A Thesis entitled "STUDIES IN ORGANIC GEOCHEMISTRY" submitted to the UNIVERSITY OF GLASGOW in part fulfilment of the requirements for admittance to the degree of DOCTOR OF PHILOSOPHY in the Faculty of Science by JAMES RANKIN MAXWELL, B.Sc. Chemistry Department April, 1967 ProQuest Number: 11011805 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 11011805 Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 To t:vv rorontn , v/if^ and dna^ktor, I wish to express my gratitude to Drs. G.Eglinton and J.D, Loudon for their close interest and guidance throughout the work of this thesis. My appreciation is also due to Dr. A.G, Douglas, whose assistance at all times proved to he invaluable. I would also like to thank Miss F. Greene and Miss T.Devit for technical assistance, my colleagues of the Organic Geochemistry Unit and Dr. A, McCormick for their advice and help, Mr, J.M.L. Cameron and his staff for the micro-analyses, Mrs. F. Lawrie and Miss A. Roberts for the infra-red spectra, Mr. J. Gall for the nuclear magnetic resonance spectra, Drs. McCormick and J. Martin and their staffs for the mass spectra and Mrs. M Benzie for her typing. The work was supported by a maintenance grant from the Science Research Council. _A_ 3_ S T R A C T_. Organic geocherr.istry is the study of organic matter in geological situations, including contemn ora.ry environments. One facet of the subject is the isolation and identification of * organic compounds from fossils and sediments. Correlations are then sought between such compounds and the biological compounds present in contemporary organisms, bearing in nind the chemical changes which could have taken place. in this thesis an attempt has been made to relate chemically a living alga, Botryococcus braunii , a derived rubbery deposit called Cocrengite and Torbanite which is a sediment 500 million years in age. The thesis can be divided into six pnrts, five of which are concerned with organic geochemistry. The Introduction reviews the more significant contributions to organic geochemistry and describes the types of compounds found in sediments, with special reference to alkanes. Some of the various facets of the subject and the possible derivations of geological isoprenoid alkanes ere also discussed. Section I is concerned with the alkanes present in two samples of a young sediment (ca. 30 x 10^ yrs. ) from IT.'A. Bohemia, Czechoslovakia. The distributions of the normal alkanes are reminiscent of those of the normal alkanes of the surface waxes of most contemporary plants. Furthermore the predominance of triterpene hydrocarbons in the branchea-cyclic a Inarm fraction is \n i accordance with the fact that the plant species identified in the sediment are mainly angiosperms. The diterpeue hydrocarbon fichtelite was identified in one of the samples. Section II deals with the alkr.nos of a number of samples g from the Scottish Carboniferous Formation (ca, 30C x 10 yrs.). The normal alka.nes of these samples have smooth distributions in contrast to those found for the young sediment examined (Section i). A number of acyclic isoprenoid hydrocarbons were identified, indicating that the samples hove a biological origin. Triterpene hydrocarbons were isol.ated from one of the samples, viz. the ’festvood Shale and their occurrence reflects the difference in source material between this and a closely related sediment called Torbanite. The hestvood Shale is the oldest geological sample from which triterpanes have been isolated in a pure state. Section III describes the hydrocarbons of a rubbery deposit called Coorongite (ca, 40 yrs.) which is the presumed precursor of Torbanite. The unusual hydrocarbon distributions found in Coorongite are thought by the author to be the result of bacterial activity. Three acyclic isoprenoid hydrocarbons were identified in the sample examined. Section IV deals with the hydrocarbons of a living alga, Botryococcus braunii, which gives rise to Coorongite, No saturated hydrocarbons were detected in the alga and the hydrocarbon fraction was found to consist almost entirely of two n o v e l hydrocarbons. Approaches to the structural elucidation of these hydrocarbons are described. The Appendix is concerned with the interactions which can take place between a nitro-group and a side chain in ortho­ substituted nitrobenzenes, The types of interaction which have been observed are reviewed and two new examples are descri ed. A mass spectral moth.od for the identification of the N-oxide function in aromatic N-oxides is discussed. CONTENTS Page INTRODUCTIONS Organic Geochemistry • • • 1 . Formulae ........ 000 19 GENERAL EXPERIMENTAL » • • • • • » I • • • 23 EXPERIMENTAL: Figures • • • • • • • • • ♦ • 31 SECTION I: The Hydrocarbons of a Lower Miocene Lignite. Introduction...... ....................... 33 Discussion............................... 37 Experimental ...................... 45 Figures and Formulae ............. 48 SECTION lit The Hydrocarbons of Certain Samples from the Scottish Carboniferous Formation, Introduction ... ... 56 Discussion ... ... 6o Experimental ... ... 72 Figures ... ... 82 SECTION III: The Hydrocarbons of Coorongite Introduction ... ... • • • 102 Discussion ......... 0 0 0 104 Experimental ... ... 110 Figures ......... 114 SECTION IV; The Botryococcenes - Hydrocarbons of Novel Structure from the Alga Botryococcus Braunii, Kutzing. Introduction ... ... ......... 118 Discussion . •. ... ... ... 123 Experimental ... ... ... ... 144 Figures and Formulae ............... 158 CONCLUDING REMARKS 173 REFERENCES 177 APPENDIX: Substituent Interactions in Ortho-Substituted Nitrobenzenes. Introduction ... ... ... ... 187 Discussion ... ... ... ... 1^2 Experiment al ... ... ... ... 202 Figures and Formulae ... ... ... 210 References ... ... ... ... 216 INTRODUCTION Organic Geochemistry„ Organic geochemistry may he broadly defined as the study of the organic matter occurring in geological situations. The greatest activity in this field has been directed towards the isolation and identification of organic compounds from sediments, fossils and crude oils with a view to elucidating the geological and biochemical implications of the occurrence of these compounds. The most-studied classes of compounds have been the amino acids, fatty acids, alkanes, alkenes, aromatic hydrocarbons, porphyrins and carbohydrates. In recent years organic geochemistry has been investigated as a possible tool for the detection of remnants of former life- processes, both on Earth and certain other planets of the solar system and their satellites, notably the Moon. At present this involves the isolation and identification of biologically-derived compounds from ancient sediments for which no adequate fossil record exists. Such experiments, when applied to samples from other planets, could only detect life-processes if the life were based on the carbon atom and a terrestrial biochemistry. This might not necessarily be the case. The two main prerequisites for these investigations are that these compounds must be stable over geological time and cannot be synthesised in significant concentrations by simple abiogenic means such as the treatment of mixtures of methane, water vapour and ammonia (the presumed primitive atmosphere of the Earth ) with ionising radiation or an electric discharge. The latter restriction excludes, for example, the biologically-important amino acids, certain of which may 3 4 5 6 he synthesised by the action of an electric discharge or ionising 7 radiation on mixtures of the gases presumed to be the major constituents Q of the Earth’s prebiotic atmosphere. In fact,Harada and Pox have synthesised all the amino acids common to protein, except cystine (l) and methionine (2), simply by heating a mixture of methane, water vapour and ammonia to 1000°C in the presence of silica. In other experiments simulating prebiological conditions a wide array of biologically- 7 significant molecules have been prepared, notably sugars , nucleic-acid bases (adenine (3)^’^ and guanine (4 )^), adenosine (5)^\ mono- 12 nucleotides , adenosine diphosphate (ADP)(6) and adenosine triphosphate (ATP)(7)^, a l k a n e s ^ , and carboxylic acids^. However certain alkanes and fatty acids are still valid as evidence of life-processes in the past since they exhibit great specificity of structure and have not been synthesised in primitive atmosphere experiments. Thus the acyclic isoprenoid hydrocarbons, steroid and triterpene hydrocarbons (see below), and the isoprenoid fatty acids are suitable as "biological markers". Isoprenoid fatty acids have been isolated from the Green River Shale of Wyoming and 6 17 18 1Q Colorado (Eocene, 60 x 10 yrs.) ’ , and from a California petroleum , Porphyrins are also valid as "biological markers" because of their stability and specificity of structure and have been isolated from a large number of sediments and crude oils, the oldest source at present being the Nonesuch Shale of Michigan2^ (Precambrian, 1 x 10^ yrs,). The p.orphyrins are thought to