CN108191771A - A kind of 3,4- dihydropyrimidine-2-ketos class function monomer and polymer and its their preparation method - Google Patents
A kind of 3,4- dihydropyrimidine-2-ketos class function monomer and polymer and its their preparation method Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- 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
- C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
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- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
The invention discloses a kind of 3,4 dihydro-pyrimidin, 2 ketone function monomer and polymer and its their preparation methods.The preparation method of monomer of the present invention includes the following steps：In organic solvent, aromatic aldehyde, acetoacetoxyethyl methacrylate, raw material 1 and lewis acid compound and organic acid are mixed to get component A, the reaction was continued obtains component B, and separation obtains 3,4 dihydro-pyrimidin, 2 ketone function monomer, structure is shown in formula I.The preparation method of monomer of the present invention includes the following steps：In organic solvent, 3,4 dihydro-pyrimidin, 2 ketone function monomer and radical initiator are mixed, and is passed through inert gas and is reacted, obtain component C, separation obtains 3,4 dihydro-pyrimidin, 2 ketone functional polymer, and structure is as shown in formula III.
Description
Technical field
The present invention relates to 3,4- of one kind dihydropyrimidine-2-keto class function monomers and polymer and its their preparation method,
Belong to chemical industry synthesis field.
Background technology
Recent study finds that some 3,4- dihydropyrimidine-2-keto classes compounds have important pharmacological activity, are such as used as
Calcium antagonist, depressor and A1aAntagonist.3,4- dihydropyrimidine-2-keto class compounds are also used as developing anticancer drug
Primer.Also contain 3,4- dihydro-pyrimidins -2- in the biologically active alkaloid of some isolated from marine organisms
Ketone.Therefore, the synthesis of this kind of compound causes the great interest of people in recent years.3,4- dihydropyrimidine-2-keto class compounds
To be conventionally synthesized reacted using traditional Biginelli, under concentrated hydrochloric acid catalysis, using ethyl acetoacetate, aromatic aldehyde and
Urea condensation is realized, belongs to three component condensation reactions.There are the shortcomings of reaction time length, low yield for traditional Biginelli reactions.
In order to improve yield and shorten the reaction time, some new catalyst are found successively, such as LaCl3、FeCl3、NiCl2·6H2O、
LiBr and the concentrated sulfuric acid etc..New synthetic technology such as synthesis in solid state, microwave technology, ultrasonic technique and ion liquid solvent method etc. are also first
After be applied in the reaction.The application of these new methods causes Biginelli reactions to have, and post processing is simple, reaction condition is mild
The advantages that environmentally friendly.
Invention content
The object of the present invention is to provide a kind of 3,4- dihydropyrimidine-2-ketos class function monomer and polymer and its their systems
Preparation Method, present invention energy is quick, mass, 3, the 4- dihydropyrimidine-2-keto class polymerisable monomers for largely preparing a variety of high-purities,
And further obtain a variety of 3,4- dihydropyrimidine-2-ketos class functional polymers；This method post-reaction treatment is simple, yield is high.
A kind of 3,4- dihydropyrimidine-2-ketos class function monomer provided by the invention, structural formula is shown in formula I：
In Formulas I, R1、R2For hydrogen atom, C atomicities be 1-5 alkyl, hydroxyl or C atomicities be 1-5 alkoxy, R3For
C atomicities are the alkyl of 1-3；Y is O or S atom.
The present invention also provides 3, the 4- dihydropyrimidine-2-ketos class function monomer preparation method, including walking as follows
Suddenly：In organic solvent, by aromatic aldehyde, acetoacetoxyethyl methacrylate, raw material 1 and lewis acid compound and organic
Acid is mixed to get component A, continues Biginelli and component B is obtained by the reaction, and is then detached from the component B to get to described
3,4- dihydropyrimidine-2-keto class function monomers；
Wherein, the structural formula of the raw material 1 is as shown in Formula II,
In Formula II, R3The alkyl for being 1-3 for C atomicities, Y are O or S atom.
In the preparation method of above-mentioned monomer, the aromatic aldehyde, the acetoacetoxyethyl methacrylate and the original
The molar ratio of material 1 can be 1：1：1.5~3.0, concretely 1：1：1.5 or 1：1：1.5~2.5；
The molar ratio of the magnesium halide and the aromatic aldehyde can be 0.1~1：1, concretely 0.2：1；
The molar ratio of the organic acid and the magnesium halide can be 1：1.0~5.0；
The temperature of the Biginelli reactions can be 50~100 DEG C, concretely 100 DEG C or 60~100 DEG C, described
The Biginelli reaction time can be 2~10h, concretely 2h, 2~5h or 2~8h.
In the preparation method of above-mentioned monomer, the aromatic aldehyde includes benzaldehyde derivative；The benzaldehyde derivative is selected from
At least one of benzaldehyde, P-methoxybenzal-dehyde and cumaldehyde；
The raw material 1 is selected from least one of urea, thiocarbamide, methylurea, methylthiourea, ethyl carbamide and ethyl thiourea；
The lewis acid compound includes magnesium halide；Halogen in the magnesium halide is Cl or Br；
The organic acid is acetic acid and/or trifluoroacetic acid；
The organic solvent is at least one of acetic acid, dioxane, tetrahydrofuran and N, N- dimethyl phenacyl；
The operation of the isolated 3,4- dihydropyrimidine-2-ketos class function monomer is as follows in the step (1)：By described in
Component B is poured into water, and is carried out supersound washing, centrifugation, filtering successively, is then collected filter residue, and the filter residue is organic with low polarity
Solvent cleans at least 1 time, is finally freeze-dried.
In the preparation method of above-mentioned monomer, the time of the supersound washing can be 20~40min, concretely 30min；
The number of the filter residue cleaning can be 2~3 times, concretely 2 times.
The present invention also provides one kind 3,4- dihydropyrimidine-2-keto class functional polymers, and structural formula is as shown in formula III：
In formula III, R1、R2For hydrogen atom, C atomicities be 1-5 alkyl, hydroxyl or C atomicities be 1-5 alkoxy, R3
The alkyl for being 1-3 for C atomicities；Y is O or S atom.
Invention further provides the preparation methods of the polymer, include the following steps：In the organic solvent
In, 3,4- dihydropyrimidine-2-ketos class function monomer described in claim 1 and radical initiator are mixed, and be passed through indifferent gas
Body is reacted, and obtains component C, is then detached the component C and is gathered to get to 3, the 4- dihydropyrimidine-2-ketos class function
Close object.
In the preparation method of above-mentioned polymer, the radical initiator and 3, the 4- dihydropyrimidine-2-ketos class work(
The molar ratio of energy monomer can be 0.01~0.5：1, concretely 0.02：1；
The inert gas is nitrogen or argon gas；
The bubbling time of the inert gas can be 15~30min, concretely 15min, 15~20min or 15~
250min, flow velocity can be 10~100mL/min, concretely 20mL/min, 20~100mL/min, 10~20mL/min or 15
~80mL/min；
The temperature of the reaction can be 50~100 DEG C, concretely 70 DEG C, 50~70 DEG C, 70~100 DEG C or 60~90
DEG C, the time can be 6~20h, concretely 12h, 6~12h, 12~20h or 10~15h.
In the preparation method of above-mentioned polymer, the radical initiator includes azo-initiator and/or peroxidating
Object initiator；The azo-initiator is selected from azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), the peroxidating
Object initiator is selected from dibenzoyl peroxide (BPO)；
The organic solvent is at least one of acetic acid, dioxane, tetrahydrofuran and N, N- dimethyl phenacyl；
The operation of the isolated 3,4- dihydropyrimidine-2-ketos class functional polymer is as follows：The component C is added drop-wise to
In the low polar organic solvent of stirring, filtering collects filter residue, is cleaned with the low polar organic solvent, finally carry out institute
State freeze-drying.
In the preparation method of above-mentioned polymer, the low polar organic solvent is in ether, petroleum ether and n-hexane
It is at least one；
The rate of the stirring can be 500~1000r/min, concretely 800r/min, 500~800r/min, 800~
1000r/min or 600~900r/min；
The temperature of the freeze-drying can be -20~-50 DEG C, and concretely -50 DEG C or -30~-50 DEG C, vacuum degree can be
0.1~30Pa, concretely 30Pa.
In the structural formula formula IV specific as follows for the 3,4- dihydropyrimidine-2-ketos class function monomer that the present invention is prepared
(a) shown in-(c).
The present invention has the following advantages：
The present invention is with different aromatic aldehydes and different (sulphur) urea derivatives and acetoacetoxyethyl methacrylate
Biginelli reactions are carried out at the same time, product can obtain a variety of pure 3,4- dihydropyrimidine-2-ketos classes through simple process to be gathered
Close monomer；3,4- dihydropyrimidine-2-keto classes monomeric compound is caused with radical initiator and carries out free radical polymerization, can obtain more
Kind 3,4- dihydropyrimidine-2-keto class functional polymers.The present invention can quickly, mass, the 3,4- for largely preparing a variety of high-purities
Dihydropyrimidine-2-keto class polymerisable monomer, and further obtain a variety of 3,4- dihydropyrimidine-2-ketos class functional polymers.The party
Method reaction rate is fast, post processing is simple, yield is high.
Description of the drawings
Fig. 1 is the synthetic route chart of 3,4- dihydropyrimidine-2-ketos class functional polymer of the present invention；
Fig. 2 be the embodiment of the present invention 1 in synthesize 3,4- dihydropyrimidine-2-keto class function monomers hydrogen nuclear magnetic spectrogram (1H-
NMR)；
Fig. 3 be the embodiment of the present invention 1 in synthesize 3,4- dihydropyrimidine-2-keto class function monomers carbon nuclear magnetic spectrogram (13C-
NMR)；
Fig. 4 is the hydrogen nuclear magnetic spectrogram of 3,4- dihydropyrimidine-2-keto class functional polymers synthesized in the embodiment of the present invention 2
(1H-NMR)；
Fig. 5 is the gel infiltration color of 3,4- dihydropyrimidine-2-keto class functional polymers synthesized in the embodiment of the present invention 2
It composes (GPC)；
Fig. 6 be the embodiment of the present invention 3 in synthesize 3,4- dihydropyrimidine-2-keto class function monomers hydrogen nuclear magnetic spectrogram (1H-
NMR)；
Fig. 7 is the hydrogen nuclear magnetic spectrogram of 3,4- dihydropyrimidine-2-keto class functional polymers synthesized in the embodiment of the present invention 4
(1H-NMR)；
Fig. 8 is the gel infiltration color of 3,4- dihydropyrimidine-2-keto class functional polymers synthesized in the embodiment of the present invention 4
It composes (GPC).
Fig. 9 be the embodiment of the present invention 5 in synthesize 3,4- dihydropyrimidine-2-keto class function monomers hydrogen nuclear magnetic spectrogram (1H-
NMR)；
Figure 10 is the proton magnetic spectrum of 3,4- dihydropyrimidine-2-keto class functional polymers synthesized in the embodiment of the present invention 6
Figure (1H-NMR)；
Figure 11 is the gel infiltration of 3,4- dihydropyrimidine-2-keto class functional polymers synthesized in the embodiment of the present invention 6
Chromatography (GPC).
Figure 12 is the structural formula of 3,4- dihydropyrimidine-2-ketos class function monomer of the present invention；Wherein Figure 12 (a), (b), (c) point
It Wei not the structural formula of 3,4- dihydropyrimidine-2-keto class function monomers that is prepared of the embodiment of the present invention 1,2,3.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The method of the present invention is illustrated, but the present invention is not limited thereto below by specific embodiment, it is all at this
All any modification, equivalent and improvement done within the spirit and principle of invention etc., should be included in the protection model of the present invention
Within enclosing.
The synthesis of 3,4- dihydropyrimidine-2-keto class monomers that embodiment 1, urea, benzaldehyde participate in
1) according to the synthetic route of Fig. 1,1.06g (10mmol) benzaldehyde, 2.14g (10mmol) are added in 10mL reaction bulbs
Acetoacetate methacrylic acid glycol ester (AEMA) and 0.90g (15mmol) urea, 0.2g (2mmol) anhydrous magnesium chlorides and
1.5mL acetic acid is placed in 100 DEG C of oil baths and reacts as solvent.
2) mixed liquor of reaction 2h in step 1) is poured into deionized water and precipitates, filter residue is obtained by filtration, with ionized water and
Ether/petroleum ether (1:4) twice, white solid is obtained by filtration in mixed solvent difference supersound washing 30min, ultrasound, -50 DEG C, true
During reciprocal of duty cycle 30Pa, freeze-drying for 24 hours, obtains 3.0g (yield 88%) white powder 3, and 4- dihydropyrimidine-2-keto class monomers divide
Not carry out1H-NMR、13C-NMR is characterized.Shown in its structure such as Figure 12 (a).
By Fig. 2 and Fig. 3 it is found that the present invention gained 3,4- dihydropyrimidine-2-keto class monomers on nuclear magnetic spectrogram with its structure
Characteristic peak corresponds, and illustrates that product is very pure, without other impurity.
The synthesis of 3,4- dihydropyrimidine-2-keto class functional polymers that embodiment 2, urea, benzaldehyde participate in
The 3,4- dihydropyrimidine-2-keto classes that 0.5g (1.5mmol) embodiment of the present invention 1 synthesizes are added in 10mL reaction bulbs
Monomer, 7.4mg (0.03mmol) azobisisoheptonitrile (ABVN) and 1.5mL n,N-Dimethylformamide (DMF) as solvent,
Magneton is added in, is stirred evenly.Reaction bulb leads to nitrogen (flow velocity 20mL/min), bubbling 15min or passes through liquid nitrogen frozen-pumping three times
Vacuum-thaw cycles operation, removes out the air in system.Reaction bulb is put in 70 DEG C of constant temperature oil bath, it will be molten after reaction 12h
Liquid is added dropwise in the ether of quick stirring (rotating speed 800r/min) and precipitates, and filters, and collects filter residue, adds in ether washing three
Polymer, vacuum degree 30Pa are obtained after secondary, -50 DEG C of freeze-dryings obtain 0.45g (yield 90%) functional polymer afterwards for 24 hours, point
Not carry out1H-NMR and GPC characterizations.
As shown in Figure 4, the present invention gained 3,4- dihydropyrimidine-2-keto class functional polymers on nuclear magnetic spectrogram with its structure
It corresponds, it was demonstrated that the generation of polymerisation, and with higher conversion ratio；The polymer synthesized as shown in Figure 5 point
In typical normal distribution, GPC test results are for son amount distribution：Number-average molecular weight Mn=5.84 × 104g·mol-1, gmol-1
Weight average molecular weight Mw=11.05 × 104g·mol-1, molecular weight distribution index 1.89.
The synthesis of 3,4- dihydropyrimidine-2-keto class monomers that embodiment 3, urea, vanillic aldehyde participate in
1) according to the synthetic route of Fig. 1,1.52g (10mmol) vanillic aldehyde, 2.14g (10mmol) are added in 10mL reaction bulbs
Acetoacetate methacrylic acid glycol ester (AEMA) and 0.90g (15mmol) urea, 0.2g (2mmol) anhydrous magnesium chlorides and
1.5mL acetic acid is placed in 100 DEG C of oil baths and reacts as solvent.
2) mixed liquor of reaction 2h in step 1) is poured into deionized water and precipitates, filter residue is obtained by filtration, with ionized water and
Ether/petroleum ether (1:4) twice, white solid is obtained by filtration, vacuum degree is in mixed solvent difference supersound washing 30min, ultrasound
30Pa, -50 DEG C of freeze-dryings for 24 hours, obtain 3.2g (yield 90%) white powder 3, and 4- dihydropyrimidine-2-keto class monomers divide
Not carry out1H-NMR is characterized.Shown in its structure such as Figure 12 (b).
It will be appreciated from fig. 6 that the present invention gained 3,4- dihydropyrimidine-2-keto class monomers on nuclear magnetic spectrogram with its structure feature peak
It corresponds, illustrates that product is very pure, without other impurity.
The synthesis of 3,4- dihydropyrimidine-2-keto class functional polymers that embodiment 4, urea, vanillic aldehyde participate in
The 3,4- dihydropyrimidine-2-keto classes that 0.5g (1.4mmol) embodiment of the present invention 3 synthesizes are added in 10mL reaction bulbs
Monomer, 7.0mg (0.028mmol) azobisisoheptonitrile (ABVN) and 1.5mL n,N-Dimethylformamide (DMF) as solvent,
Magneton is added in, is stirred evenly.Reaction bulb leads to nitrogen (flow velocity 20mL/min), bubbling 15min or passes through liquid nitrogen frozen-pumping three times
Vacuum-thaw cycles operation, removes out the air in system.Reaction bulb is put in 70 DEG C of constant temperature oil bath, after reaction 12h dropwise
It is added in the quick ether for stirring (rotating speed 800r/min) and precipitates, filter, collect filter residue, add in ether washing and obtain afterwards three times
Polymer, vacuum degree 30Pa, -50 DEG C of freeze-dryings obtain 0.45g (yield 90%) functional polymer, carry out respectively afterwards for 24 hours1H-NMR and GPC characterizations.
As shown in Figure 7, the present invention gained 3,4- dihydropyrimidine-2-keto class functional polymers on nuclear magnetic spectrogram with its structure
It corresponds, it was demonstrated that the generation of polymerisation, and with higher conversion ratio；The polymer synthesized as shown in Figure 8 point
In typical normal distribution, GPC test results are for son amount distribution：Number-average molecular weight Mn=6.40 × 104g·mol-1, divide equally again
Son amount Mw=10.44 × 104g·mol-1, molecular weight distribution index 1.63.
The synthesis of 3,4- dihydropyrimidine-2-keto class monomers that embodiment 5, thiocarbamide, benzaldehyde participate in
1) according to the synthetic route of Fig. 1,1.06g (10mmol) benzaldehyde, 2.14g (10mmol) are added in 10mL reaction bulbs
Acetoacetate methacrylic acid glycol ester (AEMA) and 1.14g (15mmol) thiocarbamide, 0.2g (2mmol) anhydrous magnesium chlorides and
1.5mL acetic acid is placed in 100 DEG C of oil baths and reacts as solvent.
2) mixed liquor of reaction 2h in step 1) is poured into deionized water and precipitates, filter residue is obtained by filtration, with ionized water and
Ether/petroleum ether (1:4) twice, white solid is obtained by filtration in mixed solvent difference supersound washing 30min, vacuum degree 30Pa ,-
50 DEG C of freeze-dryings for 24 hours, obtain 3.6g (yield 87%) white powder 3, and 4- dihydropyrimidine-2-keto class monomers carry out1H-
NMR is characterized.Shown in its structure such as Figure 12 (c).
As shown in Figure 9, gained 3,4- dihydropyrimidine-2-keto class monomers are a pair of with its structure feature peak one on nuclear magnetic spectrogram
Should, illustrate that product is very pure, without other impurity.
The synthesis of 3,4- dihydropyrimidine-2-keto class functional polymers that embodiment 6, thiocarbamide, benzaldehyde participate in
The 3,4- dihydropyrimidine-2-ketos that 0.5g (1.45mmol) embodiment of the present invention 5 synthesizes are added in 10mL reaction bulbs
Class monomer, 7.2mg (0.029mmol) azobisisoheptonitrile (ABVN) and 1.5mL n,N-Dimethylformamide (DMF) are as molten
Agent adds in magneton, stirs evenly.Reaction bulb leads to nitrogen (flow velocity 20mL/min), bubbling 15min or cold by liquid nitrogen three times
Freeze-vacuumize-thaw cycles operation, remove out the air in system.Reaction bulb is put in 70 DEG C of constant temperature oil bath, reacts 12h
It is added dropwise in the ether of quick stirring (rotating speed 800r/min) and precipitates afterwards, filter, collect filter residue, add in ether washing three
Polymer, vacuum degree 30Pa are obtained after secondary, -50 DEG C of freeze-dryings obtain 0.43g (yield 86%) functional polymer afterwards for 24 hours, point
Not carry out1H-NMR and GPC characterizations.
As shown in Figure 10, present invention gained 3,4- dihydropyrimidine-2-keto class functional polymers are tied on nuclear magnetic spectrogram with it
Structure corresponds, it was demonstrated that the generation of polymerisation, and with higher conversion ratio；The polymer synthesized as shown in Figure 11
Molecular weight distribution is in typical normal distribution, and GPC test results are：Number-average molecular weight Mn=12.86 × 104g·mol-1, weight is
Molecular weight Mw=26.58 × 104g·mol-1, molecular weight distribution index 2.07.
Comparative example,
Using 10mmol benzaldehydes, 10mmol ethyl acetoacetates, 15mmol urea or thiocarbamide as reactant, using chlorosulfonic acid as
3,4- dihydropyrimidinonesands/thioketone is obtained by the reaction in catalyst, ethylene glycol solvent.Reaction temperature is 120~130 DEG C, instead
When being 5h between seasonable, product yield is about 70%, when reacted between when being 7h, product yield is more than 90%.
The present invention is compared with comparative example, and used catalyst is safer, green, and reaction temperature is lower, in shorter time
Reaction, and higher product yield can be obtained.
Claims (10)
1. one kind 3,4- dihydropyrimidine-2-keto class function monomers, structural formula is shown in formula I：
In Formulas I, R1、R2For hydrogen atom, C atomicities be 1-5 alkyl, hydroxyl or C atomicities be 1-5 alkoxy, R3For C originals
Subnumber is the alkyl of 1-3；Y is O or S atom.
2. the preparation method of 3,4- dihydropyrimidine-2-ketos class function monomer, includes the following steps described in claim 1：Organic
In solvent, aromatic aldehyde, acetoacetoxyethyl methacrylate, raw material 1 are mixed with lewis acid compound and organic acid
To component A, continue Biginelli and component B is obtained by the reaction, then detached from the component B to get to 3, the 4- dihydros
Pyrimid-2-one class function monomer；
Wherein, the structural formula of the raw material 1 is as shown in Formula II,
In Formula II, R3The alkyl for being 1-3 for C atomicities, Y are O or S atom.
3. preparation method according to claim 2, it is characterised in that：The aromatic aldehyde, the acetoacetyl methyl-prop
The molar ratio of olefin(e) acid ethyl ester and the raw material 1 is 1：1：1.5~3.0；
The molar ratio of the magnesium halide and the aromatic aldehyde is 0.1~1：1；
The molar ratio of the organic acid and the magnesium halide is 1：1.0~5.0；
The temperature of the Biginelli reactions is 50~100 DEG C, and the Biginelli reaction time is 2~10h.
4. the preparation method according to Claims 2 or 3, it is characterised in that：The aromatic aldehyde includes benzaldehyde derivative；Institute
It states benzaldehyde derivative and is selected from least one of benzaldehyde, P-methoxybenzal-dehyde and cumaldehyde；
The raw material 1 is selected from least one of urea, thiocarbamide, methylurea, methylthiourea, ethyl carbamide and ethyl thiourea；
The lewis acid compound includes magnesium halide；Halogen in the magnesium halide is Cl or Br；
The organic acid is acetic acid and/or trifluoroacetic acid；
The organic solvent is at least one of acetic acid, dioxane, tetrahydrofuran and N, N- dimethyl phenacyl；
The operation of the isolated 3,4- dihydropyrimidine-2-ketos class function monomer is as follows in the step (1)：By the component
B is poured into water, and is carried out supersound washing, centrifugation, filtering successively, filter residue is then collected, by the filter residue low polar organic solvent
Cleaning at least 1 time, is finally freeze-dried.
5. preparation method according to claim 4, it is characterised in that：The time of the supersound washing is 20~40min；
The number of the filter residue cleaning is 2~3 times.
6. one kind 3,4- dihydropyrimidine-2-keto class functional polymers, structural formula is as shown in formula III：
In formula III, R1、R2For hydrogen atom, C atomicities be 1-5 alkyl, hydroxyl or C atomicities be 1-5 alkoxy, R3For C originals
Subnumber is the alkyl of 1-3；Y is O or S atom.
7. the preparation method of the polymer described in claim 6, includes the following steps：It, will by right in the organic solvent
13, the 4- dihydropyrimidine-2-ketos class function monomer and radical initiator is asked to mix, and be passed through inert gas and reacted,
Component C is obtained, then detaches the component C to get to 3, the 4- dihydropyrimidine-2-ketos class functional polymer.
8. preparation method according to claim 7, it is characterised in that：The radical initiator and the 3,4- dihydros are phonetic
The molar ratio of pyridine -2- ketone function monomers is 0.01~0.5：1；
The inert gas is nitrogen or argon gas；
The bubbling time of the inert gas is 15~30min, and flow velocity is 10~100mL/min；
The temperature of the reaction is at 50~100 DEG C, and the time is 6~20h.
9. preparation method according to claim 7 or 8, it is characterised in that：The radical initiator draws including azo
Send out agent and/or peroxide initiator；The azo-initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, the mistake
Peroxide initiator is selected from dibenzoyl peroxide；
The organic solvent is at least one of acetic acid, dioxane, tetrahydrofuran and N, N- dimethyl phenacyl；
The operation of the isolated 3,4- dihydropyrimidine-2-ketos class functional polymer is as follows：The component C is added drop-wise to stirring
The low polar organic solvent in, filtering, collect filter residue, cleaned, finally carried out described cold with the low polar organic solvent
It is lyophilized dry.
10. according to the preparation method described in any one of claim 7-9, it is characterised in that：The low polar organic solvent is
At least one of ether, petroleum ether and n-hexane；
The rate of the stirring is 500~1000r/min；
The temperature of the freeze-drying is -20~-50 DEG C, and vacuum degree is 0.1~30Pa.
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| CN110357993A (en) * | 2019-07-09 | 2019-10-22 | 清华大学 | A kind of novel high polymer for the structure of dihydropyridine containing 1,4- can be used as antibacterial additive |
| CN111808241A (en) * | 2020-07-15 | 2020-10-23 | 清华大学 | 4-aryl 3, 4-dihydropyrimidine (sulfur) ketone polymer and preparation and application thereof |
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Cited By (3)
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| CN110357993A (en) * | 2019-07-09 | 2019-10-22 | 清华大学 | A kind of novel high polymer for the structure of dihydropyridine containing 1,4- can be used as antibacterial additive |
| CN111808241A (en) * | 2020-07-15 | 2020-10-23 | 清华大学 | 4-aryl 3, 4-dihydropyrimidine (sulfur) ketone polymer and preparation and application thereof |
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