[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][CH:19]=1)[NH:5][C:6]1[C:7]2[CH:14]=[C:13]([CH2:15][OH:16])[NH:12][C:8]=2[N:9]=[CH:10][N:11]=1.P(Br)(Br)Br.Cl[C:25]1C=C(C=CC=1)NC1C2C=C(CBr)NC=2N=CN=1.C[O-].[Na+]>C(OCC)C.CO>[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][CH:19]=1)[NH:5][C:6]1[C:7]2[CH:14]=[C:13]([CH2:15][O:16][CH3:25])[NH:12][C:8]=2[N:9]=[CH:10][N:11]=1To an ice cooled suspension of 82.5 mg (0.30 mmol) of 4-(3-chloro-anilino)-6-hydroxymethyl-7H-pyrrolo[2,3-d]pyrimidin (cf. Example 49) in 5 ml of diethyl ether are added under argon 14 μl (0.15 mmol) of phosphorus tribromide. After stirring for 18 h at 0° C. and 18 h at RT (→4-(3-chloro-anilino)-6-bromomethyl-7H-pyrrolo[2,3-d]pyrimidin), 2 ml of methanol are added. The mixture is stirred for 2 h and then 1 ml of sodium methanolate (5.4 M in methanol) is added dropwise. After 18 h, the mixture is concentrated in vacuo; the residue is redissolved in methanol, silica gel is added and the mixture is evaporated to a dry powder. This powder is put on top of a chromatography column (SiO2 ; CH2Cl2 /ethanol [2:1]). Eluation with CH2Cl2 /ethanol [2:1], concentration and washing with ethyl acetate/diethyl ether/hexane affords the title compound; m.p. 226-230° C.; TLC-Rf =0.59 (CH2Cl2 /methanol [10:1]); HPLC: tRet (Grad20)=9.7.
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