CN107162970A - A kind of ionic liquid-catalyzed synthesis dihydro 4 of 2 aryl 2,3 of highly acidity（1H）The method of qualone derivative - Google Patents
A kind of ionic liquid-catalyzed synthesis dihydro 4 of 2 aryl 2,3 of highly acidity（1H）The method of qualone derivative Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
Abstract
The invention discloses a kind of method of ionic liquid-catalyzed synthesis 2 aryl 2,3 dihydro 4 (1H) qualone derivative of highly acidity, belong to technical field of chemical material preparation.A kind of highly acidity 2 aryl 2 of ionic liquid-catalyzed synthesis of the present invention, the method of 3 dihydro 4 (1H) qualone derivatives, this method is using o-aminoacetophenone and aromatic aldehyde as reaction raw materials, 2 aryl 2 are synthesized under the catalytic action of highly acidity ionic-liquid catalyst, 3 dihydro 4 (1H) qualone derivatives, by being used as catalyst from specific highly acidity ionic liquid, and design is optimized to reaction process parameter, so as to effectively overcome the usage amount of catalyst present in existing synthesis technique larger, recycle performance relatively poor, purification of products process complexity and products therefrom yield need the deficiency further improved.
Description
Technical field
The present invention relates to a kind of (the 1H)-qualone derivative of presence of acidic ionic liquid catalyst synthesis 2- aryl -2,3- dihydro -4
New method, belong to technical field of chemical material preparation.This method is applied to aromatic aldehyde and adjacent amino with different substituents
Acetophenone is the occasion that reaction raw materials synthesize (the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4.
Background technology
Quinolinone is the nitrogen-containing heterocycle compound that a class has good bioactivity and pharmacological activity, sterilization, anti-inflammatory,
Excellent activity is shown in terms of anti-spasm, analgesic, anticancer, is the focus of medicine scholar research.Recent domestic on
The synthesis of such compound and the research of bioactivity are very active.And it is used as one kind in quinolinone, 2- aryl -2,3- bis-
Hydrogen -4 (1H)-qualone derivative is the aza analogues of flavanones, it may have the bioactivity of spectrum, in terms of pharmaceutical chemistry
It is of great interest.Therefore, study on the synthesis is carried out to such compound to have very important significance.
It is typically to use inorganic or organic acid, such as dense H in the prior art2SO4, p-methyl benzenesulfonic acid, ZnCl2、InCl3Deng work
For catalyst, catalysis distinct fragrance aldehyde occur condensation reaction with o-aminoacetophenone synthesize 2- aryl -2,3- dihydro -4 (1H) -
Qualone derivative.But this kind of method has low severe reaction conditions, reaction yield, reaction time length, environmental pollution tight
The shortcomings of weight, catalyst can not be recycled.Therefore, a kind of green, high yield, reaction condition are found gentle, workable
(the 1H)-qualone derivative synthetic method of 2- aryl -2,3- dihydro -4 turn into organic synthesis worker study focus.
Ionic liquid refers in room temperature or is bordering on the salt being in a liquid state at room temperature, because it has non-volatile, wider liquid
Phase scope and preferable chemical stability and applied to as green solvent in organic synthesis.Zwitterion is with acid
Property functional group, such as-COOH ,-SO3H etc. ionic liquid, or anion are referred to as Bu Langsi for the ionic liquid of inorganic acid radical ion
Special acidic ion liquid, it not only can also have green catalyst effect concurrently as green solvent in the reaction, can be by it
Apply to the mistake that catalysis aromatic aldehyde reacts (the 1H)-qualone derivative of synthesis 2- aryl -2,3- dihydro -4 with o-aminoacetophenone
Cheng Zhong.
Such as domestic Liu Changchun has synthesized three kinds using two-step method and has carried single-SO3H acidic ion liquid, is investigated
They live respectively as the catalysis of catalyst one pot process 2- aryl -2,3- dihydro -4 (1H)-qualone derivative
Property and repeat performance.As a result find, three kinds of acidic ion liquids are respectively provided with higher catalytic activity, and catalyst passes through vacuum
It may be reused after drying process 5 times, and its catalytic activity is without obvious reduction.This method has that reaction condition is gentle, product
High income, without using volatile organic solvent and to environment it is relatively friendly the features such as (Acid ion liquid catalyst is closed
Into (the 1H)-quinolinone [J] of 2- aryl -2,3- dihydro -4, fine chemistry industry, 2012,29 (8)：778~782).
But when synthesizing 2- aryl -2,3- -4 (1H)-qualone derivative of dihydro using above-mentioned catalyst, catalyst
Usage amount is relatively large, and the purification process of products therefrom is complex to be extracted and recrystallization process, it is necessary to pass through, and these are complicated
Process also result in catalyst loss amount it is larger, number of times can be recycled relatively fewer.In addition, although the reaction of this method
Condition is more gentle, but its reaction time is relatively long, and the yield of products therefrom also needs further raising.
The content of the invention
1. the invention technical problem to be solved
It is an object of the invention to overcome existing (the 1H)-qualone derivative synthesis technique of 2- aryl -2,3- dihydro -4 to deposit
More than not enough there is provided a kind of ionic liquid-catalyzed (the 1H)-quinolinone of synthesis 2- aryl -2,3- dihydro -4 derivative of highly acidity
The method of thing.The present invention is carried out excellent by being used as catalyst from specific highly acidity ionic liquid to reaction process parameter
Change design, the usage amount of catalyst of existing synthesis technique presence is larger, it is relative to recycle performance so as to effectively overcome
Poor, purification of products process complexity and products therefrom yield need the deficiency further improved.
2. technical scheme
To reach above-mentioned purpose, the technical scheme that the present invention is provided is：
A kind of ionic liquid-catalyzed (the 1H)-qualone derivative of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the present invention
Method, this method using o-aminoacetophenone and aromatic aldehyde as reaction raw materials, highly acidity ionic-liquid catalyst catalysis make
(the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4 is synthesized with getting off, the structural formula of the catalyst is：
Further, the synthesizer of (the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4 is mixed including raw material
Clutch, ultrasonic assistant reactor, Suction filtration device, wash mill and drying device, by ultrasonic assistant reactor to raw material
Mixed material in blender carries out ultrasonic assistant reaction, and the Suction filtration device, wash mill and drying device are respectively used to
Suction filtration, washing and drying process are carried out to reaction products therefrom.
Further, the material mixer uses the single-necked flask with condenser pipe, and described drying device is used
Vacuum drying chamber, temperature is 75 DEG C.
Further, described synthesizer also include ice-water bath cooling device, the ice-water bath cooling device be used for pair
Reaction gained reaction system carries out cooling crystallization processing.
Further, building-up process of the invention is specific as follows：By reaction raw materials o-aminoacetophenone and aromatic aldehyde and
Catalyst is added separately in material mixer, is sufficiently mixed uniformly, is then added under Ultrasonic Radiation with reaction dissolvent
Hot back flow reaction, the reaction time is 1.0~3.5h, and reaction is cooled to room temperature and separates out a large amount of solids, then mixes raw material after terminating
Clutch, which is placed in ice-water bath cooling device, to be continued to cool down, and the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, institute
Filter residue it is scrubbed, vacuum drying after i.e. obtain (the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4.
Further, the mol ratio of the o-aminoacetophenone and aromatic aldehyde is 1：1, the mole of the catalyst is
The 8~12% of aromatic aldehyde mole used.
Further, described aromatic aldehyde be benzaldehyde, it is 4-chloro-benzaldehyde, parahydroxyben-zaldehyde, 4-Fluorobenzaldehyde, right
Methoxybenzaldehyde, p-tolyl aldehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, m chlorobenzaldehyde, m-nitrobenzaldehyde,
Any of o-bromobenzaldehye, o-tolualdehyde and salicylaldhyde.
Further, described reaction dissolvent uses ethanol water, and the volumetric concentration of ethanol water for 94~
97%.
Further, the volume that the reaction dissolvent ethanol water is counted using milliliter as aromatic aldehyde by mM in terms of
8~10 times of the amount of material.
Further, described cleaning solution uses absolute ethyl alcohol.
3. beneficial effect
The technical scheme provided using the present invention, compared with prior art, with following remarkable result：
(1) a kind of ionic liquid-catalyzed (the 1H)-quinolinone of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the invention derives
The method of thing, using o-aminoacetophenone and aromatic aldehyde as reaction raw materials, is used as by the highly acidity ionic liquid from the present invention
Catalyst, the catalytic activity of the catalyst is of a relatively high, so as to effectively improve the yield of products therefrom, and uses the catalysis
Usage amount when agent catalyzes and synthesizes 2- aryl -2,3- -4 (1H)-qualone derivative of dihydro and the damage during recycling
Vector is less, and the recycling performance of the catalyst is also preferable, and its recycling number of times is relatively more, therefore, it is possible to effective
Resource loss is reduced, production cost is advantageously reduced.
(2) a kind of ionic liquid-catalyzed (the 1H)-quinolinone of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the invention derives
The method of thing, the mode reacted by using Microwave-assisted firing derives to synthesize (the 1H)-quinolinone of 2- aryl -2,3- dihydro -4
Thing, so as to improve the catalytic activity of catalyst, is conducive to accelerating reaction rate, shortens the reaction time, and reduce catalyst
Usage amount.
(3) a kind of ionic liquid-catalyzed (the 1H)-quinolinone of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the invention derives
The method of thing, design is optimized by the usage amount to catalyst and reaction process parameter, so as to make urging for catalyst
Change activity and obtain best performance, it is ensured that products therefrom yield highest, and can also effectively reduce the generation of side reaction simultaneously, enter
And the purity of products therefrom is also effectively ensured.
(4) a kind of ionic liquid-catalyzed (the 1H)-quinolinone of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the invention derives
The method of thing, reaction dissolvent is used as by the ethanol water from certain concentration, consequently facilitating the purification processes of products therefrom,
Product is easily separated with catalyst, and the purification operations of product are simple and convenient, it is not necessary to extracted, recrystallization is handled.
(5) a kind of ionic liquid-catalyzed (the 1H)-quinolinone of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the invention derives
The method of thing, the complete reaction raw materials of last unreacted can be reused in next secondary response, the profit of reaction raw materials
High with rate, Atom economy is good；Pretreatment of the catalyst before recycling simultaneously is simple, is conducive to energy-saving and emission-reduction.
Brief description of the drawings
Fig. 1 is of the invention that highly acidity ionic-liquid catalyst catalyzes and synthesizes (the 1H)-quinolinone of 2- aryl -2,3- dihydro -4
The structural representation of the device of derivative.
Embodiment
A kind of ionic liquid-catalyzed (the 1H)-qualone derivative of synthesis 2- aryl -2,3- dihydro -4 of highly acidity of the present invention
Method, this method using o-aminoacetophenone and aromatic aldehyde as reaction raw materials, highly acidity ionic-liquid catalyst catalysis make
(the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4 is synthesized with getting off.As shown in figure 1,2- aryl -2,3- in the present invention
The synthesizer of dihydro -4 (1H)-qualone derivative includes material mixer, ultrasonic assistant reactor, ice-water bath cooling dress
Put, Suction filtration device, wash mill and drying device, the mixed material in material mixer is entered by ultrasonic assistant reactor
Row ultrasonic assistant reacts, and the ice-water bath cooling device is used to carry out cooling crystallization processing, institute to reaction gained reaction system
Suction filtration device, wash mill and drying device is stated to be respectively used to carry out suction filtration, washing and drying process to reaction products therefrom.On
State material mixer and use the single-necked flask with condenser pipe, described drying device uses vacuum drying chamber at 75 DEG C.
The structural formula of used catalyst of the present invention is：
The preparation method of above-mentioned catalyst, with reference to related data (Synthesis of a novel multi-SO3H
functionalized ionic liquid and its catalytic activities for biodiesel
Synthesis [J], Green Chemistry, 2010,12：201-204；A kind of preparation of multi-sulfonic functional ion liquid
Method [P], CN 101348487A).
The building-up process of (the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4 is specific as follows in the present invention：Will reaction original
Material o-aminoacetophenone is added separately in material mixer with aromatic aldehyde and catalyst, is sufficiently mixed uniformly with reaction dissolvent,
Then heating reflux reaction is carried out under Ultrasonic Radiation, the reaction time is 1.0~3.5h, and reaction is cooled to room temperature analysis after terminating
Go out a large amount of solids, then material mixer is placed in ice-water bath cooling device and continues to cool down, is pulverized when amount of solid is not further added by
The solid of precipitation, stands, suction filtration, and gained filter residue is scrubbed, obtain (the 1H)-quinoline of 2- aryl -2,3- dihydro -4 after vacuum drying
Quinoline ketone derivatives.The chemical equation of the reaction is：
Wherein, described aromatic aldehyde be benzaldehyde, 4-chloro-benzaldehyde, parahydroxyben-zaldehyde, 4-Fluorobenzaldehyde, to methoxyl group
Benzaldehyde, p-tolyl aldehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, m chlorobenzaldehyde, m-nitrobenzaldehyde, bromophenyl
Any of formaldehyde, o-tolualdehyde and salicylaldhyde.The mol ratio of o-aminoacetophenone and aromatic aldehyde in reaction
For 1：1, the mole of the catalyst is the 8~12% of aromatic aldehyde mole used.Described reaction dissolvent is dense using volume
Spend the ethanol water for 94~97%, and the volume counted using milliliter of reaction dissolvent ethanol water as aromatic aldehyde with mM
8~10 times of the amount of the material of meter.Described cleaning solution uses absolute ethyl alcohol.
The present invention exists primarily directed to existing (the 1H)-qualone derivative synthesis technique of 2- aryl -2,3- dihydro -4
Catalyst usage amount is big, the recycling number of times of catalyst is relatively fewer, synthesis technique is complicated and products therefrom yield need into
The problem of one step is improved, inventor combines (the 1H)-quinolinone derivative of 2- aryl -2,3- dihydro -4 by lot of experiments
The characteristics of building-up process of thing, the highly acidity ionic-liquid catalyst of the final choice present invention, catalyst synthesis 2- virtues
Base -2,3- dihydro -4 (1H)-qualone derivative active and selectivity are of a relatively high, thus the usage amount of catalyst it is less,
Reaction time is short, products therefrom yield is of a relatively high.
The control of the usage amount of catalyst and reaction process parameter is for the yield of final products therefrom and pure in the present invention
Degree is most important.Inventor optimizes design by the usage amount to catalyst and reaction process parameter, so as to effective
Ensure that the catalytic activity of catalyst is not fully exerted, and effectively prevent the generation of side reaction, and then advantageously ensure that gained is produced
The yield and purity of thing.The present invention is also reacted by way of Microwave-assisted firing simultaneously, so as to further raising
The catalytic activity of catalyst, advantageously reduces the usage amount of catalyst, shortens the reaction time.Because the catalyst of the present invention is being followed
Loss amount during ring use is less, and it is more that it can be recycled number of times, and its catalytic activity decline in recycling compared with
It is few, so as to ensure the stability of products therefrom yield.
Derive in addition, synthesizing (the 1H)-quinolinone of 2- aryl -2,3- dihydro -4 by using the catalyst of the present invention
Thing, and the ethanol water for selecting certain concentration, so as to ensure that the abundant progress of reaction, is conducive to improvement as reaction dissolvent
The recycling performance of catalyst, and purification of products is simple to operate.The complete reaction raw materials of last unreacted may be used also in the present invention
To be reused in next secondary response, the utilization rate of reaction raw materials is higher, and Atom economy is good；Catalyst is being followed simultaneously
Pretreatment before ring use is simple, is conducive to energy-saving and emission-reduction.
The substantive features and remarkable result of the present invention can be emerged from from following embodiments, but they are not to this
Invention is imposed any restrictions, and those skilled in the art makes some nonessential modifications and adaptations according to present disclosure,
Belong to protection scope of the present invention.Below by embodiment, the present invention is further illustrated, wherein in embodiment
The examination of infrared spectrum of reaction product characterizes the infrared spectrometers of model EQUINOX 55 for using German Bruker companies
(KBr tablettings)；Hydrogen spectrum nuclear magnetic resonance characterizes the core for the model AVANCE-II 400MHz for using German Bruker companies
Magnetic resonance device；The fusing point of reaction product is determined using capillary tube method.
Embodiment 1
1mmol benzaldehydes, 1mmol o-aminoacetophenones and 0.10mmol highly acidity ionic liquids are added separately to fill
In the 50ml single port bottles with condenser pipe of 8ml94% ethanol waters, it is stirred at room temperature uniform.It is heated to reflux, Ultrasonic Radiation
Lower reaction 2.1h, TLC (thin plate chromatography) detection, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids, is put
Enter to continue to cool down in ice-water bath and separate out solid, the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter residue is through nothing
Water-ethanol washing (3ml × 3), be dried in vacuo at 75 DEG C after obtain (the 1H)-quinolinone of 2- phenyl -2,3- dihydro -4, efficient liquid phase
Its purity of chromatographic determination is 99.1%, and calculated yield is 92%.It is directly added into after benzaldehyde, o-aminoacetophenone and carries out in filtrate
Reuse.
(the 1H)-quinolinone of 2- phenyl -2,3- dihydro -4 obtained by the present embodiment：M.p.150~152 DEG C；IR (KBr) performance
Parameter is as follows：3309,1692,1632,1361,1259,1134cm-1；1H NMR (400MHz, CDCl3)：δ=7.52~7.58
(m, 2H), 7.07~7.28 (m, 6H), 6.88~6.92 (m, 1H), 5.25 (t, 1H), 4.73 (s, 1H), 3.06 (dd, 1H),
2.72 (dd, 1H).
Embodiment 2
1mmol paranitrobenzaldehydes, 1mmol o-aminoacetophenones and 0.08mmol highly acidity ionic liquids are separately added into
Into the 50ml single port bottles with condenser pipe for filling the ethanol waters of 9ml 94%, it is stirred at room temperature uniform.It is heated to reflux, ultrasound
1.0h is reacted under wave radiation, TLC (thin plate chromatography) detections, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids,
It is put into ice-water bath to continue to cool down and separates out solid, the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter
Slag obtained after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C 2- (4- nitros)-phenyl -2,3- dihydro -4 (1H) -
Quinolinone, it is 99.4% that high performance liquid chromatography, which determines its purity, and calculated yield is 98%.P-nitrophenyl first is directly added into filtrate
Reused after aldehyde, o-aminoacetophenone.
2- (4- nitros)-phenyl -2,3- dihydro -4 (1H)-quinolinone obtained by the present embodiment：M.p.169~171 DEG C；IR
(KBr)：3371,3169,1745,1687,1602,1397,1168cm-1；1H NMR (400MHz, CDCl3) performance parameter such as
Under：δ=8.04 (d, 2H), 7.51~7.60 (m, 2H), 7.24~7.31 (m, 3H), 6.87 (d, 1H), 5.27 (t, 1H), 4.66
(s, 1H), 3.19 (dd, 1H), 2.92 (dd, 1H).
Embodiment 3
1mmol P-methoxybenzal-dehyde, 1mmol o-aminoacetophenones and 0.10mmol highly acidity ionic liquid are added respectively
Enter into the 50ml single port bottles with condenser pipe for filling the ethanol waters of 10ml 97%, be stirred at room temperature uniform.It is heated to reflux,
2.3h is reacted under Ultrasonic Radiation, TLC (thin plate chromatography) detections, raw material point disappears, and reaction end is cooled to room temperature and separated out largely
Solid, is put into ice-water bath and continues to cool down precipitation solid, the solid of precipitation is pulverized when amount of solid is not further added by, stands, takes out
Filter, filter residue obtains 2- (4- methoxyl groups)-phenyl -2,3- dihydro-after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C
4 (1H)-quinolinones, it is 99.2% that high performance liquid chromatography, which determines its purity, and calculated yield is 91%.It is directly added into filtrate to first
Reused after epoxide benzaldehyde, o-aminoacetophenone.
The performance parameter of 2- (4- methoxyl groups)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：
M.p.196~198 DEG C；IR(KBr)：3294,3056,1729,1641,1593,1327,1225,1140,1078,1006cm-1；1H NMR (400MHz, CDCl3)：δ=7.55~7.64 (m, 2H), 7.18~7.27 (m, 3H), 6.80~6.91 (m, 3H),
5.17 (t, 1H), 4.77 (s, 1H), 3.72 (s, 3H), 3.04 (dd, 1H), 2.73 (dd, 1H).
Embodiment 4
1mmol 4-Fluorobenzaldehydes, 1mmol o-aminoacetophenones and 0.09mmol highly acidity ionic liquids are added separately to
In the 50ml single port bottles with condenser pipe for filling the ethanol waters of 8ml 95%, it is stirred at room temperature uniform.It is heated to reflux, ultrasonic wave
Lower reaction 1.6h, TLC (thin plate chromatography) detection of radiation, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids, will
It, which inserts in ice-water bath to continue to cool down, separates out solid, and the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter residue
2- (4- fluorine)-phenyl -2,3- dihydro -4 (1H)-quinoline is obtained after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C
Ketone, it is 99.0% that high performance liquid chromatography, which determines its purity, and calculated yield is 94%.4-Fluorobenzaldehyde, neighbour are directly added into filtrate
Reused after aminoacetophenone.
The performance parameter of 2- (4- fluorine)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：m.p.164
~166 DEG C；IR(KBr)：3453,3094,1705,1661,1572,1315,1208,1149,1012cm-1；1H NMR
(400MHz, CDCl3)：δ=7.52~7.60 (m, 2H), 7.20~7.29 (m, 3H), 7.02~7.09 (m, 2H), 6.88 (d,
1H), 5.30 (t, 1H), 4.78 (s, 1H), 3.05 (dd, 1H), 2.71 (dd, 1H).
Embodiment 5
1mmol m chlorobenzaldehydes, 1mmol o-aminoacetophenones and 0.09mmol highly acidity ionic liquids are added separately to
In the 50ml single port bottles with condenser pipe for filling the ethanol waters of 8ml 96%, it is stirred at room temperature uniform.It is heated to reflux, ultrasonic wave
Lower reaction 1.8h, TLC (thin plate chromatography) detection of radiation, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids, will
It, which inserts in ice-water bath to continue to cool down, separates out solid, and the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter residue
2- (3- chlorine)-phenyl -2,3- dihydro -4 (1H)-quinoline is obtained after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C
Ketone, it is 99.1% that high performance liquid chromatography, which determines its purity, and calculated yield is 92%.M chlorobenzaldehyde, neighbour are directly added into filtrate
Reused after aminoacetophenone.
The performance parameter of 2- (3- chlorine)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：m.p.164
~171 DEG C；IR(KBr)：3295,3093,1718,1644,1527,1312,1239cm-1；1H NMR (400MHz, CDCl3)：δ
=7.57~7.65 (m, 2H), 7.32~7.37 (m, 2H), 7.20~7.26 (m, 2H), 7.06 (d, 1H), 6.91 (d, 1H),
5.29 (t, 1H), 4.68 (s, 1H), 3.19 (dd, 1H), 2.76 (dd, 1H).
Embodiment 6
1mmol m-nitrobenzaldehydes, 1mmol o-aminoacetophenones and 0.08mmol highly acidity ionic liquids are separately added into
Into the 50ml single port bottles with condenser pipe for filling the ethanol waters of 9ml 94%, it is stirred at room temperature uniform.It is heated to reflux, ultrasound
1.2h is reacted under wave radiation, TLC (thin plate chromatography) detections, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids,
It is put into ice-water bath to continue to cool down and separates out solid, the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter
Slag obtained after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C 2- (3- nitros)-phenyl -2,3- dihydro -4 (1H) -
Quinolinone, it is 98.9% that high performance liquid chromatography, which determines its purity, and calculated yield is 95%.M-nitro first is directly added into filtrate
Reused after aldehyde, o-aminoacetophenone.
The performance parameter of 2- (3- nitros)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：
M.p.147~149 DEG C；IR(KBr)：3391,3085,1737,1652,1584,1239,1196,1005cm-1；1H NMR
(400MHz, CDCl3)：δ=8.14~8.21 (m, 2H), 7.74 (d, 1H), 7.52~7.60 (m, 2H), 7.41 (t, 1H),
7.23 (t, 1H), 6.95 (d, 1H), 5.38 (t, 1H), 4.77 (s, 1H), 3.13 (dd, 1H), 2.78 (dd, 1H).
Embodiment 7
1mmol o-bromobenzaldehyes, 1mmol o-aminoacetophenones and 0.09mmol highly acidity ionic liquids are added separately to
In the 50ml single port bottles with condenser pipe for filling the ethanol waters of 8ml 96%, it is stirred at room temperature uniform.It is heated to reflux, ultrasonic wave
Lower reaction 1.9h, TLC (thin plate chromatography) detection of radiation, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids, will
It, which inserts in ice-water bath to continue to cool down, separates out solid, and the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter residue
2- (2- bromines)-phenyl -2,3- dihydro -4 (1H)-quinoline is obtained after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C
Ketone, it is 99.4% that high performance liquid chromatography, which determines its purity, and calculated yield is 90%.O-bromobenzaldehye, neighbour are directly added into filtrate
Reused after aminoacetophenone.
The performance parameter of 2- (2- bromines)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：m.p.225
~227 DEG C；IR(KBr)：3394,3248,3040,1714,1609,1233,1125,1006cm-1；1H NMR (400MHz,
CDCl3)：δ=7.54~7.63 (m, 2H), 7.43~7.47 (m, 1H), 7.24~7.35 (m, 3H), 6.95~7.01 (m,
2H), 5.34 (t, 1H), 4.78 (s, 1H), 3.15 (dd, 1H), 2.84 (dd, 1H).
Embodiment 8
1mmol salicylaldhydes, 1mmol o-aminoacetophenones and 0.12mmol highly acidity ionic liquids are separately added into
Into the 50ml single port bottles with condenser pipe for filling the ethanol waters of 9ml 97%, it is stirred at room temperature uniform.It is heated to reflux, ultrasound
3.5h is reacted under wave radiation, TLC (thin plate chromatography) detections, raw material point disappears, and reaction end is cooled to room temperature and separates out a large amount of solids,
It is put into ice-water bath to continue to cool down and separates out solid, the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration, filter
Slag obtained after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C 2- (2- hydroxyls)-phenyl -2,3- dihydro -4 (1H) -
Quinolinone, it is 99.0% that high performance liquid chromatography, which determines its purity, and calculated yield is 84%.O-hydroxy first is directly added into filtrate
Reused after aldehyde, o-aminoacetophenone.
The performance parameter of 2- (2- hydroxyls)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：
M.p.238~240 DEG C；IR(KBr)：3384,3247,3052,1683,1642,1594,1307,1219,1102,1020cm-1；1H NMR (400MHz, CDCl3)：δ=10.13 (s, 1H), 7.57~7.64 (m, 2H), 7.22~7.38 (m, 3H), 6.87~
6.94 (m, 2H), 6.69~6.74 (m, 2H), 5.21 (t, 1H), 4.59 (s, 1H), 3.05 (dd, 1H), 2.73 (dd, 1H).
Embodiment 9
1mmol o-tolualdehydes, 1mmol o-aminoacetophenones and 0.10mmol highly acidity ionic liquids are separately added into
Into the 50ml single port bottles with condenser pipe for filling the ethanol waters of 10ml 97%, it is stirred at room temperature uniform.It is heated to reflux, surpasses
2.6h is reacted under acoustic irradiation, TLC (thin plate chromatography) detections, raw material point disappears, and it is a large amount of solid that reaction end is cooled to room temperature precipitation
Body, is put into ice-water bath and continues to cool down precipitation solid, the solid of precipitation is pulverized when amount of solid is not further added by, is stood, suction filtration,
Filter residue obtains 2- (2- methyl)-phenyl -2,3- dihydro -4 after washing (3ml × 3) through absolute ethyl alcohol, be dried in vacuo at 75 DEG C
(1H)-quinolinone, it is 99.5% that high performance liquid chromatography, which determines its purity, and calculated yield is 87%.Adjacent first is directly added into filtrate
Reused after benzaldehyde, o-aminoacetophenone.
The performance parameter of 2- (2- methyl)-phenyl -2,3- dihydro -4 (1H)-quinolinone is as follows obtained by the present embodiment：
M.p.133~135 DEG C；IR(KBr)：3407,3240,1648,1601,1302,1236,1128,1014cm-1；1H NMR
(400MHz, CDCl3)：δ=7.52~7.61 (m, 2H), 7.24 (t, 1H), 7.00~7.06 (m, 3H), 6.89~6.91 (m,
2H), 5.40 (t, 1H), 4.77 (s, 1H), 3.03 (dd, 1H), 2.74 (dd, 1H), 2.16 (s, 3H).
Embodiment 10
It is probe reaction with embodiment 1, makees the active replica test of catalysts highly acidity ionic liquid, highly acidity
Ionic liquid is reused 9 times, and the purity of (the 1H)-quinolinone of product 2- phenyl -2,3- dihydro -4, yield change are shown in Table 1.
Activity repeatability of the highly acidity ionic liquid of table 1 in (the 1H)-quinolinone of 2- phenyl -2,3- dihydro -4 is catalyzed and synthesized
Result of the test
Embodiment 11
It is probe reaction with embodiment 2, makees the active replica test of catalysts highly acidity ionic liquid, highly acidity
Ionic liquid is reused 8 times, the purity of product 2- (4- nitros)-phenyl -2,3- dihydro -4 (1H)-quinolinone, yield change
It is shown in Table 2.
The highly acidity ionic liquid of table 2 is in 2- (4- nitros)-phenyl -2,3- dihydro -4 (1H)-quinolinone is catalyzed and synthesized
Active replica test result
| Highly acidity ionic liquid access times | Purity/% | Calculated yield/% |
| 1 | 99.4 | 98 |
| 2 | 99.2 | 97 |
| 3 | 99.0 | 97 |
| 4 | 98.9 | 96 |
| 5 | 98.7 | 96 |
| 6 | 98.6 | 96 |
| 7 | 98.5 | 94 |
| 8 | 98.4 | 94 |
| 9 | 98.2 | 92 |
Embodiment 12
It is probe reaction with embodiment 5, makees the active replica test of catalysts highly acidity ionic liquid, highly acidity
Ionic liquid is reused 8 times, and the purity of product 2- (3- chlorine)-phenyl -2,3- dihydro -4 (1H)-quinolinone, yield change are shown in
Table 3.
Work of the highly acidity ionic liquid of table 3 in 2- (3- chlorine)-phenyl -2,3- dihydro -4 (1H)-quinolinone is catalyzed and synthesized
Property replica test result
Embodiment 13
It is probe reaction with embodiment 8, makees the active replica test of catalysts highly acidity ionic liquid, highly acidity
Ionic liquid is reused 8 times, the purity of product 2- (2- hydroxyls)-phenyl -2,3- dihydro -4 (1H)-quinolinone, yield change
It is shown in Table 4.
The highly acidity ionic liquid of table 4 is in 2- (2- hydroxyls)-phenyl -2,3- dihydro -4 (1H)-quinolinone is catalyzed and synthesized
Active replica test result
| Highly acidity ionic liquid access times | Purity/% | Calculated yield/% |
| 1 | 99.0 | 84 |
| 2 | 98.8 | 83 |
| 3 | 98.7 | 81 |
| 4 | 98.6 | 82 |
| 5 | 98.4 | 80 |
| 6 | 98.3 | 81 |
| 7 | 98.2 | 82 |
| 8 | 98.0 | 80 |
| 9 | 98.0 | 79 |
It can be seen that by table 2~4：The highly acidity ionic liquid of the present invention contains different type, diverse location in catalysis
The aromatic aldehyde of substituent (electron withdraw group or electron-donating group) and a series of 2- aryl -2 of o-aminoacetophenone reaction synthesis,
During 3- dihydros -4 (1H)-qualone derivative, its recycle 8 times after corresponding product calculated yield reduction amplitude be respectively less than
5%.In addition, though with the increase for recycling number of times, the high-efficient liquid phase color spectral purity of product decreases, but still greater than
98%.Therefore, highly acidity ionic-liquid catalyst of the invention is catalyzing and synthesizing (the 1H)-quinolinone of 2- aryl -2,3- dihydro -4
It can be recycled and can at least recycle 8 times during derivative, and its its catalytic activity is not obviously lowered.
Claims (10)
1. a kind of method of ionic liquid-catalyzed (the 1H)-qualone derivative of synthesis 2- aryl -2,3- dihydro -4 of highly acidity, it is special
Levy and be, this method is made using o-aminoacetophenone and aromatic aldehyde as reaction raw materials in the catalysis of highly acidity ionic-liquid catalyst
(the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4 is synthesized with getting off, the structural formula of the catalyst is：
2. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 1
The method of ketone derivatives, it is characterised in that：The synthesizer bag of (the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4
Material mixer, ultrasonic assistant reactor, Suction filtration device, wash mill and drying device are included, is reacted by ultrasonic assistant
Device carries out ultrasonic assistant reaction, the Suction filtration device, wash mill and drying device to the mixed material in material mixer
It is respectively used to carry out suction filtration, washing and drying process to reaction products therefrom.
3. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 2
The method of ketone derivatives, it is characterised in that：The material mixer uses the single-necked flask with condenser pipe, and described dries dress
Put and use vacuum drying chamber, temperature is 75 DEG C.
4. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 2
The method of ketone derivatives, it is characterised in that：Described synthesizer also includes ice-water bath cooling device, the ice-water bath cooling device
For carrying out cooling crystallization processing to reaction gained reaction system.
5. ionic liquid-catalyzed synthesis 2- aryl-2, the 3- dihydro of a kind of highly acidity according to any one of claim 1-4-
The method of 4 (1H)-qualone derivatives, it is characterised in that its building-up process is specific as follows：By reaction raw materials o-aminoacetophenone
It is added separately in material mixer, is sufficiently mixed uniformly with reaction dissolvent, then in ultrasonic amplitude with aromatic aldehyde and catalyst
Lower carry out heating reflux reaction is penetrated, the reaction time is 1.0~3.5h, and reaction is cooled to room temperature and separates out a large amount of solids after terminating, so
Material mixer is placed in ice-water bath cooling device afterwards and continues to cool down, the solid of precipitation is pulverized when amount of solid is not further added by, it is quiet
Put, suction filtration, gained filter residue is scrubbed, obtain (the 1H)-qualone derivative of 2- aryl -2,3- dihydro -4 after vacuum drying.
6. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 5
The method of ketone derivatives, it is characterised in that：The mol ratio of the o-aminoacetophenone and aromatic aldehyde is 1：1, the catalyst
Mole is the 8~12% of aromatic aldehyde mole used.
7. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 5
The method of ketone derivatives, it is characterised in that：Described aromatic aldehyde be benzaldehyde, 4-chloro-benzaldehyde, parahydroxyben-zaldehyde, to fluorobenzene
Formaldehyde, P-methoxybenzal-dehyde, p-tolyl aldehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, m chlorobenzaldehyde, a nitro
Any of benzaldehyde, o-bromobenzaldehye, o-tolualdehyde and salicylaldhyde.
8. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 5
The method of ketone derivatives, it is characterised in that：Described reaction dissolvent uses ethanol water, and the volumetric concentration of ethanol water
For 94~97%.
9. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 8
The method of ketone derivatives, it is characterised in that：The volume that the reaction dissolvent ethanol water is counted using milliliter is aromatic aldehyde with milli
8~10 times of amount of the material of mole meter.
10. ionic liquid-catalyzed (the 1H)-quinoline of synthesis 2- aryl -2,3- dihydro -4 of a kind of highly acidity according to claim 9
The method of quinoline ketone derivatives, it is characterised in that：Described cleaning solution uses absolute ethyl alcohol.
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