History - People - William Edward Garner

William Edward Garner Tenure: Senior Lecturer 1921-1924 Reader 1924-1927

We know little of Garner and the dates given above, which come from College Records, must be wrong. Garner's first paper (1914) was lists the Birmingham organic chemist Percy Faraday Frankland (the son of the great Edward Frankland who invented the term valency and who made the first organometallic compounds, particularly the pyrophoric organozincs) as one of the authors. In his next paper, written at UCL on the synthesis of amines, Garner thanks the then UCL Head of Department Norman Collie for his interest. Garner's interests then moved steadily across towards physical chemistry, presumably under the guidance of Frederick Donnan, with whom he published one paper. He published papers on thermodynamics, kinetics, catalysis and crystallization. He moved on to Bristol around 1927.

Garner was remembered by Bill Woodings, lab superintendent after the war, as "a mild-mannered sort of bloke".

Publications

• The heats of crystallization of the ethyl esters of the monobasic aliphatic acids. King, Annie M.; Garner, William E.. Journal of the Chemical Society (1934), 1449-56. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 29:335 AN 1935:335 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The thermal data for the Et esters of the monobasic acids between C14 and C30 were detd. These esters exist in 2 forms, one with a vertical and the other with a tilted chain. The form stable at the m. p. possesses a vertical chain when C is greater than 20 and a tilted chain when C is less than 20. The heats of crystn. of the vertical forms vary linearly with C, but there is a change of slope for the tilted forms when C = 20. This is attributed to a change in the mode of orientation of the ester group in the lattice. The vertical forms possess the highest m. p., and this is ascribed to a greater rate of attachment of the chain to the surface of a solid.
• The thermal decomposition and detonation of lead azide crystals. Garner, Wm. E.; Gomm, A. S. Journal of the Chemical Society (1931), 2123-34. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 25:51867 AN 1931:51867 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The critical increments (I) of the rate of thermal decompn. of alpha - and beta -azides were detd. at 210-295 Deg, and an approx. value was obtained for the I of detonation. The temp. coeffs, for alpha -azide were found to be const. (2.43 av.) between 220 Deg and 280 Deg, from which I was calcd. as 47,600 cals. For the beta -azide the av. value of the temp. coeff. between 200 Deg and 270 Deg is 2.06, from which I was calcd. as 38,800 cal. The detonation expts. at 295 Deg and 292.5 Deg give the temp. coeff. as 2.2 for 2.5 Deg, from which I was calcd. as 200,000 cal. (approx.). The greater instability of the beta -form is ascribed to the lower value of its I. It was shown that, at 260 Deg, for crystals of the same area the decompn. is about 20 times as rapid as that of the alpha -form. The detonating temp. of Pb azide is lower in a vacuum than in air. No difference could be detected between the infra-red spectra for the two short axes of these crystals.
• Melting points and heats of crystallization of the normal long-chain hydrocarbons. Garner, Wm. E.; Van Bibber, Katherine; King, Annie M. Journal of the Chemical Society (1931), 1533-41. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 25:42338 AN 1931:42338 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The heats of crystn. of the alpha form of the following hydrocarbons in kg.-cal./g. mol. are: C22H46 11.7; C26H54 14.04; C30H62, 16.45; C34H70 19.11; C35H72, 20.65. The heat of crystn., Q, and Q/T, plotted against, n, the no. of C atoms, gives a linear relationship. Between C20 and C70 the setting points of the hydrocarbons are given by the equation T = (0.6085 n - 1.75)/(0.001491 n + 0.00404). The increment in the heat of crystn. for one CH2 group in the alpha form is 0.608 kg.-cal., and 1.0 kg.-cal. for the beta form. The heat of transition of the alpha -> beta form is 6 to 11 kg.-cal., varying with chain length.
• Melting point curves of the monobasic fatty acids. King, Annie Millicent; Garner, Wm. Edw.. Journal of the Chemical Society (1931), 578-80. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 25:26248 AN 1931:26248 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The entropy change on crystn. can be accurately represented by the equation Q/T = 0.002698n - 0.0061 + 0-00475 Sigma 24n log 10n/(n - 2), where n is the no. of C atoms. In order to make a calcn. of the m. p. of an unknown acid, it is necessary to be able to det. a value for Q. The manner in which the heat of crystn. varies with the no. of atoms in the C chain has not been interpreted theoretically, so that it is only possible to employ an empirical relationship. For acids having more than 12 C atoms, Q increases at the rate of 2.060 cal./g. mol. for every 2CH2 groups added to the chain.
• The heats of association of acetic and heptoic acids in the vapor state. Fenton, Temple M.; Garner, William Edw.. Journal of the Chemical Society (1930), 694-700. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 24:34710 AN 1930:34710 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The heats of assocn. of HOAc find heptoic acid were detd. with a modified form of the app. used by Ramsay and Young and were found to be 13,790 cal. per g. mol. from 110 Deg to 194 Deg for the former and 7050 cal. per g. mol. for the latter between 185 Deg and 230 Deg, this value varying with temp. The decrease in Heat with increase in length of chain accords with the view that linkage occurs through the carboxyl groups.
• The dehydration of copper Sulfate pentahydrate. Garner, Wm E.; Tanner, M. G. Journal of the Chemical Society (1930), 47-57. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 24:22618 AN 1930:22618 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The rates of dehydration of CuSO4.5H2O crystals 0.2-0.5 g. each) are measured in a vacuum at 20-56 Deg, their surfaces being activated to insure an even intersurface from which H2O is liberated) by rubbing (15 min.) with a CuSO4.H2O crystal enmeshed in silk. The partly dehydrated crystals show a core of unchanged hydrate, whose surface runs parallel to that of the original crystal. It is shown experimentally that there is a const. unidirectional stream of mols. from a unit of the CuSO4.5H2O-CuSO4.H2O intersurface to the crystal surface. The dehydration product of the pentahydrate below 46 Deg is CuSO4.H2O; this loses H2O very slowly. On dehydrating at 56 Deg, the first product is CuSO4.3H2O, which does not dehydrate further until all the pentahydrate has disappeared. A plot of log k (k = the velocity coeff. per unit area of intersurface) against the reciprocal of abs. temps. (1/T) shows that the values at 56.0 Deg lie on the same straight line as those of the other temps. The crit. increment is 10,300 cal., and calcd. from this micro = 2.77, which corresponds to one of the vibration frequencies of H2O.
• Alteration in the heats of crystallization of the normal monobasic fatty acids. IV. Garner, Wm. E.; King, Annie M. Journal of the Chemical Society (1929), 1849-61. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 24:562 AN 1930:562 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract cf. C. A. 21, 2874. The heats of crystn. of the following acids are given in cals./g.-mol.; Margaric 12.22; tricosanoic 17.60; pentacosanoic 20.00; behenic 18.75; lignoceric 21.10; that of cerotic acid is 52.25 cals./g. Q. and Q/T when plotted against n give linear relationships. Cerotic acid is an exception but this is a mixt. of at least 2 acids. The equation Tm = (0.9651n-4.49)/(0.002505n-0.0071) has been obtained for the setting points of the odd acids and gives a curve of similar shape to that previously obtained for the even acids. There is a difference of 3 Deg in the convergence temps. of the odd and even acids, which is almost within exptl. error. A detailed study of the transition of the alpha -and beta -forms of the odd acids has been made and the heats of transition alpha -> beta have been measured and found to be const. within the exptl. error (1.55, 1.62 and 1.47 cals./mol. for C17, C23 and C25). For acids above C11 the change beta -> alpha does not occur readily on raising the temp. This lack of reversibility is considered to provide a further example of unilateral equil. The results are correlated with the x-ray measurements of Piper and in agreement with his results, it is shown that metastable forms make their appearance on passing from C11 to C13.
• Effect of the addition of hydrogen and water on the radiation emitted from the carbon monoxide flame. Garner, Wm. E.; Roffey, F. Journal of the Chemical Society (1929), 123-40. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 23:37916 AN 1929:37916 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The addn. of H2 or water decreases the radiation from the flame and increases the speed of flame. The difference between the effects of the two gases is slight. There is a crit. region at 0.02-0.04% of H2, where the radiation falls abruptly, and the properties of the flame undergo a marked change. Radiation-compn. and radiation-speed curves give a break at this point. Logarithmic relationships are found to hold between the speed of flame and the radiation emitted. These apply to mixts. above and below the crit. point. They support the "energothermic" theory of catalysis. The step on the radiation curves is considered to be due to a change in the nature of the chem. reaction.
• The ionization of aromatic nitro compounds in liquid ammonia. II. Garner, William E.; Gillbe, Henry F. University College, London, J. Chem. Soc. (London) (1928), 2889-904. Journal language unavailable. CAN 23:11731 AN 1929:11731 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract cf. C. A. 19, 2588. The velocity of ionization in solns. of m-dinitrobenzene and of m-dinitrotoluene in liquid NH3 was found to follow a first-order law, even in those cases where the ionization did not go to completion. The ionic concns. were detd. by measuring the extinction coeffs. of the colored solns. The ionic concn. at any time was found to be proportional to the cond. The most probable course of the reaction is R(NO2)2 + 2NH3 .dblharw. R(NO2)2.2NH3 .dblharw. R(NO2)2-- + (N2H6)++, the velocity of the reaction being governed by the first step. The color is very probably due to the org. anion R(NO2)2--. The temp. coeff. is that of ordinary chem. reactions. The calcd. crit. increment is 7520 cal. No evidence was obtained for the existence in the solid state of complexes such as R(NO2)2.xNH3.
• The critical increment of chemical reactions. Garner, Wm. Edw.. Philosophical Magazine (1798-1977) (1925), 49 463-5. CODEN: PHMAA4 ISSN: 0031-8086. Journal language unavailable. CAN 19:13942 AN 1925:13942 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract If a given reaction is made up of successive or parallel steps, the failure of the crit. increment calcd. from the temp. coeff. of the total resultant reaction to agree with the activation energy does not necessarily mean the failure of the radiation theory of reaction.
• Alternation in molecular volume of the normal monobasic fatty acids. Garner, Wm. E.; Ryder, E. A. Journal of the Chemical Society, Transactions (1925), 127 720-30. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 19:12901 AN 1925:12901 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract cf. G. and Randall, C. A. 18, 2637. The following d. are reported: C8H16O2, 50.27 Deg, 0.8862; 20.02 Deg, 0.9101. C9H18O2, 50.17 Deg, 0.8813; 15 Deg, 0.9087. C10H20O2, 50.17 Deg, 0.8773; 35.05 Deg, 0.8884. C11H22O2, 50.15 Deg, 0.8741; 30 Deg, 0.8889. C12H24O2, 50.25 Deg, 0.8707; 45.10 Deg, 0.7844. The following figures give the sp. vol. of the solid and liquid acids at the m. p. and of the liquid acids at 50 Deg (the first by the air-thermometer method, the last 2 by the pyknometer method) and Delta -MV at the m. p.: C8H16O2, 0.9737, 1.0951, 1.1283, 17.51; C9H18O2, 1.0104, 1.0979, 1.1347, 13.95; C10H20O2, 0.9870, 1.1220, 1.1398, 23.24; C11H22O2, 1.0121, 1.1232, 1.1440, 20.68; C12H24O2, 0.9971, 1.1423, 1.1483, 29.07. The mean temp. coeff. of the sp. vol. is: solids, 0.00077 per 1 Deg; liquids, 0.00103 per 1 Deg. The mol. vols. for the liquid state at 50 Deg increase by 16.8 cc./g. mol. for each CH2 group added to the chain, whereas those for the solid state alternate in a marked manner as the series is ascended. The area of cross section of 1 mol. in the crystal, 23.8 .ANG.., is non-alternating, hence the alternation in mol. vol. is due entirely to changes in the chain length from member to member. The magnitude of the alteration is in agreement with the views expressed by G. and R. with regard to the constitution of these acids in the solid state.
• The explosion of acetylene and nitrogen. IV. Spectra of explosions of gases containing hydrogen, carbon, nitrogen and oxygen. Garner, Wm. E.; Saunders, S. W. Journal of the Chemical Society, Transactions (1925), 127 77-82. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 19:9928 AN 1925:9928 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract cf. C. A. 18, 2331. The origin of the Swan and CN band spectra has been much investigated and discussed. The results obtained by G. and S. indicate that the presence of both C and N is essential for the production of the CN spectrum. The nature of the spectrum emitted during explosion of C2H2 in O and N is very largely dependent on the ratio of g.-atoms of C to O in the mixt. The Swan and CN spectra appear and disappear together as the O percentage increases. Their disappearance occurs approx. at the concns. for the disappearance of free C and HCN from the final products of the explosion which is when the ratio of O to C becomes unity. Thus the presence of free C is essential not only to the production of HCN but also for both the Swan and the CN spectra. On the mol. collision view of the propagation of the explosion wave, undecomposed C2H2 mols. immediately in front of the wave will be bombarded by swiftly moving mols. of C, H, O, CO, etc., from the explosion wave itself. An O mol., in collision with an C2H2 mol., would be likely to give CO, but no free C, thus (C2H2 + O2 -> 2CO + H2), but any other mol. may bring about the change (C2H2 -> 2C + H2). Hence even in the presence of excess O free C may be momentarily formed, and if the av. life of the C particles, before conversion to CO, is long enough the Swan spectrum may be emitted.
• The heat of adsorption of oxygen by charcoal. Blench, E. A.; Garner, Wm. E.. Journal of the Chemical Society, Transactions (1924), 125 1288-95. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 18:21085 AN 1924:21085 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract "The heat of adsorption of O2 by charcoal for the first small quantities of O2 adsorbed ranges from 60 to 220 cal./mol. of O2 adsorbed as the temp. of adsorption rises from 18 Deg to 450 Deg, and falls off rapidly as the surface becomes satd. The rapid rise in the heat of adsorption is ascribed to changes in the mode of orientation of the O atoms on the surface with temp. At low temp. O2 mols. are adsorbed without chem. change but at high temp. intimate combination occurs with the formation of groups CxOy on the surface. Some of these groups are stable and others unstable at any particular temp. The heat of formation of the stable groups increases with increase in the temp. of adsorption."
• The rapid admixture of hot combustible gases with air. Cray, F. M.; Garner, Wm. E.. Journal of the Chemical Society, Transactions (1924), 125 57-69. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 18:10325 AN 1924:10325 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract Expts. are described in which picric acid in steel containers and mixts. of C2H2 and O in glass bulbs were exploded in a limited vol. of air. The combustion products were analyzed to det. the degree of ignition which had occurred. With picric acid, representing a high explosive, the phenomenon of "after-ignition" is partly detd. by the vol. of air into which the gases are projected, ignition occurring when the ratio of the wt. of explosive to the vol. of air exceeds a definite value. Interpretation of the results is made difficult by the unknown amt. of cooling brought about by disruption of the container. On the other hand, the gaseous products from mixts. of C2H2 and O, because of their much slower rates of explosion compared with the velocity of detonation of high explosives, in all cases underwent partial ignition on admixt. with air. The degree of ignition depended partly on the ratio of the vol. of air to vol. of explosive and slightly on changes in compn. of the gaseous mixt. The ignition is more complete the slower the velocity of explosion of the gases, confirming the view that the ignition temp. of hot gases projected into cold air depends on the rapidity of admixt. The app. and technic are described.
• Note on the effect of a magnetic field on catalysis by ions in the presence of a paramagnetic salt. Garner, Wm. E.; Jackman, D. N. Journal of the Chemical Society, Transactions (1922), 121 1298-9. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 16:22265 AN 1922:22265 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The mutarotation of dextrose and the hydrolysis of sucrose by HCl, both in the presence of the paramagnetic salt MnCl2, were not affected measurably by a magnetic field of 8000 units.
• Catalysis of the mutarotation of dextrose by metals. Garner, Wm. E.; Jackman, D. N. Journal of the Chemical Society, Transactions (1921), 119 1936-48. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 16:5986 AN 1922:5986 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The mutarotation of dextrose, lactose and maltose is catalyzed by metallic Ni, Co, Fe, and Cu. Most of the expts. were performed with dextrose and Ni or Co. The catalyst was added to the dextrose soln. in a polarimeter tube. A second tube contg. the soln. without catalyst was always used as a blank. The tubes were kept at 25 Deg and agitated by rocking. At intervals the rotation of the solns. in the 2 tubes was detd. and the difference taken as the catalytic effect of the metal. The metals are much more active after a preliminary oxidation at 800 Deg followed by reduction in H2. The catalyst is most active when the reduction is carried out at 340-60 Deg; the activity falls off rapidly at higher or lower temps. The catalytic effect decreases with time; it is max. about 48 min. after the beginning of the reaction. After use in one expt. the catalytic-effect is destroyed, but the soln. from one expt. is often capable of catalyzing a fresh dextrose soln. The addn. of NaOH or NH4OH to the soln. does not affect the catalysis, but it is inhibited by N/50,000 HCl. Since the temp. coeff. of the velocity const. is about the same as for the ordinary mutarotation, i. e., doubled for every 5 Deg rise in temp., it is unlikely that the catalysis occurs on the metal surface. Both metal and hydroxyl ions can be detected in the solns. even when dissolved O2 is entirely absent. The OH- concn. obtained is of the order necessary to produce the observed change in the velocity of mutarotation. It is concluded that the function of the metal is to produce OH- by soln. of some of the freshly reduced metal as the hydroxide.
• A metal-glass tap. Garner, Wm. Edward. University Coll., London, Journal of the Society of Chemical Industry, London (1920), 39 347-8T. CODEN: JSCIAN ISSN: 0368-4075. Journal language unavailable. CAN 15:3538 AN 1921:3538 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract cf. C. A. I4, 2567. A joint is made between a metal disk brazed to the metal capillary and a glass disk formed on the end of the glass capillary. The capillary opening is bored straight through the glass disk, but obliquely through the metal disk, and the two are held in eccentric position by screw compression members, so that when the metal capillary with its disk is rotated, the capillaries may be made to communicate, an indicator on the rotating capillary engaging with a pin at this point.
• Effect of the addition of certain fatty acids on the inter-facial tension between B. P. paraffin oil and mercury. Bhatnagar, S. S.; Garner, Wm. E.. Journal of the Society of Chemical Industry, London (1920), 39 185-7T. CODEN: JSCIAN ISSN: 0368-4075. Journal language unavailable. CAN 14:14747 AN 1920:14747 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract Since there is no method yet known for measuring the solid-liquid interfacial tension, the liquid metal Hg was chosen. B. P. paraffin was selected on account of its definite compn. and its high viscosity and b. p., properties which are good characteristics of an oil for lubrication purposes. The fatty acids (oleic, stearic, palmitic and linolic) examd. were pure except the last-named, which was a technical product. The inter-facial tension between Hg and the solns. of fatty acids in paraffin oil was detd. by the dropping pipet method, already used by Donnan (cf. Z. physik. Chem. 31, 42). The bulk of the pipet was filled with carefully cleaned Hg up to a definite mark, and the head of the Hg was always kept const. by an adjustable side-reservoir of Hg (see original for cut). This kept the rate of the falling drop quite const. The end of the capillary dipping in the oil solns. was made smooth and as regular as possible by careful grinding, the inner capillary being protected by sealing wax. The capillary was so narrowed that only 2 drops of Hg were formed in about a min. The rate of formation of the drop must be very slow; otherwise the size and shape will be irregular, as pointed out by Rayleigh (cf. Proc. Roy. Inst. 13, 857). The results obtained with the materials and pipet above indicated were plotted in 4 curves, the 3 involving oleic, stearic and palmitic acids being very similar in nature, especially at higher molar concn., while the linolic acid being impure shows a diminution in the wt. of the drop of Hg very much greater than in the case of stearic and palmitic acids. The curve for oleic acid shows an inflexion pt. at a concn. of about 0. 25 %. Similar abnormalities were observed by Donnan and also by Forch in the case of nonylic acid. The resemblance of these curves to those for fatty acids obtained by Langmuir (J. Am. Chem. Soc. 39, 1879; C. A. 11, 2849) is very striking. It appears that the increased efficiency of a mineral oil as a lubricant to which an org. acid is added runs parallel with a lowering of tension at the metal-oil surface.
• Equilibria across a copper ferrocyanide and an amyl alcohol membrane. Donnan, Frederick George; Garner, William Edward. Journal of the Chemical Society, Transactions (1919), 115 1313-28. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 14:4734 AN 1920:4734 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract Solns. of Na4Fe(CN)6 and K4Fe(CN)6 were sepd. by a Cu2Fe(CN)6 membrane which is permeable to K+ and Na+ ions but not permeable to Fe(CN)6 ions. The solns. were held in contact with the membrane until equil. was reached as shown by the cond. of the solns. Analysis of the solns. at equil. proved the following equation to be true: (Na1+) (K2+) = (Na2+) (K2+) where Na1+ and K1+ are the concn. on one side of the membrane and Na2+ and K2+ are the concn. on the other side of the membrane. Similar expts. were carried out in which amyl alc. was used as a membrane. The actual procedure in this case differed from that used with the Cu2Fe(CN)6. The distribution of LiCl between amyl alc. and water was detd. A soln. of KCl (insol. in amyl alc.) and Licl was then shaken with amyl alc. and the amt. of LiCl in each layer detd. It was then possible to calc. the concn. of the LiCl soln. which would be in equil. with the same amyl alc. soln. The following relation was shown to exist: (Li1+) (Cl1-) = (Li2+) (Cl2-) where Li1+ and Cl1- are the concn. of these ions in the soln. containing KCl and Li2+ and Cl2- are the concns. of the ions in the LiCl soln. LiCl was found to exist as double mols. in amyl alc.
• Preparation of diethylamine. Garner, William E.; Tyrer, Daniel. Univ. Coll., London, Journal of the Chemical Society, Transactions (1916), 109 174-5. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 10:6986 AN 1916:6986 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract A modification of Hofmann's method. While H. could not sep. a mixt. of Et3NH2, Et2NH, and Et3N, G. and T. have found that practically pure Et2NH may be fractionated from a mixt. of the 3. 8000 cc. alc. and 3000 g. EtBr were satd. with NH3 several times during the day, the temp. gradually rizing to 30 Deg, and NH4Br crystg. out. After 24 hrs. the soln, was sepd. from the salt, and the alc. and unchanged EtBr distd. off, adding H2O and boiling to remove the last traces of alc. Concd. NaOH was then added and the amines distd. off. The alc. NH3-EtBr was used in the prepn. of a new lot. Using a 10-bulb column, there was no difficulty in sepg. the amines. Yields, 10.9% EtNH2, 17.9% Et2NH, 19.1% Et3N. About 80% of the Et2NH (b. within 1 Deg) can be obtained by 2 fractional distns. The crude EtNH2 fraction was worked up as follows: 500 g. (containing about 10% Et2NH) were dissolved in 2500 cc. alc. and 1000 g. EtBr added, cooling with ice. After 24 hrs. 2oo g. NH4Br were added to fix any free amines present, and the soln. was treated as above. Yields, 38.7% EtNH2, 30.1% Et2NH, 17.3% Et3N. As the EtNH2 can be again used, about 50% of this can be converted into Et2NH. New model to illustrate the Walden inversion. Garner, William E.. Proceedings of the Chemical Society, London (1914), 29 198-201. CODEN: PCSLAW ISSN: 0369-8718. Journal language unavailable. CAN 8:22687 AN 1914:22687 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R))
• Action of thionyl chloride on lactic acid and on ethyl lactate. Frankland, Percy F.; Garner, William E.. Birmingham, Journal of the Chemical Society, Transactions (1914), 105 1101-15. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 8:16061 AN 1914:16061 CAPLUS (Copyright (C) 2010 ACS on SciFinder (R)) Abstract The action of SOCl2 and Ag2O upon optically active HO compds. falls into 2 classes, in both of which inversion occurs: (1) l-OH -> l-Cl -> d-OH. (2) l-OH -> d-Cl -> d-OH. A study of lactic acid shows that the reaction belongs to (2). The complete analogy between the transformations of malic and lactic acids may now be regarded as established. 38 g. MeCH(OH)CO2H ([alpha ]D18 1.68 Deg), heated with 116 g. SOCl2 3 hrs. at 95 Deg and then 8 hrs. at 113 Deg, gave l-chloropropionyl chloride (A), b. 110-3 Deg, [alpha ]D18 0.2 Deg. (In the work no attempt was made to isolate optically pure substances.) This gave l-chloropropionic acid, [alpha ]D17 -2.36 Deg. Ethyl ester (D), b746 143.5 Deg, [alpha ]D17 -2.92 Deg. When 20 g. MeCH(OH)CO2H and 65 g. SOCl2 are heated 3 hrs. at 100 Deg (bath temp.) and 6-7 hrs. at 105-8 Deg (temp. of liquid not over 97 Deg), chlorosulfinyllactyl chloride (B), MeCH(OSOCl)COCl results, pungent smelling liquid, b12 72.5 Deg, alpha D 42 Deg, fumes in the air. It decomps. very slowly at 100 Deg but at 125 Deg readily gives (A). (B) cannot be prepd. by the action of SO2 or SOCl2 upon (A). MeCH(OH)CO2H and SOCl2 heated at 110-15 Deg for 16-17 hrs. gives a mixt. of (A) and chloropropionyllactyl chloride, MeCH(OCOCHClMe)COCl, b13 93-4 Deg, alpha D 3.60 Deg. It is not changed by further b. with SOCl2. Free acid, m. 48-50 Deg, [alpha ]D58 4.04 Deg. 22 g. SOCl2 and 14.5 g. MeCH(OH)CO2Et, heated 2 hrs. at 100 Deg, gave ethyl chlorosulfinyllactate (C), b12 96.5-7 Deg, [alpha ]D18 77.62 Deg. It fumes in the air and is decompd. by H2O. Heated with MeCH(OH)CO2Et 1.5 hrs. at 120-5 Deg, it gives ethyl thionyllactate, SO(OCHMeCO2Et)2, b13 167 Deg, [alpha ]D15 42.64. It is not affected by cold alk. With SOCl2 at 100-10 Deg it gives (C). C5H5N.HCl acting upon (C) 6 hrs. at 80 Deg gave (D), [alpha ]D16 -3.82 Deg. 4.5 g. (D) and 5 g. C5H5N.HCl heated 19 hrs. at 105 Deg gave an inactive ester. PhNH2.HCl and (C) heated 8 hrs. at 90-100 Deg gave (D) with [alpha ]D20 -4.32 Deg and -4.76 Deg. PhNH2 and (C) give a different product, probably MeCH(OSONHPh)CO2Et.

This page last modified 20 September, 2010