Phenol → HCID 22872085, compound

HRID 1780451Notes

Reaction equation

HRID 1780451 reaction equation
[CH3:1][N:2]1[C@H:11]2[C@@:6]([CH3:19])([C:7]3[CH:15]=[CH:14][C:13]([C:16]([OH:18])=[O:17])=[CH:12][C:8]=3[CH2:9][CH2:10]2)[CH2:5][CH2:4][C:3]1=[O:20].C(Cl)(=O)C(Cl)=O.[C:27]1(O)[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.N1C=CC=CC=1>CN(C)C=O.C1COCC1.C(OCC)(=O)C.C1C=CC=CC=1>[CH3:1][N:2]1[C@H:11]2[C@@:6]([CH3:19])([C:7]3[CH:15]=[CH:14][C:13]([C:16]([O:18][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)=[O:17])=[CH:12][C:8]=3[CH2:9][CH2:10]2)[CH2:5][CH2:4][C:3]1=[O:20]

Participants

9

Reactant 4

HCID 996PhenolHCID 1049PyridineHCID 65578Oxalyl chlorideHCID 22872084HCID 22872084, compound

Product 1

HCID 22872085HCID 22872085, compoundYield 11%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 241BenzeneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A 50 mL round bottom flask was charged with (+)-(4aR)-(10bR)-4-methyl-8-carboxy-10b-methyl-1,2,3,4,4a,5,6,10b-octahydrobenzo[f]quinolin-3-one (300 mg, 1.10 mmol) and 6 mL of benzene. Oxalyl chloride (3.3 mmol) was added dropwise via syringe to the stirred mixture, followed by a catalytic amount of dimethylformamide (two drops). It was allowed to stir at room temperature for 75 min. and then the volatiles were removed in vacuo. Four mL of THF was added, followed by a solution of phenol and pyridine (4 eq) in 2 mL of THF at 0°. It was allowed to warm to room temperature, diluted with 50 mL of ethyl acetate, and washed with 0.1N hydrochloric acid (2×25 mL), 10% sodium bicarbonate (2×25 mL), water, (2×25 mL), and brine (2×25 mL). The combined organic extracts were dried over sodium sulfate, concentrated and chromatographed on silica (0-2% methanol/dichloromethane gradient eluent), followed by additional chromatography (80% ethyl acetate/hexanes eluent) to give 43 mg (11%) of the title compound as a yellow solid. mp 194°-196°. FDMS: m/e=349. α[D]589 =+78.53 (c=1.00, chloroform).

Workup

  1. customthe volatiles were removed in vacuo
  2. additionFour mL of THF was added
  3. temperatureto warm to room temperature
  4. washwashed with 0.1N hydrochloric acid (2×25 mL), 10% sodium bicarbonate (2×25 mL), water, (2×25 mL), and brine (2×25 mL)
  5. dry with materialThe combined organic extracts were dried over sodium sulfate
  6. concentrationconcentrated
  7. customchromatographed on silica (0-2% methanol/dichloromethane gradient eluent)

Sources & evidence

ORD record
ord-5cf6a17e226145079e8e00bc24759c27
Source dataset
uspto-grants-1997_05
Patent number
US05629007

Reaction notes

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