CN106220495B - The method that the alpha-acyloxy ketone derivatives containing ethylenic unsaturation are directly synthesized by α-reaction kinetic of ketone - Google Patents

The method that the alpha-acyloxy ketone derivatives containing ethylenic unsaturation are directly synthesized by α-reaction kinetic of ketone Download PDF

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CN106220495B
CN106220495B CN201610622507.XA CN201610622507A CN106220495B CN 106220495 B CN106220495 B CN 106220495B CN 201610622507 A CN201610622507 A CN 201610622507A CN 106220495 B CN106220495 B CN 106220495B
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ketone
alpha
ethylenic unsaturation
containing ethylenic
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CN106220495A (en
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郭欣
徐静文
郭灿城
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Jiaxing Sangao Technology Consulting Co.,Ltd.
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YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a kind of methods directly synthesizing the alpha-acyloxy ketone derivatives containing ethylenic unsaturation by α-reaction kinetic of ketone, this method is under air environment, cinnamic acid derivative, ketone compounds and organic peroxide, in copper compound/tetraalkyl ammonium salt catalyst system and catalyzing, the alpha-acyloxy ketone derivatives containing ethylenic unsaturation are synthesized by one pot reaction；This method first passage cinnamic acid derivative and ketone compounds directly synthesize the alpha-acyloxy ketone derivatives containing ethylenic unsaturation, have the characteristics that high selectivity, yield are high, reaction condition is mild, step is simple, are conducive to industrialized production.

Description

The alpha-acyloxy ketone containing ethylenic unsaturation is directly synthesized by α-reaction kinetic of ketone to derive The method of object
Technical field
The synthetic method of the present invention relates to a kind of alpha-acyloxy ketone derivatives containing ethylenic unsaturation, more particularly to one kind is by meat Cinnamic acid derivative and ketone compounds directly synthesize α-acyl-oxygen containing ethylenic unsaturation by α-reaction kinetic of ketone compounds The method of base ketone derivatives, belongs to organic synthesis field.
Background technology
α-reaction kinetic of ketone compounds has important meaning in organic synthesis, has become and grinds for many years The focus studied carefully.And alpha-acyloxy ketone belongs to one kind in α-reaction kinetic products of ketone compounds, is organic synthesis process The middle essential intermediate of one kind.At present, it was recently reported that many different methods for preparing alpha-acyloxy ketone, due to transition metal There is higher catalytic activity to c h bond activation, become the hot spot of research, document (Jia, W.G.；Zhang, H.；Li, D.D.； Yan, L.Q.RSC Adv.2016,6,27590-27593) report is closed using pybox-copper (II) catalyzing ketone compounds At acyl-oxygen compound.
Alpha-acyloxy ketone derivatives containing ethylenic unsaturation are the important intermediates of organic synthesis, and high active double bond is various officials The conversion medium of energy group, it is hereby achieved that a variety of alpha-acyloxy ketone derivatives.Theoretically pass through ketone α-C (sp3)-H and α, β It is the method for most succinct alpha-acyloxy ketone derivatives of the preparation containing ethylenic unsaturation that unsaturated carboxylic acid is directly coupled, but due to not Saturated carboxylic acid easily decarboxylation, can not obtain coupling product.Currently, only ketone α-C-H and α, pass through decarboxylation between β unsaturated carboxylic acids Reaction generates furan nucleus report.Document (Yang, Y.；Yao, J.；Zhang, Y.Org.Lett.2013,15,3206.) it reports Alkyl ketone and α, β unsaturated carboxylic acids generate furan derivatives, specific reaction equation under copper (I) and copper (II) catalytic action As shown in formula (1).
Document (Ghosh, M.；Mishra, S.；Monir, K.；Hajra, A.Org.Biomol.Chem.2015,13, 309.) selectivity synthesis furan derivatives, specific reaction under copper (II) catalytic action by ketone and unsaturated carboxylic acid are reported Equation such as formula (2).But up to the present, there are no pass through ketone α-C (sp3)-H and the directly coupled shape of α, β unsaturated carboxylic acid At the relevant report of the alpha-acyloxy ketone containing ethylenic unsaturation.
Invention content
For in the prior art due to α, β unsaturated acids is easy decarboxylation, and it can not be utilized directly anti-with ketone compounds The defect of the alpha-acyloxy ketone derivatives containing ethylenic unsaturation should be prepared, the purpose of the invention is to provide one kind to be spread out by cinnamic acid Biology and ketone compounds substrate pass through copper compound/tetraalkyl ammonium salt catalyst system and catalyzing catalytic one-stage in the presence of a peroxide The method of alpha-acyloxy ketone derivatives of the reaction synthesis containing ethylenic unsaturation, this method have highly selective, high yield, reaction condition Mildly, the simple feature of step, is conducive to industrialized production.
In order to achieve the above technical purposes, it is directly synthesized the present invention provides a kind of α-reaction kinetic by ketone and contains insatiable hunger With the method for the alpha-acyloxy ketone derivatives of alkene, this method is 1 structure cinnamic acid derivative of formula, 2 structure of formula under air environment Ketone compounds and organic peroxide synthesize formula in copper compound/tetraalkyl ammonium salt catalyst system and catalyzing by one pot reaction Alpha-acyloxy ketone derivatives of 3 structures containing ethylenic unsaturation；
Wherein,
R1Selected from halogen, trifluoromethyl, alkyl, alkoxy, nitro, phenyl, alkoxy acyl or alkyl acyl；
R2Selected from for hydrogen, aryl, alkyl, alkoxy acyl or heterocyclic substituent；
R3And R4Independently selected from alkyl, aryl, aroyl, alkoxy acyl or heterocyclic substituent；Alternatively, R3And R4For ring Alkane chain.
Preferred scheme, R3For phenyl, substituted-phenyl, quinary heterocyclic radical or C1~C5Alkyl；R4For C1~C5Alkyl or benzene Formoxyl；Alternatively, R3And R4For C5Cycloalkanes chain.More preferably scheme, R3For chlorophenyl, difluorophenyl, aminomethyl phenyl, methoxy Base phenyl, phenyl, furyl or ethyl；R4For methyl, ethyl or benzoyl；Alternatively, R3And R4For C5Cycloalkanes chain.
Most preferred ketone compounds are a kind of in following structural formula：
Preferred scheme, R1For fluorine, trifluoromethyl, methyl, methoxyl group, nitro, bromine or phenyl；R2For hydrogen, methyl or benzene Base.The following structural formula of most preferred cinnamic acid derivative：
The temperature of preferred scheme, the reaction is 70 DEG C~120 DEG C, and the time is 8~16h.More preferably scheme, temperature It it is 80 DEG C~110 DEG C, the time is 10~14h.Further preferred scheme, temperature are 100 DEG C, time 12h.
Preferred scheme, copper compound CuCl, CuBr, CuI, Cu2O、CuCl2At least one of.More preferably side Case, at least one of copper compound CuCl, CuBr, CuI.Most preferably CuI.
Preferred scheme is reacted with DMSO, CH3At least one of CN, toluene are used as solvent.
Preferred scheme, tetraalkyl ammonium salt are 4-butyl ammonium hydrogen sulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, four At least one of second ammonium bromide.More preferably scheme, tetraalkyl ammonium salt are tetrabutylammonium bromide and/or tetrem ammonium bromide.
Preferred scheme, organic peroxide are tert-butyl hydroperoxide and/or di-t-butyl peroxide.More preferably side Case, organic peroxide are di-t-butyl peroxide.
The usual reaction molar ratio of preferred scheme, cinnamic acid derivative, ketone compounds and organic peroxide is 1: 1 : 3, and ratio can be adjusted in proper range, belong to it will be appreciated by those skilled in the art that range.
Preferred scheme, the dosage of copper compound are the 10~30mol%, most preferably 20mol% of cinnamic acid derivative
Preferred scheme, the dosage of tetraalkyl ammonium salt are 5~15mol% of cinnamic acid derivative；Most preferably 10mol%.
The cinnamic acid derivative of the present invention is reacted with ketone compounds and organic peroxide generates the α-containing ethylenic unsaturation The reaction of acyloxy ketone derivatives is as follows：
It is reported based on a large amount of experimental summary and with reference to prior document, the present invention proposes following rational reaction machine System.Using propiophenone and cinnamic acid as raw material, di-t-butyl peroxide be oxidant for be specifically described.First, peroxidating Di-t-butyl teabrom effect under by heat resolve at tertiary butyl oxygen radical, tertiary butyl oxygen radical is to propiophenone α hydrogen carry out attack, generate propiophenone free radical, propiophenone free radical by Cu (II) de-electromation, generate propiophenone cation； Tertiary butyl oxygen radical obtains electronics from copper (I), and immediately receives the Hydrogen Proton from cinnamic acid to form the tert-butyl alcohol, and certainly Cinnamic acid becomes Chinese cassia tree acid anion after losing Hydrogen Proton, and Chinese cassia tree acid anion generates target product with propiophenone cation；Tool Vivo reaction type is as follows：
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
1) technical scheme of the present invention first passage cinnamic acid derivative and ketone compounds one-step synthesis contain ethylenic unsaturation Alpha-acyloxy ketone derivatives, overcome in the prior art since α, β unsaturated acids are easy depickling, cause reaction generate furans Ring, and the defect of the alpha-acyloxy ketone derivatives of ethylenic unsaturation cannot be contained.
2) technical scheme of the present invention generates the alpha-acyloxy ketone derivatives containing ethylenic unsaturation by one kettle way single step reaction, Step is simple, and flow is short, and yield is high, is conducive to industrialized production.
3) technical scheme of the present invention can carry out in air environment, and reaction condition is mild, and reaction selectivity is high, meet Demand of industrial production.
Specific implementation mode
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention It encloses.
Cinnamic acid derivative and ketone compounds raw material and solvent, copper compound catalysis involved in following embodiment Agent, quaternary alkylammonium halides etc. are commercial product.
Product separation uses chromatography, chromatographic column silica gel (300-400 mesh).
1HNMR (400MHz), 13C NMR (100MHz), with CDCl3For solvent, using TMS as internal standard.
Multiplicity is defined as follows：S (unimodal)；D (doublet)；T (triplet)；Q (quartet) and m (multiplet).Coupling Constant(hertz).
Mass spectrum is obtained by the sources mass spectrograph EI.
Embodiment 1~13 presses following conditioned response：
By α, β cinnamic acid derivatives (0.5mmol), propiophenone (0.5mmol), CuI (20mol%), TEAB (10mol%), DTBP (3.0equiv), DMSO (2.0mL) are added in 10mL reactors, under air environment, are heated to 100 DEG C reaction 12h, reaction product passes through chromatography post separation.
Embodiment 1
Chinese cassia tree acid starting material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield is 90%；
1-oxo-1-phenylpropan-2-yl cinnamate：yellow solid；1H NMR (400MHz, CDCl3)δ 7.99 (d, J=7.8Hz, 2H), 7.75 (d, J=16.0Hz, 1H), 7.59 (t, J=7.3Hz, 1H), 7.56-7.46 (m, 4H), 7.38 (d, J=5.0Hz, 3H), 6.54 (d, J=16.0Hz, 1H), 6.12 (q, J=7.0Hz, 1H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.93 (s), 166.26 (s), 145.95 (s), 134.49 (s), 134.28 (s), 133.60 (s), 130.50 (s), 128.92 (s), 128.81 (s), 128.55 (s), 128.24 (s), 117.24 (s), 77.37 (s), 77.05 (s), 76.73 (s), 71.45 (s), 17.24 (s)
Embodiment 2
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 82%；
1-oxo-1-phenylpropan-2-yl(E)-3-(4-fluorophenyl)acrylate：yellow solid； m.p.155-157℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.7Hz, 2H), 7.71 (d, J=16.0Hz, 1H), 7.60 (t, J=7.3Hz, 1H), 7.51 (dd, J=16.9,8.5Hz, 4H), 7.08 (t, J=8.4Hz, 2H), 6.46 (d, J= 16.0Hz, 1H), 6.12 (q, J=7.0Hz, 1H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3)δ 196.87 (s), 166.13 (s), 144.60 (s), 134.38 (s), 133.63 (s), 130.16 (s), 130.08 (s), 128.82 (s), 128.54 (s), 116.99 (s), 116.20 (s), 115.98 (s), 77.50 (s), 77.03 (s), 76.71 (s), 71.46 (s), 17.24 (s)
Embodiment 3
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 85%
1-oxo-1-phenylpropan-2-yl(E)-3-(4-(trifluoromethyl)phenyl)acrylate： yellow solid；m.p.167-169℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.7Hz, 2H), 7.75 (d, J= 16.1Hz, 1H), 7.65 (d, J=9.0Hz, 4H), 7.60 (d, J=7.3Hz, 1H), 7.50 (t, J=7.6Hz, 2H), 6.61 (d, J=16.0Hz, 1H), 6.14 (q, J=7.0Hz, 1H), 1.62 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.65 (s), 165.68 (s), 143.96 (s), 137.64 (s), 134.37 (s), 133.70 (s), 128.86 (s), 128.53 (s), 128.32 (s), 125.91 (s), 125.88 (s), 125.84 (s), 119.87 (s), 77.34 (s), 77.02 (s), 76.71 (s), 71.70 (s), 17.26 (s)
Embodiment 4
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 76%；
1-oxo-1-phenylpropan-2-yl(E)-3-(m-tolyl)acrylate：yellow solid； m.p.165-167℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.8Hz, 2H), 7.71 (d, J=16.0Hz, 1H), 7.59 (t, J=7.3Hz, 1H), 7.48 (t, J=7.6Hz, 2H), 7.33 (d, J=6.6Hz, 2H), 7.28 (d, J=7.5Hz, 1H), 7.20 (d, J=7.4Hz, 1H), 6.52 (d, J=16.0Hz, 1H), 6.11 (q, J=7.0Hz, 1H), 2.36 (s, 3H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.96 (s), 166.32 (s), 146.13 (s), 138.57 (s), 134.51 (s), 134.23 (s), 133.58 (s), 131.35 (s), 128.90 (s), 128.80 (s), 128.59 (s), 128.55 (s), 125.43 (s), 117.01 (s), 77.37 (s), 77.06 (s), 76.74 (s), 71.41 (s), 21.32 (s), 17.23(s).
Embodiment 5
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 82%；
1-oxo-1-phenylpropan-2-yl(E)-3-(2-methoxyphenyl)acr.ylate：yellow solid；m.p.185-187℃；1H NMR (400MHz, CDCl3) δ 8.04 (d, J=16.2Hz, 1H), 7.99 (d, J=7.7Hz, 2H), 7.58 (t, J=7.4Hz, 1H), 7.49 (dd, J=13.8,6.8Hz, 3H), 7.34 (t, J=7.8Hz, 1H), 7.00- 6.87 (m, 2H), 6.63 (d, J=16.2Hz, 1H), 6.11 (q, J=7.0Hz, 1H), 3.87 (s, 3H), 1.60 (d, J= 7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 197.14 (s), 166.84 (s), 158.52 (s), 141.48 (s), 134.61 (s), 133.51 (s), 131.72 (s), 129.22 (s), 128.78 (s), 128.57 (s), 123.25 (s), 120.71 (s), 117.66 (s), 111.18 (s), 77.39 (s), 77.07 (s), 76.76 (s), 71.28 (s), 55.47 (s), 17.21 (s)
Embodiment 6
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 92%；
1-oxo-1-phenylpropan-2-yl(E)-3-(4-methoxyphenyl)acr.ylate：yellow solid；m.p.187-189℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.8Hz, 2H), 7.70 (d, J=16.0Hz, 1H), 7.59 (t, J=7.3Hz, 1H), 7.55-7.43 (m, 4H), 6.90 (d, J=8.5Hz, 2H), 6.40 (d, J=15.9Hz, 1H), 6.11 (q, J=7.0Hz, 1H), 3.83 (s, 3H), 1.60 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3)δ 197.09 (s), 166.58 (s), 161.57 (s), 145.63 (s), 134.55 (s), 133.55 (s), 129.93 (s), 128.79 (s), 128.56 (s), 127.04 (s), 114.65 (s), 114.36 (s), 77.36 (s), 77.05 (s), 76.73 (s), 71.26 (s), 55.39 (s), 17.23 (s)
Embodiment 7
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 56%；
1-oxo-1-phenylpropan-2-yl(E)-3-(4-nitrophenyl)acrylate：yellow solid； m.p.148-149℃；1H NMR (400MHz, CDCl3) δ 8.26 (d, J=8.6Hz, 2H), 7.99 (d, J=7.6Hz, 2H), 7.77 (d, J=16.1Hz, 1H), 7.69 (d, J=8.6Hz, 2H), 7.62 (t, J=7.4Hz, 1H), 7.51 (t, J=7.7Hz, 2H), 6.67 (d, J=16.1Hz, 1H), 6.15 (q, J=7.0Hz, 1H), 1.63 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.71-196.32 (m), 165.31 (s), 148.64 (s), 142.82 (s), 140.35 (s), 134.29 (s), 133.78 (s), 128.89 (s), 128.78 (s), 128.53 (s), 124.21 (s), 121.60 (s), 77.34 (s), 77.02 (s), 76.71 (s), 71.89 (s), 17.28 (s)
Embodiment 8
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 87%.
1-oxo-1-phenylpropan-2-yl(E)-3-(3-fluorophenyl)acrylate：yellow solid； m.p.155-157℃；1H NMR (400MHz, CDCl3) δ 7.98 (d, J=7.8Hz, 2H), 7.67 (d, J=16.0Hz, 1H), 7.60 (t, J=7.4Hz, 1H), 7.53-7.46 (m, 3H), 7.40 (d, J=7.3Hz, 1H), 7.36 (d, J=7.8Hz, 1H), 7.34-7.29 (m, 1H), 6.53 (d, J=16.0Hz, 1H), 6.11 (q, J=7.0Hz, 1H), 1.61 (d, J=7.0Hz, 3H) ；13C NMR (101MHz, CDCl3) δ 196.73 (s), 165.82 (s), 144.23 (s), 136.09 (s), 134.95 (s), 134.41 (s), 133.66 (s), 130.35 (s), 130.17 (s), 128.84 (s), 128.54 (s), 127.97 (s), 126.35 (s), 118.77 (s), 77.37 (s), 77.05 (s), 76.73 (s), 71.63 (s), 17.24 (s)
Embodiment 9
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 76%；
1-oxo-1-phenylpropan-2-yl(E)-3-(4-bromophenyl)acrylate：yellow solid； m.p.213-215℃；1H NMR (400MHz, CDCl3) δ 7.98 (d, J=7.8Hz, 2H), 7.67 (d, J=16.0Hz, 1H), 7.60 (t, J=7.3Hz, 1H), 7.50 (dd, J=15.2,7.8Hz, 4H), 7.39 (d, J=8.2Hz, 2H), 6.52 (d, J= 16.0Hz, 1H), 6.12 (q, J=7.0Hz, 1H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3)δ 196.78 (s), 165.98 (s), 144.51 (s), 134.42 (s), 133.65 (s), 133.20 (s), 132.19 (s), 129.58 (s), 128.83 (s), 128.54 (s), 124.80 (s), 117.96 (s), 77.34 (s), 77.03 (s), 76.71 (s), 71.54 (s), 17.25 (s)
Embodiment 10
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 63%；
1-oxo-1-phenylpropan-2-yl(E)-3-([1,1 '-biphenyl]-4-yl)acrylate：yellow solid；m.p.220-222℃；1H NMR (400MHz, CDCl3) δ 8.00 (d, J=7.9Hz, 2H), 7.78 (d, J=16.0Hz, 1H), 7.66-7.57 (m, 7H), 7.53-7.43 (m, 4H), 7.37 (t, J=7.2Hz, 1H), 6.57 (d, J=16.0Hz, 1H), 6.13 (q, J=6.9Hz, 1H), 1.62 (d, J=6.9Hz, 3H)；13CNMR (101MHz, CDCl3) δ 196.96 (s), 166.30 (s), 145.48 (s), 143.27 (s), 140.13 (s), 134.50 (s), 133.61 (s), 133.24 (s), 128.92 (s), 128.82 (s), 128.75 (s), 128.57 (s), 127.89 (s), 127.57 (s), 127.07 (s), 117.06 (s), 77.36 (s), 77.04 (s), 76.72 (s), 71.46 (s), 17.26 (s)
Embodiment 11
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 63%；
1-oxo-1-phenylpropan-2-yl(E)-3-(3-methoxyphenyl)acrylate：yellow solid；m.p.179-181℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.8Hz, 2H), 7.71 (d, J=16.0Hz, 1H), 7.59 (t, J=7.3Hz, 1H), 7.49 (t, J=7.6Hz, 2H), 7.29 (t, J=7.9Hz, 1H), 7.12 (d, J= 7.6Hz, 1H), 7.05 (s, 1H), 6.94 (d, J=8.2Hz, 1H), 6.52 (d, J=16.0Hz, 1H), 6.12 (q, J= 7.0Hz, 1H), 3.82 (s, 3H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.90 (s), 166.19 (s), 159.91 (s), 145.87 (s), 135.62 (s), 134.47 (s), 133.61 (s), 129.91 (s), 128.82 (s), 128.55 (s), 120.99 (s), 117.53 (s), 116.50 (s), 112.93 (s), 77.39 (s), 77.07 (s), 76.75 (s), 71.46 (s), 55.31 (s), 17.25 (s)
Embodiment 12
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 91%；
1-oxo-1-phenylpropan-2-yl(E)-2-methyl-3-phenylacr.ylate：yellow solid； m.p.140-142℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.8Hz, 2H), 7.79 (s, 1H), 7.59 (t, J= 7.3Hz, 1H), 7.49 (t, J=7.5Hz, 2H), 7.43-7.36 (m, 4H), 7.35-7.29 (m, 1H), 6.09 (q, J= 7.0Hz, 1H), 2.15 (s, 3H), 1.62 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 197.15 (s), 168.07 (s), 139.97 (s), 135.76 (s), 134.58 (s), 133.57 (s), 129.76 (s), 128.81 (s), 128.53 (s), 128.48 (s), 128.39 (s), 127.70 (s), 77.38 (s), 77.07 (s), 76.75 (s), 71.82 (s), 17.19 (s), 14.07 (s)
Embodiment 13
Cinnamic acid derivative raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 86%；
1-oxo-1-phenylpropan-2-yl (E) -2,3-diphenylacrylate：yellow solid； m.p.221-223℃；1H NMR (400MHz, CDCl3) δ 7.94 (d, J=7.9Hz, 2H), 7.90 (s, 1H), 7.57 (t, J= 7.3Hz, 1H), 7.46 (t, J=7.6Hz, 2H), 7.37-7.30 (m, 3H), 7.25-7.22 (m, 2H), 7.19 (d, J= 6.9Hz, 1H), 7.15 (t, J=7.4Hz, 2H), 7.06 (d, J=7.7Hz, 2H), 6.06 (q, J=7.0Hz, 1H), 1.55 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 197.14 (s), 167.24 (s), 141.19 (s), 135.50 (s), 134.57 (s), 134.55 (s), 133.49 (s), 131.89 (s), 130.72 (s), 129.89 (s), 129.19 (s), 128.75 (s), 128.58 (s), 128.56 (s), 128.20 (s), 127.88 (s), 77.37 (s), 77.06 (s), 76.74 (s), 72.39 (s), 17.11 (s)
Embodiment 14~23 presses following conditioned response：
By cinnamic acid derivative (0.5mmol), ketone compounds (0.5mmol), CuI (20mol%), TEAB (10mol%), DTBP (3.0equiv), DMSO (2.0mL) are added in 10mL reactors, under air environment, are heated to 100 DEG C reaction 12h, reaction product passes through chromatography post separation.
Embodiment 14
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 76%；
1-(4-chlorophenyl)-1-oxopropan-2-yl cinnamate：yellow solid；m.p.185- 187℃；1H NMR (400MHz, CDCl3) δ 7.93 (d, J=8.1Hz, 2H), 7.74 (d, J=16.0Hz, 1H), 7.59-7.50 (m, 2H), 7.47 (d, J=8.1Hz, 2H), 7.43-7.35 (m, 3H), 6.52 (d, J=16.0Hz, 1H), 6.04 (q, J= 6.9Hz, 1H), 1.60 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 195.88 (s), 166.24 (s), 146.17 (s), 140.10 (s), 134.19 (s), 132.81 (s), 130.59 (s), 129.95 (s), 129.17 (s), 128.94 (s), 128.26 (s), 117.01 (s), 77.35 (s), 77.04 (s), 76.72 (s), 71.35 (s), 17.11 (s)
Embodiment 15
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 81%；
1-(4-fluorophenyl)-1-oxopropan-2-yl cinnamate：yellow solid；m.p.154- 157℃；1H NMR (400MHz, CDCl3) δ 8.03 (dd, J=7.7,5.8Hz, 2H), 7.74 (d, J=16.0Hz, 1H), 7.53 (d, J=2.7Hz, 2H), 7.40 (s, 3H), 7.17 (t, J=8.4Hz, 2H), 6.53 (d, J=16.0Hz, 1H), 6.06 (q, J =7.0Hz, 1H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 195.43 (s), 166.26 (s), 146.12 (s), 134.21 (s), 131.30 (s), 131.20 (s), 130.57 (s), 128.93 (s), 128.25 (s), 117.07 (s), 116.13 (s), 115.91 (s), 77.34 (s), 77.02 (s), 76.71 (s), 71.29 (s), 17.09 (s)
Embodiment 16
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 86%；
1-oxo-1-(p-tolyl)propan-2-yl cinnamate：yellow solid；m.p.162-164℃；1H NMR (400MHz, CDCl3) δ 7.89 (d, J=7.8Hz, 2H), 7.74 (d, J=16.0Hz, 1H), 7.57-7.47 (m, 2H), 7.44-7.33 (m, 3H), 7.28 (d, J=7.9Hz, 2H), 6.53 (d, J=16.0Hz, 1H), 6.10 (q, J=6.9Hz, 1H), 2.41 (s, 3H), 1.60 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.45 (s), 166.25 (s), 145.85 (s), 144.54 (s), 134.31 (s), 131.92 (s), 130.47 (s), 129.50 (s), 128.91 (s), 128.68 (s), 128.22 (s), 117.35 (s), 77.39 (s), 77.07 (s), 76.75 (s), 71.39 (s), 21.72 (s), 17.34 (s).
Embodiment 17
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 82%；
1-(3-chlorophenyl)-1-oxopropan-2-yl cinnamate：yellow solid；m.p.153- 155℃；1H NMR (400MHz, CDCl3) δ 7.96 (s, 1H), 7.86 (d, J=7.7Hz, 1H), 7.74 (d, J=16.0Hz, 1H), 7.60-7.51 (m, 3H), 7.45 (d, J=7.8Hz, 1H), 7.40 (t, J=5.5Hz, 3H), 6.52 (d, J=16.0Hz, LH), 6.02 (q, J=7.0Hz, 1H), 1.61 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 195.93 (s), 166.23 (s), 146.20 (s), 136.08 (s), 135.19 (s), 134.20 (s), 133.52 (s), 130.59 (s), 130.14 (s), 128.94 (s), 128.64 (s), 128.26 (s), 126.55 (s), 116.98 (s), 77.34 (s), 77.03 (s), 76.71 (s), 71.46 (s), 17.09 (s)
Embodiment 18
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 82%；
1-(4-methoxyphenyl)-1-oxopropan-2-yl cinnamate：yellow solid；m.p.189- 191℃；1H NMR (400MHz, CDCl3) δ 7.98 (d, J=8.7Hz, 2H), 7.74 (d, J=16.0Hz, 1H), 7.57-7.49 (m, 2H), 7.44-7.34 (m, 3H), 6.96 (d, J=8.7Hz, 2H), 6.54 (d, J=16.0Hz, 1H), 6.09 (q, J= 6.8Hz, 1H), 3.87 (s, 3H), 1.60 (d, J=7.0Hz, 3H)；13C NMR (101MHz, CDCl3) δ 195.27 (s), 166.28 (s), 163.91 (s), 145.83 (s), 134.32 (s), 130.91 (s), 130.46 (s), 128.91 (s), 128.22 (s), 127.31 (s), 117.37 (s), 114.03 (s), 77.36 (s), 77.04 (s), 76.72 (s), 71.18 (s), 55.53 (s), 17.44 (s)
Embodiment 19
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 85%；
1-oxo-1-phenylpentan-2-yl cinnamate：yellow liquid；m.p.165-167℃；1H NMR (400MHz, CDCl3) δ 7.99 (d, J=7.8Hz, 2H), 7.74 (d, J=16.0Hz, 1H), 7.59 (t, J=7.4Hz, 1H), 7.56-7.52 (m, 2H), 7.49 (t, J=7.6Hz, 2H), 7.42-7.35 (m, 3H), 6.56 (d, J=16.0Hz, 1H), 6.03 (t, J=6.4Hz, 1H), 1.92 (dd, J=14.6,7.3Hz, 2H), 1.54 (td, J=13.9,6.9Hz, 2H), 0.98 (t, J=7.4Hz, 3H)；13C NMR (101MHz, CDCl3) δ 196.79 (s), 166.53 (s), 145.85 (s), 134.92 (s), 134.32 (s), 133.52 (s), 130.47 (s), 128.91 (s), 128.80 (s), 128.48 (s), 128.23 (s), 117.30 (s), 77.36 (s), 77.04 (s), 76.72 (s), 75.13 (s), 33.54 (s), 18.93 (s), 13.76 (s)
Embodiment 20
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 62%；
1-(furan-2-yl)-1-oxobutan-2-yl cinnamate：yellow solid；m.p.158-160℃；1H NMR (400MHz, CDCl3) δ 7.75 (d, J=16.0Hz, 1H), 7.63 (s, 1H), 7.59-7.51 (m, 2H), 7.45-7.36 (m, 3H), 7.33 (d, J=3.5Hz, 1H), 6.62-6.50 (m, 2H), 5.74 (dd, J=7.8,4.8Hz, 1H), 2.01 (dtt, J=29.2,14.7,7.2Hz, 2H), 1.09 (t, J=7.4Hz, 3H)；13C NMR (101MHz, CDCl3) δ 185.32 (s), 166.40 (s), 150.88 (s), 146.88 (s), 145.95 (s), 134.28 (s), 130.50 (s), 128.91 (s), 128.24 (s), 118.59 (s), 117.20 (s), 112.46 (s), 77.36 (s), 77.04 (s), 76.72 (s), 76.44 (s), 24.79 (s), 9.84 (s)
Embodiment 21
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 47%；
2-oxocyclohexyl cinnamate：yellow solid；m.p.121-123℃；1H NMR (400MHz, CDCl3) δ 7.75 (d, J=16.0Hz, 1H), 7.61-7.51 (m, 2H), 7.48-7.33 (m, 3H), 6.53 (d, J=16.0Hz, 1H), 5.32 (dd, J=11.7,6.4Hz, 1H), 2.56 (d, J=13.3Hz, 1H), 2.46 (dd, J=13.5,6.0Hz, 1H), 2.42-2.35 (m, 1H), 2.17-2.07 (m, 1H), 2.01 (d, J=9.6Hz, 1H), 1.92-1.78 (m, 2H), 1.72-1.64 (m, 1H)；13C NMR (101MHz, CDCl3) δ 204.67 (s), 165.88 (s), 145.73 (s), 134.36 (s), 130.41 (s), 128.89 (s), 128.20 (s), 117.41 (s), 77.37 (s), 77.05 (s), 76.74 (s), 76.63 (s), 40.79 (s), 33.28 (s), 27.24 (s), 23.83 (s)
Embodiment 22
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 42%；
3-oxopentan-2-yl cinnamate：yellow liquid；m.p.72-74℃；1H NMR (400MHz, CDCl3) δ 7.75 (d, J=16.0Hz, 1H), 7.54 (d, J=3.2Hz, 2H), 7.46-7.36 (m, 3H), 6.51 (d, J= 16.0Hz, 1H), 5.25 (q, J=7.0Hz, 1H), 2.67-2.44 (m, 2H), 1.47 (d, J=7.0Hz, 3H), 1.10 (t, J= 7.2Hz, 3H)；13C NMR (101MHz, CDCl3) δ 208.62 (s), 166.28 (s), 145.96 (s), 134.21 (s), 130.57 (s), 128.95 (s), 128.22 (s), 117.20 (s), 77.35 (s), 77.03 (s), 76.71 (s), 74.68 (s), 31.47 (s), 16.47 (s), 7.27 (s)
Embodiment 23
Ketone compounds raw material：
Alpha-acyloxy ketone derivatives product containing ethylenic unsaturation：Yield 58%；
1,3-dioxo-1,3-diphenylpropan-2-yl cinnamate：yellow solid；m.p.285-287 ℃；1H NMR (400MHz, CDCl3) δ 8.09 (d, J=7.9Hz, 4H), 7.79 (d, J=16.1Hz, 1H), 7.60 (t, J= 7.4Hz, 2H), 7.53-7.46 (m, 6H), 7.38 (d, J=5.4Hz, 3H), 7.14 (s, 1H), 6.57 (d, J=16.0Hz, 1H)；13C NMR (101MHz, CDCl3) δ 191.26 (s), 165.20 (s), 147.23 (s), 134.44 (s), 134.22 (s), 133.99 (s), 130.85 (s), 129.51 (s), 128.97 (s), 128.81 (s), 128.39 (s), 116.28 (s), 79.93 (s), 77.37 (s), 77.05 (s), 76.73 (s)
Control experiment group
It is as follows using material quantity in experimental group 1~21：Cinnamic acid derivative (0.5mmol) and propiophenone (1.0equiv).
The catalyst (20mol%) of use, quaternary ammonium salt (10mol%), oxidant (3.0equiv), solvent (2.0mL), choosing It selects as shown in table 1；Reaction condition：12h is reacted under air environment, other conditions are as shown in table 1.
Table 1
As can be seen from Table 1：Cinnamic acid and propiophenone are substrate, in stannous chloride (20 moles of %)/TEAB (tetraethyls Ammonium bromide, 10 moles of %) DMSO solution system in, in the presence of DTBP (di-t-butyl peroxide, 3 equivalents), reaction progress Smoothly, the target product obtained has 73% (experimental group 1).
From, as can be seen that in copper compound catalyst, the catalytic effect of halogenated cuprous salt is relatively good in experimental group 2-5, And the relatively other halogenated mantoquitas of catalytic effect (experimental group 3) of CuI will be got well.Other halogenated metal salts, such as frerrous chloride (experimental group 6) it, is hardly obtained target product, equally, in the case of no addition catalyst, also cannot get target product (experimental group 7)。
The selection of oxidant, preferably organic peroxide, and organic peroxide is preferably having without hydroperoxyl Machine peroxide, as DTBP effects are best.If it is only to replace DTBP, obtained product using TBHP (tert-butyl hydroperoxide) There is 21% (experimental group 8), if K2S2O8When replacing DTBP or not adding peroxide, reaction cannot occur (experimental group 9,10).
Quaternary ammonium salt additives preferably use tetraalkyl ammonium salt (experimental group 11-13).TEAB shows excellent work Property, obtain target product, yield 90% (experimental group 12).
Solvent preferably uses polar non-solute, such as DMSO, CH3CN or toluene are used as solvent, and reaction productivity is (real Test group 1,14 and 15).However, when reaction carries out in DCE or THF, product trace (experimental group 16,18) is only obtained.It will reaction In mixed solvent DMSO/H2Proton solvent water, reaction failure is added in O (experimental group 17).
Reaction temperature is reduced to 80 DEG C, obtains product, only 28% (experimental group 19).And when it is thus lifted to 110 DEG C (in fact It is little to test the productivity variation of group 21).
Check experiment group 22
Cinnamic acid (0.5mmol) and 2- hydroxypropiophenonepreparations (1.0equiv), CuI (20mol%), TEAB (10mol%), DTBP (3.0equiv), DMSO (2.0mL) are heated to 100 DEG C of reaction 12h, without α-acyl containing ethylenic unsaturation under air environment Oxygroup ketone derivatives target product generates.

Claims (5)

1. the method for directly synthesizing the alpha-acyloxy ketone derivatives containing ethylenic unsaturation by α-reaction kinetic of ketone, feature exist In：Under air environment, 1 structure cinnamic acid derivative of formula, 2 structure ketone compounds of formula and organic peroxide, in copper chemical combination In object/tetraalkyl ammonium salt catalyst system and catalyzing, alpha-acyloxy ketone of 3 structure of formula containing ethylenic unsaturation is synthesized by one pot reaction and is derived Object；
Wherein,
R1Selected from halogen, trifluoromethyl, alkyl, alkoxy, nitro, phenyl, alkoxy acyl or alkyl acyl；
R2Selected from for hydrogen, aryl, alkyl, alkoxy acyl or heterocyclic substituent；
R3And R4Independently selected from alkyl, aryl, aroyl, alkoxy acyl or heterocyclic substituent；Alternatively, R3And R4For cycloalkanes chain；
The copper compound is CuCl, CuBr, CuI, Cu2O、CuCl2At least one of；
The reaction is with DMSO, CH3At least one of CN, toluene are used as solvent；
The tetraalkyl ammonium salt is in 4-butyl ammonium hydrogen sulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrem ammonium bromide At least one；
The organic peroxide is di-t-butyl peroxide.
2. according to claim 1 directly synthesize the derivative of the alpha-acyloxy ketone containing ethylenic unsaturation by α-reaction kinetic of ketone The method of object, it is characterised in that：
R3For phenyl, substituted-phenyl, quinary heterocyclic radical or C1~C5Alkyl；
R4For C1~C5Alkyl or benzoyl；
Alternatively, R3And R4For C5Cycloalkanes chain.
3. according to claim 1 directly synthesize the derivative of the alpha-acyloxy ketone containing ethylenic unsaturation by α-reaction kinetic of ketone The method of object, it is characterised in that：
R1For fluorine, trifluoromethyl, methyl, methoxyl group, nitro, bromine or phenyl；
R2For hydrogen, methyl or phenyl；
R3For chlorophenyl, difluorophenyl, aminomethyl phenyl, methoxyphenyl, phenyl, furyl or ethyl；
R4For methyl, ethyl or benzoyl；
Alternatively, R3And R4For C5Cycloalkanes chain.
4. directly synthesizing α-acyl containing ethylenic unsaturation by α-reaction kinetic of ketone according to claims 1 to 3 any one of them The method of oxygroup ketone derivatives, it is characterised in that：The temperature of the reaction is 70 DEG C~120 DEG C, and the time is 8~16h.
5. according to claim 4 directly synthesize the derivative of the alpha-acyloxy ketone containing ethylenic unsaturation by α-reaction kinetic of ketone The method of object, it is characterised in that：The temperature of the reaction is 80 DEG C~110 DEG C, and the time is 10~14h.
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