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Reaction of inorganic cyanates with halides. II. Reactions of chlorohydrins
Author(s) -
Phillips Brian L.,
Argabright Perry A.
Publication year - 1966
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570030118
Subject(s) - chemistry , cyanate , anhydrous , dimethylformamide , organic chemistry , polymer chemistry , yield (engineering) , chloride , isocyanate , alkylation , medicinal chemistry , catalysis , polyurethane , solvent , metallurgy , materials science
The reaction of ethylene and trimethylene chlorohydrins with cyanate ion in anhydrous dimethylformamide (DMF) forms 2‐oxazolidinone and tetrahydro‐2 H ‐1, 3‐oxazin‐2‐one, respectively. These are the major products over a wide concentration range, and at initial chlorohydrin concentration of 1 M and lower, the yields are high enough to make the reaction useful for synthesis of oxazine and oxazolidine derivatives. The corresponding reaction with tetramethylene chlorohydrin gave tetrahydrofuran as the major product with the by‐products being polymeric. Pentamethylene and hexamethylene chlorohydrins yield linear polyurethanes when allowed to react with cyanate in DMF. Examination of the relative rates of reaction of these chlorohydrins indicate that the mechanism by which urethanes are formed (both cyclic and polymeric) is an S N 2 displacement of chloride by cyanate ion to give an isocyanate intermediate which then reacts with an alcohol group to form urethane.