CN108516941A - A kind of 3-（Phenyl amino）The preparation method of ethyl propionate class compound - Google Patents
A kind of 3-（Phenyl amino）The preparation method of ethyl propionate class compound Download PDFInfo
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- CN108516941A CN108516941A CN201810251567.4A CN201810251567A CN108516941A CN 108516941 A CN108516941 A CN 108516941A CN 201810251567 A CN201810251567 A CN 201810251567A CN 108516941 A CN108516941 A CN 108516941A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
Abstract
The invention belongs to chemosynthesis technical fields, and in particular to 3（Phenyl amino）The preparation method of ethyl propionate class compound, this method through the following steps that realize：Aromatic amine compounds and ethyl acrylate are mixed, are reacted in the mixed solvent under sodium dihydrogen phosphate catalysis, by obtaining 3 after column chromatography（Phenyl amino）Ethyl propionate class compound.Method provided by the invention carries out, substrate dissolubility is good, applicability is wide under sodium dihydrogen phosphate catalysis in the mixed liquor of water and alcohol；Reaction yield is high, and controllability is strong.Method provided by the invention is environmentally protective, and side reaction product is few, green, efficient.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to 3-（Phenyl amino）The preparation of ethyl propionate class compound
Method.
Background technology
3-（Phenyl amino）Ethyl propionate class compound belongs to beta-amino acid compounds, and beta-amino acids are beta-amino carboxylics
One of most important intermediate in based compound, such as beta-lactam and taxol have the bioactive substance of medical value
It can further be synthesized by beta-amino acids, while beta-amino acids are also research peptide chain primary structure and secondary structure activity
With the important substance of stability.Therefore, 3- is synthesized（Phenyl amino）Ethyl propionate class compound has very important pharmacy valence
Value and economic value.
The azepine Michael addition reaction of amine and electron deficient olefins is to synthesize the effective way of beta-amino carbonyls.Virtue
The azepine Michael addition reaction of fragrant race's amine can carry out under strong acid or strong basicity catalytic condition, but often with a large amount of secondary
Product generates, and can also bring the residual of harmful substance.In order to it is more green, efficiently synthesize aromatic series beta-amino carbonyls
Various catalyst and new technology are used.Tetrahedron Lett.2013,54 (21), 2669-73, which are provided, a kind of using carbonic acid
Sodium water solution is the 3- of catalyst（Phenyl amino）The preparation method of ethyl propionate class compound.This method can obtain single alkane
The product of base.But the reaction effect of the solid-state aromatic amine of some poorly water-solubles is poor.Therefore a kind of synthetic method is developed
Simply, the good technique of selectivity becomes urgent problem to be solved.
Invention content
In view of the problems of the existing technology, the invention discloses a kind of 3-（Phenyl amino）Ethyl propionate class compound
Preparation method, this method is easy to operate, wide application range of substrates, and yield is high, and application is strong.
In order to achieve the above objectives, as follows using technical solution：
The present invention provides a kind of 3-（Phenyl amino）The preparation method of ethyl propionate class compound, includes the following steps：It will be fragrant
Fragrant aminated compounds and ethyl acrylate mixing, are reacted in the mixed solvent under sodium dihydrogen phosphate catalysis, pass through column layer
3- is obtained after analysis（Phenyl amino）Ethyl propionate class compound；
Wherein, the product 3-（Phenyl amino）Ethyl propionate class structural formula of compound is：
In formula, the R is alkyl, halogen, alkoxy or hydrogen.
Further, the molar ratio of the aromatic amine and ethyl acrylate is 1：1.0-1.5；Preferred molar ratio is 1：
1.2。
The general formula of aromatic amine compounds of the present invention is as follows：
；
The R is alkyl, halogen, alkoxy or hydrogen.
Further, the aromatic amine and sodium dihydrogen phosphate molar ratio are 1：0.05-0.20；Most preferred molar ratio is 1：
0.10。
Further, the solid-liquid ratio of the mixed solvent and sodium dihydrogen phosphate is 1mL：0.1mmol；The mixed solvent is
Water mixes gained with isometric alcohol.
Above-mentioned alcohol is methanol or ethyl alcohol；Most preferably methanol.
Further, the temperature of the reaction is 50-80 DEG C；It optimizes, the temperature of reaction is 60 DEG C.
Further, the eluant, eluent of the column chromatography is ethyl acetate and n-hexane according to volume ratio 1：6 compositions.
Reaction formula is as follows in the present invention：
。
Beneficial effects of the present invention are：
（1）Method provided by the invention carries out, substrate dissolubility under sodium dihydrogen phosphate catalysis in the mixed liquor of water and alcohol
Well, applicability is wide；Reaction yield is high, and controllability is strong.
（2）Method provided by the invention is environmentally protective, and side reaction product is few, green, efficient.
Specific implementation mode
Following embodiment further illustrates technical scheme of the present invention, but not as limiting the scope of the invention.
Embodiment 1
Aniline（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）With etc.
48h, ethyl acetate extraction are reacted in the mixed solution of volumes methanol and at 60 DEG C（3X20 mL）, merge organic layer, saturation food
Salt water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）
Product 3-（Phenyl amino）Ethyl propionate, yield 90%.
1H NMR (400 MHz, CDCl3) δ 7.21-7.18 (m,2H), 6.76-6.73 (m, 1H), 6.64-
6.61 (m, 2H), 4.17 (q, J = 8.0 Hz, 2H), 3.46 (t, J = 6.0 Hz, 2H), 2.60 (t, J
= 6.0 Hz, 2H), 1.27 (t, J = 8.0 Hz, 3H)；13C NMR (100 MHz, CDCl3) δ 172.4,
147.7, 129.3, 117.5, 113.0, 60.5, 39.4, 33.8, 14.2.。
Embodiment 2
4- fluoroanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）
48h is reacted in the mixed solution of isometric methanol and at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic layer, satisfy
And brine It（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：
6）Obtain product 3-（4- Fluorophenylaminos）Ethyl propionate, yield 85%.
1H NMR(CDCl3, 400 MHz)：δ 6.93 (m, 4H), 4.15 (m, 2H), 3.41 (t, J=6.0 Hz, 2H),
2.61 (t, J=6.0 Hz, 2H), 1.26 (t, J=8.0 Hz, 3H)；13C NMR(CDCl3, 100 MHz)：δ 171.0,
155.8,143.2,118.9,116.4,61.3,37.8,35.8,14.2.
Embodiment 3
4- chloroanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）
48h is reacted in the mixed solution of isometric methanol and at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic layer, satisfy
And brine It（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：
6）Obtain product 3-（4- chlorphenylaminos）Ethyl propionate, yield 75%.
1H NMR (400 MHz, CDCl3)δ7.14 (d, J = 8.0 Hz, 2H), 6.56 (d, J = 8.0 Hz,
2H), 4.17 (q, J = 8.0 Hz, 2H),4.09 (m, 1H), 3.42 (t, J = 4.0, 2H), 2.57 (t, J
= 4.0 Hz, 2H), 1.28 (t, J = 8.0 Hz,3H); 13C NMR (100 MHz, CDCl3) δ 172.4,
146.3, 129.2, 122.4, 114.1, 60.7, 39.6, 33.7, 14.2。
Embodiment 4
4- bromanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）
48h is reacted in the mixed solution of isometric methanol and at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic layer, satisfy
And brine It（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：
6）Obtain product 3-（4- bromophenylaminos）Ethyl propionate, yield：70%.
1H NMR (400 MHz, CDCl3) δ7.26 (d, J = 8.0 Hz, 2H), 6.51 (d, J = 12 Hz,
2H), 4.18 (q, J = 8.0 Hz, 2H),3.40 (t, J = 6.0 Hz, 2H), 2.58 (t, J = 6.0 Hz,
2H), 1.27 (t, J = 8.0 Hz, 3H); 13CNMR (100 MHz, CDCl3) δ 172.3, 146.7, 132.0,
114.7, 109.3, 60.7, 39.4, 33.8,14.2.
Embodiment 5
4- methylanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2
mL）48h is reacted in the mixed solution of isometric methanol and at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic
Layer, saturated common salt water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/just oneself
Alkane=1：6）Obtain product 3-（4- MethYlphenylaminos）Ethyl propionate, yield 95%.
1H NMR(CDCl3, 400 MHz)：δ 7.03 (d, J=7.5 Hz, 2H), 6.50 (d, J=7.5 Hz, 2H),
4.13 (m, 2H), 3.52 (t, J=6.5 Hz, 2H), 2.65 (t, J=6.5 Hz, 2H), 2.34 (S, 3H), 1.29 (t, J=7.0
Hz, 3H)13C NMR(CDCl3, 100 MHz)：δ 170.9,144.7,129.8,129.6,113.4,61.3,37.8,
35.7,21.3,14.2.
Embodiment 6
4- oxygen methylanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2
mL）48h is reacted in the mixed solution of isometric methanol and at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic
Layer, saturated common salt water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/just oneself
Alkane=1：6）Obtain product 3-（4- oxygen MethYlphenylaminos）Ethyl propionate, yield 98%.
1H NMR(CDCl3, 400 MHz)：δ 6.69-6.63 (m, 4H), 4.16-4.13 (m, 2H), 3.74 (S, 3H),
3.40 (t, J=6.5 Hz, 2H), 2.59 (t, J=6.5 Hz, 2H), 1.26 (t, J=7.5 Hz, 3H)13C NMR(CDCl3,
100 MHz)：δ 171.0,151.8,139.9,115.1,113.4,61.3,55.8,37.8,35.7,14.2.
Embodiment 7
Aniline（4 mmol）And ethyl acrylate（4 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）With equal bodies
48h, ethyl acetate extraction are reacted in the mixed solution of product methanol and at 50 DEG C（3X20 mL）, merge organic layer, saturated common salt
Water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）It must produce
Object 3-（Phenyl amino）Ethyl propionate, yield 75%.
Embodiment 8
Aniline（4 mmol）And ethyl acrylate（6 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）With equal bodies
48h, ethyl acetate extraction are reacted in the mixed solution of product methanol and at 80 DEG C（3X20 mL）, merge organic layer, saturated common salt
Water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）It must produce
Object 3-（Phenyl amino）Ethyl propionate, yield 84%.
Comparative example 1
4- methylanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to aqueous sodium carbonate（0.1M, 4 mL）And
48h is reacted at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous slufuric acid
Sodium is dried, and is filtered, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（4- MethYlphenylaminos）Third
Acetoacetic ester, yield 75%.
Comparative example 2
Aniline（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.1M, 4 mL）And
60 DEG C of reaction 48h, ethyl acetate extraction（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous sodium sulfate
It is dry, it filters, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（Phenyl amino）Ethyl propionate,
Yield is 70%.
Comparative example 3
Aniline（4 mmol）And ethyl acrylate（4.8 mmol）It is added to the mixed solution of water and methanol（1：Isosorbide-5-Nitrae mL）And
60 DEG C of reaction 48h, ethyl acetate extraction（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous sodium sulfate
It is dry, it filters, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（Phenyl amino）Ethyl propionate,
Yield is 65%.
Comparative example 4
Aniline（4 mmol）And ethyl acrylate（4.8 mmol）It is added to the water（4 mL）And 48h, acetic acid second are reacted at 60 DEG C
Ester extracts（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column
Chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（Phenyl amino）Ethyl propionate, yield 15%.
Comparative example 5
Aniline（4 mmol）And ethyl acrylate（4.8 mmol）It is added in methanol（4 mL）And 48h, acetic acid are reacted at 60 DEG C
Ethyl ester extracts（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.
Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（Phenyl amino）Ethyl propionate, yield 10%.
Comparative example 6
Aniline（4 mmol）And ethyl acrylate（6.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）With etc.
48h, ethyl acetate extraction are reacted in the mixed solution of volumes methanol and at 60 DEG C（3X20 mL）, merge organic layer, saturation food
Salt water washing（20 mL）, anhydrous sodium sulfate drying, filtering, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）
Product 3-（Phenyl amino）Ethyl propionate, the by-product contained in product increase, and yield declines.
Comparative example 7
4- chloroanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）,
48h is reacted at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous slufuric acid
Sodium is dried, and is filtered, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（4- chlorphenylaminos）Propionic acid
Ethyl ester, yield 40%.
Comparative example 8
4- bromanilines（4 mmol）And ethyl acrylate（4.8 mmol）It is added to biphosphate sodium water solution（0.2M, 2 mL）,
48h is reacted at 60 DEG C.Ethyl acetate extracts（3X20 mL）, merge organic layer, saturated common salt water washing（20 mL）, anhydrous slufuric acid
Sodium is dried, and is filtered, concentration.Column chromatography（Eluant, eluent：Ethyl acetate/n-hexane=1：6）Obtain product 3-（4- bromophenylaminos）Propionic acid
Ethyl ester, yield 28%.
Claims (9)
1. a kind of 3-（Phenyl amino）The preparation method of ethyl propionate class compound, which is characterized in that include the following steps：It will be fragrant
Fragrant aminated compounds and ethyl acrylate mixing, are reacted in the mixed solvent under sodium dihydrogen phosphate catalysis, pass through column layer
3- is obtained after analysis（Phenyl amino）Ethyl propionate class compound；
Wherein, the product 3-（Phenyl amino）Ethyl propionate class structural formula of compound is：
In formula, the R is alkyl, halogen, alkoxy or hydrogen.
2. preparation method according to claim 1, which is characterized in that the molar ratio of the aromatic amine and ethyl acrylate is
1：1.0-1.5；Preferred molar ratio is 1：1.2.
3. preparation method according to claim 1 or 2, which is characterized in that the general formula of the aromatic amine compounds is as follows：；
The R is alkyl, halogen, alkoxy or hydrogen.
4. preparation method according to claim 1 or 2, which is characterized in that the aromatic amine and sodium dihydrogen phosphate molar ratio
It is 1：0.05-0.20；Preferred molar ratio is 1：0.10.
5. preparation method according to claim 1, which is characterized in that the solid-liquid ratio of the mixed solvent and sodium dihydrogen phosphate
For 1mL：0.1mmol；The mixed solvent is that water mixes gained with isometric alcohol.
6. preparation method according to claim 5, which is characterized in that the alcohol is methanol or ethyl alcohol；Preferably methanol.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that the temperature of the reaction is 50-80 DEG C.
8. preparation method according to claim 7, which is characterized in that the temperature of the reaction is 60 DEG C.
9. preparation method according to claim 1, which is characterized in that the eluant, eluent of the column chromatography is for ethyl acetate and just
Hexane is according to volume ratio 1：6 compositions.
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| CN111153807A (en) * | 2020-01-16 | 2020-05-15 | 河南豫辰药业股份有限公司 | Preparation method of N, N-dimethylamino chloropropane hydrochloride |
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