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CAS No. : | 7685-44-1 | MDL No. : | MFCD00063103 |
Formula : | C5H9NO2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | WNNNWFKQCKFSDK-UHFFFAOYSA-N |
M.W : | 115.13 | Pubchem ID : | 14044 |
Synonyms : |
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Chemical Name : | 2-Aminopent-4-enoic acid |
Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H317-H319-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With sodium hydroxide; In 1,4-dioxane; water; at 0℃; for 16h; | A solution of di-tert-butyl dicarbonate (11.4 g, 52.1 mmol) in 1,4-dioxane (15 mL) was slowly added to a second solution of 2-amino-5-pentenoic acid (5 g, 43.4 mmol) in 1 N NAOH (55 mL) at 0 C. After stirring for 16h, the solution was acidified with 5% HC1 to pH 2, and the resulting mixture was extracted with ethyl acetate (3 x 80 mL). The combined organic layers were dried OVER MGS04 and concentrated. The resulting residue was dissolved in DMF (50 mL) and treated with K2CO3 (7 g, 51 MMOL). After stirring for 15 min, the solution was cooled to 0 C and treated with iodomethane (3.4 mL, 51 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for another 4 h, filtered and the resulting solid was washed with ethyl acetate (200 mL). The filtrate was washed successively with 5% aq HC1, sat. aq NaCl, dried over MGS04 and concented. Purification by flash column chromatography (5% ethyl acetate in heptane) provided 2-tert-Butoxycarbonylamino-5-pentenoic acid methyl ester (9.03 g, 94%) as an oil. 1H NMR (CDC13), 5.73 (m, 1 H), 5.12 (m, 1 H), 5.03 (m, 1 H), 4.38 (dd, J = 6, 12 Hz, 1 H), 3.74 (s, 3 H), 2.51 (m, 2 H), 1.46 (s, 9 H). |
93% | rac. )-2-tert-Butoxycarbonylamiiio-pent-4-enoic acid (A); A solution of DL-allylglycine (20.2 g; 175mmol) in THF/H2O (670/670 ml) was cooled to 0 0C. NaHCO3 (44.11g; 525mmol) was added portionwise and BoC2O (68.8g; 315mmol) was added also portionwise. The reaction mixture was stirred at 0 C under N2 for 5 min, then at rt overnight. The pH of the milky mixture was adjusted to 4 by carefully addition of saturated citric acid at 0C, and the mixture was extracted with EtOAc. The combined org. layers were washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The title compound was isolated as a white solid (35.1 g, 93%). | |
58% | A mixture of 2-aminopent-4-enoic acid (230mg, 2mmol), water (3mL) and tert-butanol (1mL) was treated with NaOH (88mg, 2.2mmol) and stirred until a clear solution was obtained (2-5min). Then Boc-anhydride (654mg, 3mmol) in tert-butanol (1.3mL) was added and stirred at r.t. overnight. The reaction mixture was extracted with diethyl ether (2×25mL). The combined ethereal layer was extracted with saturated Na2CO3 (2×25mL) and the combined aqueous layer was acidified with conc. HCl to pH 1. The aqueous layer was extracted with diethyl ether (3×25mL). The combined organic extracts were washed with brine (25mL), dried (MgSO4) and the solvent was evaporated to give a light brownish oil. Yield: 250mg (58%). 1H NMR (CDCl3) δ 1.42 (s, 9H, CH3), 2.57 (br m, 2H, H-3), 4.22 (br m, 0.25 H, H-2), 4.39 (br m, 0.75 H, H-2), 5.10 (br m, 0.75 H, NH), 5.13 (s, 1H, H-5cis), 5.18 (d, 3J=9Hz, H-5trans), 5.74 (m, 1H, H-4), 6.11 (br m, 0.25 H, NH), 8.24 (br s, 1H, CO2H). 13C NMR (CDCl3) δ 28.3 (q, CH3), 36.4 (t, C-3), 52.8 (d, C-2), 80.3 (s, O-C), 119.3 (t, C-5), 132.2 (d, C-4), 155.5 (s, Boc), 176.2 (s, C-1). |
With sodium hydroxide; potassium hydrogensulfate; In 1,4-dioxane; ethyl acetate; | Step 1: N-Boc-L-2-amino-4-pentenoic acid To a solution of L-2-amino-4-pentenoic acid (1.15 g, 10.0 mmol) in a mixture of dioxane (10 mL) and 1N NaOH (10 mL) was stirred in an ice bath. Di-tert-butyl pyrocarbonate (2.4 g, 11.0 mmol) was added and stirring was continued for 1 h. The solution was concentrated to 10 mL and 30 mL of EtOAc was added. The solution was made acidic (pH = 3) by the addition of solid KHSO4. The aqueous phase was extracted with EtOAc (2 x 10 mL) and dried over MgSO4. Evaporation of the solvent afforded the N-Boc protected amino acid as a white solid. 1H NMR (CDCl3) δ 5.75 (m, 1H), 5.20 (m, 2H), 5.05 (d, J=5.0 Hz, 1H), 4.40 (d, J=5.0 Hz, 1H), 4.57 (m, 2H), 1.47 (s, 9H). | |
Reference Example 34 2-Amino-5-[4-(methyl-pyrimidin-2-ylamino)phenyl]pent-4-enoic acid methyl ester [Show Image] (1) Allylglycine (1.82 g) was dissolved in 1N aqueous sodium hydroxide solution (60 ml), and di-tert-butyl dicarbonate (4.15 g) was added thereto, followed by stirring the resulting mixture at room temperature for 11 hours. Di-tert-butyl dicarbonate (4.15 g) was further added to the reaction solution and the resulting mixture was stirred at room temperature overnight. After adding water to the reaction solution and washing it with ether, the solution was acidified with 3N hydrochloric acid. The solution was extracted twice with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain N-Boc-allylglycine (3.09 g). | ||
With sodium hydroxide; In water; at 20℃; | Reference Example 34 2-Amino-5-[4-(methyl-pyrimidin-2-ylamino)phenyl]pent-4-enoic acid methyl ester [Show Image] (1) Allylglycine (1.82 g) was dissolved in 1N aqueous sodium hydroxide solution (60 ml), and di-tert-butyl dicarbonate (4.15 g) was added thereto, followed by stirring the resulting mixture at room temperature for 11 hours. Di-tert-butyl dicarbonate (4.15 g) was further added to the reaction solution and the resulting mixture was stirred at room temperature overnight. After adding water to the reaction solution and washing it with ether, the solution was acidified with 3N hydrochloric acid. The solution was extracted twice with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain N-Boc-allylglycine (3.09 g). | |
Allylglycine (1.82 g) was dissolved in 1N aqueous sodium hydroxide solution (60 ml), and di-tert-butyl dicarbonate (4.15 g) was added thereto, followed by stirring the resulting mixture at room temperature for 11 hours. Di-tert-butyl dicarbonate (4.15 g) was further added to the reaction solution and the resulting mixture was stirred at room temperature overnight. After adding water to the reaction solution and washing it with ether, the solution was acidified with 3N hydrochloric acid. The solution was extracted twice with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain N-Boc-allylglycine (3.09 g). |