CN107011162A - A kind of method that α acyloxy ketone compounds are prepared with end group acetylene compound - Google Patents

A kind of method that α acyloxy ketone compounds are prepared with end group acetylene compound Download PDF

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CN107011162A
CN107011162A CN201710275646.4A CN201710275646A CN107011162A CN 107011162 A CN107011162 A CN 107011162A CN 201710275646 A CN201710275646 A CN 201710275646A CN 107011162 A CN107011162 A CN 107011162A
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methyl
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nmr
acetylene
benzyls
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周从山
杨赞
杨涛
李姣
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Hunan Institute of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/12—Formation or introduction of functional groups containing oxygen of carboxylic acid ester groups
    • 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
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D333/40—Thiophene-2-carboxylic acid

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Abstract

The invention provides a kind of method for efficiently synthesizing the α acyloxy ketone compounds containing different substitution functional groups, it uses acetylacetone copper as catalysts, tert-Butanol peroxide is used as oxidant, using ketone compounds with end acetylene compound as reaction substrate, reaction system adds organic solvent.The advantage of this method：Catalyst is cheap and easy to get；Reaction condition is gentle, safe and reliable；Gained target product yield is higher.The problem of traditional α acyloxylations reaction system is single is this method solve, and there is provided a kind of new acyloxylating agent, with good prospects for commercial application.

Description

A kind of method that alpha-acyloxy ketone compounds are prepared with end group acetylene compound
Technical field
Field is synthesized the present invention relates to the applied catalysis of alpha-acyloxy ketone compounds, one kind is related in particular to and is urged with copper Change the method that ketone compounds and end acetylene compound prepare alpha-acyloxy ketones derivant in the presence of oxidant.
【Background technology】
Alpha-acyloxy ketone compounds are the important intermediate of a class in Synthetic Organic Chemistry, the Alpha-hydroxy ketone after its hydrolysis Compound has extensive physiologically active, can apply to many natural products（Terpene compound and alkaloid）Synthesis, It is the very important synthon of a class；It is existed in many natural products and active organic compounds simultaneously, is that a class is non- Often important structural framework.Therefore, its synthetic methodology is studied significant.
With development in recent years on methodology of organic synthesis, the synthesis on alpha-acyloxy ketone compounds is achieved Larger progress.The sp that ketone is α3- c h bond is influenceed by carbonyl, with faintly acid, and to import one at its α has electricity negative The group of property, is relatively difficult.Its synthetic method is broadly divided into：（1）The nucleophilic substitution of α-halogenatedketone and carboxylate； （2）The transition metal-catalyzed direct acyloxylation of ketone compounds α；（3）The direct acyl of ketone compounds α without metal catalytic Epoxide.The new synthetic methodology of development has great importance.
The acyloxylation used in metal and the direct acyloxylation reaction of nonmetal catalyzed ketone compounds α is tried Agent, mainly includes：Acid, aromatic aldehyde, benzylalcohol, acid anhydrides, toluene, olefin compound.End-group alkyne is as acyloxylating agent, for ketone α acyloxylations of class compound do not have been reported that.And reaction system is more single in these reactions（TBAI/TBHP）.Development is new Acyloxylating agent and catalyst system and catalyzing have great importance.
For the deficiency of existing alpha-acyloxy ketone compounds synthesis technique, it is green, cheap that industry just puts forth effort on development Catalyst system and catalyzing synthesize alpha-acyloxy ketone compounds.
【The content of the invention】
It is an object of the invention to provide it is a kind of by ketone compounds cheap and easy to get and end group acetylene compound as raw material in Cu/ Under TBHP catalyst system and catalyzings, the method for synthesizing corresponding alpha-acyloxy ketone compounds, to overcome drawbacks described above of the prior art.
One object of the present invention provides a kind of by ketone compounds cheap and easy to get and end group acetylenic compound synthesis pair The method for the alpha-acyloxy ketone compounds answered, includes following step：Take ketone compounds, the end group acetylenic chemical combination of reacting dose Thing, catalyst, oxidant and organic solvent are placed in reactor under air atmosphere and mixed；Under agitation at 120 DEG C After reaction 12 hours, corresponding alpha-acyloxy ketone compounds are produced.Specific reaction equation is as follows：
Wherein, R1Be selected from alkyl, alkoxy, benzyl, 4- chlorobenzyls, 3- nitrobenzyls, 4- methoxy-benzyls, 4- bromobenzyls, The groups such as 4- luorobenzyls, 3- luorobenzyls, 4- methyl-benzyls, thiophene；
R2It is selected from groups such as methyl, hydrogen, benzyl, ethyl, ester groups；
R3It is to be selected from benzyl, 4- luorobenzyls, 4- chlorobenzyls, 4- bromobenzyls, 4- methyl-benzyls, 4- methoxy-benzyls, 4- nitrobenzyls The groups such as base, 3,4- dimethoxy-benzyls, naphthyl, 3- methyl-benzyls, 2- methyl-benzyls, thiophene.
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, ketone compounds refer to propiophenone, 4- methyl phenyl ketones, 4- methoxybenzenes acetone, 4- chlorophenyl acetones, 4- fluorobenzene acetone, 4- brom-acetophenones, 3- nitros propiophenone, 3- fluorobenzene acetone, benzene second Ketone, phenyl propyl ketone, 1- (2- thienyls) -1- acetone, ethyl benzoylacetate, cyclohexanone, dimethyl malenate etc..
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, end group acetylene compound refers to phenylacetylene, 4- fluorophenethyls Alkynes, 4- chlorobenzenes acetylene, 4- bromobenzenes acetylene, 4- methyl phenylacetylene, 4- Methoxy-phenylacetylenes, 3,4- dimethoxys phenylacetylene, 4- nitre Base phenylacetylene, 2- naphthalenes acetylene, 3- methyl phenylacetylene, 2- methyl phenylacetylene or 2- thiophene acetylene etc..
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, the catalyst described in reactions steps is to be selected from chlorination Iron, copper bromide, copper acetate, copper chloride, trifluoroacetic acid ketone, copper nitrate, copper sulphate or acetylacetone copper.
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, oxidant refers to tert-Butanol peroxide, hydrogen peroxide, two tertiary fourths Base peroxide, ammonium persulfate-sodium bisulfate.
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, organic solvent refer to tetrahydrofuran, toluene, ethyl acetate, Chlorobenzene, 1,2- dichloroethanes, acetonitrile, dimethyl sulfoxide, carbon tetrachloride.
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, the mol ratio of ketone compounds and end group acetylene compound For 1：2.
In the method for above-mentioned synthesis alpha-acyloxy ketone compounds, the consumption of catalyst is（5%-20%）, the use of oxidant Measure and be（4.0 eq- 6.0 eq）.
Method provided by the present invention by end group acetylenic compound synthesis alpha-acyloxy ketone compounds, course of reaction is gentle It is easy to control.While higher yields are obtained, this method is simple and easy to apply, and used catalyst is cheap and easy to get, prepares simple, tool There is good prospects for commercial application.
【Embodiment】
With reference to embodiments of the invention, the present invention will be further described：
First, test and analysis
The structural analysis of reaction product uses the Bruker Avance-III that Bruker companies produce in the following embodiments of the present invention 400 magnetic nuclear resonance analyzers.
2nd, embodiment
Embodiment 1
By 0.4 mmol propiophenone, 0.2 mmol phenylacetylene, appropriate tert-Butanol peroxide, 1 ml chlorobenzenes under air ambient Add in Schlenk pipes, proper catalyst (iron chloride, copper bromide, copper acetate, copper chloride, trifluoro second are added under air ambient Sour ketone, copper nitrate, copper sulphate or acetylacetone copper), in 120oStirring reaction 12 hours under C.By column chromatography, in levulinic When ketone copper is as catalyst, the yield of the reaction can reach 70% yield.
Embodiment 2
By 0.4 mmol propiophenone, 0.2 mmol phenylacetylene, appropriate acetylacetone copper, 1 ml chlorobenzenes under air ambient Add in Schlenk pipes, appropriate oxidant (tert-Butanol peroxide, hydrogen peroxide, di-tert-butyl peroxide are added under air ambient Thing, ammonium persulfate-sodium bisulfate), in 120oStirring reaction 12 hours under C.By column chromatography, oxidation is used as in tert-Butanol peroxide During agent, the yield of the reaction can reach 70% yield.
Embodiment 3
By 0.4 mmol propiophenone, 0.2 mmol phenylacetylene, appropriate acetylacetone copper, appropriate oxidant in air ambient In lower addition Schlenk pipes, solvent (tetrahydrofuran, toluene, ethyl acetate, chlorobenzene, the chloroethenes of 1,2- bis- are added under air ambient Alkane, acetonitrile, dimethyl sulfoxide, carbon tetrachloride), in 120oStirring reaction 12 hours under C.By column chromatography, solvent is used as in chlorobenzene When, the yield of the reaction can reach 70% yield.
Embodiment 4
The preparation of 2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol phenylacetylene, appropriate acetylacetone,2,4-pentanedione Copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 hours.Treat After reaction terminates, separating-purifying can obtain the 2- benzoyloxy group propiophenones of 68% separation yield.Pass through1H、13C NMR are identified The product.
1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 7.5 Hz, 2 H), 8.00 (d, J = 7.5 Hz, 2 H), 7.58 (q, J = 7.2 Hz, 2 H), 7.46 (dt, J = 15.8, 7.8 Hz, 4 H), 6.21 (q, J = 6.9 Hz, 1 H), 1.67 (d, J = 7.0 Hz, 3 H); 13C NMR(100 MHz, CDCl3) δ 196.66, 165.92, 134.43, 133.53, 133.18, 129.81, 129.44, 128.74, 128.45, 128.33,, 71.84, 17.09.
Embodiment 5
The preparation of 4 '-fluoro- 2- benzoyloxy groups propiophenone：By 0.4 mmol propiophenone, 0.2 mmol 4- fluorobenzene acetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes added under air ambient in Schlenk pipes, in 120 oCLower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain 4 '-fluoro- 2- benzoyloxy groups propiophenone of 65% separation yield.It is logical Cross1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.22 – 8.05 (m, 2 H), 8.05 – 7.90 (m, 2 H), 7.66 – 7.55 (m, 1 H), 7.49 (t, J = 7.6 Hz, 2 H), 7.11 (t, J = 8.6 Hz, 2 H), 6.20 (q, J = 7.0 Hz, 1 H), 1.67 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 196.72, 167.37, 165.12, 164.84, 134.53, 133.77, 132.64, 132.55, 128.96, 128.62, 125.92, 125.89, 115.82, 115.60, 72.12, 17.34.
Embodiment 6
The preparation of 4 '-chloro- 2- benzoyloxy groups propiophenone：By 0.4 mmol propiophenone, 0.2 mmol 4- chlorobenzenes acetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes added under air ambient in Schlenk pipes, in 120 oCLower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain 4 '-chloro- 2- benzoyloxy groups propiophenone of 66% separation yield.It is logical Cross1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.00 (q, J = 8.0 Hz, 4 H), 7.57 (t, J = 7.4 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 2 H), 7.40 (d, J = 7.6 Hz, 2 H), 6.19 (q, J = 6.9 Hz, 1 H), 1.66 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 196.38, 164.98, 139.63, 134.23, 133.56, 131.15, 128.73, 128.65, 128.37, 72.30, 17.09.
Embodiment 7
The preparation of 4 '-bromo- 2- benzoyloxy groups propiophenone：By 0.4 mmol propiophenone, 0.2 mmol 4- bromobenzenes acetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes added under air ambient in Schlenk pipes, in 120 oCLower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain 4 '-bromo- 2- benzoyloxy groups propiophenone of 43% separation yield.It is logical Cross1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ7.96 (q, J = 7.8 Hz, 4 H), 7.56 (d, J = 7.4 Hz, 3 H), 7.46 (t, J = 7.5 Hz, 2 H), 6.19 (q, J = 6.9 Hz, 1 H), 1.65 (d, J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ196.33, 165.10, 134.22, 133.55, 131.63, 131.25, 129.73, 128.72, 128.36, 128.33, 72.04, 17.09.
Embodiment 8
The preparation of 4 '-methyl -2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 4- methyl phenylacetylene, Appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring Reaction 12 hours.After question response terminates, separating-purifying can obtain 4 '-methyl -2- benzoyloxy group phenylpropyl alcohols of 70% separation yield Ketone.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ7.98 (t, J = 6.5 Hz, 4 H), 7.55 (t, J = 7.3 Hz, 1 H), 7.45 (t, J = 7.4 Hz, 2 H), 7.21 (d, J = 7.7 Hz, 2 H), 6.17 (q, J = 6.9 Hz, 1 H), 2.37 (s, 3 H), 1.64 (d, J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ196.73, 165.87, 143.88, 134.38, 133.39, 129.75, 128.98, 128.64, 128.36, 126.64, 71.61, 21.52, 17.03.
Embodiment 9
The preparation of 4 '-methoxyl group -2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 4- methoxybenzenes Acetylene, appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oC Lower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain 4 '-methoxyl group -2- benzoyls of 63% separation yield Epoxide propiophenone.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.01 (q, J = 8.0 Hz, 4 H), 7.55 (t, J = 7.3 Hz, 1 H), 7.45 (t, J = 7.5 Hz, 2 H), 6.90 (d, J = 8.7 Hz, 2 H), 6.16 (q, J = 6.9 Hz, 1 H), 3.80 (s, 3 H), 1.64 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ196.84, 165.49, 163.51, 134.37, 133.35, 131.76, 128.61, 128.33, 121.70, 113.51, 71.47, 55.24, 17.01.
Embodiment 10
The preparation of 3 ', 4 '-dimethoxy -2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 3,4- bis- Methoxy-phenylacetylene, appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, In 120 oCLower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain 3 ', the 4 '-two of 52% separation yield Methoxyl group -2- benzoyloxy group propiophenones.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.07 – 7.92 (m, 2 H), 7.73 (dd, J = 8.4, 1.9 Hz, 1 H), 7.64 – 7.34 (m, 4 H), 6.87 (d, J = 8.5 Hz, 1 H), 6.16 (q, J = 7.0 Hz, 1 H), 3.91 (s, 3 H), 3.89 (s, 3 H), 1.64 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 196.96, 165.74, 153.29, 148.61, 134.52, 133.51, 128.75, 128.48, 124.02, 121.90, 112.13, 110.25, 71.72, 56.01, 55.96, 17.16.
Embodiment 11
The preparation of 4 '-nitro -2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 4- nitrobenzene acetylenes, Appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring Reaction 12 hours.After question response terminates, separating-purifying can obtain 4 '-methoxyl group -2- benzoyloxy group benzene of 45% separation yield Acetone.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.40 – 8.15 (m, 4 H), 7.99 (d, J = 7.8 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.50 (t, J = 7.6 Hz, 2 H), 6.25 (q, J = 7.0 Hz, 1 H), 1.70 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.94, 164.09, 150.70, 134.90, 134.11, 133.84, 130.96, 130.96, 128.90, 128.45, 123.53, 72.78, 17.25.
Embodiment 12
The preparation of 2- Naphthoyloxy propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 2- naphthalenes acetylene, appropriate levulinic Ketone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 hours. After question response terminates, separating-purifying can obtain the 2- Naphthoyloxy propiophenones of 51% separation yield.Pass through1H、13C NMR reflect The fixed product.
1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1 H), 8.17 – 7.77 (m, 6 H), 7.68 – 7.38 (m, 5 H), 6.27 (q, J = 6.9 Hz, 1 H), 1.72 (d, J = 7.0 Hz, 3 H). 13C NMR (100 MHz, CDCl3) δ 196.79, 166.12, 135.68, 134.50, 133.58, 132.43, 131.50, 129.41, 128.80, 128.65, 128.53, 128.38, 128.19, 127.76, 126.72, 126.66, 125.30 , 72.01, 17.27.
Embodiment 13
The preparation of 3 '-methyl -2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 3- methyl phenylacetylene, Appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring Reaction 12 hours.After question response terminates, separating-purifying can obtain 3 '-methyl -2- benzoyloxy group phenylpropyl alcohols of 45% separation yield Ketone.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.0 Hz, 2 H), 7.89 (d, J = 9.1 Hz, 2 H), 7.55 (t, J = 7.3 Hz, 1 H), 7.45 (t, J = 7.5 Hz, 2 H), 7.36 – 7.28 (m, 2 H), 6.19 (q, J = 6.9 Hz, 1 H), 2.36 (s, 3 H), 1.65 (d, J = 7.0 Hz, 3H) ; 13C NMR (100 MHz, CDCl3) δ 196.64, 165.98, 138.04, 134.36, 133.92, 133.41, 130.21, 129.30, 128.65, 128.17, 126.88, 71.70, 21.07, 17.04.
Embodiment 14
The preparation of 2 '-methyl -2- benzoyloxy group propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 2- methyl phenylacetylene, Appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring Reaction 12 hours.After question response terminates, separating-purifying can obtain 2 '-methyl -2- benzoyloxy group phenylpropyl alcohols of 45% separation yield Ketone.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.00 (t, J = 6.8 Hz, 3 H), 7.56 (t, J = 7.3 Hz, 1 H), 7.46 (t, J = 7.5 Hz, 2 H), 7.38 (t, J = 7.5 Hz, 1 H), 7.23 (t, J = 8.3 Hz, 2 H), 6.19 (q, J = 6.9 Hz, 1 H), 2.58 (s, 3 H), 1.64 (d, J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 196.78, 166.82, 140.36, 134.41, 133.45, 132.15, 131.54, 130.77, 128.85, 128.70, 128.38, 125.64, 71.65, 21.52, 17.06.
Embodiment 15
The preparation of 2- thiophene acyloxy propiophenones：By 0.4 mmol propiophenone, 0.2 mmol 2- thiophene acetylene, appropriate second Acyl acetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 is small When.After question response terminates, separating-purifying can obtain the 2- thiophene acyloxy propiophenones of 39% separation yield.Pass through1H、13C NMR identifies the product.
1H NMR (400 MHz, CDCl3) δ 8.06 – 7.91 (m, 2 H), 7.91 – 7.75 (m, 1 H), 7.69 – 7.51 (m, 2 H), 7.46 (t, J = 7.6 Hz, 2 H), 7.14 – 7.02 (m, 1 H), 6.14 (q, J = 7.0 Hz, 1 H), 1.64 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 196.48, 161.52, 134.37, 134.10, 133.58, 132.87, 129.00, 128.78, 128.51, 127.81, 77.39, 77.07, 76.75, 72.13, 17.18.
Embodiment 16
Preparation of the 2- benzoyloxy groups to fluorobenzene acetone：By 0.4 mmol 4- fluorobenzene acetone, 0.2 mmol phenylacetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 Hour.After question response terminates, separating-purifying can obtain the 2- benzoyloxy groups of 63% separation yield to fluorobenzene acetone.Pass through1H 、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.12 - 8.04 (m, 4 H), 7.60 (t, J = 7.3 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 2 H), 7.18 (t, J = 8.1 Hz, 2 H), 6.17 (q, J = 6.9 Hz, 1 H), 1.69 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.21, 167.22, 166.96, 164.67, 133.34, 131.25, 131.16, 130.86, 130.83, 129.83, 129.35, 128.40, 116.09, 115.88, 71.72, 17.09.
Embodiment 17
Preparation of the 2- benzoyloxy groups to chlorophenyl acetone：By 0.4 mmol 4- chlorophenyl acetones, 0.2 mmol phenylacetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 Hour.After question response terminates, separating-purifying can obtain the 2- benzoyloxy groups of 65% separation yield to chlorophenyl acetone.Pass through1H 、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 7.9 Hz, 2 H), 7.96 (d, J = 7.6 Hz, 2 H), 7.59 (t, J = 7.4 Hz, 1 H), 7.45 (t, J = 7.1 Hz, 4 H), 6.15 (q, J = 6.9 Hz, 1 H), 1.67 (d, J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.58, 165.86, 139.97, 133.31, 132.72, 129.85, 129.77, 129.25, 129.07, 128.36, 71.73, 16.98.
Embodiment 18
Preparation of the 2- benzoyloxy groups to brom-acetophenone：By 0.4 mmol 4- brom-acetophenones, 0.2 mmol phenylacetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 Hour.After question response terminates, separating-purifying can obtain the 2- benzoyloxy groups of 43% separation yield to brom-acetophenone.Pass through1H 、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 7.9 Hz, 2 H), 7.86 (d, J = 7.6 Hz, 2 H), 7.67 - 7.55 (m, 3 H), 7.45 (t, J = 7.5 Hz, 2 H), 6.12 (q, J = 6.9 Hz, 1 H), 1.66 (d, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.87, 165.93, 133.38, 133.19, 132.13, 129.98, 129.84, 129.28, 128.80, 128.42, 71.75, 17.02.
Embodiment 19
The preparation of 2- benzoyloxy group P-Methyl phenylethylketones：By 0.4 mmol 4- methyl phenyl ketones, 0.2 mmol phenylacetylene, fit The acetylacetone copper of amount, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring is anti- Answer 12 hours.After question response terminates, separating-purifying can obtain the 2- benzoyloxy group P-Methyl phenylethylketones of 69% separation yield. Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 7.8 Hz, 2 H), 7.93 (d, J = 7.7 Hz, 2 H), 7.59 (t, J = 7.4 Hz, 1 H), 7.46 (t, J = 7.5 Hz, 2 H), 7.30 (d, J = 7.8 Hz, 2 H), 6.22 (q, J = 6.9 Hz, 1 H), 2.43 (s, 3 H), 1.69 (d, J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 196.21, 165.93, 144.48, 133.19, 131.87, 129.83, 129.56, 129.45, 128.62, 128.33, 71.78, 21.66, 17.25.
Embodiment 20
Preparation of the 2- benzoyloxy groups to methoxybenzene acetone：By the benzene second of 0.4 mmol 4- methoxybenzenes acetone, 0.2 mmol Alkynes, appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCUnder Stirring reaction 12 hours.After question response terminates, separating-purifying can obtain the 2- benzoyloxy groups of 58% separation yield to oxygen methyl Propiophenone.Pass through1H、13C NMR identify the product.
1HNMR (400 MHz, CDCl3) δ 8.09 – 8.10 (m, 2 H), 7.99 (d, J = 6.4 Hz, 2 H), 7.57 (t, J = 4.8 Hz, 1 H), 7.44 (t, J = 4.8 Hz, 1 H), 6.95 (t, J = 6.0 Hz, 2 H), 6.18 (q, J = 4.8 Hz, 1 H), 3.87 (s, 3 H), 1.66 (d, J = 4.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.11, 165.96, 163.95, 133.27, 130.85, 129.86, 129.63, 128.38, 127.22, 114.06, 71.79, 55.51, 17.41.
Embodiment 21
The preparation of 2- benzoyloxy group -3 '-fluorobenzene acetone：By 0.4 mmol 3- fluorobenzene acetone, 0.2 mmol phenylacetylene, appropriate Acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes added under air ambient in Schlenk pipes, in 120 oCLower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain 2- benzoyloxy group -3 '-fluorobenzene acetone of 48% separation yield.It is logical Cross1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 7.4 Hz, 2 H), 7.80 (d, J = 7.7 Hz, 1 H), 7.71 (d, J = 9.2 Hz, 1 H), 7.60 (t, J = 7.4 Hz, 1 H), 7.47 (t, J = 6.9 Hz, 3 H), 7.31 (q, J = 10.0 Hz, 1 H), 6.14 (q, J = 6.8 Hz, 1 H), 1.69 (d,J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.67, 165.95, 164.09, 161.62, 161.20, 133.38, 130.54, 130.47, 129.85, 129.29, 128.42, 124.16, 120.52, 115.45, 115.22, 71.90, 17.04.
Embodiment 22
The preparation of 2- benzoyloxy group -3 '-nitro propiophenones：By 0.4 mmol 3- nitros propiophenone, 0.2 mmol phenylacetylene, Appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring Reaction 12 hours.After question response terminates, separating-purifying can obtain -3 '-nitrobenzene of 2- benzoyloxy groups third of 46% separation yield Ketone.Pass through1H、13C NMR identify the product.
1HNMR (400 MHz, CDCl3) δ 8.86 (s, 1 H), 8.45 (d, J = 8.2 Hz, 1 H), 8.32 (d, J = 7.7 Hz, 1 H), 8.08 (d, J = 7.8 Hz, 2 H), 7.71 (t, J = 7.9 Hz, 1 H), 7.60 (t, J = 7.4 Hz, 1 H), 7.46 (t, J = 7.4 Hz, 2 H), 6.13 (q, J = 6.9 Hz, 1 H), 1.72 (d, J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 195.12, 166.00, 133.58, 130.13, 129.86, 129.74, 128.98, 128.51, 127.76, 123.39, 72.07, 16.93.
Embodiment 23
The preparation of 2- benzoyloxy group phenyl propyl ketones：By 0.4 mmol phenyl propyl ketone, 0.2 mmol phenylacetylene, appropriate acetylacetone,2,4-pentanedione Copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 hours.Treat After reaction terminates, separating-purifying can obtain the 2- benzoyloxy group phenyl propyl ketones of 51% separation yield.Pass through1H、13C NMR are identified The product.
1H NMR (400 MHz, CDCl3) δ 8.11 (d, J = 7.7 Hz, 2 H), 8.00 (d, J = 7.7 Hz, 2 H), 7.60 - 7.53 (m, 2 H), 7.50 - 7.40 (m, 4 H), 6.06 (t, J = 5.6 Hz, 1 H), 2.13 - 1.99 (m, 2 H), 1.11 (t, J = 7.3 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ196.33, 166.13, 134.89, 133.46, 133.20, 129.79, 129.56, 128.74, 128.37, 128.35, 76.69, 24.87, 9.91.
Embodiment 24
The preparation of 2- benzoyloxy group acetophenones：By 0.4 mmol acetophenone, 0.2 mmol phenylacetylene, appropriate acetylacetone,2,4-pentanedione Copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 hours.Treat After reaction terminates, separating-purifying can obtain the 2- benzoyloxy group acetophenones of 32% separation yield.Pass through1H、13C NMR are identified The product.
1H NMR (400 MHz, CDCl3) δ 8.16 - 8.12 (m, 2 H), 7.99 – 7.97 (m, 2 H), 7.66 - 7.58 (m, 2 H), 7.54 - 7.46 (m, 4 H), 5.59 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 192.28, 166.26, 134.04, 133.53, 130.45, 130.15, 129.05, 128.76, 128.65, 127.98, 66.65.
Embodiment 25
The preparation of 2- benzoyloxy group ethyl benzoylacetates：By the benzene second of 0.4 mmol ethyl benzoylacetate, 0.2 mmol Alkynes, appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCUnder Stirring reaction 12 hours.After question response terminates, separating-purifying can obtain the 2- benzoyloxy group benzoyl second of 38% separation yield Acetoacetic ester.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.11 (t, J = 9.2 Hz, 4 H), 7.67 - 7.60 (m, 2 H), 7.55 - 7.45 (m, 4 H), 6.55 (s, 1 H), 4.31 (q, J = 7.0 Hz, 2 H), 1.26 (t, J = 6.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 189.75, 165.23, 165.11, 134.28, 134.19, 133.79, 130.14, 129.27, 128.79, 128.52, 128.42, 74.94, 62.49, 13.91.
Embodiment 26
The preparation of 2- benzoyloxy group cyclohexanone：By 0.4 mmol cyclohexanone, 0.2 mmol phenylacetylene, appropriate acetylacetone,2,4-pentanedione Copper, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring reaction 12 hours.Treat After reaction terminates, separating-purifying can obtain the 2- benzoyloxy group cyclohexanone of 41% separation yield.Pass through1H、13C NMR are identified The product.
1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 7.4 Hz, 2 H), 7.57 (t, J = 7.4 Hz, 1 H), 7.45 (t, J = 7.5 Hz, 2 H), 5.41 (q, J = 9.0 Hz, 1 H), 2.57 (d, J = 12.7 Hz, 1 H), 2.51 - 2.41 (m, 2 H), 2.15 - 2.11 (m, 1 H), 2.04 (d, J = 13.2 Hz, 1 H), 1.96 - 1.83 (m, 2 H), 1.65 (q, J = 13.6 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ 204.33, 165.57, 133.14, 129.86, 129.68, 128.32, 76.68, 40.74,33.19, 27.19, 23.77.
Embodiment 27
The preparation of 2- benzoyloxy groups -1 '-(2 '-thienyl) -1 '-acetone：By 0.4 mmol 1- (2- thienyls) -1- acetone, 0.2 mmol phenylacetylene, appropriate acetylacetone copper, appropriate oxidant, 1 ml chlorobenzenes add Schlenk under air ambient Guan Li, in 120 oCLower stirring reaction 12 hours.After question response terminates, separating-purifying can obtain the 2- benzene of 37% separation yield Acyloxy -1 '-(2 '-thienyl) -1 '-acetone.Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 7.2 Hz, 2 H), 7.87 (t, J = 3.6 Hz, 1 H), 7.69 (t, J = 4.8 Hz, 1 H), 7.60- 7.56 (m, 1 H), 7.44 (t, J = 7.6 Hz, 2 H), 7.16 – 7.15 (m, 1 H), 5.97 (q, J = 7.2 Hz, 1 H), 1.71 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 189.75, 165.99, 140.57, 134.56, 133.47, 132.87, 130.03, 128.60, 127.94, 126.30, 72.94, 17.75.
Embodiment 28
The preparation of 2- benzoyloxy group dimethyl malenates：By 0.4 mmol dimethyl malenate, 0.2 mmol phenylacetylene, fit The acetylacetone copper of amount, appropriate oxidant, 1 ml chlorobenzenes are added in Schlenk pipes under air ambient, in 120 oCLower stirring is anti- Answer 12 hours.After question response terminates, separating-purifying can obtain the 2- benzoyloxy group dimethyl malenates of 40% separation yield. Pass through1H、13C NMR identify the product.
1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 7.9 Hz, 2 H), 7.61 (t, J = 7.2 Hz, 1 H), 7.48 (t, J = 7.5 Hz, 2 H), 5.81 (s, 1 H), 3.87 (s, 6 H); 13C NMR (100 MHz, CDCl3) δ 165.06, 164.91, 133.88, 130.20, 128.53, 128.33, 71.82, 53.34.
As can be seen from the above-described embodiment, it is of the present invention to be closed using different ketone compounds and end group acetylene compound Method into the alpha-acyloxy ketone compounds accordingly containing different substitution functional groups has that reaction condition is gentle, catalyst is cheap The advantages of being easy to get and prepare simple.In addition, this method also has the advantages that substrate applicability is wide, higher there is provided one for yield Plant the method for efficiently synthesizing the alpha-acyloxy ketone compounds containing different substitution functional groups.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (8)

1. one kind has structural formula（I）Alpha-acyloxy ketone compounds preparation method,
（I）
Characterized in that, including following step：
Take ketone compounds, end group acetylene compound, catalyst, oxidant and the organic solvent of reacting dose underlying in air atmosphere Mixed in reactor；Under agitation after being reacted 12 hours at 120 DEG C, corresponding alpha-acyloxy ketone chemical combination is produced Thing；
Wherein,
R1It is to be selected from alkyl, alkoxy, benzyl, 4- chlorobenzyls, 3- nitrobenzyls, 4- methoxy-benzyls, 4- bromobenzyls, 4- fluorine benzyls The groups such as base, 3- luorobenzyls, 4- methyl-benzyls, thiophene；
R2It is selected from groups such as methyl, hydrogen, benzyl, ethyl, ester groups；
R3It is to be selected from benzyl, 4- luorobenzyls, 4- chlorobenzyls, 4- bromobenzyls, 4- methyl-benzyls, 4- methoxy-benzyls, 4- nitrobenzyls The groups such as base, 3,4- dimethoxy-benzyls, naphthyl, 3- methyl-benzyls, 2- methyl-benzyls, thiophene.
2. preparation method according to claim 1, it is characterised in that the ketone compounds refer to propiophenone, 4- methyl Propiophenone, 4- methoxybenzenes acetone, 4- chlorophenyl acetones, 4- fluorobenzene acetone, 4- brom-acetophenones, 3- nitros propiophenone, 3- fluorobenzene third Ketone, acetophenone, phenyl propyl ketone, 1- (2- thienyls) -1- acetone, ethyl benzoylacetate, cyclohexanone, dimethyl malenate etc..
3. preparation method according to claim 1, it is characterised in that end group acetylene compound refers to phenylacetylene, 4- fluorobenzene Acetylene, 4- chlorobenzenes acetylene, 4- bromobenzenes acetylene, 4- methyl phenylacetylene, 4- Methoxy-phenylacetylenes, 3,4- dimethoxys phenylacetylene, 4- Nitrobenzene acetylene, 2- naphthalenes acetylene, 3- methyl phenylacetylene, 2- methyl phenylacetylene or 2- thiophene acetylene etc..
4. preparation method according to claim 1, it is characterised in that the catalyst is to be selected from iron chloride, copper bromide, second Sour copper, copper chloride, trifluoroacetic acid ketone, copper nitrate, copper sulphate or acetylacetone copper.
5. preparation method according to claim 1, it is characterised in that the oxidant refer to tert-Butanol peroxide, hydrogen peroxide, Di-tert-butyl peroxide, ammonium persulfate-sodium bisulfate.
6. preparation method according to claim 1, it is characterised in that the organic solvent refers to tetrahydrofuran, toluene, acetic acid Ethyl ester, chlorobenzene, 1,2- dichloroethanes, acetonitrile, dimethyl sulfoxide, carbon tetrachloride.
7. preparation method according to claim 1, it is characterised in that the ketone compounds and end group acetylene compound Mol ratio is 1：2.
8. preparation method according to claim 1, it is characterised in that the consumption of the catalyst is（5%-20%）, oxidation The consumption of agent is（4.0 eq- 6.0 eq）.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110981702A (en) * 2019-11-05 2020-04-10 上海应用技术大学 Efficient synthesis method of 2, 3-dibromophenol or derivatives thereof
CN111978167A (en) * 2020-07-22 2020-11-24 广东石油化工学院 One-step synthesis method of polysubstituted cyclohex-2-enone

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DONG-LIANG MO ET AL.: "The reaction of terminal alkynes with PhI(OAc)2：a convenient procedure for the preparation of α-acyloxy letones", 《TETRAHEDRON LETTERS》 *
GANESH MAJJI ET AL.: "Cyclic ethers to esters and monoesters to bis-esters with unconventional coupling partners under metal free conditions via sp3 C-H functionalisation", 《CHEM.COMMUN.》 *
JIAO LI ET AL.: "Copper-catalyzedα-C-H acyloxylation of carbonyl compounds with terminal alkynes", 《NEW J.CHEM.》 *
SAROJ KUMAR ROUT ET AL.: "Terminal aryl alkenes and alkynes as arylcarboxy surrogates toward o-benzoxylation of 2-phenylpyridine catalyzed by copper", 《ORG.LETT.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110981702A (en) * 2019-11-05 2020-04-10 上海应用技术大学 Efficient synthesis method of 2, 3-dibromophenol or derivatives thereof
CN110981702B (en) * 2019-11-05 2022-10-14 上海应用技术大学 Efficient synthesis method of 2, 3-dibromophenol or derivatives thereof
CN111978167A (en) * 2020-07-22 2020-11-24 广东石油化工学院 One-step synthesis method of polysubstituted cyclohex-2-enone
CN111978167B (en) * 2020-07-22 2021-03-23 广东石油化工学院 One-step synthesis method of polysubstituted cyclohex-2-enone

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