655. Nucleotides. Part VIII. cycloNucleoside salts. A novel rearrangement of some toluene-p-sulphonylnucleosides

Abstract

Acid Hydrolysis of 2' : 3'-isoPropyZidene Oa : 5'-cycloCytidine Toluene-p-sulphonate.-2' : 3'-bso-Propylidene 0 2 : 6'-cydocytidine toluene-p-sulphonate (24.6 mg.) was dissolved in water (1 c.c.) and sulphuric acid added (1 C.C. ; N.). The clear solution was heated on the steam-bath for 2 hours and ethanol (10 c.c.) added. The solution was evaporated to a small bulk (1 c.c.), and acetone (5 c.c.) added. When the mixture was kept at 0" overnight, colourless needle-like prisms separated (10.3 mg.). These were collected and washed with acetone: they had m. p. 218-219" (Kofler block), undepressed on admixture with an authentic specimen of cytidine sulphate.Paper chromatography (Whatman No. 1) of the hydrolysis product with tevL-butanoI-ammoniawater (80 : 4 : 18) confirmed its homogeneity and established the presence of sulphate ion and cytidine (RF = 0.25 ; reference cytidine spot, RF = 0.25).

The crystal structure of acyclonucleoside

“…It was stated in the earlier paper (Clark et al, 1951) that a model of the molecule used in conjunction with the electron-density projection gave the separation C~-N S as approximately 1.5 /l. Since then, the positions of the atoms have been determined explicitly in the manner described in the following section.…”

“…Todd and his co-workers, who have attempted the synthesis of nucleosides, nucleotides and polynucleotides, demonstrating at each stage the constitution and configuration of their products. In the case of the particular synthesis described (Clark et al, 1951), the compound 5'-iodo, 2' :3'-isopropylidene adenosine, formula…”

Nucleic acid related compounds. 24. Transformation of tubercidin 2′,3′-O-orthoacetate into halo, deoxy, epoxide, and unsaturated sugar nucleosides

“…Prior deblocking of 100 gave the hydroxymethylfuran derivative (IOd) which underwent hydrogenation of the furan ring to give racemic 4-amino-7-(2.3-dideoxy-P-D~L-glycero-pentofura~osyl)pyrrolo[2,3-dlpyrimidine (9,111. The cis orientation of the base (1') and hydroxymethyl (4') substituents of 7,Bl was verified by 5'-0-tosylation followed by quantitative ~yclization (tlc, uv) to the PT1+5'-~~clonucleo-sides (3,9,14 …”

“…The nmr spectrum reported (6) for 7 is in agreement with that of this racemate. Treatment of a small sample of this racemate with tosyl chloride in pyridine followed by heating the isolated tosylate in acetone to effect cyclonucleoside formation (14) proceeded quantitatively (tlc) and gave a product having uv ( H 2 0 ) h,,,, 293, shoulder 273 nm (3).…”

Discussion on 13C nuclear magnetic resonance spectra of structurally rigid cyclonucleosides. Violation of Karplus relationship between 3JC,H and dihedral angles

“…sured to be 35" and a 3JC,H value around 3 Hz was expected based on the Karplus curve (3). Investigation of 3JC,H in other structurally rigid cyclonucleosides 2 through 6 (Table l), which were mainly prepared in this laboratory (12)(13)(14)(15)(16)(17), resulted in finding that the orientational effect of oxygen functional groups on 3Jc., is also similar to that observed by Schwarcz and Perlin (5) in the study on glycoside derivatives.…”