Springall, Harold Douglas (1972) Publications submitted for the degree of D.Sc. Doctoral thesis, Keele University.

Full text not available from this repository.

Abstract

The publications are given in chronological order in the accompanying list but are presented in groups of related topics in the collection of reprints submitted. These topics are (i) Molecular Structure (a) Dipole Moments
(b) Electron Diffraction (c) Thermochemistry (in chronological order of the development of my practical interest in the individual techniques).
(ii) Natural Product Organic Chemistry
and (iii) Miscellaneous.
The great majority of the publications have joint authorship, as is usual in chemical publications. I have tried to assess the extent of my con­tribution to each but it is virtually impossible to do this accurately in short form.

(i) Molecular Structure (a) Dipole Moments
Items 1, 2, 12, 13, 31, 32, 33.
Item 1. The account of the "Mills-Nixon Effect" work with dibromo­-hydrindenes and -tetralins suggested by Prof. Sidgwick. Submitted for Oxford B.A. (Part II) and D.Phil.

Item 2. Report of reading of paper on item l before Chem. Soc. Not included in the collection for this submission.

Item 12. The account of the extension of the Mills-Nixon work to dioxa-indanes and dioxatetralins. The work was mine in idea and execution. Sir Robert had had experience of some dioxaindanes ("methylene dioxy" compounds) in his alkaloid work.

Item 13. Preliminary report on work fully reported in item 31. Not included the collection for this submission.

Item 31. The account of the work on the molecular structure of tetrahalides and the tetranitrate of pentaerythritol.

Item 32. The account of the work on the mechanism of the activation of the methyl group in some nitrotoluenes.

Item 33. An extension of the work described in item 31 dealing with ethers of pentaerythritol.

With items 31, 32, 33 the ideas and writing up were mine. Much of the experimental work was also mine.

(i) Molecular Structure (b) Electron Diffraction
Items 3, 4, 6, 7.
Item 3 records the determination of the structures of trimethyl; phosphine and -arsine. This was suggested by Professor L.O. Brockway and by Professor Pauling to extend the work they had already done on trimethylamine. The preparation of the materials, the electron diffraction and the writing up were all mine. (I believe that this is still the only experimental determination of the distribution of the 3 valencies about trivalent -P and -As).

Item 4 records the investigation of interatomic distances in the molecules of methylacetylene, dimethylacetylene, diacetylene, dimethyl-diacetylene and some related cyanogen derivatives. This work, which was suggested by Prof. Pauling, arose from the reporting, from spectroscopic studies, by Herzberg of the unexpectedly short C-C single bond in methylacetylene. It was important that this bond length should be studied by electron diffraction lest there be any discrepancy between the diffraction and spectroscopic methods. The short bond was confirmed, and the finding was of interest in the early days of hyperconjugation theory. (The diacetylene work proved of interest to Sir Ewart Jones' collaborators in the early days in Manchester of his work on poly-ynes). I made the compounds and Dr. Palmer and I did the diffraction work. I began the writing up. Prof. Pauling completed it.

Item 6 records the electron diffraction studies on 4,5-dibromo-o-xylene, dibromohydrindene and dibromotetralin. The identity of the Br - Br distances in all three compounds proved the absence of Mills-Nixon fixation in the hydrindene. The idea for this work was mine. I had
made the compounds (in Oxford) I did some of the diffraction work. Dr. Kossiakoff finished it and wrote up the paper.

Item 7. This is the report of the reading of a paper describing the work carried out in Item 6, before a Chemical Society meeting in Bristol. (Item 6 was not generally available in England at that time). Item 7 is
not included in the collection for this submission.

{i) molecular Structure (c) Thermochemistrv
Items 8, 9, 10, 11, 14, 15, 20, 21, 24, 25, 34, 35, 36, 38, 40, 42, 43, 45, 49.

Item 8 records indirect evidence in favour of the, then unestablished, high value, 171 kcal gram-atom-1, for the latent heat of sublimation of graphite, the heat of atomisation of carbon, the fundamental thermochemical quantity for the evaluation of the molecular energetics of organic compounds. The evidence came from thermochemical data on mercury-dialkyls and -diphenyl. A joint effort by Prof. Sidgwick and me.

Item 9. Tha report on the section I gave to a symposium in Manchester on the heats of atomisation of carbon and nitrogen. Not included in the collection for this submission.

Item 10. An analysis on the thermochemical and spectroscopic data on cyanogen giving evidence for the higher values for the heats of atomisation of carbon and of nitrogen. (No collaborators),

Item 11. A critical discussion on the concept of bond energy calling for clear distinction in usage between "mean bond energy term, E" and "bond dissociation energy, D". (A joint effort with Dr. Skinner).

Item 14 reports the heat of combustion of ethyl iodide and the evaluation of E(C-I) and of D(C2H5-I). The idea was mine: the combustion work, Dr. White's. The interpretation of data and the writing up, mine.

Item 15. A critical review of the methods of evaluation of the heat of atomisation of carbon. (no collaborators).

Items 20, 25, 40, 49 record thermochemical (combustion) studies on unusual molecular systems formally containing alternate double and single C to C bonds; either having the molecular formula.(CH)x or derived therefrom. The studies Were aimed at detecting the presence or absence of aromatic "resonance energy". They could be linked with the Mills-Hixon work and with Prof. George B. Kistiakowsky's studies on heats of hydrogenation. With compounds of the series x = 4n + 2, Huckel' s rule, asserting that such compounds should he aromatic, was
confirmed. (My interest in cyclooctatetraene began in 1938 when Professor R. B. Woodward, then at N, I. T. , pointed out to me the similarity of the physical properties of Willstatter's compound with
those of the isomeric styrene and suggested that Willstatter's compound was, in fact, styrene. I mentioned this to Sir Robert when I returned to Oxford: he said "Nonsense, Willstatter was much too good an organic chemist to make such a mistake". So there was considerable interest when some of the first specimen of Reppe's material to reach England was made available to me, in Manchester, towards the end of the War.)

The ideas behind this (CH)x work on the writing up were mine; preparation of the substances was not mine though in the earlier work which of the calorimetry was mine.

Items 21, 24, 35, 36, 38, 43. A series of papers on the energetics of carbon to oxygen bonds. Item 36 has connections with the Mills-Nixon work. Item 38 has connections with the pentaerythritol work. The ideas for this work were mine. Most of the experimental calorimetry
was my collaborators'. The writing up was mine.

Item 34 records the molecular structural analysis of thermochemical data on nitramines, nitrate esters and C-nitro compounds. This work is partly the war-time M.O.S. work, extended and somewhat refined. Tile ideas, the compounds, and the writing-up are mine. The experimental
calorimetry is due to my collaborators. The final phase of the work, which enabled the explosive power of any compound of the above classes to be calculated from the molecular formula, was not included in item 34 but is briefly recorded in item 50, page 404.

Item 45 is a critical review of modern thermochemical techniques and results. A joint effort by Dr. Mortimer and me.

(ii) Natural Product Organic Chemistry
Items 5, 22, 26, 27, 29, 30, 37, 39, 41.

Item 5. Though my work in Sir Robert's steroid synthesis prograrmne did not lend itself to publication, Sir Robert invited me to prepare the section on "Synthesis of Steroids" for the Ann Reps for 1939. (No
collaborators).

Item 22. A review of methods for the analysis of a-amino-acid fixtures, the material accumulated in the course of setting up such analysis in Keele. (No collaborators).

Item 26. A report on the proceedings at a symposium on Peptide Chemistry, part of the Anniversary Meeting of the Chemical Society in London. (No collaborators. I chaired one of the sessions).

Item 27. A Quarterly Review article on peptide synthesis and degradation (preparation shared with Dr. Law),

Item 29. A report on the proceedings at an international Conference on Chromosomes held in Wageningen in Holland at which I was an invited speaker.

Item 30. Chapter on chemistry of proteins and nucleic acids from the full report (book) of the Conference treated in item 29.

Item 37. Preliminary report on the establishment of the structure of peptide, Evolidine: fully reported in item 39. Not included in the collection for this submission.

Item 39. Full report on the structure of Evolidine. I obtained the material (from Professor Birch), suggested the problem, wrote up the work and helped in the supervision. The main day-to-day supervision was due to Prof. Millar: most of the experimental work was done by Dr. Law.

Item 41. Chapter on Protein Structure in "Rodd-Robinson".

Item 42 reports studies on ethoxyacetylene as a coupling reagent in peptide synthesis (Dr. Cohen is the main local authority on the use of ethoxyacetylene.) I suggested the immediate use in peptide work, Dr. Cohen did most of the experimental work.

(iii) Miscellaneous
Items 16, 17, 18, 19, 28, 44, 46, 47, 48, 51.

Items 16 and 17. Two papers on the elucidation of the structure of "Knudsen's Base", an innocuous self-contained fragment of the war time work on the mechanism of the nitration of hexamine. These are both 6-author papers. Dr. Thomas and Prof. Urbanski were working independently of the Manchester group of 4, mainly on different problems but some of their data proved very helpful. Sir Edmund Hirst was directing the Manchester work. Dr. Foss did most of the experimental preparation work. Prof. Jones and I did the rest. As I recall, the idea of the correct structure occurred in discussion between Prof. Jones and me, and was confirmed in discussion with 5ir Edmund. I wrote up the papers.

Items 18 and 19. Two chapters in the first (1961) edition of the Rodd-Robinson Chemistry of Carbon Compounds. These have been superseded by the corresponding chapters in the second (1964) edition (item 46, 47) and are not included in the collection for this submission.

Item 28. An invited article for the R.I.C. series "Schools of chemistry in Great Britain and Ireland". (No collaborators).

Item 44. An account of a novel rearrangement which was found in the course of Dr. Cohen's ethoxyacetylene studies. Dr. Cohen directed the work. Dr. Banks did most of the experimental work. I advised on thermodynamic aspects and on the writing up.

Items 46 and 47. Chapters on (a) Physical properties of carbon compounds and (b) Modern views on acids and bases, in Rodd's Chemistry of Carbon Compounds, second (1964) edition.

Item 48. An account of a piece of work which arose as follows. As external examiner to the College of Technology in Belfast, I was asked for advice on the research programme of a member of the College Staff, Mr. C. Wilson. His supervisor had left Belfast. He had done a great deal of preparative work but was being greatly handicapped by the slow operation of the only U.V. spectrometer available to him (an obsolescent non-recording model). It occurred to me that Mr. Wilson's problem (electronic shifts in sterically hindered aromatic systems (durenes)) was in a field of interest to Dr. Cohen and to me, that with Dr. Cohen to supervise and instruct in the operation and interpretation of automatic recording U.V. and N.M.R. spectrometers and with Prof. Millar to look after organic problems, we could, in a few weeks of the long vacation, in Keele, given Mr. Wilson's residence and co-operation, provide him with at least a workable basis for his thesis. Mr. Wilson's, Dr. Cohen's and Prof. Millar's co-operation was immediate, and the job was done.

Item 51. This is the official account of "the state of the Nation" as far as the Keele Chemistry Department was concerned for "the Opening'', in 1968, by Lord Todd (an old friend whom I had first met in Sir Robert's lab in 1934).

I have also included the account in Nature of the Opening. This is not a "publication" but Prof. Millar and I gave the information and Mr. Vickers, of the Keele Librarv staff, provided the photograph.

Concerning the books:
Item 23. This was without collaborators.
Item 50. Prof. Millar and I shared this equally.
Item 52. Prof. Millar and I shared this equally.

(I, perhaps, did more in the actual textual revision for item 52. We both, equally, suffered from the mediaeval eccentricities of the Press, over publicity. This confirmed us in our judgment that our forthcoming
commissioned work is rightly being handled by the Cambridge University Press).

Tailpiece
Professor Lawlor, in the Keele Senate in 1950, reacting more quickly than the rest of us to our first Registrar's strange pronunciation of "Emeritus", said, "They told me, Emma Rightus, you were dead".

Item Type: Thesis (Doctoral)
Additional Information: For access to the hard copy thesis, check the University Library catalogue.
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural Sciences > School of Chemical and Physical Sciences
Depositing User: Lisa Bailey
Date Deposited: 27 Feb 2019 09:20
Last Modified: 02 May 2019 11:19
URI: http://eprints.keele.ac.uk/id/eprint/5922

Actions (login required)

View Item View Item