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Proceedings of the Chemical Society. June 1957 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue June,
1957,
Page 157-184
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PROCEEDINGS OF THE CHEMICAL SOCIETY JUNE 1957 TILDEN LECTURE* The Role of the r-Electron in Aromatic Chemistry By H. C. LONGUET-HIGGINS (CAMBRIDGE UNIVERSITY) EVERsince the discovery of benzene the character- istic properties of aromatic compounds have held a particular fascination for the organic chemist. It is not that there is anything very strange about the properties of benzene itself it is a stable colourless liquid it boils at a moderate temperature undergoes well-defined chemical reactions and so forth. The primary interest of aromatic compounds apart from their great technical importance lies in the problem which they present to the structural theorist. Struc- tural organic chemistry may be said to have come of age with the conception of the tetrahedral carbon atom.Before that organic compounds could be classified only in terms of their composition and characteristic reactions; the advent of the structural theory showed that organic molecules could properly be represented for many purposes by mechanical models of the ball and spring variety and that there was a close correspondence between the structure of the model and that of the molecule. The rules for constructing molecular models were well known long before the discovery of the electron; carbon must be assigned four valencies steric hindrance must be allowed for and so on and a molecular model satis- fying these conditions was usually found to represent quite literally the structure of a real organic molecule.* Delivered before The Chemical Society in London on Belfast on February loth 1955. Kossel Ann. Physik 1916 49 229. Lewis J. Amer. Chem. Soc. 1916 38 762. Langmuir ibid. 1919 41 868. Aromatic molecules however seemed to evade description in such terms and the revolutionary nature of KekulC’s description of benzene consisted in his recognition that the second half of a double bond unlike a single bond is a nomadic entity which cannot always be assigned a unique position in a molecule. The physical meaning of KekulC’s suggestion could not of course be understood until the advent of the electronic theory of valency. This theory dates from the monumental work of Kosse1,l Lewis,2 and Langmuir? who first introduced the idea of the electron-pair bond and the famous octet rule.These ideas immediately shed a flood of light on structural chemistry and revealed the fundamental distinction towards which KekulC had been groping namely the distinction between localized and non-localized electrons. The progress of chemical theory since the birth of wave mechanics has been so striking that it is easy to forget the great advances in chemical theory which preceded it. Indeed it might be said that the work of Lapworth Robin~on,~ and IngoId6 anticipated in conception many of the generalisations which were later seen to follow from the quantum theory. The January 20th 1955 in Dublin on February 9th 1955 and in * Lapworth and Manske J. 1928 2533; 1930 1976. Robinson et al.J. 1926 376 383 392 401 411. C. K. Ingold and E. H. Ingold J. 1926 1310. 157 curved arrows of Robinson’s notation expressed con- cisely and elegantly the stages by which one elec- tronic configurationmay be transformed into an other during a reaction and it was recognised that mole- cules such as benzene for which alternative elec- tronic structures can be formulated often though not always exhibit unusual stability. As everybody knows the early 1930’s witnessed a diligent re-examination of the valency theory on the basis of wave mechanics. The ideas of the new mechanics seemed at first so strange that it was not immediately clear how they could be translated into chemical terms. But in the hands of Pauling and others the old wine was successfully transferred to the new bottles and relabelled appropriately.The rules of covalency were shown to follow naturally from the Pauli exclusion principle; mesomeric stabilisation was attributed to quantum-mechanical resonance and for a while the measurement of resonance energies not always very clearly defined became fashionable. The Robinson-Ingold theory founded as it was on the maximum of experimental fact and the minimum of hypothesis emerged from the revolution intact and more soundly related than ever to physical principles. The new theory of resonance was not however the only heir to the future. Less conspicuous at the time but now more widely recognised was the molecular-orbital theory’ due to Hund Mulliken Hiickel and Lennard-Jones.It was understandable that this theory did not have such an immediate appeal as the resonance theory since the latter used the language of “structures” whereas the idea of a molecular orbital has no obvious counterpart in classical chemistry. However as I hope to show later there are important questions in aromatic chemistry to which the molecular-orbital theory gives a simple and clear-cut answer whereas the answers provided by the resonance theory may be ambiguous or positively misleading. Before describing the molecular-orbital theory and its application to chemical problems I should emphasise two points. First that this theory like the classical electronic theory and the theory of reson- ance is concerned entirely with the electrons in a molecule their distribution and their energy and questions relating to steric hindrance and entropies of reaction or activation lie outside its scope.The second point concerns a widespread misconception that the molecular-orbital theory is very difficult mathematically and in practice useless to the organic chemist unless he has a calculating machine and a tame mathematician to hand. Detailed quanti- tative calculations do of course require as much Huckel 2.Elektrochem. 1937,43 752 857. PROCEEDINGS time as careful experiments but it is the ideas of a theory which determine its fruitfulness and the ideas of the molecular-orbital theory are simple enough to be used as a reliable qualitative guide in many situations.First then let us see how the method of molecular orbitals applies to an isolated aromatic molecule such as benzene. We imagine that between every pair of adjacent atoms there is a localised two-electron bond called a a-bond but that the remaining six valency electrons are not localised in particular bonds but occupy orbits which extend over all six carbon atoms. These orbits or molecular orbitals are anti- symmetrical with respect to the molecular plane and electrons moving in such orbits are commonly called n-electrons. It is customary to represent each molecular orbital by an expression of the type # = -k %$2 + ‘ * * c6$6 where * * $6 are atomic orbitals on the six ring atoms (see Fig. l) and c1,c2 * -c6 is a set *of coefficients which has to be determined for each molecular orbital.The square of one of these coefficients gives the probability that an electron in the molecular orbital # will be found near the cor- responding atom. The coefficients themselves may be positive or negative but their squares must add up to unity. FIG. 1. The atomic orbitals used to form the molecular orbitals of the n-electrons in benzene. From a set of n atomic orbitals * * #n it is always possible to construct n different molecular orbitals. Whether a particular molecular orbital is occupied or not in the ground state will depend on its energy and the total number of n-electrons. If there are 2m rr-electrons these will occupy in pairs the rn molecular orbitals of lowest energy and the energy of the whole system is then taken to be twice the sum of the occupied orbital energies.To find the energy of a molecular orbital and the associated coefficients c1 * -c one has to solve a JUNE 1957 set of simultaneous equations which for benzene are xc1 = c6 + c2 xc4 = c3 + c5 xc2 = c1 + c3 xc5 = c4 + c6 xc3 = c2 + c4 xc6 = cs + c1 where x is the binding energy of the orbital in units of a quantity /3 called the C=C resonance integral. These six equations have six solutions the corres- ponding values of x being x = 2; x = 1 (twice); x = -1 (twice); x = -2 (There is a different set of coefficients for each of these energy values.) In benzene then two n-electrons go into the orbital of energy two units and two into each of the orbitals of energy one unit.The expectation number of n-electrons on atom Y is obtained by adding up the values of 2cr2 for the occupied orbitals; the answer in this case is 1 for each atom which seems rather dull and hardly surprising. But the electron density does not always turn out to be 1 on each atom. If odd-membered rings are present as in fulvene and azulene the cal- culated n-electron distribution is no longer uniform and the molecule should therefore have a dipole position product and Doering’s recent work on this material leaves no doubt that it is a salt containing the cyclic ion C,H,+-the only known carbonium ion which is stable in water! Before leaving the cyclic polyenes I must say a word about cyclubutadiene.Like benzene this mole- cule has two resonance structures and is not very severely strained so should it not be stable? The molecular-orbital theory suggests that the answer is “No”. To begin with the total binding energy of the n-electrons would be 4 units as in two ethylenic double bonds so that there should be no resonance energy. But equally important there are only two electrons in the two degenerate molecular orbitals and in a situation of this sort the electrons go one into each orbital with unpaired spins giving an open-shell structure. It is not to be wondered at then that cyclobutadiene has never been prepared. moment as indeed these molecules d . The pattern of molecular-orbital energies in benzene turns out to be typical of cyclic systems generally.One can show that the energies are given by the formula:’ x=2 x = 2 cos (2nln) (twice) x = 2 cos (477ln) (twice) where n is the number of atoms in the ring and this formula can be represented geometrically in rather an intriguing manner (see Fig. 2). An obvious im- mediate conclusion is that closed electron shells will occur at n = 2 and 6 and would occur also at 10 14 etc. if planar rings of this size were sterically pos- sible. In this way one can understand the peculiar stability of the “aromatic sextet,” whose special nature was recognised but not interpreted by the classical theory. More particularly one can see why the anion C5H,-is stable whereas the cation C,H5+ apparently is not though no clue is provided here by the number of resonance structures which is the same for both ions.Again one would expect the ion C7H7+,which has a closed-shell electronic structure to be a relatively stable entity; and indeed it is. Merling’O discovered in 1891 that distillation of cycloheptatriene dibromide gave a crystalline decom- ~ ~~~ FIG. 2. The molecular-orbital energies of the cyclic polyenes. We see then that even in molecules as simple as the cyclic polyenes the molecular-orbital theory and the descriptive resonance theory can find themselves in disagreement. It should however be said that the two theories can be shown11 to coincide in their qualitative predictions when applied to closed-shell benzenoid hydrocarbons such as naphthalene or pyrene.In such systems the molecular-orbital theory predicts a uniform 7r-electron distribution and the bond lengths as calculated by the two theories are closely correlated. Let us now turn for a while to aromatic radicals and their ions; this will pave the way for a discussion Wheland and Mann J. Chem. Phys. 1949,17,264. B. Pullman and A. Pullman “Les Theories Electroniques de la Chimie Organique,” Masson Paris 1952 Chapter 7. lo Merling Ber. 1891 24 3108. l1 Dewar and Longuet-Higgins Proc. Roy. SOC.,1952 A 214 482. of reactions in which such species are involved as intermediates. For reasons of a mathematical nature the molecular-orbital theory is at its best when dealing with so-called “alternant hydrocarbons,” that is hydrocarbons in which no odd-membered rings are present.(This is not to say that the theory cannot be applied to molecules such as azulene-indeed the properties of azulene can be very well interpreted by the theory-it is merely that the molecular-orbital theory is easier to apply to alternant systems where it yields more illuminating general results.) Let us then consider an alternant hydrocarbon radical such as the benzyl radical in which just one atom is formally tervalent. It is quite easy to see that if there are 2n -1 conjugated atoms one can divide them into a set of n “starred” atoms and n -1 unstarred atoms in such a way that every bond joins a starred atom to an unstarred one. This labelling is further- more unique.Its importance lies in the fact that the FIG. 3. The benzyl radical. (a) The starred atoms. (b) The non-bonding orbital (7k2= 1). (c) The distribution of the odd electron in the radical and of the charge in the cation or anion. orbital which contains the unpaired electron is always confined to the starred atoms only-that is to say if Y is an unstarred atom then c = 0 for this orbital.12 Further the orbital in question is invariably non-bonding in the sense that x = 0. Now the coefficients and the energy of a molecular orbital are related to one another the relationship being x times the coefficient for atom requals the sum of the coefficients at the atoms joined to r. But for the orbital containing the odd electron x = 0 so the sum of the coefficients at the neighbours of any atoms must vanish.Applying this generalisation to the benzyl radical we see that in the non-bonding orbital the coefficients must be as shown in Fig. 36 where k is an undetermined constant. In order to determine k we recall that the squares of the various coefficients determine the probability distribution of the odd electron and must add up to unity; hence k2 = 1/7 and the electron spends 4/7 of its times on the CH group and 1/7 of its time at each of the ortho-and para-positions. This seems a reasonable result and has obvious chemical implications. But it also tells us something about the corresponding ions. As I remarked earlier the distribution of v-electrons in PROCEEDINGS an alternant hydrocarbon such as benzene is uni-form and this is also true of an alternant radical.Hence if we ionize the odd electron to obtain the benzyl cation the distribution of the positive “hole” will be the same as that of the odd electron to a first approximation. Further if we add an extra electron to the radical this will pair with the odd electron already there and the resulting negative charge will be distributed in the same way over the starred atoms. It is true that these hydrocarbon ions are not species with which we often have to deal in the laboratory; but they are closely related to familiar substances. To illustrate this let us take the benzyl anion and replace one of the conjngated carbon atoms by a nitrogen atom which attracts electrons more strongly.We would then expect the resulting mole- cule to be more stable the greater the negative charge at the atom which has been replaced. In accordance with this idea the aniline molecule is perfectly stable whereas the species (IV) and (V) are not. However some stabilisation should accompany the replace- ment of the ortho-and para-carbon atoms by nitrogen; and if we examine the resulting species (I1 and 111) we see that they are none other than the prototropic isomers of a-and y-picoline which are known to possess reactive methyl groups.13 We can therefore see why the methyl groups in these species are more readily ionized than that in p-picoline. The charge distributions in the benzyl anion and cation may also be used to throw light on orientation in the benzene ring.The benzyl anion is the proto- type of a -E substituted benzene such as aniline or phenol. Such substances should therefore direct electrophilic reagents into the ortho-and para- positions the reaction proceeding more readily than in benzene. On the other hand +E substituents of which the benzyl cation provides a model merely deactivate the ortho-and para-positions so we ob- serve an unaccelerated reaction in the meta-positions. This “static” theory of the electromeric effect is of course over-simple and we shall describe a more realistic theory later. However electron densities calculated in this rough-and-ready way can often be used as a guide to the grosser features of chemical reactivity.Longuet-Higgins,J. Chem. Phys. 1950 18 265 275 283. l3 Taylor and Baker in Sidgwick‘s “The Organic Chemistry of Nitrogen,” Oxford 1937 Chapter 18. JUNE 1957 Before leaving the charge diagram of the benzyl anion it seems a pity not to mention one other application of a physicochemical nature. This con- cerns the basic strengths of the aminopyridines and other heteroaromatic amines. Spectroscopic evi-dence14 shows conclusively that in their cations the extra proton is attached to the nuclear nitrogen atom the conjugated system being preserved. Onc might expect therefore that the basic strength of the amine would be correlated with the excess charge on the appropriate position in the parent hydrocarbon anion. 2-and 4-Aminopyridine should therefore be stronger bases than 3-aminopyridine.The actual pK values are:15 2-amino- 6.86; 3-amino- 5.98; 4-amino-pyridine 9.17 ; pyridine 5-23 (all in water at 20"). If we discard the first figure as influenced by the ortho-effect the remaining two provide a rather slender confirmation of our ideas. But one can make similar elementary calculations12 on much more complicated amines,15 and then it becomes clear that there is a significant correlation between pK and the excess charge in the carbanion (see Fig. 4). Further the points which lie far from the line are all ortho- amines so there seems to be some real justification for postulating an ortho-effect. 00 //// (0rthoo) 0 0.1 0.2 0.3 Charge ot position of proton addition-(CU/Cu/atQd for &oe/ectronic carbon /on) FIG.4. Basic strengths of some amino-acridines ' -phenanthridines and -benzacridines. I should now like to discuss one or two rather more complicated test problems to show how the molecular-orbital theory enables one to predict in a quite simple way the gross effects of substituents on energies of reaction. My first example is on familiar ground and concerns anionoid attack on the phenan- threne ring system. 9-Chlorophenanthrene under normal conditions is not susceptible to hydrolysis or solvolysis; this is presumably because the inter- mediate anion (see Fig. 5) has not a sufficiently low energy to be formed. However by introducing 14 Craig and Short J. 1945 419. Albert Goldacre and Phillips J.1948 2240. electron-attracting groups into the skeleton it is possible to make the reaction proceed. The question is in what position will such a group be most effec- tive? Now the ' intermediate anion has fourteen n-electrons associated with thirteen atoms. As the number of atoms is odd there will be a non-bonding molecular orbital and the extra electron will be in this orbital. Also we know that the non-bondir;g orbital is confined to the seven starred atoms in Fig. 5. By using the rule given earlier it is then a simple process to write down the relative values of the coefficients and these are given in the diagram. The value of k is determined by the condition that the squares of the coefficients must total unity; and in this way one obtains the distribution of excess charge.The intermediate anion will therefore be stabilised most effectively by an electron-attracting group in the 10-position; and this result accounts for the lability of the chlorine atom in the quaternary salts of chlorophenanthridine. My second example relates to a less familiar ring system namely biphenylene. This example is worth attention because it is one about which the predic- tion of the molecular-orbital method and the resonance theory definitely disagree and the (a) S! FIG. 5. The hydrolysis of a chlorophenanthrene. (a) The starred atoms in the reaction complex. (b) The non-bonding molecular orbital (31P = 1). (c) The distribution of the negative charge in the complex.experimental facts are not known. 2-Amino-biphenylene has been prepared16 by Wilson Baker et-al. and is a typical aromatic amine. The correspond- ing phenol would be expected to undergo diazo- coupling in the aromatic nucleus but the question is where? If there is any significance in the static picture of aromatic orientation the position of coupling should be the position of highest negative charge in the isoelectronic carbanion. The non-bonding orbital coefficients in this anion are easily found and have the values shown in Fig. 66. The highest charge in the ring should therefore be at the 3-position and this is where 2-hydroxybiphenylene should couple. The resonance theory however suggests a different result. Biphenylene has 5 reson-ance structures and ifthese are assigned equal weight the 1 :2-and 2:3-bonds should have 3/5 and 2/5 double-bond character respectively.The molecule would then be represented best by the first structure l6 Baker Boarland and McOrnie J. 1954 1476. 162 PROCEEDINGS shown and on this basis the expected position of coupling is the 1-position as in naphthalene. It is to be hoped that the matter will soon be decided experimentally. The third example that I should like to discuss is the attack of a free radical on the naphthalene mole- cule. Here again as Dewar has shown one can use the properties of non-bonding orbitals to estimate the relative reactivities of the 1-and the 2-positions. Indeed Dewar’s method of estimating the reactivities of hydrocarbons1’ is one of the most useful results of FIG.6. Orientation in a biphenylene derivative. (a) The starred atoms. (6) The non-bonding orbital in the isoelectronic carbanion. (c) The distribution of the extra electron. (d) The five resonance structures. RH -I/JB FIG. 7. Attack of a free radical on naphthalene. (a)The radical complexes. (b)The non-bonding orbital coefficients. molecular-orbital theory. The idea behind it is this. When a free radical attacks say naphthalene the rate-determining step is in all probability the forma- tion of a loose complex in which the radical has become attached to one of the aromatic carbon atoms. The formation of this complex involves the withdrawal of one electron and one atom from the conjugated system giving an aromatic radical with 9 electrons moving over 9 atoms.A given position will be more reactive therefore the smaller the energy required to isolate a single electron at that position a suggestion which is not new in itself. But Dewar points out that one may estimate this “isola- tion energy” by considering the converse process namely the interaction between the isolated electron and the residual radical. To a first approximation this interaction energy is proportional to the ampli- tude of the odd electron at the two atom adjacent to the position of attack; and this amplitude is just the sum of the non-bonding orbital coefficients for these atoms in the residual radical. Fig. 7 shows the values of these coefficients in the two possible cases.For attack at the 1-position their sum is 3/411 and for attack at the 2-position the sum of the adjacent coeficients is 3/48. The 1-position should therefore be more easily isolated and more susceptible to attack as indeed it is. n % v) % -4 -2 0 2 2 /oglO(rote constont),as determined by Kooymon and Forenhorst FIG. 8. Aromatic substitution by CCl radicals. a Benzene. 6 Diphenyl. c Triphenylene (2- position). d Naphthalene. e Phenanthrene. f Chrysene. g Pyrene. h Stilbene. i 1:2-5 6-Dibenzanthracene. j 1 :2-Benzanthracene. k, Anthracene. f 3 :4-Benzopyrene. m Naphtha-cene. One might perhaps not feel inclined to place much reliance on these ideas if naphthalene were the only case that had been studied.But the work of Kooyman and his colleaguesls has provided information on the radical reactivities of a number of polycyclic aromatic hydrocarbons and the corresponding calculations are very easy to make. Fig. 8 compares Kooyman’s results with Dewar’s numbers. Not only is the most reactive position that with the highest “Dewar number ” in all cases except triphenylene (where the 1-position is hindered) but its absolute reactivity seems to be correlated with the value of this number. One example of particular interest is again biphenylene where the Dewar numbers indicate the 2-position as the most reactive; this prediction is at l7 Dewar J. Amer. Chem. Soc. 1952 74 3341 3345 3350 3353 3355 3357. 18 Kooyman and Farenhorst Trans.Faraday Soc.1953 49,58. JUNE 1957 163 variance with expectations based on analogy with naphthalene but has not yet been tested. A further application of this kind of calculation concerns the relative reactivities of different positions towards electrophilic reagents. In the nitration of naphthalene for example the intermediate complex differs from the corresponding radical complex only in the absence of the unpaired non-bonding electron. The binding energy of the 7-electrons is therefore the same in both complexes. But it is just this binding energy which determines the stability of the com- plex other things being equal. Hence the various positions should fall in the same order of reactivity towards NO2+ as towards free radicals this order being given by the Dewar numbers.The data given in Dewar's papers1' supports this generalisation. With these ideas in mind it is now possible to construct a rather more complete theory of orienta-tion in aromatic substitution. We saw earlier that the charge distributions in the benzyl anion and cation could be used to throw light on electromeric orienta- tion in benzene and as a preliminary picture this was reasonably acceptable. It is not altogether satisfac- tory however for two reasons. First one had to assume that electrophilic reagents tend to attack positions of low electron-density and nucleophilic reagents positions of high electron-density. In the 0 FIG. 9. Reaction complexes postulated in aromatic substitution.(a) Electrophilic. (b) Free-radical. (c) Nucleo-philic. early stages of reaction this assumption is un-doubtedly correct but as the formation of the transi- tion complex proceeds the electrons will become re- distributed with consequences that are difficult to forecast. And secondly electron-density values provide no immediate clue as to the orientation of free radicals by substituents. What one really ought to do is to inquire how the stability of the inter- mediate complex will be affected by substituents; and this we are now in a position to do. In Fig. 9 are shown the three types of complex generally postulated as intermediates in electrophilic radical and nucleophilic substitution severally. In each there is a chain of five conjugated atoms and such a system possesses a non-bonding orbital illus- trated in Fig.lO(a). In the radical complex S. this orbital contains the odd electron the total number of n-electrons at each position being unity. Hence in S+ which has no odd electron the positive charge will be shared equally between the positions shown in Fig. lo@); and in S-the negative charge will be distributed in the same way. We now ask the question how will the energy of S+ S. or S-be affected by the attachment of sub- stituents such as methyl amino or nitro? In answer- ing this question it is necessary to consider separately two different effects the inductive (I)and the electro- meric (E).A substituent is said to have an inductive effect if it modifies the electrical potential in the ring and hence alters the energy of the n-electrons.Sub- stituents such as NO and NH,+ which lower the energy of the ring electrons are said to have a +I effect whereas CH and NH which repel the ring electrons are said to have a -I effect. Generally speaking it is clear that a -I substituent will favour electrophilic and hinder nucleophilic attack and that the reverse will apply to +I substituents. If we go further and suppose that the field of a substituent is greatest at the position to which it is attached we are led to the conclusion that the effect of either type of substituent whether favourable or adverse will be greatest for ortho-or para-substitution since attack at these positions leads to the largest surplus or deficit of charge in the neighbourhood of the substituent.These conclusions harmonise of course with those of the classical theory. In free-radical sub- stitution however there is no obvious reason why substituents of either type should direct the attacking radical into one position rather than another as in FIG.10. (a) The non-bonding orbital in a reaction com- plex. (b)The distribution of the charge in S+ S- the complex the total electron density is the same at each of the five conjugated carbon atoms. An answer to this question is however provided by considering the electromeric effect. A substituent is said to have an electromeric effect if during reaction electrons can be transferred be- tween the substituent and the ring.Let us see how the molecular-orbital theory describes this phenom- enon. The electrons which contribute most strongly to the electromeric effect are the most loosely bound electrons in the ring or the substituent. Considering first the ring we have already seen that the three reaction complexes differ only in the number of elec- trons which occupy the non-bonding orbital and this is the orbital which will be most strongly in- volved in conjugation with the substituent. Let us first consider -E substituents such as amino and hydroxyl Each of these has an unshared electron pair in a non-bonding atomic orbital If such a sub-stituent is attached to the ortho- or para-position in the reaction complex the non-bonding atomic orbital will interact with the non-bonding molecular orbital of the ring to give two new orbitals one of which is bonding (B) and the other anti-bonding (A) as indicated in Fig 11 At this point we must take account of the charge on the ring If this is positive (electrophilic attack) the only two loosely bound electrons are those contributed by the substituent and both will enter the bonding orbital B We may then think of a co-ordinate bond from the substituent to the ring If the ring initially has one non-bonding electron (radical attack) it is necessary to put one electron into the anti-bonding orbital A and this weakens the co-ordinate link from the substituent id +A *A 7 -ee-84.-%8 -3e- -B% e -e% -+ s-s*-x sx x FIG 11 The stabihsation of S+ and S by a -E sub-stituent X (S-is not stabilised ) -2 -* -3 -u e- -8 -8 -848 -84 + 8% -33 ++ -63 SY s *Y s-Y FIG 12 The stabilisation of S and S by a +E sub-stituent Y (Sf is not stabilised ) Thirdly in the nucleophilic case there are four loosely bound electrons two of these must be assigned to each of the orbitals B and A so that no stabilisation is achieved at all The effect of fE substituents of which the nitro- group is an obvious example may be described along similar lines (see Fig 12) Such substituents may be characterised as possessing a low-lying vacant orbital which to a first approximation may be regarded as non-bonding (the stability of the NO molecule bears witness to this fact) Again if the attacking group enters ortho or para to the +E substituent the vacant orbital of the latter will interact with the non-bonding orbital of the ring to give a bonding (B)and an anti-bonding (A) combination In electrophilic attack there are no loosely bound electrons to be disposed of sothat both the orbitals B and A will be PROCEEDINGS empty.If the attacking reagent is a radical the odd electron will enter the orbital B,giving a one-electron bond between the substituent and the ring with a consequent gain of stability Finally in attack by nucleophilic reagents the two electrons originally in the non-bonding orbital of the ring both move into the orbital B and we obtain a co-ordinate link this time from the ring to the substituent Summarising we see that a -E substituent favours electi ophilic attack at the ortho- and para-positions by forming a co-ordinate link to the reaction com- plex a +E substituent facilitates ortho-para-substitution by nucleophilic reagents because the reaction complex can form a co-ordinate link to the substituent and that both -E and +E substituents direct radicals into the ortho-and para-positions in the former case by forining a three-electron bond and in the latter case by forming a one-electron bond with the radical complex The orientation of radicals by substituents which seemed puzzling when it was first di~covered,~~is seen to follow naturally from the molecular-orbital theory and the behaviour of free radicals in substitution need not seem so strange now as it did before 2o The above remarks have I hope served two purposes The first was to show that the molecular- orbital theory is not just a restatement of the resonance theory in unfamiliar language but occa- sionally leads to different conclusions which are borne out by experiment or to the interpretation of facts which were previously obscure My second purpose has been to show that application of the method does not always require heavy mathematical calculations but that in recent years it has provided methods of ready reckoning which to quote the advertisements “Even a child can use,” and that these methods seem on the whole to be reasonably reliable I must not end however without stressing the limitations of the molecular-orbital method in the form in which I have described it We have already seen that it is essentially an electronic theory and does not take explicit account of thermodynamic or steric effects at least as the method is normally applied to aromatic chemistry It is of course pos- sible to discuss such matters from a theoretical point of view and the work of Ingold,21 Hughes,22 and others has shown how fruitful such theoretical dis- cussions can be particularly in the chemistry of tetrahedral carbon But the absolute calculation of energies and rates lies outside the range of the molecular-orbital theory The reasons for this are I think to be found in the semi-empirical character of Grieve and Hey J 1934 1803 2o Waters “The Chermstry of Free Radicals,” Oxford 1946 p 150 21 Ingold “Structure and Mechanism in Organic Chemistry,” Bell London 1953 2a Hughes Quart Rev 1948 2 107 JUNE 1957 the method.Like any other theory of many-electron systems the molecular-orbital method is based on a simplification of Schrodinger’s equation. This simpli- fication is at one and the same time the power and the weakness of the method. On the one hand it gives us a physical picture of the electrons in a molecule each one moving in its own orbital with its own energy. On the other hand since electronic collisions are ignored the method cannot be used for non- empirical calculations. Instead all energies appear as multiples of so-called “resonance integrals,” which must be evaluated by appeal to experiment.So long as we are dealing with hydrocarbons only one parameter is needed namely the resonance integral of an aromatic C=C bond ;the method is therefore at its best when used for comparative calculations on aromatic hydrocarbons. However when other atoms are present more parameters are needed and the calculations begin to lose their value. And the more different structural features that a molecule exhibits the less reliable the method becomes. For example one would not feel inclined to attach much signific- ance to a molecular-orbital calculation of the relative acid strengths of 2 :4-dibromophenol and 2-chloro-4- iodophenol in 20% ethanol at 25O. On the other hand one would place a good deal of reliance on a molecular-orbital calculation of the relative energies of Diels-Alder addition to benzanthracene in various possible places.Diels-Alder addition incidentally is one of the reactions whose energetics seem to be particularly well explained by the molecular-orbital theory; the work of R. D. Brown on this reaction still represents one of the major successes of the method.23 In conclusion I suggest that the time has now come when the ordinary student of aromatic chem- istry can begin to think constructively in terms of the molecular-orbital theory and to make rough calcula- tions himself at least on alternant hydrocarbons and their simpler derivatives. Non-alternant hydro-carbons such as azulene are still a somewhat more awkward proposition in that the simple methods I have described cannot be applied to them; but even if energy calculations on such molecules demand a few hours or days on a calculating machine that is a relatively small price to pay for a new under- standing of their chemical behaviour.23 Brown Quart. Rev. 1952 6 63. THE EARLY GREEKS AND MODERN SCIENCE* By T. B. L. WEBSTER (UNIVERSITY LONDON) COLLEGE WITHINthe last few years two famous scientists one a German and one a Finn have published books on the early Greek philosophers pointing out connections between their world-pictures and the world-picture of modern physics. It is of course well known that certain Greek philo- sophers believed in a real world of atoms and void behind the world of objects perceived by our senses and that a Greek engineer invented a primitive jet-turbine.Both these the atoms and the jet-turbine became part of the educated man’s knowledge and so were there to be deve- loped when modern science needed them. The debt of mathematics and the biological sciences to the Greeks is probably much greater. My point however is not to argue that the progress of modern science has been swifter because modern scientists grew up with the knowledge of certain Greek ideas inventions and techniques and therefore started with a considerable number of Greek preconceptions which they developed in startling new ways. I think that is a tenable position but I have not the knowledge to work it out in detail. The question to which I want to suggest an answer is this.Twice (perhaps more often but there are two obvious examples) educated men seem to have leapt out of their world and made them- selves a new world. The first leap was made by the Greeks and the second leap is being made by ourselves now. Our world is quite different from the world two hundred years ago; our world picture is entirely different our daily life is entirely different our social and political life is entirely different our art music and literature are entirely different. The Greeks similarly between the eighth and fifth century B.C. leapt out of the context provided by contemporary civilisation and produced a civilisation as differ- ent socially politically artistically and scienti- fically from their more static Eastern neighbours as ours is from the civilisation of two hundred * Reprinted by permission from the Journal of the Chemical and Physical Society University College London 1955.PROCEEDINGS years ago. I do not think we can answer the question why such things happen but it may be possible to say how such things happen. If we can state some of the conditions of such a leap forward we may become more aware of the kind of conditions which are worth preserving. So my question is how did the Greeks come to have an outlook which people today regard as scientific? It is rash for an Arts man to try to define the scientific outlook but the attempt must be made. The scientist seems to me to make observations and to use experiments to establish how some- thing unknown works (whether the unknown is part of the natural world or of the human body) and his results are accepted if they fulfil various conditions his explanation must account for the facts and it must explain the unknown in terms of the known; his argument must be rigorous and disciplined; his methods must be such and must be explained in such a way that his colleagues know that they could use them themselves and achieve the same results; the results explain an unknown which had not been satisfactorily explained by previous scientists.A great deal of space would be needed to show that the early Greeks had the scientific outlook in this sense but details can be found in the histories of Greek philosophy and such works as Cohen and Drabkin’s Source Book in Greek Science; I shall confine myself to a minimum of examples choosing early rather than later examples even if they are less convincing.1. Observation much could be quoted from Aristotle and the doctors; about ,520 B.C. Xenophanes observed fossil fish inland and argued for an earlier wetter state of the world. 2. Experiment much again could be quoted from the doctors; Anaxagoras about 450 B.C. poured black powder into white powder to show that the senses were unable to appreciate minor changes in the constitution of things. 3. Explanation of the unknown in terms of the known the new kind of explanation that is accepted is an explanation in terms of known physical or mechanical processes instead of divine agency.Thales in the seventh century B.C. said that the earth floated on the ocean like a piece of wood on water and Anaximenes in the sixth century explained the formation of the universe by a process of condensation for which his model was human breath in cold weather. The slogan of Anaxagoras and Demokritos in the fifth century was “Sensible things are a means of seeing the unknown” which implies both the method of observation and observation as a check on theorising. 4. Disciplined argument here I think we should notice various elements first the gradual inven- tion of a technical terminology which could be used with great precision secondly the distinc- tion of two main classes of argument one which may be broadly termed inductive and whose conclusions can never be more than “probable” and the other deductive which was borrowed from the mathematicians and leads to “neces- sary” conclusions.The terminology of argu- mentation was not established until the time of Aristotle but the different kinds of argument are apparent long before. Within the inductive class we can distinguish first the working model com- parison (e.g. Empedokles’ comparison of the process of breathing to the working of a pipette) secondly the experiment thirdly the induction proper (the assembly of a number of instances to establish a general rule) and fourthly an in- teresting special kind of comparison which is commonly used in Herakleitos.Its form is either a :b ::b x or a :b ::c :x; in either case the purpose is to establish an unknown x by the use of two or three knowns. It is in- teresting because here again as in deductive arguments the method of argument was clearly taken over from the mathematicians. Mathe- matical arguments are compelling; the thinkers in other departments believe that they can borrow their compulsion with their forms. 5. Intelligible argument to make an argument intelligible needs not only a technical termino- logy but also a kind of prose which can put statements into their proper relation with each other. The earliest Greek that we possess operates almost entirely with main sentences connected by “and” and “but”. If the new explanations were to be given as argued explana- tions and not as the visions of a seer a new kind of sentence construction was needed which would emphasise the relations between sentences and between the parts within a sentence; this JUNE 1957 method of utterance which we call periodic prose became normal in the fifth century B.C.The procedure of explaining in terms that every- one who takes the trouble can understand instead of stating apocalyptically as seer prophet or priest is as important and as revolu- tionary a step forward as the choice of known physical or mechanical processes as the models for explaining the unknown instead of resorting as all previous thinkers had done to the action of god or gods; neither was achieved without many struggles and many back-slidings.The claim that the Greeks achieved a scientific outlook must be made on some such grounds as these. It is more difficult to state the conditions. It is however clear that the movement started in the Greek cities of Asia Minor and more specifically with Thales in Miletos at the end of the seventh century B.C. But we can in fact go rather further back. We can say with a high degree of probability that the IZiad and the Odyssey as we have them were composed by a great poet called Homer during the first half of the eighth century B.C. in one of the Greek cities of Asia Minor. These poems show two elements of interest to us two prerequisites of the scientific spirit. They are in the first place a distillation of masses of previous poetry preserved by the oral tradition for anything up to seven hundred years a distillation of this mass of material into a superbly organised simple design.This is the sort of thing which the scientist is trying to do to the world. Secondly Homer constantly uses long similes and there is some evidence partly linguistic and partly archaeological that the long simile is a creation of our Homer and of his immediate predecessors and not part of the old epic tradition handed down to these poets from the Mycenaean singers of mainland Greece. The long simile is an explanation of the unknown in terms of the known. It is a picture of a situa-tion in the everyday life of the poet’s audience drawn to illustrate the situation in the heroic past which the poet is trying to make them appreciate.The everyday situation illustrates the heroic situation at a number of points; it is in fact a kind of working model of the heroic situation. “But not even so could the Trojans put the Achaeans to flight but they held on just as a careful craftswoman holds the scales; she holds the balance and makes the wool equal in either pan as she draws the balance up that she may win a poor pittance for her children. Even so their battle was strained equally”. Homer wants to bring home this moment of crisis in the long-ago battle of the Trojan war when the Greeks were just holding a Trojan break-through which would carry them to the Greek ships and both save Troy and prevent the Greeks returning home.The two battle lines are taut and straining just as the two strings holding the scale pans are taut and straining but they quiver this way and that just as the two pans quiver when the woman adds a little more wool; the military operation is desperately important just as the woman’s weighing is desperately important because it is her only means of getting food for her children. This demand for an intelligible working model to explain the unknown is as far as the evidence goes something new in poetry and seems to me essentially similar to the demand made a century and a half later that the scientist should provide working models of the universe. The satisfaction of this demand is probably new.The stories go back to the Mycenaean age. The sense of form seems to have arisen in Main- land Greece particularly Athens a little before the emigrants set sail for Asia Minor. In Asia Minor where the emigrants were still arriving not more than 200 years before our Homer life was at the beginning hard and accurate observa- tion of detail and demand for intelligibility seems to me to be the response of a gifted and intel- ligent people who had left their roots behind. By the time of Thales they were well settled and in contact with the older civilisations of the East and here they found much mathematical material (though little or no mathematical theory) and a ready made cosmology in terms of divine agency. These are the conditions under which Greek science started.We can I think see one condi- tion which contributed to its continued progress at least until the third century B.C. and that is the close contact between different kinds of thinkers. Thales was himself politician and mathematician as well as physicist; Herakleitos in the late sixth century borrowed a method of argument from the mathematicians; in the fifth century philosophers doctors geographers and his-torians used the same terminology and the same kinds of inductive arguments and it is often difficult to say who is the originator and who the debtor. It is far more difficult for us with the increasing specialisation of science and scholar- ship to build bridges between the different sciences and between the sciences and the arts.Yet one of the conditions of progress in thought PROCEEDINGS would seem to be cross-fertilisation ; cross-fertilisation is only possible if we can speak intelligibly to each other; magicians with a private language have a low survival value. INDEPENDENT AND CO-OPERATIVE RESEARCH IN BRITISH AND AMERICAN INDUSTRY* By JOHNH. DUNNING (UNIVERSITY AMPTON) OF SOUTH DURING the past few months a number of publications have been issued giving details con- cerning the comparative research efforts of British and American industry. Of these two have been of particular note. First Mr. E. Rudd of the Department of Industrial and Scientific Research read a paper to last year’s British Association at Sheffield on “Expenditure on scientific research and technical development in Britain and America”.Though but a preliminary report of some research which Mr. Rudd is him- self carrying out it is one of the most informative and reliable surveys on a subject which is com- manding increasing attention from the physical and social scientist alike. Secondly the U.S. National Academy of Science has recently pub- lished the latest figures of American research efforts and expenditure and in doing so has made available for the first time some very interesting information on both the distribution of research effort between different industries and the size break-down of the relevant manufacturing con- cerns. Both these publications largely confirm beliefs already expressed concerning the much greater magnitude of U.S.research and development expenditure compared with that of the United Kingdom. Both reports are essentially factual in character and make no attempt to draw conclu- sions as to the adequacy or otherwise of the results. In brief their findings are as follows (1) British industry spent E325 million on all types of research in 1955. Of this amount private industry was responsible for 51 85 million Gov- ernmen t bodies E 124 million and research associations universities and technical colleges El6 million. Of the expenditure by private in- dustry El20 million or two-thirds of the total was on behalf of the Government and this mainly in respect of defence contracts.The dis- tribution of research between industries was such that the aircraft electrical engineering and chemical and allied trades alone accounted for three-quarters of the total research effort. In early 1956 there were some 71,100 qualified scientists and engineers employed by British in- dustry and the yearly output of graduates of this kind is now around 60 per million of the popula- tion. On the other hand U.S. industry in 1953 (the latest year for which there is any detailed information) spent E1,800 million on all kinds of research and development. Of this amount private industry spent El ,200 million about one- third of which was financed by the Federal Government. Once again the aircraft electrical engineering and chemical industries accounted for the bulk of the research effort the Government’s contribution being important in respect of the first two and negligible in the third.As far as private industry on its own account is concerned then U.K. research expenditure (in 1955) was E65 million and U.S. expenditure (in 1953) 2800 million. This means that even after allowance for differences in wage and salary levels the quantity of American research carried out is shown to be 5-6 limes that of the United Kingdom. Each year * Some of the material used in this study was previously published in an article I wrote for the District Bank Review in June 1956 entitled “Anglo-American Research Cooperation and Industrial Progress”. I am indebted to the Editor of the Review for permission to republish part of this material.t As a rough estimate the 1955 figure would be about &2,100million. JUNE 1957 American universities and colleges turn out 136 graduates in engineering and the applied sciences per million of the population. (2) As a percentage of her national product the United Kingdom spends 2 % on research and development and the United States 14 % though for privately financed industrial research the figures would be 0.4 % and 0.7 % respectively. Or again in relation to her population U.S. research effort is shown to be double that of the United Kingdom. In virtually all industries the American industrialist spends more on research and de- velopment in relation to sales turnover than his British counterpart.In fairness however it must be pointed out that the co-operative Research Association does not assume the same import- ance in the U.S. as in this country. Notwithstanding the fact that the British estimates are subject to considerable error these figures are highly illuminating. It would of course be foolish to infer that because the United States allocated so many more of its resources to research than the United Kingdom the latter's efforts are inadequate by that margin. For first because there are more firms engaged in similar lines of research in the U.S. there is numerically speaking a possibility of greater duplication of effort; secondly nothing is implied about the efficiency of the research department or the type of research engaged upon; and thirdly it by no means follows that it is profit- able for private industry in this country to assimilate all U.S. research activities (because for example of the different market structures with which the two economies are faced). What of the information on the distribution of research between firms according to size groups ? The National Science Foundation found that there were 15,500 U.S. companies involved in research in 1953 who between them spent &1,200million on research in that year. As one might expect the proportion of firms engaging in research rose as their labour force increased. Thus only 8 "/o of all firms employing below 100 workers had research budgets compared with 957; of those companies with a labour force of 5,000 or more.Of the latter companies there were only 2,280 employing more than 500 workers yet these accounted for 90 "/u of the total rcsearch expenditure ;indeed the largest 500 U.S. companies were responsible for thrce-quarters of 169 the total. Of those companies with more than 1,000employees the average (annual) expenditure per firm on research was &300,000. Comparative figures for the United Kingdom are not available but if the above proportions are assumed to hold it seems that a British firm employing over 1,000 employees spends on an average between E30,OOO and &50,000on research each year. More- over when it is remembered that a few large con- cerns such as Imperial Chemical Industries Limited spend many times that amount it is obvious that a large number of the larger British firms do not engage in any serious research at all.Of particular interest however is the fact that man for man the U.K. spends very much more on fundamental or theoretical research than the U.S. As a proportion of the former's total re- search effort it would account for more than 50% compared with the latter's 10 %. The implications of this fact will be discussed later in the article. Again of course there may be duplication of research effort amongst U.S. firms but when it is borne in mind that the economies of large- scale production apply equally to the laboratory and to the factory and that the larger firm often is in a much better position to shepherd new ideas from the initial invention to the actual marketing of the product the larger U.S.firm may well have an important advantage over its smaller U.K. counterpart. What of the implications of these statistics ? We would make two preliminary observations. The first is that the United Kingdom depends on her manufacturing exports to pay for nine-tenths of her imports. The fact that we live in an age of technology and speedy industrial developments with the prestige of being first in the field never more significant makes research and development the very lifeblood of this country's fight for world markets. At the same time for sheer lack of the appropriate resources it will be many years before we can hope to approach even the present scale of American research by which time this itself is likely to have increased even more.The second observation which leads us into our main discussion is that the U.S. economy is more complementary to the British economy than competitive with it. It is not the United States which we have most to fear as a manu-facturing competitor (our share of the newer in-dustrial exports is in fact rising faster than hers) but rather the Continental and the Asiatic countries and in particular Germany and Japan whose relative position as manufacturing ex-porters have improved out of all recognition in the past five years. Since 1945 the U.S. has in fact become gradually more reliant on the U.K. (through the media of her overseas subsidiaries) to satisfy her export outlets which have been cut off through the dollar shortage.A further fact and one of perhaps even greater consequence is that as the two countries’ pattern of resources and market requirements differ so does the relative profitability of various kinds of research. How often for example has it been said that the United Kingdom is the home of pure research whilst the United States excels in all spheres of applied development. And it is true that many British inventions and innovations have been later commercialised in the States and finally brought back into this country by way of imports Anglo-American licensing agreements or U.S. branch-plant enterprise. Penicillin fluorescent lighting the jet engine the electronic computer the fire extinguisher silicones are all examples of products largely pioneered in the United Kingdom but successfully commercialised and exploited by the United States either because her economy was better geared to making use of such knowledge than this country’s or because her business men possessed more fore- sight and initiative.That the United States recognises that Europe is still a most prolific source of new ideas is shown by the establish- ment last year of an overseas office in Zurich by the American General Electric Company “ to strengthen scientific contacts with European in-dustry” and since the two U.S.research institutes -Battelle and Arthur D. Little-have already established branch units in this country.That there are then mutual advantages to be gained by closer Anglo-American research co- operation can thus be clearly seen. In my own researches of the past three years I have been particularly concerned with one such way in which such co-operation is now being achieved viz. through the presence of U.S. manufacturing subsidiaries in the United Kingdom. The extent to which such firms have aided this country’s recent industrial development is not always appreciated as it might be. The fact that by their presence our own industrial development is able PROCEEDINGS to benefit directly from the competitiveness and dynamic quality of the American industrial system may be vaguely acknowledged. The fact that by virtue of their U.S.associations such firms are able to call upon resources of knowledge much greater than those available to their British competitors (unless the latter happen to be inter- national in scope) may be recognised in isolated cases.But the fact that of the BOOmillion spent on (private) research and development in 1953 by American industry 25-30% is made directly available to this country through the medium of branch-plant enterprise is hardly credited. And yet this is so; if one includes Anglo-American licensing agreements in which no foreign capital is usually involved but excludes Government- sponsored research then it would be no exaggera- tion to say that the post-war development of British industry owes more to research that originated in America than in this country.The resulting benefits apply to all stages of pre-production-from the initial discovery of an idea through the applied prototype and pilot stage of development to full-scale manufacturing. They apply to all kinds of research whether related to new products processes materials market or operational considerations and are both human and technological in character. The results of this investment are evident in a variety of fields. In all there are between 300 and 350 US.-financed firms operating manufactur- ing units in this country with a total investment stake of over &500 million. They turned out products worth over BOO million in 1955 and accounted for 10 % of all U.K.manufacturing exports. American participation is selective in that it is primarily concentrated in those in- dustries which are new to this economy and by their nature rely on mass-production techniques or involve a high research outlay. Most of the capital goods supplied are labour-saving in character (e.g.,office agricultural mining earth- moving bottle-washing machinery) whilst most consumer goods cater for markets with high income levels. Thus for example one has American research and development expertise vitally affecting the development of the phar- maceutical motor-car rubber-tyre petroleum- refining cosmetics and soft-drinks industries. So important in fact has the contribution of such firms been that they account for between 30 and PLATE1.Headquarters of the Society of’Cllernical Industry 14-16 Belgrave Square London S. W.I. PLATE 2. Meeting Room the Society of Chemical Industry. PLATE3. Coimcil Room the Society of' Clieriiical lndiistrjp. PLATE4. Secretary's Ofice the Society of Clieniical Indirstry. PLATE6. Centenary medal of the SociPtP Chimiqire de France (1 857-1957). JUNE 1957 40% of Britain’s newer exports and are one of the main reasons why in relation to America’s exports of similar products the U.K.’s share has risen from less than 5 % in 1938 to nearly 60 % in 1955. Through their presence British com- petitors have been given a lively stimulus to maintain and improve their efficiency and British suppliers of parts and raw materials to introduce new production methods and materials-pro-cessing techniques.For example in the latter respect my survey found that representatives of some 56 % of firms supplying U.S.-financed com- panies had visited the U.S. as a result of the contact thus established and another 45% ad-mitted that direct know-how of production methods materials processing or testing methods had been made available to them by such firms. Indeed it is this all important gap between the discovery of a new product process or material and its full acceptance and marketing which is being bridged by the presence of U.S.-affiliated concerns in this country. In some cases in fact it has been found profitable for the parent firm in the U.S.and the branch unit in this country to specialise as between the different stages of research and development. For example one precision-engineering subsidiary in this country specialises on manufacturing-design research whilst its parent concentrates on product and process development ;another enamelling branch plant devotes its research facilities to cast-iron enamelling in this country whilst the parent concern specialises in sheet-steel enamelling. The latest and one of the best examples in this field is the Anglo-American agreement between Mitchell Engineering Ltd. and A.M.F. Atomics Inc. the result of which is that the largest power organisation in the Ruhr is to be supplied with an atomic power station. Mitchell’s the U.K.con- cern is to provide the primary and secondary steam circuits the reactor vessel and heat-exchange pipes whilst A.M.F. Atomics will be responsible for the core core-control gear and instrumentation. By recognising the advantages which such co- operation offers and by a selective encourage- ment of U.S. companies into this country the United Kingdom may be able to do much both to maintain and expand her position as a leading industrial nation. Naturally of course there is no guarantee that the fruits of American research are always applicable outside the United States. It may be that the branch plants here will take up only a comparatively small proportion of the development originated from their parent plant’s laboratories or workshops but the important point is that there are many benefits-research manufacturing and managerial-which the larger American firm by reason of its economies in production is able to pass on to the British subsidiary.It is even possible that some tech- niques will ultimately prove of greater benefit to the smaller subsidiary than to the parent concern. The plain truth of the matter is that if this country does not take advantage of its very close economic and political ties with the United States in this way other European nations will undoubtedly do so. Already there are too many instances in the engineering and chemical in- dustries where important American firms have set up manufacturing units on the Continent because of the indifference and cumbersome nature of British negotiating procedure.From the American angle the Sherman Anti-Trust Act is proving to be a most powerful-and costly-deterrent to mutual research co-operation. In conclusion it cannot be too strongly emphasised that the United Kingdom must be partners with America-not simply buyers of knowledge. The United Kingdom is still amongst the leading experimental workshops in the world and in relation to her size is the most prolific source of new ideas. On the other hand it must be readily admitted that any monopoly we may enjoy is likely to be short-lived and that as regards the actual commercialisation of ideas our economic environment is much less favourable than that of the United States.It is here that Anglo-American co-operation can achieve its greatest mutual benefit. It is no use ignoring the fact that without such co-operation this country will open herself to the danger of slipping further and further behind in her bid for world manu- facturing exports. One of the most obvious truths which the British industrialist has yet to face is that the United Kingdom can never afford to stand still and rest on past laurels. The hard fact is that if she does not go forward her com- petitors will inevitably push her backwards. PROCEEDINGS THE SOCIETY OF CHEMICAL INDUSTRY ON Friday evening May loth Mr. Julian M. Leonard President of the Society of Chemical In- dustry welcomed members of sister Societies and Institutions and other guests at an informal “House- warming” at the new Headquarters of the Society at Nos.14-1 6 Belgrave Square London S.W. 1. The Society of Chemical Industry was founded in 1881 and received a Royal Charter from King Edward VII in 1907. For the early years of its life the Society had no offices of its own and its business was conducted by its Honorary Officers from their own addresses and the first five volumes of its Journal were published in Manchester. At the time of the last war the Society had registered offices in London and during the war it suffered twice from the effects of enemy action and after a series of changes and with great assistance from its Honorary Officers and from friends of the Society it succeeded in obtaining rooms in Victoria Street.This accommodation was however quite in- adequate and the Accounts Department had to be housed elsewhere while the stock of publications was distributed over nearly a dozen different places. With the cessation of hostilities it became clear that the most urgent need was adequate housing. Many premises were examined without success but ultimately a suitable building was discovered in Green Street. Negotiations for its purchase were in an advanced stage when they broke down for reasons outside the control of the Society. And so the search began again. Once more suitable premises were found in South Kensington and again negotiations at the last stage failed when the building was taken over by the Government.This occurred yet again with two other houses in Belgrave Square. So passed several years of frustration and disappointment and it was at this stage that a com- mittee was set up under the chairmanship of Dr. John Rogers with the sole aim of finding the Society a home. The new Headquarters of the Society of Chemical Industry provide in addition to the necessary administrative offices a fully equipped lecture theatre seating upwards of 150 a handsome council chamber and several committee rooms and members’ rooms (see Plates facing p. 170). Arrangements have also been made for the Institution of Chemical Engineers to occupy the larger part of No. 16 Belgrave Square and for the Society for Analytical Chemistry to be housed on the top floor of Nos.15 and 16. The Chemical Society is very pleased to offer its congratulations to the Society of Chemical Industry on the elegant new home which it has acquired. These premises will undoubtedly assist greatly in the many activities of the Society of Chemical Industry and its Subject Groups. LA SOCIETI? CHIMIQUE DE FRANCE 1857-1957 By P. LAFFITTE FAC CULT^ DES SCIENCES DE PARIS) VICE-PRESIDENT CHIMIQUE OF THE SOCI~T~ DE FRANCE THE Sociktk Chimique de France whose centen- ary is to be celebrated in Paris this year was founded-under the name Sociktk Chimique de Paris-by three young and enthusiastic chemists who wished above all to increase their knowledge of a science which they loved passionately. A little brochure published by the Sociktk Chimique in 1858 reports the foundation of the Sociktk in the following terms “In the last days of the month of May in the year 1857 three young chemists MM.Arnaudon ‘prkparateur’ to M. Chevreul at the Manufacture impkriale des Gobelins ; Collinet ‘prkparateur’ to M. Dumas of the research laboratory of the Facultk des Sciences de Paris; and Ubaldini of the laboratory of the Collkge de France con-ceived the idea of uniting as a Society and of establishing meetings which would help them in the study of chemistry and keep them in the stream of the so-rapid progress of that science. Some other chemists young like them associated themselves with this idea and founded an association under the name Sociktk Chimique setting out the aim which we have just explained.“The young Societk was very modest; at its first meeting [see Plate 51 which took place on June 4th 1857 there were barely ten members; but soon the advantages of this association be- came understood by all and the laboratories of the Facultk des Sciences de Paris of the Collkge JUNE1957 de France of the hole de MCdecine de Paris of the Conservatoire des Arts et Metiers sent numerous adherents to it.” The first President was Arnaudon in 1857; in 1858 the Swede Rosing and then Aim6 Girard. Then in 1859 the young society renewing its officers feels it necessary to put at its head men whose scientific standing is already considerable. It elects as President J. B. Dumas then 57 years of age whose worth is universally recognised; as Vice-presidents Pasteur and Cahours.Wurtz is Secretary Aime Girard and Leblanc Vice-Secre- taries Cloez Treasurer. The impetus is given; great scientists interest themselves in the Socitte Chimique; its future is assured. It would be of great interest but perhaps a little too long to give the names of all the illustrious chemists who for a century have presided over the destinies of the Societe Chimique. We shall content our-selves with reproducing the medal [see Plate 61 which has just been issued in Paris by the Administration des Monnaies et Mtdailles on the occasion of the centenary of the Socikte. On the obverse of this medal are reproduced the portraits and names of six of the most illustrious of the Presidents (J.B. Dumas L. Pasteur M. Berthelot V. Grignard H. Moissan P. Sabatier) and on the reverse the names of the successive Presidents. In an account of the initial r81e of the Socittt Chimique it will be useful to record the state of knowledge at the time of its creation and the best way of doing this is to quote part of a dis- course given by Armand Gautier when he assumed the Presidency of the Socittt in 1906 “At that time French chemical science was divided into three rival schools who were almost enemies. The old French school of Berthelot Gay-Lussac and J. B. Dumas (the precursors of physical chemistry) remained the classical school. Its most active representative at the time was H. Sainte-Claire Deviile.He led his battalion of distinguished pupils at the Ecole Normale who rzligiously preserved the dualistic system of nota-tion and conception. L’Ecole de Pharmacie the great cradle of chemists at that time marched under the banner and with the formula= of a most illustrious chemist still living,* whose works had with reason great weight in the decisions and ideas of young chemists. * This refers to M. Berthelot at that time 86 years of age Finally came Wurtz and his ardent pupils Friedel Ladenburg Lauth de Clermont Salet Crafts Grimaux Longuinine Beilstein. . . .They represented the militant school of the atomic theory the school which tried with the aid of atomic linkages to write the constitution of substances into their chemical formula=.Laurent with his researches and ideas on naphthalene and its chlorinated derivatives had been the prophet of this school in 1833. Later had come Gerhardt and Williamson with their theory of types; still later in 1849 Wurtz had taken his part with his discovery of the compound am- monias and then the glycols. Finally Friedel’s researches on the hydrogenation of acetone (1866) had shown conclusively the importance which could be attached to the position of one and the same radical in a molecule. But how often had battles to be fought to maintain defend and perfect these infant still developing theories and how many enemies had to be made! “The Socitttk Chimique thus became the en- trenched camp of atomism. Without closing the door on other sects the brilliant pupils of Wurtz received more coldly those who did not think and write as they did; so it was that in the period of its development and exuberant youth the Societe Chimique nearly fell into a sickness of growth and later of languor.Without aband- oning it many of those members whose ideas and language were not generally adopted sent their excellent papers elsewhere and the division between the schools continued increasingly. In passtng from the Lycee to the Sorbonne to the &ole de Pharmacie or Ecole de Medecine the young men obliged to change their fundamental conceptions and formulae be- came disheartened. For them the result was lassi- tude and for all an appreciable decrease in the number of chemists and in the value of French works.” But very happily this situation did not continue for very long and the Societt Chimique -and with it French chemistry-resumed its forward march.It should be recorded that at first the founders of the Socikte Chimique made it their primary concern at their meetings and in the Bulletin which they issued to note and discuss not only the work of members of the Socittk but also the most important work carried out and published who was to die in the following year. anywhere in France and abroad in such a way as to instruct the young chemists and to keep them in the stream of development and progress of the science to which they devoted themselves. All branches of chemistry including industrial chemistry were thus included.But after several years in face of the very varied applications of chemistry and the very great specialisation which was needed the SociCtC had to limit its activities and to cease taking account of work in industrial chemistry; various SociCtCs of applied chemistry were thus formed. The Sociktk Chimique then devoted almost all its activity to the different branches of pure chemistry. As the number of members grew and the proportion of young chemists diminished the meetings of the SociCte progressively changed in character ;papers pub- lished in foreign journals were read and dis- cussed less and less and at the meetings only original work by members of the SociCtC were read and discussed.However the enthusiastic spirit of the young founders persisted for very many years. The discussions arising from some of the papers were often very lively and some- times even passionate. Even 25 years ago meet- ings were occasionally very animated; some of those who took part in them or witnessed them regret nowadays the lost atmosphere and hold that the SociCte was then more alive. It is certain that this period which some have called the heroic period of the SociCte is now over and that the modern experiments and theories no longer give rise to the same discussions as in the past. As a matter of fact the experimental proofs cited at that time in support of this or that theory did not always suffice in number or precision to convince all immediately and beyond dispute.But even if it is admitted that chemistry has made immense strides since the beginning of the twentieth century it must also be recognised that considerable upheavals have taken place during the life of say a Berthelot (1820-1907). Another and important phase in the develop- ment of the Sociktk Chimique was marked by the creation in the major provincial universities of other Societies which were affiliated to the SociCtk Chimique de Paris. The latter thus represented all the chemists in France. So naturally the name was changed from Socikte Chimique de Paris to Sociktk Chimique de France. Specifically the Sociktk has sections in sixteen villes de provinces PROCEEDINGS and in Algiers all very active.These different sections have some degree of autonomy and hold meetings regularly; but the reports of these meetings are published alongside those of the meetings of the Paris section in a fortnightly bulletin. Papers by members whether from Paris or from the provinces are published monthly in the Bulletin de la SociCtk Chimique de France. We have seen that one of the objects which the founders of the SociCtC Chimique assigned to themselves was to instruct the young chemists and to keep them in the stream of development and progress of the science to which they devoted themselves. That is why from the beginning of the Socikte a certain number of “lecons” were delivered by different people generally by the scientists best qualified in the field.One can cite 1860 Researches on the molecular dissymmetry of natural organic substances by L. Pasteur; 1860 Syntheses in organic chemistry by M. Berthelot ; 1864 Dissociation by H. Sainte-Claire Deville. Later these “lecons” became lectures. Some are given each year by the most competent specialists on selected topics. These specialists are chosen from the most eminent scientists whether French or foreign. It is thus that in the last ten years members of the SociktC Chimique de France have been able to hear lectures de- livered by the following chemists from Great Britain C. N. Hinshelwood C. K. Ingold F. A. Paneth J. S. Anderson H. J. EmelCus and D. H. R. Barton. These lectures are published in the Bulletin de la SociktC Chimique whose circulation has increased considerably in recent years.Nearly 5,000 copies are now sent to members and subscribers. The Sociktk Chimique de France flourishes also in other respects. In 1956 there were 500 new members and new registrations in 1957 are following the same trend. In 1956 the Bulletin published 400 original papers to which must be added six lectures and six reviews of topical subjects. It may be noted that delay in appear- ance of papers is relatively very short since generally one to three months elapse between receipt of a paper and its publication in the Bulletin. Thus it is clear that the SociCtC Chimique de France although a centenarian is still growing and full of‘ vitality. JUNE 1957 175 COMMUNICATIONS The Pyrolysis of set-PropyI Iodide By J.L. HOLMES and ALLAN MACCOLL (UNIVERSITY GOWER LONDON, COLLEGE STREET W.C. 1) THE Arrhenius parameters for the first-order uni- molecular elimination of hydrogen bromide and hydrogen chloride from sec.-propyl bromide1 and chloride2 are well known. On the other hand investi- gations by Ogg3 and by Polanyi and their co-workers4 on the pyrolysis of sec.-propyl iodide were interpreted in terms of carbon-iodine bond fission. In view of the analogy that has been suggested between the unimolecular elimination mechanism in the gas phase and the S,l and El reactions in a polar solvent it was considered desirable to re-investigate the pyrolysis of set-propyl iodide in order to elucidate more clearly the mechanism and in particular to see whether the unimolecular elimina- tion mechanism does in fact occur.It should be noted that the stoicheiometry of the reaction is very well represented by C3H7I -+ -&C3H6+ -&C3H,+ 812 .... (A) and that a possible mechanism is C3H7I + C3H6 f HI.. ..............(I) C3H71 f HI -+ C3H8 +12 ................(2) as was indeed suggested by Jones and Ogg. However they dismissed the elimination mechanism on the grounds that step (2) would be too slow. An investigation of reaction (2) at 214" and 236" in clean glass vessels showed that it was indeed rapid at temperatures well below those at which pyrolysis set in. The results were fitted to the equation d[12]/dt = kb[C3H71][I,]&..................(B) which is consistent with the following mechanism I + 21....................... ..(3) I. + C3H7I -+ C3H7. +I2 ................(4) C3H7. + HI + C3Hg + I. ................(5) The initial iodine may have come either from decomposition of the reactants or as a trace impurity. The rapidity of reaction (2) having been estab- lished the pyrolysis was investigated in seasoned vessels over the temperature range 240-357" with initial iodide pressures varying from 8 to 150 mm. The nature and proportions of the gaseous hydro- carbons were determined by gas chromatography and confirmed the stoicheiometry suggested by reaction(A).The pyrolysis was shown to be essentially homogeneous and of first order over the temperature range 285-357".Below 285" an autocatalytic reaction which obeyed a rate law of the form (B) Maccoll and Thomas J.. 1955. 979. Barton and Head Trans Faraday Soc. 1950 46 114. became of increasing importance. However the observed rate constant was very much smaller than that observed in the reaction between sec.-propyl iodide and hydrogen iodide. The addition of nitric oxide had no appreciable effect on the rate of reaction in the first-order region but had a marked effect in the autocatalytic region. Addition of a large excess of propene retarded the reaction and this can be explained by the interven- tion of the reverse reaction corresponding to (1). That this was indeed the case was shown by a separate study in seasoned vessels of the reaction between hydrogen iodide and propene.This was found to give propane and iodine as the sole products by the reverse of (1) followed by (2). The reaction was of the second order. It is concluded that in the first-order region the mechanism of pyrolysis is that of a unimolecular elimination of hydrogen iodide (I) followed by rapid reduction of the sec.-propyl iodide by the hydrogen iodide produced (2).At low temperatures 200-250" in clean vessels the latter reaction is probably heterogeneous. In seasoned vessels the ob- served autocatalytic reaction is probably homo- geneous and occurs by reactions (3) and (4) together with (6) and (7) C3H,-+ C3H71 -+ C3H8f C3H61*.........(6) C3H,I* -+ C3H6 + 1'. .............(7) and is an iodine-induced radical-chain process.This has been confirmed by observing the catalysis brought about by added iodine. It can further be concluded from this work that processes involving fission of the carbon-iodine bond play at most a negligible r6le in the temperature range investigated. The kinetic constants for the elimination of hydrogen halides from the sec.-propyl halides are as shown in the Table. These relative rates show the same general trend namely iodide > bromide > chloride observed in the unimolecular reactions in 80% aqueous alcohol of the tert.-butyl and tert.-amyl halides.6 Chloride2 Bromide1 Iodide log A 13.40 13-61 14.46 E (kcal. mole-I) 50.5 47.8 48.2 Rate ratio (350") 1 14 94 (Received April IOth 19-57.) Jones and Ogg J.Amer. Chern. SOC.,1937 59 1939. Butler Mandel and Polanyi Trans. Faruday Soc. 1945,41 298. Maccoll and Thomas Nature 1955 176 392. Ingold "Structure and Mechanism in Organic Chemistry," Bell London 1953. 176 PROCEEDINGS Hexanitrosobenzene (Benzotrifuroxan) A Complex-forming Reagent for Aromatic Hydrocarbons By A S BAILEY and J R CASE (DYSONhRRINS LABORATORY, OXFORD) IN 1899 Drostl reported that 4 6-dinitrobenzo- furoxan (I) formed a crystalline complex with naphthalene We have extended this observation by investigating the formation of complexes between O,N \ :I aromatic hydrocarbons and nitrotetranitrosobenz- 0 ene2 (nitrobenzodifuroxan) (TI) and between aro- matic hydrocarbons and hexanitro~obenzene~ (benzotrifuroxan) (111) these two reagents having now been prepared by improved methods Equilibrium constants for the reaction X + naphthalene + X,naphthalene have been determined spectrophotometrica11y4 in chloroform solution with the followmg results X K (1 /mole) Complexes wI th hexanitrosobenzene 1 3 5-Trinitrobenzene 13 4 6-Dinitrobenzofuroxan (I) 26 N( %) Nitrotetranitrosobenzene (11) 37 Formula Found Reqd Hexanitroso benzene (111) 41 Mesitylene C1&1,06N6 227 226 9, 1 2 3-CcH3Me3 22 5 226 The value of K for trinitrobenzene is in excellent Tetralin C16H1206N6 21 7 21 9 agreement with the figure obtained by Ross and 5-Ethyltetralin C,&1606N 202 204 Labes These values suggest that compounds (I) Diphenyl C&1@6N6 203 207 (11) and (111) are more powerful complex-forming M p s are respectively 162-1165" 170-172" agents than trinitrobenzene 151-153" 144-1147" and 164-166'.We have found that a solution of hexanitroso- other reagents mesitylene styrene tetralin 5-ethyl- benzene (111) in ethanol-acetic acid yields crystalline tetralin 6-methyltetralu1 1-phenylnaphthalene 1 -n-complexes with a variety of aromatic hydro-hexylnaphthalene diphenyl Some data for typical carbons of which the following are of special interest cases are given in the annexed Table. since they do not readily yield solid complexes with (Received April 18tlz 1957 ) Drost Annalen 1899 307 49 Gaughran Picard and Kaufman J Amer Chem Soc 1954 76 2233 Turek Chime et Industrie 1931 26 785 Foster Hammick and Wardley J 1953 3817 Ross and Labes J Amer Chem Soc 1955 77,4916 1957 79 76 A New Synthesis of Derivatives and Peptides of Ornithine and ay-Diaminobutyric Acid By M ZAORAL and J RUDINGER (INSTITUTE CZECHOSLOVAK OF SCLENCE, OF CHEMISTRY ACADEMY PRAGUE) IN principle two approaches to the synthesis of Recently derivatives and peptides of glutamine peptides of polyfunctional amino-acids may be dis- have become readily available in particular through tinguished one starting from suitably protected the use of 5-0x0- 1 -toluene-p-sulphonylpyrrolidine-2-derivatives of the amino-acids themselves and the carboxylic acid and its chloride as intermediates other involving the introduction into the peptide Asparagine too is an easily accessible starting chain of an intermediate in which the characteristic material (though the synthesis of its peptides appears side-chain group is subsequently developed by suit- to present some peculiar difficulties2) It hence able reactions Hitherto this second approach has seemed of interest in accordance with the second received relatively little attention approach mentioned above to examme the pos-Rudmger CoII Czech Chem Comm 1954 19 365 375 Rudinger and Czurbova hid p 386 du Vigneaud et aI J Amer Chetn SOC 1953 75 4879 Swan and du Vigneaud ibrd 1954 76 31 10 Leach and Lmdley Austral J Chem 1954 7 173 Bomonnas Guttman Jaquenoud and Waller HeIv Chrm Acta 1955 38 1491 Rudinger Honzl and Zaoral CoIl Czech Chem Coinrn 1956 21 770 JUNE 1957 sibility of basing further synthetic procedures on these derivatives of glutamine and asparagine.We first investigated a reaction sequence involving dehydration of the amides to the nitriles and reduc- tion of the latter to yield derivatives of ornithine and ory-diaminobutyric acid respectively. Now it has recently been noted that in the course of peptide synthesis asparagine residues may be modified- evidently by dehydration3-to a form giving diamino- butyric acid on reduction$ and it has been sug- gested* that the modified derivative might be the corresponding nitrile. We therefore think it of interest to make available the results so far obtained in our preparative approach to what is evidently the same reaction sequence. (I) NH,COCH,-CH,*CH( NHTs)COX (11) NC*CH,CH,CH(NHTs)COX (111) NH,-CH,*CH,CH(NHTs)COX (IV) NH,COCH,CH(NHCbo)COX (V) NC*CH,CH(NH-Cbo)COX (Ts = p-C,H,Me-SO,-; Cbo = CH,Ph-O-CO-) Toluene-p-sulphonyl-L-glutamine methyl ester (I ; X = OMe) was dehydrated with toluene-p-sulphonyl chloride in pyridine5 to methyl y-cyano-L- or-toluene- p-sulphonamidobutyrate (I1 ;X = OMe) ; hydrogen-ation (Pt02 in HCl-AcOH-H,O at room temper- ature and pressure; or Raney Ni in NH,-MeOH -H20 at room temperature and 100 atm.) of the cyano-acid (11; X = OH) gave Na-toluene- p-sulphonyl-L-ornithine (111; X = OH) as the hemihydrate identical in properties with a sample prepared from L-ornithine by way of the N8-benzyloxycarbonyl derivative.6 Removal of the toluene-p-sulphonyl group of the acid (111; X = OH) with hydrogen bromide in acetic acid7 yielded L-ornithine; reduction of the cyano-group and removal of the toluene-p-sulphonyl group of the acid (IT; X = OH) could also be effected in a single operation by sodium in liquid ammonia-methanol.The L-ornithine was characterised as the dipicrate monohydrochloride and dihydrochloride.8 Na-Benzyloxycarbonyl-~-asparagineg (IV ; X = OH) could be directly dehydrated by toluene-p- sulphonyl chloride and pyridine to the cyano-acid (V; X = OH) though a better yield was obtained by way of the methyl esters (IV; X = OMe)9 and (V; X = OMe). Hydrogenation of the acid (V; X = OH) gave L-ay-diaminobutyric acid characterised as the picrate and dihydrochloride.'* Application of the same dehydration procedure to the peptide derivative toluene-p-sulphonyl-L-gluta-minylglycine methyl ester (I; X = NHCH,CO,Me) again gave the corresponding nitrile (11; X = NHCH,-CO,Me) in excellent yield.Mild alkaline hydrolysis hydrogenation and removal of the toluene-p-sulphonyl group with sodium in liquid ammonia yielded L-ornithylglycine isolated as the monopicrate monohydrate m.p. 149-151 The intermediate nitrile (11; X = NHCH,CO,Me) could also be obtained from the cyanobutyric acid (11; X = OH) by treatment with thionyl chloride and condensation with glycine methyl ester; these two methods of preparation exemplify two possible approaches to the synthesis of ornithine peptides. The intermediate (V; X = NHCH,CO,-CH,Ph) was similarly obtained from the cyano-acid (V; X = OH) and glycine benzyl ester by the dicyclohexyl- carbodi-imide synthesis.ll On reduction it gave L-ay-diaminobutyrylglycine,isolated as the picrol- onate (m.p.243O anhydrous). It has further been shown that treatment of Na- toluene-p-sulphonyl-L-ornithine(I11; X = OH) and Na-toluene-p-sulphonyl-L-ornithylglycine(I11; X = NH-CH2-C02H) with O-methylisourea gives toluene- p-sulphonyl-L-arginine12 and -L-arginylglycine (monohydrate m.p. 166-1 70°) respectively; an extension of the synthetic procedures described above to the preparation of peptides of arginine may thus be visualised. (Received April 26t11 1957.) Gish Katsoyannis Hess and Stedman J. Amer. Chem. SOC.,1956 78,5954. Ressler ibid.p. 5956. Stephens Bianco and Pilgrim ibid. 1955 77,1701. Synge Biochem. J. 1948 42 99. Weisblat Magerlein and Myers J. Amer. Chem. Soc. 1953 75,3630 ;Podugka Rudinger and &mn Coll. Czech. Chem. Comm. 1955 20,1174. Cf. Vickery and Cook J. Biol. Chem. 1931 94 393; Fu Rao Birnbaum and Greenstein ibid. 1952 199 207; Rivard and Carter J. Amer. Chem. Soc. 1955 77,1260. Bergmann and Zervas Ber. 1932 65 1192. lo Cf.Adamson J. 1939 1564; Kurtz J. Bid Chem. 1949 180 1253. Sheehan and Hess J. Amer. Chem. SOC.,1955 77,1067. l2 Bergmann and Fruton J. Biol. Chem. 1939 127,646. PROCEEDINGS Phosphorodimorpholidic Bromide :A New Phosphorylating Agent By H. A. C. MONTGOMERY and J. H. TURNBULL (THE UNIVERSITY 15) BIRMINGHAM PHOSPHOROAMIDIC HALIDES are known to act as phosphorylating agents1 but hitherto attempts to utilise them for preparative purposes have not proved en t ire1 y successful.We have found that phosphorodimorpholidic bromide (I; X = Br) is a useful reagent for the phosphorylation of alcohols. Treatment of morphol- ine with phosphorus oxybromide yielded phosphoro- dimorpholidic bromide as an unstable crystalline [O<(CH,.CHJ,> N J2pO.X (1) [O <(CH2CH2)2>N]2P0.0R (HO),PO*OR 01) (111) solid which in chloroform solution reacted smooth- ly with alcohols (in the presence of an organic base) affording the corresponding phosphorodirnorpholid- ates (11; R = ethyl cyclohexyl allyl). Hydrolysis of the amide linkages in the ester (11) to yield the required dihydrogen phosphates (111; R = ethyl cyclohexyl allyl) was achieved by percolating a warm aqueous solution through an acidic ion- exchange resin (Amberlite IR-120 H+ form).The dihydrogen phosphates (identified as their cyclo-hexylammonium salts) were prepared alternatively (in the case of the ethyl and cyclohexyl derivatives) from the alcohol by direct phosphorylation with phosphorus oxychloride. Phosphorodimorpholidic chloride (1; X =Cl),m.p. 80-81” (Found N 10.6; C1 13.5. C,H,,0,N2C1P requires N 11.0; C1 13-9%) prepared from morpholine and phosphorus oxychloride was found to be an alternative reagent to the bromide although it is much less reactive. The foregoing method shows particular promise for the conversion of unsaturated alcohols into their dihydrogen phosphates which are not always easily accessible by conventional phosphorylating tech- niques.We thank Professor M. Stacey F.R.S. for his encouragement. One of us (H.A.C.M.) acknowledges receipt of a maintenance grant. (Received May loth 1957.) Cook Ilett Saunders Stacey Watson Wilding and Woodcock,J. 1949 2921; Heap and Saunders J. 1948 1313 Zetzsche and Buttiker Ber. 1940 73 47; Zeile and Kruckenberg Bet-. 1942 75 1127; Bevan Brown Gregory. nd Malkin J. 1953 127. NEWS AND ANNOUNCEMENTS Library of The Chemical Society.-From July 16th until September 30th 1957 the Library will close at 5 p.m. instead of at 7.30 p.m. The Library will not be open on August 5th and 6th. Anniversary Meetings Bristol 1958.-Three Sym-posia will be held during the Anniversary Meetings of the Chemical Society in 1958 which are to be held in Bristol on March 31st to April 2nd.The subjects are “Developments in Aromatic Chemistry,’’ “Ap- plications of Electron and Nuclear Resonance in Chemistry,” and “Recent Work on the Inorganic Chemistry of Sulphur.” Full reports of these rneet- ings will be published under arrangements to be issued later. Further details will be announced in Proceedings and circulated to all Fellows. Non- Fellows may obtain further information when it is available on application to the General Secretary. Chemical Society Symposium.-Steric Efects in Conjugated Systems. A symposium will be held in the University of Hull on July 15-17th 1958.Invita- tions to read papers have been provisionally accepted by Professor H. C. Brown Professor N. B. Chapman Professor C. A. Coulson Professor M. J. S. Dewar Professor E. E. Turner Dr. G. Baddeley Dr. C. C. Barker Dr. G. W. Gray Dr. L. E. Sutton and Dr. B. M. Wepster. The papers to be presented will later be published with a full report of the discussion. Further details will be circulated to all Fellows when available. Non-Fellows should apply to the General Secretary. Local Representatives.-Durham. Dr. G. Kohnstam is to spend the next year in the United States and has resigned as Local Representative. Council has appointed Dr. F. Glockling as his successor. Birmingham. Dr. J. C. Tatlow on his election as a Member of Council has resigned as Local Repre- sentative for Birmingham and Dr.D. H. Whiffen has been appointed to succeed him. British Association.-The Annual Meeting of the British Association for the Advancement of Science will be held in Dublin on September 4-1 1th 1957 JUNE 1957 under the Presidency of Professor P. M. S. Blackett F.R.S. The British Association remains unique as an independent institution of national reputation which brings almost the whole range of science within its scope and opens its membership to all who are interested in the progress of science. Founded in 1831 to convince an indifferent public and government that science was important and worth backing the Association-as its history bears witness-succeeded magnificently in its original purposes.Today science is of paramount importance to the community and one of the Association’s main tasks is to promote a better understanding of its impact through its appli- cations on society as a whole The continuance of science is vital to modern society and this being so continued public goodwill is essential. To ensure this the methods and results of science and the nature of fundamental research must all be better understood by those concerned with government industry and business and the public at large. Such understanding is essential be- cause in any democratic state an informed public is necessary if valid decisions are to be taken; because the public-as taxpayer and consumer-pays for science; because if in the future scientists and tech- nologists are to be forthcoming in the numbers that the national interest requires the public should learn to value the contribution of science and come to appreciate the potential satisfaction and opportunity for service implicit in careers devoted to science; and above all because scientific discovery must be applied for the wellbeing of the nation.The Association’s main contribution to this end lies in its great Annual Meetings which are attended by representatives from every branch of science; by industrialists government servants agriculturalists and many who are interested and involved in the applications of science; by teachers representatives of the press radio and television (and indirectly and invisibly by their own audiences); by laymen in- terested in the progress of science and its social implications.The Meeting broadly speaking attempts to do three things. First to offer a platform on which lead- ing scientists can discuss their work in all its theoret- ical complexity-for fundamental work is not only at the heart of all progress in science but it is also important to demonstrate the “compulsion of facts” and the “dignity of expertness” and to give the public an understanding of the integrity and discipline in- volved in the search for scientific “truth”. Secondly- for such is the specialisation and fragmentation of science-to encourage scientists to discuss in joint sessions problems in related fields and to develop common problems involved in subjects on the frontiers of present knowledge.For if communica- tion between scientists is limited the advance of science is retarded; and new outlooks and avenues of enquiry may emerge from such juxta-position of the work of different specialists. Thirdly to provide for non-specialists-whether they be scientists out- side their own field or interested laymen-an annual stocktaking in intelligible language which will review the progress of science and help to make clear its significance and possible consequences. Membership of the British Association is open to all who are interested in the progress of science. The annual subscription for full membership is 3 guineas which includes the attendance at the Annual Meeting and the receipt of the quarterly publication The Ad-vancement of Science.Associate membership costs 2 guineas which includes either attendance at the Annual Meeting or the receipt of the publication. Full particulars including details of life membership and student membership may be obtained from the Secretary the British Association for the Advance- ment of Science Burlington House Piccadilly London W.l. Symposia. Micro-Chemistry 1958. The Society for Analytical Chemistry is to hold an exhibition embracing “live” and “static” demonstrations of a new and novel nature and in addition displays of historical interest during the Symposium period Wednesday August 20th to Wednesday August 27th 1958. It is intended that thedemonstrationsshallcover all aspects of chemical analysis and set periods will be allocated for the demonstrations in the Symposium scientific programme.It is stressed that it is the desire of the organisers to include all branches of pure and applied chemistry. Any one who feels that they have a potential exhibit or exhibits of relevant interest is invited to send details to the demonstrations secretary Mr. G. Ingram Research Laboratory Courtaulds Limited Maidenhead Berks. England. Second Gas Dynamics Symposium.This will be held on August 26-28th at the Technological Insti- tute of Northwestern University in Evanston Illinois under the auspices of the American Rocket Society and Northwestern University. The theme will be “Transport Properties in Gases at High Temperatures and Pressures.” Particulars may be obtained from Dr.Ali Bulent Cambel Gas Dynamics Laboratory Northwestern University Evanston Illinois U.S.A. Congresses.-The Sixth Empire Mining and Metal- lurgical Congress will be held in Canada from September 8th to October 9th. Details may be ob- tained from the Executive Secretary of Congress Mr. C. H. Mitchell 507 Metro Building 837 West Hastings Street Vancouver 1 B.C. Canada. The Second World Metallurgical Congress will take place in Chicago Illinois on November 2-8th sponsored by the American Society for Metals and held concurrently with the National Metal Congress and National Metal Exposition. Subjects to be dis- cussed include :steelmaking and refining; non-ferrous refining and fabrication ; ferrous fabrication; heat treatment welding and joining inspection and test- ing management and problems in the metals in- dustry education and research; metallurgical aspects of atomic energy.Further information can be ob- tained from Mr. W. H. Eisenman American Society fof Metals 7301 Euclid Avenue Cleveland 3 Ohio. The Fourth Symposium of the Canadian Associa- tion for Applied Spectroscopy will take place on September 11-13th at Ottawa Canada. Equiries should be addressed to Mr. J. H. D. Howarth Canada Metal Co. 721 Eastern Avenue Toronto Ontario Canada. An International Conference on Co-ordination Chemistry will take place in Rome on September 15-20th under arrangemcnts made by the Italian Chemical Socicty.Further details may be obtained from the Italian Chemical Society Via Quattro Novembre 154 Rome. An International Conference on Radioisotopcs in Scientific Research will be held in Paris on September 16-27th (tentative) under the auspices of the De- partment of Natural Sciences UNESCO 19 Avenue Kleber Paris 8e from whom further details may be obtained. An International Symposium on the Formation and Stabilization of Free Radicals will take place in Washington D.C. on September 18-20th under the joint sponsorship of the Applied Physics Labora- tory of the John Hopkins University the Catholic University of America and the National Bureau of Standards. Enquiries should be addressed to Dr. A. M. Bass Free Radicals Research Section National Bureau of Standards Washington 25 D.C.An International Symposium on Saline Water Conversion will be held in Washington during the first part of November under the sponsorship of the Office of Saline Water of the U.S. Department of the Interior and the National Academy of Sciences National Research Council. Enquiries should be addressed to the Division of Physical Sciences National Academy of Sciences 2 101 Con- stitution Avenue N.W. Washington 25 D.C. The Fourth Pan American Congress of Pharmacy and Biochemistry will be held in Washington D.C. on November 3-9th. The theme of the Congress will be “Planning the Advancement of Pharmacy throughout the Americas.” Further details may be obtained from Dr. George B.Griffinhagen PROCEEDINGS Executive Secretary of the Congress Smithsonian Institution Washington 25 D.C. The Corday-Morgan Commonwealth Fellowship- The Corday-Morgan Commonwealth Fellowship for the academic year 1957/58 has been awarded to Dr. E. A. Magnirsson Teaching Fellow in the School of Applied Chemistry at the New South Wales Univer- sity of Technology Australia. During his Fellowship Dr. Magnusson is to carry out an investigation of the theoretical basis of chemical bonds with special reference to inorganic complexes under the super- vision of Professor D. P. Craig in Professor C. K. Ingold’s Department at University College London. The Corday-Morgan Commonwealth Fellowship is awarded for post-doctorate or equivalent study in any branch of Chemistry.It is tenable for one year only in some part of the British Commonwealth other than that in which the candidate received hs scientific education. The award is made by the Corday-Morgan Memorial Fund Executive consist- ing of the Presidents and immediate Past-Presidents of The Chemical Society The Royal Institute of Chemistry and the Society of Chemical Industry. Van ’t Hoff Fund.-The Committee of the Van ’t Hoff Fund for the endowment of investigations in the field of pure and applied chemistry invites applica- tions for grants from the fund. The amount available for 1958 is about 1,000 Dutch guilders and applications should be sent by registered post to Het Bestuur der Kon. Ned. Akademie van Wetenschappen bestemd voor de Commissie van het “Van ’t Hoff Fonds” Trippen- huis Kloveniersburgwal 29 Amsterdam before March lst 1958.Applicants must state the amount of the grant desired and the purpose for which it is required . Foreign Members of the RoyaI Swiety.-The following were elected Foreign Members of the Royal Society on May 9th 1957 Hans Albrecht Bethe (Ithaca N.Y. U.S.A.). Distinguished for his contributions to many branches of theoretical physics. Albert Frey-Wyssling (Zurich). Distinguished for his studies on ultramicroscopic structure of proto- plasm and of plant cell walls. Otto Hahn (Gottingen). Distinguished for his work on the chemistry of radioactive substances for the discovery of several radio elements and especially for the discovery of the fission of uranium and thorium.Arne Wilhelm Kaurin Tiselius (Uppsala). Distin- guished for his outstanding contributions in the field of physiochemical analytical procedures and their application to labile molecules of high molecular weight and biological importance. X-Ray Powder Data File.-This File is issued as a scientific service (not a profit-making activity) by JUNE 1957 A.S.T.M. under the auspices of a Joint Committee on Chemical Analysis set up by the American Crystallographic Association American Society for Testing Materials Institute of Physics (Gt. Britain) and National Association of Corrosion Engineers. The major source of information for its cards is the published literature but the sponsors would welcome additional information in particular data which for one reason or another are not given in full in published papers or are merely referred to in passing.The data submitted should contain accurate list- ings of “d” values and intensities of reflections. Other items of information of value are hkl indices and lattice parameters if known radiation used type of X-ray recording employed method of estimating intensities (visual photometric Geiger-coun ter) plus any relevant information concerning the nature and preparation of specimens studied. Data should be sent to and further information may be obtained from Professor G. W. Brindley Editor “X-ray Powder Data File” College of Mineral Industries The Pennsylvania State Univer- sity University Park Pennsylvania U.S.A.Deaths.-The death occurred on June 3rd of Dr. Leslie H. Lampitt a Fellow of the Chemical Society since 1912. Dr. Lampitt was a Director and Head of the Research Laboratories of J. Lyons and Co. He was a past President and past Honorary Foreign Secretary of the Society of Chemical Industry past Chairman of the Chemical Council and at the time of his death Honorary Treasurer of the Inter- national lJnion of Pure and Applied Chemistry. We regret to announce the death of Mr. Arthur Harvey F.R.I.C. editor of the Journal of the Society of Leather Trades’ Chemists on April 27th and of Du.Friend Ebenezer Clark of Morgantown West Virginia U.S.A. who was elected to the Fellowship in 1925. Election of New Fellows.-244 Candidates whose names were published in the Proceedings for April and May have been elected to the Fellowship.Personal.-The University of London will cele- brate Foundation Day on Friday November 22nd 1957 when honorary degrees will be conferred in- cluding the Degree of Doctor of Science upon Sir Alexander Fleck. Sir Harold Hartley has been elected President of the Society of Instrument Technology. Sir William Ogg Director of the Rothamsted Experimental Station has been elected m associate member of the Soviet Academy of Agricultural Scierxes. Mr. J. Boulton has been elected President-Elect of the Society of Dyers and Colourists. At the Ninety-fourth Annual General Meeting of the Institution of Gas Engineers on May 14th Mr.T. A. Yarwood was presented with the Institution Gold Medal. Dr. John A. King has been appointed director of research for Armour and Co. Chicago Illinois. Dr. D. 0.Holland of the Beecham Research Laboratories has been appointed a Director. Mr. D. C.Beese has been appointed by the British Institute of Management as Manager for Scotland and Northern Ireland. Dr. D. R. Llewellyn lecturer in Chemistry in London University and Associate Professor L. H. Briggs of Auckland University College New Zealand have been appointed Professors of Chem- istry at Auckland University College. The following appointments have been announced by the Council of the University of Leeds Dr. G. R. Tristranz as Professor of Leather Industries from October lst 1957; Mu.I. R. McDougdl as Lecturer in Chemical Engineering from September 1st 1957 ; Mr.R. W.Spencer as Lecturer in Chemical Pathology from August lst 1957; Dr. R. J. Williams (at present Turner and hTewall Research Fellow in the Depart- ment of Physical Chemistry) as Brotherton Research Lecturer in Physical Chemistry for one year from October lst 1957. Dr. D. Peters and Dr. J. B. Pridham have been appointed Lecturers in Chemistry at Royal Holloway College London. Dr. J. R. Nicholls formerly Deputy Government Chemist has retired from the Department of the Government Chemist after 46 years of service. Dr. H. G. Smith has been appointed by the Minister of Agriculture Fisheries and Food as the Representative of the Department of the Govern- ment Chemist on the Food Standards Committee in succession to Dr.J. R. Nicholls. A4r. C. W. Cornwell Chief Analyst of A. Boake Roberts & Co. Ltd. will retire in June after 26 years in the service of the Company. The President has congratulated the following on the completion of terms of Fellowship as follows 70 Years of Fellowship Leonard Owen Simmons (London S.E. 1) 60 Years of Fellowsltip Harold Wallis Harrnan (London S.E.1) John Welsh (Llanfairfechan) 50 Years of Fellowship The Hon. Raymond Egerton Hubbard (Winslow) Sidney William Smith (London W.8) PROCEEDINGS OBITUARY NOTICES MARTHA ANNE WHITELEY 1866-1956 A NOTABLE figure in British academic life and a scientist who exercised a progressive influence on the position of women in professional affairs has been removed by the death at South Kensington London on May 24th 1956 of Dr.M. A. Whiteley who since her retirement in 1934 from the post of Assistant Professor at the Imperial College of Science and Technology had by her literary responsibilities de- voted her leisure years to the service of pure and applied chemistry. Born at Hammersmith on Novem- ber 1 lth 1866 daughter of William Sedgwick and Mary (nke Bargh) Whiteley she became a pupil at Kensington High School proceeding thence first to the Royal Holloway College Egham where she graduated in 1890 and then to Wimbledon High School where she served for nine years (1891-1900) as science mistress. For the last two years during which she held that appointment and for a similar period while serving as science lecturer at St.Gabriel’s Training College London she was con- tinuing her studies and investigations as a post-graduate student at the Royal College of Science then administered by the Board of Education but becoming an integral part of the Imperial College when it was constituted a few years later. She was awarded the degree of D.Sc. by the University of London in 1902 and the Associateship of the Royal College of Science in 1903 in which year Professor Sir William Tilden invited her to become a member of the academic staff of the College. She received the title of Assistant in 1904 of Demonstrator in 1908 of Lecturer in 1914 and of Assistant Professor in 1920.Throughout the 31 years of her academic service Dr. Whiteley gave her students much reason to remember not only her skill as a teacher but also her sympathetic interest in their personal aspirations or difficulties. In control she was kindly though firm maintaining discipline with a word or even a glance and engendering a respect and an affection that are still the source of frequent tributes by her former associates. She naturally regarded the welfare of the women students as her special concern sharing in the foundation in 1912 of the Imperial College Women’s Association and presiding over its activities for many years. Meanwhile she steadily pursued her experi- mental investigations which related mainly to the organic chemistry of barbituric compounds and pro- vided an ever-ready source of inspiration and guidance for her research students and junior col- leagues in the laboratories for organic chemistry.During the 1914-1918 war she took a leading part in the small-scale synthesis of certain drugs then urgently required by the medical services of the Armed Forces and participated also in investigations concerning the properties of lachrymatory and vesicant gases. In recognition of these national ser- vices she was in 1920 appointed an Officer of the Order of the British Empire. In 1918 she was elected a Fellow of the Royal Institute of Chemistry and she was the first woman to be elected a member of the Council of the Chemical Society (1928-1931). A dis- tinction which she specially prized was the honorary Fellowship of the Imperial College which was con- ferred upon her in 1945 in recognition of her out- standing services to chemical science in general and to its advancement at the Imperial College in particular.In 1904 Dr. Whiteley together with 18 other women signatories presented to the President and Council of the Chemical Society an appeal for the admission of women to Fellowship of the Society basing the request on the substantial and increasing part played by women in extending the limits of chemical knowledge as shown for example by the number of original papers by women authors accepted for publication by the Society. The sugges- tion had indeed been made more than 20 years earlier and although proposals for action had been rejected in 1880 1888 and 1892 many influential Fellows regarded the new demand with favour while others maintained the contrary view.Legal advice having been obtained the Council proposed to amend the bye-laws accordingly but after rejection of the amendments at an Extraordinary General Meeting no further action was then taken. Four years later however Dr. Whiteley and Dr. Ida Smedley (Maclean) approached their former co-signatories with reference to a petition of similar intent presented by 312 Fellows who asked the Council to ascertain the wishes of the Society as a whole in this matter; in response some 28 women chemists of appropriate status signified their desire to become Fellows of the Chemical Society.A favour- able majority view resulted however only in the offer of membership as “subscriber,” a status which most of the women concerned declined to accept. The fruits of Dr. Whiteley’s endeavours on behalf of qualified women chemists were destined not to be harvested until 1920 for much polemic and delay intervened but the fact that sex equality in scientific JUNE 1957 status is now generally accepted in Great Britain is due in no small measure to Dr. Whiteley and to the men and women associated with her in formulating and presenting the claim with so much skill tact and resolution. When Sir Edward Thorpe undertook to prepare a second edition of his “Dictionary of Applied Chemistry,” he enlisted the help of Dr.Whiteley who continued her work both as a contributor and as an editor when in its turn the second edition was replaced by the third. Later in association with Sir Jocelyn Thorpe she took part in the issue of supple- mentary volumes and in the preparation of the fourth edition of the main work the first volume of which was published in 1937. In her retirement these tasks were indeed labours of love and joy; they gave her the opportunity-intensely desired-to continue in useful service to her fellow chemists and they enabled her to keep in close touch with chemical affairs generally. In 1940 on the death of Sir Jocelyn Thorpe she became editor-in-chief and undismayed by physical disabilities meticulously discharged every duty whether at Imperial College where accom- modation was placed at her command or at her London home which she lost by enemy action or at Cambridge where she enjoyed generous hospitality or in the comfortable apartment in South Kensington where up to a very few months before her death in her ninetieth year she displayed an acute mind a firm hand and a critical eye editing manuscripts and reading proof with almost unimpaired insight and mastery.Unmarried home-loving and bound by strong family ties Dr. Whiteley was nevertheless no recluse; she had travelled abroad and gained that poise and serenity which derive from knowledge of the ways of the world-and wisdom to repudiate them. She was an active member of the British Federation of Uni- versity Women and indeed held one of the five Fellowships which were established by that body in the years 1912-1916.For her Fellowship had a very real and personal significance. As recreations she confessed only to “domestic and social duties” (though by the presentation of the Whiteley cup she encouraged sport in others) and those who enjoyed the privilege of her hospitality cherish memories of her charm and vivacity of her gentle humour and of her deep religious convictions. A. A. ELDRIDGE. J. S. BUCK 1895-1 956 JOHANNES BUCK was born in Liverpool SYLVANDT on October lst 1895 in a family of Norwegian ancestry. His training at the University of Liverpool was interrupted by four years of military service from 1914to 1918 and as a result he did not complete his graduate studies until 1922.In 1921 he was appointed Senior Exhibition Fellow and after finishing his doctoral work under Heilbron worked for the next two years at Oxford with Perkin. In 1924 Buck came to the United States. He was first at Yale as Chiris Fellow in 1925 as lecturer at Bryn Mawr and from 1925 to 1929 as Associate Professor at Duke. In 1929 he became Chief Organic Chemist of the new research laboratories set up by Burroughs Wellcome & Co. (U.S.A.) Inc. at Tuckahoe N.Y. This position he retained until January 1942 leaving to become Associate Research Director of the Winthrop (later Sterling Winthrop) Research Laboratories in Rensselaer N.Y. a posi- tion he held until his death on August 9th 1956.Entry into industrial work did not separate Buck entirely from teaching. From 1931 to 1942 he was a valued member of the Faculty of the Polytechnic Institute of Brooklyn. Later (1952-56) he taught at the Rensselaer Polytechnic Institute near the site of the Winthrop laboratories. Buck’s original chemical activities were centred on alkaloid chemistry Later he engaged in studies of the benzoin condensation in extensive syntheses of isoquinolines ureas barbituric acid derivatives and pressor amines. His operations at Tuckahoe were reported in over seventy papers but this activity went largely underground when in an administrative position. In his own words-it was possible to do a good deal of work still provided it remained anonymous.The sum of Buck’s achievement fell considerably short of his potentialities owing in large part to the readiness with which he could be persuaded to assist almost anyone who requested advice and to his conscientious attention to detail. R. BALTZLY. FORTHCOMING SCIENTIFIC MEETINGS London Monday and Tuesday July 8th and 9th 1957. Symposium “Solvent Effects and Reaction Mechan- ism.” To be held at Queen Mary College. Glasgow Thursday and Friday July 11th and 12th 1957. Official Meeting and Symposium “Recent Advances in the Chemistry of Terpenoid Compounds.” To be held in the Chemistry Department The University. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings.Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Armstrong Robert Sowerby M.Sc. 52 Porter Street Wollongong N.S.W. Australia. Bax Christopher Martin B.A. 32A Stanley Road Hoylake Wirral Cheshire. Boocock John Roger Brooke. 24 Cambridge Avenue Melton Mowbray Leicestershire. Bruck Peter B.Sc. Ph.D. 58 Firtree Estate Thurgoland nr. Sheffield. Burrows William Dickinson B.A. Ph.D. P.O. Box 526 Sheridan Road Saginaw Michigan U.S.A. Butler Kenneth B.Pharm. Ph.C. M.P.S. 12 Windsor Street Beeston Nottingham. Cambje Richard Conrad M.Sc. 63 Grafton Road, Auckland New Zealand.Christie Margaret Isabella B.Sc. M.A. Ph.D. Neale House 138 Huntingdon Road Cambridge. Collis James Gordon B.Sc. 109 Meaford Drive Blurton Stoke-on-Trent Staffordshire. Dandy Alan John B.Sc. 35 Tew Park Road Hands- worth Birmingham 21. Dintenfass Leopold Dip1.-Ing. A.R.A.C.I. 10/234 Campbell Parade Bondi Beach New South Wales Australia. Fahrenholtz Kenneth Earl B.S. Department of Chem- istry University of Rochester Rochester 20 New York USA. Fernelius W. Conrad A.M. Ph.D. 305 Adams Avenue State College Pennsylvania U.S.A. Ferrone Bennie Anthony B.S. 350-B Noyes Laboratory University of Illinois Urbana Illinois. Fowler Sheila B.Sc. Ph.D. 62 Hodge Lane Hartford Cheshire. Gaertner Gerhard B.Sc. Lynwood 2 Ave.de Berrange Fresnaye Cape South Africa. Goodison David M.A. 24 Church Road Cheadle Hulme Stockport Cheshire. Haake Paul Charles A.B. 9 Vincent Street Cambridge 40 Massachusetts U.S.A. Hall Michael Thomas. 67 Minshull New Road Crewe Cheshire. Hazlehurst David Anthony B.Sc. Ph.D. “Crantock,” 12 Maryhill Road Runcorn Cheshire. Huang ThCrbse B.S. Department of Chemistry Univer- sity of Rochester Rochester 20 New York. Jakubovic Armand Otto B.Sc. 43 St. Luke’s Road Maidstone Kent. Kofron William Gerald B.S. Department of Chemistry University of Rochester Rochester 20 New York U.S.A. Labes Mortimer M. A.B. Ph.D. Sprague Electric Company North Adams Massachusetts U.S.A. Leach Howard Frank B.Sc. A.R.C.S. Penpol Hols- worthy Devon.Leicester Jack A. M.1.Chem.E. British Launderers’ Research Association The Laboratories Hill View Gardens Hendon London N.W.4. Longone Daniel T. B.S. Department of Chemistry, Cornell University Ithaca New York U.S.A. Mahesh Virendra Bhushan M.Sc. Ph.D. Department of the Regius Professor of Medicine Radcliffe Infirmary Oxford. Mangaraj Duryodhan M.Sc. Department of Chemistry, The University Manchester 13. Marshall Donald Richard B.Sc. “Rozelle,” 12 North Crescent Ardrossan Ayrshire. Martin-Smith Michael M.Sc. Ph.D. Chemistry Depart- ment The University Glasgow W.2. Mechoulam Raphael M.Sc. Department of Organic Chemistry Weizmann Institute of Science Rehovot Israel. Miles Adrian John. 441 Whitehall Road St. George Bristol 5.Mills Ian Mark B.Sc. D.Phil. Scardroy Townsend Road Streatley Berks. Minifie Bernard Whitley Elliott F.R.I.C. J. S. Fry & Sons Ltd. Somerdale nr. Bristol. Mountfield Brian Arthur B.Sc. 234 Watford Road Croxley Green Rickmansworth Herts. Phillips Leon Francis B.Sc. 92 Mersey Street St. Albans Christchurch New Zealand. Piccolini Richard J. B.S. Department of Chemistry University of California at Los Angeles Los Angeles 24 California U.S.A. Piggin Bruce Paul B.Sc. 154 Tukes Avenue Bridgemary Gosport Hants. Pringle Thomas Grant Paterson. 21 Highfield Drive Bromley Kent. Queen Alan B.Sc. 2 Garage Flats Brockham Park Betchworth Surrey. Riley Brian John B.Sc. 417 Roman Road London E.3. Rivlin Vivian Gerald. 64 Marlborough Mansions, Cannon Hill London N.W.6.Smith Harold John B.Pharm. Ph.D. A.R.I.C. F.P.S. 12 South Road Histon Cambridge. Stove Edward Raymond M.Sc. 61 Linkfield Lane Redhill Surrey. Szirmai Endre M.D. Madhch-ut S.V. Budapest VII Hungary. Tether Leslie Richard. 2 Sybil Road Gloucester. Torrance Anthony Robert. c/o Javens 101 Crofthill Road Glasgow S.4. Triggle David John. 67 Collier Row Road Romford Essex. Tylor Christopher Max Bazett B.A. 23 Hartington Grove Cambridge. Wallis John William B.Sc. The Post Office Weldon, Corby Northamptonshire. Willbourn Anthony Horace MA. D.Phi1. 3 Guessens Walk Welwyn Garden City Herts.
ISSN:0369-8718
DOI:10.1039/PS9570000157
出版商:RSC
年代:1957
数据来源: RSC
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