Master of Science (MS)
Semester of Degree Completion
David H. Buchanan
o-Anisic acid and o-ethoxybenzoic acid were reacted with pyridine hydriodide in pyridine at 115° for 3 days to yield 81% and 18% salicylic acid respectively. o-Anisic acid with KI in pyridine at 115° for 3 days gave 58% salicylic acid while o-anisic acid with LiI·3H2O in pyridine at 85° for 3 days gave 54% salicylic acid. p-Anisic acid and o-phenoxybenzoic acid did not undergo cleavage reactions with pyridine hydriodide under similar conditions.
Beta-methylnaphthyl beta-naphthyl ether(I) or alpha-methylnaphthyl alpha-naphthyl ether(II) with pyridine hydriodide in pyridine at 100-115° for 3 days showed no cleavage. Ether I with pyridine hydriodide in the presence of pyridine insoluble Illinois No.6 coal fraction at 115° for 7 days or with added iron salts, such as FeCl2, FeS and FeS2 also showed no cleavage. Recovered ether averaged 98 ± 3%.
Since pyridine hydriodide or lithium iodide in pyridine increases the free phenolic content and reduces the apparent molecular weight of pre-asphaltene fraction of Illinois No.6 coal, presumably by ether cleavage, the coal structures reacting are not well-modeled by ethers I and II. It is proposed that oxygen atoms of the reacting ether linkages in the coal fraction are hydrogen bonded by phenol groups either on the same or adjacent aromatic cluster which activates them toward SN2 cleavage by iodide ion under mild conditions.
Sy, James Nicolas Ong, "Synthesis and Reactions of Aromatic Ethers as Model Compounds for Coal" (1983). Masters Theses. 2855.