CN106565603A - Method for synthesizing 5,7-binitro-8-carboxamidoquinoline compound - Google Patents
Method for synthesizing 5,7-binitro-8-carboxamidoquinoline compound Download PDFInfo
- Publication number
- CN106565603A CN106565603A CN201610926191.3A CN201610926191A CN106565603A CN 106565603 A CN106565603 A CN 106565603A CN 201610926191 A CN201610926191 A CN 201610926191A CN 106565603 A CN106565603 A CN 106565603A
- Authority
- CN
- China
- Prior art keywords
- nitrate
- reaction
- ethyl acetate
- quinolines
- subsequently adding
- 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.)
- Granted
Links
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
- C07D215/16—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
Abstract
The invention discloses a method for synthesizing a 5,7-binitro-8-carboxamidoquinoline compound, and belongs to the technical field of quinoline compounds. According to the key points of the technical scheme, the method comprises the steps of dissolving a 8-carboxamidoquinoline compound in a solvent; then adding nitrate and a catalyst; and performing a reaction at 80-120 DEG C to prepare the 5,7-binitro-8-carboxamidoquinoline compound. According to the method, cheap, nontoxic or low-toxicity nitrate is selected and used as a nitration reagent, and corrosive strong acid such as nitric acid, sulfuric acid and the like do not need to be used as the nitration reagent and the catalyst, so that the synthesis process is economic, efficient and environment-friendly; and an economic, practical and environment-friendly novel method is provided for synthesizing the 5,7-binitro-8-carboxamidoquinoline compound.
Description
Technical field
The invention belongs to the synthesis technical field of quinolines, and in particular to one kind 5,7- dinitro -8- amide groups
The synthetic method of quinolines.
Background technology
Used as a kind of important industrial chemicals, 5,7- dinitro -8- amide groups quinolines are in pharmacy and become more meticulous
The fields such as work have a wide range of applications.At present, the synthesis of such compound is mainly by using the mixed of excess nitrate and sulphuric acid
The nitration mixture of compound or excess is realized as nitrating agent.The method severe reaction conditions, so that the regioselectivity of reaction
It is poor with the functional group compatibility of substrate, meanwhile, serious harm is caused to environment because producing substantial amounts of spent acid also, so the party
The practicality of method is very limited.In view of this, further study and develop from the raw material being easy to get, in gentle reaction
Under the conditions of synthesize 5,7- dinitro -8- amide groups quinolines efficient, green new method have great importance.
The content of the invention
Present invention solves the technical problem that there is provided a kind of synthesis of 5,7- dinitros -8- amide groups quinolines
Method, the method with 8- amide groups quinolines as raw material, with nitrate as nitrating agent, with transition metal salt as catalysis
Agent, directly obtains 5,7- dinitro -8- amide groups quinolines by one pot reaction under conditions of existing without the need for strong acid,
The method is easy to operate, mild condition, wide application range of substrates, environmental friendliness, is adapted to industrialized production.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, 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 subsequently adding
And catalyst, 5,7- dinitro -8- amide groups quinolines, the reaction in the synthetic method is obtained in 80-120 DEG C of reaction
Equation is：
Wherein R1For alkyl, 2- thienyls, phenyl or substituted-phenyl, the substituent group on the substituted-phenyl phenyl ring is fluorine, chlorine
Or methyl, alkyl be the tert-butyl group, benzhydryl, diamantane (obsolete) -1- bases, 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, Schweinfurt green, Palladous chloride. or palladium, solvent be dichloroethanes, Isosorbide-5-Nitrae-dioxane,
Acetonitrile or trifluoroethanol.
Further limit, the ratio of the amount of the material that feeds intake of described 8- amide groups quinolines and nitrate is 1:
The ratio of the amount of the material that feeds intake of 0.5-2, described 8- amide groups quinolines and catalyst is 1:0.05-0.2.
The present invention has advantages below compared with prior art：(1) from inexpensive, nontoxic or low toxicity nitrate as nitre
Change reagent, make nitrating agent and catalyst without using the corrosivity strong acid such as nitric acid and sulphuric acid, make building-up process economy, efficiently,
Green, environmental protection；(2) raw material is easily prepared；(3) reaction is carried out below 120 DEG C, and mild condition is easy to operate；(4) substrate
It is applied widely；(5) regioselectivity reacted is high.Therefore, the present invention is 5,7- dinitro -8- amide groups quinolines
Synthesis there is provided a kind of economical and practical and environmental protection new method.
Specific embodiment
By the following examples the above of the present invention is described in further details, but this should not be interpreted as this
The scope for inventing above-mentioned theme is only limitted to below example, and all technologies realized based on the above of the present invention belong to this
Bright scope.
Embodiment 1
1a (0.5mmol, 114mg) and trifluoroethanol (TFE, 2.5mL) are added in the seal pipe of 15mL, Fe is subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 DEG C of stirring reactions 5 hours, so
Add 10mL saturated nacl aqueous solutions that reaction is quenched afterwards, be extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous slufuric acid
Sodium is dried.Filtration is spin-dried for, and crosses 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
Method as described in embodiment 1, adds 1a (0.5mmol, 114mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.25mmol, 101mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) obtain yellow solid
Body product 2a (32mg, 20%).
Embodiment 3
Method as described in embodiment 1, adds 1a (0.5mmol, 114mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (1mmol, 404mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 DEG C
Stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), merges
Organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) obtain yellow solid
Product 2a (127mg, 80%).
Embodiment 4
Method as described in embodiment 1, adds 1a (0.5mmol, 114mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.025mmol,4mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) obtain yellow solid
Body product 2a (80mg, 50%).
Embodiment 5
Method as described in embodiment 1, adds 1a (0.5mmol, 114mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Bi (NO, are subsequently adding3)3·5H2O (0.5mmol, 243mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) obtain yellow solid
Body product 2a (92mg, 58%).
Embodiment 6
Method as described in embodiment 1, adds 1a (0.5mmol, 114mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Co (NO, are subsequently adding3)2·6H2O (0.75mmol, 218mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) obtain yellow solid
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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and CuBr2(0.1mmol,22mg).In 100 DEG C of stirring reactions 5 hours, it is subsequently adding
10mL saturated nacl aqueous solutions are quenched reaction, are extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate drying.
Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) 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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and Cu (OTf)2(0.1mmol,36mg).In 100 DEG C of stirring reactions 5 hours, then
Add 10mL saturated nacl aqueous solutions that reaction is quenched, be extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate
It is dried.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) 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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and Cu (OAc)2(0.1mmol,18mg).In 100 DEG C of stirring reactions 5 hours, then
Add 10mL saturated nacl aqueous solutions that reaction is quenched, be extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate
It is dried.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) 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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and PdCl2(0.1mmol,18mg).In 100 DEG C of stirring reactions 5 hours, it is subsequently adding
10mL saturated nacl aqueous solutions are quenched reaction, are extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate drying.
Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) 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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and Pd (OAc)2(0.1mmol,22mg).In 100 DEG C of stirring reactions 5 hours, then
Add 10mL saturated nacl aqueous solutions that reaction is quenched, be extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate
It is dried.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) 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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 80 DEG C of stirring reactions 5 hours, then
Add 10mL saturated nacl aqueous solutions that reaction is quenched, be extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate
It is dried.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) 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 subsequently adding
(NO3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 120 DEG C of stirring reactions 5 hours, so
Add 10mL saturated nacl aqueous solutions that reaction is quenched afterwards, be extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous slufuric acid
Sodium is dried.Filtration is spin-dried for, and crosses 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 are subsequently adding3)3·
9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100 DEG C of stirring reactions 5 hours, it is subsequently adding
10mL saturated nacl aqueous solutions are quenched reaction, are extracted with ethyl acetate (10mL × 3), merge organic faciess, anhydrous sodium sulfate drying.
Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) yellow solid product 2a (64mg, 40%).
Embodiment 15
Method as described in embodiment 1, adds 1b (0.5mmol, 138mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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
Method as described in embodiment 1, adds 1c (0.5mmol, 140mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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
Method as described in embodiment 1, adds 1d (0.5mmol, 148mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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
Method as described in embodiment 1, adds 1e (0.5mmol, 146mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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
Method as described in embodiment 1, adds 1f (0.5mmol, 124mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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
Method as described in embodiment 1, adds 1g (0.5mmol, 138mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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
Method as described in embodiment 1, adds 1h (0.5mmol, 127mg) and trifluoroethanol in the seal pipe of 15mL
(2.5mL) Fe (NO, are subsequently adding3)3·9H2O (0.5mmol, 202mg) and CuCl2·2H2O(0.1mmol,17mg).In 100
DEG C stirring reaction 5 hours, is subsequently adding 10mL saturated nacl aqueous solutions and reaction is quenched, be extracted with ethyl acetate (10mL × 3), closes
And organic faciess, anhydrous sodium sulfate drying.Filtration is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=5:1) obtain 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 ultimate principle, principal character and the advantage of the present invention.The technical staff of the industry should
Understand, the present invention is not restricted to the described embodiments, the original for simply illustrating the present invention described in above-described embodiment and description
Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall 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, is subsequently adding nitrate and catalyst, and 5,7- dinitro -8- amide is obtained in 80-120 DEG C of reaction
Base quinolines, the reaction equation in the synthetic method is：
Wherein R1For alkyl, 2- thienyls, phenyl or substituted-phenyl, the substituent group on the substituted-phenyl phenyl ring is fluorine, chlorine or first
Base, alkyl are the tert-butyl group, benzhydryl, diamantane (obsolete) -1- bases, phenethyl, benzyl or substituted benzyl, on the substituted benzyl phenyl ring
Substituent group be fluorine, chlorine or methoxyl group, R2For hydrogen or methyl, nitrate is ferric nitrate, bismuth nitrate or cobalt nitrate, and catalyst is bromination
Copper, copper chloride, trifluoromethanesulfonic acid ketone, Schweinfurt green, Palladous chloride. or palladium, solvent are dichloroethanes, Isosorbide-5-Nitrae-dioxane, acetonitrile
Or trifluoroethanol.
2. the synthetic method of 5,7- dinitros -8- amide groups quinolines according to claim 1, its feature exist
In：The ratio of the amount of the material that feeds intake of described 8- amide groups quinolines and nitrate is 1:0.5-2, described 8- amide
The ratio of the amount of the material that feeds intake of base quinolines and catalyst is 1:0.05-0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610926191.3A CN106565603B (en) | 2016-10-31 | 2016-10-31 | A kind of synthetic method of 5,7- dinitro -8- amide groups quinolines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610926191.3A CN106565603B (en) | 2016-10-31 | 2016-10-31 | A kind of synthetic method of 5,7- dinitro -8- amide groups quinolines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106565603A true CN106565603A (en) | 2017-04-19 |
| CN106565603B CN106565603B (en) | 2019-01-01 |
Family
ID=58534351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610926191.3A Active CN106565603B (en) | 2016-10-31 | 2016-10-31 | A kind of synthetic method of 5,7- dinitro -8- amide groups quinolines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106565603B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314644A (en) * | 2018-01-19 | 2018-07-24 | 浙江工业大学 | A kind of synthetic method of naphthylamine derivative |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712289A (en) * | 1993-06-04 | 1998-01-27 | Ball State University | Quinoline-5,8-diones and methods of using them |
| US6030983A (en) * | 1993-06-04 | 2000-02-29 | Ball State University | Lavendamycin analogs, quinoline-5,8-diones and methods of using them |
| CN1854114A (en) * | 2005-04-21 | 2006-11-01 | 北京清华紫光英力化工技术有限责任公司 | Use of bismuth nitrate and iron nitrate as nitrification agent in aromatic compound nitrification |
-
2016
- 2016-10-31 CN CN201610926191.3A patent/CN106565603B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712289A (en) * | 1993-06-04 | 1998-01-27 | Ball State University | Quinoline-5,8-diones and methods of using them |
| US6030983A (en) * | 1993-06-04 | 2000-02-29 | Ball State University | Lavendamycin analogs, quinoline-5,8-diones and methods of using them |
| CN1854114A (en) * | 2005-04-21 | 2006-11-01 | 北京清华紫光英力化工技术有限责任公司 | Use of bismuth nitrate and iron nitrate as nitrification agent in aromatic compound nitrification |
Non-Patent Citations (4)
| Title |
|---|
| MARIA GRAZIA FERLIN等: "Synthesis and Characterization of some N-Mannich Bases of [1,2,3]Triazoloquinolines", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
| PRADEEP SADHU等: "Room-Temperature Cu(II)-Catalyzed Chemo- and Regioselective Ortho-Nitration of Arenes via C-H Functionalization", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| 张继昌，等: "选择性酚类化合物的单硝化及二硝化作用", 《河南师范大学学报(自然科学版)》 * |
| 李润莱，等: "5,7-二硝基-8-羟基喹哪啶合成工艺研究", 《化工时刊》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314644A (en) * | 2018-01-19 | 2018-07-24 | 浙江工业大学 | A kind of synthetic method of naphthylamine derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106565603B (en) | 2019-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109369610A (en) | A kind of synthetic method of cyclobutanol and nitro substituted naphthol class compound | |
| CN105801575A (en) | Synthetic method of imidazo[1,2-a]pyridine | |
| CN107188832A (en) | A kind of method that utilization carbon dioxide synthesizes the carbamate containing trifluoromethyl | |
| CN108640917A (en) | A kind of synthetic method of indoles simultaneously [2,1-a] isoquinoline compound | |
| CN107501278B (en) | A kind of synthetic method of 5H- furans -2- ketone and piperidines | |
| CN110483507A (en) | A kind of synthetic method of naphtho- [1 ', 2 ': 4,5] imidazo [1,2-a] pyridine compounds and their | |
| CN106565603A (en) | Method for synthesizing 5,7-binitro-8-carboxamidoquinoline compound | |
| CN106749071B (en) | A kind of preparation method of aromatics 1,2,4,5- tetrazine compound | |
| CN107602452B (en) | Synthetic method of 3-acyl pyridine compound | |
| CN106046002B (en) | A kind of synthetic method of pyridine-imidazole simultaneously [1,2,3] triazoloquinoline class compound | |
| CN106431800B (en) | (E) synthetic method of -4- oxo -2- butylene aldehyde compound | |
| CN107573270B (en) | A kind of synthetic method of α-formylpyrrole alkanes compound | |
| CN112876404B (en) | Synthesis method of phthalimide trifluoro-methionation reagent | |
| JP2016198736A (en) | Catalyst having amino-salicylaldimine ligand coordinated to metal and method for producing iodine cyclized product using the same | |
| CN106278989B (en) | The synthetic method of 3- cyanogen radical indole compounds | |
| CN112047896B (en) | Method for synthesizing aromatic ring group or aromatic heterocyclic group tetrazole | |
| CN106565604B (en) | A kind of synthetic method of 5- nitro -8- amide groups quinolines | |
| CN112194559B (en) | Synthesis method of chiral and achiral 2,2' -dihalogenated biaryl compound | |
| CN106748953A (en) | A kind of synthetic method of the formic ether compounds of pyrrolin 3 | |
| CN108516952A (en) | A kind of synthetic method of the hexa-atomic nitrogen-containing hetero cyclics of 3- acyl groups | |
| CN107266411A (en) | A kind of synthetic method of 9,10 Benzophenanthrene compound | |
| CN101454272A (en) | Fluoroamine having perfluoroalkyl group, process for producing the same, method of fluorination therewith, and method of recovering amide having perfluoroalkyl group | |
| CN108503572A (en) | A kind of synthetic method of 3- acyl pyrrolines class compound | |
| CN107663165A (en) | The new method that a kind of C H bond activations of the positions of indoles C 3 are efficiently esterified | |
| CN113039175A (en) | Preparation method of aryl sulfonyl acrylonitrile |
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 |