m-Chloroperbenzoic acid → HCID 14503106, compound

HRID 1494517Notes

Reaction equation

HRID 1494517 reaction equation
[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:11]2[O:17][C@H:16]([CH2:18][OH:19])[C@@H:14]([OH:15])[C@@H:12]2[OH:13])=[C:4]([S:20][NH2:21])[N:3]=1.ClC1C=C(C=CC=1)C(OO)=[O:27]>C(O)C.O>[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:11]2[O:17][C@H:16]([CH2:18][OH:19])[C@@H:14]([OH:15])[C@@H:12]2[OH:13])=[C:4]([S:20]([NH2:21])=[O:27])[N:3]=1

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 14503101HCID 14503101, compound

Product 1

HCID 14503106HCID 14503106, compoundYield 64.6%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

A solution of 49 (1.5 g, 4.7 mmol) in ethanol (350 mL) and water (50 mL) was cooled to 0° C. To this cold solution was added m-chloroperoxybenzoic acid (80%, 0.90 g, 4.45 mmol) in ethanol (50 mL) during 1.5 h. After the addition, the reaction mixture was stirred at ice-bath temperature for 1.5 h. The solvent was evaporated under reduced pressure and the residue was dissolved in methanol (50 mL). Silica gel (≈5 g) was added and evaporated to dryness. The dried silica gel was placed on top of a flash silica gel column and the column was eluted with ethyl acetate→methanol gradient. The pure compound crystallized out after concentration of the homogeneous fractions. The product was collected by filtration and dried to give 0.95 g (60%) of the title compound, mp >200° C. (dec.): IR (KBr): 1120 (S=O), 3100-3600 (NH2, OH)cm-1 : UV: λmax (pH 1) 220 nm (ε17,900), 249 (7,600), 330 (5,100): λmax (pH 7) 225 nm (ε24,100), 248 (sh) (6,100), 323 (8,000): λmax (pH 11) 224 nm (ε 21,000), 244 (sh) (6,600), 322 (6,600): 1H NMR (DMSO-d6): δ 6.17 (d, J 4.08 Hz, C1'H), 6.50 (s, 2, SONH2, exchanged with D2O), 6.97 (s, 2, NH2, exchanged with D2O), 8.25 (s, 1, C8H), and other sugar protons. Anal. Calcd. for C10H14N6O5S (330.32): C, 36.36; H, 4.27; N, 25.44; S, 9.71. Found: C, 36.65; H, 4.09; N, 25.19; S, 9.56.

Workup

  1. additionAfter the addition
  2. customThe solvent was evaporated under reduced pressure
  3. dissolutionthe residue was dissolved in methanol (50 mL)
  4. additionSilica gel (≈5 g) was added
  5. customevaporated to dryness
  6. washthe column was eluted with ethyl acetate→methanol gradient
  7. customThe pure compound crystallized out after concentration of the homogeneous fractions
  8. filtrationThe product was collected by filtration
  9. customdried

Sources & evidence

ORD record
ord-4f8683a48b714f9ba5be2ffcbe6ac71b
Source dataset
uspto-grants-1991_06
Patent number
US05026836

Reaction notes

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