CN105315168B - N (4 carboethoxyphenyl) N ' methyl Ns ' phenyl formamidine intermediate green preparation process - Google Patents
N (4 carboethoxyphenyl) N ' methyl Ns ' phenyl formamidine intermediate green preparation process Download PDFInfo
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Abstract
The invention discloses a kind of N (4 carboethoxyphenyl) N ' methyl Ns ' green preparation process of phenyl formamidine intermediate, including paranitrobenzoic acid carries out esterification with ethanol under the catalysis of the concentrated sulfuric acid, the material after esterification post-processed and the obtained ethylaminobenzoate of catalytic hydrogenation；The post processing includes the material after esterification stratification after ethanol is evaporated off, and neutralisation treatment is carried out to lower floor's material.The material of the green preparation process of the present invention after esterification first separate the concentrated sulfuric acid before neutralisation treatment, so will not only produce a large amount of high-salt wastewaters, reduces pollution on the environment, and can improve esterification yield.
Description
Technical field
The invention belongs to technical field of fine, and in particular to and a kind of N- (4- carboethoxyphenyls)-N '-methyl-
The green preparation process of N '-phenyl formamidine intermediate ethylaminobenzoate.
Background technology
N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine is a kind of efficient uvioresistant additive, can
With the ultraviolet light of efficient absorption 240-340nm wave bands.N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine is with having
Machine macromolecular has good compatibility, and light and heat stability, is widely used in the high scores such as polyurethane, adhesive, foam
In sub- material.It is liquid under N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine normal temperature, processing characteristics is preferable, and
And compared with the ultra-violet absorber of benzophenone or benzotriazole, N- (4- carboethoxyphenyls)-N '-methyl-N '-benzene
The anti-ultraviolet property of base carbonamidine is more excellent, thus with wide market prospects.
The method for preparing N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine at present is with p-aminophenyl
Ethyl formate is initiation material, is condensed with the methyl/ethyl ester of orthoformic acid three and methylphenylamine through two steps（Such as american documentation literature
US4021471A, US4839405A, Chinese patent literature CN101481330A, CN101838222A）Or one step condensation（As in
State patent document CN102060734A）It is made.But, either two step condensation reactions or a step condensation reaction can be produced
Substantial amounts of ethanol, and these ethanol, so as to can not directly apply, do not only result in wave due to the impurity produced containing condensation reaction
Take, and environment can be polluted.
The preparation of ethylaminobenzoate is mainly using paranitrobenzoic acid as initiation material, through esterification and hydrogenation
Reaction is made.The catalyst that wherein esterification is used is mainly the concentrated sulfuric acid.But the concentrated sulfuric acid that prior art is used is city
The pure concentrated sulfuric acid is sold, so that cost is of a relatively high, and the concentrated sulfuric acid is directly entered acid-base neutralization process after esterification, so
A large amount of high-salt wastewaters can be not only produced, larger pollution are caused to environment, but also the water of ethyl p-nitrobenzoate can be caused
Solution, so as to cause esterification yield to reduce.
The content of the invention
It is an object of the invention to solve the above problems, there is provided a kind of environmentally friendly, N- that esterification yield is higher
The green preparation process of (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine intermediate.
Realizing the technical scheme of above-mentioned purpose of the present invention is：A kind of N- (4- carboethoxyphenyls)-N '-methyl-N '-benzene
The green preparation process of base carbonamidine intermediate, including paranitrobenzoic acid carry out being esterified instead under the catalysis of the concentrated sulfuric acid with ethanol
, the material after esterification should be post-processed and ethylaminobenzoate is made in catalytic hydrogenation；Locate after described
Reason includes the material after esterification stratification after ethanol is evaporated off, and neutralisation treatment is carried out to lower floor's material.
In order to reduce production cost and further improve esterification yield, the concentrated sulfuric acid that the esterification is used for
Recycle the concentrated sulfuric acid；It is described recycling the concentrated sulfuric acid be by the upper materials after above-mentioned stratification vacuum ＜-
Vacuum distillation is carried out under 0.09Mpa, after steaming to 120~122 DEG C, control is distilled to anhydrous distillate in the temperature to be produced.
Further, green preparation process of the invention also includes the process for reclaiming paranitrobenzoic acid：It is to above-mentioned
Organic solvent is added in material after neutralisation treatment, stratification, lower aqueous solution salt acid for adjusting pH value is 5, is made to nitro
Benzoic acid is isolated after separating out.
Described organic solvent is toluene, and the temperature for adding organic solvent is 45 ± 2 DEG C.
In order to further reduce the pollution to environment and reduce production cost, the ethanol that the esterification is used for return
Receive processing ethanol；It is described recycling ethanol be by ethylaminobenzoate condensation prepare N- (4- carboethoxyphenyls)-
The ethanol produced during N '-methyl-N '-phenyl formamidine is obtained after collecting through recycling.The recovery and treatment method is as follows：
First rectifying makes purity of alcohol reach 96%~97%, is then handled with sodium hydroxide, and finally distillation obtains purity >=99.5%
Recycle ethanol.
The other conditions and prior art of the esterification are essentially identical, such as reaction temperature is general more than 78 DEG C,
But no more than 100 DEG C, be preferred with 78 DEG C~90 DEG C, it is optimal more with 78 DEG C~82 DEG C；The alkyd of esterification（Anhydrous second
Alcohol and paranitrobenzoic acid）Mol ratio is 1: 1~10: 1, preferably 3: 1~7: 1, more preferably 5: 1~6: 1；It is catalyzed in esterification
The mol ratio of agent and paranitrobenzoic acid is 1: 1~1: 6, preferably 1: 2~1: 5, more preferably 1: 3~1: 4.
The condition of the catalytic hydrogenation and prior art are essentially identical.
The good effect that the present invention has：（1）During the material of the green preparation process of the present invention after esterification is carried out
With first the concentrated sulfuric acid is separated before processing, so will not only produce a large amount of high-salt wastewaters, reduce the dirt caused to environment
Dye, and esterification yield can be improved.（2）The green preparation process of the present invention is by the dense sulphur separated after esterification
Acid is used further to esterification after being recycled, and not only reduce further production cost, and due to the recycling after
The concentrated sulfuric acid in contain a small amount of paranitrobenzoic acid, therefore can also further improve esterification yield.（3）The present invention's is green
Color preparation technology can also effectively reclaim paranitrobenzoic acid, can further reduce production cost and reduce to environment
Pollution.（4）The present invention green preparation process by ethylaminobenzoate condensation prepare N- (4- carboethoxyphenyls)-
The ethanol produced during N '-methyl-N '-phenyl formamidine is used in esterification after being recycled, and not only further subtracts
Lack the pollution to environment, and reduce further production cost, the especially ethanol after present invention recycling and city
Absolute ethyl alcohol is sold to have little to no effect compared to esterification effect.
Embodiment
（Comparative example 1）
This comparative example is the preparation method of existing N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine, tool
Body step is as follows：
1. by 80kg commercial anhydrous ethanol（1.74kmol）Put into reactor, then stir lower input 50kg pair
Nitrobenzoic acid（0.30kmol）And the 10kg commercially available pure concentrated sulfuric acid（0.10kmol）, stirring is warming up to 80 ± 2 DEG C after adding,
Back flow reaction 6h.
After reaction terminates, ethanol is first distilled out, then material insulation is moved in neutralization kettle, 60 ± 2 DEG C are naturally cooled to
Afterwards, then add water and control temperature to be 50~55 DEG C, then it is 8 to adjust pH value with 5wt% aqueous sodium carbonate, after stirring 0.5h
Repetition measurement pH.After neutralization terminates, 90kg toluene is added, 45 ± 2 DEG C of temperature, stratification is controlled.Upper organic layer carries out follow-up
Catalytic hydrogenation, lower aqueous layer enter waste liquid kettle in.
2. the organic layer and 100g, 5wt% Pd/C catalyst 1. step obtained is added in autoclave pressure, first uses nitrogen
Gas is replaced three times, and logical hydrogen is to 0.6MPa under then stirring, and 3~5h of progress catalytic hydrogenation at a temperature of 80 ± 2 DEG C.
After catalytic hydrogenation terminates, be incubated 2h, by reaction system press filtration while hot, cool down suction filtration, centrifugation, filter cake through 60~
41.6kg ethylaminobenzoate is obtained after 70 DEG C of dryings, purity is 99.2%（HPLC）, two step yields are 83.5%.
3. 249kg triethyl orthoformate is first pumped into reactor, 41.6kg pairs that 2. step obtains then is put into again
Benzocaine, is warming up to 90 ± 2 DEG C, now there is distillate appearance, and distillate access receiving tank is reclaimed into ethanol, then will material
Temperature rise is to 140 ± 2 DEG C, insulation reaction 1h.
After insulation reaction terminates, triethyl orthoformate is reclaimed in vacuum distillation, and obtains 50.0kg NE, and purity is 99.2%
（HPLC）Yield 90.1%.
4. the 50.0kg 3. step obtained NE is pumped into reactor, then is pumped into 25.1kg methylphenylamine, is heated up
To 100 ± 2 DEG C of insulation reaction 15h.
After insulation reaction terminates, ethanol and methylphenylamine are reclaimed in vacuum distillation, and obtain 62.6kg N- (4- ethyoxyls
Carbonyl phenyl)-N '-methyl-N '-phenyl formamidine, purity is 99.2%（HPLC）Yield is 98.0%.
（Example 1）
The step of this example is comparative example 1 3. with step is 4. middle collects obtained ethanol recovery and treatment method：
To first obtained ethanol progress rectifying be collected, obtain the preliminary recovery ethanol that purity is 96%~97%；Then to this
Preliminary reclaim in ethanol adds sodium hydroxide（Addition is 1% or so of ethanol weight）, backflow is heated to, 2h is incubated；Finally open
Beginning air-distillation, collects cut, stops heating when interior temperature reaches 85 DEG C, obtains the recycling ethanol of purity >=99.5%.
（Embodiment 1）
The present embodiment prepares work for the green of N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine intermediate
Skill, is comprised the following steps that：
1. by 80kg commercial anhydrous ethanol（1.74kmol）Put into reactor, then stir lower input 50kg pair
Nitrobenzoic acid（0.30kmol）And the 10kg commercially available concentrated sulfuric acid（0.10kmol）, stirring is warming up to 80 ± 2 DEG C after adding, and returns
Stream reaction 6h.
After reaction terminates, first air-distillation goes out ethanol, after steaming to 95~98 DEG C, starts vacuum distillation and goes out ethanol, works as steaming
To after 80 ± 2 DEG C, stop heating, stratification.
By overlying catalyst layer（Namely concentrated sulfuric acid layer）Move in distillation still, vacuum distillation（Vacuum ＜ -0.09MPa）,
After steaming to 120~122 DEG C, control is distilled to anhydrous in the temperature to be distillated, and is recycled the processing concentrated sulfuric acid.
Lower organic layer insulation is moved in neutralization kettle, naturally cooled to after 60 ± 2 DEG C, with 5wt% aqueous sodium carbonate
It is 8 to adjust pH value, repetition measurement pH after stirring 0.5h.After neutralization terminates, 90kg toluene is added, 45 ± 2 DEG C of temperature is controlled, stands and divides
Layer.Upper organic layer carries out follow-up catalytic hydrogenation, and lower aqueous layer is evacuated in raw materials recovery kettle, is 5 with salt acid for adjusting pH value, stirs
Mix centrifugation after 10min and reclaim the paranitrobenzoic acid for obtaining 2.5kg, filtrate enters in waste liquid kettle.
2. the organic layer and 100g, 5wt% Pd/C catalyst 1. step obtained is added in autoclave pressure, first uses nitrogen
Gas is replaced three times, and logical hydrogen is to 0.6MPa under then stirring, and 3~5h of progress catalytic hydrogenation at a temperature of 80 ± 2 DEG C.
After catalytic hydrogenation terminates, be incubated 2h, by reaction system press filtration while hot, cool down suction filtration, centrifugation, filter cake through 60~
46.0kg ethylaminobenzoate is obtained after 70 DEG C of dryings, purity is 99.7%（HPLC）, two step yields are 97.7%（To detain
Except the paranitrobenzoic acid meter after recovery）.
（Embodiment 2）
Remaining is same as Example 1 for the present embodiment, and difference is：The concentrated sulfuric acid of step 1. middle use is according to implementation
The step of example 1 1. in the obtained recycling concentrated sulfuric acid of recovery and treatment method（The concentrated sulfuric acid is referred to as recycled in table 1）, instead
1 should be the results are shown in Table.
（Embodiment 3）
Remaining is same as Example 1 for the present embodiment, and difference is：The ethanol of step 1. middle use is according to example 1
The obtained recycling ethanol of recovery and treatment method（Ethanol is referred to as recycled in table 1）, reaction result is shown in Table 1.
（Embodiment 4）
Remaining is same as Example 1 for the present embodiment, and difference is：The concentrated sulfuric acid of step 1. middle use is according to implementation
The step of example 1 1. in the obtained recycling concentrated sulfuric acid of recovery and treatment method；The ethanol of use is at the recovery according to example 1
The recycling ethanol that reason method is obtained, reaction result is shown in Table 1.
（1~comparative example of comparative example 4）
Remaining is same as Example 1 for each comparative example, and difference is：The step 1. ethanol of middle use and the concentrated sulfuric acid
Source, is specifically shown in Table 1.
Table 1
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Ethanol is originated | Commercial anhydrous second Alcohol | Commercial anhydrous second Alcohol | Commercial anhydrous ethanol | Recycle second Alcohol | Recycle ethanol | Commercial anhydrous ethanol | Recycle ethanol | Reclaim untreated second Alcohol | Reclaim untreated ethanol |
| The concentrated sulfuric acid is originated | Commercially available pure dense sulphur Acid | Commercially available pure dense sulphur Acid | Recycle dense sulphur Acid | Commercially available pure dense sulphur Acid | Recycle dense sulphur Acid | Reclaim untreated dense sulphur Acid | Reclaim untreated dense sulphur Acid | The commercially available pure concentrated sulfuric acid | Recycle the concentrated sulfuric acid |
| Dense sulfuric acid treatment side Formula | In being directly entered With | Separation and recovery | Separation and recovery | Separation and recovery | Separation and recovery | Separation and recovery | Separation and recovery | Separation and recovery | Separation and recovery |
| BZ weight | 41.6kg | 46.0kg | 46.4kg | 45.4kg | 46.0kg | 21.3kg | 20.9kg | 43.3kg | 43.8kg |
| BZ purity | 99.2% | 99.7% | 99.7% | 99.6% | 99.5% | 99.2% | 99.1% | 96.9% | 97.5% |
| BZ yields | 83.5% | 97.7% | 98.6% | 96.4% | 97.5% | 45.0% | 44.1% | 89.4% | 91.0% |
BZ represents ethylaminobenzoate in table 1.
As can be seen from Table 1：
（1）The yield of esterification can be significantly improved compared to being directly entered N-process after the concentrated sulfuric acid is separated and recovered
（Referring to comparative example 1 and embodiment 1）.
（2）The result of esterification is carried out compared with using the commercially available pure concentrated sulfuric acid using the recycling concentrated sulfuric acid of the present invention
Yield is also slightly improved, and both are significantly better than that the untreated concentrated sulfuric acid of recovery（Referring to comparative example 1 and comparative example 2）, and as right
Ratio 1 and comparative example 2 so low yield in fact show that the untreated concentrated sulfuric acid being catalyzed after use is typically to be unsuitable for using
's.
（3）The result of esterification is carried out with using commercial anhydrous ethanol difference not using the recycling ethanol of the present invention
It is many, and it is significantly better than that the untreated ethanol of recovery（Referring to comparative example 3 and comparative example 4）.
Claims (5)
1. a kind of preparation technology of N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine intermediate, including to nitro
Benzoic acid carries out esterification with ethanol under the catalysis of the concentrated sulfuric acid, the material after esterification is post-processed and is catalyzed
Ethylaminobenzoate is made in hydrogenation；It is characterized in that：The post processing includes the material after esterification being evaporated off
Stratification after ethanol, neutralisation treatment is carried out to lower floor's material；
The concentrated sulfuric acid that the esterification is used is the recycling concentrated sulfuric acid；The recycling concentrated sulfuric acid is to divide described stand
Upper materials after layer carry out vacuum distillation under vacuum ＜ -0.09Mpa, after steaming to 120~122 DEG C, control in the temperature
Produced after degree distillation to anhydrous distillate.
2. the preparation of N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine intermediate according to claim 1
Technique, it is characterised in that also include the process of recovery paranitrobenzoic acid：It is added into the material after the neutralisation treatment
Organic solvent, stratification, lower aqueous solution salt acid for adjusting pH value is 5, makes paranitrobenzoic acid isolated after separating out.
3. the preparation of N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine intermediate according to claim 2
Technique, it is characterised in that：Described organic solvent is toluene, and the temperature for adding organic solvent is 45 ± 2 DEG C.
4. in the middle of N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine according to one of claims 1 to 3
The preparation technology of body, it is characterised in that：The ethanol that the esterification is used is recycling ethanol；The recycling ethanol
It is to be produced during prepared by ethylaminobenzoate condensation into N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine
Raw ethanol is obtained after collecting through recycling.
5. the preparation of N- (4- carboethoxyphenyls)-N '-methyl-N '-phenyl formamidine intermediate according to claim 4
Technique, it is characterised in that the recovery and treatment method is as follows：First rectifying makes purity of alcohol reach 96%~97%, then uses hydroxide
Sodium is handled, and finally distillation obtains the recycling ethanol of purity >=99.5%.
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| CN108314627A (en) * | 2018-04-26 | 2018-07-24 | 常州永和精细化学有限公司 | Benzocainum green preparation process |
| CN110075773A (en) * | 2019-05-31 | 2019-08-02 | 常州瑞曦生物科技有限公司 | The method of its synthesis benzocainum of micro-reactor apparatus and application |
| CN114014761A (en) * | 2021-12-02 | 2022-02-08 | 西安淳甄新材料有限公司 | Method for separating o-nitrobenzoic acid based on esterification |
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| US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
| CN1760117A (en) * | 2005-10-19 | 2006-04-19 | 兰州大学 | Method for recovering vitriol from waste vitrol containing metal salt |
| CN101481330A (en) * | 2009-01-20 | 2009-07-15 | 常州市阳光医药原料有限公司 | Preparation of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine |
-
2015
- 2015-11-27 CN CN201510839392.5A patent/CN105315168B/en active Active
Patent Citations (3)
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|---|---|---|---|---|
| US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
| CN1760117A (en) * | 2005-10-19 | 2006-04-19 | 兰州大学 | Method for recovering vitriol from waste vitrol containing metal salt |
| CN101481330A (en) * | 2009-01-20 | 2009-07-15 | 常州市阳光医药原料有限公司 | Preparation of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine |
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| Title |
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