Isoamyl Nitrite → HCID 14886877, compound

HRID 1647529Notes

Reaction equation

[C:1]([O:4][C@@H:5]1[C@H:9]([O:10][C:11](=[O:13])[CH3:12])[C@@H:8]([CH2:14][O:15][C:16](=[O:18])[CH3:17])[O:7][C@H:6]1[N:19]1[CH:27]=[N:26][C:25]2[C:20]1=[N:21][C:22](N)=[N:23][C:24]=2[Cl:28])(=[O:3])[CH3:2].C(ON=O)CC(C)C.[CH3:38][S:39]SC>C(#N)C>[C:1]([O:4][C@@H:5]1[C@H:9]([O:10][C:11](=[O:13])[CH3:12])[C@@H:8]([CH2:14][O:15][C:16](=[O:18])[CH3:17])[O:7][C@H:6]1[N:19]1[CH:27]=[N:26][C:25]2[C:20]1=[N:21][C:22]([S:39][CH3:38])=[N:23][C:24]=2[Cl:28])(=[O:3])[CH3:2]

Participants

Conditions

Temperature: 100 °C

Procedure

9-(2',3',5'-Tri-O-acetyl-β-D-ribofuranosyl)-2-amino-6-chloro-9H-purine (see Example 9) (4.0 g, 9.3 mmol) was dissolved in acetonitrile (100 ml). Isoamylnitrite (10.84 g, 93 mmol) was introduced followed by methyl disulphide (4.14 ml, 46 mmol) and the reaction mixture was heated at an oil bath temperature of 100° C. for 2 h. The evolved gas was removed via a hypochlorite scrubber. The reaction mixture was cooled, evaporated and purified by flash chromatography on silica gel. Elution initially with dichloromethane, followed by dichloro-methane/methanol (100/1) provided 9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-6-chloro-2-methylthio-9H-purine (3.1 g, 72%) as a foam, 1H NMR (CDCl3) δ2.12, 2.14, 2.18 (9H, 3s, 2',3' and 5'-O-acetyl CH3), 2.66 (3H, s, --SCH3), 4.28-4.51 (3H, m, H-5'a, H-5' b and H-4'), 5.66 (1H, t, H-3'), 6.0 (1H, t, H-2'), 6.13 (1H, d, H-1'), 8.11 (1H, s, H-8).

Workup

customThe evolved gas was removed via a hypochlorite scrubber
temperatureThe reaction mixture was cooled
customevaporated
custompurified by flash chromatography on silica gel
washElution initially with dichloromethane

Sources & evidence

ORD record: ord-6ec662fe11594ef79bb2649baf9663ab
Source dataset: uspto-grants-1995_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05432164

Reaction notes

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