CN107216280A - A kind of chalcone of carbazolyl-containing and ethyl acetoacetate Micheal addition compound products and preparation method thereof - Google Patents
A kind of chalcone of carbazolyl-containing and ethyl acetoacetate Micheal addition compound products and preparation method thereof Download PDFInfo
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- CN107216280A CN107216280A CN201710198072.5A CN201710198072A CN107216280A CN 107216280 A CN107216280 A CN 107216280A CN 201710198072 A CN201710198072 A CN 201710198072A CN 107216280 A CN107216280 A CN 107216280A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention discloses a kind of chalcone of carbazolyl-containing and ethyl acetoacetate Micheal addition compound products and preparation method thereof, its structural formula is：
Description
Technical field
The invention belongs to the field of chemical synthesis, the chalcone and ethyl acetoacetate of more particularly to a kind of carbazolyl-containing
Micheal addition compound products and preparation method thereof.
Background technology
Carbazole is a kind of important heterocyclic compound, and carbazole ring easily forms metastable cation, many natural
The medicine of carbazole-containing compound core texture is found in plant extensively, its bioactivity and pharmaceutical interest cause vast chemical work
The research interest of author.Its conjugated system contained is larger and the strong electro transfer of intramolecular, the electron donation and sky having
Cave transmittability is stronger, and heat endurance and photochemical stability it is higher；Its derivative is in photoelectric material, dyestuff, medicine, oversubscription
The fields such as sub- identification, chemical sensitisation have potential extensive use.What is more important carbazole compound easily carries out functional group
Structural modification, its 3,6 and 9 are easily introduced, and cause carbazole spin-off to have many unique performances and bioactivity, and
There is very strong absorption in ultraviolet light range, and band gap, in 3.2eV or so and the characteristic such as blue light-emitting, its raw material is readily obtained.Carbazole
It is that two double bonds of pyrroles are replaced by phenyl ring, the chemical constitution containing pyrroles, the compound of the property with biphenyl and diphenylamines,
To heat, alkali and it is cold all stablize.Except incident electrophilic substitution reaction on carbazole phenyl ring, the generable reaction of imino group of carbazole
There are acylated, alkylation and nitrosation etc..Nitrogen azole compounds because medicine (antibacterial, anticancer, the agent of resistance amine, anti-oxidant, anti-inflammatory,
Nerve suppresses etc.), dyestuff, the multi-field wide application prospect such as material enjoy the favor of researcher always.As can be seen here, click
The research of azole compounds turns into most attractive goal in research.
1,3- diphenylprop ketenes, which is called, does chalcone, it be by aromatic aldehyde ketone by condensation formed, it have anti-inflammatory,
Antibacterial, effect of weeding, are also the important intermediate for synthesizing flavone compound, therefore extensively should in medicine and household chemicals field
With.From the point of view of structure, chalcone is two beta-unsaturated carbonyl compounds for being terminated with aromatic ring, the changeable substitution form of two ends aromatic radical
Give chalcone compound multifarious feature.Wherein, there is 1 in the ketenes fragment of chalcone and 3 two nucleophilic sites are
It occurs 1,4 additions and laid a good foundation.Some chalcones can open carbon-carbon double bond therein to send out under appropriate catalytic condition
Raw a series of addition reaction, such as Micheal addition reactions, therefore, application prospect of the chalcone in organic synthesis is very
Extensively.
Micheal addition reactions be it is a kind of carbon is born example or nitrogen bears example as nucleopilic reagent, and attack carbon-carbon double bond
Conjugated system so as to occurring Isosorbide-5-Nitrae conjugate addition reaction, be a kind of important to constitute carbon-carbon double bond in Synthetic Organic Chemistry
One of method, is also the problem that scientists are keen to research all the time therefore.The purpose of Michael addition reaction is to add
Long carbon chain length, generation carbon-carbon bond and carbon-nitrogen bond, are also the important channel for synthesizing miscellaneous nitrogen Michael addition reaction.Michael
The advantage of addition reaction is that accessory substance is few, zero-emission, meets the appealing of national green synthesis, because its unique structure is special
Point, as the important intermediate of organic synthesis field, while having the effect such as antibacterial, anti-inflammatory, weeding, its scientific value and grinds
Study carefully meaning extremely important.Relevant report at present on the Michael addition compound products of carbazolyl-containing is considerably less, and is mostly to use
Highly basic makees catalyst, and the easy etching apparatus of highly basic causes added cost.
The content of the invention
It is an object of the invention to provide a kind of chalcone of carbazolyl-containing and ethyl acetoacetate Micheal addition compound products
And preparation method thereof, the specific name of the addition compound product is 1- (3-N- substitutions-carbazyl) -3- aryl -3- (1- acetyl group -1-
Group-4 ethyl formate-methine)-acetone, this method is simple to operate, reaction condition is gentle, obtained product have sterilization, it is antibacterial,
The effects such as weeding.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of chalcone of carbazolyl-containing and ethyl acetoacetate Micheal addition compound products, its general structure are as follows：
Wherein, Ar is phenyl, halogenophenyl, aminomethyl phenyl, methoxyphenyl, nitrobenzophenone, hydroxy phenyl, aminobenzene
Base, ethenylphenyl or quinary heterocyclic radical；
R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, benzene Oxymethylene, sub- to chlorobenzene oxygen
Methyl, adjacent chlorobenzene Oxymethylene, 2,4 dichloro benzene Oxymethylene, a chlorobenzene Oxymethylene, to fluorobenzene Oxymethylene, to bromobenzene oxygen
Methylene, to iodobenzene Oxymethylene, to methoxybenzene Oxymethylene, 2- nitrobenzene Oxymethylene, benzene oxygen ethyl, alpha-naphthoxy methylene
Base, β-naphthalene Oxymethylene or β-naphthalene oxygen ethyl.
The halogenophenyl is o-fluorophenyl, p-fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, bromophenyl
Base, m-bromophenyl or p-bromophenyl；
Described aminomethyl phenyl is o-methyl-phenyl, an aminomethyl phenyl or p-methylphenyl；
Described methoxyphenyl is m-methoxyphenyl or p-methoxyphenyl；
Described nitrobenzophenone is m-nitro base, 3,5- dinitrophenyls or p-nitrophenyl；
Described hydroxy phenyl is o-hydroxy-phenyl or p-hydroxybenzene；
Described aminophenyl is o-aminophenyl, m-aminophenyl base or p-aminophenyl；
Described quinary heterocyclic radical is furyl or thienyl.
The chalcone of described carbazolyl-containing and the preparation method of ethyl acetoacetate Micheal addition compound products, including with
Lower step：
Step 1) by A mol 1- (3-N- replaces-carbazyl) -3- aryl-propenone, B mol base catalysts, C mol
Ethyl acetoacetate and solvent absolute ethyl alcohol are added in reaction vessel, carry out heating reflux reaction, wherein A:B:C=1:(5~
6):(5~6)；
Step 2) after completion of the reaction, reaction solution is cooled to room temperature, 0~5 DEG C of cold water is added, there is solid precipitation, to analysis
The solid gone out is washed, suction filtration, filter cake recrystallization, is then dried, that is, obtains the chalcone and acetyl second of carbazolyl-containing
Acetoacetic ester Micheal addition compound products.
The preparation method of 1- (3-N- substitutions-the carbazyl) -3- aryl-propenone is：With acetyl group carbazole, aromatic aldehyde
For raw material, with NaOH/K2CO3Reaction is ground for catalyst, washes repeatedly after completion of the reaction, be dried to obtain crude product, crude product warp
Silica gel column chromatography carries out separating-purifying, that is, obtains 1- (3-N- substitutions-carbazyl) -3- aryl-propenone.
The reaction temperature being heated to reflux is 70~80 DEG C, and the reaction time is 1~2h.
During the heating reflux reaction with TLC monitor reaction process, when 1- (3-N- substitutions-carbazyl) -3- aryl -
The raw material point of propenone represents that raw material reaction is complete when disappearing；Wherein TLC solvent is that volume ratio is 1:3 ethyl acetate with
The mixed solvent of petroleum ether.
The step 1) middle addition D mL absolute ethyl alcohols, A:D=1:(20000~30000).
Reaction system is stirred with 60~80rad/min speed during the heating reflux reaction.
The base catalyst is granular solid NaOH.
The step 2) in washing, suction filtration are repeated to the solid of precipitation, until the pH value of filtrate is in neutrality, Ran Houyong
Absolute ethyl alcohol is recrystallized to filter cake, then dry 20~30h at 20~30 DEG C.
Relative to prior art, beneficial effects of the present invention are：
The present invention explores carbazyl Michael addition compound products and preparation method containing new substituted radical, and optimizes
Experiment condition, shortens the reaction time, is that green syt is made that contribution.The chalcone for the carbazolyl-containing that the present invention is provided with
Ethyl acetoacetate Micheal addition compound products, i.e. 1- (3-N- substitutions-carbazyl) -3- aryl -3- (1- acetyl group -1- formic acid second
Ester group-methine)-acetone is a series of brand-new ketone compounds, the effects such as with sterilization, antibacterial, weeding, available for curing
The field such as medicine field and household chemicals field.
The chalcone for the carbazolyl-containing that the present invention is provided and the preparation method of ethyl acetoacetate Micheal addition compound products,
1- (3-N- replaces-carbazyl) -3- aryl-propenone, base catalyst, ethyl acetoacetate and solvent absolute ethyl alcohol are added
Heating reflux reaction in reaction vessel, is post-processed to reaction product and obtains target product.Compared with prior synthesizing method,
Substantially, course of reaction is simple, and simple to operate, the reaction time is short for the reacting phenomenon of the present invention, and reaction condition is gentle, under water-bath
Reacted, equipment requirement is low, and the post processing of this method is simple, accessory substance is few, and the yield of product is high (up to 85%).Overcome
Prior synthesizing method equipment requirement is high, the shortcomings of reaction time is long, have the advantages that it is economical, conveniently, efficiently, green.
Further, the present invention uses TLC monitoring reaction courses, solvent used is that volume ratio is in preparation process
1:3 ethyl acetate and petroleum ether, monitoring is accurate, beneficial to control extent of reaction and end.Catalyst used in simultaneously of the invention
For granular solid NaOH, cheap and easy to get, catalytic effect is good, makes reaction more rapid and complete, and post processing is simple.
Brief description of the drawings
Fig. 1 is the infared spectrum of product made from embodiment 1；
Fig. 2 is the infared spectrum of product made from embodiment 2；
Fig. 3 is product made from embodiment 51HNMR collection of illustrative plates；
Fig. 4 is product made from embodiment 31HNMR collection of illustrative plates.
Embodiment
The chalcone for the carbazolyl-containing that the present invention is provided and the reaction equation of ethyl acetoacetate Micheal addition compound products
It is as follows：
Wherein Ar be aryl, specially phenyl, rubigan, p-bromophenyl, p-fluorophenyl, p-methylphenyl, to methoxy
Base phenyl, m-nitro base, p-hydroxybenzene, o-hydroxy-phenyl, ethenylphenyl, o-methyl-phenyl, an aminomethyl phenyl, a first
Phenyl, 2- fluorophenyls, p-aminophenyl, m-aminophenyl base, o-aminophenyl, Chloro-O-Phenyl, 2,4 dichloro benzene base, to nitre
Base phenyl, 3,5- dinitrophenyls, o-bromophenyl, m-bromophenyl, furyl or thienyl.
R is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, benzene Oxymethylene, sub- to chlorobenzene oxygen
Methyl, adjacent chlorobenzene Oxymethylene, 2,4 dichloro benzene Oxymethylene, a chlorobenzene Oxymethylene, to fluorobenzene Oxymethylene, to bromobenzene oxygen
Methylene, to iodobenzene Oxymethylene, to methoxybenzene Oxymethylene, 2- nitrobenzene Oxymethylene, benzene oxygen ethyl, alpha-naphthoxy methylene
Base, β-naphthalene Oxymethylene or β-naphthalene oxygen ethyl.
The present invention is described in further details below in conjunction with preferred embodiments of the present invention.
Embodiment 1
0.006mol ethyl acetoacetates, 0.006mol NaOH (solid, granular), 30mL are weighed with weighing balance anhydrous
Ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After uniform, 0.001mol 1- (3-N- Ethy-Carbazoles base) -3- phenyl-acryloyl ketone is added, stirs and is to slowly warm up to 80
DEG C, make its 80 DEG C temperature and 70rad/min mixing speeds under back flow reaction 80min, supervised during reaction with thin-layer chromatography
Reaction process is surveyed, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop anti-
Should, reaction system is slowly decreased to room temperature, add 3 DEG C of cold water of 30mL, stand, have solid precipitation, suction filtration, filter cake is washed repeatedly
Recrystallized after to neutrality with absolute ethyl alcohol, Rotary Evaporators boil off solvent, then in 25 DEG C of dry 25h, obtain dark red solid, i.e.,
For 1- (3-N- Ethy-Carbazoles base) -3- phenyl -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.m.p.107℃-
110℃。
IR (KBr, ν/cm-1):2933,1371,2866,1432,1705,1672,1549,1315,801,706；
As seen from Figure 1,2933,1371cm-1For-CH3Stretching vibration absworption peak and flexural vibrations peak, 2866,1432cm-1
For-CH2Stretching vibration absworption peak and flexural vibrations peak, 1705,1672cm-1For C=O stretching vibration peak, 1315cm-1For N-
R2Stretching vibration peak, 801,706 be phenyl ring substituting group position characteristic peak, 1549 be phenyl ring skeletal vibration Absorption Characteristics
Peak.
1HNMR:1.21-1.25(t,3H,CH3),1.46-1.49(t,3H,CH3),2.23(d,2H,COCH2-),3.31
(d,1H,-CH),3.56-3.87(q,2H,N-CH2-),4.02-4.25(q,1H,-CH),4.33-4.46(q,2H,-COOCH2),
7.25-7.63(m,8H,Ph-H),8.21-8.32(m,3H,Ph-H).
Embodiment 2
Weigh 0.006mol ethyl acetoacetates with weighing balance, 0.006mol NaOH (solid, granular), 30mL is anhydrous
Ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After uniform, 0.001mol 1- (3-N- Ethy-Carbazoles base) -3- (rubigan)-propenone is added, stirs and slowly heats up
To 80 DEG C, make its 80 DEG C temperature and 70rad/min mixing speeds under back flow reaction 80min, thin layer color is used during reaction
Spectrum monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Reaction, makes reaction system be slowly decreased to room temperature, adds 3 DEG C of cold water of 30mL, stands, and has a solid precipitation, suction filtration, filter cake water repeatedly
It is washed till after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 25 DEG C of dry 25h, obtain dark red solid,
As 1- (3-N- Ethy-Carbazoles base) -3- (rubigan) -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
m.p.113℃-115℃。
IR (KBr, ν/cm-1)：2979,1371,2898,1432,1739,1672,1560,1326,807,757；
From Figure 2 it can be seen that 2979,1371cm-1For-CH3Stretching vibration absworption peak and flexural vibrations peak, 2898,1432cm-1
For-CH2Stretching vibration absworption peak and flexural vibrations peak, 1739,1672cm-1For C=O stretching vibration peak, 1326cm-1For N-
R2Stretching vibration peak, 807,757 be phenyl ring substituting group position characteristic peak, 1560 be phenyl ring skeletal vibration Absorption Characteristics
Peak.
1HNMR:1.03-1.14(t,3H,CH3),1.34-1.42(t,3H,CH3),2.51(d,2H,COCH2-),3.26
(d,1H,-CH),3.42-3.65(q,2H,N-CH2-),4.07-4.33(q,1H,-CH),4.56-4.72(q,2H,-COOCH2),
7.31-7.59(m,8H,Ph-H),8.02-8.27(m,3H,Ph-H).
Embodiment 3
Weigh 0.006mol ethyl acetoacetates with weighing balance, 0.006mol NaOH (solid, granular), 30mL is anhydrous
Ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After uniform, 0.001mol 1- (3-N- Ethy-Carbazoles base) -3- (p-bromophenyl)-propenone is added, stirs and slowly heats up
To 80 DEG C, make its 80 DEG C temperature and 70rad/min mixing speeds under back flow reaction 80min, thin layer color is used during reaction
Spectrum monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Reaction, makes reaction system be slowly decreased to room temperature, adds 3 DEG C of cold water of 30mL, stands, and has a solid precipitation, suction filtration, filter cake water repeatedly
It is washed till after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 25 DEG C of dry 25h, obtain dark red solid,
As 1- (3-N- Ethy-Carbazoles base) -3- (p-bromophenyl) -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
m.p.118℃-120℃。
IR (KBr, ν/cm-1)：2986,1382,2856,1453,1701,1610,1535,1316,802,756；
1HNMR:1.11-1.14(t,3H,CH3),1.44-1.47(t,3H,CH3),2.19(d,2H,COCH2-),3.25
(d,1H,-CH),3.74-3.83(q,2H,N-CH2-),4.09-4.14(q,1H,-CH),4.36-4.41(q,2H,-COOCH2),
7.42-7.53(m,8H,Ph-H),8.10-8.19(m,3H,Ph-H).
From fig. 4, it can be seen that 1.11-1.14ppm is the proton peak of methyl on group-4 ethyl formate, the group adjacent with it is methylene
Base, therefore be triplet, integration shows three H；1.44-1.47ppm is the methyl on connected alkyl on N atoms in carbazole structure
Proton peak, is triplet, and integration shows three H；It is doublet at 2.19ppm, is COCH2- on methene proton peak, integration
It is shown as 2 H；Go out doublet at 3.25ppm, integral area is shown as 1 H, is-CH proton peak；3.74-3.83ppm place
It is 4 heavy peaks for the proton peak of carbazole structure methylene, integral area shows 2 H；4.36-4.41ppm place is 4 heavy peaks, show
That show is-COOCH2The proton peak of structure methylene；It is multiplet at 7.42-7.53ppm and at 8.10-8.19ppm, represents
Be in structure proton sum for 11 two phenyl ring proton peak.
Embodiment 4
Weigh 0.006mol ethyl acetoacetates with weighing balance, 0.006mol NaOH (solid, granular), 30mL is anhydrous
Ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After uniform, 0.001mol 1- (3-N- Ethy-Carbazoles base) -3- (p-fluorophenyl)-propenone is added, stirs and slowly heats up
To 80 DEG C, make its 80 DEG C temperature and 70rad/min mixing speeds under back flow reaction 80min, thin layer color is used during reaction
Spectrum monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Reaction, makes reaction system be slowly decreased to room temperature, adds 1 DEG C of cold water of 30mL, stands, and has a solid precipitation, suction filtration, filter cake water repeatedly
It is washed till after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 25 DEG C of dry 25h, obtain light tan solid,
As 1- (3-N- Ethy-Carbazoles base) -3- (p-fluorophenyl) -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
m.p.113℃-115℃。
IR (KBr, ν/cm-1)：2995,1374,2837,1455,1721,1608,1523,1321,812,747；
1HNMR:1.32-1.54(t,3H,CH2CH3),1.43-1.72(t,3H,CH2CH3),4.29-4.37(m,1H,-
CH),3.59-3.81(q,2H,N-CH2),2.14(s,3H,-COCH3),3.86-4.05(q,2H,-COOCH2),2.61-2.73
(d,2H,-COCH2-),8.53-8.69(m,3H,Ph-H),7.74-7.93(m,4H,Ph-H),7.25-7.48(m,4H,Ph-
H).
Embodiment 5
Weigh 0.006mol ethyl acetoacetates with weighing balance, 0.006mol NaOH (solid, granular), 30mL is anhydrous
Ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After uniform, 0.001mol 1- (3-N- Ethy-Carbazoles base) -3- (p-nitrophenyl)-propenone is added, stirs and slowly rises
Temperature to 80 DEG C, make its 80 DEG C temperature and 70rad/min mixing speeds under back flow reaction 80min, use thin layer during reaction
Chromatogram monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Only react, reaction system is slowly decreased to room temperature, add 3 DEG C of cold water of 30mL, stand, there is a solid precipitation, suction filtration, filter cake is repeatedly
It is washed to after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 25 DEG C of dry 25h, obtain brown solid,
As 1- (3-N- Ethy-Carbazoles base) -3- (p-nitrophenyl) -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
m.p.124℃-125℃。
IR (KBr, ν/cm-1)：2986,1382,2856,1453,1701,1610,1535,1316,802,756；
1HNMR:1.46-1.48(t,3H,CH2CH3),1.50-1.53(t,3H,CH2CH3),4.39-4.46(m,1H,-
CH),3.74-3.95(q,2H,N-CH2),2.07(s,3H,-COCH3),3.95-4.11(q,2H,-COOCH2),2.75-2.86
(d,2H,-COCH2-),8.79-8.99(m,3H,Ph-H),7.86-7.91(m,4H,Ph-H),7.45-7.52(m,4H,Ph-
H) is as shown in Figure 3.
Embodiment 6
0.005mol ethyl acetoacetates, 0.005mol NaOH (solid, granular), 20mL are weighed with weighing balance anhydrous
Ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After uniform, 0.001mol 1- (3-N- methyl-carbazolyl groups) -3- p-methylphenyls-propenone is added, stirs and slowly heats up
To 70 DEG C, make its 70 DEG C temperature and 60rad/min mixing speeds under back flow reaction 120min, thin layer color is used during reaction
Spectrum monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Reaction, makes reaction system be slowly decreased to room temperature, adds 0 DEG C of cold water of 30mL, stands, and has a solid precipitation, suction filtration, filter cake water repeatedly
It is washed till after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 20 DEG C of dry 30h, that is, obtain 1- (3-N- first
Base-carbazyl) -3- p-methylphenyls -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
Embodiment 7
Weighed with weighing balance 0.0055mol ethyl acetoacetates, 0.0055mol NaOH (solid, granular), 25mL without
Water-ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After closing uniformly, 0.001mol 1- (3-N- propyl group-carbazyl) -3- p-hydroxybenzenes-propenone are added, stirs and simultaneously slowly rises
Temperature to 75 DEG C, make its 75 DEG C temperature and 80rad/min mixing speeds under back flow reaction 60min, use thin layer during reaction
Chromatogram monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Only react, reaction system is slowly decreased to room temperature, add 5 DEG C of cold water of 30mL, stand, there is a solid precipitation, suction filtration, filter cake is repeatedly
It is washed to after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 30 DEG C of dry 20h, that is, obtain 1- (3-N-
Propyl group-carbazyl) -3- p-hydroxybenzenes -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
Embodiment 8
Weighed with weighing balance 0.0052mol ethyl acetoacetates, 0.0052mol NaOH (solid, granular), 22mL without
Water-ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After closing uniformly, 0.001mol 1- (3-N- butyl-carbazyl) -3- p-amino phenyl- propenone is added, stirs and simultaneously slowly rises
Temperature to 72 DEG C, make its 72 DEG C temperature and 65rad/min mixing speeds under back flow reaction 100min, use thin layer during reaction
Chromatogram monitoring reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely, stop
Only react, reaction system is slowly decreased to room temperature, add 2 DEG C of cold water of 30mL, stand, there is a solid precipitation, suction filtration, filter cake is repeatedly
It is washed to after neutrality and is recrystallized with absolute ethyl alcohol, Rotary Evaporators boils off solvent, then in 22 DEG C of dry 28h, that is, obtain 1- (3-N-
Butyl-carbazyl) -3- p-amino phenyl-s 3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
Embodiment 9
Weighed with weighing balance 0.0058mol ethyl acetoacetates, 0.0058mol NaOH (solid, granular), 28mL without
Water-ethanol is added in the dry there-necked flask equipped with condensing reflux pipe and agitating device, makes it that 5min is stirred at room temperature, and is mixed
After closing uniformly, 0.001mol 1- (3-N- amyl groups-carbazyl) -3- p-methoxyphenyls-propenone are added, stir simultaneously slow
Be warming up to 78 DEG C, make its 78 DEG C temperature and 75rad/min mixing speeds under back flow reaction 90min, with thin during reaction
Layer chromatography monitors reaction process, is V (ethyl acetate) from volume ratio：V (petroleum ether)=1:3 solvent.After reaction completely,
Stop reaction, reaction system is slowly decreased to room temperature, add 4 DEG C of cold water of 30mL, stand, have solid precipitation, suction filtration, filter cake is anti-
Rehydration is washed till after neutrality to be recrystallized with absolute ethyl alcohol, and Rotary Evaporators boil off solvent, then in 28 DEG C of dry 22h, that is, obtain 1- (3-
N- amyl groups-carbazyl) -3- p-methoxyphenyls -3- (1- acetyl group -1- group-4 ethyl formates-methine)-acetone.
In addition to the implementation, raw material 1- (3-N- substitutions-carbazyl) -3- aryl-propenone can also use following material,
Wherein substituent be hexyl, heptyl, octyl group, nonyl, benzene Oxymethylene, to chlorobenzene Oxymethylene, adjacent chlorobenzene Oxymethylene, 2,4-
Dichlorophenoxy methylene, a chlorobenzene Oxymethylene, to fluorobenzene Oxymethylene, to bromobenzene Oxymethylene, to iodobenzene Oxymethylene, right
Methoxybenzene Oxymethylene, 2- nitrobenzene Oxymethylene, benzene oxygen ethyl, alpha-naphthoxy methylene, β-naphthalene Oxymethylene or β-naphthalene oxygen
Ethyl；Aryl is m-nitro base, o-hydroxy-phenyl, ethenylphenyl, o-methyl-phenyl, an aminomethyl phenyl, meta-methoxy benzene
Base, 2- fluorophenyls, m-aminophenyl base, o-aminophenyl, Chloro-O-Phenyl, 2,4 dichloro benzene base, 3,5- dinitrophenyls, bromophenyl
Base, m-bromophenyl, furyl or thienyl；It is numerous to list herein.
In addition, 1- (3-N- substitutions-carbazyl) -3- aryl-propenone in the present invention can be prepared using following methods：
1) N- substitutions-carbazole is prepared by raw material of acetyl group carbazole；
2) replaced using N--carbazole prepares 3- acetyl group-N- substitutions-carbazole as raw material；
3) using 3- acetyl group-N- substitutions-carbazole and aromatic aldehyde as raw material, with NaOH/K2CO3It is ground instead for catalyst
Should, wash repeatedly after completion of the reaction, be dried to obtain crude product, crude product carries out separating-purifying through silica gel column chromatography, that is, obtains 1- (3-
N- substitutions-carbazyl) -3- aryl-propenone.
The present invention explores carbazyl Michael addition compound products and preparation method containing new substituted radical, and optimizes
Experiment condition, shortens the reaction time, is that green syt is made that contribution.The chalcone for the carbazolyl-containing that the present invention is provided with
Ethyl acetoacetate Micheal addition compound products, i.e. 1- (3-N- substitutions-carbazyl) -3- aryl -3- (1- acetyl group -1- formic acid second
Ester group-methine)-acetone is a series of brand-new ketone compounds, the effects such as with sterilization, antibacterial, weeding, available for curing
The field such as medicine field and household chemicals field.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent structure transformation that technical spirit is made to above example, still fall within skill of the present invention
In the protection domain of art scheme.
Claims (10)
1. a kind of chalcone of carbazolyl-containing and ethyl acetoacetate Micheal addition compound products, it is characterised in that：Its general structure
It is as follows：
Wherein, Ar is phenyl, halogenophenyl, aminomethyl phenyl, methoxyphenyl, nitrobenzophenone, hydroxy phenyl, aminophenyl, second
Alkenyl phenyl or quinary heterocyclic radical；
R be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, benzene Oxymethylene, to chlorobenzene oxygen methylene
Base, adjacent chlorobenzene Oxymethylene, 2,4 dichloro benzene Oxymethylene, a chlorobenzene Oxymethylene, to fluorobenzene Oxymethylene, it is sub- to bromobenzene oxygen
Methyl, to iodobenzene Oxymethylene, to methoxybenzene Oxymethylene, 2- nitrobenzene Oxymethylene, benzene oxygen ethyl, alpha-naphthoxy methylene
Base, β-naphthalene Oxymethylene or β-naphthalene oxygen ethyl.
2. the chalcone of carbazolyl-containing according to claim 1 and ethyl acetoacetate Micheal addition compound products, its feature
It is：The halogenophenyl be o-fluorophenyl, p-fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl,
M-bromophenyl or p-bromophenyl；
Described aminomethyl phenyl is o-methyl-phenyl, an aminomethyl phenyl or p-methylphenyl；
Described methoxyphenyl is m-methoxyphenyl or p-methoxyphenyl；
Described nitrobenzophenone is m-nitro base, 3,5- dinitrophenyls or p-nitrophenyl；
Described hydroxy phenyl is o-hydroxy-phenyl or p-hydroxybenzene；
Described aminophenyl is o-aminophenyl, m-aminophenyl base or p-aminophenyl；
Described quinary heterocyclic radical is furyl or thienyl.
3. the preparation side of the chalcone of the carbazolyl-containing described in claim 1 or 2 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：Comprise the following steps：
Step 1) by Amol 1- (3-N- replaces-carbazyl) -3- aryl-propenone, B mol base catalysts, C mol acetyl
Ethyl acetate and solvent absolute ethyl alcohol are added in reaction vessel, carry out heating reflux reaction, wherein A:B:C=1:(5~6):(5
~6)；
Step 2) after completion of the reaction, reaction solution is cooled to room temperature, 0~5 DEG C of cold water is added, has solid precipitation, to precipitation
Solid is washed, suction filtration, filter cake recrystallization, is then dried, that is, obtains the chalcone and acetoacetate second of carbazolyl-containing
Ester Micheal addition compound products.
4. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：The preparation method of 1- (3-N- substitutions-the carbazyl) -3- aryl-propenone is：With acetyl group click
Azoles, aromatic aldehyde are raw material, with NaOH/K2CO3Reaction is ground for catalyst, washes, be dried to obtain slightly repeatedly after completion of the reaction
Product, crude product carries out separating-purifying through silica gel column chromatography, that is, obtains 1- (3-N- substitutions-carbazyl) -3- aryl-propenone.
5. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：The reaction temperature being heated to reflux is 70~80 DEG C, and the reaction time is 1~2h.
6. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：Reaction process is monitored with TLC during the heating reflux reaction, when 1- (3-N- substitutions-carbazole
Base) raw material point of -3- aryl-propenone represents that raw material reaction is complete when disappearing；Wherein TLC solvent is that volume ratio is 1:3
Ethyl acetate and petroleum ether mixed solvent.
7. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：The step 1) middle addition D mL absolute ethyl alcohols, A:D=1:(20000~30000).
8. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：Reaction system is stirred with 60~80rad/min speed during the heating reflux reaction
Mix.
9. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：The base catalyst is granular solid NaOH.
10. the preparation of the chalcone of carbazolyl-containing according to claim 3 and ethyl acetoacetate Micheal addition compound products
Method, it is characterised in that：The step 2) in washing, suction filtration are repeated to the solid of precipitation, in the pH value of filtrate is in
Property, then filter cake is recrystallized with absolute ethyl alcohol, then dry 20~30h at 20~30 DEG C.
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| CN109232485A (en) * | 2018-11-07 | 2019-01-18 | 陕西科技大学 | One kind chalcone derivative containing pyrenyl and preparation method thereof |
| CN111978167A (en) * | 2020-07-22 | 2020-11-24 | 广东石油化工学院 | One-step synthesis method of polysubstituted cyclohex-2-enone |
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2017
- 2017-03-29 CN CN201710198072.5A patent/CN107216280A/en active Pending
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109232485A (en) * | 2018-11-07 | 2019-01-18 | 陕西科技大学 | One kind chalcone derivative containing pyrenyl and preparation method thereof |
| CN111978167A (en) * | 2020-07-22 | 2020-11-24 | 广东石油化工学院 | One-step synthesis method of polysubstituted cyclohex-2-enone |
| CN111978167B (en) * | 2020-07-22 | 2021-03-23 | 广东石油化工学院 | One-step synthesis method of polysubstituted cyclohex-2-enone |
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