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

HRID 1509741Notes

Reaction equation

HRID 1509741 reaction equation
[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]

Participants

8

Reactant 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

Product 1

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

Reagents, catalysts & solvents 3

HCID 2724126TempoCatalystHCID 3776IsopropanolSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
2.5 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-a85a004082d3427f9e723a4986329673
Source dataset
uspto-grants-2015_12
Patent number
US09221833B2

Reaction notes

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