Hydroxylamine → HCID 58121056, compound

HRID 1186687Notes

Reaction equation

HRID 1186687 reaction equation
[C:1]1([C:7]#[C:8][C:9]2[CH:18]=[CH:17][CH:16]=[CH:15][C:10]=2[C:11](OC)=[O:12])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[NH2:19][OH:20].[OH-].[K+]>C1COCC1.CO>[OH:20][NH:19][C:11](=[O:12])[C:10]1[CH:15]=[CH:16][CH:17]=[CH:18][C:9]=1[C:8]#[C:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 787HydroxylamineHCID 14797Potassium HydroxideHCID 10537767Benzoic acid, 2-(2-phenylethynyl)-, methyl ester

Product 1

HCID 58121056HCID 58121056, compoundYield 43%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In a 100 mL round-bottomed flask was added methyl 2-(phenylethynyl)benzoate 36 (157 mg, 0.665 mmol) in THF (1.33 mL) and MeOH (1.33 mL) and the solution was cooled to 0° C. Then, a 50% aqueous solution of hydroxylamine (2195 mg, 33.2 mmol) was added followed by a 4M aqueous solution of KOH (0.33 mL, 1.329 mmol) and the resulting colorless solution was stirred at 0° C. and allowed to slowly warm to rt for 20 h. The reaction mixture was partitioned between EtOAc and H2O. The aqueous layer was extracted with EtOAc (2×) and the combined organic layers were washed with brine, dried over MgSO4, filtered and concentrated in vacuo. The yellow oil was crystallized in Et2O and the filtrate was evaporated and triturated again in Et2O. The solids were combined to afford title compound 37 (67 mg, 43% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ (ppm): 10.98 (s, 1H), 9.20 (s, 1H), 7.61 (d, J=7.4 Hz, 1H), 7.55-7.43 (m, 814). LRMS (ESI): (calc.) 237.25 (found) 238.2 (MH)+

Workup

  1. temperatureto slowly warm to rt for 20 h
  2. customThe reaction mixture was partitioned between EtOAc and H2O
  3. extractionThe aqueous layer was extracted with EtOAc (2×)
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe yellow oil was crystallized in Et2O
  9. customthe filtrate was evaporated
  10. customtriturated again in Et2O

Sources & evidence

ORD record
ord-9d4df0a1380b4848a2b7406c1594c310
Source dataset
uspto-grants-2014_03
Patent number
US08673911B2

Reaction notes

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