CN104478945A - 1-ferrocenyl-3-aryl-3-(acetyl-methylene)-acetone and preparation method thereof - Google Patents
1-ferrocenyl-3-aryl-3-(acetyl-methylene)-acetone and preparation method thereof Download PDFInfo
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Abstract
The invention discloses 1-ferrocenyl-3-aryl-3-(acetyl-methylene)-acetone and a preparation method thereof. 1-ferrocenyl-3-aryl-3-(acetyl-methylene)-acetone has a structural formula described in the description. The preparation method comprises the following steps: adding A mol of 1-ferrocenyl-3-aryl-acrylketone, B mol of anhydrous K2CO3 (or NaOH) and C mol of acetone into a dried mortar, quickly grinding for D min, performing TLC (Thin Layer Chromatography) detection until complete reaction, washing with water, performing suction filtration, and drying to obtain 1-ferrocenyl-3-aryl-3-(acetyl-methylene)-acetone. The preparation method has the advantages of being short in reaction time, free of solvent, environment friendly, good in economic property, simple in operation, mild in reaction conditions, simple in after-treatment and high in yield.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone and preparation method thereof.
Background technology
Luxuriant iron-based cinnamophenone has a, a β-unsaturated double-bond due to it, so carry out around Michael addition reaction about the reaction of biferrocenyl chalcone is many.Can there is Michael addition reaction with hydrazine class, thiocarbamide, nitrile, active methylene compound or amine etc. in it, generate the heterogeneous ring compound with ferrocenyl, morely has bioactive ferrocenyl Hete rocyclic derivatives for developing and provide method.
Michael addition reaction forms C-C, one of most effective means of carbon-nitrogen bond, thus applies widely in organic and biosynthesizing.Michael addition reaction under conventional conditions is mostly carry out in organic solvent with strong alkali as a catalyst, but the violent effect of highly basic is often along with a lot of side reaction, as further condensation or cracking, anti-Michael addition, the polymerization etc. of substrate self-condensation, rearrangement, two addition, adduct, thus productive rate is undesirable, also bring inconvenience to the purifying of product.Avoid the problems referred to above, condition of no solvent is a kind of important means.Wherein, mechanical chemical technique is successfully applied in organic synthesis gradually, obtains a series of important achievement, and demonstrates huge superiority.
Based on this, have no bibliographical information and adopt polishing to synthesize a series of Michael adduct by acetone and cinnamophenone.And the preparation of existing ketone compounds is main mainly with liquid-phase reflux method, there is the shortcomings such as long reaction time, yield are not high, solvent usage quantity is large in this method.
Summary of the invention
First object of the present invention is open new compound 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone.Second object is to provide the method preparing new compound 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone.The method reaction times is short, need not solvent, green, environmental protection, economy and simple to operate, reaction conditions is gentle, aftertreatment is simple, productive rate is high.
For achieving the above object, the present invention is by the following technical solutions:
A kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone, its general structure is as follows:
Wherein, described aryl is phenyl, halogenophenyl, aminomethyl phenyl, ethylphenyl, propyl group phenyl, p-methoxy-phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl, quinary heterocyclic radical or hexa-member heterocycle base.
Described halogenophenyl is adjacent fluorophenyl, to fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl or to bromophenyl;
Described aminomethyl phenyl is o-methyl-phenyl-, an aminomethyl phenyl or p-methylphenyl;
Described ethyl be between ethylphenyl, to ethylphenyl;
Described propyl group be between n-propyl phenyl, isopropyl phenyl;
Described p-methoxy-phenyl is m-methoxyphenyl or p-methoxyphenyl.
Described nitrophenyl is m-nitro base, 3,5-dinitrophenyls or p-nitrophenyl;
Described hydroxy phenyl is o-hydroxy-phenyl or p-hydroxybenzene;
Described aminophenyl is adjacent aminophenyl, m-aminophenyl base or p-aminophenyl.
Described quinary heterocyclic radical is furyl or thienyl;
Described hexa-member heterocycle base is pyridyl.
A kind of preparation method of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone, comprises the following steps:
Step 1) by A mol 1-ferrocenyl-3-aryl-acrylketone, B mol basic catalyst, C mol acetone adds in dry reaction vessel, is ground to raw material complete reaction, obtains crude product; Wherein A:B:C=1:(1 ~ 1.5): (1 ~ 2.0);
Step 2) crude product through washing, suction filtration obtains filter cake, by filter cake vacuum-drying, obtains 1-ferrocenyl-3-aryl-3-Nitromethylene-acetone.
Aryl in described 1-ferrocenyl-3-aryl-acrylketone is phenyl, halogenophenyl, aminomethyl phenyl, ethylphenyl, propyl group phenyl, p-methoxy-phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl, quinary heterocyclic radical or hexa-member heterocycle base;
Described halogenophenyl is adjacent fluorophenyl, to fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl or to bromophenyl;
Described aminomethyl phenyl is o-methyl-phenyl-, an aminomethyl phenyl or p-methylphenyl;
Described ethyl be between ethylphenyl, to ethylphenyl;
Described propyl group be between n-propyl phenyl, isopropyl phenyl;
Described p-methoxy-phenyl is m-methoxyphenyl or p-methoxyphenyl;
Described nitrophenyl is m-nitro base, 3,5-dinitrophenyls or p-nitrophenyl;
Described hydroxy phenyl is o-hydroxy-phenyl or p-hydroxybenzene;
Described aminophenyl is adjacent aminophenyl, m-aminophenyl base or p-aminophenyl;
Described quinary heterocyclic radical is furyl or thienyl;
Described hexa-member heterocycle base is pyridyl.
Further, step 1) in process of lapping with TLC monitoring, represent raw material complete reaction when the raw material point of 1-ferrocenyl-3-aryl-acrylketone disappears; The developping agent adopted during TLC detects is volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil.
Further, step 1) in grinding carry out in mortar, being ground to the raw material complete reaction time is 25 ~ 30min.
Further, step 1) described in basic catalyst be anhydrous K
2cO
3or NaOH.
Further, step 2) in suction filtration time washing until filtrate pH value is in neutral.
Relative to prior art, the present invention has the following advantages:
The invention provides a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone and preparation method thereof; the method reaction times is short, need not solvent, green, environmental protection, economy and simple to operate, reaction conditions is gentle, aftertreatment is simple, productive rate is high.1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone prepared by the present invention is a kind of brand-new ketone, can be used for agricultural chemicals and field of medicaments etc.
Further, this reaction uses raw material few, and raw material is easy to get, and alternative material is many.
1-ferrocenyl-3-aryl-acrylketone, basic catalyst and acetone add in dry reaction vessel by the present invention; griding reaction obtains 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone; the method reaction times is short, need not solvent, green, environmental protection, economy and simple to operate, reaction conditions is gentle, aftertreatment is simple, productive rate is high.Compared with prior synthesizing method, reactant is placed in mortar directly griding reaction by preparation method of the present invention, and reacting phenomenon is obvious, reaction process is simple, simple to operate, only raw mill evenly can need be reacted, reaction times is short, and reaction conditions is gentle, can react under room temperature, equipment requirements is low, and the aftertreatment of the method is simple, the productive rate of product is high, overcomes prior synthesizing method equipment requirements high, the shortcomings such as long reaction time, have economy, convenience, efficient, green advantage.
Further, crude product prepared by the present invention can obtain product for different type selecting washing suction filtration, improves the productive rate of product.Adopt washing not introduce other material, the composition of product can not be affected, as long as subsequent disposal is dry.
Further, the present invention's TLC monitoring reaction course used, ethyl acetate and the sherwood oil of developping agent used to be volume ratio be 1:3.Monitoring accurately, is beneficial to and controls extent of reaction and end.
Further, the catalyzer that the present invention is used is anhydrous K
2cO
3(or NaOH), it is cheap and easy to get, and aftertreatment is simple.
Accompanying drawing explanation
Fig. 1 is 1-ferrocenyl-3-(to fluorophenyl)-3-(ethanoyl methylene radical)-acetone IR spectrogram;
Fig. 2 is 1-ferrocenyl-3-(p-methoxyphenyl)-3-(ethanoyl methylene radical)-acetone IR spectrogram;
Fig. 3 is 1-ferrocenyl-3-(to fluorophenyl)-3-(ethanoyl methylene radical)-acetone
1h-NMR spectrogram;
Fig. 4 is 1-ferrocenyl-3-(p-methoxyphenyl)-3-(ethanoyl methylene radical)-acetone
1h-NMR spectrogram;
Fig. 5 is 1-ferrocenyl-3-(to fluorophenyl)-3-(ethanoyl methylene radical)-acetone
13c-NMR spectrogram;
Fig. 6 is 1-ferrocenyl-3-(p-methoxyphenyl)-3-(ethanoyl methylene radical)-acetone
13c-NMR spectrogram.
Embodiment
The reaction equation of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone of the present invention and preparation method thereof is such as formula shown in (2).
Wherein aryl substituent be phenyl, rubigan, to bromophenyl, to fluorophenyl, p-methylphenyl, to ethylphenyl, an ethylphenyl, n-propyl phenyl, isopropyl phenyl, p-methoxyphenyl, m-nitro base, p-hydroxybenzene, o-hydroxy-phenyl, ethenylphenyl, o-methyl-phenyl-, an aminomethyl phenyl, m-methoxyphenyl, p-aminophenyl, m-aminophenyl base, adjacent aminophenyl, Chloro-O-Phenyl, 2,4-dichlorophenyl, p-nitrophenyl, 3,5-dinitrophenyls, o-bromophenyl, a bromophenyl, furyl, thienyl, pyridyl etc.
Below in conjunction with preferred embodiment of the present invention, the present invention is described in further details.
Embodiment 1
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-phenyl-acryloyl ketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain red brown solid, obtain 1-ferrocenyl-3-phenyl-3-(ethanoyl methylene radical)-acetone.Productive rate 74%, m.p.145 DEG C ~ 146 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2980,2828,1652,1591,1506,1454,1411,138,1230;
1H-NMR:7.15-7.65(m，5H，Ar-H)，4.96(s，2H，C
5H
4)，4.65(s，2H，C
5H
4)，4.27(s，5H，C
5H
5)，3.40(d，2H，COCH
2)，2.53(m，1H，CH)，2.21(S，3H，COCH
3)；
13C-NMR:192.3，140.4，135.8，129.7，128.5，127.8，122.5，55.4，43.4，35.4。
Embodiment 2
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(rubigan)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(rubigan)-3-(ethanoyl methylene radical)-acetone.Productive rate 72%, m.p.106 DEG C ~ 107 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2980,2943,1702,1653,1592,1487,1453,1369,1253;
1H-NMR:7.07-7.54(m，5H，Ar-H)，4.81(s，2H，C
5H
4)，4.59(s，2H，C
5H
4)，4.15(s，5H，C
5H
5)，3.42(d，2H，COCH
2)，2.74(m，1H，CH)，2.09(S，3H，COCH
3)；
13C-NMR:192.5，139.8，138.7，132.5，129.1，126.3，120.5，55.4，42.9，34.8。
Embodiment 3
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(to bromophenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid; obtain 1-ferrocenyl-3-(to bromophenyl)-3-(ethanoyl methylene radical)-acetone productive rate 70%, m.p.117 DEG C ~ 118 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2980,2887,1650,1592,1592,1489,1453,1372,1287;
1H-NMR:7.02-7.54(m，5H，Ar-H)，4.99(s，2H，C
5H
4)，4.63(s，2H，C
5H
4)，4.18(s，5H，C
5H
5)，3.57(d，2H，COCH
2)，2.59(m，1H，CH)，1.91(S，3H，COCH
3)；
13C-NMR:192.3，139.8，138.6，130.2，128.2，125.7，121.3，55.2，43.8，32.7。
Embodiment 4
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(to fluorophenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(to fluorophenyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 74%, m.p.126 DEG C ~ 127 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2987,2828,1649,1598,1592,1492,1453,1328,1289;
1H-NMR:7.47-7.70(m，5H，Ar-H)，4.96(s，2H，C
5H
4)，4.65(s，2H，C
5H
4)，4.27(s，5H，C
5H
5)，3.40(d，2H，COCH
2)，2.53(m，1H，CH)，2.05(S，3H，COCH
3)；
13C-NMR:192.6，141.4，132.3，126.6，121.6，33.6，23.3。
Embodiment 5
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(p-methylphenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(p-methylphenyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 70%, m.p.109 DEG C ~ 111 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2982,2920,1645,1589,1557,1512,1448,1375,1240;
1H-NMR:7.14-7.83(m，5H，Ar-H)，4.94(s，2H，C
5H
4)，4.53(s，2H，C
5H
4)，4.14(s，5H，C
5H
5)，3.42(d，2H，COCH
2)，2.94(m，1H，CH)，2.03(S，3H，COCH
3)，1.28(s，3H，CH
3)；
13C-NMR:192.8，140.4，140.1，134.2，126.3，121.5，56.2，44.8，34.8，21.1。
Embodiment 6
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(p-methoxyphenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(p-methoxyphenyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 68%, m.p.138 DEG C ~ 140 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2970,2833,1711,1648,1579,1509,1453,1329,1249;
1H-NMR:6.99-7.79(m，5H，Ar-H)，4.95(s，2H，C
5H
4)，4.61(s，2H，C
5H
4)，4.25(s，5H，C
5H
5)，3.53(S，3H，COCH
3)，3.10(d，2H，COCH
2)，2.43(s，1H，CH)；
13C-NMR:192.6，140.4，132.3，126.6，121.6，53.7，33.6，23.1。
Embodiment 7
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar with 0.0012mol NaOH to mix rapidly, then add 0.001mol 1-ferrocenyl-3-(3-nitrophenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(3-nitrophenyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 78%, m.p.93 DEG C ~ 95 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2980,2920,1711,1651,1592,1525,1452,1347,1277;
1H-NMR:7.35-7.73(m，5H，Ar-H)，4.83(s，2H，C
5H
4)，4.57(s，2H，C
5H
4)，4.25(s，5H，C
5H
5)，3.63(d，2H，COCH
2)，2.79(m，1H，CH)，2.08(S，3H，COCH
3)；
13C-NMR:192.8，139.6，138.2，136.4，134.2，132.1，130.8，127.9，55.2，43.5，27.8。
Embodiment 8
Take 0.0015mol acetone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(p-hydroxybenzene)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain brown solid, obtain 1-ferrocenyl-3-(p-hydroxybenzene)-3-(ethanoyl methylene radical)-acetone.Productive rate 65%, m.p.79 DEG C ~ 80 DEG C.
IR (KBr compressing tablet, v/cm
-1): 3296,2987,2930,1658,1581,1454,1368,1276;
1H-NMR:11.8(s，1H，OH)，7.06-7.80(m，5H，Ar-H)，4.79(s，2H，C
5H
4)，4.53(s，2H，C
5H
4)，4.01(s，5H，C
5H
5)，3.74(d，2H，COCH
2)，2.60(m，1H，CH)，2.19(S，3H，COCH
3)；
13C-NMR:201.7，140.6，138.2，127.9，126.7，120.9，120.5，55.2，43.2，27.0。
Embodiment 9
Take 0.0015mol acetone, 0.0012mol NaOH is placed in mortar and mixes rapidly, then adds 0.001mol 1-ferrocenyl-3-(4-isopropyl phenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(4-isopropyl phenyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 69%, m.p.121 DEG C ~ 123 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2961,2870,1659,1595,1510,1450,13801275;
1H-NMR:11.8(s，1H，OH)，7.03-7.54(m，5H，Ar-H)，4.92(s，2H，C
5H
4)，4.67(s，2H，C
5H
4)，4.23(s，5H，C
5H
5)，3.63(d，2H，COCH
2)，2.72(m，1H，CH)，2.19(S，3H，COCH
3)，1.09(s，6H，CH
3)；
13C-NMR:192.8，140.2，138.9，127.6，126.4，120.7，115.8，55.2，43.6，35.7，27.8，23.5。
Embodiment 10
Take 0.0015mol acetone, 0.0012mol NaOH is placed in mortar and mixes rapidly, then adds 0.001mol 1-ferrocenyl-3-(2-furyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain brown solid, obtain 1-ferrocenyl-3-(2-furyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 62%, m.p.84 DEG C ~ 85 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2982,2877,1658,1582,1454,1369,1278;
1H-NMR:7.05-7.70(m，5H，Ar-H)，4.80(s，2H，C
5H
4)，4.53(s，2H，C
5H
4)，4.23(s，5H，C
5H
5)，3.70(d，2H，COCH
2)，2.66(m，1H，CH)，1.72(S，3H，COCH
3)；
13C-NMR:201.8，140.2，137.6，130.8，127.5，127.0，120.8，55.2，43.8，27.0。
Embodiment 11
Take 0.0015mol acetone, and 0.0012mol NaOH is placed in mortar and mixes rapidly, then add 0.001mol 1-ferrocenyl-3-(2-thienyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(2-thienyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 70%, m.p.131 DEG C ~ 133 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2980,2884,1711,1641,1581,1515,1453,1372,1281;
1H-NMR:6.92-7.95(m，5H，Ar-H)，4.61(s，2H，C
5H
4)，4.46(s，2H，C
5H
4)，4.14(s，5H，C
5H
5)，3.61(d，2H，COCH
2)，2.67(m，1H，CH)，2.20(S，3H，COCH
3)；
13C-NMR:192.1，140.2，132.9，130.9，127.8，127.4，121.5，55.8，44.3，37.0。
Embodiment 12
Take 0.0015mol acetone, and 0.0012mol NaOH is placed in mortar and mixes rapidly, then add 0.001mol 1-ferrocenyl-3-(ethenylphenyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(ethenylphenyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 72%, m.p.87 DEG C ~ 88 DEG C.
IR (KBr compressing tablet, v/cm
-1): 3092,2980,2870,1661,1593,1444,1392,1275;
1H-NMR:7.13-7.75(m，5H，Ar-H)，6.35(d，1H，CH＝CH)，4.52(s，2H，C
5H
4)，4.19(s，2H，C
5H
4)，4.14(s，5H，C
5H
5)，3.72(d，2H，COCH
2)，2.66(m，1H，CH)，2.20(S，3H，COCH
3)；
13C-NMR:192.3，141.4，132.4，128.5，127.8，120.7，55.1，43.4，39.9，35.0。
Embodiment 13
Take 0.0015mol acetone, and 0.0012mol NaOH is placed in mortar and mixes rapidly, then add 0.001mol 1-ferrocenyl-3-(pyridyl)-acrylketone, mixed grinding.Mixture can start to become glutinous along with the carrying out of reaction; continue grinding until material no longer changes; use thin-layer chromatography monitoring reaction process; repeatedly wash suction filtration with pure water after question response completes and obtain dark red solid, obtain 1-ferrocenyl-3-(pyridyl)-3-(ethanoyl methylene radical)-acetone.Productive rate 72%, m.p.68 DEG C ~ 69 DEG C.
IR (KBr compressing tablet, v/cm
-1): 2957,2870,1663,1589,1451,1338,1277;
1H-NMR:7.08-7.70(m，5H，Ar-H)，4.81(s，2H，C
5H
4)，4.54(s，2H，C
5H
4)，4.13(s，5H，C
5H
5)，3.63(d，2H，COCH
2)，2.91(m，1H，CH)，2.21(S，3H，COCH
3)；
13C-NMR:192.8，140.6，139.2，128.7，125.6，120.1，119.8，55.8，42.2，27.8，27.0。
Claims (10)
1. 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone, is characterized in that: its general structure is as follows:
Wherein, described aryl is phenyl, halogenophenyl, aminomethyl phenyl, ethylphenyl, propyl group phenyl, p-methoxy-phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl, quinary heterocyclic radical or hexa-member heterocycle base.
2. a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 1, is characterized in that:
Described halogenophenyl is adjacent fluorophenyl, to fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl or to bromophenyl;
Described aminomethyl phenyl is o-methyl-phenyl-, an aminomethyl phenyl or p-methylphenyl;
Described ethyl be between ethylphenyl, to ethylphenyl;
Described propyl group be between n-propyl phenyl, isopropyl phenyl;
Described p-methoxy-phenyl is m-methoxyphenyl or p-methoxyphenyl.
3. a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 1, is characterized in that:
Described nitrophenyl is m-nitro base, 3,5-dinitrophenyls or p-nitrophenyl;
Described hydroxy phenyl is o-hydroxy-phenyl or p-hydroxybenzene;
Described aminophenyl is adjacent aminophenyl, m-aminophenyl base or p-aminophenyl.
4. a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 1, is characterized in that:
Described quinary heterocyclic radical is furyl or thienyl;
Described hexa-member heterocycle base is pyridyl.
5. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl the methylene radical)-acetone described in Claims 1-4 any one, is characterized in that: comprise the following steps:
Step 1) by A mol 1-ferrocenyl-3-aryl-acrylketone, B mol basic catalyst, C mol acetone adds in dry reaction vessel, is ground to raw material complete reaction, obtains crude product; Wherein A:B:C=1:(1 ~ 1.5): (1 ~ 2.0);
Step 2) crude product through washing, suction filtration obtains filter cake, by filter cake vacuum-drying, obtains 1-ferrocenyl-3-aryl-3-Nitromethylene-acetone.
6. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 5, is characterized in that:
Aryl in described 1-ferrocenyl-3-aryl-acrylketone is phenyl, halogenophenyl, aminomethyl phenyl, ethylphenyl, propyl group phenyl, p-methoxy-phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl, quinary heterocyclic radical or hexa-member heterocycle base;
Described halogenophenyl is adjacent fluorophenyl, to fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl or to bromophenyl;
Described aminomethyl phenyl is o-methyl-phenyl-, an aminomethyl phenyl or p-methylphenyl;
Described ethyl be between ethylphenyl, to ethylphenyl;
Described propyl group be between n-propyl phenyl, isopropyl phenyl;
Described p-methoxy-phenyl is m-methoxyphenyl or p-methoxyphenyl;
Described nitrophenyl is m-nitro base, 3,5-dinitrophenyls or p-nitrophenyl;
Described hydroxy phenyl is o-hydroxy-phenyl or p-hydroxybenzene;
Described aminophenyl is adjacent aminophenyl, m-aminophenyl base or p-aminophenyl;
Described quinary heterocyclic radical is furyl or thienyl;
Described hexa-member heterocycle base is pyridyl.
7. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 5, it is characterized in that: step 1) in process of lapping with TLC monitoring, when 1-ferrocenyl-3-aryl-acrylketone raw material point disappear time represent raw material complete reaction; The developping agent adopted during TLC detects is volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil.
8. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 5, is characterized in that:
Step 1) in grinding carry out in mortar, being ground to the raw material complete reaction time is 25 ~ 30min.
9. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 5, is characterized in that: step 1) described in basic catalyst be anhydrous K
2cO
3or NaOH.
10. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-(ethanoyl methylene radical)-acetone according to claim 5, is characterized in that: step 2) in suction filtration time washing until filtrate pH value is in neutral.
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Non-Patent Citations (3)
| Title |
|---|
| FURDIK MIKULAS等,: "Derivatives of ferrocenes. XIV. Synthesis of new substances by Michael addition starting from chalcones of cinnamoylferrocene type with active reactants", 《CHEMICKE ZVESTI》 * |
| ZHI-LIANG SHEN等,: "Microwave-Assisted Michael Addition of Diethyl Malonate with Ferrocenyl Substituted Chalcones Under Solvent-Free Conditions", 《SYNTHETIC COMMUNICATIONS》 * |
| 张泽等,: "机械化学条件下乙酰乙酸乙酯与查尔酮的Michael加成反应", 《化学研究与应用》 * |
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