Water → 9-bromo-3-(2-bromoacetyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one

HRID 590651노트

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HRID 590651 반응식
[Br:1][CH:2]1[CH2:23][CH2:22][C:5]2=[CH:6][C:7]3[C:8]4[CH:17]=[CH:16][C:15]([CH:18]([OH:21])[CH2:19][Br:20])=[CH:14][C:9]=4[CH2:10][O:11][C:12]=3[CH:13]=[C:4]2[C:3]1=[O:24].C(=O)(O)[O-].[Na+].[Br-].[Na+].O>C(Cl)Cl.CC1(C)N([O])C(C)(C)CCC1.C(O)(C)C>[Br:1][CH:2]1[CH2:23][CH2:22][C:5]2=[CH:6][C:7]3[C:8]4[CH:17]=[CH:16][C:15]([C:18](=[O:21])[CH2:19][Br:20])=[CH:14][C:9]=4[CH2:10][O:11][C:12]=3[CH:13]=[C:4]2[C:3]1=[O:24]

참가 물질

8

반응물 4

HCID 962WaterHCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 866883739-Bromo-3-(2-bromo-1-hydroxyethyl)-10,11-dihydro-5H-benzo[d]naphtho[2,3-b]pyran-8(9H)-one

생성물 1

HCID 866883729-bromo-3-(2-bromoacetyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one수율 76%

시약·촉매·용매 3

HCID 2724126Tempo촉매HCID 3776Isopropanol용매HCID 6344Dichloromethane용매

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온도
2.5 °C

실험 절차

To 9-bromo-3-(2-bromo-1-hydroxyethyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (approx. 54.4 mmol) in DCM (365 mL) was added sodium bicarbonate (5.45 g), sodium bromide (6.14 g), TEMPO (16.55 mg) and water (60 mL). The solution was cooled between 0-5° C. and 6% bleach (91.5 mL) was added. After 1 h isopropyl alcohol (20 mL) was added and the reaction mixture was warmed to room temperature. Agitation was stopped, the layers separated and the lower organic layer was collected and concentrated removing approximately 345 g of solvent. The slurry was filtered and the cake washed with 50 mL water and then 50 mL DCM (pre-cooled to 5° C.). The solids were collected and dried under vacuum to obtain 9-bromo-3-(2-bromoacetyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (18.6 g, 76% yield). 400 MHz 1H NMR (CDCl3) δ 8.03-8.01 (m, 1H), 7.85 (d, J=8.2 Hz, 1H), 7.82 (s, 1H), 7.71 (s, 1H), 7.67 (s, 1H), 5.19 (s, 2H), 4.74 (dd, J=4.1, 4.1 Hz, 1H), 4.45 (s, 2H), 3.37-3.29 (m, 1H), 2.99-2.92 (m, 1H), 2.59-2.46 (m, 2H); 100 MHz 13C NMR (CDCl3) δ 190.4, 189.6, 154.2, 136.6, 134.1, 133.9, 132.9, 131.8, 129.3, 127.2, 125.6, 124.2, 123.3, 117.0, 68.1, 49.9, 31.8, 30.4, 25.5.

후처리

  1. addition6% bleach (91.5 mL) was added
  2. temperaturethe reaction mixture was warmed to room temperature
  3. customthe layers separated
  4. customthe lower organic layer was collected
  5. concentrationconcentrated
  6. customremoving approximately 345 g of solvent
  7. filtrationThe slurry was filtered
  8. washthe cake washed with 50 mL water
  9. custom50 mL DCM (pre-cooled to 5° C.)
  10. customThe solids were collected
  11. customdried under vacuum

출처 및 근거

ORD 기록
ord-9144b3d513e14258a6f7425edc7aab7c
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09233974B2

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