CN108689907A - A method of preparing 2- nitroindole derivatives - Google Patents

A method of preparing 2- nitroindole derivatives Download PDF

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CN108689907A
CN108689907A CN201810171850.6A CN201810171850A CN108689907A CN 108689907 A CN108689907 A CN 108689907A CN 201810171850 A CN201810171850 A CN 201810171850A CN 108689907 A CN108689907 A CN 108689907A
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pyridine
formoxyls
methyl
indoles
cyano
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CN108689907B (en
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邹建平
钱海峰
达莫拉·苏布
李成坤
陶泽坤
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Weng Houke
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/36—Oxygen atoms in position 3, e.g. adrenochrome
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a kind of methods preparing 2- nitroindole derivatives.The present invention is starting material using picolinoyl indoles, and raw material is easy to get, and type is extensive;The product types obtained using the method for the present invention are various, widely used, not only can be used directly, but also can be used for synthetic drug;In addition, method and step disclosed by the invention is simple, reaction condition is mild, target product high income, the small, operation of pollution and last handling process are simple, it is suitable for industrialized production.

Description

A method of preparing 2- nitroindole derivatives
Technical field
The invention belongs to the preparing technical fields of organic compound, and in particular to a kind of 2- nitroindole derivatives and correlation The preparation method of derived product.
Background technology
2- aminoindole derivatives(A)It can be as a kind of inhibitor of monoamine oxidase, for treating Alzheimer's disease (With reference to:Ondrej Benek., Ondrej Soukup., Marketa Pasdiorova., Lukas Hr℃h.., Vendula Sepsova., Petr Jost.,Martina Hrabinova, Daniel Jun.,Kamil Kuca., Dominykas Zala., Rona R. Ramsay., Jos Marco-Contelles., Kamil Musilek. ChemMedChem. 2016, 11, 1264 – 1269).
In nature, 2- aminoindole derivatives are basic structural unit or the important composition portion of many natural alkaloids Point.In the prior art, the synthetic method of 2- aminoindole derivatives is using 2- nitroindole derivatives as raw material, but existing synthesis The route raw material of 2- nitroindole derivatives is difficult to obtain, narrow scope of application, step are more, of high cost;In addition it needs to use folded Sodium nitride and hydrogen sulfide, thus with certain explosion and poisoning risk.Therefore need to research and develop new method with it is mild, efficient, The preparation 2- nitroindole derivatives of low cost.
Invention content
The object of the present invention is to provide a kind of methods preparing 2- nitroindole derivatives and related derivative product, have The advantages that raw material sources are simple, reaction condition is mild, post-processing is simple, yield is high.
To achieve the above object of the invention, the technical solution adopted by the present invention is:
A method of 2- nitroindole derivatives are prepared, are included the following steps, by picolinoyl indole derivatives, nitrous acid The tert-butyl ester, copper catalyst are dissolved in solvent, are reacted at room temperature ~ 100 DEG C, and 2- nitroindole derivatives are obtained.
The 2- nitroindole derivatives prepared using the present invention is raw materials, in the presence of ferric trichloride/activated carbon, hydrazine hydrate, 2- aminoindole derivatives can be prepared.
The invention also discloses application of the copper catalyst in preparing 2- nitroindole derivatives.
In the present invention, the picolinoyl indole derivatives are as shown in following chemical structure of general formula:
Wherein R1,R2,R3,R4And R5Selection take one of following scheme:
(1) R1For a kind of in hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R2,R3,R4With R5All it is hydrogen;
(2) R2For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R3,R4And R5 All it is hydrogen;
(3) R3For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R2,R4And R5 All it is hydrogen;
(4) R4For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R2,R3And R5 All it is hydrogen;
(5) R5For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, carboxaldehyde radicals or methyl formate base when, R1,R2,R3With R4All it is hydrogen;
The general structure of the 2- nitroindole derivatives is:
The chemical formula of the copper catalyst is CuXn, wherein X is Cl, Br, I, CN, (OAc)2In one kind;N is 1 or 2;
The solvent is selected from methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, N, N- dimethyl One kind in formamide, 1,4- dioxane.
In above-mentioned technical proposal, the picolinoyl indole derivatives are selected from:1- (pyridine -2- formoxyls) indoles, 1- (pyridine -2- formoxyls) -5- methyl indols, 1- (pyridine -2- formoxyls) -6- methyl indols, 1- (pyridine -2- formoxyls) -7- Methyl indol, 1- (pyridine -2- formoxyls) -5- methoxy-Indoles, 1- (pyridine -2- formoxyls) -5- benzyloxy indoles, 1- (pyrroles Pyridine -2- formoxyls) -4- fluoro indoles, 1- (pyridine -2- formoxyls) -6- fluoro indoles, 1- (pyridine -2- formoxyls) -5- chloro-indoles, 1- (pyridine -2- formoxyls) -6- chloro-indoles, 1- (pyridine -2- formoxyls) -4- bromo indoles, 1- (pyridine -2- formoxyls) -5- bromines Indoles, 1- (pyridine -2- formoxyls) indoles -4- methyl formates, 1- (pyridine -2- formoxyls) indole -5-carboxylic acid methyl esters, 1- (pyrroles Pyridine -2- formoxyls) -5- cyanoindoles, 1- (pyridine -2- formoxyls) -5- nitroindolines, 1- (pyridine -2- formoxyls) -3- methyl Indoles, 1- (pyridine -2- formoxyls) -3- methoxy-Indoles, 1- (pyridine -2- formoxyls) -3- Phenylindoles, 1- (pyridine -2- first Acyl group) indole -3-formaldehyde, 1- (pyridine -2- formoxyls) indole -3-carboxylic acid methyl esters, 1- (pyridine -2- formoxyls) -3- cyano Yin One kind in diindyl, 1- (pyridine -2- formoxyls) -3- cyano -6- chlorine, 1- (pyridine -2- formoxyls) -3- cyano -6- oxyindoles.
In above-mentioned technical proposal, the reaction carries out in air;Utilize thin-layer chromatography chromatography(TLC)Tracking reaction until It is fully completed.
In above-mentioned technical proposal, in molar ratio, picolinoyl indole derivatives: nitrite tert-butyl: copper catalyst 1 :(1~3):(0.05~0.15).Preferred ratio is picolinoyl indole derivatives: nitrite tert-butyl: copper catalyst is 1:2:0.10。
The reaction process of above-mentioned technical proposal is represented by:
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art:
1, the present invention is starting material using picolinoyl indole derivatives, and raw material is easy to get, is of low cost, type is more.
2, the reagent used in the present invention is cheap and easily-available, of low cost.
3, in method disclosed by the invention, reaction condition is mild, target product yield is high, operation and last handling process Simply, it is suitable for industrialized production.
Specific implementation mode
With reference to embodiment, the invention will be further described:
Embodiment one:The synthesis of 2- nitroindolines
Using 1- (pyridine -2- formoxyls) indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) indoles is added in reaction bulb(0.111 gram, 0.5 mmol), nitrite tert-butyl(0.2 Ml, 1.5 mmol), copper acetate (0.00453 g, 0.025 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 92%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ12.66 (s, 1H), 8.66 (s, 1H), 8.10 (s, 1H), 7.57 (s, 1H), 7.36 (s, 2H)。
1- (pyridine -2- formoxyls) indoles is added in reaction bulb(0.111 gram, 0.5 mmol), nitrite tert-butyl (0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 96%).
Embodiment two:The synthesis of 2- nitro -5- methyl indols
Using 1- (pyridine -2- formoxyls) -5- methyl indols, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- methyl indols are added in reaction bulb(0.118 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.07 ml, 0.5 mmol), copper acetate (0.014 g, 0.075 mmol) and methanol(2 mL), 40 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 84%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.59 (s, 1H), 8.63 (s, 1H), 7.94(s, 1H), 7.49-7.51(d, J = 8.3 Hz, 1H), 7.20-7.22 (dd, J = 8.4, 1.2 Hz, 1H), 2.50 (s, 3H)。
1- (pyridine -2- formoxyls) -5- methyl indols are added in reaction bulb(0.118 gram, 0.5 mmol), nitrous acid The tert-butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and methanol(2 mL), 40 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 91%).
Embodiment three:The synthesis of 2- nitro -6- methyl indols
Using 1- (pyridine -2- formoxyls) -6- methyl indols, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -6- methyl indols are added in reaction bulb(0.118 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and ethyl alcohol(2 mL), room temperature reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 87%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.55 (s, 1H), 8.60 (d, J = 3.5 Hz, 1H), 7.98-8.00 (d, J = 8.2 Hz, 1H), 7.38 (s, 1H), 7.21-7.23 (d, J = 8.1 Hz, 1H), 2.46 (s, 3H)。
1- (pyridine -2- formoxyls) -6- methyl indols are added in reaction bulb(0.118 gram, 0.5 mmol), nitrous acid The tert-butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and ethyl alcohol(2 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 93%).
Example IV:The synthesis of 2- nitro -7- methyl indols
Using 1- (pyridine -2- formoxyls) -7- methyl indols, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -7- methyl indols are added in reaction bulb(0.118 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), cuprous cyanide (0.005g, 0.05 mmol) and n,N-Dimethylformamide(3 mL), 90 DEG C reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 88%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 13.05 (s, 1H), 8.76 (s, 1H), 8.01-8.02(d, J = 1.9 Hz, 1H), 7.52 (d, J=1.8 Hz, 1H), 7.38 (s, 1H), 3.99 (s, 3H)。
Embodiment five:The synthesis of 2- nitro -5- methoxy-Indoles
Using 1- (pyridine -2- formoxyls) -5- methoxy-Indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- methoxy-Indoles are added in reaction bulb(0.126 gram, 0.5 mmol), nitrous acid The tert-butyl ester(0.14 ml, 1.0 mmol), copper chloride (0.0067 g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C Reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 82%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.59 (s, 1H), 8.59- 8.60 (d, J = 3.4 Hz, 1H), 7.49-7.58 (dd, J = 31.8, 5.4 Hz, 1H), 7.10-7.40 (m, 1H), 6.98-7.01 (dd, J=8.8,2.1 Hz, 1H), 3.87 (s, 3H).
Embodiment six:The synthesis of 2- nitro -5- benzyloxy indoles
Using 1- (pyridine -2- formoxyls) -5- benzyloxy indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- benzyloxy indoles are added in reaction bulb(0.164 gram, 0.5 mmol), nitrous acid The tert-butyl ester(0.14 ml, 1.0 mmol), cuprous bromide (0.0071 g, 0.05 mmol) and acetonitrile(2 mL), 60 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 78%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.58 (s, 1H), 8.57 (d, J = 3.4 Hz, 1H), 7.67 (d, J = 2.3 Hz, 1H), 7.48-7.51 (dd, J = 8.0, 4.0 Hz, 3H), 7.39-7.42 (t, J = 7.4 Hz, 2H), 7.32-7.35 (t, J = 7.2 Hz, 1H), 7.05 (dd, J = 8.9, 2.4 Hz, 1H), 5.83 (s, 2H)。
Embodiment seven:The synthesis of 2- nitro -4- fluoro indoles
Using 1- (pyridine -2- formoxyls) -4- fluoro indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -4- fluoro indoles are added in reaction bulb(0.120 gram, 0.5 mmol), the tertiary fourth of nitrous acid Ester(0.14 ml, 1.0 mmol), cuprous iodide (0.0095 g, 0.05 mmol) and toluene(2 mL), 80 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 91%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.92 (s, 1H), 8.70 (s, 1H), 7.41-7.43 (d, J = 8.1 Hz, 1H), 7.342-7.37(td, J = 7.9, 4.7 Hz, 1H), 7.10-7.15 (dd, J = 11.5, 7.9 Hz, 1H)。
Embodiment eight:The synthesis of 2- nitro -6- fluoro indoles
Using 1- (pyridine -2- formoxyls) -6- fluoro indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -6- fluoro indoles are added in reaction bulb(0.120 gram, 0.5 mmol), the tertiary fourth of nitrous acid Ester(0.14 ml, 1.0 mmol), cuprous iodide (0.0095 g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C anti- It answers;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 90%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.71 (s, 1H), 8.67- 8.68 (d, J = 3.0 Hz, 1H), 8.08-8.10 (dd, J = 8.8, 5.4 Hz, 1H), 7.40-7.42(dd,J = 9.4, 2.3 Hz, 1H), 7.23-7.42 (m, 1H)。
Embodiment nine:The synthesis of 2- nitro -5- chloro-indoles
Using 1- (pyridine -2- formoxyls) -5- chloro-indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- chloro-indoles are added in reaction bulb(0.128 gram, 0.5 mmol), the tertiary fourth of nitrous acid Ester(0.14 ml, 1.0 mmol), copper bromide (0.11 g, 0.05 mmol) and acetone(2 mL), 50 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 89%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.79 (s, 1H), 8.67 (s, 1H), 8.00 (s, 1H), 7.55-7.56 (d, J = 6.4 Hz, 1H), 7.33 (s, 1H)。
Embodiment ten:The synthesis of 2- nitro -6- chloro-indoles
Using 1- (pyridine -2- formoxyls) -6- chloro-indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -6- chloro-indoles are added in reaction bulb(0.128 gram, 0.5 mmol), the tertiary fourth of nitrous acid Ester(0.14 ml, 1.0 mmol), CuCl2(0.07g, 0.05 mmol) and 1,4- dioxane(2 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 86%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.75 (s, 1H), 8.69 (s, 1H), 8.06-8.08 (d, J = 8.5 Hz, 1H), 7.63 (s, 1H), 7.39-7.41 (d, J = 8.2 Hz, 1H)。
Embodiment 11:The synthesis of 2- nitro -4- bromo indoles
Using 1- (pyridine -2- formoxyls) -4- bromo indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -4- bromo indoles are added in reaction bulb(0.149 gram, 0.5 mmol), the tertiary fourth of nitrous acid Ester(0.14 ml, 1.0 mmol), copper chloride (0.0067 g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 80 DEG C anti- It answers;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 85%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.82 (s, 1H), 8.68 (d, J = 2.0 Hz, 1H), 7.53-7.59 (ddd, J = 15.5, 7.9, 0.8 Hz, 2H), 7.20-7.24 (m, 1H)。
Embodiment 12:The synthesis of 2- nitro -5- bromo indoles
Using 1- (pyridine -2- formoxyls) -5- bromo indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- bromo indoles are added in reaction bulb(0.149 gram, 0.5 mmol), the tertiary fourth of nitrous acid Ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and ethyl acetate(2 mL), 60 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 92%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.83 (s, 1H), 8.70 (s, 1H), 8.19 (d, J = 1.3 Hz, 1H), 7.47-8.56 (dt, J = 8.7, 5.1 Hz, 2H)。
Embodiment 13:The synthesis of 2- nitroindoline -4- methyl formates
Using 1- (pyridine -2- formoxyls) indoles -4- methyl formates, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) indoles -4- methyl formates are added in reaction bulb(0.140 gram, 0.5 mmol), nitrous Tert-butyl acrylate(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 100 DEG C reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 95%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.92 (s, 1H), 8.75 (s, 1H), 7.76-7.78 (d, J = 8.1 Hz, 1H), 7.51-7.52 (d, J = 6.9 Hz, 1H), 7.43- 7.47 (t, J = 7.7 Hz, 1H), 3.85 (s, 3H)。
Embodiment 14:The synthesis of 2- nitroindoline -5- methyl formates
Using 1- (pyridine -2- formoxyls) indole -5-carboxylic acid methyl esters, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) indole -5-carboxylic acid methyl esters is added in reaction bulb(0.140 gram, 0.5 mmol), nitrous Tert-butyl acrylate(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 88%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.96 (s, 1H), 8.73- 8.81 (d, J = 30.8 Hz, 2H), 7.69-7.95 (d, J = 104.9 Hz, 2H), 3.93 (s, 3H)。
Embodiment 15:The synthesis of 2- nitro -5- cyanoindoles
Using 1- (pyridine -2- formoxyls) -5- cyanoindoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- cyanoindoles are added in reaction bulb(0.123 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), cuprous bromide (0.0071 g, 0.05 mmol) and 1,2- dichloroethanes(2 mL), 60 DEG C Reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 92%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 13.12 (s, 1H), 8.88 (s, 1H), 8.49 (s, 1H), 7.76-8.80 (t, J = 6.9 Hz, 2H)。
Embodiment 16:The synthesis of 2,5- dinitro indoles
Using 1- (pyridine -2- formoxyls) -5- nitroindolines, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -5- nitroindolines are added in reaction bulb(0.133 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and water(2 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 75%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 13.15 (s, 1H), 8.92 (s, 1H), 8.60 (s, 1H), 7.81-8.85 (t, J = 6.9 Hz, 2H)。
Embodiment 17:The synthesis of 2- nitro -3- methyl indols
Using 1- (pyridine -2- formoxyls) -3- methyl indols, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -3- methyl indols are added in reaction bulb(0.118 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), under air 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 75%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 11.21 (s, 1H), 7.51- 7.3 (d, J = 7.5 Hz, 1H), 7.42-7.46 (t, J = 7.7 Hz, 1H), 7.10-7.14 (t, J = 7.6 Hz, 1H), 7.02-7.04 (d, J = 7.8 Hz, 1H), 1.96 (s, 3H)。
Embodiment 18:The synthesis of 2- nitro -3- methoxy-Indoles
Using 1- (pyridine -2- formoxyls) -3- methoxy-Indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -3- methoxy-Indoles are added in reaction bulb(0.126 gram, 0.5 mmol), nitrous acid The tert-butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C Reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 78%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 11.22 (s, 1H), 7.50- 7.30 (d, J = 7.5 Hz, 1H), 7.42-7.46 (t, J = 7.7 Hz, 1H), 7.09-7.15 (t, J = 7.6 Hz, 1H), 7.02-7.06 (d, J = 7.8 Hz, 1H), 3.96 (s, 3H)。
Embodiment 19:The synthesis of 2- nitro -3- Phenylindoles
Using 1- (pyridine -2- formoxyls) -3- Phenylindoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -3- Phenylindoles are added in reaction bulb(0.149 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), copper chloride (0.0067 g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C anti- It answers;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 81%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 11.25 (s, 1H), 7.50- 7.30 (m, 3H), 7.42-7.46 (m, 2H), 7.09-7.15 (m, 2H), 7.02-7.06 (m, 2H)。
Embodiment 20:The synthesis of 2- nitroindoline -3- formaldehyde
Using 1- (pyridine -2- formoxyls) indole -3-formaldehyde, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) indole -3-formaldehyde is added in reaction bulb(0.125 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), CuI2(0.16g, 0.05 mmol) and 1,4- dioxane(2 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 83%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.66 (s, 1H), 8.65- 8.66 (d, J = 3.5 Hz, 1H), 8.09 (dd, J = 6.2, 2.6 Hz, 1H), 7.57-7.59 (dd, J = 6.1, 2.4 Hz, 1H), 7.32– 7.39 (m, 2H)。
Embodiment 21:The synthesis of 2- nitroindoline -3- methyl formates
Using 1- (pyridine -2- formoxyls) indole -3-carboxylic acid methyl esters, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) indole -3-carboxylic acid methyl esters is added in reaction bulb(0.140 gram, 0.5 mmol), nitrous Tert-butyl acrylate(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), 70 DEG C reaction;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 85%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.59 (s, 1H), 8.48 (d, J = 3.1 Hz, 1H), 8.41-8.42(d, J = 2.0 Hz, 1H), 8.15-8.17 (d, J = 8.9 Hz, 1H), 8.07-8.10 (dd, J = 8.9, 2.1 Hz, 1H), 3.87 (s, 3H)。
Embodiment 22:The synthesis of 2- nitro -3- cyanoindoles
Using 1- (pyridine -2- formoxyls) -3- cyanoindoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -3- cyanoindoles are added in reaction bulb(0.123 gram, 0.5 mmol), nitrous acid uncle Butyl ester(0.14 ml, 1.0 mmol), copper acetate (0.0091g, 0.05 mmol) and Isosorbide-5-Nitrae-dioxane(2 mL), under air 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (Yield 83%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.86 (s, 1H), 8.65 (d, J = 2.2 Hz, 1H), 8.48 (d, J = 1.8 Hz, 1H), 8.11-8.13 (dd, J = 8.8, 1.9 Hz, 1H), 7.87-7.89 (d, J = 8.8 Hz, 1H)。
Embodiment 23:The synthesis of 2- nitro -3- cyano -6- chloro-indoles
Using 1- (pyridine -2- formoxyls) -3- cyano -6- chloro-indoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -3- cyano -6- chloro-indoles are added in reaction bulb(2.8 grams, 10 mmol), nitrous acid The tert-butyl ester(2.8 ml, 20 mmol), copper acetate (0.182g, 1.0 mmol) and Isosorbide-5-Nitrae-dioxane(40 mL), 70 DEG C anti- It answers;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (1.86 grams, yield 84%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 12.87 (s, 1H), 8.67 (d, J = 2.2 Hz, 1H), 8.50 (d, J = 1.8 Hz, 1H), 8.12 (dd, J = 8.8, 1.9 Hz, 1H)。
2- Amino 3 cyano -6- chloro-indoles are prepared by raw material of 2- nitro -3- cyano -6- chloro-indoles, reaction step is such as Under:
(1)2- nitro -3- cyano -6- chloro-indoles are added in reaction bulb(1.86 gram), 95% ethyl alcohol(15 milliliters), ferric trichloride/ Activated carbon(0.10 gram)And hydrazine hydrate(1.5 milliliter), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (1.50 grams, yield 93%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 10.83 (s, 1H), 7.10 (d, J = 8.3 Hz, 1H), 7.08 (d, J = 1.7 Hz, 1H), 6.92 (s, 2H), 6.88 (dd, J = 8.3, 1.9 Hz, 1H)。
Embodiment 24:The synthesis of 2- nitro -3- cyano -6- oxyindoles
Using 1- (pyridine -2- formoxyls) -3- cyano -6- oxyindoles, as raw material, reaction step is as follows:
1- (pyridine -2- formoxyls) -3- cyano -6- oxyindoles are added in reaction bulb(2.62 grams, 10.0 mmol), sub- The nitric acid tert-butyl ester(2.8 ml, 20.0 mmol), copper acetate (0.182g, 1.0 mmol) and Isosorbide-5-Nitrae-dioxane(40 mL), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (1.73 grams, yield 85%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 10.62 (s, 1H), 8.73 (s, 1H), 6.80 (d, J = 8.4 Hz, 1H), 6.54 (d, J = 2.3 Hz, 1H), 6.31 (dd, J = 8.4, 2.3 Hz, 1H).
2- Amino 3 cyano -6- oxyindoles, reaction are prepared with the raw material that synthesizes of 2- nitro -3- cyano -6- oxyindoles Steps are as follows:
(1)2- nitro -3- cyano -6- oxyindoles are added in reaction bulb(1.73 gram), 95% ethyl alcohol(15 milliliters), tri-chlorination Iron/activated carbon(0.10 gram)And hydrazine hydrate(1.5 milliliter), 70 DEG C of reactions;
TLC tracking reactions are until be fully completed;
Crude by column chromatography separation (the ethyl acetate obtained after reaction:Petroleum ether=1:4) target product, is obtained (1.40 grams, yield 95%).The analysis data of product are as follows:1H NMR (400 MHz, DMSO-d 6 ):δ 10.61 (s, 1H), 8.75 (s, 1H), 6.92 (s, 2H), 6.81 (d, J = 8.4 Hz, 1H), 6.51 (d, J = 2.3 Hz, 1H), 6.36 (dd, J = 8.4, 2.3 Hz, 1H)。
The invention discloses a kind of methods preparing 2- nitroindole derivatives can through reduction from 2- nitroindolines One-step synthesis 2- aminoindole derivatives;The synthetic method route is short, wide application range of substrates, and yield is high, is suitable for industrializing Production.

Claims (10)

1. a kind of method preparing 2- nitroindole derivatives, which is characterized in that include the following steps:By picolinoyl indoles Derivative, nitrite tert-butyl, copper catalyst are dissolved in solvent, are reacted at room temperature~100 DEG C, are obtained 2- nitroindolines and are derived Object;
The picolinoyl indole derivatives are as shown in following chemical structure of general formula:
Wherein R1,R2,R3,R4And R5Selection take one of following scheme:
(1) R1For a kind of in hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R2,R3,R4With R5All it is hydrogen;
(2) R2For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R3,R4And R5All For hydrogen;
(3) R3For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R2,R4And R5All For hydrogen;
(4) R4For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R2,R3And R5All For hydrogen;
(5) R5For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, carboxaldehyde radicals or methyl formate base when, R1,R2,R3And R4 All it is hydrogen;
The general structure of the 2- nitroindole derivatives is:
The chemical formula of the copper catalyst is CuXn, wherein X is Cl, Br, I, CN, (OAc)2In one kind;N is 1 or 2.
2. the preparation method of 2- nitroindole derivatives according to claim 1, it is characterised in that:In molar ratio, pyridine first Acyl indol derivatives: nitrite tert-butyl: copper catalyst 1:(1~3):(0.05~0.15).
3. the preparation method of 2- nitroindole derivatives according to claim 1, it is characterised in that:After reaction to product Carry out column chromatography for separation purification processes.
4. the preparation method of 2- nitroindole derivatives according to claim 1, it is characterised in that:The solvent is selected from first Alcohol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane In one kind.
5. the preparation method of 2- nitroindole derivatives according to claim 1, it is characterised in that:The picolinoyl Yin Diindyl derivative is selected from 1- (pyridine -2- formoxyls) indoles, 1- (pyridine -2- formoxyls) -5- methyl indols, 1- (pyridine -2- formyls Base) -6- methyl indols, 1- (pyridine -2- formoxyls) -7- methyl indols, 1- (pyridine -2- formoxyls) -5- methoxy-Indoles, 1- (pyridine -2- formoxyls) -5- benzyloxy indoles, 1- (pyridine -2- formoxyls) -4- fluoro indoles, 1- (pyridine -2- formoxyls) -6- Fluoro indole, 1- (pyridine -2- formoxyls) -5- chloro-indoles, 1- (pyridine -2- formoxyls) -6- chloro-indoles, 1- (pyridine -2- formyls Base) -4- bromo indoles, 1- (pyridine -2- formoxyls) -5- bromo indoles, 1- (pyridine -2- formoxyls) indoles -4- methyl formates, 1- (pyridine -2- formoxyls) indole -5-carboxylic acid methyl esters, 1- (pyridine -2- formoxyls) -5- cyanoindoles, 1- (pyridine -2- formyls Base) -5- nitroindolines, 1- (pyridine -2- formoxyls) -3- methyl indols, 1- (pyridine -2- formoxyls) -3- methoxy-Indoles, 1- (pyridine -2- formoxyls) -3- Phenylindoles, 1- (pyridine -2- formoxyls) indole -3-formaldehyde, 1- (pyridine -2- formoxyls) Yin Diindyl -3- methyl formates, 1- (pyridine -2- formoxyls) -3- cyanoindoles, 1- (pyridine -2- formoxyls) -3- cyano -6- chlorine, 1- One kind in (pyridine -2- formoxyls) -3- cyano -6- oxyindoles.
6. the preparation method of 2- nitroindole derivatives according to claim 1, it is characterised in that:Utilize thin-layer chromatography chromatography Tracking reaction is until be fully completed.
7. the preparation method of 2- nitroindole derivatives according to claim 1, it is characterised in that:The reaction is in air It carries out.
8. application of the copper catalyst in preparing 2- nitroindole derivatives.
9. application according to claim 8, which is characterized in that the method for preparing 2- nitroindole derivatives includes following step Suddenly:Picolinoyl indole derivatives, nitrite tert-butyl, copper catalyst are dissolved in solvent, reacted at room temperature ~ 100 DEG C, Obtain 2- nitroindole derivatives
The picolinoyl indole derivatives are as shown in following chemical structure of general formula:
Wherein R1,R2,R3,R4And R5Selection take one of following scheme:
(1) R1For a kind of in hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R2,R3,R4With R5All it is hydrogen;
(2) R2For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R3,R4And R5All For hydrogen;
(3) R3For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R2,R4And R5All For hydrogen;
(4) R4For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, methyl formate base or nitro when, R1,R2,R3And R5All For hydrogen;
(5) R5For a kind of in methyl, methoxyl group, fluorine, chlorine, bromine, cyano, carboxaldehyde radicals or methyl formate base when, R1,R2,R3And R4 All it is hydrogen;
The chemical structure of general formula of the 2- nitroindole derivatives is:
The chemical formula of the copper catalyst is CuXn, wherein X is Cl, Br, I, CN, (OAc)2In one kind;N is 1 or 2.
10. 2- nitroindole derivatives prepared by preparation method according to claim 1.
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