Pyridine → Triethylammonium

HRID 1475128Notes

Reaction equation

HRID 1475128 reaction equation
[CH2:1]1N([P:7]([O:10][CH2:11][C@H:12]2[O:16][C@@H:15]([N:17]3[C:23](=[O:24])[NH:22][C:20](=[O:21])[C:19]([I:25])=[CH:18]3)[C@H:14]([OH:26])[C@@H:13]2[OH:27])([OH:9])=[O:8])CCO[CH2:2]1.[N:28]1[CH:33]=[CH:32]C=[CH:30][CH:29]=1.[CH2:34]([OH:49])[C@H:35]1[O:40][C@H:39]([O:41][P:42](O)([OH:44])=[O:43])[C@H:38]([OH:46])[C@@H:37]([OH:47])[C@H:36]1[OH:48].N1C=NN=N1.CN(C=[O:59])C>C(#N)C>[OH:41][C@H:39]1[O:40][C@H:35]([CH2:34][OH:49])[C@H:36]([OH:48])[C@H:37]([OH:47])[C@H:38]1[OH:46].[P:7]([O:10][CH2:11][C@H:12]1[O:16][C@@H:15]([N:17]2[CH:18]=[C:19]([I:25])[C:20](=[O:21])[NH:22][C:23]2=[O:24])[C@H:14]([OH:26])[C@@H:13]1[OH:27])([O:9][P:42]([OH:44])([OH:43])=[O:41])(=[O:8])[OH:59].[CH2:1]([NH+:28]([CH2:29][CH3:30])[CH2:33][CH3:32])[CH3:2]

Participants

8

Reactant 5

HCID 1049Pyridine2×HCID 6228DimethylformamideHCID 123912Galactose-1-phosphateHCID 44829125HCID 44829125, compoundHCID 178418441HCID 178418441, compound

Product 2

HCID 1385867TriethylammoniumHCID 131732778HCID 131732778, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

5-Iodouridine-5′-phosphoromorpholidate (107 mg, 0.21 mmol) was co-evaporated (3×) with dry pyridine (5 mL). Galactose-1-phosphate (tributylamine salt, 326 mg, 0.55 mmol) was 17 added, and the mixture was further co-evaporated (3×) with pyridine (5 mL). Under a nitrogen atmosphere, the dry residue was dissolved in dry DMF (2 mL) and a 0.05M solution of tetrazole (80 mg, 1.14 mmol) in dry acetonitrile was added. The reaction was stirred at room temperature for 5 h, by which time the reaction had reached completion. All solvents were removed under reduced pressure, and the crude residue was purified sequentially by purification methods 1 and 2. The title compound 2 was obtained in its triethylammonium salt form as a colourless, glassy solid in 42% yield (60 mg). δH (400 MHz, D2O) 3.70-3.76 (2H, m, H-6″), 3.77-3.82 (1H, m, H-2″), 3.92 (1H, dd, J=3.3 and 10.1 Hz, H-3″), 4.01 (1H, d, J=3.7 Hz, H-4″), 4.16-4.19 (1H, m, H-5″), 4.20-4.23 (2H, m, H-5′), 4.25-4.28 (1H, m, H-4′), 4.33-4.39 (2H, m, H-2′, H-3′), 5.64 (1H, dd, J=3.6 and 6.6 Hz, H-1″), 5.93 (1H, d, J=5.9 Hz, H-1′), 8.25 (1H, s, H-6); δC (75.5 MHz, D2O) 59.6, 61.8, 65.8 (d, J=3.0 Hz), 69.3, 69.8, 70.0, 70.4, 72.7, 74.6, 84.2 (d, J=5.3 Hz), 89.3, 96.6 (d, J=3.8 Hz), 146.6, 152.4, 164.1; δP (121.5 MHz, D2O) −9.21 (d, J=21.2 Hz), −7.71 (d, J=21.2 Hz). m/z (ESI) 709.9863 [M+NH4]+, C15H27N3O17P2I requires 709.9855.

Workup

  1. additionadded
  2. customAll solvents were removed under reduced pressure
  3. customthe crude residue was purified sequentially by purification methods 1 and 2

Sources & evidence

ORD record
ord-74922b06c61048999d3f9c532df869cd
Source dataset
uspto-grants-2015_04
Patent number
US09018370B2

Reaction notes

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