cf. C.A. 46, 3959e.The title compounds and other glycosyl-v-triazolo[d]pyrimidine were synthesized from chloromercuri derivatives of appropriate triazolopyrimidines (I) prepared by modifications of standard methods, acetylated, and the AcO derivatives(II) converted into chloromercuri compounds(III) which were condensed with acylglycosyl halides as described for the corresponding purines (cf. Davoll and Lowy, C.A. 45, 10202d).AcOH (22 mL.) and 200 mL. aqueous 5,6-diamino-4-D-glucosylamino-2-methylthiopyrimidine, prepared according to Holland, et. al. (C.A. 43, 146c), from 6.5 g. 6-amino-4-D-glucosylamino-2-methylthiopyrimidine, were stirred with dropwise addition of 1.43 g. NaNO2 in 20 mL. H2O, the mixture was kept 2 h. at room temperature, the solution evaporated in vacuo below 40°, the residue acetylated with Ac2O-C5H5N at room temperature, the product (3.64 g.) extracted with CHCl3, the amorphous powder refluxed 2 h. in 250 mL. alc. containing Raney Ni (from 28 g. alloy), filtered hot and the filtrate and washings evaporated, the residue (1.77 g.) deacetylated with NH3 in MeOH at 0°, and the product converted into 1.41 g. picrate, m. 201° (decomposition after 4 recrystallizations from H2O).Treatment of the picrate with Dowex Number 1 anion exchange resin gave I (R = H, R1 = NH2, R2 = β-D-glucopyranosyl) (Ia), m. 241° (decomposition) (H2O), [α]20D -22° (c 1.0, H2O).II in 10 volumes cold H2O solubilized by the addition of 1 or 2 equivalents of N NaOH, the filtered solution treated with 1 mol HgCl2 in hot alc. (8 mL./g. 20 volumes H2O, and 1.5 parts by weight (of I) Hyflo Supercel, the mixture cooled and filtered, and the residue washed, dried, and powd. gave 80-90% III.In the reaction of III with tetra-O-acetylglucosyl bromide the procedure of D. and L. (loc. cit.) was followed; reactions using tri-O-benzoyl-D-ribofuranosyl chloride (IV) were carried out according to Kissman, et al. (C.A. 49, 8298e), except that the final extraction of the crude condensation product with Et2O was omitted.The crude wet product from the nitrosation of 35 g. 4,6-diamino-2-mercaptopyrimidine refluxed 1 h. with stirring with 3 l. H2O, 120 mL. NH4OH (d. 0.88), and Raney Ni (from 180 g. alloy) and the mixture filtered hot, evaporated in vacuo to 1.2 l. and shaken with C, the hot filtrate treated with 75 cc. AcOH and stirred with dropwise addition of 13 g. NaNO2 in 100 mL. H2O gave 13.5 g. I (R = R2 = H, R1 = NH2) (lb).Ib (2 g.) and 20 mL. Ac2O refluxed 4 h. and the cooled mixture filtered, the residue washed with alc. and dried gave 2.06 g. acetamido compound, C6H6N6O, m. 293-4° (50% EtOCH2CH2OH).The corresponding IIIb (9.05 g.) and 10 g. tetra-ο-acetyl-D-glucopyranosyl bromide gave 8.5 g. sirup, crystallized from 150 mL. alc. to give 0.5 g. needles, m. 270°, not giving a crystalline product on deacetylation with NH3 in MeOH.The alc. filtrate evaporated and the residue deacetylated with NH3 in MeOH at 0° gave 0.85 g. (?) 7-amino-1-β-D-glucopyranosyl-v-triazolo[d]pyrimidine (V) (R = H, R1 = NH, R2 = β-D-glucopyranosyl) (Va), C10H14N6O5, m. 250-1° (decomposition) (H2O); picrate, m. 160° (effervescence of 1 mol alc. of crystallization) (50% alc.).Addition of picric acid to the filtrate from Va gave 1.53 g. Ia picrate, converted to Ia with UV absorption spectrum identical with that of the above synthetic material.IIIb (16.7 g.) condensed with 1.09 mol IV, the sirup (24.5 g.) deacetylated with NaOMe, the mixture neutralized with CO2 and evaporated, the residue triturated with dry Et2O and the dried, BzOMe-free material crystallized from 125 mL. H2O and decolorized with C yielded 16% 8-azaadenosine (I, R = H, R1 = NH, R2 = 3-β-D-ribofuranosyl) (Ic), m. 218-19° (H2O), [α]22D -79° (c 0.46, H2O); picrate, m. 184° (decomposition) (H2O).Addition of picric acid to the mother liquor from Ic gave 7.25 g. impure picrate, converted to amorphous material, λ 273 mμ (0.1N HCl), λ 287 mμ (0.1N NaOH).Ic (2 g.) and 5 g. NaNO2 in 25 mL. hot H2O cooled rapidly, the solution treated with 5 mL. AcOH, kept 1 h., diluted with 25 mL. H2O, stored 18 h., treated with aqueous Pb(OAc)2 and NH4OH, and filtered, the Pb salt taken up in 20% AcOH, the solution saturated with H2S, the filtered solution evaporated, and the residue (1.87 g.) repeatedly recrystallized (80% alc.) gave 1.38 g. 8-azainosine (I, R = H, R1 = HO, R2 = β-D-ribofuranosyl) (Id), C9H11N5O5, m. 199-200°, [α]21D -54° (c 1.78, H2O).NaNO2 (4.85 g.) in 30 mL. H2O added dropwise with stirring to 8.5 g. 2,4,6-triaminopyrimidine in 220 mL. 10% AcOH, the mixture kept 1 h., diluted with 115 mL. AcOH, and hydrogenated 1 h. with 5% Pd-C, the filtered solution treated dropwise with 4.85 g. NaNO2 in 30 mL. H2O with stirring and filtered, the product treated with C in hot dilute aqueous NH4OH, and the hot filtrate acidified with AcOH gave 7.55 g.I (R = R1 = NH, R2 = H) (Ie).Ie (9.76 g.) refluxed 30 min. in 98 mL. Ac2O, the cooled mixture filtered, the residue washed with alc., the triacetyl compound, m. 210° (decomposition), boiled with 200 mL. moist EtOC2H4OH and filtered and the residue washed with EtOH gave 9.94 g. diacetamido derivative, m. 280° (decomposition), converted to the chloromercuri compound (IIIe).IIIe (8 g.) and 1 mol IV condensed and the pale yellow glass (11.4 g.) deacylated with NaOMe yielded 42% (?) 5,7-diamino-β-D-ribofuranosyl-v-triazolo[d]pyrimidine(s) (VI), m. 127-50° (H2O).PhCH2MeNH (9 mL.) and 3 g. 2,4-diamino-6-chloropyrimidine refluxed 1 h., the cooled mixture extracted with 60 mL. boiling EtOAc, the extract washed with 5% AcOH, and the dried (Na2SO4) extract evaporated gave 2.15 g. 2,4-diamino-6-(N-methylbenzylamino)pyrimidine acetate, m. 146-8°, which, nitrosated in 20% AcOH, the product hydrogenated in 50% AcOH with 10% Pd-C, and the filtered solution treated with 1 mol aqueous NaNO2 and filtered, gave I (R = R1 = NH, R2 = Me) (If), C5H7N7, m. 294-5° (H2O), insoluble in alkali.IIIe and IV condensed and the crude product (18.9 g.) deacylated with NH3 in MeOH, treated with HNO2 and deacylated with NaOMe gave 1.26 g. (?) V (R = NH2, R1 = HO, R2 = β-D-ribofuranosyl) (Vb), C9H12N6O5, m. above 200° (decomposition), [α]20D -75° (c 0.9, H2O), hydrolyzed 2 h. in boiling N HCl to give material with the spectrum of I (R = NH2, R1 = HO, R2 = H).VI (0.45g.) refluxed 45 min. in 5 mL. Ac2O and the solution evaporated, the residue treated as above also gave 24% Vb, identified by UV spectra in acid and alkali.2-Methylthio-9-β-D-ribofuranosyladenine (D. and L., loc. cit.) (0.5 g.) in 100 mL. 0.4N H2SO4 treated with 1.2 g. NaNO2 and the mixture kept 18 h., neutralized with NH4OH and evaporated to 15 mL. gave 0.46 g. 2-methylthio-9-β-D-ribofuranosylhypoxanthine, (VII), m. 246° (decomposition).VII (0.5 g.) in 4 mL. aqueous NH4OH (d. 0.88) and 4 mL. alc. NH3 (saturated at 0°) heated 18 h. at 130-2° in a sealed tube, the cooled mixture evaporated and the residue recrystallized (H2O) 4 times with decolorizing C gave 0.12 g. authentic guanosine.NaNO2 (0.69 g.) in a min. of H2O added to 1.71 g. 4,5,6-triamino-2-methylthiopyrimidine in 55 mL. 10% AcOH and filtered, the precipitate treated with C in hot dilute aqueous NH4OH, and the filtered solution acidified with AcOH gave 1.55 g. I (R = MeS, R1 = NH, R2 = H), m. 282° (decomposition), refluxed (1 g.) 2 h. in 5 mL. Ac2O and the cooled mixture diluted with 10 mL. anhydrous Et2O to give 1.06 g. crystalline diacetyl compound, m. 153-5°, transformed on standing in the open with loss of 1 Ac group to give 7-acetamido-5-methylthio-v-triazolo[d]pyrimidine (Ig), m. 215-17°, recrystallized (70% alc.) to give solvated needles, C7H8N6OS.C2H6O, m. 219-220°, transformed to the corresponding chloromercuri compound (IIIg).IIIg (23 g.) and 1 mol IV condensed and the product (31 g.) deacylated with NaOMe, taken up in 175 mL. hot H2O and treated with C, the solution kept 1.5 h. at room temperature and filtered gave 3.79 g.I (R = MeS, R1 = NH2, R2 = β-D-ribofuranosyl) (Ih), m. 200-1° (H2O).The filtrate kept 20 h. at 3° and filtered gave 2.8 g. (?) V (R = MeS, R1 = NH2, R2 = β-D-ribofuranosyl) (Vc), m. 156-8° (H2O).Treatment of Ih with Ac2O-C5H5N at room temperature yielded 84% I (R = H, R1 = NH2, R2 = tri-O-acetyl-β-D-ribofuranosyl), m. 152-3° (alc.), boiled (0.14 g.) 2 h. in 10 mL. alc. with 1 g. Raney Ni and the product deacetylated with NH3 in MeOH to give 18 mg. Ic.Desulfurization of Vc gave an amorphous product producing gelatinous solutions in H2O, λ 285 mμ (0.1N HCl), 292 mμ (0.1N NaOH).Ih (0.5 g.) in 100 mL. N HNO3 treated 20 h. at room temperature with 1.2 g. NaNO2 and the mixture filtered gave 0.43 g.I (R = MeS, R1 = HO, R2 = β-D-ribofuranosyl) (Ii), m. 181-3° (sintering above 178°) (H2O).Ii (0.5 g.) aminated as above (preparation of guanosine) and the product isolated through the Pb salt yielded 8% 8-azaguanosine (I, R = NH, R1 = HO, R2 = β-D-ribofuranosyl) (Ij), C9H12N6O5, m. 250-2° (decomposition) (H2O), hydrolyzed 2 h. with boiling N HCl to give a compound with the UV absorption spectrum of 5-amino-7-hydroxy-v-triazolo[d]pyrimidine, λ 250 mμ (0.1N HCl).Vc (0.5 g.) and 1.2 g. NaNO2 in 12 mL. hot H2O and the rapidly cooled solution treated with 1.2 mL. AcOH, the mixture kept 24 h. and the product isolated through the Pb salt yielded 56% (?) V (R = MeS, R1 = HO, R1 = β-D-ribofuranosyl) (Vd), m. 214-15°.I (R = NH2, R1 = HO, R2 = H) (15.5 g.) refluxed 2 h. in 155 mL. Ac2O and the cooled mixture filtered, the product washed with alc. and dried gave 23.2 g. diacetyl derivative, m. 219°.The corresponding chloromercuri compound (31 g.) condensed with 1.15 mol IV, the pale yellow gum (41.5 g.) refluxed 1 h. with NaOMe (from 2.5 g. Na in 400 mL. MeOH), the mixture evaporated, the residue in 500 mL. H2O made just acidic with AcOH, boiled and treated with C, the filtered solution kept 18 h. at room temperature and filtered gave 7.33 g. material, recrystallized to give 6.28 g. (?) 5-amino-7-hydroxy-2-β-D-ribofuranosyl-v-triazolo[d]pyrimidine (VIII), m. 230-5° (sintering) (H2O), [α]20D -79° (c 0.77, 0.1N NaOH).The filtrate evaporated to 200 mL. and cleared by heat, kept 5 h. and filtered yielded 4.62 g. material recrystallized (H2O) to give 3.9 g.Ij, [α]21D -97° (c 1.0, 0.1N NaOH).The mother liquors evaporated to 50 mL. gave 4.13 g. material containing 85% Ij, deaminated to yield pure I (R = R1 = HO, R2 = β-D-ribofuranosyl) (I-k).Ij (0.3 g.) and 1 g. Ba(NO3)2.H2O in 4 mL. hot H2O and the rapidly cooled solution treated with 1 mL. AcOH, kept 5 h. and treated with 8.06 mL. N H2SO4, the filtered solution evaporated in vacuo below 15° and the residue crystallized (4 mL. 5:2 alc.-H2O) gave 0.14 g. Ik, 8-azaxanthosine, m. 198-9° (decomposition), [α]20D -103° (c 1.02, 0.1N NaOH).The spectral characteristics of the products were tabulated [pyrimidine, λmaximum in mμ (10-3 ε) in HCl (normality indicated), at pH 6.8, and in NaOH (normality indicated) recorded]: Va, 244, 286 (5.3, 11.6, 0.1N), 246, 299 (5.5, 10.3), 245, 299 (5.3, 9.8, 0.1N); Ia, 263 (12.5, 0.1N), 280 (11.7), 280 (11.2, 0.1N); Ic, 260 (12.4, 0.1N), 279 (12.0), 278 (12.4, 0.1N); Id, 255 (9.4, 0.1N), 256 (8.8), 277 (10.5, 0.1N); VI, 260, 286 (11.5, 10.0, 0.1N), 222, 291 (21.7, 7.2), 329 (7.4, 0.1N); If, 254, 284 (9.1, 6.7, 0.1N), 258, 287 (5.1, 8.8), 259, 287 (5.1, 8.8, 0.1N); Vc, 230, 285, 303 (12.3, 13.3, 12.6, 0.05N), 223, 248, 279, 308 (15.9, 13.3, 10.5, 9.8), 248, 279, 310 (14.4, 10.3, 10.1, 0.05N); Ih, 245, 280 (13.7, 14.7, 0.05N), 248, 289 (19.4, 13.5), 247, 289 (18.9, 12.9, 0.05N); Vd, 222, 238, 287 (14.0, 14.8, 9.9, 0.05N), 219, 242, 288 (15.0, 14.3, 9.8), 244, 276, 300 (15.0, 9.8, 10.8, 0.05N); Ii, 232, 273 (9.5, 18.0, 0.05N), 242, 276 (12.5, 15.1), 242, 283 (16.8, 14.8, 0.05N); Vb, 285 (6.3, 0.01N), 238, 297 (8.4, 7.1), 254, 256, 304 (5.6, 5.6, 8.8, 0.03N); Ij, 255, 269 (13.6, 10.3, 0.01N), 256, 275 (13.7, 9.5), 221, 279 (23.0, 11.6, 0.03N); Ik, 240, 256 (5.9, 9.5, 0.1N), 252, 277 (9.7, 8.8), 251, 280 (7.1, 9.5, 0.1N); VII, 265 (15.1, 0.05N), 262 (14.8), 225, 271 (19.2, 14.8, 0.05N).