Ethyl chloroformate → 7-Nitro-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid ethyl ester

HRID 925229노트

반응식

HRID 925229 반응식
[N+:1]([C:4]1[CH:14]=[CH:13][C:7]2[CH2:8][CH2:9][NH:10][CH2:11][CH2:12][C:6]=2[CH:5]=1)([O-:3])=[O:2].CCN(C(C)C)C(C)C.Cl[C:25]([O:27][CH2:28][CH3:29])=[O:26]>C(Cl)Cl.Cl>[CH2:28]([O:27][C:25]([N:10]1[CH2:11][CH2:12][C:6]2[CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:14]=[CH:13][C:7]=2[CH2:8][CH2:9]1)=[O:26])[CH3:29]

참가 물질

6

반응물 3

HCID 10928Ethyl chloroformateHCID 81531DiisopropylethylamineHCID 113100427-Nitro-2,3,4,5-tetrahydro-1H-benzo[D]azepine

생성물 1

HCID 584953837-Nitro-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid ethyl ester

시약·촉매·용매 2

HCID 313Hydrochloric Acid용매HCID 6344Dichloromethane용매

반응 조건

온도
0 °C

실험 절차

To a stirred solution of the product from Example 36, step (a) (5 g, 26.0 mmol) dissolved in DCM (75 ml), DIEA (6.8 ml, 39 mmol) was added. The reaction mixture was cooled to 0° C. and ethyl chloroformate was added (3.0 ml, 31.2 mmol). The reaction mixture was stirred at 0° C. for 2 hours and then allowed to warm to room temperature. The reaction mixture was diluted with 2N HCl (150 ml) and extracted with DCM (3×). The combined DCM extracts were washed with brine, dried over Na2SO4, and solvent evaporated in vacuo to give the crude product. Purification by silica-gel chromatography (gradient elution: 0 to 50% EtOAc in hexane) gave the sub-title compound as a light yellow solid (4.7 g). 1H NMR (300 MHz, DMSO-d6) δ 8.07 (d, J=2.4 Hz, 1H); 8.01 (dd, J=8.1 Hz, 2.4 Hz, 1H); 7.45 (d, J=8.1 Hz, 1H); 4.07 (q, J=6.9 Hz, 2H); 3.54-3.51 (m, 4H); 3.04-3.01 (m, 4H); 1.19 (t, J=7.2 Hz, 3H).

후처리

  1. temperatureto warm to room temperature
  2. extractionextracted with DCM (3×)
  3. washThe combined DCM extracts were washed with brine
  4. dry with materialdried over Na2SO4, and solvent
  5. customevaporated in vacuo
  6. customto give the crude product
  7. customPurification
  8. washby silica-gel chromatography (gradient elution: 0 to 50% EtOAc in hexane)

출처 및 근거

ORD 기록
ord-cbb657eccd994f81a6d8e52d8e970240
출처 데이터셋
uspto-grants-2016_03
특허 번호
US09284277B2

반응 노트

불러오는 중…