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1,2-Dichloroethane → Ethyl (+/-)-10,11-dihydro-3-[[[2-(2-pyridylamino)ethyl]amino]carbonyl]-5H-dibenzo[a,d]cycloheptene-10-acetate

HRID 613390
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HRID 613390 반응식
C(Cl)CCl.[C:5]([C:8]1[CH:9]=[CH:10][C:11]2[CH2:17][CH:16]([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:15]3[CH:24]=[CH:25][CH:26]=[CH:27][C:14]=3[CH2:13][C:12]=2[CH:28]=1)(O)=[O:6].Cl.Cl.[NH2:31][CH2:32][CH2:33][NH:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][N:36]=1.C1C=CC2N(O)N=NC=2C=1.O.C(N(C(C)C)CC)(C)C>CN(C=O)C>[N:36]1[CH:37]=[CH:38][CH:39]=[CH:40][C:35]=1[NH:34][CH2:33][CH2:32][NH:31][C:5]([C:8]1[CH:9]=[CH:10][C:11]2[CH2:17][CH:16]([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:15]3[CH:24]=[CH:25][CH:26]=[CH:27][C:14]=3[CH2:13][C:12]=2[CH:28]=1)=[O:6]
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

8

반응물 6

HCID 111,2-DichloroethaneHCID 962WaterHCID 757711-HydroxybenzotriazoleHCID 81531DiisopropylethylamineHCID 14238461N~1~-(Pyridin-2-yl)ethane-1,2-diamine--hydrogen chloride (1/2)HCID 15516628Ethyl (+/-)-10,11-dihydro-3-carboxy-5H-dibenzo[a,d]cycloheptene-10-acetate

생성물 1

HCID 54300392
Ethyl (+/-)-10,11-dihydro-3-[[[2-(2-pyridylamino)ethyl]amino]carbonyl]-5H-dibenzo[a,d]cycloheptene-10-acetate
수율 92%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

실험 절차

EDC (112.7 mg, 0.59 mmole) was added all at once to a solution of ethyl (±)-10,11-dihydro-3-carboxy-5H-dibenzo[a,d]cycloheptene-10-acetate (157.8 mg, 0.49 mmole), 2-[(2-aminoethyl)amino]pyridine dihydrochloride (123.5 mg, 0.59 mmole), HOBt.H2O (79.5 mg, 0.59 mmole), and diisopropylethylamine (0.43 mL, 2.45 mmole) in anhydrous DMF (2.5 mL) at RT. The reaction was stirred at RT for 18 hr, then was concentrated. The residue was reconcentrated from xylenes, then was diluted with H2O (5 mL) and extracted sequentially with EtOAc (2×5 mL) and CHCl3 (2×5 mL). The organic layers were combined and treated with a little MeOH to dissolve a small amount of insoluble material. Drying (MgSO4), concentration, and silica gel chromatography (5% MeOH/CHCl3) gave the title compound (199.1 mg, 92%) as a yellow oil: TLC (5% MeOH/CHCl3) Rf 0.42; 1H NMR (400, CDCl3) δ 8.10 (d, J=3.5 Hz, 1 H), 8.02 (br s, 1 H), 7.60 (app. narrow d, 1 H), 7.53 (app. dd, 1 H), 7.33-7.42 (m, 1 H), 7.08-7.22 (m, 5 H), 6.57-6.65 (m, 1 H), 6.45 (d, J=8.3 Hz, 1 H), 4.79-4.90 (m, 1 H), 4.36 (d,J=15.1 Hz, 1 H), 4.11-4.26 (m, 2 H), 3.92 (d, J=15.1 Hz, 1 H), 3.80-3.95 (m, 1 H), 3.55-3.72 (m, 4 H), 3.38 (dd, J=15.2, 4.1 Hz, 1 H), 3.03 (dd, J=15.2, 9.5 Hz, 1 H), 2.66 (dd, J=15.8,4.8 Hz, 1 H), 2.50 (dd, J=15.8, 9.6 Hz, 1 H), 1.27 (t, J=7.2 Hz, 3 H); MS (ES) m/e 444 (M+H)+.

후처리

  1. customat RT
  2. concentrationwas concentrated
  3. additionwas diluted with H2O (5 mL)
  4. extractionextracted sequentially with EtOAc (2×5 mL) and CHCl3 (2×5 mL)
  5. additiontreated with a little MeOH
  6. dissolutionto dissolve a small amount of insoluble material
  7. customDrying
  8. concentration(MgSO4), concentration, and silica gel chromatography (5% MeOH/CHCl3)

출처 및 근거

ORD 기록
ord-d56b59534d314cb2b7c69255d7a3e17d
출처 데이터셋
uspto-grants-1999_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06008213

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