Hydrochloric Acid → HCID 10277798, compound

HRID 2119322Notes

Reaction equation

HRID 2119322 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([S:14]([N:17]3[CH2:22][CH2:21][S:20][C:19]([CH3:24])([CH3:23])[C@@H:18]3[C:25]([OH:27])=O)(=[O:16])=[O:15])=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.C(Cl)(=O)C(Cl)=O.Cl.[NH2:35][OH:36].C(=O)(O)[O-].[Na+].Cl>ClCCl.O1CCCC1.C(OCC)(=O)C.O.CN(C)C=O>[OH:36][NH:35][C:25]([C@H:18]1[C:19]([CH3:24])([CH3:23])[S:20][CH2:21][CH2:22][N:17]1[S:14]([C:11]1[CH:12]=[CH:13][C:8]([C:5]2[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][CH:4]=2)=[CH:9][CH:10]=1)(=[O:16])=[O:15])=[O:27]

Participants

11

Reactant 5

HCID 313Hydrochloric AcidHCID 65578Oxalyl chlorideHCID 443297Hydroxyamine hydrochlorideHCID 516892Sodium BicarbonateHCID 10276904HCID 10276904, compound

Product 1

HCID 10277798HCID 10277798, compoundYield 90.3%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

The carboxylic acid obtained in Example 1 (12.2 g, 0.026 mol) was diluted with dichloromethane (150 mL) and oxalyl chloride (16.5 g, 0.13 mol). N,N-Dimethylformamide was added as a catalyst. The solution was stirred at room temperature for 14 hours, at which time the solvent was concentrated in vacuo. The crude acid chloride was triturated with hexane and collected by filtration. The solid was diluted with tetrahydrofuran (75 mL) and added dropwise to a mixture of hydroxylamine hydrochloride (9 g, 0.13 mol) and sodium bicarbonate (16.4 g, 0.19 mol) in tetrahydrofuran (150 mL)/water (75 mL) cooled to 0° C. The reaction mixture gradually warmed to room temperature and was stirred for 14 hours. Ethyl acetate and aq. HCl (1M) were added, the layers were separated, and the organic portion was washed with brine, dried (MgSO4), and concentrated. The resulting viscous liquid yielded a white solid (11.4 g, 90%) upon treatment with cold diethyl ether/petroleum ether (4:1), mp 190-192° C.; 1HNMR (DMSO-d6) δ 10.7 (s, 1H), 8.9 (s, 1H), 4.1 (s, 1H), 4.0 (m, 1H), 3.8 (m, 1H), 2.9 (m, 1H), 2.5 (m, 1H), 1.4, (s, 3H), 1.1 (s, 3H) ppm.

Workup

  1. concentrationwas concentrated in vacuo
  2. customThe crude acid chloride was triturated with hexane
  3. filtrationcollected by filtration
  4. additionThe solid was diluted with tetrahydrofuran (75 mL)
  5. temperaturecooled to 0° C
  6. temperatureThe reaction mixture gradually warmed to room temperature
  7. stirringwas stirred for 14 hours
  8. customthe layers were separated
  9. washthe organic portion was washed with brine
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-3d14557ebaee41e2944843cc406bbb1c
Source dataset
uspto-grants-2004_02
Patent number
US06686355B2

Reaction notes

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