Tetrahydrofuran → HCID 17932203, compound

HRID 1468571Notes

Reaction equation

HRID 1468571 reaction equation
[CH2:1]([O:8][C:9](=[O:20])[NH:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([C:17](=[O:19])[CH3:18])[CH:12]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1COCC1.[Br:26]Br.C([O-])(O)=O.[Na+]>C(OCC)C.[Cl-].[Al+3].[Cl-].[Cl-].C(OCC)(=O)C>[CH2:1]([O:8][C:9](=[O:20])[NH:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([C:17](=[O:19])[CH2:18][Br:26])[CH:12]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 8028TetrahydrofuranHCID 24408BromineHCID 516892Sodium BicarbonateHCID 4935692Carbamic acid, (3-acetylphenyl)-, phenylmethyl ester

Product 1

HCID 17932203HCID 17932203, compoundYield 57%

Reagents, catalysts & solvents 3

HCID 6451240Aluminum(III) ChlorideCatalystHCID 3283Diethyl EtherSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

3-acetylphenyl carbamic acid benzyl ester (3.50 g, 13.0 mmol) was dissolved in diethyl ether (70 mL) and THF (20 mL) and brought to 0° C. A catalytic amount of aluminum (III) chloride (0.010 g) was added followed by the drop-wise addition of bromine (0.731 mL, 14.3 mmol) in diethyl ether (10 mL). The reaction was kept at 0° C. for 30 mins before being allowed to warm to room temperature on its own accord. Sat. NaHCO3 (30 mL) was added to quench the reaction and the solution was poured into ethyl acetate (30 mL). The combined organics were washed with sat. NaHCO3 (3×30 mL) and brine (1×30 mL) before being dried (Na2SO4), filtered, and evaporated to dryness. Trituration of the resulting crude product with a 2:1 mixture of dichloromethane/diethyl ether (6 mL) followed by filtration afforded 2.57 g (57%) of 3-(2-bromoacetyl)phenyl carbamic acid benzyl ester as a light pink solid: 1H NMR (400 MHz, DMSO-d6) δ 10.04 (s, 1H), 8.11 (s, 1H), 7.69 (m, 2H), 7.43 (m, 6H), 5.18 (s, 2H), 4.88 (s, 2H); 13C NMR (100 MHz, DMSO-d6) δ 201.5, 163.4, 149.8, 146.5, 144.6, 139.4, 138.5, 138.2, 133.3, 131.9, 127.6, 126.7, 76.0, 44.1; HRMS (ESI) calcd for C16H14BrNO3 (M+) 347.0157. found 347.0151.

Workup

  1. custombrought to 0° C
  2. customto quench
  3. customthe reaction
  4. washThe combined organics were washed with sat. NaHCO3 (3×30 mL) and brine (1×30 mL)
  5. dry with materialbefore being dried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated to dryness
  8. additionTrituration of the resulting crude product with a 2:1 mixture of dichloromethane/diethyl ether (6 mL)
  9. filtrationfollowed by filtration

Sources & evidence

ORD record
ord-c739a123b79045caaaefd3c1ee6171a8
Source dataset
uspto-grants-2015_04
Patent number
US09005643B2

Reaction notes

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