Hydrochloric Acid → Ethyl 4,5,6,7-Tetrahydroisoindole-1-carboxylate

HRID 1434811

반응식

HRID 1434811 반응식
N12[CH2:11][CH2:10][CH2:9][N:8]=[C:7]1[CH2:6][CH2:5][CH2:4][CH2:3]C2.[N+](C1CCCCC=1)([O-])=O.[CH2:21]([O:23][C:24](=[O:28])C[N+]#[C-])[CH3:22].Cl>CC(O)C.C1COCC1.CCOC(C)=O>[CH2:21]([O:23][C:24]([C:7]1[NH:8][CH:9]=[C:10]2[C:6]=1[CH2:5][CH2:4][CH2:3][CH2:11]2)=[O:28])[CH3:22]

참가 물질

8

반응물 4

HCID 313Hydrochloric AcidHCID 757131-NitrocyclohexeneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 533707Ethyl isocyanoacetate

생성물 1

HCID 10035498Ethyl 4,5,6,7-Tetrahydroisoindole-1-carboxylate

시약·촉매·용매 3

HCID 3776Isopropanol용매HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매

실험 절차

1,8-Diazabicyclo[5.4.0]-undec-7-ene (6.2 mL, 41.5 mmol) in 2-propanol (45 mL) was added by addition funnel over ˜25 minutes to a stirring solution of 1-nitrocyclohexene (5.0441 g, 39.67 mmol) and ethylisocyanoacetate (4.3340 g, 37.16 mmol) in THF (45 mL). The reaction was judged complete after stirring overnight at room temperature. 2N HCl (˜100 mL) and EtOAc (˜50 mL) were added. The organic layer was removed, then washed with H2O, 5% NaHCO3, and H2O. The crude product was dried with Na2SO4, filtered, concentrated, and purified by silica gel chromatography (Combiflash column, 100% CH2Cl2) to obtain 171 contaminated with a minor impurity. Attempts to recrystallize from hexanes were unsuccessful at removing the impurity, so the product was carried on to the next step with no further purification. 1H (CDCl3, 400 MHz): δ 9.01 (1H, broad s), 6.64 (1H, s), 4.31 (3H, q, J=7.2 Hz), 2.82 (2H, t, J=5.6 Hz), 2.55 (2H, t, J=5.6 Hz), 1.80-1.68 (4H, m), 1.36 (3H, t, J=7.2 Hz) ppm. 13C (CD3OD, 100 MHz): 6161.71, 128.06 and 127.84, 121.98 and 121.96, 118.74 and 118.55, 118.03 and 117.71, 59.62, 23.41 and 23.39, 23.36 and 23.33, 23.16 and 23.13, 21.88 and 21.86, 14.48 ppm. DEPT (CD3OD, 100 MHz): CH3 carbons: 14.48; CH2 carbons: 59.62, 23.41 and 23.39, 23.36 and 23.33, 23.16 and 23.13, 21.88 and 21.86; CH carbons: 118.74 and 118.55 ppm. HPLC: 10.689 min.

후처리

  1. customThe organic layer was removed
  2. washwashed with H2O, 5% NaHCO3, and H2O
  3. dry with materialThe crude product was dried with Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified by silica gel chromatography (Combiflash column, 100% CH2Cl2)

출처 및 근거

ORD 기록
ord-fe780ddeef8e44949416a03a61b491f9
출처 데이터셋
uspto-grants-2009_11
특허 번호
US07615572B2

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