Reaction of 5-halocytosine derivatives with cysteine

Journal Article · Fri Jan 01 04:00:00 EST 1988 · Nucleosides and Nucleotides; (United States)

DOI:https://doi.org/10.1080/07328318808068699· OSTI ID:5576965

Pal, B C; Ghosh, C; Sethi, S K; Suttle, B E; McCloskey, J A ^[1]

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1. ORNL, Oak Ridge, TN (United States) Univ. of Utah, Salt Lake City, UT (United States)

5-Bromo-(1) and 5-iodo-2[prime]-deoxycytidine (2) undergo 100 percent dehalogenation to 2[prime]-deoxycytidine on heating with cysteine in 1N aq K[sub 2]CO[sub 3] in a nitrogen atmosphere at 50[degrees] for 72 h and 21 h, respectively. 5-Chloro-2[prime]-deoxycytidine (3) and 1-methyl-5-chlorocytosine (3m) on the other hand undergo very little dehalogenation, forming instead two products, 4, 5 and 4m, 5m respectively, whose structures have been determined by mass spectrometry and proton magnetic resonance spectroscopy of the 3m products: 1-methyl-5(cystein-S-yl)cytosine (4m) and 3-methyl-2,6,7,8-tetrahydro-2-oxo-3H-pyrimido [5,4-b][1,4]-thiazine-7-carboxylic acid (5m), mp. 236[degrees]C, 78 percent yield. Initially produced 4m undergoes a novel and facile cyclization to form 5m with loss of NH[sub 3] in the presence of cysteine. The compound 3m, mp. 258[degrees]C, has been synthesized by treating 1-methylcytosine with N-chlorosuccinimide in acetic acid at 105[degrees] for 3 h in 56 percent yield. Ultraviolet absorption spectral properties of 1, 2, 3, 3m, 4, 4m, 5, and 5m are reported.

• OSTI ID: 5576965
• Journal Information: Nucleosides and Nucleotides; (United States), Journal Name: Nucleosides and Nucleotides; (United States) Vol. 7:1; ISSN NUNUD5; ISSN 0732-8311
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
AMINES
AMINO ACIDS
AZINES
CARBOXYLIC ACIDS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CYSTEINE
CYTOSINE
DEHALOGENATION
HETEROCYCLIC COMPOUNDS
MAGNETIC RESONANCE
MASS SPECTROSCOPY
NUCLEAR MAGNETIC RESONANCE
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PYRIMIDINES
RESONANCE
SPECTROSCOPY
THIOLS
YIELDS