Graduate Thesis Or Dissertation

 

I. Isolation of certain toxic components of kraft mill waste and attempts to determine their structure. ; II. Studies of the mechanism of the cope rearrangement of 1,2-divinyl-1, 2-cyclohexanediol Public Deposited

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  • Isolation of certain toxic components of kraft mill waste and attempts to determine their structure
  • Studies of the mechanism of the Cope reaarangement of 1,2-divinyl -1, 2-cyclohexanediol
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  • PART I. A chemical examination of the materials toxic to fish in kraft pulp mill wastes has been made as part of a water pollution study. Thirty gallons of "foul condensate" from a typical kraft mill gave 14 g of organic material when extracted with methylene chloride, and an additional 10 g was obtained when the residue was extracted with diethyl ether, Each extract was separated into approximately 20 fractions by column chromatography over silica gel. The fractions were tested for toxicity to guppies, and the most toxic fractions were then studied in some detail. Four compounds were identified with certainty: guaiacol (13.2% of the total organic material), cis-tenpin hydrate (1.4%), α-terpineol (1.1%), and 4-(p-tolyl)-1-pentanol (8.0%). Two other compounds were tentatively identified as ethyl guaiacol (2.9%) and trans-sylveterpin (0.2%). The remainder of the organic material contained two major components and an extensive series of minor constituents. Both major components were relatively low in toxicity but were nevertheless examined in some detail. A ketone, = 1720 cm⁻¹, constituted about 26.6% of the isolated material. It was converted to two derivatives, both oils. The suspicion that this ketone was not pure was confirmed by mass spectrometry since early scans on a sample passed to the ionizing chamber by a molecular leak differed significantly from later scans. All attempts to separate this mixture failed. The most interesting substance was a keto-alcohol that was present to the extent of 8.7%. While not highly toxic itself, this keto-alcohol could be reduced to a diol which appears to be the most toxic compound to fish we have studied. The diol seems to be present in the waste in only minor amounts, but could account for a considerable fraction of the total toxicity. The keto-alcohol does not produce a single solid derivative. It appears to be uniform, according to all tests we could apply. It is optically active and has three CHCH₃ groups present; the composition C₁₅H₂₈O₂ appears most probable. Apparently it is derived from a monocyclic sesquiterpene, but to date we have not been able to degrade it to a known substance. PART II. Thermal reaction of 1, 2-divinylcyclohexane-1,2-diol was found to produce 1(7)-bicyclo[5.3.0] decen-2-one in good yield. This is the aldol product derived from 1, 6-cyclodecanedione, the product expected from direct ketonization of the initial Cope rearrangement process. Since such 1, 3-hydrogen shifts are forbidden in the Woodward-Hoffmann theory it seemed of some importance to learn more about the mechanism of this reaction. Thus 1, 2-dideuteroxy-1, 2-divinylcyclohexane was vaporized into a nitrogen stream at low pressure and passed through a reactor at 350° C. The 1(7)-bicyclo[5.3.0] decen-2-one was trapped and purified and its deuterium content was determined by mass spectrometry. The unsaturated ketone was reduced by lithium in liquid ammonia and the saturated ketone was treated with methoxide ion in methanol. Analysis for deuterium content was again made by mass spectrometry. The unsaturated ketone contained 29 ± 6% D₀, 39 ± 2% D₁, 23 ± 3% D₂, and 7 ± 1% D₃ species. Each of these had the following percent of alpha deuterium: D₁ 3 ± 3%, D₂ 14 ± 1%, and D₃ 75 ± 12%. We assume that the aldol condensation involves a mono-enol monoketo form as the reactant. To account for the data obtained in this study it is necessary to postulate that a series of rapid enol-keto interconversions follow the initial Cope rearrangement. The series, is terminated either by the intramolecular aldol condensation or the dehydration to the unsaturated ketone.
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