, J1=8.4Hz, J2=4.2Hz, 1H), 7.97 (d, J=3.6Hz, 1H), 9.06 (s, 1H), 9.08 (dd, J1=4.2Hz, J2=1.2Hz, 1H), 9.33 (dd, J1=9.0Hz, J2=1.2Hz, 1H), 10.70 (br s, 1H)13C NMR(100MHz,CDCl3)δ122.2,123.0,126.7,128.4, 131.5,133.5,133.7,136.9,138.9,140.1,151.0,159.3(two carbon overlapping).HRMS calcd for C14H9N4O5S:345.0288[M+H]+,found:345.0298。
Embodiment above describes basic principles and main features of the invention and advantages.The technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. one kind 5, the synthetic method of 7- dinitro -8- amide groups quinolines, it is characterised in that: by 8- amide groups quinoline Class compound is dissolved in solvent, and nitrate and catalyst is then added, and reacts in 80-120 DEG C and 5,7- dinitro -8- amide is made Base quinolines, the reaction equation in the synthetic method are as follows:
Wherein R1For tert-butyl, benzhydryl, adamantane -1- base, phenethyl, benzyl, substituted benzyl, 2- thienyl, phenyl or take For phenyl, the substituent group on substituted benzyl phenyl ring is fluorine, chlorine or methoxyl group, the substituent group on substituted-phenyl phenyl ring be fluorine, chlorine or Methyl, R2For hydrogen or methyl, nitrate is ferric nitrate, bismuth nitrate or cobalt nitrate, and catalyst is copper bromide, copper chloride, fluoroform Sulfonic acid ketone, copper acetate, palladium chloride or palladium acetate, solvent are dichloroethanes, Isosorbide-5-Nitrae-dioxane, acetonitrile or trifluoroethanol.
2. the synthetic method of 5,7- dinitro -8- amide groups quinolines according to claim 1, feature exist In: the ratio between described amount for the substance that feeds intake of 8- amide groups quinolines and nitrate is 1:0.5-2, the 8- amide The ratio between amount for the substance that feeds intake of base quinolines and catalyst is 1:0.05-0.2.
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