6-Bromo-2-methoxycarbonylmethyl-8-nitro-N-ethoxalyltetrahydroquinoline → Methyl 2-(9-bromo-2,3-dioxo-2,3,6,7-tetrahydro-1H,5H-pyrido[1,2,3-de]quinoxalin-5-yl)acetate

HRID 52484

반응식

HRID 52484 반응식
[Br:1][C:2]1[CH2:3][CH:4]2[C:9](=[C:10]([N+:12]([O-])=O)[CH:11]=1)[N:8]([C:15]([C:17](OCC)=[O:18])=[O:16])[CH:7]([CH2:22][C:23]([O:25][CH3:26])=[O:24])[CH2:6][CH2:5]2>CC(C)=O.O.[Cl-].[Cl-].[Cl-].[Ti+3]>[Br:1][C:2]1[CH:3]=[C:4]2[CH2:5][CH2:6][CH:7]([CH2:22][C:23]([O:25][CH3:26])=[O:24])[N:8]3[C:15](=[O:16])[C:17](=[O:18])[NH:12][C:10]([CH:11]=1)=[C:9]23

참가 물질

5

반응물 1

HCID 676513916-Bromo-2-methoxycarbonylmethyl-8-nitro-N-ethoxalyltetrahydroquinoline

생성물 1

HCID 10066635Methyl 2-(9-bromo-2,3-dioxo-2,3,6,7-tetrahydro-1H,5H-pyrido[1,2,3-de]quinoxalin-5-yl)acetate수율 49%

시약·촉매·용매 3

HCID 10313229titanium(III) trichloride촉매HCID 180Acetone용매2회HCID 962Water용매2회

반응 조건

온도
0 °C

실험 절차

To a mixture of 20% aqueous titanium trichloride (540 g, 0.7 mol), water (500 mL), and acetone (500 mL) was added dropwise 6-bromo-2-methoxycarbonylmethyl-8-nitro-N-ethoxalyltetrahydroquinoline (46 g, obtained above) in acetone (500 mL) over 1 h at 0° C. The mixture was stirred for 3 h at 0° C., diluted with water (1 L) and extracted with dichloromethane (1 L and 500 mL). The organic layers were washed successively with 1N hydrochloric acid, water, and brine, dried over magnesium sulfate, and concentrated. The residual solid was rinsed with a 1:1 mixture of hexane and toluene (400 mL) to give 17.4 g of the title compound (49% from 2-methoxycarbonylmethyltetrahydroquinoline hydrochloride): mp 185°~187° C.; 1H NMR (270 MHz, DMSO-d6) δ12.04 (bs, 1H), 7.20 (d, 1H, J=2 Hz), 7.15 (d, 1H, J=2 Hz), 5.04~5.13 (m, 1H), 3.62 (s, 3H), 2.94 (ddd, 1H, J=17.1, 13.5, 4.5 Hz), 2.78 (dm, 1H, J=17.1 Hz), 2.63 (dd, 1H, J =18, 7.2 Hz), 2.57 (dd, 1H, J=18, 3.6 Hz), 2.09 (dm, 1H, J=13.5 Hz), 1.80~1.95 (m, 1H).

후처리

  1. extractionextracted with dichloromethane (1 L and 500 mL)
  2. washThe organic layers were washed successively with 1N hydrochloric acid, water, and brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. washThe residual solid was rinsed with a 1:1 mixture of hexane and toluene (400 mL)

출처 및 근거

ORD 기록
ord-6245e9d57e5e409694559f1a533cdef4
출처 데이터셋
uspto-grants-1997_04
특허 번호
US05616586

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