Acetic Acid → HCID 86671547, compound

HRID 1422968Notes

Reaction equation

HRID 1422968 reaction equation
[CH2:1](N(CC)CC)C.[CH3:8][O:9][C:10]1[CH:11]=[C:12]2[C:21](=[CH:22][CH:23]=1)[N:20]=[CH:19][C:18]1[O:17][CH2:16][CH:15]([C:24]([OH:26])=O)[CH2:14][C:13]2=1.ClC(OCC)=O.[N+](=C)=[N-].[BrH:36].C(O)(=O)C>O1CCCC1.C(OCC)C.C(OCC)(=O)C>[Br:36][CH2:1][C:24]([CH:15]1[CH2:14][C:13]2[C:12]3[C:21](=[CH:22][CH:23]=[C:10]([O:9][CH3:8])[CH:11]=3)[N:20]=[CH:19][C:18]=2[O:17][CH2:16]1)=[O:26]

Participants

10

Reactant 6

HCID 176Acetic AcidHCID 260Hydrogen BromideHCID 8471TriethylamineHCID 9550DiazomethaneHCID 10928Ethyl chloroformateHCID 67247248HCID 67247248, compound

Product 1

HCID 86671547HCID 86671547, compoundYield 25%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Triethylamine (110 μL, 0.77 mmol, 2.0 eq) is added at 0° C. to a stirred solution of 6-methoxy-3,4-dihydro-2H-1-oxa-9-aza-phenanthrene-3-carboxylic acid (100 mg, 0.39 mmol, 1.0 eq) in tetrahydrofuran (10 mL), followed by ethyl chloroformate (73 μL, 0.77 mmol, 2.0 eq). After 1 hour stirring at 0° C., a solution of diazomethane in diethyl ether (20 mL, freshly prepared) is added at 0° C. to the reaction mixture. After 2 hours stirring at 0° C., a 33% hydrobromic acid solution in acetic acid (200 μL, 1.16 mmol, 3.0 eq) is added at 0° C. to the reaction mixture. After 1 hour stirring at 0° C., solvent is removed to give a crude product that is purified by column chromatography (silica gel, eluent: petroleum ether:ethyl acetate, 3:1, v/v) to afford 2-bromo-1-(6-methoxy-3,4-dihydro-2H-1-oxa-9-aza-phenanthren-3-yl)-ethanone as a light yellow oil (33 mg, 25% yield)

Workup

  1. additionis added at 0° C. to the reaction mixture
  2. stirringAfter 2 hours stirring at 0° C.
  3. stirringAfter 1 hour stirring at 0° C.
  4. customsolvent is removed
  5. customto give a crude product that
  6. customis purified by column chromatography (silica gel, eluent

Sources & evidence

ORD record
ord-398c46ae67db4240ad475548e333e1d2
Source dataset
uspto-grants-2015_01
Patent number
US08927541B2

Reaction notes

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