7H-Pyrrolo(2,3-d)pyrimidine-5-carbonitrile, 4-amino-7-((2-hydroxyethoxy)methyl)- → Methyl 4-amino-7-[(2-hydroxyethoxy)methyl]-7H-pyrrolo[2,3-d]pyrimidine-5-carboximidate

HRID 442565Notes

Reaction equation

HRID 442565 reaction equation
[NH2:1][C:2]1[C:3]2[C:10]([C:11]#[N:12])=[CH:9][N:8]([CH2:13][O:14][CH2:15][CH2:16][OH:17])[C:4]=2[N:5]=[CH:6][N:7]=1.[CH3:18][O-:19].[Na+]>CO>[NH2:1][C:2]1[C:3]2[C:10]([C:11](=[NH:12])[O:19][CH3:18])=[CH:9][N:8]([CH2:13][O:14][CH2:15][CH2:16][OH:17])[C:4]=2[N:5]=[CH:6][N:7]=1

Participants

4

Reactant 2

HCID 4524867H-Pyrrolo(2,3-d)pyrimidine-5-carbonitrile, 4-amino-7-((2-hydroxyethoxy)methyl)-HCID 10942334Sodium Methoxide

Product 1

HCID 5271703Methyl 4-amino-7-[(2-hydroxyethoxy)methyl]-7H-pyrrolo[2,3-d]pyrimidine-5-carboximidate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

Methyl 4-amino7-(2-hydroxyethoxymethyl)pyrrolo[2,3-d]-pyrimidine-5-formimidate was prepared by first dissolving compound (17a) (0.5 g; 2.15 mmole) in dry MeOH (15 ML). A sodium methoxide (1 M) solution (5 mL) was added and the mixture was stirred at room temperature for 3 hours. This solution was adjusted to pH7 by adding small portions of Dowex 50 (H+ form, prewashed with dry CH3OH). The solution was then quickly filtered to remove the ion-exchange resin followed by concentration of the filtrate in vacuo to a semisolid mass. The residue was purified by a column (2×60 cm; prepacked in CH2Cl2) of silica gel (15 g; 60-200 mesh). Elution of the column with CH2Cl2 :CH3OH (96:4, V:V) afforded the desired nucleoside which was crystallized from dry CH3OH-ET2O to afford the pure imidate (0.13 g; yield 23%); mp. 124° C.; IR (KBr)γ3350 (OH) and 1600 cm-1 ; UVλmax nm:(pH 1), 237 (14700) 280 (12710); (MeOH), 278 (15770); (pH 11), 217 (26100) 278 (13880). 1H NMR (DMSO-d6): δ3.50 (nm, 4, CH2), 3.75 (s, 3, OCH3), 5.58 (s, 2, C1 ''CH2), 7.25 (brs 1, NH2), 7.75 (s, 1, C6 --H), 8.06 (s, 1, C2 --H), 8.20 (brs, 1, C=NH, 9.98 (brs,1,NH2). Anal. (C11H15N5O3) C,H,N.

Workup

  1. filtrationThe solution was then quickly filtered
  2. customto remove the ion-exchange resin
  3. customThe residue was purified by a column (2×60 cm; prepacked in CH2Cl2) of silica gel (15 g; 60-200 mesh)
  4. washElution of the column with CH2Cl2 :CH3OH (96:4, V:V)

Sources & evidence

ORD record
ord-10a66eb24a8d48f09711b5f00d40e62b
Source dataset
uspto-grants-1999_04
Patent number
USRE036187

Reaction notes

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