CN106008309A - Method for preparing isatin derivative by visible-light photocatalysis - Google Patents
Method for preparing isatin derivative by visible-light photocatalysis Download PDFInfo
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- CN106008309A CN106008309A CN201610357787.6A CN201610357787A CN106008309A CN 106008309 A CN106008309 A CN 106008309A CN 201610357787 A CN201610357787 A CN 201610357787A CN 106008309 A CN106008309 A CN 106008309A
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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
- C07D209/32—Oxygen atoms
- C07D209/38—Oxygen atoms in positions 2 and 3, e.g. isatin
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Abstract
The invention discloses a method for preparing an isatin derivative by visible-light photocatalysis, and belongs to the technical field of visible-light catalytic synthesis. The synthetic route of the isatin derivative is shown in the description, wherein the structural formula of DPZ is shown in the description, R<1> is -H, -OMe, -F or -Cl, and R<2> is -Me, -Bn or -Ph; the synthesis procedures are that a compound I, DPZ, H2O (water) and LiBr(Lithium Bromide) are dissolved in CH3CN (Acetonitrile), in the oxygen atmosphere, a constant-temperature reaction is carried out at the temperature of 25 DEG C under a blue light source, tracing monitoring of TLC is performed, and a compound II is obtained by post-treatment after the reaction is finished. According to the invention, isatin compounds can be prepared by a green and environmental protection manner, and the method for preparing the isatin derivative by the visible-light photocatalysis disclosed by the invention is green and environment-friendly in reaction, low in cost, high in efficiency and short in reaction path.
Description
Technical field
The invention belongs to visible light catalytic synthesis technical field, be specifically related to a kind of method that visible light catalytic prepares Isatine derivatives.
Background technology
Isatin is mainly used as dyestuff and medicine intermediate, can produce medicine cinchophen, dyestuff disperse yellow E-3G, it is possible to as chemical reagent, analytical reagent, is used for analyzing mensuration cuprous ion, mercaptan, thiophenol, thiophene, indican etc..The method of traditional synthesis isatin is that aniline is condensed to obtain oximido antifebrin with Chloral oxime, then prepares isatin through cyclization, hydrolysis.
Photocatalysis method received everybody extensive concern due to its advantage such as relative clean and rich reserves in recent years.The aerobic oxidation reaction of visible light catalytic utilizes this abundant and reproducible eco-friendly power source of visible ray, using oxygen as oxidant, complies fully with the requirement that " Green Chemistry " develops, and causes chemists interest greatly in organic synthesis.Dicyano Pyrazine photosensitizer (DPZ) can be as a kind of novel photocatalyst, this catalyst applies in different types of photoredox reaction, and correlated response shows that this catalyst shows the highest catalytic efficiency (consumption normally only needs 0.5% to 0.01%) and some distinctive catalytic properties.
Summary of the invention
It is an object of the invention to provide a kind of method that visible light catalytic prepares Isatine derivatives.
Based on above-mentioned purpose, the present invention adopts the following technical scheme that:
A kind of visible light catalytic prepares the method for Isatine derivatives, and synthetic route is as follows:
Wherein, the structural formula of DPZ is as follows:(synthetic method list of references: Zhao, Y.；Zhang,C.；Chin,K.F.；Pytela,O.；Wei,G.；Liu,H.；F.；Jiang, Z.Dicyanopyrazine-Derived Push-Pull Chromophores for Highly Efficient Photoredox Catalysis, RSC Adv.2014,4,30062-30067.), R1For-H ,-OMe ,-F or-Cl, R2For-Me ,-Bn or-Ph；
Synthesis step is: by compound 1, DPZ, H2O, LiBr are dissolved in CH3In CN, 25 DEG C of isothermal reactions under oxygen atmosphere, blue lamp source, TLC tracking and monitoring, reaction i.e. obtains compound 2 through column chromatography for separation after terminating.
Further, compound thing 1, DPZ, H2The mol ratio of O and LiBr is 1 0.005 30 0.2.
Described blue lamp refer to power be 3W, wavelength be the blue lamp of 450-455nm.
The present invention can prepare isatin compounds with environmental protection, present invention have an advantage that reaction environmental protection, low cost, and efficiency is high, and response path is short.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in further detail, but protection scope of the present invention is not limited thereto.
Instrument and Primary Chemical
Bruker AV-400 type nuclear magnetic resonance analyser (German)；Agilent 1200 high performance liquid chromatograph (U.S.).
Raw material, solvent used in implementation process of the present invention are commercial sources and buy.
Embodiment 1:
The structural formula of compound 2a is as follows:
The synthetic route of compound 2a is as follows:
The synthesis step of compound 2a is as follows:
(1) the DPZ solution (1mg is dissolved in 160 μ l acetonitriles) of 28 μ L (0.0005mmol, 0.005equiv) is joined in the reaction bulb of 10mL, then use rotation that solvent is evaporated off；
(2) magneton, N-methylindole 1a (0.1mmol, 1.0equiv.), solvent (2.0mL, CH it are then respectively adding3CN)、H2O (54 μ l, 30equiv.) and LiBr (0.02mmol, 0.2equiv.), uses plug seal reaction bulb, and inserts an oxygen ball on bottle stopper, in order to provide oxygen in reaction bulb；
(3) finally reaction is put in 25 DEG C of calorstats, in the stirring reaction of distance 3W indigo plant lamp (λ=450-455nm) 5cm distance, reaction is detected by TLC plate, question response is completely (response time is about 12～13h), it is extracted with ethyl acetate, it is spin-dried for, crosses pillar (column chromatography silica gel dress post), (first eluting is carried out by volume ratio 10/1 by petrol ether/ethyl acetate, eluting is carried out again by volume ratio 5/1) eluting, it is spin-dried for solvent and obtains product N-methyl-isatin 2a.
1-methylisatin, red solid, MP 121.7 124.5 DEG C, 63%yield；1H NMR(300MHz,CDCl3) δ 7.59 7.54 (m, 2H), 7.10 (t, J=7.5,1H), 6.88 (d, J=7.8,1H), 3.23 (s, 3H).13C NMR(75MHz,CDCl3)δ183.3,158.2,151.4,138.4,125.1,123.8,117.3,109.9,26.1.HRMS(ESI)m/z 162.0554(M+H+),
calc.for C9H8NO2 162.0555.
Embodiment 2:
Product title: 1-benzyl isatin
In step (2), between using, N-benzylindole 1b replaces N-methylindole 1a, and other preparation process and purification mode are carried out with reference to embodiment 1；Red solid, MP 121 123 DEG C；65%yield；1H NMR(300MHz,CDCl3) δ 7.53 (d, J=7.4,1H), 7.40 (t, J=7.8,1H), 7.26 (s, 5H), 7.01 (t, J=7.5,1H), 6.70 (d, J=8.0,1H), 4.85 (s, 2H).13C NMR(75MHz,CDCl3)δ183.2,158.2,150.7,138.30,134.4,129.0,128.1,127.4,125.4,123.8,117.6,111.0,44.0.HRMS(ESI)m/z 260.0694(M+Na+),calc.For C15H11NO2Na 260.0687.
Embodiment 3:
Product title: 1-phenylisatin
In step (2), between using, N-Phenylindole 1c replaces N-methylindole 1a, and other preparation process and purification mode are carried out with reference to embodiment 1；Red solid, MP 127.3 128.7 DEG C；67%yield；1H NMR(300MHz,CDCl3) δ 7.69 (d, J=7.3,1H), 7.56 7.54 (m, 3H), 7.43 7.41 (m, 3H), 7.17 (t, J=7.5,1H), 6.90 (d, J=7.9,1H).13C NMR(75MHz,CDCl3)δ182.9,157.3,151.6,138.3,132.8,129.9,128.8,126.0,125.6,124.3,117.4,111.3.HRMS(ESI)m/z 224.0715(M+H+),calc.For C14H10NO2 224.0712.
Embodiment 4:
Product title: 4-methoxyl group-1-methylisatin
In step (2), between using, 4-methoxy-. N-methyl base indole 1d replaces N-methylindole 1a, and other preparation process and purification mode are carried out with reference to embodiment 1；Red solid, MP 151 152 DEG C；60%yield；1H NMR(300MHz,CDCl3) δ 7.53 (t, J=8.2,1H), 6.60 (t, J=11.1,1H), 6.40 (t, J=23.9,1H), 3.97 (s, 3H), 3.22 (s, 3H).13C NMR(75MHz,CDCl3)δ179.9,158.7,158.6,152.3,140.3,107.6,105.7,102.1,56.3,26.4.HRMS
(ESI)m/z 192.0659(M+H+),calc.For C10H12NO3 192.0661.
Embodiment 5:
Product title: 5-fluoro-1-methylisatin
In step (2), between using, 5-fluoro-N-methylindole 1e replaces N-methylindole 1a, and other experimental procedure and purification mode are carried out with reference to embodiment 1；Red solid, MP150.7 152.5 DEG C；65%yield；1H NMR(300MHz,CDCl3) δ 7.30-7.21 (m, 7.7,2H), 6.82 (d, J=7.0,1H), 3.19 (s, 3H).13C NMR(75MHz,CDCl3)δ182.7,160.9,157.9,157.7,147.5,124.8,124.5,117.9,117.8,112.4,112.1,111.1,111.0,26.3.HRMS(ESI)m/z 180.0466(M+H+),calc.for C9H7FNO2 180.0461.
Embodiment 6:
Product title: 5-chloro-1-methylisatin
In step (2), between using, 5-chloro-n-methyl indole 1f replaces N-methylindole 1a, and other experimental procedure and purification mode are carried out with reference to embodiment 1；
Red solid, MP 165.1 166.8 DEG C；71%yield；1H NMR(300MHz,CDCl3) δ 7.56 (d, J=10.3,2H), 6.86 (d, J=8.2,1H), 3.25 (s, 3H).13C NMR(75MHz,CDCl3)δ182.3,157.6,149.6,137.7,129.6,125.2,118.1,111.2,26.3.HRMS(ESI)m/z 196.0161(M+H+),calc.for C9H7ClNO2196.0165。
Claims (3)
1. the method that a visible light catalytic prepares Isatine derivatives, it is characterised in that synthetic route is as follows:
Wherein, the structural formula of DPZ is as follows:, R1For、、Or, R2For、Or；
Synthesis step is: by compound 1, DPZ, H2O, LiBr are dissolved in CH3In CN, under oxygen atmosphere, blue lamp source 25oC isothermal reaction, TLC tracking and monitoring, reaction i.e. obtains compound 2 through column chromatography for separation after terminating.
Visible light catalytic the most according to claim 1 prepares the method for Isatine derivatives, it is characterised in that compound 1, DPZ, H2The mol ratio of O and LiBr is 1 0.005 30 0.2.
Visible light catalytic the most according to claim 1 prepares the method for Isatine derivatives, it is characterised in that described blue lamp refer to power be 3W, wavelength be the blue lamp of 450-455nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017580A (en) * | 2017-11-22 | 2018-05-11 | 河南大学 | A kind of method of visible light catalytic amino acid decarboxylase synthesis 1,2,3,4- Tetrahydroquinolinesas |
| CN109734645A (en) * | 2019-02-21 | 2019-05-10 | 南京金浩医药科技有限公司 | A kind of synthesis technology of isatin |
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2016
- 2016-05-26 CN CN201610357787.6A patent/CN106008309B/en active Active
Non-Patent Citations (5)
| Title |
|---|
| CHENHAO ZHANG ET AL.: "Visible Light Photocatalytic Aerobic Oxygenation of Indoles and pH as a Chemoselective Switch", 《ACS CATAL.》 * |
| PEIJUN LIU ET AL.: "Iodine-Catalyzed Oxidation of N-Substituted Indoles by using Chloramine-B: A Facile and Practical Approach to Isatins", 《EUR.J.ORG.CHEM.》 * |
| XINFEI LIU ET AL.: "Controllable Chemoselectivity in Visible-Light Photoredox Catalysis:Four Diverse Aerobic Radical Cascade Reactions", 《ANGEW.CHEM.INT.ED.》 * |
| YU ZHAO ET AL.: "Dicyanopyrazine-derived push–pull chromophores for highly efficient photoredox catalysis", 《RSC ADV.》 * |
| 张宸浩: "DPZ参与可见光催化化学选择多样性氧化吲哚衍生物", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017580A (en) * | 2017-11-22 | 2018-05-11 | 河南大学 | A kind of method of visible light catalytic amino acid decarboxylase synthesis 1,2,3,4- Tetrahydroquinolinesas |
| CN108017580B (en) * | 2017-11-22 | 2021-02-02 | 河南大学 | Method for synthesizing 1,2,3, 4-tetrahydroquinoline compound by decarboxylation of amino acid under catalysis of visible light |
| CN109734645A (en) * | 2019-02-21 | 2019-05-10 | 南京金浩医药科技有限公司 | A kind of synthesis technology of isatin |
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