CN104311607A - 1-Ferrocenyl-3-aryl-3-diacetylmethylene-acetone and preparation method thereof - Google Patents
1-Ferrocenyl-3-aryl-3-diacetylmethylene-acetone and preparation method thereof Download PDFInfo
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Abstract
The invention discloses 1-ferrocenyl-3-aryl-3-diacetylmethylene-acetone and a preparation method thereof. The structural formula of the above compound is shown in the specification. The preparation method comprises the following steps: adding 1-ferrocenyl-3-aryl-acrylketone, anhydrous K2CO3 (or NaOH) and acetylacetone into a dry mortar, rapidly grinding, detecting the reaction process through TLC, washing with water after the reaction, carrying out pumping filtration, and carrying out vacuum drying to obtain 1-ferrocenyl-3-aryl-3-diacetylmethylene-acetone. The method has the advantages of simple operation, mild reaction conditions, simple post-treatment and high yield, and the product prepared in the invention is a brand new ketone, and can be used for in the fields of pesticides and medicines.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone and preparation method thereof.
Background technology
The shortcomings such as traditional high and low productive rate of methodology of organic synthesis energy consumption, environmental pollution are serious, do not meet in recent years people to the requirement of " Green Chemistry ".Michael addition is one of important reaction building C-C in organic synthesis, is therefore the interested research topic of synthetic organic chemist always.In recent years, organic catalysis asymmetric Michael addition reaction developed rapidly, became a new focus of asymmetry catalysis research field.
Cinnamophenone is the beta-unsaturated carbonyl compounds that class two ends are connected to aromatic ring, and the polytropy of two ends aryl imparts the multifarious feature of this compounds.Ketenes segment in cinnamophenone has 1,3 two nucleophilic site, this be the material of they and other first occur Isosorbide-5-Nitrae addition again cyclization construct new member ring systems and lay a good foundation.Carbon-carbon double bond in some cinnamophenone can open the cinnamophenone initial ring addition reaction with another molecule under light-catalysed condition.Therefore, cinnamophenone is ask body in the important organic synthesis of a class in organic synthesis, and application prospect is very extensive.
Biferrocenyl chalcone 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 group etc. in it, generate the heterogeneous ring compound with ferrocenyl, morely has bioactive ferrocenyl Hete rocyclic derivatives for developing and provide method.There is the shortcomings such as long reaction time, yield are not high, solvent usage quantity is large in the preparation of existing chalcone compound.
Summary of the invention
The object of the present invention is to provide a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone and preparation method thereof, the method is simple to operate, reaction conditions is gentle, and aftertreatment is simple and productive rate is high, and the product of preparation can be used for sterilization, antibacterial etc.
For achieving the above object, the present invention is by the following technical solutions:
A kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone, its general structure is as follows:
Wherein, Ar is aryl, and aryl is phenyl, halogenophenyl, aminomethyl phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl or quinary heterocyclic radical.
As a further improvement on the present invention, described halogenophenyl be 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 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.
A preparation method for 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone, comprises the following steps:
Step 1) by A mol1-ferrocenyl-3-aryl-acrylketone, B mol basic catalyst, C mol methyl ethyl diketone adds in dry reaction vessel, is ground to raw material complete reaction, obtains crude product; Wherein A:B:C=1:(1-1.2): (1-1.2);
Step 2) crude product through washing, suction filtration obtains filter cake, by filter cake vacuum-drying, obtains 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone.
As a further improvement on the present invention, the aryl in described 1-ferrocenyl-3-aryl-acrylketone is phenyl, halogenophenyl, aminomethyl phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl or quinary heterocyclic radical;
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 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.
As a further improvement on the present invention, 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 that TLC detection adopts is volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil.
As a further improvement on the present invention, step 1) in grinding carry out in mortar, being ground to the raw material complete reaction time is 5 ~ 10min.
As a further improvement on the present invention, step 1) described in basic catalyst be anhydrous K
2cO
3or NaOH.
As a further improvement on the present invention, step 2) crude product obtains filter cake through washing, suction filtration, will in vacuum drying for filter cake step during suction filtration washing until filtrate pH value is in neutral.
As a further improvement on the present invention, step 1) reaction at room temperature carry out.
As a further improvement on the present invention, step 2) vacuum-drying temperature be 20-30 DEG C, time 20-30h.
Relative to prior art, the present invention has the following advantages:
The invention provides a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone and preparation method thereof, the method is simple to operate, reaction conditions is gentle, aftertreatment is simple and productive rate is high.1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone prepared by the present invention is a kind of brand-new ketone, can be used for agricultural chemicals and field of medicaments etc.Compared with prior synthesizing method, reactant is placed in mortar directly griding reaction by 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, at the bottom of the raw materials cost that this reaction adopts, easily obtain, alternative material of the same type is many, and follow-up batch production can be selected many.
Further, crude product prepared by the present invention can select the method for washing suction filtration to obtain product, improves the productive rate of product.Adopt washing not introduce other material, can not affect the composition of product, as long as subsequent disposal is dry, operability is high.
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.
Embodiment
The reaction equation of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone of the present invention is such as formula shown in (1):
Wherein Ar is aryl, and aryl substituent be phenyl, rubigan, to bromophenyl, to fluorophenyl, p-methylphenyl, p-methoxyphenyl, m-nitro base, p-hydroxybenzene, o-hydroxy-phenyl, styryl, o-methyl-phenyl-, an aminomethyl phenyl, m-methoxyphenyl, 2-fluorophenyl, p-aminophenyl, m-aminophenyl base, adjacent aminophenyl, Chloro-O-Phenyl, 2,4-dichlorophenyl, p-nitrophenyl, 3,5-dinitrophenyls, o-bromophenyl, a bromophenyl, furyl, thienyl etc.
A preparation method for 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone, comprises the following steps:
Step 1) by A mol1-ferrocenyl-3-aryl-acrylketone, B mol anhydrous K
2cO
3(or NaOH), C mol methyl ethyl diketone adds in dry mortar and is ground to rapidly reaction under normal temperature and terminates, milling time 5 ~ 10min, adopts TLC detection reaction process in reflection, represent raw material complete reaction when the raw material point of 1-ferrocenyl-3-aryl-acrylketone disappears; The developping agent of TLC is volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil, after question response is complete, obtains crude product.
Step 2) crude product through repeatedly washing, suction filtration, washing during suction filtration is until filtrate pH value is in neutral, and by filter cake vacuum-drying, vacuum-drying temperature is 20-30 DEG C, time 20-30h, both 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone.
In 1-ferrocenyl-3-aryl-acrylketone aryl substituent be phenyl, rubigan, to bromophenyl, to fluorophenyl, p-methylphenyl, p-methoxyphenyl, m-nitro base, p-hydroxybenzene, o-hydroxy-phenyl, styryl, o-methyl-phenyl-, an aminomethyl phenyl, m-methoxyphenyl, 2-fluorophenyl, p-aminophenyl, m-aminophenyl base, adjacent aminophenyl, Chloro-O-Phenyl, 2,4-dichlorophenyl, p-nitrophenyl, 3,5-dinitrophenyls, o-bromophenyl, a bromophenyl, furyl, thienyl etc.
Below in conjunction with preferred embodiment of the present invention, the present invention is described in further details.
Embodiment 1
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-phenyl-acryloyl ketone, mixed at room temperature grinding 9min.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; raw material complete reaction is represented when the raw material point of 1-ferrocenyl-3-phenyl-acryloyl ketone disappears; repeatedly suction filtration is washed with pure water after question response completes; washing during suction filtration is until filtrate pH value is in neutral; vacuum-drying; vacuum-drying; vacuum-drying temperature is 25 DEG C; time 24h, obtains red brown solid, obtains 1-ferrocenyl-3-phenyl-3-diacetyl methyne-acetone.M.p. be 106 DEG C-108 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3100,2937,2869,1712,1391;
1h NMR:7.09-8.01 (m, 5H, Ar-H), 4.45-4.93 (m, 9H, Cp), 4.17 (d, 1H, CH), 3.23-3.58 (m, 1H, CH), 2.19 (s, 3H, COCH
3);
13c NMR:207.0,193.0 (2C), 140.7 (2C), 138.6 (2C), 138.0,137.2,136.2 (2C), 135.3 (2C), 134.5,130.3,127.9,123.8,120.8,114.4,45.6,39.4,31.0,27.4.
Embodiment 2
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(rubigan)-acrylketone, mixed at room temperature grinding 8min.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; raw material complete reaction is represented when the raw material point of 1-ferrocenyl-3-(rubigan)-acrylketone disappears; repeatedly suction filtration is washed with pure water after question response completes; washing during suction filtration is until filtrate pH value is in neutral; vacuum-drying; vacuum-drying; vacuum-drying temperature is 25 DEG C; time 24h, obtains dark red solid, obtains 1-ferrocenyl-3-(rubigan)-3-diacetyl methyne-acetone.M.p. be 147 DEG C-150 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3150,2971,2839,1647,1374,825;
1h NMR:7.21-7.96 (m, 5H, Ar-H), 4.28-4.90 (m, 9H, Cp), 4.08 (d, 1H, CH), 3.08-3.52 (m, 1H, CH), 2.10 (s, 3H, COCH
3);
13c NMR:205.1,192.5 (2C), 140.8 (2C), 139.9 (2C), 138.2,136.4,134.6 (2C), 132.8 (2C), 131.5,130.3,128.0,126.2,120.0,115.0,48.1,41.2,30.5,28.8.
Embodiment 3
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(to bromophenyl)-acrylketone, mixed at room temperature grinding 5min.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; raw material complete reaction is represented when the raw material point of 1-ferrocenyl-3-(to bromophenyl)-acrylketone disappears; repeatedly suction filtration is washed with pure water after question response completes; washing during suction filtration is until filtrate pH value is in neutral; vacuum-drying; vacuum-drying; vacuum-drying temperature is 25 DEG C; time 24h, obtains dark red solid, obtains 1-ferrocenyl-3-(to bromophenyl)-3-diacetyl methyne-acetone.M.p. be 164 DEG C-165 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3058,2910,2881,1648,1378,824;
1h NMR:7.11-7.76 (m, 5H, Ar-H), 4.53-4.93 (m, 9H, Cp), 4.23 (d, 1H, CH), 2.42-3.08 (m, 1H, CH), 2.19 (s, 3H, COCH
3);
13c NMR:205.1,192.5 (2C), 140.8 (2C), 139.9 (2C), 138.2,136.4,134.6 (2C), 132.8 (2C), 131.5,130.3,128.0,126.2,120.0,115.0,48.1,41.2,30.5,28.8.
Embodiment 4
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(to fluorophenyl)-acrylketone, mixed at room temperature grinding 10min.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; raw material complete reaction is represented when the raw material point of 1-ferrocenyl-3-(to fluorophenyl)-acrylketone disappears; repeatedly suction filtration is washed with pure water after question response completes; washing during suction filtration is until filtrate pH value is in neutral; vacuum-drying; vacuum-drying; vacuum-drying temperature is 25 DEG C; time 24h, obtains dark red solid, obtains 1-ferrocenyl-3-(to fluorophenyl)-3-diacetyl methyne-acetone.M.p. be 151 DEG C-153 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3067,2910,2853,1692,1374,821;
1h NMR:7.06-7.81 (m, 5H, Ar-H), 4.46-4.94 (m, 9H, Cp), 4.25 (d, 1H, CH), 2.42-4.03 (m, 1H, CH), 2.03 (s, 3H, COCH
3);
13c NMR:207.6,192.8 (2C), 141.0 (2C), 140.2 (2C), 139.8,136.0,135.2 (2C), 131.8 (2C), 130.7,128.6,127.5,126.1,118.0,114.9,47.2,44.5,31.2,27.9.
Embodiment 5
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(p-methoxyphenyl)-acrylketone, mixed at room temperature grinding 9min.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 after question response completes with pure water, washing during suction filtration is until filtrate pH value is in neutral; vacuum-drying; vacuum-drying, vacuum-drying temperature is 30 DEG C, time 24h; obtain dark red solid, obtain 1-ferrocenyl-3-(p-methoxyphenyl)-3-diacetyl methyne-acetone.M.p. be 136 DEG C-138 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3048,2959,2890,1649,1371;
1h NMR:6.96-7.81 (m, 5H, Ar-H), 4.52-5.28 (m, 9H, Cp), 4.18 (d, 1H, CH), 3.84-3.88 (m, 1H, CH), 2.19 (s, 3H, COCH
3), 3.70 (s, 3H, OCH3);
13c NMR:206.9,193.1 (2C), 139.8 (2C), 138.2 (2C), 137.1,136.4,132.6 (2C), 131.8 (2C), 130.2,129.6,127.0,125.4,117.0,116.2,55.4,47.9,42.0,31.5,28.7.
Embodiment 6
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar with 0.0012mol NaOH to mix rapidly, then add 0.001mol1-ferrocenyl-3-(3-nitrophenyl)-acrylketone, mixed at room temperature grinding 5min.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, wash until filtrate pH value is in neutral during suction filtration, vacuum-drying; vacuum-drying temperature is 30 DEG C; time 20h, obtains dark red solid, obtains 1-ferrocenyl-3-(3-nitrophenyl)-3-diacetyl methyne-acetone.M.p. be 67 DEG C-68 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3028,2922,2890,1658,1378,1450;
1h NMR:7.28-8.53 (m, 5H, Ar-H), 4.51-4.95 (m, 9H, Cp), 4.22 (d, 1H, CH), 2.39-2.88 (m, 1H, CH), 2.17 (s, 3H, COCH
3);
13c NMR:206.9,193.1 (2C), 139.8 (2C), 138.1 (2C), 137.2,136.6,134.2 (2C), 133.2 (2C), 131.8,130.0,128.5,126.5,118.8,114.0,48.4,41.5,30.9,28.9.
Embodiment 7
Take 0.0012mol methyl ethyl diketone, 0.0012mol anhydrous K
2cO
3be placed in mortar to mix rapidly, then add 0.001mol1-ferrocenyl-3-(p-hydroxybenzene)-acrylketone, mixed at room temperature grinding 6min.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, wash until filtrate pH value is in neutral during suction filtration, vacuum-drying; vacuum-drying temperature is 30 DEG C; time 20h, obtains dark red solid, obtains 1-ferrocenyl-3-(p-hydroxybenzene)-3-diacetyl methyne-acetone.M.p. be 80 DEG C-83 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3334,3092,2981,2854,1707,1374;
1h NMR:10.5 (s, 1H ,-OH), 7.29-7.81 (m, 5H, Ar-H), 4.44-5.01 (m, 9H, Cp), 4.22 (d, 1H, CH), 2.25-2.57 (m, 1H, CH), 2.18 (s, 3H, COCH
3);
13c NMR:205.3,192.8 (2C), 140.1 (2C), 139.2 (2C), 138.0,136.5,134.8 (2C), 132.1 (2C), 131.5,130.8,128.5,126.1,119.3,114.5,48.6,42.0,30.9,27.9.
Embodiment 8
Take 0.0012mol methyl ethyl diketone, 0.0012mol NaOH is placed in mortar and mixes rapidly, then adds 0.001mol1-ferrocenyl-3-(2-hydroxy phenyl)-acrylketone, mixed at room temperature grinding 10min.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, wash until filtrate pH value is in neutral during suction filtration, vacuum-drying; vacuum-drying temperature is 20 DEG C; time 30h, obtains dark red solid, obtains 1-ferrocenyl-3-(2-hydroxy phenyl)-3-phenyl-3-diacetyl methyne-acetone.M.p. be 78 DEG C-80 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3445,3091,2952,2822,1730,1372;
1h NMR:10.8 (s, 1H ,-OH), 7.29-7.80 (m, 5H, Ar-H), 4.23-4.79 (m, 9H, Cp), 4.01 (d, 1H, CH), 2.35-2.58 (m, 1H, CH), 2.19 (s, 3H, COCH
3);
13c NMR:206.1,193.5 (2C), 139.1 (2C), 138.5 (2C), 136.2,134.8,132.5 (2C), 130.8 (2C), 129.5,128.3,126.0,125.4,118.8,114.8,47.8,42.2,31.1,29.0.
Embodiment 9
Take 0.0012mol methyl ethyl diketone, 0.0012mol NaOH is placed in mortar and mixes rapidly, then adds 0.001mol1-ferrocenyl-3-(2-furyl)-acrylketone, mixed at room temperature grinding 7min.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, wash until filtrate pH value is in neutral during suction filtration, vacuum-drying; vacuum-drying temperature is 20 DEG C; time 24h, obtains dark red solid, obtains 1-ferrocenyl-3-(2-furyl)-3-diacetyl methyne-acetone.M.p. be 81 DEG C-83 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3028,2962,2895,1662,1372;
1h NMR:7.29-7.60 (m, 3H, Ar-H), 4.35-4.79 (m, 9H, Cp), 4.12 (d, 1H, CH), 3.35-3.58 (m, 1H, CH), 2.12 (s, 3H, COCH
3);
13c NMR:206.5,192.9 (2C), 140.1,138.9,137.6,135.4,134.2 (2C), 132.9 (2C), 130.5,128.3,126.8,125.1,120.0,113.9,48.6,40.8,31.2,29.0.
Embodiment 10
Take 0.0012mol methyl ethyl diketone, and 0.0012mol NaOH is placed in mortar and mixes rapidly, then add 0.001mol1-ferrocenyl-3-(2-thienyl)-acrylketone, mixed at room temperature grinding 9min.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, wash until filtrate pH value is in neutral during suction filtration, vacuum-drying; vacuum-drying temperature is 25 DEG C; time 24h, obtains dark red solid, obtains 1-ferrocenyl-3-(2-thienyl)-3-diacetyl methyne-acetone.M.p. be 145 DEG C-146 DEG C.
IR (KBr compressing tablet) ν (cm
-1): 3063,2915,2885,1648,1377;
1h NMR:6.93-7.95 (m, 3H, Ar-H), 4.46-4.92 (m, 9H, Cp), 4.22 (d, 1H, CH), 3.42-3.58 (m, 1H, CH), 2.15 (s, 3H, COCH
3);
13c NMR:207.1,193.2 (2C), 140.6,139.1,138.3,136.4,134.8 (2C), 132.5 (2C), 131.2,128.8,126.9,124.1,119.2,114.9,48.9,41.1,31.5,29.4.
Embodiment 11 ~ 25 is identical with operating parameters with the step of embodiment 1, and raw material 1-ferrocenyl-3-aryl-acrylketone that it adds is specifically as shown in table 1 with the product 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone obtained.
Table 1
Claims (10)
1. 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone, is characterized in that: its general structure is as follows:
Wherein, Ar is aryl, and aryl is phenyl, halogenophenyl, aminomethyl phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl or quinary heterocyclic radical.
2. a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-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 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.
3. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone described in claim 1 or 2, is characterized in that: comprise the following steps:
Step 1) by A mol1-ferrocenyl-3-aryl-acrylketone, B mol basic catalyst, C mol methyl ethyl diketone adds in dry reaction vessel, is ground to raw material complete reaction, obtains crude product; Wherein A:B:C=1:(1-1.2): (1-1.2);
Step 2) crude product through washing, suction filtration obtains filter cake, by filter cake vacuum-drying, obtains 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone.
4. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, is characterized in that: the aryl in described 1-ferrocenyl-3-aryl-acrylketone is phenyl, halogenophenyl, aminomethyl phenyl, nitrophenyl, hydroxy phenyl, aminophenyl, styryl or quinary heterocyclic radical;
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 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.
5. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, 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 that TLC detection adopts is volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil.
6. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, is characterized in that: step 1) in grinding carry out in mortar, being ground to the raw material complete reaction time is 5 ~ 10min.
7. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, is characterized in that: step 1) neutral and alkali catalyzer is anhydrous K
2cO
3or NaOH.
8. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, is characterized in that: step 2) in suction filtration time washing until filtrate pH value is in neutral.
9. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, is characterized in that: step 1) in reaction at room temperature carry out.
10. the preparation method of a kind of 1-ferrocenyl-3-aryl-3-diacetyl methyne-acetone according to claim 3, is characterized in that: step 2) in vacuum-drying temperature be 20-30 DEG C, time 20-30h.
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| CN110724169A (en) * | 2019-11-22 | 2020-01-24 | 陕西科技大学 | Method for preparing 1-ferrocenyl-3-aryl-3-diacetyl methylene-acetone |
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| CN110724169B (en) * | 2019-11-22 | 2022-04-12 | 陕西科技大学 | Method for preparing 1-ferrocenyl-3-aryl-3-diacetyl methylene-acetone |
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