Ammonia → HCID 510972, compound

HRID 722001Notes

Reaction equation

HRID 722001 reaction equation
[CH3:1][C@:2]1([CH2:17][OH:18])[O:6][C@@H:5]([N:7]2[CH:14]=[CH:13][C:11](=S)[NH:10][C:8]2=[O:9])[C@H:4]([OH:15])[C@@H:3]1[OH:16].[NH3:19]>>[CH3:1][C@:2]1([CH2:17][OH:18])[O:6][C@@H:5]([N:7]2[CH:14]=[CH:13][C:11]([NH2:19])=[N:10][C:8]2=[O:9])[C@H:4]([OH:15])[C@@H:3]1[OH:16]

Participants

3

Reactant 2

HCID 222AmmoniaHCID 86590642HCID 86590642, compound

Product 1

HCID 510972HCID 510972, compound

Procedure

Compound 11 (890 mg, 1.93 mmol) was treated with methanolic ammonia (previously saturated at −10° C.), (12 mL) at 100° C. in a stainless-steel bomb for 3 hours, then cooled to room temperature. The solvent was evaporated under reduced pressure and the residue was partitioned between methylene chloride (40 mL) and water (40 mL). The aqueous layer was washed with methylene chloride (2×40 mL), concentrated under reduced pressure. The crude material was purified by silica gel column chromatography [eluent: methylene chloride/methanol/ammonium hydroxide 65:30:5]. The collected fractions were evaporated under reduced pressure and in absolute ethanol (6.3 mL). To the solution was added a 2N hydrochloric acid solution (1.5 mL) and the mixture was stirred before being concentrated under reduced pressure. The procedure was repeated twice and 12 was precipitated from absolute ethanol. Mp: 213–214 (dec.); UV (methanol): λmax=280 nm (ε=9800), λmin=245 nm (ε=3600); 1H-NMR (DMSO-d6): δ 9.82 (s, 1H, NH2), 8.72 (s, 1H, NH2), 8.34 (d, 1H, H-6, J6-5=7.8 Hz), 6.21 (d, 1H, H-5, J5-6=7.8 Hz), 5.83 (d, 1H, H-1′, J1′-2′=5.8 Hz), 4.22 (d, 1H, OH-2′, JOH-2′=6.5 Hz), 5.6–4.7 (m, 3H, OH-2′, OH-3′ and OH-5′), 4.28 (t, 1H, H-2′, J=5.6 Hz), 3.99 (d, 1H, H-3′, J=5.3 Hz), 3.43 (m, 2H, H-5′ and H-5″), 1.14 (s, 3H, CH3); MS (matrix GT): FAB>0 m/z 515 (2M+H)+, 258 (M+H)+, 147 (S)+, 112 (BH2)+ FAB<0 m/z 256 (M−H)−.

Workup

  1. customThe solvent was evaporated under reduced pressure
  2. customthe residue was partitioned between methylene chloride (40 mL) and water (40 mL)
  3. washThe aqueous layer was washed with methylene chloride (2×40 mL)
  4. concentrationconcentrated under reduced pressure
  5. customThe crude material was purified by silica gel column chromatography [eluent: methylene chloride/methanol/ammonium hydroxide 65:30:5]
  6. customThe collected fractions were evaporated under reduced pressure and in absolute ethanol (6.3 mL)
  7. additionTo the solution was added a 2N hydrochloric acid solution (1.5 mL)
  8. concentrationbefore being concentrated under reduced pressure
  9. custom12 was precipitated from absolute ethanol

Sources & evidence

ORD record
ord-8983a6396f174d37b894fc7aa3067904
Source dataset
uspto-grants-2006_11
Patent number
US07138376B2

Reaction notes

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