(+)-Epichlorohydrin → (2S,9S)-2-[(tert-Butoxycarbonyl)amino]-10-chloro-9-hydroxy-7-azadecanoic Acid tert-Butyl Ester

HRID 1068073노트

반응식

HRID 1068073 반응식
Cl.[C:2]([O:6][C:7](=[O:22])[C@H:8]([CH2:17][CH2:18][CH2:19][CH2:20][NH2:21])[NH:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])([CH3:5])([CH3:4])[CH3:3].[CH2:23]([C@H:25]1[O:27][CH2:26]1)[Cl:24]>C(Cl)(Cl)Cl.C([O-])(O)=O.[Na+].O>[C:2]([O:6][C:7](=[O:22])[C@@H:8]([NH:9][C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11])[CH2:17][CH2:18][CH2:19][CH2:20][NH:21][CH2:26][C@H:25]([OH:27])[CH2:23][Cl:24])([CH3:5])([CH3:3])[CH3:4]

참가 물질

6

반응물 2

HCID 149428(+)-EpichlorohydrinHCID 51358437(S)-tert-Butyl 6-amino-2-((tert-butoxycarbonyl)amino)hexanoate hydrochloride

생성물 1

HCID 10810670(2S,9S)-2-[(tert-Butoxycarbonyl)amino]-10-chloro-9-hydroxy-7-azadecanoic Acid tert-Butyl Ester수율 39%

시약·촉매·용매 3

HCID 962Water용매HCID 6212Chloroform용매HCID 516892Sodium Bicarbonate용매

실험 절차

A solution of 3 (4.83 g, 14.3 mmol) in chloroform (100 mL) was extracted with saturated NaHCO3 solution (2×100 mL) and water (100 mL). The organic layer was dried, concentrated, and further dried in vacuo. The resulting oil was dissolved in cyclohexane (26 mL), and (S)-(+)-epichlorohydrin (1.58 g, 17.1 mmol) was added under an Ar atmosphere. The precipitated product was filtered after 27 h, washed with cold cyclohexane, and dried in vacuo to give 12a (2.20 g, 39%) as a fine, white powder: mp 87-88° C.; 1H NMR δ 1.30-1.83 (m, 6H), 1.44 (s, 9H), 1.46 (s, 9H), 2.57-2.66 (m, 3H), 2.77 (dd, 1H, J=12.2, 3.9), 3.51 (dd, 1H, J=11.2, 5.7), 3.56 (dd, 1H, J=11.2, 5.2), 3.84-3.91 (m, 1H), 3.94 (dd, 1H, J=8.6, 5.3); 13C NMR 6 24.6, 28.3, 28.7, 30.0, 32.6, 48.2, 50.3, 53.5, 55.8, 71.1, 80.4, 82.5, 158.1, 173.8; HRMS m/z calcd for C18H36ClN2O5 395.2313, found 395.2303. Anal. calcd. for C18H35ClN2O5: C54.74, H 8.93, Cl 8.98, N 7.09. Found: C 54.80, H. 8.99, Cl 9.02, N 7.08 [α]22D−26.1° (c 1.00, CH3OH).

후처리

  1. customThe organic layer was dried
  2. concentrationconcentrated
  3. customfurther dried in vacuo
  4. dissolutionThe resulting oil was dissolved in cyclohexane (26 mL)
  5. filtrationThe precipitated product was filtered after 27 h
  6. washwashed with cold cyclohexane
  7. customdried in vacuo

출처 및 근거

ORD 기록
ord-447e88a649b64535b55e347f884d4418
출처 데이터셋
uspto-grants-2001_06
특허 번호
US06248866B1

반응 노트

불러오는 중…