Acetic Acid → HCID 10249791, compound

HRID 1684106Notes

Reaction equation

HRID 1684106 reaction equation
C(O)(=O)C.S(=O)(=O)(O)O.[CH3:10][O:11][CH2:12][C:13]([NH:15][C:16]1[C:21]([C:22](=[O:25])[NH:23][CH3:24])=[C:20]([O:26][CH3:27])[C:19]([NH:28][C:29](=O)[CH2:30][O:31][CH3:32])=[C:18]([C:34](=[O:37])[NH:35][CH3:36])[C:17]=1[O:38][CH3:39])=O.[K+].[Br-]>C(OCC)(=O)C.CO>[CH3:32][O:31][CH2:30][C:29]1[N:35]([CH3:36])[C:34](=[O:37])[C:18]2[C:19]([N:28]=1)=[C:20]([O:26][CH3:27])[C:21]1[C:22](=[O:25])[N:23]([CH3:24])[C:13]([CH2:12][O:11][CH3:10])=[N:15][C:16]=1[C:17]=2[O:38][CH3:39]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 1118Sulfuric AcidHCID 253877Potassium BromideHCID 10410192HCID 10410192, compound

Product 1

HCID 10249791HCID 10249791, compound

Reagents, catalysts & solvents 1

HCID 21584119Ethylacetate methanolSolvent

Conditions

Temperature
100 °C

Procedure

To 100 mL acetic acid and 4 mL concentrated sulfuric acid, was added 1.80 g (4.22 mmol) of 11 and the mixture was heated at 100° C. for 5 hours. After evaporating the solvents down to ca 5 mL, the oily residue was poured over 100 mL of ice water, neutralized with sodium carbonate, and the resulting solution extracted with 3×100 mL portions of chloroform. The combined extracts were evaporated to a small volume, placed on a silica column, and purified by flash chromatography employing ethyl acetate as the eluant. The product fraction was collected and evaporated to dryness. Recrystallization was carried out by redissolving the product in a minimum amount of chloroform followed by addition of hexane: 1.10 g (67%) yield; mp 223°-224° C.; TLC (ethyl acetate/methanol [9:1], Rf =0.22; IR (KBr pellet) 1688, 1614, 1474, 1428, 1375, 1342, 1269, 1097, 1036, 797 cm-1 ; 1H NMR (dimethyl-d6 sulfoxide) δ4.58 (4H, s, methylenes), 3.93, 3.62 and 3.42 (18H, 3×s, N- and O-methyls, no assignments made); mass spectrum (EI mode) m/z 390 (P+). Anal. Calcd for C18H22N4O6. 0.3H2O: C, 54.75; H, 5.74; N, 14.19. Found: C, 54.39; H, 5.63; N, 14.25.

Workup

  1. customAfter evaporating the solvents down to ca 5 mL
  2. additionthe oily residue was poured over 100 mL of ice water
  3. extractionthe resulting solution extracted with 3×100 mL portions of chloroform
  4. customThe combined extracts were evaporated to a small volume
  5. custompurified by flash chromatography
  6. customThe product fraction was collected
  7. customevaporated to dryness
  8. customRecrystallization
  9. dissolutionby redissolving the product in a minimum amount of chloroform
  10. additionfollowed by addition of hexane
  11. custom1.10 g (67%) yield

Sources & evidence

ORD record
ord-f6db7955011c4f07a2c9df0f845740f8
Source dataset
uspto-grants-1997_06
Patent number
US05639881

Reaction notes

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