Tert-Butyl nitrite → Ammonia

HRID 1939613Notes

Reaction equation

HRID 1939613 reaction equation
C(O[C@@H]1[C@H](OC(=O)C)[C@@H](COC(=O)C)O[C@H]1[N:19]1C2N=C(N)N=C(N)C=2N=C1)(=O)C.N(OC(C)(C)C)=O.N([O-])=O.[Na+].[C:41]([O:44][C@@H:45]1[C@H:49]([O:50][C:51](=[O:53])[CH3:52])[C@@H:48]([CH2:54][O:55][C:56](=[O:58])[CH3:57])[O:47][C@H:46]1[N:59]1[C:68]2[N:67]=[C:66]([F:69])[N:65]=[C:63]([NH2:64])[C:62]=2[N:61]=[CH:60]1)(=[O:43])[CH3:42]>COCCOC.N1C=CC=CC=1>[NH3:19].[C:41]([O:44][C@@H:45]1[C@H:49]([O:50][C:51](=[O:53])[CH3:52])[C@@H:48]([CH2:54][O:55][C:56](=[O:58])[CH3:57])[O:47][C@H:46]1[N:59]1[C:68]2[N:67]=[C:66]([F:69])[N:65]=[C:63]([NH2:64])[C:62]=2[N:61]=[CH:60]1)(=[O:43])[CH3:42]

Participants

8

Reactant 4

HCID 10906Tert-Butyl nitriteHCID 21782950HCID 21782950, compoundHCID 218162712',3',5'-Tri-O-acetyl-2-fluoroadenosineHCID 23668193Sodium Nitrite

Product 2

HCID 222AmmoniaHCID 218162712',3',5'-Tri-O-acetyl-2-fluoroadenosine

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

It is further known in the literature that 2-aminoadenosine-2',3',5'-tri-O-acetate can be converted with tert-butyl nitrite or sodium nitrite in 50% HF/pyridine to a mixture of the corresponding 2-fluoroadenosine-2',3',5'-tri-O-acetate and 2,6-difluoro-nebularine-2',3',5'-tri-O-acetate, which, with dry ammonia gas in 1,2-dimethoxy-ethane, yields pure 2-fluoroadenosine-2',3',5'-tri-O-acetate in about a 60% yield (M. J. Robins, B. Uznanski, Can. J. Chem. 59, 2608 (1961)). A drawback of this process, however, is that because of the obtained mixture, another reaction step is necessary to obtain the pure 2-fluoronucleoside.

Sources & evidence

ORD record
ord-d5987d89ae56403792488f5c2f08311a
Source dataset
uspto-grants-1997_12
Patent number
US05696255

Reaction notes

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