Acetic Acid → HCID 70873748, 화합물

HRID 2208851노트

반응식

HRID 2208851 반응식
[NH2:1][C:2]1[C:3]([O:13][CH3:14])=[C:4]([CH:9]=[C:10]([Cl:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[O:15]1[CH2:20][CH2:19][C:18](=O)[CH2:17][CH2:16]1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>ClCCCl.O>[Cl:12][C:10]1[CH:11]=[C:2]([NH:1][CH:18]2[CH2:19][CH2:20][O:15][CH2:16][CH2:17]2)[C:3]([O:13][CH3:14])=[C:4]([CH:9]=1)[C:5]([O:7][CH3:8])=[O:6]

참가 물질

8

반응물 5

HCID 176Acetic AcidHCID 121599Tetrahydro-4H-pyran-4-oneHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 63023142Methyl 3-amino-5-chloro-2-methoxybenzoate

생성물 1

HCID 70873748HCID 70873748, 화합물수율 73.2%

시약·촉매·용매 2

HCID 111,2-Dichloroethane용매HCID 962Water용매

실험 절차

To a solution of methyl 3-amino-5-chloro-2-methoxybenzoate (440 mg, 2 mmol) in 1,2-dichloroethane (8 ml) at temperature under nitrogen was added oxan-4-one (0.38 ml, 4.0 mmol) followed by acetic acid (0.7 ml, 12 mmol). This solution was stirred for 5 minutes before the addition of sodium triacetoxyborohydride (1.3 g, 6.1 mmol) at room temperature. After stirring for 23 hours deionized water (16 ml) was added and the mixture was neutralized with solid NaHCO3. The phases were separated and the aqueous layer was extracted with EtOAc (2×16 ml). The combined organic extracts were dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by FCC (10 g silica, Isolute cartridge, gradient of eluents; 9:1 Heptane:EtOAc to 7:3 Heptane:EtOAc) to give 439 mg (72%) of the title compound as a white solid. LC-MS 97%, m/z=300.3/302.0, 1H NMR (500 MHz, Chloroform-d) δ ppm 7.06 (1H, d, J=2.52 Hz), 6.73 (1H, d, J=2.52 Hz), 4.38-4.45 (1H, m), 4.02 (2H, dt, J=11.78, 3.49 Hz), 3.91 (3H, s), 3.81 (3H, s), 3.54 (2H, td, J=11.47, 2.13 Hz), 3.40-3.50 (1H, m), 2.03 (2H, br. d, J=13.70 Hz), 1.48-1.55 (2H, m).

후처리

  1. additionwas added
  2. customThe phases were separated
  3. extractionthe aqueous layer was extracted with EtOAc (2×16 ml)
  4. dry with materialThe combined organic extracts were dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by FCC (10 g silica, Isolute cartridge, gradient of eluents; 9:1 Heptane:EtOAc to 7:3 Heptane:EtOAc)

출처 및 근거

ORD 기록
ord-765a5413567342f988800b0aef6dac7e
출처 데이터셋
uspto-grants-2016_06
특허 번호
US09376422B2

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