CN110372529A - N- [(3,4,5- trifluoro) phenyl] acrylamide and preparation method thereof - Google Patents
N- [(3,4,5- trifluoro) phenyl] acrylamide and preparation method thereof Download PDFInfo
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- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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Abstract
The invention belongs to technical field of organic synthesis, and in particular to a kind of N- [(3,4,5- trifluoro) phenyl] acrylamide and preparation method thereof.Specific step is as follows for acrylamide preparation method by N- [(3,4,5- trifluoro) phenyl]: (1) by 3,4,5- trifluoromethyl anilines, reaction dissolvent and catalyst are added in reaction vessel, stir and evenly mix, acryloyl chloride is added, in -10 DEG C~30 DEG C 1~7h of reaction；(2) add water into step (1) resulting reaction solution, stir and evenly mix, filter, isolate sediment, sediment both obtains N- [(3,4,5- trifluoro) phenyl] acrylamide through being dried.Preparation method raw material of the invention is simple and easy to get, at low cost, easy to operate, N- [(3,4,5- trifluoro) phenyl] acrylamide high income, purity is high；Alkalescent catalyst --- sodium bicarbonate to react amplification technique simple possible, and the three wastes for reacting generation are few, environmentally protective.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of N- [(3,4,5- trifluoro) phenyl] acrylamide and
Preparation method.
Background technique
Fluorine is the maximum element of electronegativity, and atom covalence radius (0.064nm) is very small, the very big (485KJ/ of C-F key bond energy
Mol), and fluorine atom carbon skeleton outer layer arrangement closely, " screen effect " can be formed to main chain and interior molecules, fluorine
Changing acrylamide monomers has unique function because of the presence of fluorin radical.Fluorinated acrylamide amides monomer is used not only for
It is prevented from the fungicide of diseases and pests of agronomic crop, tyrosine kinase inhibitor is also applied to and is widely used in treating cancer, artery
The diseases such as atherosis, restenosis, mullerianosis and psoriasis.In the field of polymers, contain fluorinated acrylamide amide monomer
The polymer of structure has broad-spectrum sterilization performance.They can be with the monomers such as methacrylate or N- substituted maleimide amine certainly
It is copolymerized by base, some performances of copolymer, such as heat resistance, water resistance, transparency, hardness is made to have different degrees of improvement.
The especially groups thermal stability such as phenolic hydroxyl group, sulfoamido and fluorine atom is more excellent, what the N- aryl comprising such group replaced
(methyl) acrylamide can effectively improve the glass transition temperature and heat resistance of polymer as comonomer.
In the method for existing synthesis fluorinated acrylamide amides monomer, mostly using triethylamine as catalyst, triethylamine has poison
Property, strong and stimulating and corrosivity, it is big to human body and environmental hazard and inflammable, it is explosive, belong to hazardous chemical；In addition, with three
When ethamine is as catalyst, further polymerization occurs for the fluorinated acrylamide amides monomer generated in reaction process in order to prevent, leads to
Often need to be added polymerization inhibitor (such as DBPC 2,6 ditertiary butyl p cresol) in the reaction system.Therefore, existing synthesis fluorinated acrylamide amide
That there are catalyst toxicities is big for the method for class monomer, big to human body and environmental hazard, does not meet current environmentally protective requirement, and
And also needing additionally to add polymerization inhibitor in reaction process, reaction cost is high.
Summary of the invention
In view of the problems of the existing technology and insufficient, the object of the present invention is to provide a kind of N- [(3,4,5- trifluoro) benzene
Base] preparation method of acrylamide and its N- [(3,4,5- trifluoro) phenyl] acrylamide product of preparation.
To realize goal of the invention, The technical solution adopted by the invention is as follows:
N- [(3,4,5- trifluoro) phenyl] acrylamide, which is characterized in that its structural formula is as follows:
The preparation method of above-mentioned N- [(3,4,5- trifluoro) phenyl] acrylamide, comprising the following steps:
(1) 3,4,5- trifluoromethyl anilines, reaction dissolvent and catalyst are added in reaction vessel, stir and evenly mix, adds third
Alkene acyl chlorides, in -10 DEG C~30 DEG C 1~7h of reaction；
(2) add water into step (1) resulting reaction solution, stir and evenly mix, filter, isolate sediment, sediment is through dry
Dry processing both obtains N- [(3,4,5- trifluoro) phenyl] acrylamide.
The reaction equation of the reaction is as follows:
According to above-mentioned preparation method, it is preferable that the catalyst is sodium bicarbonate.
According to above-mentioned preparation method, it is preferable that the sodium bicarbonate and 3, the mass ratio of 4,5- trifluoromethyl anilines are (0.01
~0.1): 1.
According to above-mentioned preparation method, it is preferable that described 3, the molar ratio of 4,5- trifluoromethyl anilines and acryloyl chloride is 1:(1
~2.5).
According to above-mentioned preparation method, it is preferable that the reaction dissolvent is methanol, in ethyl alcohol, acetone, dimethylformamide
At least one.
According to above-mentioned preparation method, it is preferable that the adding manner of the acryloyl chloride is to be added dropwise.
It is a kind of to utilize N- [(3,4,5- trifluoro) phenyl] acrylamide product made from above-mentioned preparation method.
The presence that above-mentioned N- [(3,4,5- trifluoro) phenyl] acrylamide product is good for due to amide group and C-F, not only
It is used to prevent the fungicide of diseases and pests of agronomic crop, it can also be with the monomers such as methacrylate or N- substituted maleimide amine certainly
It is copolymerized by base, some performances of copolymer, such as heat resistance, water resistance, transparency, hardness is made to have different degrees of improvement.
Compared with prior art, the positive beneficial effect that the present invention obtains are as follows:
(1) present invention with 3,4,5- trifluoromethyl anilines and acryloyl chloride for reaction raw materials, using sodium bicarbonate as catalyst
Synthesize N- [(3,4,5- trifluoro) phenyl] acrylamide, compared with triethylamine, sodium bicarbonate is safe and non-toxic, to human body and environment without
Harm, environmentally protective, cost of material is low, moreover, the alkalinity of sodium bicarbonate is relatively weak, using sodium bicarbonate as catalytic reaction
Agent, reaction system is more steady, is not required to additionally add polymerization inhibitor (2,6-di-tert-butyl p-cresol) in reaction process, reduces anti-
Answer cost.
(2) using sodium bicarbonate as catalyst, sodium bicarbonate can promote the present invention with byproduct of reaction hcl reaction
The positive of reaction carries out, and N- [(3,4,5- trifluoro) phenyl] acrylamide yield is improved, moreover, sodium bicarbonate and hcl reaction
Free of contamination sodium chloride is generated, post-reaction treatment is simple, and the three industrial wastes of generation are few, environmentally protective.
(3) for the present invention using methanol, ethyl alcohol, acetone or dimethylformamide as reaction dissolvent, reaction dissolvent is readily soluble
Yu Shui, after reaction by into reaction system plus water, filtering, reaction dissolvent and reaction product can be realized --- N- [(3,
4,5- trifluoros) phenyl] acrylamide separation, remove reaction dissolvent from reaction system, it is easy to operate, moreover, reaction it is molten
Agent is cheap, and post-processing has fewer environmental impacts.
(4) preparation method raw material of the invention is simple and easy to get, at low cost, after reaction, by simple filtration treatment,
It is able to achieve the separation of N- [(3,4,5- trifluoro) phenyl] acrylamide and catalyst, byproduct of reaction, reaction dissolvent, operation letter
It is single, facilitate feasible, and N- [(3,4,5- trifluoro) phenyl] acrylamide high income, purity is high；In addition, alkalescent is catalyzed
Agent --- sodium bicarbonate to react amplification technique simple possible, and the three wastes for reacting generation are few, environmentally protective.(5) present invention system
Standby N- [(3,4,5- trifluoro) phenyl] acrylamide and N- in the prior art [(the bromo- 3,5- difluoro of 4-) phenyl] acrylamide
It compares, the fluorine atom inside group increases, and fluorine is the maximum element of electronegativity, and atom covalence radius (0.064nm) is very small, C-
F key bond energy is very big (485KJ/mol), and fluorine atom carbon skeleton outer layer arrangement closely, can be to main chain and inner part
Son forms " screen effect ".When being applied to N- [(3,4,5- trifluoro) phenyl] acrylamide to prepare polymer, " the screen of F atom
Cover effect " surface tension that polymer can be enhanced, improves the hydrophobic performance of polymer.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by embodiment 1.
Fig. 2 is the high-efficient liquid phase chromatogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by embodiment 1.
Fig. 3 is the high-efficient liquid phase chromatogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by embodiment 7.
Fig. 4 is the high-efficient liquid phase chromatogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by embodiment 13.
Fig. 5 is the high-efficient liquid phase chromatogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by embodiment 19.
Fig. 6 is the high-efficient liquid phase chromatogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by embodiment 9.
Fig. 7 is the high-efficient liquid phase chromatogram of N- [(3,4,5- trifluoro) phenyl] acrylamide prepared by comparative example 1.
Specific embodiment
Below by way of specific embodiment, invention is further described in detail, but does not limit the scope of the invention.
(1) catalyst amount inquires into experiment
In order to inquire into catalyst amount to preparation N- [(3,4,5- trifluoro) phenyl] acrylamide yield (yield=N- [(3,
4,5- trifluoro) phenyl] acrylamide the amount of actually generating (mol)/N- [(3,4,5- trifluoro) phenyl] acrylamide theory it is raw
At amount (mol)) and purity influence, inventor carried out following experiment, i.e. 1~embodiment of embodiment 6, corresponding experiment knot
Fruit is referring to table 1.
Embodiment 1:
A kind of preparation method of N- [(3,4,5- trifluoro) phenyl] acrylamide, the specific steps are as follows:
By 14.7 grams of 3,4,5- trifluoromethyl aniline (0.1mol) and 50 grams of reaction dissolvents (reaction dissolvent is dimethylformamide)
It is added in 500ml four-hole bottle, sodium bicarbonate, sodium bicarbonate and 3 is added, the mass ratio of 4,5- trifluoromethyl anilines is 0.01:1, stirring
Under be cooled to 5 DEG C, be added dropwise 22.6 grams of acryloyl chloride (0.25 mole), after being added dropwise, reacted 5 hours at 5 DEG C, reaction solution is dropped
To room temperature, 300ml deionized water is then added into reaction solution, sediment is collected in filtering, and sediment, which is dried, both obtains N-
[(3,4,5- trifluoro) phenyl] acrylamide.Using the N- [(3,4,5- trifluoro) phenyl] third of high performance liquid chromatograph measurement preparation
The purity of acrylamide.
2~embodiment of embodiment 6:
The content of 2~embodiment of embodiment 6 is substantially the same manner as Example 1, the difference is that: sodium bicarbonate and 3,4,
The mass ratio of 5- trifluoromethyl aniline is different, referring specifically to table 1.
1 catalyst amount of table inquires into experiment
As shown in Table 1, sodium bicarbonate and 3, when 4,5- trifluoromethyl aniline mass ratioes are 0.01:1, N- [(3,4,5- trifluoro) benzene
Base] acrylamide yield it is lower, only 35.3%, this is because catalyst amount is few, reactivity is low, leads to product yield
It is low.With sodium bicarbonate and 3, the increase of 4,5- trifluoromethyl aniline mass ratioes, the receipts of N- [(3,4,5- trifluoro) phenyl] acrylamide
Rate is gradually increased, and when sodium bicarbonate and 3,4,5- trifluoromethyl aniline mass ratio 0.05:1, product yield has reached 74.2%, into one
Step is further added by the dosage of sodium bicarbonate, and the influence to product yield is simultaneously little, therefore, sodium bicarbonate and 3,4,5- trifluoromethyl aniline matter
Amount is than being preferably 0.05:1.
(2) 3,4,5- trifluoromethyl aniline and acryloyl chloride dosage, which are inquired into, tests
In order to inquire into the molar ratio of 3,4,5- trifluoromethyl aniline and acryloyl chloride to preparation N- [(3,4,5- trifluoro) phenyl] third
Acrylamide yield (the amount of actually generating (mol)/the N- [(3,4,5- tri- of yield=N- [(3,4,5- trifluoro) phenyl] acrylamide
Fluorine) phenyl] acrylamide theoretical production quantity (mol)) and purity influence, inventor carried out following experiment, i.e. embodiment 7
~embodiment 11, corresponding experimental result is referring to table 2.
Embodiment 7:
A kind of preparation method of N- [(3,4,5- trifluoro) phenyl] acrylamide, the specific steps are as follows:
By 14.7 grams of 3,4,5- trifluoromethyl aniline (0.1mol) and 50 grams of reaction dissolvents (reaction dissolvent is dimethylformamide)
It is added in 500ml four-hole bottle, is added 0.735 gram of sodium bicarbonate, the mass ratio of sodium bicarbonate and 3,4,5- trifluoromethyl anilines is 0.05:
1, it is cooled to 5 DEG C under stirring, is added dropwise acryloyl chloride, the molar ratio of 3,4,5- trifluoromethyl anilines and acryloyl chloride is 1:1, is added dropwise
Afterwards, it is reacted 5 hours at 5 DEG C, reaction solution is down to room temperature, 300ml deionized water is then added into reaction solution, filtered, collected
Sediment, sediment, which is dried, both obtains N- [(3,4,5- trifluoro) phenyl] acrylamide.It is surveyed using high performance liquid chromatograph
Customize the purity of standby N- [(3,4,5- trifluoro) phenyl] acrylamide.
8~embodiment of embodiment 11:
The content of 8~embodiment of embodiment 11 is substantially the same manner as Example 7, the difference is that: 3,4,5- trifluoro-benzenes
Amine is different from the molar ratio of acryloyl chloride, referring specifically to table 2.
The molar ratio of 2 3,4,5- trifluoromethyl aniline of table and acryloyl chloride inquires into experiment
As shown in Table 2, when the molar ratio of 3,4,5- trifluoromethyl anilines and acryloyl chloride is 1:1, N- [(3,4,5- trifluoro) benzene
Base] acrylamide yield it is lower, with the increase of the molar ratio of 3,4,5- trifluoromethyl anilines and acryloyl chloride, N- [(3,4,5- tri-
Fluorine) phenyl] yield of acrylamide is gradually increased, when the molar ratio of 3,4,5- trifluoromethyl anilines and acryloyl chloride is 1:1.2, N-
[(3,4,5- trifluoro) phenyl] acrylamide yield highest 74.8%, is further further added by the dosage of acryloyl chloride, N- [(3,4,
5- trifluoro) phenyl] acrylamide yield does not significantly improve, and excessive acryloyl chloride is not easily recycled, and is wasted raw material, pollution
Environment.Therefore, 3,4,5- trifluoromethyl anilines and acryloyl chloride optimum mole ratio are 1:1.2.
(3) reaction temperature inquires into experiment
In order to inquire into reaction temperature to preparation N- [(3,4,5- trifluoro) phenyl] acrylamide yield (yield=N- [(3,4,
5- trifluoro) phenyl] the theoretical of the amount of actually generating (mol)/N- [(3,4,5- trifluoro) phenyl] acrylamide of acrylamide generate
Measure (mol)) and purity influence, inventor carried out following experiment, i.e. 12~embodiment of embodiment 17, and corresponding experiment is tied
Fruit is referring to table 3.
Embodiment 12:
A kind of preparation method of N- [(3,4,5- trifluoro) phenyl] acrylamide, the specific steps are as follows:
By 14.7 grams of 3,4,5- trifluoromethyl aniline (0.1mol) and 50 grams of reaction dissolvents (reaction dissolvent is dimethylformamide)
It is added in 500ml four-hole bottle, is added 0.735 gram of sodium bicarbonate, the mass ratio of sodium bicarbonate and 3,4,5- trifluoromethyl anilines is 0.05:
1, it is cooled to -10 DEG C under stirring, is added dropwise acryloyl chloride, the molar ratio of 3,4,5- trifluoromethyl anilines and acryloyl chloride is 1:1.2, is added dropwise
After, it is reacted 5 hours at -10 DEG C, reaction solution is down to room temperature, 300ml deionized water, mistake are then added into reaction solution
Sediment is collected in filter, and sediment, which is dried, both obtains N- [(3,4,5- trifluoro) phenyl] acrylamide.Using high-efficient liquid phase color
The purity of N- [(3,4,5- trifluoro) phenyl] acrylamide of spectrometer measurement preparation.
13~embodiment of embodiment 17:
The content of 13~embodiment of embodiment 17 is substantially the same manner as Example 12, the difference is that: reaction temperature is not
Together, referring specifically to table 3.
3 reaction temperature of table inquires into experiment
As shown in Table 3, reaction temperature at 5 DEG C hereinafter, N- [(3,4,5- trifluoro) phenyl] acrylamide yield is higher, but it is anti-
Answering temperature is more than after 5 DEG C, and the yield of N- [(3,4,5- trifluoro) phenyl] acrylamide is reduced with the raising of reaction temperature, former
Because being: when reaction temperature is more than 5 DEG C, acryloyl chloride activity is too high, and the amide groups of anilino- and generation is to the carbonyl in acyl chlorides
Nucleophilie nucleus ability is all very strong, and side reaction enhancing causes N- [(3,4,5- trifluoro) phenyl] acrylamide yield very low；Reaction temperature is small
When being equal to 5 DEG C, very strong and amide groups the activity of the activity of anilino- is very weak, and reaction can be generated towards target product is conducive to
Direction carries out, and shows good reaction selectivity, the yield of N- [(3,4,5- trifluoro) phenyl] acrylamide is higher.Reaction temperature
When degree is 5 DEG C, the yield of N- [(3,4,5- trifluoro) phenyl] acrylamide has reached 76.3%, when reaction temperature is lower than 5 DEG C, N-
Less, therefore, from energy-saving and environment-friendly angle, reaction temperature is excellent for the yield variation of [(3,4,5- trifluoro) phenyl] acrylamide
It is selected as 5 DEG C.
(4) reaction time inquires into experiment
In order to inquire into the reaction time to preparation N- [(3,4,5- trifluoro) phenyl] acrylamide yield (yield=N- [(3,4,
5- trifluoro) phenyl] the theoretical of the amount of actually generating (mol)/N- [(3,4,5- trifluoro) phenyl] acrylamide of acrylamide generate
Measure (mol)) and purity influence, inventor carried out following experiment, i.e. 18~embodiment of embodiment 23, and corresponding experiment is tied
Fruit is referring to table 4.
Embodiment 18:
A kind of preparation method of N- [(3,4,5- trifluoro) phenyl] acrylamide, the specific steps are as follows:
By 14.7 grams of 3,4,5- trifluoromethyl aniline (0.1mol) and 50 grams of reaction dissolvents (reaction dissolvent is dimethylformamide)
It is added in 500ml four-hole bottle, is added 0.735 gram of sodium bicarbonate, the mass ratio of sodium bicarbonate and 3,4,5- trifluoromethyl anilines is 0.05:
1, it is cooled to 5 DEG C under stirring, is added dropwise acryloyl chloride, the molar ratio of 3,4,5- trifluoromethyl anilines and acryloyl chloride is 1:1.2, is dripped
Bi Hou reacts 1 hour at 5 DEG C, reaction solution is down to room temperature, and 300ml deionized water is then added into reaction solution, filters, and receives
Collect sediment, sediment, which is dried, both obtains N- [(3,4,5- trifluoro) phenyl] acrylamide.Using high performance liquid chromatograph
Measure the purity of N- [(3,4,5- trifluoro) phenyl] acrylamide of preparation.
19~embodiment of embodiment 23:
The content of 19~embodiment of embodiment 23 is substantially the same manner as Example 18, the difference is that: the reaction time is not
Together, referring specifically to table 4.4 reaction time of table inquires into experiment
As shown in Table 4, the reaction time is affected to N- [(3,4,5- trifluoro) phenyl] acrylamide yield.When reaction
Between be less than 5h when, acryloyl chloride and 3,4,5- trifluoromethyl anilines react it is insufficient, lead to N- [(3,4,5- trifluoro) phenyl] acryloyl
Amine yield is lower.When reaching 5h between when reacted, N- [(3,4,5- trifluoro) phenyl] acrylamide yield reaches 76.3%, continues
Increase the reaction time, N- [(3,4,5- trifluoro) phenyl] acrylamide yield is without significant change；Therefore, the reaction time is preferably
5h。
Embodiment 24:
The content of embodiment 24 is substantially the same manner as Example 9, the difference is that: the reaction dissolvent is methanol.
Embodiment 25:
The content of embodiment 25 is substantially the same manner as Example 9, the difference is that: the reaction dissolvent is acetone.
Embodiment 26:
The content of embodiment 26 is substantially the same manner as Example 9, the difference is that: the reaction dissolvent is ethyl alcohol.
Embodiment 27:
The content of embodiment 27 is substantially the same manner as Example 9, the difference is that: the reaction dissolvent is methanol and second
The mixed liquor of alcohol, methanol and ethyl alcohol are arbitrary proportion in mixed liquor.
Embodiment 28:
The content of embodiment 28 is substantially the same manner as Example 9, the difference is that: the reaction dissolvent is dimethyl methyl
The mixed liquor of amide and acetone, dimethylformamide and acetone are arbitrary proportion in mixed liquor.
Embodiment 29:
The content of embodiment 29 is substantially the same manner as Example 9, the difference is that: the reaction dissolvent is methanol, second
The mixed liquor of alcohol, dimethylformamide and acetone, methanol, ethyl alcohol, dimethylformamide and acetone are arbitrary proportion in mixed liquor.
(5) comparative experiments:
Pair in order to compare the catalytic efficiency of sodium bicarbonate and triethylamine, inventor has carried out following comparative experiments respectively, i.e.,
Ratio 1 and comparative example 2.
Comparative example 1:
A kind of preparation method of N- [(3,4,5- trifluoro) phenyl] acrylamide, the specific steps are as follows:
3,4,5- trifluoromethyl aniline 14.7 grams (0.1mol) and 50 grams of dimethylformamides are added in 500ml four-hole bottle, then
Triethylamine and polymerization inhibitor 2,6-di-tert-butyl p-cresol, triethylamine and 3 is added, the mass ratio of 4,5- trifluoromethyl anilines is 0.05:1,
The additive amount of 2,6-di-tert-butyl p-cresol is the 1% of 3,4,5- trifluoromethyl aniline quality, and 5 DEG C are cooled under stirring, and propylene is added dropwise
The molar ratio of acyl chlorides, 3,4,5- trifluoromethyl anilines and acryloyl chloride is 1:1.2, after being added dropwise, in 5 DEG C of reaction 5h, by reaction solution
It is down to room temperature, 300ml deionized water is then added into reaction solution, sediment is collected in filtering, and sediment, which is dried, both to be obtained
N- [(3,4,5- trifluoro) phenyl] acrylamide.
Comparative example 2:
The content of comparative example 2 and comparative example 1 are essentially identical, the difference is that: polymerization inhibitor is not added in reaction system
DBPC 2,6 ditertiary butyl p cresol.
5 different catalysts catalytic performance comparative experiments of table
As shown in Table 5, with individually using triethylamine as catalyst compared with, using sodium bicarbonate as catalyst n-[(3,
4,5- trifluoro) phenyl] yield of acrylamide improves 28.9%；Polymerization inhibitor 2 is added simultaneously with catalyst is made using triethylamine,
6- di-tert-butyl p-cresol is compared, the yield using sodium bicarbonate as catalyst n-[(3,4,5- trifluoro) phenyl] acrylamide
Improve 22.1%.Therefore, sodium bicarbonate is apparently higher than triethylamine as the catalytic efficiency of catalyst, and without adding polymerization inhibitor
Agent 2,6-di-tert-butyl p-cresol, improves product yield, reduces reaction cost.
The foregoing is merely illustrative of the preferred embodiments of the present invention, but is not limited only to examples detailed above, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1.N- [(3,4,5- trifluoro) phenyl] acrylamide, which is characterized in that its structural formula is as follows:
The preparation method of N- described in claim 1 2. [(3,4,5- trifluoro) phenyl] acrylamide, which is characterized in that including following
Step:
(1) 3,4,5- trifluoromethyl anilines, reaction dissolvent and catalyst are added in reaction vessel, stir and evenly mix, adds acryloyl
Chlorine, in -10 DEG C~30 DEG C 1~7h of reaction；
(2) it into step (1) resulting reaction solution plus water, stirs and evenly mixs, filters, isolate sediment, sediment is through at dry
Reason both obtains N- [(3,4,5- trifluoro) phenyl] acrylamide.
3. preparation method according to claim 2, which is characterized in that the catalyst is sodium bicarbonate.
4. preparation method according to claim 3, which is characterized in that the sodium bicarbonate and 3, the matter of 4,5- trifluoromethyl anilines
Amount is than being (0.01~0.1): 1.
5. the preparation method according to claim 4, which is characterized in that described 3,4,5- trifluoromethyl anilines and acryloyl chloride rub
You are than being 1:(1~2.5).
6. preparation method according to claim 5, which is characterized in that the reaction dissolvent is methanol, ethyl alcohol, acetone, two
At least one of methylformamide.
7. preparation method according to claim 6, which is characterized in that the adding manner of the acryloyl chloride is to be added dropwise.
8. a kind of utilize N- [(3,4,5- trifluoro) phenyl] acrylamide made from any preparation method of claim 2~7
Product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910731248.8A CN110372529B (en) | 2019-08-08 | 2019-08-08 | N- [ (3,4, 5-trifluoro) phenyl ] acrylamide and preparation method thereof |
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| CN201910731248.8A CN110372529B (en) | 2019-08-08 | 2019-08-08 | N- [ (3,4, 5-trifluoro) phenyl ] acrylamide and preparation method thereof |
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| Publication Number | Publication Date |
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| CN110372529A true CN110372529A (en) | 2019-10-25 |
| CN110372529B CN110372529B (en) | 2022-05-24 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844993A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Photo-curing monomer with ortho-phenolic hydroxyl structure, preparation method and bond thereof |
| CN102827025A (en) * | 2012-09-21 | 2012-12-19 | 西华大学 | 2-methoxy-N-(4-fluorophenyl) benzamide as well as preparation method and application of 2-methoxy-N-(4-fluorophenyl) benzamide |
| CN102947316A (en) * | 2010-06-23 | 2013-02-27 | 韩美科学株式会社 | Novel fused pyrimidine derivatives for inhibition of tyrosine kinase activity |
-
2019
- 2019-08-08 CN CN201910731248.8A patent/CN110372529B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844993A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Photo-curing monomer with ortho-phenolic hydroxyl structure, preparation method and bond thereof |
| CN102947316A (en) * | 2010-06-23 | 2013-02-27 | 韩美科学株式会社 | Novel fused pyrimidine derivatives for inhibition of tyrosine kinase activity |
| CN102827025A (en) * | 2012-09-21 | 2012-12-19 | 西华大学 | 2-methoxy-N-(4-fluorophenyl) benzamide as well as preparation method and application of 2-methoxy-N-(4-fluorophenyl) benzamide |
Non-Patent Citations (9)
| Title |
|---|
| CHEMICAL ABSTRACT SERVICE: "RN: 1340077-14-6", 《CA网络版STN REGISTRY数据库》 * |
| CHEMICAL ABSTRACT SERVICE: "RN: 1340077-14-6", 《CA网络版STN REGISTRY数据库》, 3 November 2011 (2011-11-03) * |
| HE LIU等: "Design and synthesis of sulfonamide-substituted diphenylpyrimidines (SFA-DPPYs) as potent Bruton"s tyrosine kinase (BTK) inhibitors with improved activity toward B-cell lymphoblastic leukemia", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》, vol. 135, 14 April 2017 (2017-04-14), pages 60 - 69, XP085047547, DOI: 10.1016/j.ejmech.2017.04.037 * |
| 姚新鼎: "UV固化预聚体的制备及其固化涂层性能研究", 《郑州大学博士学位论文》 * |
| 姚新鼎: "UV固化预聚体的制备及其固化涂层性能研究", 《郑州大学博士学位论文》, 15 January 2012 (2012-01-15) * |
| 袁加程: "酰化反应合成N-(2-溴-4-甲氧基苯基)丙烯酰胺的研究", 《化学世界》 * |
| 袁加程: "酰化反应合成N-(2-溴-4-甲氧基苯基)丙烯酰胺的研究", 《化学世界》, no. 12, 31 December 2012 (2012-12-31), pages 737 - 739 * |
| 高英新等: "N-[4-(磺酰胺)苯基](甲基)丙烯酰胺的合成", 《合成化学》 * |
| 高英新等: "N-[4-(磺酰胺)苯基](甲基)丙烯酰胺的合成", 《合成化学》, vol. 13, no. 1, 31 December 2005 (2005-12-31), pages 22 - 24 * |
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