(S)-4-Chloro-2,5-diformamido-6-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxyamino)pyrimidine → (S)-6-chloro-9-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxy)-2-formamidopurine

HRID 1089277Notes

Reaction equation

[Cl:1][C:2]1[C:7]([NH:8][CH:9]=O)=[C:6]([NH:11][O:12][CH2:13][C@@H:14]2[CH2:18][O:17][C:16]([CH3:20])([CH3:19])[O:15]2)[N:5]=[C:4]([NH:21][CH:22]=[O:23])[N:3]=1>C(OC(OCC)OCC)(=O)C>[Cl:1][C:2]1[N:3]=[C:4]([NH:21][CH:22]=[O:23])[N:5]=[C:6]2[C:7]=1[N:8]=[CH:9][N:11]2[O:12][CH2:13][C@@H:14]1[CH2:18][O:17][C:16]([CH3:20])([CH3:19])[O:15]1

Participants

Conditions

Temperature: 25 °C

Procedure

A solution of (S)-4-chloro-2,5-diformamido-6-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxyamino)pyrimidine (2.1 g, 6.08 mmol) in diethoxymethyl acetate (30 ml) was stirred at 120° C. for 3 h. The reaction was evaporated to dryness, the residue dissolved in methanol (40 ml) and 0.88 ammonia (1 ml) and stirred for 1.5 h. at 25° C. Evaporation and chromatography of the residue on silica eluting with ethyl acetate-hexane 1:1 gave (S)-6-chloro-9-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxy)-2-formamidopurine (1.3 g, 65%) as a white solid; m.p. 147°-8° C.; υmax (KBr) 3420, 3200, 1700, 1610, 1580, 1510, and 1440 cm-1 ; δH(CDCl3) 1.40(3H,S,CH3), 1.44(3H,S,CH3), 3.89(1H,m,CH2OCMe2), 4.16(1H,m,CH2OCMe2), 4.50(3H,m,CH+CH2ON), 8.23(1H,S,H- 8), 8.45(1H,br.d,J11.5 Hz,D2O exchangeable, NH) and 9.59(1H,d,J11.5 Hz,HCONH). Found C, 43.75; H, 4.29; N, 21.23%; M+ 327.0734; C12H14ClN5O4 requires C, 43.98; H, 4.31; N, 21.37%; M+ 327.0734.

Workup

customThe reaction was evaporated to dryness
dissolutionthe residue dissolved in methanol (40 ml)
customEvaporation and chromatography of the residue on silica eluting with ethyl acetate-hexane 1:1

Sources & evidence

ORD record: ord-7819001cc40c4fa388ac0ff776e5878a
Source dataset: uspto-grants-1990_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04965270

Reaction notes

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