Ammonia → HCID 54313128, compound

HRID 1082101Notes

Reaction equation

HRID 1082101 reaction equation
C([O:9][C@@H:10]1[C@H:14]([O:15]C(=O)C2C=CC=CC=2)[C@@H:13]([CH:24]=[CH2:25])[O:12][C@H:11]1[N:26]1[C:48]2[N:47]=[C:46]([Cl:49])[N:45]=[C:30]([NH:31][N:32]3[CH2:37][CH2:36][CH:35]([S:38][C:39]4[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=4)[CH2:34][CH2:33]3)[C:29]=2[N:28]=[CH:27]1)(=O)C1C=CC=CC=1.NN1CCC(SC2C=CC=CC=2)CC1.N>CO>[Cl:49][C:46]1[N:45]=[C:30]([NH:31][N:32]2[CH2:33][CH2:34][CH:35]([S:38][C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[CH2:36][CH2:37]2)[C:29]2[N:28]=[CH:27][N:26]([C:48]=2[N:47]=1)[C@@H:11]1[O:12][C@H:13]([CH:24]=[CH2:25])[C@@H:14]([OH:15])[C@H:10]1[OH:9]

Participants

5

Reactant 3

HCID 222AmmoniaHCID 10679905HCID 10679905, compoundHCID 22868438HCID 22868438, compound

Product 1

HCID 54313128HCID 54313128, compoundYield 29%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

2',3'-Di-O-benzoyl-2-chloro-5'-deoxy-5'-methylene-N-(4-phenylthio-1-piperidinyl)adenosine, prepared as described in Example 25 from 2,6-dichloro-9-(5'-deoxy-2',3'-di-O-benzoyl-5'-methylene-β-D-ribofuranosyl)-9H-purine (1.0 g, 1.9 mmol) and 1-amino-4-phenylthiopiperidine (0.44 g, 2.1 mmol), was dissolved in methanol (20 ml) and sat. methanolic ammonia (2.5 ml) was introduced. The reaction mixture was stirred at ambient temperature for 18 h, evaporated and purified by flash chromatography eluting with a mixture of dichloromethane and ethanol (50:1) to provide the title 2-chloro-5'-deoxy-5'-methylene-N-(4-phenylthio-1-piperidinyl)adenosine (0.27 g, 29%) as a foam, 1H-NMR (400 MHz, DMSO-d6) δ1.70 (2H, br q, piperidine C--H), 1.99 (2H, br d, piperidine C--H), 2.77 (2H, br m, piperidine C--H), 3.06 (2H, br m, piperidine C--H), 4.07 (1H, q, H-3'), 4.32 (1H, dt, H-2'), 4.58 (1H, m, H-4'), 5.20 (1H, dd, C=C--H), 5.29 (1H, d, C=C--H), 5.39, 5.56 (2H, 2d, 2'-and 3'-OH), 5.86 (1H, d, H-1'), 6.07 (1H, m, C=C--H), 7.23-7.45 (5H, 3 m, Ar--H), 8.36 (1H, s, H-8), 9.34 (1H, s, N--H). HPLC retention time 13.46 min. (gradient elution over 30 min; 25-45% acetonitrile/0.1% ammonium sulfate in water), purity 100% at 250 nm).

Workup

  1. customevaporated
  2. custompurified by flash chromatography
  3. washeluting with a mixture of dichloromethane and ethanol (50:1)

Sources & evidence

ORD record
ord-837fb82464b4439eba25303f756ad773
Source dataset
uspto-grants-1996_12
Patent number
US05589467

Reaction notes

Loading…