Tosylchloramide → HCID 69861565, compound

HRID 2294085Notes

Reaction equation

HRID 2294085 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N:14]2[CH2:18][CH:17]([CH2:19][NH:20][C:21](=[O:23])[CH3:22])[O:16][C:15]2=[O:24])[CH:5]=[CH:6][C:7]=1[N:8]1[CH2:13][CH2:12][S:11][CH2:10][CH2:9]1.[CH3:25][C:26]1[CH:27]=[CH:28][C:29]([S:32]([NH:35]Cl)(=[O:34])=[O:33])=[CH:30][CH:31]=1.CO.C(Cl)(Cl)Cl>C(Cl)Cl.[Br-].C([P+](CCCC)(CCCC)CCCC)CCCCCCCCCCCCCCC.ClCl>[F:1][C:2]1[CH:3]=[C:4]([N:14]2[CH2:18][C@H:17]([CH2:19][NH:20][C:21](=[O:23])[CH3:22])[O:16][C:15]2=[O:24])[CH:5]=[CH:6][C:7]=1[N:8]1[CH2:9][CH2:10][S:11](=[N:35][S:32]([C:29]2[CH:30]=[CH:31][C:26]([CH3:25])=[CH:27][CH:28]=2)(=[O:33])=[O:34])[CH2:12][CH2:13]1

Participants

7

Reactant 3

HCID 31388TosylchloramideHCID 18535983HCID 18535983, compoundHCID 21584188Chloroform methanol

Product 1

HCID 69861565HCID 69861565, compoundYield 99.6%

Reagents, catalysts & solvents 3

HCID 84716Hexadecyltributylphosphonium bromideCatalystHCID 6344DichloromethaneSolventHCID 24526ChlorineSolvent

Procedure

The N-[[3-[3-fluoro-4-(4-thiomorpholinyl)phenyl]-2-oxo-5-oxazolidinyl]methyl]acetamide (213 mg, 0.603 mmol) was dissolved in dry CH2Cl2 (11.5 mL) and then treated with hexadecyl-tributylphosphonium bromide (138 mg, 0.271 mmol). To this clear, colorless solution, the chloramine-T (165 mg, 0.723 mmol) was added. The resultant cloudy solution was stirred at room temperature for three hours. At this time, the reaction was determined to be complete by TLC (10% MeOH/CHCl3, UV short wave). The reaction mixture was transferred to a separatory funnel and diluted with CH2 Cl2 (10 mL). This solution was washed with cold 5% NaOH (20 mL), water (20 mL), and brine (20 mL). The aqueous portions were combined and then back-extracted with more CH2Cl2 (3×20 mL). The organic layers were combined, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The resultant material was chromatographed on silica gel (100 g), eluting with a gradient of 0-6% MeOH in 10% CH3CN/CHCl3 to give 314 mg (99%) of the title compound as a white solid which decomposes at 79° C. and has a HRMS (FAB) calculated for C23H28FN4O5S2 (M+H)+, 523.1485, found 523.1477.

Workup

  1. customThe reaction mixture was transferred to a separatory funnel
  2. washThis solution was washed with cold 5% NaOH (20 mL), water (20 mL), and brine (20 mL)
  3. extractionback-extracted with more CH2Cl2 (3×20 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe resultant material was chromatographed on silica gel (100 g)
  8. washeluting with a gradient of 0-6% MeOH in 10% CH3CN/CHCl3

Sources & evidence

ORD record
ord-e56a44b11da442a3ac9d8804d8938e62
Source dataset
uspto-grants-1997_11
Patent number
US05688792

Reaction notes

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