CN106345521A - 5-arylidenebarbituric acid derivative and preparation method thereof by simple catalysis - Google Patents
5-arylidenebarbituric acid derivative and preparation method thereof by simple catalysis Download PDFInfo
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- CN106345521A CN106345521A CN201610614749.4A CN201610614749A CN106345521A CN 106345521 A CN106345521 A CN 106345521A CN 201610614749 A CN201610614749 A CN 201610614749A CN 106345521 A CN106345521 A CN 106345521A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/60—Three or more oxygen or sulfur atoms
- C07D239/62—Barbituric acids
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- C07—ORGANIC CHEMISTRY
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/60—Three or more oxygen or sulfur atoms
- C07D239/66—Thiobarbituric acids
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Abstract
The invention discloses a 5-arylidenebarbituric acid derivative, a preparation method thereof by simple catalysis and a catalyst prepared from the 5-arylidenebarbituric acid derivative and belongs to the technical field of ionic liquid catalysis. The preparation method includes performing refluxing reaction for 1-5 minutes at an atmospheric pressure, wherein the molar ratio of aromatic aldehyde to barbituric acid or thiobarbituric acid is 1.0-1.2:1, the molar weight of an acidic ionic liquid catalyst accounts for 1.5-2% of that of the aromatic aldehyde, and the volume dose of a reaction solvent, namely an ethanol water solution (calculated by milliliter) is 7-10 times of the molar weight of the aromatic aldehyde (calculated by millimole); cooling to the room temperature after reaction is completed, conducting suction filtration, and washing filter residues prior to vacuum drying so as to obtain the 5-arylidenebarbituric acid derivative. Compared with preparation methods with other catalysts, the preparation method has the advantages of little catalyst consumption, recyclability, reusability without treatment, high raw material utilization rate, simplicity and convenience in operation of the whole preparation process and the like, thereby being convenient for large-scale industrialized application.
Description
Technical field
The invention belongs to ionic liquid-catalyzed technical field, more particularly, it relates to a kind of 5- arlydene barbituratess spread out
Biology, the Simple Catalytic preparation method of this derivant and its catalyst for preparing.
Background technology
Barbituric acid derivatives are the compounds of the highly important azepine ring structure with physiologically active of a class, wherein,
5- arlydene barbituric acid derivatives are synthetic drug and the important intermediate of other heterocyclic compound, and they are typically by fragrance
Aldehyde and barbituratess, in organic solvent or water, are prepared through knoevenagel condensation reaction.
The liquid that ionic liquid is made up of a kind of nitrogenous heterocyclic organic cation and a kind of inorganic or organic anion
Salt.In organic synthesiss, compared with traditional organic solvent, ionic liquid has that non-volatile, solvability is strong, nonflammable,
A features such as full ionic environment can be provided for reaction, ionic liquid has obtained extensively as solvent in organic synthesiss in recent years
General application.Such as Wang Chun etc. in the presence of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, using grinding at room temperature and
The method of microwave radiation, is prepared through knoevenagel condensation reaction by aromatic aldehyde and barbituratess or thiobarbituricacidα-
A series of 5- arlydene barbituratess or 5- Asia aryl thiobarbituricacidα- derivant.The method have reactivity high,
Response time is short and a little (the 5- arlydene bar that ionic liquid at room temperature promotes such as catalyst environmental friendliness, recyclable recycling
The ratio synthesis [j] of appropriate acid derivative, organic chemistry, 2006,26 (5): 723～726).But because above-mentioned ionic liquid has difficulty
Belong to neutral ion liquid, thus lead to whole preparation process green degree in biodegradable imidazoles circulus and in itself
Not high, and usage amount is larger.
In addition, acidic ion liquid as a kind of functionalized ion liquid due to there is preferable heat stability, distribution all
Even acidic site and easily and the preparation of 5- arlydene barbituric acid derivatives can be applied to the advantages of product separates and recovers
During.Such as farhad shirini etc. using the sulphuric acid hydrogenation salt acidic ionic liquid of succimide as catalyst,
The aromatic aldehyde containing different substituents can be effectively catalyzed in water and with barbituratess, the preparation of knoevenagel condensation reaction occurs
A series of 5- arlydene barbituric acid derivatives, the method has the features such as reaction yield is high, catalyst preparation is simple
(succinimidinium hydrogensulfate([h-suc]hso4)as an efficient ionic liquid
Catalyst for the synthesis of5-arylidenepyrimidine-2,4,6- (1h, 3h, 5h)-trione
And pyrano-pyrimidinones derivatives [j], journal of the iranian chemical
Society, 2016,13:457～463).But because the acidity of acidic ionic liquid catalysts used in above-mentioned reaction is relatively low, urge
Usage amount in preparation process for the agent is larger, and its mole dosage accounts for the 5% of aromatic aldehyde usage amount.
In order to improve the acidity of acidic ion liquid and then reduce its consumption, farhad shirini etc. is in water to contain
[dabco] (so of disulfonic acid root3h)2(cl)2Acidic ion liquid, as heterogeneous catalysis, can be catalyzed different virtues at 70 DEG C
Fragrant aldehyde and barbituratess react prepares a series of 5- arlydene barbituric acid derivatives, and catalyst mole dosage only accounts for virtue
Fragrant aldehyde usage amount 2.5% and 6 (bi-so can be recycled3h functionalized ionic liquid based
On dabco as a mild and efficient catalyst for the synthesis of 1,8-dioxo-
Octahydro-xanthene and5-arylmethylene-pyrimidine-2,4,6-trione derivatives [j],
Research on chemcial intermediates, 2015,41:8483～8497).Although above-mentioned synthetic method catalysis is received
Rate is of a relatively high, but whole process is more complicated, including the recrystallization to product 5- arlydene barbituric acid derivatives
Purification operations and acidic ion liquid recycle before dried, thus bringing, feedstock circulation utilization rate is relatively low, power consumption
Higher shortcoming, and then lead to the method to be difficult to by large-scale use in industrialized production；Additionally, in said method acidity is relatively
Low catalyst using still bringing higher usage amount, and recycle performance and also need to improve further.
Content of the invention
1. invent technical problem to be solved
It is an object of the invention to overcome utilizing presence of acidic ionic liquid catalyst to prepare 5- arlydene barbital in prior art
Have during acid derivative that ionic-liquid catalyst usage amount is larger, recycle before process cumbersome, raw material availability is low, produce
The deficiency of the shortcomings of thing purification process is complicated, and a kind of 5- arlydene barbituric acid derivatives, simply the urging of this derivant are provided
Change preparation method and its catalyst for preparing.During using method of the present invention preparation 5- arlydene barbituric acid derivatives, raw material
Utilization rate is higher, purification of products is easy, and the catalysis activity of catalyst is higher, usage amount is few and easy to use, is easy to extensive
Popularization and application.
2. technical scheme
For reaching above-mentioned purpose, the technical scheme that the present invention provides is:
First, a kind of 5- arlydene barbituric acid derivatives catalyst for preparing of the present invention, this catalyst be acid from
Sub- liquid catalyst, its structural formula is:
Second, a kind of Simple Catalytic preparation method of 5- arlydene barbituric acid derivatives of the present invention, the method be with
Aromatic aldehyde and barbituratess or thiobarbituricacidα- are reaction raw materials, close under the catalytic action of acidic ionic liquid catalysts
Become 5- arlydene barbituric acid derivatives, its chemical equation is:
The concretely comprising the following steps of the Simple Catalytic preparation method of above-mentioned 5- arlydene barbituric acid derivatives:
(1) weighing of reaction raw materials: by reaction raw materials aromatic aldehyde and barbituratess or thiobarbituricacidα- according to mol ratio
Carry out precise for 1.0～1.2:1；
(2) catalytic reaction: the reaction raw materials weighing up are added in ethanol water, after fully dissolving and stirring
Continue to be added thereto to acidic ionic liquid catalysts, the mole of this catalyst be aromatic aldehyde mole used 1.5～
2%, then make reaction raw materials that back flow reaction occurs under stirring condition, obtain solid precipitate；Above-mentioned reaction in terms of milliliter
The volume of etoh solvent aqueous solution be by mM in terms of 7～10 times of aromatic aldehyde mole, and reaction pressure be one big
Air pressure, reflux time is 1～5min；
(3) product separates: reaction is cooled to room temperature after terminating, and the solid obtaining precipitate is cooled to after room temperature and first carries out
Pulverize, then carry out standing, sucking filtration operation, its filtering residue is scrubbed, obtain the 5- arlydene bar ratio of the present invention after vacuum drying
Appropriate acid derivative.
Further, the structural formula of described acidic ionic liquid catalysts is:
Further, described aromatic aldehyde be benzaldehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, paranitrobenzaldehyde,
Nitrobenzaldehyde, 1-Formyl-2-nitrobenzene, hydroxy benzaldehyde, salicylaldhyde, P-methoxybenzal-dehyde, O-methoxy benzene first
Any one in aldehyde.
Further, in described step (2), the concentration of volume percent of ethanol contained by ethanol water is 88～91%.
Further, in described step (2), the concentration of volume percent of ethanol contained by ethanol water is 90%.
Further, using the ethanol water that concentration of volume percent is 90%, filtering residue is entered in described step (3)
Row washing.
Further, the acidic ionic liquid catalysts containing in the filtrate after step (3) sucking filtration can not be treated
Reuse at least 7 times.
Third, a kind of 5- arlydene barbituric acid derivatives of the present invention, this derivant is the preparation side by the present invention
Method preparation, its structural formula is:
3. beneficial effect
The technical scheme being provided using the present invention, compared with prior art, has a following remarkable result:
(1) the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives of the present invention, be with aromatic aldehyde and
Barbituratess or thiobarbituricacidα- are reaction raw materials, the sub- virtue of synthesis 5- under the catalytic action of acidic ionic liquid catalysts
Base barbituric acid derivatives, inventor is by the acidic ionic liquid of a large amount of theory analysises and the experimentation final choice present invention
Body catalyst is higher to synthesize 5- arlydene barbituric acid derivatives, the catalysis activity of catalyst, urges such that it is able to significantly improve
Change efficiency, the response time substantially shortens, and the usage amount of catalyst is relatively fewer；Additionally, above-mentioned catalyst can not be treated direct
It is circulated use, simple to operate, and loss during recycling for the catalyst is less, recycles number of times more.
(2) the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives of the present invention, by each component
Content and reaction process parameter be optimized design, such that it is able to significantly improve the synthesis of 5- arlydene barbituric acid derivatives
Rate and its purity of synthesis, reduce side reaction and the generation of impurity, higher to the utilization rate of raw material, Atom economy is good.This
Bright and design is optimized to its volume by volume concentration also by from ethanol water as reaction dissolvent, thereby may be ensured that
The abundant dissolving of reaction raw materials, is conducive to improving its reaction efficiency further.
(3) the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives of the present invention, its back flow reaction
Reaction pressure is an atmospheric pressure, and reflux time is 1～5min, and reaction condition is gentleer, is easy to practical operation, and produces
The purification process of thing easy it is not necessary to through recrystallization process, consequently facilitating industrialization large-scale production.
(4) the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives of the present invention, its used catalyst
Biological degradability preferably, and its number of dropouts is few, such that it is able to greatly reduce the pollution to environment.
Brief description
Fig. 1 is a kind of technological process of the Simple Catalytic preparation method of 5- arlydene barbituric acid derivatives of the present invention
Figure；
Fig. 2 is that the acidic ion liquid of the present invention prepares 5- (4- chlorobenzene methylene) pyrimidine -2 in catalysis, and 4,6- triketones are anti-
Product yield variation diagram when should middle recycle；
Fig. 3 is that acidic ionic liquid catalysts of the present invention are phonetic in catalysis preparation 5- (4- chlorobenzene methylene) -2- sulfenyl -2h-
Pyridine -4, product yield variation diagram when recycling in 6- bis- reactive ketone；
Fig. 4 be acidic ionic liquid catalysts of the present invention catalysis preparation 5- (2- methoxybenzylidene) pyrimidine -2,4,
Product yield variation diagram when recycling in 6- tri- reactive ketone；
Fig. 5 be acidic ionic liquid catalysts of the present invention catalysis preparation 5- (2- methoxybenzylidene) -2- sulfenyl -
2h- pyrimidine -4, product yield variation diagram when recycling in 6- bis- reactive ketone.
Specific embodiment
For further appreciating that present disclosure, in conjunction with drawings and Examples, the present invention is described in detail.
A kind of Simple Catalytic preparation method of 5- arlydene barbituric acid derivatives of the present invention, the method is with aromatic aldehyde
And barbituratess or thiobarbituricacidα- are reaction raw materials, synthesize 5- under the catalytic action of acidic ionic liquid catalysts
Arlydene barbituric acid derivatives, its chemical equation is:
Above-mentioned aromatic aldehyde is benzaldehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde, neighbour
Any one in nitrobenzaldehyde, hydroxy benzaldehyde, salicylaldhyde, P-methoxybenzal-dehyde, o-methoxybenzaldehyde,
Because length is limited, only list wherein several in embodiment, no longer enumerated.Acidic ion liquid used by the present invention
The structural formula of catalyst is:
The process chart of the Simple Catalytic preparation method of above-mentioned 5- arlydene barbituric acid derivatives as shown in figure 1, its
Concretely comprise the following steps:
(1) weighing of reaction raw materials: by reaction raw materials aromatic aldehyde and barbituratess or thiobarbituricacidα- according to mol ratio
Carry out precise for 1.0～1.2:1.
(2) catalytic reaction: the reaction raw materials weighing up are added in ethanol water, after fully dissolving and stirring
Continue to be added thereto to acidic ionic liquid catalysts, the mole of this catalyst be aromatic aldehyde mole used 1.5～
2%, then make reaction raw materials that back flow reaction occurs under stirring condition, obtain solid precipitate；Above-mentioned reaction in terms of milliliter
The volume of etoh solvent aqueous solution be by mM in terms of 7～10 times of aromatic aldehyde mole, second contained by this ethanol water
The concentration of volume percent of alcohol is 88～91%, and wherein when the concentration of volume percent of ethanol is 90%, effect is best.Above-mentioned
Reaction pressure is an atmospheric pressure, and reflux time is 1～5min.
The present invention is by being used as reaction dissolvent from ethanol water, and is optimized design to its volume by volume concentration, from
And can ensure that the abundant dissolving of reaction raw materials, be conducive to improving its reaction efficiency, and inventor finds in experimentation, when
When the volume by volume concentration of ethanol contained by ethanol water is 90%, its effect is best, the receipts of 5- arlydene barbituric acid derivatives
Rate highest.Additionally, the reaction condition of the present invention is gentleer, it is easy to practical operation, and the purification process of product is simple, thus just
Produce in industrialization promotion.
(3) product separates: reaction is cooled to room temperature after terminating, and the solid obtaining precipitate is cooled to after room temperature and first carries out
Pulverize, then carry out standing, sucking filtration operation, ethanol water washing that its filtering residue is 90% through concentration of volume percent, vacuum
The 5- arlydene barbituric acid derivatives of the present invention are obtained after drying.
The preparation method of acidic ionic liquid catalysts used in the present invention, with reference to associated materials (novel
multiple-acidic ionic liquids:green and efficient catalysts for the synthesis
of bis-indolylmethanes under solvent-free conditions[j],journal of
Industrial＆engineering chemistry, 2015,24:127～131).By the acidic ionic liquid from the present invention
Body catalyst is higher to synthesize 5- arlydene barbituric acid derivatives, the catalysis activity of catalyst, urges such that it is able to significantly improve
Change efficiency, the response time substantially shortens, and the usage amount of catalyst is relatively fewer；Additionally, above-mentioned catalyst can not be treated direct
It is circulated use, simple to operate, and loss during recycling for the catalyst is less, recycling number of times is more, can
Not treated reuse at least 7 times.
Meanwhile, the biological degradability of used catalyst of the present invention is preferable, and its loss loss amount is few, such that it is able to significantly subtract
Few pollution to environment.Inventor is optimized design also by the content of each component and reaction process parameter, such that it is able to
Significantly improve the synthetic ratio of 5- arlydene barbituric acid derivatives and its purity of synthesis, reduce side reaction and the generation of impurity,
Higher to the utilization rate of raw material.
The substantive features of the present invention and remarkable result can emerge from from following embodiments, but they are not to this
Invention imposes any restrictions, and those skilled in the art makes some nonessential improvement according to present disclosure and adjusts, all
Belong to protection scope of the present invention.Below by specific embodiment, the present invention is further illustrated, wherein in embodiment
The test of product characterizes the nuclear magnetic resonance analyser of the model avance-ii 400mhz using German bruker company；
The fusing point of product adopts capillary tube method to measure.
Embodiment 1
1mmol 4-chloro-benzaldehyde, 1mmol barbituratess and 0.018mmol acidic ion liquid are added separately to fill
In the 50ml single port bottle with stirrer and condensing tube of 8ml90% ethanol water.Heating reflux reaction 1min, tlc (thin plate
Chromatography) detection, raw material point disappears, is cooled to room temperature, pulverizes the solid of precipitation, stands, sucking filtration, filtering residue is through 90% ethanol water
5- (4- chlorobenzene methylene) pyrimidine -2,4,6- triketones are obtained, yield is 96%, is directly added in filtrate after washing, vacuum drying
Reused after 4-chloro-benzaldehyde and barbituratess.
The present embodiment gained 5- (4- chlorobenzene methylene) pyrimidine -2, the performance parameter of 4,6- triketones is as follows: m.p.297～
299℃；1H nmr (400mhz, dmso-d6): δ=7.57 (d, j=8.5hz, 2h), 8.09 (d, j=8.5hz, 2h), 8.23
(s, 1h), 11.30 (s, 1h), 11.52 (s, 1h).
Embodiment 2
1.1mmol 4-chloro-benzaldehyde, 1mmol thiobarbituricacidα- and 0.018mmol acidic ion liquid are separately added into
To in the 50ml single port bottle with stirrer and condensing tube filling 8ml 90% ethanol water.Heating reflux reaction 2min,
Tlc (thin plate chromatography) detects, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, and filtering residue is through 90%
5- (4- chlorobenzene methylene) -2- sulfenyl -2h- pyrimidine -4,6- diketone are obtained, yield is after ethanol water washing, vacuum drying
93%, reused after being directly added into 4-chloro-benzaldehyde and thiobarbituricacidα- in filtrate.
The present embodiment gained 5- (4- chlorobenzene methylene) -2- sulfenyl -2h- pyrimidine -4, the performance parameter of 6- diketone is as follows:
M.p.290～292 DEG C；1H nmr (400mhz, dmso-d6): δ=7.52 (d, j=8.5hz, 2h), 8.10 (d, j=8.5hz,
2h), 8.28 (s, 1h), 12.41 (s, 1h), 12.53 (s, 1h).
Embodiment 3
1mmol m-nitrobenzaldehyde, 1mmol barbituratess and 0.020mmol acidic ion liquid are added separately to contain
Have in the 50ml single port bottle with stirrer and condensing tube of 9ml 90% ethanol water.Heating reflux reaction 5min, tlc
(thin plate chromatography) detects, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, and filtering residue is through 90% ethanol
5- (3- nitro benzylidene) pyrimidine -2,4,6- triketones are obtained, yield is 88%, in filtrate after solution washing, vacuum drying
Reused after being directly added into m-nitrobenzaldehyde and barbituratess.
The present embodiment gained 5- (3- nitro benzylidene) pyrimidine -2, the performance parameter of 4,6- triketones is as follows: m.p.241～
243℃；1H nmr (400mhz, dmso-d6): δ=7.67～8.36 (m, 4h), 8.94 (s, 1h), 11.42 (s, 1h), 11.53
(s, 1h).
Embodiment 4
1.2mmol m-nitrobenzaldehyde, 1mmol thiobarbituricacidα- and 0.018mmol acidic ion liquid are added respectively
Enter in the 50ml single port bottle with stirrer and condensing tube filling 9ml 90% ethanol water.Heating reflux reaction
4min, tlc (thin plate chromatography) detect, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, filtering residue warp
5- (3- nitro benzylidene) -2- sulfenyl -2h- pyrimidine -4 are obtained after 90% ethanol water washing, vacuum drying, 6- diketone,
Yield is 91%, is reused after being directly added into m-nitrobenzaldehyde and thiobarbituricacidα- in filtrate.
The present embodiment gained 5- (3- nitro benzylidene) -2- sulfenyl -2h- pyrimidine -4, the performance parameter of 6- diketone is as follows:
M.p.266～268 DEG C；1H nmr (400mhz, dmso-d6): δ=7.81 (s, 1h), 7.88 (t, j=8.0hz, 1h), 8.03
(d, j=7.5hz, 1h), 9.36 (d, j=7.5hz, 1h), 10.17 (s, 1h), 11.79 (s, 1h).
Embodiment 5
1mmol P-methoxybenzal-dehyde, 1mmol barbituratess and 0.015mmol acidic ion liquid are added separately to
Fill in the 50ml single port bottle with stirrer and condensing tube of 7ml 90% ethanol water.Heating reflux reaction 3min, tlc
(thin plate chromatography) detects, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, and filtering residue is through 90% ethanol
5- (4- methoxybenzylidene) pyrimidine -2,4,6- triketones are obtained, yield is 92%, filtrate after solution washing, vacuum drying
In be directly added into P-methoxybenzal-dehyde and barbituratess after reused.
The present embodiment gained 5- (4- methoxybenzylidene) pyrimidine -2, the performance parameter of 4,6- triketones is as follows: m.p.296
～298 DEG C；1H nmr (400mhz, dmso-d6): δ=3.91 (s, 1h), 7.17 (d, j=8.4hz, 2h), 8.30 (s, 1h),
8.49 (d, j=8.4hz, 2h), 11.12 (s, 1h), 11.21 (s, 1h).
Embodiment 6
By 1.1mmol P-methoxybenzal-dehyde, 1mmol thiobarbituricacidα- and 0.016mmol acidic ion liquid respectively
It is added in the 50ml single port bottle with stirrer and condensing tube filling 8ml 90% ethanol water.Heating reflux reaction
5min, tlc (thin plate chromatography) detect, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, filtering residue warp
5- (4- methoxybenzylidene) -2- sulfenyl -2h- pyrimidine -4,6- bis- is obtained after 90% ethanol water washing, vacuum drying
Ketone, yield is 89%, is reused after being directly added into P-methoxybenzal-dehyde and thiobarbituricacidα- in filtrate.
The present embodiment gained 5- (4- methoxybenzylidene) -2- sulfenyl -2h- pyrimidine -4, the performance parameter of 6- diketone is such as
Under: m.p. > 300 DEG C；1H nmr (400mhz, dmso-d6): δ=3.94 (s, 3h), 7.12 (d, j=9.0hz, 2h), 8.31 (s,
1h), 8.45 (d, j=9.0hz, 2h), 12.30 (s, 1h), 12.42 (s, 1h)
Embodiment 7
1.2mmol o-methoxybenzaldehyde, 1mmol barbituratess and 0.019mmol acidic ion liquid are separately added into
To in the 50ml single port bottle with stirrer and condensing tube filling 7ml 90% ethanol water.Heating reflux reaction 5min,
Tlc (thin plate chromatography) detects, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, and filtering residue is through 90% second
5- (2- methoxybenzylidene) pyrimidine -2,4,6- triketones are obtained, yield is 87%, filter after alcohol-water solution washing, vacuum drying
Reused after being directly added into o-methoxybenzaldehyde and barbituratess in liquid.
The present embodiment gained 5- (2- methoxybenzylidene) pyrimidine -2, the performance parameter of 4,6- triketones is as follows: m.p.266
～268 DEG C；1H nmr (400mhz, dmso-d6): δ=3.84 (s, 3h), 7.02 (t, j=7.6hz, 1h), 7.16 (d, j=
8.2hz, 1h), 7.51～7.56 (m, 1h), 8.07 (dd, j=1.2hz, 7.5hz, 1h), 8.55 (s, 1h), 11.18 (s, 1h),
11.39 (s, 1h).
Embodiment 8
By 1.2mmol o-methoxybenzaldehyde, 1mmol thiobarbituricacidα- and 0.020mmol acidic ion liquid respectively
It is added in the 50ml single port bottle with stirrer and condensing tube filling 7ml 90% ethanol water.Heating reflux reaction
5min, tlc (thin plate chromatography) detect, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, filtering residue warp
5- (2- methoxybenzylidene) -2- sulfenyl -2h- pyrimidine -4,6- bis- is obtained after 90% ethanol water washing, vacuum drying
Ketone, yield is 84%, is reused after being directly added into o-methoxybenzaldehyde and thiobarbituricacidα- in filtrate.
The present embodiment gained 5- (2- methoxybenzylidene) -2- sulfenyl -2h- pyrimidine -4, the performance parameter of 6- diketone is such as
Under: m.p.284～286 DEG C；1H nmr (400mhz, dmso-d6): δ=3.86 (s, 3h), 6.97 (t, j=7.5hz, 2h),
7.08 (d, j=8.5hz, 1h), 7.51～7.59 (m, 1h), 8.08 (d, j=8.0hz, 1h), 8.50 (s, 1h), 12.23 (s,
1h), 12.44 (s, 1h).
Embodiment 9
1mmol hydroxy benzaldehyde, 1mmol barbituratess and 0.020mmol acidic ion liquid are added separately to contain
Have in the 50ml single port bottle with stirrer and condensing tube of 10ml 90% ethanol water.Heating reflux reaction 5min, tlc
(thin plate chromatography) detects, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, and filtering residue is through 90% ethanol
5- (4- phenol methylene) pyrimidine -2,4,6- triketones are obtained, yield is 91%, in filtrate after solution washing, vacuum drying
Reused after being directly added into hydroxy benzaldehyde and barbituratess.
The present embodiment gained 5- (4- phenol methylene) pyrimidine -2, the performance parameter of 4,6- triketones is as follows: m.p. > 300
℃；1H nmr (400mhz, dmso-d6): δ=6.93 (d, j=8.1hz, 2h), 8.24 (s, 1h), 8.35 (d, j=8.1hz,
2h), 10.79 (s, 1h), 11.08 (s, 1h), 11.27 (s, 1h).
Embodiment 10
1mmol 4-chloro-benzaldehyde, 1mmol barbituratess and 0.018mmol acidic ion liquid are added separately to fill
In the 50ml single port bottle with stirrer and condensing tube of 8ml88% ethanol water.Heating reflux reaction 1min, tlc (thin plate
Chromatography) detection, raw material point disappears, is cooled to room temperature, pulverizes the solid of precipitation, stands, sucking filtration, filtering residue is through 90% ethanol water
5- (4- chlorobenzene methylene) pyrimidine -2,4,6- triketones are obtained, yield is 94%, is directly added in filtrate after washing, vacuum drying
Reused after 4-chloro-benzaldehyde and barbituratess.
Embodiment 11
1.1mmol 4-chloro-benzaldehyde, 1mmol thiobarbituricacidα- and 0.018mmol acidic ion liquid are separately added into
To in the 50ml single port bottle with stirrer and condensing tube filling 8ml 91% ethanol water.Heating reflux reaction 2min,
Tlc (thin plate chromatography) detects, raw material point disappears, and is cooled to room temperature, pulverizes the solid of precipitation, standing, sucking filtration, and filtering residue is through 90% second
5- (4- chlorobenzene methylene) -2- sulfenyl -2h- pyrimidine -4,6- diketone are obtained, yield is after alcohol-water solution washing, vacuum drying
92%, reused after being directly added into 4-chloro-benzaldehyde and thiobarbituricacidα- in filtrate.
Embodiment 12
With embodiment 1 as probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid
Reuse 7 times, product 5- (4- chlorobenzene methylene) pyrimidine -2, Fig. 2 is shown in the yield change of 4,6- triketones.
Embodiment 13
With embodiment 2 as probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid
Reuse 7 times, product 5- (4- chlorobenzene methylene) -2- sulfenyl -2h- pyrimidine -4, Fig. 3 is shown in the yield change of 6- diketone.
Embodiment 14
With embodiment 7 as probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid
Reuse 7 times, product 5- (2- methoxybenzylidene) pyrimidine -2, Fig. 4 is shown in the yield change of 4,6- triketones.
Embodiment 15
With embodiment 8 as probe reaction, make the active replica test of catalysts acidic ion liquid, ionic liquid
Reuse 7 times, product 5- (2- methoxybenzylidene) -2- sulfenyl -2h- pyrimidine -4, Fig. 5 is shown in the yield change of 6- diketone.
By Fig. 2,3,4 and 5, it can be seen that acidity of catalyst ionic liquid is recycling catalysis preparation 5-, (4- chlorobenzene is sub-
Methyl) pyrimidine -2,4,6- triketones, 5- (4- chlorobenzene methylene) -2- sulfenyl -2h- pyrimidine -4, (2- methoxybenzene is sub- for 6- diketone, 5-
Methyl) pyrimidine -2,4,6- triketones and 5- (2- methoxybenzylidene) -2- sulfenyl -2h- pyrimidine -4, receive during 6- diketone
Rate is in a slight decrease, but it is all smaller to reduce amplitude.It could therefore be concluded that going out this acidity of catalyst ionic liquid in catalysis preparation 5-
Can be recycled during arlydene barbituric acid derivatives, its catalysis activity is not obviously lowered.
Claims (9)
1. a kind of 5- arlydene barbituric acid derivatives catalyst for preparing it is characterised in that: this catalyst be acidic ionic liquid
Body catalyst, its structural formula is:
2. a kind of Simple Catalytic preparation method of 5- arlydene barbituric acid derivatives it is characterised in that: the method is with fragrance
Aldehyde and barbituratess or thiobarbituricacidα- are reaction raw materials, synthesize 5- under the catalytic action of acidic ionic liquid catalysts
Arlydene barbituric acid derivatives, it concretely comprises the following steps:
(1) weighing of reaction raw materials: reaction raw materials aromatic aldehyde and barbituratess or thiobarbituricacidα- are 1.0 according to mol ratio
～1.2:1 carries out precise；
(2) catalytic reaction: the reaction raw materials weighing up are added in ethanol water, continue after fully dissolving and stirring
It is added thereto to acidic ionic liquid catalysts, the mole of this catalyst is the 1.5～2% of aromatic aldehyde mole used, so
Make reaction raw materials that back flow reaction occurs under stirring condition, obtain solid precipitate；Above-mentioned reaction dissolvent second in terms of milliliter
The volume of alcohol-water solution be by mM in terms of 7～10 times of aromatic aldehyde mole, and reaction pressure is an atmospheric pressure, returns
The stream response time is 1～5min；
(3) product separates: reaction is cooled to room temperature after terminating, and the solid obtaining precipitate is cooled to after room temperature and is first ground
Broken, then carry out standing, sucking filtration operation, its filtering residue is scrubbed, obtain the 5- arlydene barbital of the present invention after vacuum drying
Acid derivative.
3. the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives according to claim 2, its feature
It is: the structural formula of described acidic ionic liquid catalysts is:
4. the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives according to Claims 2 or 3, it is special
Levy and be: described aromatic aldehyde be benzaldehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde,
Arbitrary in 1-Formyl-2-nitrobenzene, hydroxy benzaldehyde, salicylaldhyde, P-methoxybenzal-dehyde, o-methoxybenzaldehyde
Kind.
5. the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives according to claim 4, its feature
It is: in described step (2), the concentration of volume percent of ethanol contained by ethanol water is 88～91%.
6. the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives according to claim 5, its feature
It is: in described step (2), the concentration of volume percent of ethanol contained by ethanol water is 90%.
7. the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives according to claim 4, its feature
It is: using the ethanol water that concentration of volume percent is 90%, filtering residue is washed in described step (3).
8. the Simple Catalytic preparation method of a kind of 5- arlydene barbituric acid derivatives according to claim 7, its feature
It is: the acidic ionic liquid catalysts containing in the filtrate after step (3) sucking filtration treated can not reuse at least 7
Secondary.
9. a kind of 5- arlydene barbituric acid derivatives it is characterised in that: this derivant is by any one of claim 2-8
Described method preparation, its structural formula is:
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