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A mixture of (R) -tert-butyl 3-azidopyrrolidine-1-carboxylate (250 mg, 1.18 mmol) and Pd/C (10, 50 mg) in methanol (10 mL) was stirred at rt under HThe compound (R) -3- azido-pyrrolidine-1-carboxylate (250mg, 1.18mmol) and Pd / C (10percent, 50mg) wasdissolved in methanol (10mL of), at room temperature, normal pressure hydrogen reduction, the reaction isstopped after 12h the reaction, filtration, and the filtrate was concentrated to give 210mg of colorless liquid: (R) -3- Amino-pyrrolidine-1-carboxylate, yield: 96percent.To a solution of product 178 (907 mg, 4.27 mmol, 1.0 eq.) in 25 mL of methanol, palladium on charcoal (454 mg, 0.43 mmol, 0.1 eq.) is added. The reaction medium is submitted to hydrogenation at atmospheric pressure and at room temperature for 6 hours. The reaction medium is then filtered on celite and concentrated under dry conditions under reduced pressure. The expected compound is obtained as a yellow oil (740 mg, 93percent).Step 5-1: Production of (R)-1-(tert-butoxycarbonyl)-3-aminopyrrolidine; To 5.56 g of (S)-1-(tert-butoxycarbonyl)-3-(methanesulfonyloxy)pyrrolidine produced by the method described in Production was added 36.4 g of a 28percent by weight aqueous ammonia solution, and the mixture was stirred at 90°C for 19 hrs (internal pressure: about 4 barr). After cooling, ammonia was removed by distillation, and thereto were added 10 ml of water and 3.21 g of a 30percent by weight aqueous sodium hydroxide solution. After the aqueous solution was concentrated under reduced pressure, 10 ml of a saturated brine was added thereto, and the target substance was extracted with 20 ml of ethyl acetate three times. Thus obtained organic layer was washed with 3 ml of a saturated brine, followed by concentration under reduced pressure to give the title compound as 3.20 g of a yellow liquid (chemical purity: 63.5 areapercent, , optical purity: 100percent e.e., yield: 64percent). It was ascertained that 41.4percent of the optically active 1-(tert-butoxycarbonyl)-3-hydroxypyrrolidine represented by the above formula (3) was contaminated with respect to the HPLC area value of the title compound, while 7.8percent of 1-(tert-butoxycarbonyl)-3, 4-dehydropyrrolidine represented by the above formula (4) was contaminated with respect to the HPLC area value of the title compound.; Step 6-1: Production of (R)-1-(tert-butoxycarbonyl)-3-aminopyrrolidine; To 11.2 g of a solution in toluene including 7.83 g of (S)-1-(tert-butoxycarbonyl)-3-(methanesulfonyloxy)pyrrolidine produced by the method described in Production was added 62.7 g of a 40percent by weight aqueous ammonia solution, and the mixture was stirred at 80°C for 10 hrs (internal pressure: about 8 barr). After cooling, the reaction mixture was concentrated under reduced pressure, to which 31.3 g of a saturated brine, 19.6 g of toluene, and 4.13 g of a 30percent by weight aqueous sodium hydroxide solution were added. Thus obtained organic layer was concentrated under reduced pressure to give the title compound as 5.09 g of a yellow liquid (chemical purity: 74.5 areapercent, yield: 74percent, optical purity: 99.4percent ee). It was ascertained that 18.1percent of the optically active 1-(tert-butoxycarbonyl)-3-hydroxypyrrolidine represented by the above formula (3) was contaminated with respect to the HPLC area value of the title compound, while 4.1percent of 1-(tert-butoxycarbonyl)-3, 4-dehydropyrrolidine represented by the above formula (4) was contaminated with respect to the HPLC area value of the title compound.
View more+(3R)-(+)-1-(tert-Butoxycarbonyl)-3-aminopyrrolidine (3R)-(+)-1-Boc-3-aminopyrrolidine (3R)-(+)-3-Amino-1-(tert-butoxycarbonyl)pyrrolidine (3R)-(+)-3-Amino-1-Boc-pyrrolidine (3R)-3-amino-1-(tert-butoxycarbonyl)pyrrolidine (3R)-3-Amino-1-pyrrolidinecarboxylic acid 1,1-dimethylethyl ester (3R)-3-Aminopyrrolidine, N1-BOC protected (3R)-3-Aminopyrrolidine-1-carboxylic Acid T-butyl Ester (R)-(+)-N-BOC-3-AMINOPYRROLIDINE (R)-(+)-N-tert-Butoxycarbonyl-3-aminopyrroli (R)-1-Boc-3-Aminopyrrolidine (R)-3-Amino-1-Boc-pyrroli... (R)-3-AMINO-1-BOC-PYRROLIDINE (R)-3-AMINO-1-N-BOC-PYRROLIDINE (R)-3-amino-N-(t-butoxycarbonyl)-pyrrolidine (R)-3-AMINO-N-BOC-PYRROLIDINE (R)-TERT-BUTYL 3-AMINOPYRROLIDINE-1-CARBOXYLATE 1-Boc-3-(R )-aminopyrrolidine 1-Boc-3-(R)-aminopyrrolidine 1-PYRROLIDINECARBOXYLIC ACID, 3-AMINO-, 1,1-DIMETHYLETHYL ESTER, (3R) 1-Pyrrolidinecarboxylic acid, 3-amino-, 1,1-dimethylethyl ester, (3R)- 2-Methyl-2-propanyl (3R)-3-amino-1-pyrrolidinecarboxylate 3-AMINO-PYRROLIDINE-1-CARBOXYLIC ACID TERT-BUTYL ESTER, (R) MFCD03419272 R-(+)-1-Boc-3-aminopyrrolidine R-1-N-BOC-3-AMINO PYRROLIDINE T5NTJ AVOX1&1&1 CZ &&R Form Tert-butyl (3R)-3-aminopyrrolidine-1-carboxylate tert-butyl (R)-3-amino-pyrrolidine-1-carboxylate tert-Butyl-(3R)-3-aminopyrrolidin-1-carboxylat
Hazard Codes:?C,
Xn
Risk Statements: 22-41-44
R22: (R)-(+)-1-Boc-3-aminopyrrolidine (CAS NO.147081-49-0) is harmful if swallowed.?
R41: Risk of serious damage to the eyes.?
R44: Risk of explosion if heated under confinement.
Safety Statements: 26-36/37/39
S26: In case of contact with eyes, rinse immediately with plenty of water and seek medical advice.?
S36/37/39: Wear suitable protective clothing, gloves and eye/face protection.
RIDADR: UN 2810 6.1/PG 3
Acute toxicity - Oral, Category 3
Serious eye damage, Category 1
Pictogram(s) | ![]() ![]() |
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Signal word | Danger |
Hazard statement(s) | H301 Toxic if swallowed H318 Causes serious eye damage |
Precautionary statement(s) | |
Prevention | P264 Wash ... thoroughly after handling. P270 Do not eat, drink or smoke when using this product. P280 Wear protective gloves/protective clothing/eye protection/face protection. |
Response | P301+P310 IF SWALLOWED: Immediately call a POISON CENTER/doctor/\u2026 P321 Specific treatment (see ... on this label). P330 Rinse mouth. P305+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P310 Immediately call a POISON CENTER/doctor/\u2026 |
Storage | P405 Store locked up. |
Disposal | P501 Dispose of contents/container to ... |
none
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Literatures:
Kaneka Corporation Patent: EP2050735 A1, 2009 ; Location in patent: Page/Page column 19-20 ; ![]() Yield: ~63% |
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