Kissman, Henry M.; Baker, B. R. published an article in 1957, the title of the article was Synthesis of certain 5-deoxy-D-ribofuranosylpurines.Name: (3aS,4S,6R,6aR)-4-(Iodomethyl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole And the article contains the following content:
Me 2,3-O-isopropylidene-D-ribofuranoside (I) (30.6 g.) in 90 cc. pyridine treated dropwise with stirring and cooling with 17.4 g. MeSO2Cl, kept at 5° overnight, poured into 400 cc. ice H2O, and extracted with CHCl3, the extract washed, dried, treated with C, and evaporated in vacuo, the residue dissolved in 500 cc. Et2O, the solution filtered through Norite, and the filtrate concentrated gave 26.8 g. 5-mesylate (II) of I, m. 78-9° (EtOAc-cyclohexane) (all m.ps. are corrected), [α]24D -53.0° (c 1.86, CHCl3). II (8.5 g.) in 90 cc. HCONMe2 refluxed 1.5 hrs. with stirring with 5.06 g. NaI, cooled, and filtered, the residue washed with Et2O, the combined filtrates concentrated in vacuo at 70° to about 30 cc., diluted with 300 cc. H2O, and extracted with Et2O, the extract dried, decolorized with Norite, and evaporated in vacuo, and the oily residue (8.4 g.) distilled gave 7.2 g. 5-deoxy-5-iodo analog (III) of II, b0.1 75-80°, [α]24.5D -68.6° (c 2, CHCl3). III (3.22 g.) in 30 cc. MeOH containing 1.56 cc. Et3N treated with a small piece of Dry Ice, hydrogenated over 0.322 g. 10% Pd-C, and filtered through Celite, the filtrate concentrated in vacuo at 30°, mixed with 50 cc. CH2Cl2, washed with 10 cc. H2O and 10 cc. saturated aqueous NaHCO3, dried, and evaporated in vacuo, and the residue distilled yielded 1.08 g. 5-deoxy analog (IV) of II, b20 92-5°. III (32.5 g.) in 100 cc. MeOH containing 30 cc. Et3N hydrogenated 19 min. at 35 lb. over 3 g. Raney Ni in 20 cc. MeOH, filtered, and evaporated in vacuo at room temperature, the residue triturated with Et2O and filtered to give 19.9 g. Et3N.HI, and the filtrate washed, dried, and distilled gave 13.96 g. IV, b20-25 95-9°. IV (825 mg.) and 12 cc. 0.4N HCl heated 2 hrs. on the steam bath with occasional shaking, cooled to room temperature, diluted with 40 cc. H2O, neutralized with Duolite A-4 resin (OH form), and filtered, the filtrate evaporated in vacuo at 50°, and the residue evaporated twice with C6H6 and dried over P2O5 in vacuo yielded 575 mg. 5-deoxy-D-ribose (V), light yellow sirup. V (269 mg.) in 0.5 cc. H2O added to 396 mg. 2,4-(O2N)2C6H3-NHNH2 in 12 cc. absolute EtOH, refluxed, 12 hrs., and evaporated to dryness in vacuo gave 453 mg. 2,4-dinitrophenylhydrazone, of V, m. 151-2° (decomposition) (C6H6-CH2Cl2), [α]25D -30.2° (c 0.99, MeOH). V (575 mg.) in 20 cc. pyridine kept 3 days at room temperature with 3 cc. Ac2O, treated with 50 cc. cold saturated aqueous NaHCO3, and extracted with CHCl3, the residue from the extract evaporated with PhMe, dissolved in dry Et2O, treated with Darco, and evaporated, and the final residue (960 mg.) distilled in vacuo yielded 746 mg. 1,2,3-triacetate (VI) of V, b0.2 118-20°. IV (1.88 g.) hydrolyzed and acetylated, the Et2O solution of the product evaporated, and the residue (2.49 g.) of mixed acetates crystallized from hexane yielded 766 mg. β-anomer of VI, m. 64-5° (hexane-Et2O), [α]25D -26.9° (c 2.42, CHCl3); the mother liquor distilled gave 829 mg. oil (mainly α-VI), b0.1 100-3°, [α]25D 17.0° (c 2.71, CHCl3). Mixed VI (2.6 g.) in 80 cc. Et2O (saturated at 0° with HCl) kept 72 hrs. at -3° and evaporated in vacuo, the residual gummy 1-chloro-2,3-di-O-acetyl-5-deoxy-D-ribose (VII) dissolved in 25 cc. xylene, the solution added to a dry suspension of 6.25 g. chloromercuri-6-dimethylaminopurine-Celite (containing 3.88 g. purine derivative) in 100 cc. xylene, refluxed 3 hrs. with stirring, and filtered, the residue washed with CHCl3, the combined filtrates evaporated in vacuo, the residue dissolved in 80 cc. CHCl3 and filtered, the filtrate washed with 20 cc. 30% aqueous KI and with 20 cc. H2O, dried, clarified with Darco, filtered, and evaporated in vacuo, the residual dark yellow gum (3.14 g.) containing a maximum of 72% 2,3-diacetate (VIII) of 6-dimethylamino-9-(5-deoxy-D-ribofuranosyl)purine (IX) dissolved in 50 cc. absolute MeOH, the solution refluxed 0.5 hr. with 0.3 cc. N NaOMe-MeOH and evaporated in vacuo, and the dark residue decolorized in dry Me2CO with C and evaporated gave 771 mg. IX, m. 163-5° (iso-PrOH), [α]24.5D -50.7° (c 2.02, EtOH). VII from 1.3 g. VI in 10 cc. xylene added to 4 g. mixture of chloromercuri-6-chloropurine and Celite (2 g.) in 140 cc. xylene, refluxed 3 hrs. with stirring and processed in the usual manner gave 1.63 g. diacetate (X) of 6-chloro-9-(5-deoxy-β-D-ribofuranosyl)-purine (XI) (74% pure). VII (1.6 g.) kept 16 hrs. at -3° with 25 cc. MeOH (saturated at 3° with NH3) and evaporated in vacuo at 25°, the residue dissolved in hot EtOAc, filtered through C, and evaporated to dryness, the residue (1.03 g.) dissolved in a min. of EtOAc, and the solution seeded and diluted with C6H5 until cloudy gave 355 g. XI, m. 154-6°, [α]24D -45.5° (c 1.69, EtOH). VII from 2.60 g. VI added to 10.2 g. mixture of chloromercuri-6-benzamidopurine and Celite (containing 4.74 g. purine derivative) in 120 cc. xylene, refluxed 3 hrs. with stirring, and worked up in the usual manner, the resulting dark gummy product deacetylated in the usual manner, the product dissolved in 50 cc. MeOH, and the solution refluxed 0.5 hr. with 1 cc. N NaOMe-MeOH and evaporated in vacuo gave 1.92 g. dark gum; 1.2 g. dissolved in 60 cc. H2O, filtered, treated with Amberlite IRC-50 (H form) and then with C, and evaporated in vacuo, the residue (770 mg.) dissolved in 5 cc. H2O (saturated with EtOAc), mixed with 10 g. Celite, packed on top of a column of 230 g. Celite packed with 115 cc. H2O (saturated with EtOAc), and developed gave 183 mg. 6-amino-9-(5-deoxy-β-D-ribofuranosyl)purine (5′-deoxyadenosine) (XII), m. 210-12° after liquefaction at 180° and resolidification, [α]25D -52.7° (c 1.00, EtOH). Crude condensation product from 10 millimoles of VI refluxed 75 min. in 50 cc. MeOH containing 1 cc. N NaOMe-MeOH and evaporated in vacuo, the residue dissolved in 50% aqueous EtOH, neutralized with stirring with Amberlite IRC-50 resin, filtered, and evaporated in vacuo, the residue in 50 cc. H2O extracted with EtOAc and evaporated in vacuo, the residual glass (1.49 g.) dissolved in absolute EtOH, filtered through C, concentrated to 15 cc., seeded with XII, and the deposit washed with a little EtOH and Et2O and dried in vacuo gave 472 mg. XII, m. 205-7° with shrinking at 120 and 185°; the combined mother liquors evaporated, the residual glass dissolved in hot EtOAc-EtOH, and the solution concentrated at the b. p. gave successive fractions of gummy precipitate which crystallized from EtOH at 0° yielded 123 mg. α-anomer of XII, m. 173-5° with shrinking at 115-20°, [α]24.5D -9.9° (c 1.62, EtOH). Crude XII (1.3 g.) from a similar run (containing a maximum of 71% XII) partitioned in EtOAc-H2O on 210 g. Celite gave 279 mg. β-anomer of XII, m. 206-8° with partial melting and resolidification at 125-30°, [α]24D -26.9° (c 1.5, EtOH), 173 mg. mixture of α- and β-XII, m. unsharply at 115°, and 67 mg. solid, m. 110-15°, [α]24D 53.0° (c 0.75, EtOH). VI (0.65 g.) converted to X gave 777 mg. crude gum containing a maximum of 67% X; the gum in 25 cc. MeOH (saturated at 0° with NH3), heated 5 hrs. in a sealed tube at 100°, cooled, and evaporated in vacuo, and the residue in a small amount of hot EtOH decolorized with C and cooled yielded 141 mg. crude II, m. above 125° (unsharp), [α]24D -48.2° (c 1.02, EtOH); the mother liquor evaporated, the residue dissolved in H2O, treated with C, evaporated in vacuo, dissolved in the min. amount of EtOH, diluted to cloudiness with EtOAc, and filtered, the filtrate evaporated, the residue dissolved in the min. amount hot H2O, and the solution allowed to stand several days in an open vessel gave 88% pure XII, [α]24D -49.7° (c 0.19, EtOH); the combined crude XII recrystallized from EtOH gave 136 mg. β-XII, m. 208-9°, [α]24D -54.0° (c -54.0°) (c 0.63, EtOH). X from 1.40 g. VI in 50 cc. EtOH hydrogenated 3 hrs. at atm. pressure 367 mg. 10% Pd-C (wetted with 2 cc. Methyl Cellosolve) and 151 mg. MgO and filtered through Celite, the residue washed with EtOH, the combined filtrates evaporated in vacuo, the residue dissolved in 50 cc. CHCl3, the solution washed with H2O, dried, and evaporated in vacuo, and the residue (1.33 g.) dissolved in 20 cc. Et2O and diluted to cloudiness with hexane gave 404 mg. 9-(2,3-di-O-acetyl-5-deoxy-β-D-ribofuranosyl)purine (XIII), m. 119-20°, [α]24D -26.8° (c 1.49, EtOH). XIII (320 mg.) in 15 cc. absolute MeOH containing 0.2 cc. N NaOMe-MeOH refluxed 0.5 hr. and evaporated in vacuo, the residue dissolved in hot EtOAc containing some MeOH, filtered, and evaporated in vacuo, and the gummy residue (277 mg.) recrystallized from Et2O-CH2Cl2 yielded 60 mg. 9-(5-deoxy-β-D-ribofuranosyl)purine (5′-deoxynebularine) (XIV), m. 115-16°, [α]25D -28.3° (c 1.83, EtOH). XI (270 mg.) in 43 cc. H2O hydrogenated 75 min. with stirring at atm. pressure over 98 mg. 10% Pd-C and 40 mg. MgO, filtered through Celite, and evaporated in vacuo, the residual glass 271 mg. dissolved in hot CHCl3 containing some MeOH, cooled, filtered, and evaporated in vacuo, and the residue crystallized from Et2O-CH2Cl2 yielded 69 mg. XIV, m. 115-16°. The experimental process involved the reaction of (3aS,4S,6R,6aR)-4-(Iodomethyl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole(cas: 38838-06-1).Name: (3aS,4S,6R,6aR)-4-(Iodomethyl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole
(3aS,4S,6R,6aR)-4-(Iodomethyl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole(cas:38838-06-1) belongs to dioxoles. Dioxoles, particularly fluorinated dioxoles, are used as co-monomers to make polymers that find use in forming protective coatings for chemical resistance. Name: (3aS,4S,6R,6aR)-4-(Iodomethyl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole
Referemce:
1,3-Benzodioxole – Wikipedia,
Dioxole | C3H4O2 – PubChem