CN106187792B - The synthesis of difunctional ionic liquid-catalyzed Beta-aminoketones compound - Google Patents
The synthesis of difunctional ionic liquid-catalyzed Beta-aminoketones compound Download PDFInfo
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- CN106187792B CN106187792B CN201510230433.0A CN201510230433A CN106187792B CN 106187792 B CN106187792 B CN 106187792B CN 201510230433 A CN201510230433 A CN 201510230433A CN 106187792 B CN106187792 B CN 106187792B
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- ionic liquid
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Abstract
The invention discloses a kind of synthetic method of difunctional ionic liquid-catalyzed β amino ketone compounds.Its key problem in technology is to use to have concurrentlyIonic liquid with Lewis acid difunctionals is as catalyst, and for water/ethanol as reaction medium, raw material aromatic aldehyde, ketone, aromatic amine react under room temperature, normal pressure obtains target product.Advantage is：(1) raw material sources are extensive, and it is convenient to prepare；(2) catalyst has a double functional group, in molecule
Description
One technical field
The present invention relates to a kind of synthetic method of difunctional ionic liquid-catalyzed Beta-aminoketones compound, belong to chemical material
Expect preparing technical field.This method is suitable for using aromatic aldehyde, ketone, aromatic amine as raw material, has concurrentlyWith the double officials of Lewis acid
The ionic liquid that can be rolled into a ball is reaction medium as catalyst, water/ethanol, the field of synthesising target compound under room temperature, normal pressure
Close.
Two background technologies
Beta-aminoketones compound, also referred to as Mannich base, in organic synthesis, pharmacy, papermaking, explosive, high molecular material
Have been widely used Deng field tool.Therefore, the research work of the related synthesis of such compound since the advent of the world is very active always.
The synthesis of such compound is mainly reacted by the Mannich of three component of one kettle way, and common catalyst has：1st, with concentrated hydrochloric acid
It is representative Deng inorganic mineral acidAcid (Zou J H.The Mannich reaction of dialkyl
Ketones, aromatic aldehydes and aromatic amines.Synth Commun.1996,28 (5)：618-
622；Uraguchi D, Terada M.Chiralacid-catalyzed direct Mannich reactions
Via electrophilic activation.J Am Chem Soc.2004,126 (17)：5356-5357)；2 transition metal
Halide is Lewis acid (Keshavarzipour F, the Tavakol H.Deep eutectic solvent as a of representative
recyclable catalyst for three-component synthesis of b-amino carbonyls.Catal
Lett.2015,145：1062-1066；Rondot C, Zhu J P.Synthesis of chiral vicinal diamines
by highly diastereoselective three-component phenolic Mannich reaction：
Temperature-dependent stereodivergency.Org Lett.2005,7 (8)：1641-1644；Loh T P,
Chen S L.InCl3-catalyzed three-component asymmetric Mannich-type reaction in
Methanol.Org Lett.2002,4 (21)：3647-3650)；3rd, amino acid is amphoteric compound (the List B.The of representative
direct catalytic asymmetric three-component Mannich reaction.J Am Chem
Soc.2000,122 (38)：9336-9337)；4th, metallo-organic compound (Xu L W, Xia C G, Li L.Transition
Metal salt-catalyzed direct three-component Mannich reactions of aldehydes,
Ketones, and carbamates：Efficient synthesis of N-protectedβ-aryl-β-amino
Ketone compounds.J Org Chem.2004,69 (24)：8482-8484)；5th, the inorganic base such as potassium hydroxide.Related
Research emphasis mainly screen catalyst, with reach reduce environmental pollution, shortens the reaction time, raising Beta-aminoketones compound
Yield.There are the problem of following 1 therein or more than 1 for the above method：Catalyst is difficult to recycle, catalyst is to air
Or the stability of water is poor, the reaction time is long, yield is not high；Wherein have document (Catal Lett.2015,145：1062-
1066) empirical tests find to be unable to reach effect described herein.
A kind of synthetic method of difunctional ionic liquid-catalyzed Beta-aminoketones compound of the present invention is different from upper
Disclosed synthetic method is stated, using having concurrentlyIonic liquid with Lewis acid double functional groups is as catalyst so that
In catalyst moleculeAcid and Lewis acid functional groups act on, act synergistically at the same time, are situated between by the use of water/ethanol as reaction
Matter, reaction is stirred under room temperature, condition of normal pressure, crude product is obtained by filtration after reaction, crude product is recrystallized to give pure product；
It need not be separated containing catalyst in filtrate, directly charging carries out the reaction of next batch.
Three content of the invention
It is an object of the invention to provide a kind of synthetic method of difunctional ionic liquid-catalyzed Beta-aminoketones compound.
The technical solution for realizing the object of the invention is：A kind of difunctional ionic liquid-catalyzed Beta-aminoketones compound
Synthetic method, key technology is using having concurrentlyWith the ionic liquid of Lewis acid double functional groups as catalyst,
In the catalyst moleculeAcid and Lewis acid functional groups act at the same time, concerted catalysis, catalyst to air and water all
It is very stable, it is therefore possible to use water/alcohol mixed solvent is reaction medium, using aromatic aldehyde, ketone, aromatic amine as raw material, normal
The synthesis of the target compound is synthesized under temperature, normal pressure.
Difunctional ionic-liquid catalyst used in the present invention (is abbreviated as ChCl2ZnCl2), structure such as formula (1)：
The method for preparing catalyst：1: 2 material ratio in molar ratio, by trimethyl radical ammonium chloride and anhydrous chlorine
After change zinc ground and mixed is uniform, 2h is placed at 100 DEG C, it is the catalysis used in the present invention to be cooled to room temperature to obtain white solid
Agent.Trimethyl radical ammonium chloride used can directly buy commercially available reagent or bibliography self-control (J Mol CatalA：
Chem.2014,391：41-47).Reaction equation such as formula (2)：
The raw materials used aromatic aldehyde of the present invention, ketone, aromatic amine have respectively as formula (3), (4), (5) structure：
In formula (3), R1Can be H, 4-OCH3, 2-NO2, 4-NO2In any one；
In formula (4), R2Can be C6H5Or CH3；
In formula (5), R3Can be H, 4-Cl, 3-NO2, 4-NO2In any one；
The raw materials used molar ratio of the present invention is aromatic aldehyde: ketone: aromatic amine=1: 1: 1, reaction medium water/ethanol (V/V=
1: 1~1: 5) dosage of mixed solvent is the 100~1000% of raw material gross mass, catalyst amount is the 5 of aromatic aldehyde molal quantity
~20%, the mixing wherein material and water/ethanol proportionally feed intake.
The temperature of reaction of the present invention is 20~30 DEG C of room temperature.
When the time of reaction of the present invention is 4~20 small.
A kind of synthetic method of difunctional ionic liquid-catalyzed Beta-aminoketones compound of the present invention, its feature exist
In：The present invention carries out Mannich reactions with difunctional ionic liquid-catalyzed aromatic aldehyde, ketone, aromatic amine in water/ethanol, reacts
After crude product is obtained by filtration, crude product is recrystallized to give pure product；Filtrate is mixed solvent, a small amount of unreacted original
Material, a small amount of product, the mixture of catalyst, without further separating-purifying, can put into raw material according to first time ingredient proportion,
Carry out the reaction of next batch.After repeatedly circulation, such as there is the phenomenon that yield is decreased obviously (>=5%), it may be possible to mix molten
Caused by agent, catalyst have a small amount of be lost in, only mixed solvent, catalyst need to be supplemented.
The chemical principle such as formula (6) of institute's foundation of the present invention：
According to a kind of synthetic method of difunctional ionic liquid-catalyzed Beta-aminoketones compound provided by the invention, its skill
Art key is to use to have concurrentlyIonic liquid with Lewis acid difunctionals is as catalyst, and water/ethanol is as reaction
Medium, aromatic aldehyde, ketone, aromatic amine are stirred under room temperature, normal pressure and synthesized.Crude product is obtained by filtration after reaction, thick production
Product are recrystallized to give pure product；Contained catalyst can directly feed intake without separating-purifying and carry out next batch in filtrate
Reaction.Compared with prior art, the present invention its advantage is：(1) raw material sources are extensive, and it is convenient to prepare；(2) catalyst has double officials
Can group, in moleculeWith Lewis acid functional groups can concerted catalysis, the catalytic activity than single functional group is high；
(3) using water/ethanol as reaction medium in building-up process, safety and steady is reacted, easily industry amplification；(4) catalyst, reaction medium
It can be recycled, the positive effect of energy-saving and emission-reduction, be environmental-friendly chemical process.
Four embodiments
The present invention will be further described for the following examples, and the purpose is to can be best understood from present disclosure.But
It is that embodiment does not limit the scope of the invention in any way.The technical staff of this professional domain is in scope of the invention as claimed
The modifications and adaptations inside made should also belong to the right and protection domain of the present invention.
Embodiment 1
Catalyst (ChCl2ZnCl2) preparation：The method for preparing catalyst：1: 2 material ratio in molar ratio, will
The trimethyl radical ammonium chloride of 10mmol and 20mmol anhydrous zinc chlorides are after ground and mixed is uniform in mortar, in baking oven
2h is placed at 100 DEG C, is cooled to room temperature to obtain white solid catalyst spare.
Embodiment 2
In 25mL round-bottomed flasks, 10mmol benzaldehydes, 10mmol acetophenones, 10mmol aniline, 0.5mmol catalysis are added
Agent (ChCl2ZnCl2) and 5mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 5), stirring reaction 12 is small at 20 DEG C
When terminate, filter, washing obtain white solid, yield 95%.
Embodiment 3
In 25mL round-bottomed flasks, add 10mmol o-nitrobenzaldehydes, 10mmol acetophenones, 10mmol aniline,
1.8mmol catalyst (ChCl2ZnCl2) and 30mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 5), at 20 DEG C
Stirring reaction 4 terminates when small, filters, and washing obtains white solid, yield 80%.
Embodiment 4
In 25mL round-bottomed flasks, 10mmol benzaldehydes, 10mmol acetone, 10mmol aniline, 1.0mmol catalyst are added
(ChCl·2ZnCl2) and 10mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 1), when stirring reaction 6 is small at 30 DEG C
Terminate, filtering, washing obtains white solid, yield 85%.
Embodiment 5
In 25mL round-bottomed flasks, add 10mmol P-methoxybenzal-dehyde, 10mmol acetophenones, 10mmol aniline,
0.9mmol catalyst (ChCl2ZnCl2) and 10mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 4), at 25 DEG C
Stirring reaction 8 terminates when small, filters, and washing obtains buff white solid, yield 89%.
Embodiment 6
In 25mL round-bottomed flasks, 10mmol paranitrobenzaldehydes, 10mmol acetanisole, 10mmol benzene are added
Amine, 1.5mmol catalyst (ChCl2ZnCl2) and 15mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 5), 20 DEG C
It is lower stirring reaction 10 it is small when terminate, filter, washing obtain yellow solid, yield 80%.
Embodiment 7
In 25mL round-bottomed flasks, 10mmol benzaldehydes, 10mmol acetophenones, 10mmol parachloroanilinum, 1.2mmol are added
Catalyst (ChCl2ZnCl2) and 20mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 4.5), stir at 20 DEG C anti-
Answer 15 it is small when terminate, filter, washing obtain faint yellow solid, yield 91%.
Embodiment 8
In 25mL round-bottomed flasks, 10mmol benzaldehydes, 10mmol acetone, 10mmol meta nitro anilines, 2.0mmol are added
Catalyst (ChCl2ZnCl2) and 10mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 2), reaction is stirred at 25 DEG C
18 terminate when small, and filtering, washing obtains white solid, yield 75%.
Embodiment 9
In 100mL round-bottomed flasks, add 40mmol benzaldehydes, 40mmol acetophenones, 40mmol paranitroanilinum,
5mmol catalyst (ChCl2ZnCl2) and 50mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 5), stir at 25 DEG C
Mix reaction 9 it is small when terminate, filter, washing obtain yellow solid, yield 95%.
Embodiment 10
In 25mL round-bottomed flasks, 10mmol benzaldehydes, 10mmol acetophenones, l0mmol aniline, 1.1mmol catalysis are added
Agent (ChCl2ZnCl2) and 10mL water/alcohol mixed solvent (water and ethanol volume ratio be 1: 3.5), stirring reaction 20 at 20 DEG C
Hour terminates, and filters, and washing obtains white solid, yield 93%.
Embodiment 11
For the actual effect of more difunctional ionic-liquid catalyst, according to the operating procedure of embodiment 2, it is respectively adopted
A, tri- kinds of different catalyst of B, C：A, the trimethyl radical ammonium chloride (ChCl) of 1mmol；B, the anhydrous zinc chloride of 1mmol
(ZnCl2)；C, mixture (ChCl+2ZnCls of the B of the A and 0.67mmol of 0.33mmol under normal temperature condition2), instead of embodiment
Catalyst (ChCl2ZnCl in 22), remaining method is constant, and the results are shown in Table 1, no matter is single use
(A), Lewis sour (B) and both simple mixtures at normal temperatures, reaction yield is significantly lower than double used in the present invention
Catalysis of functional ionic liquid agent.
The yield of 1 different catalysts of table compares
Claims (8)
1. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound, it is characterised in that：To have concurrently
Ionic liquid with Lewis acid double functional groups uses water/alcohol mixed solvent as reaction medium, with fragrance as catalyst
Aldehyde, ketone, aromatic amine are raw material, and a period of time is stirred under room temperature, normal pressure, synthesizes the target compound；Wherein, difunctional ion
Shown in liquid catalyst structure such as formula (I)：
Raw material aromatic aldehyde used, ketone, aromatic amine have respectively as formula (II), (III), (IV) structure：
In formula (II), R1Can be H, 4-OCH3, 2-NO2, 4-NO2In any one；
In formula (III), R2Can be C6H5Or CH3；
In formula (IV), R3Can be H, 4-Cl, 3-NO2, 4-NO2In any one.
2. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：The method for preparing catalyst is in molar ratio 1: 2 ratio, by trimethyl radical ammonium chloride and anhydrous zinc chloride
After ground and mixed is uniform, 2h is placed at 100 DEG C, is cooled to room temperature to obtain white solid, is the catalyst of the present invention.
3. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：Raw materials used aromatic aldehyde, ketone, the molar ratio of aromatic amine are 1: 1: 1.
4. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：The dosage of water/alcohol mixed solvent is the 100~1000% of raw material gross mass.
5. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：Catalyst amount is the 5~20% of aromatic aldehyde molal quantity.
6. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：Wherein described raw material, catalyst, mixed solvent proportionally feed intake mixing successively.
7. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：When reaction time is 4~20 small.
8. the method for difunctional ionic liquid-catalyzed synthesis Beta-aminoketones compound according to claim 1, its feature
It is：Crude product is obtained by filtration after reaction, crude product is recrystallized to give pure product；Filtrate is mixed solvent, Shao Liangwei
The raw material of reaction, a small amount of product, the mixture of catalyst, can be according to first time ingredient proportion without further separating-purifying
Raw material is put into, carries out the reaction of next batch.
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Non-Patent Citations (2)
| Title |
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| BASIC FUNCTIONALIZED IONIC LIQUID CATALYZED ONE-POT MANNICH-TYPE REACTION:THREE COMPONENT SYNTHESIS OF β-AMINO CARBONYL COMPOUNDS;KAI GONG 等;《MONATSHEFTE FUR CHEMIE》;20071017(第138期);1195-1198 * |
| HETEROPOLYANION-BASED SULFATED IONIC LIQUID CATALYZED FORMAMIDES SYNTHESIS BY GRINDSTONE CHEMISTRY;SHAILESH P.等;《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》;20140415(第391期);41-47 * |
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