CN102775288A - Synthetic method of chalcone compounds - Google Patents
Synthetic method of chalcone compounds Download PDFInfo
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- CN102775288A CN102775288A CN2012102413885A CN201210241388A CN102775288A CN 102775288 A CN102775288 A CN 102775288A CN 2012102413885 A CN2012102413885 A CN 2012102413885A CN 201210241388 A CN201210241388 A CN 201210241388A CN 102775288 A CN102775288 A CN 102775288A
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- WVDDGKGOMKODPV-UHFFFAOYSA-N OCc1ccccc1 Chemical compound OCc1ccccc1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- KMYYHJAOYNJWQV-UHFFFAOYSA-N CC(C1)C(C(C)=O)=CC=C1C(F)(F)F Chemical compound CC(C1)C(C(C)=O)=CC=C1C(F)(F)F KMYYHJAOYNJWQV-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N CC(c(cc1)ccc1Cl)=O Chemical compound CC(c(cc1)ccc1Cl)=O BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- OPXJRVQPIBWRRY-UHFFFAOYSA-N CC1=CC=C(CO)CC1=C Chemical compound CC1=CC=C(CO)CC1=C OPXJRVQPIBWRRY-UHFFFAOYSA-N 0.000 description 1
- KXJRYNOBBVODML-IZZDOVSWSA-N O=C(/C=C/c1ccccc1)c1ccc(C(F)(F)F)cc1 Chemical compound O=C(/C=C/c1ccccc1)c1ccc(C(F)(F)F)cc1 KXJRYNOBBVODML-IZZDOVSWSA-N 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N OCc1ccc[o]1 Chemical compound OCc1ccc[o]1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a catalysis system using copper salt-2,2' bipyridine-TEMPO. Alcohol and ketone oxidative condensation reaction is carried out under the condition of room temperature and no nitrogen protection, and a synthetic method can achieve the fact that alcohol which is lower in cost and easy to obtain replaces aldehyde to be reacted with ketone under the condition of room temperature to synthesize a series of chalcone compounds. The catalysis system used in the synthetic method can achieve alcohol oxidation and Aldol condensation reaction under the condition of the room temperature aqueous phase, the catalysis system is low in price, mild in condition, easy in reaction operation and capable of greatly reducing possible pollution of an organic solvent on environment, and the reaction can be smoothly carried out under the condition of the room temperature, is low in reaction condition requirements and has a good industrial application prospect.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of compound method of chalcone compounds.
Background technology
Cinnamophenone, i.e. α, β-alkenyl ketone, a kind of in the alpha, beta-unsaturated ketone.Because the two keys (carbonyl) of carbon-to-carbon double bond and carbon-oxygen exist with the conjugated form; Influence each other, each other activation; The chalcone compounds reaction property is active, reaction type is various; Can the Michael addition reaction take place with various types of nucleophilic reagents and make up carbon-to-carbons or carbon-heterodesmic synthetic all kinds of very useful organic, medicinal intermediates, perhaps make up the comparatively complicated multi-functional polynuclear compound of cyclisation product, heterogeneous ring compound and molecular structure through the cyclization (comprising D-A reaction or the like) with types such as [3+2] of other unsaturated compounds, [4+2].Therefore, cinnamophenone and verivate thereof are the one type of organic synthesis intermediate important in C-C, carbon-heteroatom bond structure and the important building block of carbon skeleton structure, and it is synthetic innumerable with the applied research report.Nearly twenty or thirty over year under the overall background of asymmetric catalysis research; Cinnamophenone and verivate thereof more are used in the study on the synthesis of asymmetry catalysis, in a lot of straight chains and heterocyclic organic compounds, chipal compounds, medicine, CBAC material and natural product synthesize, have countless application.Seeing that there are a large amount of widely demand to cinnamophenone in research circle and industry member; The compound method of exploiting economy, green, pollution is little and selectivity is high cinnamophenone compound is necessary very much, also very urgent, can solve research and produce in many problems.
The traditional compound method of chalcone compounds is synthesized through the Aldol condensation reaction of classics; Promptly use more active aldehyde and the ketone that contains active methylene radical under the alkaline condition of a large amount of mineral alkalis, to use alcoholic solvent or alcohol-water mixed solvent, under relatively gentle, simpler condition, prepare.But, because aldehyde is more active, side reactions such as Cannizzaro take place under the highly basic condition easily, can reduce reaction efficiency, cause needing to use more a large amount of raw materials, pollute and waste; And the rate of addition of the reaction needs of one kettle way control reaction, otherwise cause reacting overheated, and not only increase the side reaction odds, and can make the generation of more (Z)-type product, cause (E)-type product selectivity to reduce; Under the situation of a large amount of preparations because heat radiation is inhomogeneous, especially true, be difficult to the control product selectivity, the cinnamophenone of therefore a lot of commercial grades are (Z)-types with (E)-the type mixture of products, separation and purification is difficulty comparatively.Most methods of reporting on the document in recent years still adopt the Aldol condensation reaction, realize through changing, optimize conditions such as catalyzer, alkali, auxiliary agent, but still have some shortcomings of the inherent of reaction own.
In addition, use aldehyde many shortcomings also to be arranged as reaction raw materials, heavy such as stink, unstable, be prone to oxidized, be difficult to preserve transportation, need through the underpressure distillation purifying before using, and have than high toxicity, reaction conditions is harshness comparatively, water funk fearness oxygen, or the like.Since alcohol compound is people obtain the most easily, originate the widest, price is low, toxicity is less; Be one of very stable organic cpds, compare that alcohol all is more green reagent again aspect a lot of with aldehyde compound; And, a lot of application is arranged aspect Green Chemistry in recent years.The method that adopts alcohol to substitute aldehyde has lot of advantages, in a step, uses one-pot synthesis to realize such as the condensation two-step reaction with pure oxidation and aldehyde and MIBK, can simplify reactions step, reduces consuming, and raises the efficiency; Difficulty that the preservation of the aldehyde that runs in the time of can also avoiding the use of aldehyde and use bring and higher reaction conditions can improve resource and rate of energy, reduce to consume or the like.
At present, the minority bibliographical information has been arranged utilized alcohol to replace the method that aldehyde comes the synthesizing chalcone compounds, but these methods still all exist many defectives.Such as; Use the catalyzer of noble metal palladium, gold from pure and mild MIBK, (3 equivalent) the at high temperature method of (110 ° of C) reaction, so exacting terms in the presence of purity oxygen and a large amount of alkali; Add the use noble metal catalyst, be difficult to further apply; Perhaps at heterogeneous titanium catalyst (TiO
2Perhaps TiN
3) effect under, (150 ° of C) carries out under the high temperature in organic solvent, under inert conditions, but the selectivity of reaction is bad, also has alkylation, the multiple by product of two key reductive to generate.Therefore, at present in the method for reported in literature, still do not have the high again catalystsystem of a kind of applied widely, green, gentle, efficient, economy, selectivity can catalytic alcohol and the oxidative dimerization of ketone come the synthesizing chalcone compounds.
Summary of the invention
The problem that the present invention will solve is to provide a kind of low in raw material cost to be easy to get, environmental pollution is little, the compound method of efficient, chalcone compounds that selectivity is high.
Reaction related among the present invention can be represented with following general formula:
R
1Can be phenyl or all kinds of substituted aryl that various functional groups are substituted in 2-, 3-or 4-; The alkyl of various carbon chain lengths and substitution in side chain; All kinds of substituted heteroaryls such as the substituted furans of 2-, 2-substituted thiophene, 2-substituted pyridinyl, can also be substituting group be thiazolinyl, alkynyl all kinds of replacement vinyl carbinols, replace all kinds of unsaturated alcohols such as propynol.
The R2 group can be that various functional groups are substituted in 2-, 3-, or the phenyl of 4-or all kinds of aryl, all kinds of substituted heteroaryls, various carbochains and substituted alkyl such as 2-, the substituted pyridyl of 3-or 4-position.
R
2Group can be a Wasserstoffatoms, perhaps like R
1, R
2Shown all kinds of groups.
The solvent of reaction can be organic solvent such as toluene, DMSO, benzene, YLENE, DMF, methylene dichloride, THF, chloroform, methyl alcohol, ethanol, ETHYLE ACETATE, acetonitrile, 1; Conventional solvents such as 4-dioxane a kind of; Perhaps be the mixed solvent of inorganic solvent, be preferably water like alcohol and water.
Mantoquita involved in the present invention, can be for cupric bromide, cupric chloride, copper sulfate, neutralized verdigris, cuprous chloride, cuprous bromide a kind of, preferred cuprous iodide.
In the reaction of the present invention, used part is the N of dipyridyl and so on, N-bitooth ligand, the preferred 0.001 ~ 20mol% of its consumption.
In the reaction of the present invention, used oxidation promotor is all kinds of replacement nitrogen oxide types (N-O) compound of TEMPO and so on, the preferred 0.001 ~ 20mol% of its consumption.
In the reaction of the present invention, used alkali is alkali such as LiOH, NaOH, KOH, CsOH, t-BuOK, t-BuONa, the Mg (OH) of basic metal or earth alkali metal
2, Ca (OH) 2 etc., further be optimized for NaOH.
In the reaction of the present invention, additive therefor is a kind of in the organic basess such as Pyrrolidine, nitrogen-Methylimidazole.
In the reaction of the present invention, the preferred 0.001 ~ 20mol% of the consumption of used mantoquita, the preferred 3:1 of the mol ratio of employed alcohol and MIBK is to 1:3.
In the reaction of the present invention, employed oxygenant can be air or oxygen, and reaction effect is fine under air conditions.
The temperature that reaction is carried out is-10 ~ 100 ° of C, preferred 30-40 ° of C.Reaction times is 10 ~ 96 hours, preferred 24-48 hour.
Employed mantoquita directly can be bought and obtain among the present invention, uses this catalystsystem, still can be implemented in the oxidative dimerization of the pure and mild MIBK under room temperature and the air conditions under can ground catalyst levels condition.Other system of reporting in this catalystsystem and the document is compared, low price, mild condition, and reaction easy handling.It is that green solvent, normal alkali carries out under the water condition that this reaction makes water; Can reduce pollution that organic solvent possibly cause environment and the problem of using excess base to cause greatly; And this reaction can be carried out at ambient temperature smoothly; Requirement to reaction conditions is very low, has favorable industrial application prospect.
Embodiment
To help to understand the present invention through following embodiment, but be not restricted to content of the present invention.
Embodiment 1
The reaction of benzylalcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-cinnamophenone, separation yield 95%.
1H?NMR(500MHz,CDCl
3):δ8.01(m,2H),7.82-7.79(d,J=15.5Hz,1H),7.62(m,2H),7.58-7.54(m,2H),7.51-7.47(m,2H),7.41-7.38(m,3H).
13C?NMR(125.4MHz,CDCl
3):δ190.4,144.8,138.2,134.9,132.8,130.5,128.9,128.6,128.5,128.4,122.0.MS(EI):m/z(%)209(11),208(74),207(100),180(4),179(15),178(8),152(2),132(4),131(40),130(15),105(29),104(4),103(36),102(10),78(5),77(59),76(8),51(16).
Embodiment 2
The reaction of 2-chlorobenzyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0076g, 2mol%), 2,2 '-dipyridyl (0.0062g; 2mol%), TEMPO (0.0126g, 4mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 2-chlorobenzyl alcohol (0.3422g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(2 '-chloro-phenyl-)-1-phenyl-2-propylene-1-ketone, separation yield 87%.
1H?NMR(500MHz,CDCl
3):δ8.20-8.16(d,J=15.5Hz,1H),8.01(m,2H),7.74(m,1H),7.60-7.57(m,1H),7.52-7.47(m,3H),7.43(m,1H),7.34-7.30(m,2H).
13C?NMR(125.4MHz,CDCl
3):δ190.4,140.6,137.9,135.5,133.2,132.9,131.2,130.3,128.7,128.6,127.8,127.1,124.8.MS(EI):m/z(%)244(4),243(3),242(13),219(7),208(17),207(100),179(9),178(11),165(7),137(8),131(6),105(19),102(10),101(14),89(8),87(5),85(27),83(40),78(7),77(38),76(8),75(11),69(9),63(6),51(12).
Embodiment 3
The reaction of 3-chlorobenzyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 3-chlorobenzyl alcohol (0.3422g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(3 '-chloro-phenyl-)-1-phenyl-2-propylene-1-ketone, separation yield 90%.
1H?NMR(500MHz,CDCl
3):δ8.02(m,2H),7.77(d,J=15.5Hz,1H),7.60-7.57(m,3H),7.53-7.49(m,3H),7.41-7.38(m,2H).
13C?NMR(125.4MHz,CDCl
3):δ190.3,143.3,138.1,136.5,133.4,132.9,129.6,129.3,128.7,128.5,122.5.MS(EI):m/z245(5),244(33),243(37),242(100),241(67),214(4),208(14),207(79),180(8),179(52),178(32),177(5),176(5),167(18),165(56),139(11),137(32),130(30),106(5),105(63),102(49),101(38),89(27),78(7),77(92),76(21),75(24),74(6),63(4),51(28),50(9).
Embodiment 4
The reaction of 4-chlorobenzyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0076g, 2mol%), 2,2 '-dipyridyl (0.0062g; 2mol%), TEMPO (0.0126g, 4mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 4-chlorobenzyl alcohol (0.3422g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-chloro-phenyl-)-1-phenyl-2-propylene-1-ketone, separation yield 83%.
1HNMR(500MHz,CDCl
3):δ8.02(m,2H),7.77(d,J=15.5Hz,1H),7.65-7.62(dd,J=8.5Hz，J=5.5Hz,2H),7.60-7.57(m,1H),7.52-7.49(m,2H),7.48-7.45(d,J=15.5Hz,1H),7.12-7.09(m,2H).
13C?NMR(125.4MHz,CDCl
3):δ190.2,143.3,138.0,136.4,133.4,132.9,130.0,129.3,128.7,128.5,122.5.MS(EI):m/z(%)244(9),243(32),242(35),242(98),240(63),208(13),207(80),180(7),179(46),178(29),166(14),164(45),139(12),137(34),130(33),105(70),103(8),102(56),101(43),89(32),78(7),77(100),76(24),75(27),74(7),51(36),50(11).
Embodiment 5
The reaction of 4-fluoro benzyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0076g, 2mol%), 2,2 '-dipyridyl (0.0062g; 2mol%), TEMPO (0.0126g, 4mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 4-fluoro benzyl alcohol (0.3027g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-chloro-phenyl-)-1-phenyl-2-propylene-1-ketone, separation yield 92%.
1HNMR(500MHz,CDCl
3):δ8.02(m,2H),7.77-7.74(d,J＝16.0Hz,1H),7.61-7.57(m,3H),7.53-7.49(m,3H),7.39(d,J=8.5Hz,2H).
13C?NMR(125.4MHz,CDCl
3):δ190.3,164.1,143.5,138.1,132.9,131.2,130.4,128.7,128.5,121.8,116.2.MS(EI):m/z(%)227(17),226(16),225(62),198(8),197(21),196(8),178(4),177(6),150(5),149(51),122(4),121(41),120(10),106(4),105(48),78(5),77(67),76(6),75(18),51(23),50(7).
Embodiment 6
The reaction of 4-bromobenzyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 4-bromobenzyl alcohol (0.4489g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-bromophenyl)-1-phenyl-2-propylene-1-ketone, separation yield 89%.
1H?NMR(500MHz,CDCl
3):δ8.02(m,2H),7.76-7.73(d,J=15.5Hz,1H),7.62-7.58(m,1H),7.57-7.50(m,7H).
13C?NMR(125.4MHz,CDCl
3):δ190.3,143.4,138.0,133.8,133.0,132.2,129.8,128.7,128.5,124.8,122.6.MS(EI):m/z(%)288(7),287(42),286(32),285(45),284(27),280(5),252(5),210(15),209(21),208(18),207(100),190(3),182(8),180(9),179(37),178(29),177(4),152(4),131(5),130(29),105(50),103(11),102(79),101(15),89(25),88(4),77(66),76(26),75(19),74(7),63(5),52(4),51(25),50(11).
Embodiment 7
The reaction of 3-methoxyl group benzylalcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 3-methoxyl group benzylalcohol (0.3316g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(3 '-p-methoxy-phenyl)-1-phenyl-2-propylene-1-ketone, separation yield 80%.
1HNMR(500MHz,CDCl
3):δ8.02(m,2H),7.77(d,J=15.5Hz,1H),7.60-7.57(m,1H),7.51(m,3H),7.34-7.32(m,1H)，7.25(m,1H),7.16(m,1H),6.97(m,1H),3.86(s,3H).
13C?NMR(125.4MHz,CDCl
3):δ190.6,160.0，144.8,138.2,136.3,132.8,130.0,128.6,128.5,122.4,121.1,116.3,113.5,55.4.MS(EI):m/z(%)239(16),238(100),237(78),223(11),209(11),208(15),207(92),194(12),179(13),178(11),167(7),165(11),161(31),133(17),118(17),105(32),90(13),89(10),84(14),82(20),77(54),63(5),51(10).
Embodiment 8
The reaction of 4-methoxyl group benzylalcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 3-methoxyl group benzylalcohol (0.3316g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-p-methoxy-phenyl)-1-phenyl-2-propylene-1-ketone, separation yield 75%.
1H?NMR(500MHz,CDCl
3):δ8.01(m,2H),7.79(d,J=15.5Hz,1H),7.59-7.54(m,3H),7.49-7.46(m,2H),7.40(d,J=18.5Hz,1H),6.92-6.91(m,2H),3.86(s,3H).
13C?NMR(125.4MHz,CDCl
3):δ190.5,161.7,144.7,138.5,132.5,130.2,128.6,128.4,127.6,119.8,114.4,55.4.MS(EI):m/z(%)239(17),238(100),237(52),223(24),207(25),195(16),194(7),179(9),178(6),167(12),166(5),165(14),162(5),161(50),152(10),133(39),118(17),108(70),105(36),103(11),90(18),89(21),79(10),78(10),77(81),63(11),51(21),50(6).
Embodiment 9
The reaction of 4-xylyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 4-xylyl alcohol (0.2932g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-aminomethyl phenyl)-1-phenyl-2-propylene-1-ketone, separation yield 81%.
1H?NMR(500MHz,CDCl
3):δ8.01(d,J=7.0Hz,2H),7.81-7.78(d,J=15.5Hz,1H),7.60-7.54(m,3H),7.52-7.48(m,3H),7.23(d,J=7.5Hz,2H),2.39(s,3H).
13C?NMR(125.4MHz,CDCl
3):δ190.7,145.0,141.1,138.4,132.7,132.2,129.7,128.6,128.5,121.2,21.6.MS(EI):m/z(%)222(22),221(35),208(17),207(100),193(4),189(4),179(21),178(25),176(6),165(6),152(10),151(5),146(4),145(34),130(17),117(34),116(13),115(65),105(35),102(15),96(8),91(32),89(16),84(15),82(26),77(71),76(14),75(9),65(17),63(13),51(23).
Embodiment 10
The reaction of 2-furfuralcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 2-furfuralcohol (0.2354g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(2 '-furyl)-1-phenyl-2-propine-1-ketone, separation yield 92%.
1H?NMR(500MHz,CDCl
3):δ8.02(m,2H),7.61-7.44(m,6H),6.72(d,J=3.5Hz,1H),6.52(m,1H).
13C?NMR(125.4MHz,CDCl
3):δ189.8,151.7,144.9,138.2,132.8,130.7,128.6,128.4,119.3,116.2,112.7.MS(EI):m/z(%)199(9),198(60),197(6),170(8),169(9),157(2),145(2),144(18),142(7),141(28),121(32),106(8),105(100),93(6),78(4),77(49),65(27),64(3),63(7),55(4),51(18),50(5).
Embodiment 11
The reaction of 2-thiophen(e)alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), 2-thiophen(e)alcohol (0.2740g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-1-phenyl-3-(2 '-thienyl)-2-propylene-1-ketone, separation yield 86%.
1H?NMR(500MHz,CDCl
3):δ8.01(m,2H),7.95(d,J=15.5Hz,1H),7.58(m,1H),7.50(m,2H),7.42(d,J=5.5Hz,1H),7.37(d,J=3.5Hz,1H),7.35-7.32(d,J=15.5Hz,1H),7.09(dd,J=5.0Hz,J=3.5Hz,1H).
13C?NMR(125.4MHz,CDCl
3):δ189.9,140.4,138.1,137.2,132.8,132.1,128.8,128.6,128.41,128.36,120.8.MS(EI):m/z(%)214(17),213(100),212(26),186(10),185(39),184(8),181(16),171(6),153(10),152(8),141(7),139(5),138(6),137(64),131(4),130(37),109(39),108(6),105(30),93(4),92(6),84(9),77(57),65(23),51(23),50(6).
Embodiment 12
The reaction of phthalyl alcohol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), phthalyl alcohol (0.3316g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E) E)-3-(2-(methylol) phenyl)-1-phenyl-2-propylene-1-ketone, separation yield 81%.
1H?NMR(500MHz,CDCl
3):δ7.99(d,J=7.5Hz，2H),7.58-7.55(m,1H),7.48-7.45(m,2H),7.30-7.23(m,4H),5.92-5.89(m,1H),5.17-5.08(d,J=12.0Hz,2H),3.57-3.52(dd,J=16.5Hz，J=7.5Hz，1H),3.38-3.33(dd,J=16.5Hz，J=5.0Hz,1H).
13C?NMR(125.4MHz,CDCl
3):δ197.8,141.4,139.3,137.1,133.2,128.6,128.3,127.8,127.5,121.5,121.0,80.2,72.6,45.6.MS(EI):m/z(%)238(1),237(6),222(12),220(8),219(15),218(14),207(4),160(3),131(3),119(7),118(71),117(100),106(6),104(58),102(5),91(46),90(21),88(8),84(27),82(43),77(41),65(14),51(11),50(4).
Embodiment 13
The reaction of benzylalcohol and 2-acetyl furan
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 2-acetyl furan (0.2643g; 1.2equiv.), benzylalcohol (0.2163g; 2mmol) join in the common response device, add entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-1-(2-furyl)-3-phenyl-2-propylene-1-ketone, separation yield 89%.
1HNMR(500MHz,CDCl
3):δ7.88(d,J=16.0Hz,1H),7.67-7.65(m,3H),7.46(d,J=15.5Hz,1H),7.43-7.41(m,3H),7.35(m,1H),6.60(dd,J=3.5Hz,J=1.5Hz,1H).
13C?NMR(125.4MHz,CDCl
3):δ178.1,153.7,146.5,144.0,134.8,130.6,129.0,128.6,121.2,117.5,112.6.MS(EI):m/z(%)198(7),196(5),170(7),169(8),153(2),145(2),144(18),142(6),141(27),139(3),122(2),121(29),116(4),115(14),106(8),105(100),102(3),92(2),85(2),78(3),77(46),76(3),71(5),65(26),63(6),51(16),50(4).
Embodiment 14
The reaction of benzylalcohol and 4-methoxyacetophenone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 4-methoxyacetophenone (0.3004g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-p-methoxy-phenyl)-1-phenyl-2-propylene-1-ketone, separation yield 75%.
1H?NMR(500MHz,CDCl
3):δ8.05(d,J=9.0Hz,2H),7.82-7.79(d,J=15.5Hz,1H),7.67-7.64(m,2H),7.57-7.54(d,J=15.5Hz,1H),7.42(m,3H),6.99-6.97(m,2H),3.89(s,3H).
13C?NMR(125.4MHz,CDCl
3):δ188.8,163.5,144.0,135.1,131.1,130.8,130.3,128.9,128.4,121.9,113.9,55.5.MS(EI):m/z(%)240(2),239(17),238(100),237(85),222(18),210(11),208(10),207(6),206(28),195(15),194(7),179(8),178(7),167(15),165(13),160(7),152(10),136(8),135(91),131(18),108(8),107(21),103(33),102(9),92(29),77(76),64(16),63(12),51(15),50(6).
Embodiment 15
The reaction of benzylalcohol and 1-Tetralone an intermediate of Sertraline
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 1-Tetralone an intermediate of Sertraline (0.2924g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-2-benzyl-3,4-dihydro naphthyl-1 (2H)-ketone, separation yield 52%.
1H?NMR(500MHz,CDCl
3):δ8.14(d,J=7.0Hz,1H),7.88(s,1H),7.51-7.34(m,7H),7.25(d,J=6.0Hz,1H),3.14(dt,J=6.5Hz,J=1.5Hz,2H),2.97-2.94(t,J=6.5Hz,2H).
13C?NMR(125.4MHz,CDCl
3):δ187.9,143.3,136.7,135.9,135.5,133.5,133.3,129.9,128.6,128.5,128.3,128.2,127.0,28.9,27.2.MS(EI):m/z235(7),234(46),233(100),231(5),215(5),203(5),202(8),189(4),128(9),116(7),115(11),102(4),101(6),91(23),90(13),89(15),77(7),63(5),51(4).
Embodiment 16
The reaction of benzylalcohol and 4-fluoro acetophenone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 4-fluoro acetophenone (0.2763g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-1-(4 '-fluorophenyl)-3-phenyl-2-propylene-1-ketone, separation yield 71%.
1H NMR (500MHz, CDCl
3): δ 8.06-8.03 (m, 2H), 7.82-7.79 (d, J=15.5Hz, 1H), 7.62 (m, 2H), 7.51-7.48 (d, J=16.0Hz, 1H), 7.41-7.39 (m, 3H), 7.17-7.13 (m, 2H).
13C NMR (125.4MHz, CDCl
3): δ 188.7,165.6 (d, J=253.7Hz), 145.0,134.8,134.5,131.1,130.6,129.0; 128.5,121.6,115.7.MS (EI): m/z (%) 226 (11), 225 (72), and 224 (100), 197 (14), 196 (7), 182 (7); 177 (5), 148 (15), 131 (27), 123 (45), 120 (5), 103 (41), 102 (10), 98 (7); 95 (54), 89 (4), 78 (5), 77 (38), 76 (8), 75 (22), 51 (16), 50 (7).
Embodiment 17
The reaction of benzylalcohol and 4-chloro-acetophenone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 4-chloro-acetophenone (0.3092g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-1-(4 '-chloro-phenyl-)-3-phenyl-2-propylene-1-ketone, separation yield 90%.
1H NMR (500MHz, CDCl
3): δ 7.97 (m, 2H), 7.84-7.80 (d, J=15.5Hz, 1H), 7.67-7.64 (m, 2H), 7.50-7.47 (m, 3H), 7.43 (m, 1H).
13C NMR (125.4MHz, CDCl
3): δ 189.2,145.4, and 139.2,136.5,134.7,130.8,129.9,129.02,128.97; 128.5,121.6.MS (EI): m/z244 (3), 243 (22), 242 (41), 241 (63), 240 (100), 207 (8), 206 (49), 179 (21); 177 (28), 176 (4), 151 (3), 140 (9), 138 (29), 131 (32), 112 (11), 110 (31), 103 (40); 102 (9), 89 (18), 77 (30), 76 (14), 75 (16), 63 (3), 51 (10), 50 (5).
Embodiment 18
The reaction of benzylalcohol and 4-trifluoromethyl acetophenone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 4-trifluoromethyl acetophenone (0.3763g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-phenyl-1-(4 '-trifluoromethyl)-2-propylene-1-ketone, separation yield 70%.
1H NMR (500MHz, CDCl
3): δ 8.10 (d, J=8.0Hz, 2H), 7.86-7.82 (d, J=16.0Hz, 1H), 7.78 (d, J=8.5Hz, 2H), 7.66 (m, 2H), 7.51-7.48 (d, J=15.5Hz, 1H), 7.45 (m, 3H).
13C NMR (125.4MHz, CDCl
3): δ 189.7,146.1, and 141.1,134.6,134.2,133.9,131.0,129.1,128.8; 128.6,125.7 (q, J=3.8Hz), 121.7.MS (EI): m/z277 (9), 176 (60), 275 (100), 207 (13), 179 (11), 178 (13); 173 (11), 145 (41), 131 (38), 128 (4), 125 (6), 105 (5), 103 (52), 102 (10), 95 (10); 84 (11), 82 (16), 78 (8), 77 (43), 76 (10), 75 (10), 63 (5), 51 (16), 50 (7).
Embodiment 19
The reaction of 4-fluoro benzyl alcohol and 4-methoxyacetophenone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 4-methoxyacetophenone (0.3003g; 2mmol), 4-fluoro benzyl alcohol (0.3027g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtained (E)-3-(4 '-fluorophenyl)-1-(4 '-methoxyl group)-2-propylene-1-ketone, separation yield 91%.
1H NMR (500MHz, CDCl
3): δ 8.04 (d, J=9.0Hz, 2H), 7.77 (d, J=15.5Hz, 1H), 7.66-7.62 (m, 2H), 7.48 (d, J=15.5Hz, 1H); 7.13-7.09 (m, 2H), 6.99 (d, J=9.0Hz, 2H) .13C NMR (125.4MHz, CDCl3): δ 188.5,165.0,163.2 (d, J=68.5Hz), 142.7; 131.4,131.0,130.8,130.2 (d, J=8.4Hz), 121.6,116.1,113.9,55.5.MS (EI): m/z (%) 257 (16), 256 (100); 255 (33), 241 (23), 228 (16), 227 (5), 225 (13), 213 (20), 212 (5), 206 (16), 197 (5), 196 (4); 185 (5), 183 (9), 165 (14), 160 (10), 149 (16), 136 (7), 135 (83), 121 (22), 120 (8), 114 (7); 107 (19), 101 (29), 95 (6), 92 (27), 77 (37), 75 (13), 64 (13), 63 (10), 51 (6), 50 (4).
Embodiment 20
The reaction of benzylalcohol and 2-heptanone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 2-heptanone (0.2741g; 1.2equiv.), benzylalcohol (0.2163g; 2mmol) join in the common response device, add entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-1-phenyl-1-octene-3-ketone, separation yield 79%.
1HNMR (500MHz, CDCl
3): δ 7.56-7.53 (m, 3H), 7.38 (m, 3H), 6.74 (d, J=16.0Hz, 1H), 2.66-2.63 (t, J=7.5Hz, 2H), 1.70-1.67 (m, 2H), 1.36-1.32 (m, 4H), 0.91 (t, J=7.0Hz, 3H).
13C NMR (125.4MHz, CDCl
3): δ 200.6,142.3, and 134.6,130.4,128.9,128.2,126.3; 40.9,31.5,24.1,22.5,14.0.MS (EI): m/z (%) 202 (5), 172 (3), and 147 (6); 145 (53), 144 (13), 131 (10), 130 (100), 117 (6), 115 (4); 104 (5), 103 (42), 102 (5), 91 (2), 77 (18), 51 (4).
Embodiment 21
The reaction of benzylalcohol and 2 pentanone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 2 pentanone (0.2066g; 1.2equiv.), benzylalcohol (0.2163g; 2mmol) join in the common response device, add entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-1-phenyl-1-hexene-3-one, separation yield 94%.
1H NMR (500MHz, CDCl
3): δ 7.56-7.52 (m, 3H), 7.37 (m, 3H), 6.75-6.71 (d, J=16.5Hz, 1H), 2.63 (t, J=7.3Hz, 2H), 1.73-1.67 (m, 2H), 0.99-0.96 (t, J=7.3Hz, 2H).
13C NMR (125.4MHz, CDCl
3): δ 200.4,142.3, and 134.7,130.4,128.9,128.2,126.3; 42.8,17.8,13.9.MS (EI): m/z (%) 175 (2), 174 (15), and 173 (2), 146 (7), 145 (2); 132 (9), 131 (100), 115 (2), 104 (6), 103 (55), 102 (8), 78 (3); 77 (33), 76 (4), 75 (2), 63 (2), 52 (2), 51 (11), 50 (3).
Embodiment 22
The reaction of benzylalcohol and BENZALACETONE
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 4-phenyl-3-butene-2-ketone (0.2924g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (1E, 4E)-1,5-phenylbenzene-1,4-pentadiene-3-ketone, separation yield 80%.
1H NMR (500MHz, CDCl
3): δ 7.76-7.73 (d, J=16.0Hz, 2H), 7.62 (m, 4H), 7.43-7.40 (m, 6H), 7.12-7.08 (d, J=15.5Hz, 2H).
13C NMR (125.4MHz, CDCl
3): δ 188.9,143.3,134.9,130.5,129.0,128.4, and 125.5.MS (EI): m/z (%) 236 (5), 234 (17), and 233 (100), 232 (96); 205 (6), 204 (14), 202 (7), 201 (5), 191 (14), 190 (6), 188 (4), 177 (4), 164 (4); 156 (5), 155 (14), 132 (4), 130 (40), 129 (8), 128 (25), 116 (4), 115 (7), 104 (9); 103 (67), 102 (15), 101 (5), 91 (26), 89 (7), 78 (5), 63 (3), 51 (12), 50 (3).
Embodiment 23
The reaction of benzylalcohol and acetone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), acetone (0.1394g; 1.2equiv.), benzylalcohol (0.2163g; 2mmol) join in the common response device, add entry (1.0mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-BENZALACETONE, separation yield 40%.
1H NMR (500MHz, CDCl
3): δ 7.54-7.52 (m, 2H), 7.52-7.48 (d, J=16.5Hz, 1H), 7.38 (m, 3H), 6.72-6.69 (d, J=16.5Hz, 1H), 2.36 (s, 3H).
13C NMR (125.4MHz, CDCl
3): δ 198.3,143.4,134.4,130.5,129.0,128.3,127.1,27.5.MS (EI): m/z (%) 147 (6); 146 (56), 145 (62), 132 (9), 131 (93), 117 (3), 115 (5), 104 (9), 103 (100); 102 (13), 91 (3), 78 (5), 77 (53), 76 (8), 75 (6), 74 (5); 65 (3), 63 (7), 62 (3), 58 (2), 52 (4), 51 (29), 50 (9).
Embodiment 24
The reaction of styryl carbinol and methyl phenyl ketone
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), methyl phenyl ketone (0.2403g; 2mmol), styryl carbinol (0.3220g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (2E, 4E)-1,5-phenylbenzene-2,4-pentadiene-1-ketone, separation yield 79%.
1H NMR (500MHz, CDCl
3): δ 7.98 (d, J=7.5Hz, 2H), 7.63-7.55 (m, 2H), 7.50-7.30 (m, 7H), 7.10-7.07 (d, J=15.0Hz, 1H), 7.01 (m, 2H).
13C NMR (125.4MHz, CDCl
3): δ 190.5,144.8, and 141.9,138.3,136.2,132.6,129.2,128.9,128.6,127.3,127.0; 125.5.MS (EI): m/z (%) 235 (2), 234 (18), 233 (100), 232 (39), 218 (3), 216 (3), 215 (4), 214 (12), 206 (4), 204 (11), 203 (4); 202 (7), 201 (6), 190 (9), 189 (5), 178 (3), 165 (4), 158 (5), 157 (45), 156 (10), 130 (5), 129 (50); 128 (92), 127 (31), 126 (5), 115 (13), 106 (5), 105 (59), 104 (4), 103 (9), 102 (17), 101 (6), 91 (32); 89 (10), 78 (12), 77 (91), 76 (9), 75 (5), 74 (3), 65 (3), 52 (4), 51 (31), 50 (7).
Embodiment 25
The reaction of benzylalcohol and 2 acetyl naphthalene
Take by weighing successively CuI (0.0190g, 5mol%), 2,2 '-dipyridyl (0.0155g; 5mol%), TEMPO (0.0315g, 10mol%), NaOH (0.088g, 1.1equiv.), 2-acetonaphthone (0.3401g; 2mmol), benzylalcohol (0.2596g; 1.2equiv.) join in the common response device, adding entry (0.5mL) and be solvent, (35 ° of C the bests) uncovered reaction is about 48 hours under the room temperature.Follow the tracks of detection reaction, trans selectivity of product with GC-MS or TLC then>99/1.After reaction finished, chloroform extraction water, mixture concentrated the back and use sherwood oil to separate as developping agent rapid column chromatography (silica gel is stationary phase) with ETHYLE ACETATE, obtain (E)-1-(2-naphthyl)-3-phenyl-2-propylene-1-ketone, separation yield 95%.
1H NMR (500MHz, CDCl
3): δ 8.54 (s, 1H), 8.11 (dd, J=8.5Hz, J=1.5Hz, 1H), 8.00 (d, J=8.0Hz, 1H), 7.95 (d, J=9.0Hz, 1H), 7.90 (d, J=7.0Hz, 1H), 7.86 (s, 1H), 7.71-7.68 (m, 3H), 7.63-7.57 (m, 2H), 7.44 (m, 3H).
13CNMR (125.4MHz, CDCl
3): δ 190.3,144.8, and 135.6,135.5,135.0,132.6,130.6,129.9,129.5; 129.0,128.6,128.5,128.4,127.9,126.8,124.5,122.2.MS (EI): m/z (%) 259 (2), 258 (19); 257 (100), 256 (92), 240 (3), 229 (11), 228 (28), 227 (11), 226 (3), 225 (3), 214 (8); 201 (3), 180 (5), 179 (14), 155 (3), 154 (26), 151 (7), 131 (20), 129 (8), 128 (19); 127 (54), 125 (9), 114 (7), 103 (23), 102 (4), 101 (8), 76 (19), 74 (3), 51 (4).
Claims (5)
1. the compound method of a chalcone compounds, it is characterized in that: under the alkaline condition, catalyzer is a mantoquita-2; 2 '-dipyridyl-TEMPO system; At the oxidative dimerization of connecting that need not catalytic alcohol and ketone under the air conditions of protection of inert gas, the mol ratio of ketone and alcohol be 3:1 to 1:3, temperature of reaction is-10 ~ 100 ℃; Reaction times is 10 ~ 96 hours, and reaction formula is:
Wherein:
R
1Be aryl, heteroaryl or alkyl;
R
2Be aryl, heteroaryl or alkyl;
R
3Be hydrogen, aryl, heteroaryl or alkyl;
The solvent of reaction is toluene, DMSO, benzene, YLENE, DMF, methylene dichloride, THF, chloroform, methyl alcohol, ethanol, ETHYLE ACETATE, acetonitrile and 1, and 4-dioxane a kind of perhaps is a kind of of alcohol and water;
Described alkali is LiOH, NaOH, KOH, CsOH, t-BuOK, t-BuONa, Mg (OH)
2Or Ca (OH)
2
2. the compound method of a kind of chalcone compounds as claimed in claim 1; It is characterized in that: in the said catalyzer; Mantoquita is a kind of of cupric bromide, cupric chloride, copper sulfate, neutralized verdigris, cuprous chloride and cuprous bromide, and the consumption of mantoquita is 0.001 ~ 20mol%; The TEMPO consumption is 0.001-20mol%, and the dipyridyl consumption is 0.001 ~ 20mol%.
3. the compound method of a kind of chalcone compounds as claimed in claim 1, it is characterized in that: described alkali is NaOH.
4. the compound method of a kind of chalcone compounds as claimed in claim 1, it is characterized in that: the mantoquita of said catalyzer is a cuprous iodide.
5. the compound method of a kind of chalcone compounds as claimed in claim 1, it is characterized in that: temperature of reaction is 30 ~ 45 ℃, the reaction times is 24 ~ 48 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085222A (en) * | 2014-05-04 | 2015-11-25 | 中国科学院大连化学物理研究所 | Synthetic method for [alpha],[beta]-unsaturated ketone |
| CN105622378A (en) * | 2014-11-05 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method for preparing chalcone compound |
| PL422404A1 (en) * | 2017-07-31 | 2019-02-11 | Uniwersytet Przyrodniczy we Wrocławiu | 2'-hydroxy-4-propoxychalcone and method for obtaining 2'-hydroxy-4-propoxychalcone |
| CN111792990A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院上海药物研究所 | Unsaturated ketone compound, preparation method and application thereof |
| CN113461501A (en) * | 2021-07-05 | 2021-10-01 | 温州大学 | Green method for high-selectivity synthesis of chalcone compounds |
| CN114394922A (en) * | 2022-01-26 | 2022-04-26 | 河南农业大学 | Preparation method of N-substituted pyrrolyl aryl propenone compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990446A (en) * | 2005-12-28 | 2007-07-04 | 中国科学院上海药物研究所 | Chalcone compound, its preparing method, compound comprising same and use thereof |
| WO2011151789A2 (en) * | 2010-05-31 | 2011-12-08 | University Of The Free State | Aminoalkyl substituted chalcones and analogues and derivatives thereof |
| CN102531957A (en) * | 2012-01-11 | 2012-07-04 | 温州大学 | Synthesis method for imine compounds |
-
2012
- 2012-07-12 CN CN2012102413885A patent/CN102775288A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990446A (en) * | 2005-12-28 | 2007-07-04 | 中国科学院上海药物研究所 | Chalcone compound, its preparing method, compound comprising same and use thereof |
| WO2011151789A2 (en) * | 2010-05-31 | 2011-12-08 | University Of The Free State | Aminoalkyl substituted chalcones and analogues and derivatives thereof |
| CN102531957A (en) * | 2012-01-11 | 2012-07-04 | 温州大学 | Synthesis method for imine compounds |
Non-Patent Citations (1)
| Title |
|---|
| 刘翔峰等: "查尔酮合成方法的研究进展", 《应用化学》, vol. 38, no. 8, 31 August 2009 (2009-08-31) * |
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| CN105085222A (en) * | 2014-05-04 | 2015-11-25 | 中国科学院大连化学物理研究所 | Synthetic method for [alpha],[beta]-unsaturated ketone |
| CN105085222B (en) * | 2014-05-04 | 2018-11-27 | 中国科学院大连化学物理研究所 | A method of synthesis alpha, beta-unsaturated ketone |
| CN105622378A (en) * | 2014-11-05 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method for preparing chalcone compound |
| CN105622378B (en) * | 2014-11-05 | 2019-06-11 | 中国科学院大连化学物理研究所 | A method of preparing chalcone compounds |
| PL422404A1 (en) * | 2017-07-31 | 2019-02-11 | Uniwersytet Przyrodniczy we Wrocławiu | 2'-hydroxy-4-propoxychalcone and method for obtaining 2'-hydroxy-4-propoxychalcone |
| CN111792990A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院上海药物研究所 | Unsaturated ketone compound, preparation method and application thereof |
| CN113461501A (en) * | 2021-07-05 | 2021-10-01 | 温州大学 | Green method for high-selectivity synthesis of chalcone compounds |
| CN114394922A (en) * | 2022-01-26 | 2022-04-26 | 河南农业大学 | Preparation method of N-substituted pyrrolyl aryl propenone compound |
| CN114394922B (en) * | 2022-01-26 | 2024-06-11 | 河南农业大学 | Preparation method of N-substituted pyrrolyl aryl propenone compound |
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