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UBC Theses and Dissertations

Direct carbonylation of aromatic nitriles using dicabalt octacarbonyl Gervay, Joseph Edmund


A new method of synthesizing N-substituted phthalimidines is described. When benzonitrile was reacted with carbon monoxide containing about 0.04 volume percent of hydrogen and in the presence of dicobalt octacarbonyl and pyridine in benzene solution at 235° and 3400 p.s.i. pressure the following compounds were produced: N-benzyphthalimidine (8%), N-phenylphthalimidine (3.7%), and benzamide (3.9%). When 40 p.s.i. hydrogen was added under the same reaction conditions, the yield of N-benzylphthalimidine increased (16%). When benzonitrile was subjected to the same reaction conditions using 240 p.s.d. hydrogen and no pyridine, N-benzylphthalimidine (15%) and sym-dibenzylurea (8%) were produced. A study on the mechanism of the ring closure process using deuterium gas revealed, that the ortho- hydrogen of the aromatic ring is not transferred directly to the unsaturated carbon-nitrogen bond in the course of the reaction. When phenylacetonitrile was reacted with carbon monoxide and 350 p.s.i. hydrogen at 250° in the presence of dicobalt octacarbonyl the following compounds were isolated: phenacetyl- β-phenethylamine (30%), di-β-phenylethylamine (23%), di- β-phenylethylurea (3.1%) and phenylacetamide (3%). When m-tolunitrile was reacted under similar reaction conditions with 185 p.s.i. hydrogen at 240°, N-m-xylylurea (9.5%), N,N'-di-m-xylylurea (13.5%), and m-toluamide (11.5%) were produced. Organometallic complexes were also obtained in all the reactions described above. The infrared spectra of all the compounds obtained, and the n.m.r.. spectra of N-benzylphthalimidine and N phenylphthalimidine are described.

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