CN108558665A - A kind of method that the catalysis of excited by visible light disulfide prepares Alpha-hydroxy-beta-dicarbonyl compound - Google Patents

A kind of method that the catalysis of excited by visible light disulfide prepares Alpha-hydroxy-beta-dicarbonyl compound Download PDF

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CN108558665A
CN108558665A CN201810466328.0A CN201810466328A CN108558665A CN 108558665 A CN108558665 A CN 108558665A CN 201810466328 A CN201810466328 A CN 201810466328A CN 108558665 A CN108558665 A CN 108558665A
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beta
compound
disulfide
method described
dicarbonyl compound
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CN108558665B (en
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孟庆伟
赵静喃
杨帆
刘广志
唐晓飞
武玉峰
尹航
冯世豪
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

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Abstract

The present invention provides a kind of method that the catalysis of excited by visible light disulfide prepares α hydroxyl beta-dicarbonyl compounds, belongs to photocatalysis synthesis technical field.This method is in a solvent using disulfide compound as light-sensitive catalyst, and beta-dicarbonyl compound is substrate, and molecular oxygen is as oxidant, it is seen that light prepares α hydroxyl beta-dicarbonyl compounds for excitation light source.For the present invention using the disulfide compound for being commercially easy to get, inexpensively stablizing as catalyst, the yield for obtaining α hydroxyl beta-dicarbonyl compounds reaches as high as 99%.Reaction condition is mild, and α hydroxyl beta-dicarbonyl compounds can efficiently be prepared by not needing added metal, alkali, reducing agent etc., easy to operate, has good substrate applicability and environment friendly, at low cost, is suitble to commercial scale.

Description

A kind of excited by visible light disulfide catalysis prepares Alpha-hydroxy-beta-dicarbonyl compound Method
Technical field
The invention belongs to photocatalysis synthesis technical field, it is related to a kind of disulfide as light sensitivity catalyst, in visible light Excitation is lower to use the method that air oxygen prepares Alpha-hydroxy-beta-dicarbonyl compound as Green Oxidant.
Technical background
The reaction system of visible light-inducing provides a kind of green, sustainable strategy for Synthetic Organic Chemistry.It is the most frequently used Visible light catalyst include metal Ru or rhodium bipyridyl complexes (such as：Ru(bpy)3Cl2,fac-Ir(ppy)3) and Organic dye molecule (such as：Eosin Y, rose-red).In recent years, there is the example of the light reaction of document report disulphide catalysis Son, wherein disulphide by photodestruciton be catalyzed terminal alkyne two boronations reaction (Chem.Eur.J.2015,21,13930- 13933 and carbon-halogen bond reduction (Adv.Synth.Catal.2013,355,3522-3526) and [3+2] cycloaddition reaction (Angew.Chem.Int.Ed.2016,55,8081–8085).Ultraviolet light is often required to use in these reactions to excite two Sulfide breaks to form Thiyl Radical.Shanghai Institute for Advanced Study of the Chinese Academy of Sciences in 2017, Harvard University and Dutch PSV Eindhoven The joint team of Polytechnics is by the combination tested and calculated, and using Electron rich aromatic disulfide as catalyst, oxygen is made For oxidant, single, polysubstituted aromatic olefin is realized under visible light conditions at normal temperatures to the conversion of aldehydes or ketones (Angew.Chem.Int.Ed.2017,56,832–836)。
The selective C-H hydroxylatings that carbonyls is carried out using molecular oxygen have been achieved for significant progress.It is general and Speech realizes that the key method of these compounds is related to harmful oxidant or transition metal or metal oxide and additive (phosphine work For reducing agent) (Angew.Chem., Int.Ed.2014,53,548.), the shortcomings that this is said program.Recently, no transition metal Carbonyls ɑ-the hydroxylating participated in reducing agent is reported, but system needs the alkali that stoichiometry is added (Org.Lett.2017,19,3628-3631).The application of visible light and molecular oxygen as efficient oxidation agent, it may be said that be it One of most important Science and Technology challenge, because they have environmental-friendly, abundant and sustainable characteristic.It can to find It realizes ɑ-hydroxylating of carbonyls and avoids using metallic catalyst, alkali, dangerous phosphino- additive, cryogenic conditions and guarantor The Light lnduced Free Radicals of group are protected, we have developed a kind of photooxidation bodies for being used as ideal catalyst by disulphide System.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of disulfides as catalyst, under the action of visible light, Without added metal, alkali, radical initiator and reducing agent, the method for preparing Alpha-hydroxy-beta-dicarbonyl compound (II).
Technical scheme of the present invention：
A kind of method that the catalysis of excited by visible light disulfide prepares Alpha-hydroxy-beta-dicarbonyl compound, steps are as follows：Molten In agent, light-sensitive catalyst is made with disulfide compound, beta-dicarbonyl compound makees substrate, molecular oxygen as oxidant, it is seen that light is made Excitation light source carries out light-catalyzed reaction, and Alpha-hydroxy-beta-dicarbonyl compound is prepared.
The disulfide compound such as Formulas I：
Wherein, R1And R2For C1-C8 alkyl, phenyl ring base, five yuan of heteroaromatics or hexa-atomic heteroaromatic, R1And R2It is identical or different；
Beta-dicarbonyl compound such as Formula II：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl, alkoxy or naphthenic base, R1、R2And R3It is identical or different；R4 For alkyl, alkoxy, aromatic amine or fatty amine；N takes 1 or 2；
Alpha-hydroxy-beta-dicarbonyl compound such as formula III：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl, alkoxy or naphthenic base, R1、R2And R3It is identical or different；R4 For alkyl, alkoxy, aromatic amine or fatty amine；N takes 1 or 2.
R in the disulfide compound (Formulas I)1, R2For phenyl ring base when, such as following formula：
Wherein, on each phenyl ring have adjacent to, it is alternate in or to positioned at disulfide bond substituent R3、R4；R3And R4For halogen Element, NO2, cyano, C1-C8 alkyl or C1-C8 alkoxyl；R3And R4It is identical or different.
Further, the disulfide compound is the diphenyl disulfide of 4-F substitutions, such as Formulas I a：Corresponding photocatalysis Reaction equation such as formula (1)：
The temperature of the light-catalyzed reaction is -30~100 DEG C；The molar ratio of disulfide compound and beta-dicarbonyl compound It is 0.0001~3:1, the wavelength of the visible light is 365nm~700nm.
Further, the reaction temperature is 10 DEG C~50 DEG C；The disulfide compound and beta-dicarbonyl compound Molar ratio be 0.005~0.5:1.
The solvent is water, toluene, paraxylene, ortho-xylene, mesitylene, n-hexane, tetrahydrofuran, acetic acid second Ester, acetonitrile, DMF, DMAP, DMSO, chloroform, carbon tetrachloride, dichloromethane, bromomethane, methylene bromide, 1,2- dichloroethanes, 1, One or more of 3- dibromopropanes, carbon disulfide, dioxane, petroleum ether, methanol, ethyl alcohol, naphthane, morpholine are mixed It closes.The molecular oxygen be purity oxygen, air or contain oxygen molecule mixture.
Beneficial effects of the present invention：The present invention using be commercially easy to get, inexpensively stablize to fluorine diphenyl disulfide as be catalyzed Agent, blue light illumination issue raw photooxidation and obtain target product, and yield reaches as high as 99%.Reaction condition is mild, need not be outer Add metal, alkali, reducing agent etc. that can effectively prepare Alpha-hydroxy-beta-dicarbonyl compound, it is easy to operate, have good substrate suitable It is at low cost with property and environment friendly, it is suitble to commercial scale.
Specific implementation mode
Specific embodiments of the present invention are described in detail with reference to technical solution.
Embodiment 1 prepares 5-Chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indole-2-carboxylic acid methyl ester (formula III, wherein R1, R3For H, R2For Cl, R4For OMe)
5- chloro- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R are added into 4mL DMF solutions1, R3For H, R2For Cl, R4For OMe, 0.0224g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W Blue light illumination 8 hours, quantitative analysis show that chloro- 2, the 3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters of 5- occur>99% conversion, Generate 5-Chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indole-2-carboxylic acid methyl ester, yield 96%.1H NMR(500MHz,CDCl3) δ 7.74 (d, J=8.3Hz, 1H), 7.50 (s, 1H), 7.43 (d, J=8.2Hz, 1H), 3.97 (s, 1H), 3.75 (s, 3H), 3.71 (d, J=17.5Hz, 1H), 3.24 (d, J=17.5Hz, 1H).
Embodiment 2 prepares 2,3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- carboxylate methyl ester (formula III, wherein R1, R2, R3 For H, R4For OMe)
2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl ester (Formula II, wherein R are added into 4mL DMF solutions1, R2, R3 For H, R4For Me, 0.0190g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 Hour, generate 2,3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- carboxylate methyl esters, yield 63%.1H NMR(500MHz,CDCl3) δ 7.74 (d, J=8.3Hz, 1H), 7.50 (s, 1H), 7.43 (d, J=8.2Hz, 1H), 3.97 (s, 1H), 3.75 (s, 3H), 3.71 (d, J=17.5Hz, 1H), 3.24 (d, J=17.5Hz, 1H).
Embodiment 3 prepares 5- bromo- 2,3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R1, R3For H, R2For Br, R4For OMe)
5- bromo- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R are added into 4mL DMF solutions1, R3For H, R2For Br, R4For Me, 0.0269g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W is blue Light irradiates 8 hours, generates bromo- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters of 5-, yield 98%.1H NMR (500MHz,CDCl3) δ 7.69 (m, 1H), 7.66 (d, J=8.2Hz, 1H), 7.59 (d, J=8.2Hz, 1H), 3.75 (s, 3H), 3.71 (d, J=17.4Hz, 1H), 3.24 (d, J=17.4Hz, 1H).
Embodiment 4 prepares 6- bromo- 2,3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R1, R2For H, R3For Br, R4For OMe)
6- bromo- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R are added into 4mL DMF solutions1, R2For H, R3For Br, R4For Me, 0.0269g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W is blue Light irradiates 8 hours, generates bromo- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters of 6-, yield 98%.1H NMR (500MHz,CDCl3) δ 7.93 (d, J=2.0Hz, 1H), 7.78 (dd, J=8.2,2.0Hz, 1H), 7.39 (d, J=8.2Hz, 1H), 3.75 (s, 3H), 3.67 (d, J=17.4Hz, 1H), 3.20 (d, J=17.3Hz, 1H).
Embodiment 5 prepares 4- bromo- 2,3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R2, R3For H, R1For Br, R4For OMe)
4- bromo- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R are added into 4mL DMF solutions2, R3For H, R1For Br, R4For OMe, 0.0269g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W Blue light illumination 8 hours generates bromo- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters of 4-, yield 85%.1H NMR(500MHz,CDCl3) δ 7.85 (dd, J=7.8,1.0Hz, 1H), 7.76 (dd, J=7.8,0.9Hz, 1H), 7.37 (dt, J =7.7,0.9Hz, 1H), 3.97 (s, 1H), 3.77 (s, 3H), 3.68 (d, J=17.8Hz, 1H), 3.19 (d, J=17.8Hz, 1H)。
Preparation 6- methoxyl group -2, the 3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- of embodiment 6 carboxylate methyl esters (formula III, Middle R1, R2For H, R3For-OCH3, R4For OMe)
Be added into 4mL DMF solutions 6- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (Formula II, Middle R1, R2For H, R3For-OCH3, R4For OMe, 0.0220g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 6- methoxyl group -2,3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- carboxylic acids Methyl esters, yield 63%.1H NMR(500MHz,CDCl3) δ 7.39 (d, J=8.4Hz, 1H), 7.27 (dd, J=8.4,2.6Hz, 1H), 7.22 (d, J=2.6Hz, 1H), 3.85 (s, 3H), 3.75 (s, 3H), 3.65 (d, J=16.9Hz, 1H), 3.18 (d, J= 16.9Hz,1H)。
Preparation 4- methoxyl group -2, the 3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- of embodiment 7 carboxylate methyl esters (formula III, Middle R2, R3For H, R1For-OCH3, R4For OMe)
Be added into 4mLDMF solution 4- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R2, R3For H, R1For-OCH3, R4For Me, 0.0220g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 4- methoxyl group -2,3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- carboxylate methyl esters, yield 67%.1H NMR(500MHz,CDCl3) δ 7.45-7.36 (m, 2H), 7.11 (dd, J=7.1,1.7Hz, 1H), 3.92 (s, 3H), 3.74 (s, 3H), 3.66 (d, J=17.7Hz, 1H), 3.12 (d, J=17.7Hz, 1H).
Preparation 5,6- methoxyl group -2, the 3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- of embodiment 8 carboxylate methyl esters (formula III, Wherein R1For H, R2, R3For OCH3, R4For OMe)
Be added into 4mL DMF solutions 5,6- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (Formula II, Wherein R1For H, R2, R3For-OCH3, R4For Me, 0.0250g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 5,6- methoxyl group -2,3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- carboxylics Sour methyl esters, yield 51%.1H NMR(500MHz,CDCl3)δ7.20(s,1H),6.91(s,1H),4.00(s,3H),3.92(s, 3H), 3.75 (s, 3H), 3.65 (d, J=16.9Hz, 1H), 3.17 (d, J=16.9Hz, 1H).
Preparation 6- methyl -2, the 3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- of embodiment 9 carboxylate methyl esters (formula III, wherein R1, R2For H, R3For-CH3, R4For OMe)
Be added into 4mL DMF solutions 6- methyl -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R1, R2For H, R3For-CH3, R4For Me, 0.0204g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 6- methyl -2,3- dihydro -2- hydroxyl -1- oxo -1H- indenes -2- carboxylate methyl esters, yield 81% 。1HNMR(500MHz,CDCl3) δ 7.60 (d, J=1.8Hz, 1H), 7.50 (dd, J=7.8,1.8Hz, 1H), 7.38 (dd, J= 7.8Hz, 1H), 3.74 (s, 3H), 3.68 (d, J=17.1Hz, 1H), 3.21 (d, J=17.1Hz, 1H), 2.42 (s, 3H).
Fluoro- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters of the preparation 6- of embodiment 10 (formula III, wherein R1, R2For H, R3For-F, R4For OMe)
6- fluoro- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R are added into 4mL DMF solutions1, R2For H, R3For-F, R4For Me, 0.0208g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W is blue Light irradiates 8 hours, generates fluoro- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylate methyl esters of 6-, yield 68%.1H NMR (500MHz,CDCl3) δ 7.52-7.36 (m, 3H), 3.76 (s, 3H), 3.69 (d, J=17.1Hz, 1H), 3.22 (d J= 17.1,1H)。
Chloro- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylic acid isopropyls of the preparation 5- of embodiment 11 (formula III, wherein R1, R3For H, R2For Cl, R4For isopropoxy)
6- fluoro- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (Formula II, wherein R are added into 4mL DMF solutions1, R2For H, R3For-F, R4For Me, 0.0208g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W is blue Light irradiates 8 hours, generates chloro- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylic acid isopropyls of 5-, yield 93%.1H NMR(500MHz,CDCl3) δ 7.73 (d, J=8.2Hz, 1H), 7.50 (d, J=1.5Hz, 1H), 7.42 (dd, J=8.2, 1.7Hz, 1H), 5.08 (hept, J=6.2Hz, 1H), 4.00 (s, 1H), 3.66 (d, J=17.3Hz, 1H), 3.22 (d, J= 17.3Hz, 1H), 1.21 (d, J=6.3Hz, 3H), 1.14 (d, J=6.2Hz, 3H).
Chloro- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylic acids Buddha's warrior attendant esters of the preparation 5- of embodiment 12 (formula III, wherein R1, R3For H, R2For Cl, R4For Buddha's warrior attendant oxygroup)
Be added into 4mL DMF solutions 5- chloro- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylic acids Buddha's warrior attendant esters (Formula II, wherein R1, R3For H, R2For Cl, R4For adamantyl, 0.0345g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate chloro- 2, the 3- dihydros -2- hydroxyls -1- oxos -1H- indenes -2- carboxylic acid Buddha's warrior attendants of 5- Ester, yield 92%.1H NMR(500MHz,CDCl3) δ 7.74 (d, J=8.2Hz, 1H), 7.52 (s, 1H), 7.42 (d, J= 8.2Hz, 1H), 4.03 (s, 1H), 3.68 (d, J=17.2Hz, 1H), 3.28 (d, J=17.2Hz, 1H), 1.96-1.22 (m, 15H)。
Preparation 2- hydroxyl -1- oxo-N-phenyl -2, the 3- dihydro -1H- indenes -2- of embodiment 13 formamides (formula III, wherein R1, R2,R3For H, R4For anilino-)
1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- formamide (Formula II, wherein R are added into 4mL DMF solutions1, R2,R3For H, R4For anilino-, 0.0251g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W is blue Light irradiates 8 hours, generates 2- hydroxyl -1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- formamides, yield 92%.1H NMR (500MHz,Chloroform-d)δ8.76(s,1H),7.77(m,1H),7.65(m,1H),7.50(m,2H),7.41(m,1H), 7.31-7.24 (m, 2H), 7.10 (t, J=7.4Hz, 1H), 3.85 (d, J=16.8Hz, 1H), 3.17 (d, J=16.8Hz, 1H)。
Preparation 2- hydroxyl -1- oxo-N- isopropyl -2, the 3- dihydro -1H- indenes -2- of embodiment 14 formamides (formula III, wherein R1, R2,R3For H, R4For isopropylamine base)
Be added into 4mL DMF solutions 1- oxo-N- isopropyl -2,3- dihydro -1H- indenes -2- formamides (Formula II, wherein R1, R2,R3For H, R4For isopropylamine base, 0.0231g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 2- hydroxyl -1- oxo-N- isopropyl -2,3- dihydro -1H- indenes -2- formamides, yield 83% 。1H NMR (500MHz, Chloroform-d) δ 7.78 (d, J=7.7Hz, 1H), 7.65 (td, J=7.5,1.3Hz, 1H), 7.54-7.35 (m, 2H), 6.63 (s, 1H), 4.07-3.90 (m, 1H), 3.73 (d, J=16.7Hz, 1H), 3.11 (d, J= 16.7Hz,1H),1.17(m,6H)。
The preparation 2- hydroxy-N-phenyl -1- oxos -1,2 of embodiment 15,3,4- naphthane -2- carboxylic acid, ethyl esters (formula III, wherein R1, R2, R3 H, n=2, R4 are anilino-)
Addition N- phenyl -1- oxos -1,2 into 4mL DMF solutions, 3,4- naphthane -2- carboxylic acid, ethyl esters (Formula II, wherein R1, R2, R3For H, n=2, R4For anilino-, 0.0231g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 2- hydroxy-N-phenyl -1- oxos -1,2,3,4- naphthane -2- carboxylic acid second Ester, yield 71%.1H NMR (500MHz, Chloroform-d) δ 8.81 (s, 1H), 8.04 (d, J=7.8Hz, 1H), 7.54 (dd, J=13.5,7.8Hz, 3H), 7.38-7.23 (m, 4H), 7.10m, 1H), 4.84 (s, 1H), 3.62 (m, 1H), 3.06- 2.92(m,1H),2.61(m,1H),2.33(m,1H)。
The preparation 2- hydroxyl -1- oxos-N- of embodiment 15 (p-methylphenyl) -2,3- dihydro -1H- indenes -2- formamides (formula III, Wherein R1, R2, R3 H, R4 are open-chain crown ether base)
Be added into 4mL DMF solutions 1- oxos-N- (p-methylphenyl) -2,3- dihydro -1H- indenes -2- formamides (Formula II, Wherein R1, R2, R3 H, R4 are open-chain crown ether base, 0.0265g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 2- hydroxyl -1- oxos-N- (p-methylphenyl) -2,3- dihydro -1H- indenes -2- Formamide, yield 94%.1H NMR (500MHz, Chloroform-d) δ 8.72 (s, 1H), 7.74 (d, J=7.8Hz, 1H), 7.63 (dd, J=7.5,1.2Hz, 1H), 7.46 (d, J=7.7Hz, 1H), 7.37 (t, J=8.0Hz, 3H), 7.05 (d, J= 8.1Hz, 2H), 3.83 (d, J=16.7Hz, 1H), 3.14 (d, J=16.7Hz, 1H), 2.28 (s, 3H).
The preparation 2- hydroxyl -1- oxos-N- of embodiment 16 (o-tolyl) -2,3- dihydro -1H- indenes -2- formamides (formula III, Wherein R1, R2, R3 H, R4 are o-methyl-benzene amido)
Be added into 4mL DMF solutions 1- oxos-N- (o-tolyl) -2,3- dihydro -1H- indenes -2- formamides (Formula II, Wherein R1, R2, R3 H, R4 are o-methyl-benzene amido, 0.0265g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 2- hydroxyl -1- oxos-N- (o-tolyl) -2,3- dihydro -1H- indenes -2- Formamide, yield 91%.1H NMR(500MHz,Chloroform-d)δ8.63(s,1H),7.91–7.78(m,1H),7.75 (d, J=7.8Hz, 1H), 7.64 (td, J=7.6,1.2Hz, 1H), 7.47 (d, J=7.7Hz, 1H), 7.39 (t, J=7.5Hz, 1H), 7.13 (t, J=7.1Hz, 2H), 7.03 (td, J=7.3,1.3Hz, 1H), 3.84 (d, J=16.9Hz, 1H), 3.17 (d, J=16.9Hz, 1H), 2.24 (s, 3H).
Preparation 5- chlorine-2-hydroxyl -1- oxo-N-phenyl -2, the 3- dihydro -1H- indenes -2- of embodiment 17 formamides (formula III, Wherein R1, R2, R3 H, R4 are anilino-)
Be added into 4mL DMF solutions 5- chloro- 1- oxo-N-phenyls -2,3- dihydro -1H- indenes -2- formamides (Formula II, Middle R1, R2, R3 H, R4 are anilino-, 0.0285g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 5- chlorine-2-hydroxyl -1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- first Amide, yield 92%.1HNMR (500MHz, Chloroform-d) δ 8.72 (s, 1H), 7.72 (d, J=8.2Hz, 1H), 7.56- 7.48 (m, 3H), 7.43-7.39 (m, 1H), 7.34-7.27 (m, 2H), 7.20-7.05 (m, 1H), 3.84 (d, J=17.0Hz, 1H), 3.17 (d, J=17.0Hz, 1H).
Embodiment 17 prepares 2- hydroxyl -6- methoxyl group -1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- formamide (formulas III, wherein R1, R2For H, R3=OMe, R4 are anilino-)
6- methoxyl group -1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- formamide (formulas are added into 4mL DMF solutions II, wherein R1, R2For H, R3=OMe, R4 are anilino-, 0.0281g, 0.1mmol) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 2- hydroxyl -6- methoxyl group -1- oxo-N-phenyl -2,3- dihydro -1H- indenes - 2- formamides, yield 73%.1H NMR(500MHz,Chloroform-d)δ8.79(s,1H),7.52–7.41(m,2H),7.34 (d, J=8.4Hz, 1H), 7.29-7.20 (m, 3H), 7.14 (d, J=2.6Hz, 1H), 7.11-7.04 (m, 1H), 3.79 (s, 3H), 3.75 (d, J=16.4Hz, 1H), 3.06 (d, J=16.4Hz, 1H).
Embodiment 17 prepares 2- hydroxyl -5,6- dimethoxy -1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- formamides (formula III, wherein R1=H, R2, R3It is anilino- for OMe, R4)
5,6- dimethoxy -1- oxo-N-phenyl -2,3- dihydro -1H- indenes -2- formamides are added into 4mL DMF solutions (Formula II, wherein R1=H, R2, R3It is anilino-, 0.0311g, 0.1mmol for OMe, R4) and to fluorine diphenyl disulfide (0.00127g, 0.005mmol), 10W blue light illuminations 8 hours generate 2- hydroxyl -5,6- dimethoxy -1- oxo-N-phenyls - 2,3- dihydro -1H- indenes -2- formamides, yield 66%.1H NMR(500MHz,Chloroform-d)δ8.77(s,1H),7.61– 7.46(m,2H),7.34–7.24(m,2H),7.18(s,1H),7.14–7.05(m,1H),6.91(s,1H),3.99(s,3H), 3.89 (s, 3H), 3.76 (d, J=16.4Hz, 1H), 3.10 (d, J=16.4Hz, 1H).

Claims (10)

1. a kind of method that the catalysis of excited by visible light disulfide prepares Alpha-hydroxy-beta-dicarbonyl compound, which is characterized in that step It is as follows：In a solvent, light-sensitive catalyst is made with disulfide compound, beta-dicarbonyl compound makees substrate, molecular oxygen as oxidant, Visible light makees excitation light source and carries out light-catalyzed reaction, and Alpha-hydroxy-beta-dicarbonyl compound is prepared.
2. according to the method described in claim 1, it is characterized in that, the disulfide compound such as Formulas I：
Wherein, R1And R2For C1-C8 alkyl, phenyl ring base, five yuan of heteroaromatics or hexa-atomic heteroaromatic, R1And R2It is identical or different；
Beta-dicarbonyl compound such as Formula II：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl, alkoxy or naphthenic base, R1、R2And R3It is identical or different；R4For alkane Base, alkoxy, aromatic amine or fatty amine；N takes 1 or 2；
Alpha-hydroxy-beta-dicarbonyl compound such as formula III：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl, alkoxy or naphthenic base, R1、R2And R3It is identical or different；R4For alkane Base, alkoxy, aromatic amine or fatty amine；N takes 1 or 2.
3. according to the method described in claim 2, it is characterized in that, R in the disulfide compound1、R2For phenyl ring base when, Such as following formula：
Wherein, on each phenyl ring have adjacent to, it is alternate in or to positioned at disulfide bond substituent R3、R4；R3And R4For halogen, NO2, cyano, C1-C8 alkyl or C1-C8 alkoxyl；R3And R4It is identical or different.
4. according to the method described in claim 3, it is characterized in that, the disulfide compound is the hexichol two of 4-F substitutions Thioether, such as Formulas I a, corresponding light-catalyzed reaction formula such as formula (1)：
5. according to the method described in claim 1-4, which is characterized in that the temperature of the light-catalyzed reaction is -30~100 DEG C； The molar ratio of disulfide compound and beta-dicarbonyl compound is 0.0001~3:1, the wavelength of the visible light be 365nm~ 700nm。
6. according to the method described in claim 1-4, which is characterized in that the solvent is water, toluene, paraxylene, neighbour two Toluene, mesitylene, n-hexane, tetrahydrofuran, ethyl acetate, acetonitrile, DMF, DMAP, DMSO, chloroform, carbon tetrachloride, dichloro Methane, bromomethane, methylene bromide, 1,2- dichloroethanes, 1,3- dibromopropanes, carbon disulfide, dioxane, petroleum ether, methanol, One or more of ethyl alcohol, naphthane, morpholine mix；The molecular oxygen is purity oxygen, air or contains oxygen molecule Mixture.
7. according to the method described in claim 5, it is characterized in that, the solvent is water, toluene, paraxylene, adjacent diformazan Benzene, mesitylene, n-hexane, tetrahydrofuran, ethyl acetate, acetonitrile, DMF, DMAP, DMSO, chloroform, carbon tetrachloride, dichloromethane Alkane, bromomethane, methylene bromide, 1,2- dichloroethanes, 1,3- dibromopropanes, carbon disulfide, dioxane, petroleum ether, methanol, second One or more of alcohol, naphthane, morpholine mix；The molecular oxygen is purity oxygen, air or is mixed containing oxygen molecule Close object.
8. according to the method described in claim 1,2,3,4 or 7, which is characterized in that the reaction temperature is 10 DEG C~50 DEG C； The molar ratio of the disulfide compound and beta-dicarbonyl compound is 0.005~0.5:1.
9. according to the method described in claim 5, it is characterized in that, the reaction temperature is 10 DEG C~50 DEG C；Two sulphur The molar ratio of ether compound and beta-dicarbonyl compound is 0.005~0.5:1.
10. according to the method described in claim 6, it is characterized in that, the reaction temperature is 10 DEG C~50 DEG C；Two sulphur The molar ratio of ether compound and beta-dicarbonyl compound is 0.005~0.5:1.
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