CN106431990B - N-（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine - Google Patents
N-（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine Download PDFInfo
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- CN106431990B CN106431990B CN201610882188.6A CN201610882188A CN106431990B CN 106431990 B CN106431990 B CN 106431990B CN 201610882188 A CN201610882188 A CN 201610882188A CN 106431990 B CN106431990 B CN 106431990B
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- ethylaminobenzoate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a kind of N（4 carboethoxyphenyls）The preparation method of N ' methyl Ns ' phenyl formamidine.For this method using ethylaminobenzoate, alkyl orthoformate, N methylanilines as starting material, activated alumina is catalyst, and N is made in single step reaction（4 carboethoxyphenyls）N ' methyl Ns ' phenyl formamidine.The method of the invention is simple for process, easy to operate, pollution-free, and product purity is high, the used recyclable reuse of alumina catalyst.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of N-（4- carboethoxyphenyls）- N '-methyl-N '-benzene
The preparation method of base carbonamidine.
Background technology
N-（4- carboethoxyphenyls）- N '-methyl-N '-phenyl formamidine is a kind of excellent ultra-violet absorber, extensively
Suitable for materials such as polyurethane, polyvinyl chloride, adhesive, foams, it can effectively prevent product caused by uv damage
Aging, the color stability of enhanced article, prolongs the service life.
N- is prepared at present（4- carboethoxyphenyls）There are mainly three types of the methods of-N '-methyl-N '-phenyl formamidine：
（1）Ethylaminobenzoate is reacted with alkyl orthoformate is made intermediate imine ester, and intermediate is through distillation
Condensation reaction obtains N- at high temperature with methylphenylamine after purification（4- carboethoxyphenyls）- N '-methyl-N '-phenyl formamidine,
Such as patent CN101481330A, US4021471, US4839405 schemes.The shortcoming of this method is that reaction process is long, operation
It is cumbersome, and intermediate imine ester is very active, is easy to during distilation rotten and influences the next step.
（2）Ethylaminobenzoate is condensed to yield N- with N- methyl formyl anilines in the presence of phosphorus oxychloride（4- ethoxies
Base carbonyl phenyl）- N '-methyl-N '-phenyl formamidine, such as patent EP0491280A schemes.Although this method single step reaction, makes
With the strong phosphorus oxychloride of corrosivity, and a large amount of acid waste waters are generated, thus also limits the industrial applications of the method.
（3）Ethylaminobenzoate is with triethyl orthoformate, methylphenylamine one pot in the presence of propionic acid or glacial acetic acid
Reaction purifies to obtain N- through vacuum distillation（4- carboethoxyphenyls）- N '-methyl-N '-phenyl formamidine, such as patent
CN102060734A schemes.One step of this method is completed, and enormously simplifies production process, but Bronsted acid propionic acid is used in reaction process
Or glacial acetic acid makees catalyst, side reaction is more, and product composition is complicated.Main side reaction has：
Under Protic Acid Catalyzed, with triethyl orthoformate formyl occurs for raw material ethylaminobenzoate and methylphenylamine
Change reaction：
Meanwhile glacial acetic acid is excellent acetylation reagent, ethylaminobenzoate and methylphenylamine contain active hydrogen,
Acetylization reaction can occur with glacial acetic acid：
Therefore, this method will produce a large amount of by-products, cause separation and purification of products difficult.In addition, propionic acid or glacial acetic acid pair are set
It is standby that there is very strong corrosivity and not recyclable, cause cost to increase.
Invention content
The present invention is in view of the deficienciess of the prior art, provide that a kind of safety and environmental protection, product purity are high, are suitble to industrial metaplasia
The N- of production（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine.
To achieve the above object, the present invention provides a kind of N-（4- carboethoxyphenyls）- N '-methyl-N '-phenyl formamidine
Preparation method.Include the following steps：
（1）Simultaneously by ethylaminobenzoate, alkyl orthoformate, methylphenylamine, catalyst activity aluminium oxide
It is added in reaction kettle, 50 DEG C ~ 60 DEG C is warming up to, while decompression steams the methanol or ethyl alcohol of generation, until stopping when being distillated without alcohol.
（2）It filters while hot, recycles catalyst, mother liquor is evaporated under reduced pressure to N-（4- carboethoxyphenyls）- N '-methyl-N '-
Phenyl formamidine.
Ethylaminobenzoate, methylphenylamine, alkyl orthoformate, catalyst activity oxidation in the preparation method
The molar ratio of aluminium is：
Ethylaminobenzoate：1；
Alkyl orthoformate：1~2；
Methylphenylamine：1~1.5；
Catalyst：0.1~1.
Alkyl orthoformate described in the preparation method includes trimethyl orthoformate and triethyl orthoformate.
Activated alumina crystal form described in the preparation method is γ types or η types.
Activated alumina specific surface area described in the preparation method is more than or equal to 100m2/g。
The method of the present invention has following remarkable advantage：（1）N- is made in one step of the method for the present invention（4- carboethoxyphenyls）-
N '-methyl-N '-phenyl formamidine, it is simple for process, it is easy to operate, it is pollution-free.（2）Reaction condition of the present invention is mild, and side reaction is few,
Simple distillation is only needed to can be obtained the product of high-purity.（3）The recyclable repetition of catalyst activity aluminium oxide used in the present invention
It uses, reduces cost.
Specific implementation mode
Embodiment 1
By 165 grams（1mol）Ethylaminobenzoate, 107（1mol）Gram methylphenylamine, 106 grams（1mol）Orthoformic acid
Trimethyl and 5.1 grams（0.05mol）Specific surface area is 137m2In the γ type activated aluminas input 500ml reaction bulbs of/g, stirring
And 50 DEG C ~ 60 DEG C are warming up to, insulation reaction 2h.Vacuum pump to be opened, vacuum degree is stepped up, decompression steams the methanol of generation, until
No methanol distillates.
Reaction solution is filtered while hot, the activated alumina of recycling is reused, and mother liquor vacuum distillation obtains thick pale yellow liquid
Body N-（4- carboethoxyphenyls）- N '-methyl-N ' -266.5 grams of phenyl formamidine, yield 94.5%, purity 99.7%.
The activated alumina of recycling is reused 3 times, the preparation method is the same as that of Example 1 for other, the results are shown in Table 1.
Embodiment 2
By 165 grams（1mol）Ethylaminobenzoate, 117.7 grams（1.1mol）Methylphenylamine, 177.8 grams
（1.2mol）Triethyl orthoformate and 10.2 grams（0.1mol）Specific surface area is 137m2The γ type activated aluminas of/g are put into
In 500ml reaction bulbs, stirs and be warming up to 50 DEG C ~ 60 DEG C, insulation reaction 2h.Vacuum pump is opened, vacuum degree is stepped up, is depressurized
The ethyl alcohol of generation is steamed, until being distillated without ethyl alcohol.
Reaction solution is filtered while hot, the activated alumina of recycling is reused, and mother liquor vacuum distillation obtains thick pale yellow liquid
Body N-（4- carboethoxyphenyls）- N '-methyl-N ' -268 grams of phenyl formamidine, yield 95%, purity 99.6%.
The activated alumina of recycling is reused 3 times, other preparation methods the results are shown in Table 1 with embodiment 2.
Embodiment 3
By 165 grams（1mol）Ethylaminobenzoate, 112.35 grams（1.05mol）Methylphenylamine, 159 grams
（1.5mol）Trimethyl orthoformate and 10.2 grams（0.1mol）Specific surface area is 137m2The γ type activated aluminas of/g are put into
In 500ml reaction bulbs, stirs and be warming up to 50 DEG C ~ 60 DEG C, insulation reaction 2h.Vacuum pump is opened, vacuum degree is stepped up, is depressurized
The methanol of generation is steamed, until being distillated without methanol.
Reaction solution is filtered while hot, the activated alumina of recycling is reused, and mother liquor vacuum distillation obtains thick pale yellow liquid
Body N-（4- carboethoxyphenyls）- N '-methyl-N ' -270 grams of phenyl formamidine, yield 95.7%, purity 99.5%.
The activated alumina of recycling is reused 3 times, other preparation methods the results are shown in Table 1 with embodiment 3.
1 catalyst circulation of table applies mechanically reaction result
Claims (3)
1. a kind of N-（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine, it is characterised in that：The system
Preparation Method is by ethylaminobenzoate, alkyl orthoformate, methylphenylamine, catalyst while to be added in reaction kettle,
It is warming up to 50 DEG C ~ 60 DEG C, while decompression steams the methanol or ethyl alcohol of generation and filtered while hot until stopping when being distillated without alcohol, recycling is urged
Agent, mother liquor are evaporated under reduced pressure to N-（4- carboethoxyphenyls）- N '-methyl-N '-phenyl formamidine, the catalyst be than
Surface area is more than or equal to 100m2The γ type activated aluminas of/g.
2. N- as described in claim 1（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine,
It is characterized in that, the alkyl orthoformate is trimethyl orthoformate or triethyl orthoformate.
3. N- as described in claim 1（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine,
Be characterized in that, the ethylaminobenzoate, alkyl orthoformate, methylphenylamine, catalyst molar ratio be：
Ethylaminobenzoate：1；
Alkyl orthoformate：1~2；
Methylphenylamine：1~1.5；
Catalyst：0.1~1.
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| CN201610882188.6A CN106431990B (en) | 2016-10-10 | 2016-10-10 | N-（4- carboethoxyphenyls）The preparation method of-N '-methyl-N '-phenyl formamidine |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108640857B (en) * | 2018-06-07 | 2021-03-30 | 烟台新秀化学科技股份有限公司 | Synthesis process of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylamidine |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
| US4839405A (en) * | 1986-07-08 | 1989-06-13 | Plasticolors, Inc. | Ultraviolet stabilizer compositions, stabilized organic materials, and methods |
| US5243055A (en) * | 1990-12-19 | 1993-09-07 | Givaudan Corporation | Heterocyclic formamidines useful as ultraviolet light absorbers |
| CN101481330B (en) * | 2009-01-20 | 2012-06-20 | 常州市阳光药业有限公司 | Preparation of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine |
| CN101838222B (en) * | 2010-04-24 | 2013-10-09 | 遵义市倍缘化工有限责任公司 | Preparation method of N-(4-ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformamidine |
| CN102060734B (en) * | 2011-01-14 | 2015-05-20 | 江苏尚莱特医药化工材料有限公司 | Method for preparing N-(4-ethyoxylcarbonylphenyl)-N'-methyl-N'-phenyl carbonamidine |
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