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ited per coulomb, grams per ampere hour, pounds per 1,000 ampere hours, and several reciprocals and derivatives of these. They are given for each of the separate valencies which an element may show, or for the changes of valency it may undergo. A list of the elements with their practical valencies, compiled by J. W. Richards, accompanies the table. By practical valency is meant the apparent valency of an element in a compound irrespective of any theory as to structural formula or double linkings ; e. g.,Pb, tetravalent in PbO, ; C, univalent in C,H,. This idea is an application to electrolysis of 0. C. Johnson'stheory of and - bonds. T h e illustrative examples given are numerous and well chosen, and will interest any chemist having to make electrochemical calculations. J. W. RICHARDS.
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ORGANIC CHEnISTRY. On Sodium Phenyl and the Action of Sodium on Ketones. BY S. F. ACREE. , A m . Chem. J., 29, 585-60g.-Sodium phenyl was prepared from mercury phenyl and sodium, and found to react with alkyl, aryl and acyl halides, with ketones and other reagents, giving practically the same products as are formed when these substances are treated in ether solution with brombenzene and sodium, from which it is concluded that in thosereactions where brombenzene and sodium are used (Fittig's, Frey's, KekulC's, Wurtz's reactions), sodium phenyl is the intermediate product. EXPERIMENTAL. Preparation of Sodium Phenyl.-Mercury phenyl was dissolved in dry benzene or ligri'on and treated with fine sodium wire. Sodium amalgam collects on the bottom of the flask, while sodium phenyl remains suspended in the solution as a light brown powder. Sodium phenyl is rapidly decomposed by moisture and soon takes fire when exposed to the air on filter-paper. Sodium phenyl reacts with ethyl bromide or ethyl iodide to give ethylbenzene, and small amounts of benzene and ethylene ; with isoamyl iodide, it gives isoamylbenzene, isoamylene and benzene ; with benzyl chloride, diphenylmethane and stilbene ; with brombenzene, diphenyl and a resinous liquid (not identified) ; with benzophenone, a nearly quantitative yield of triphenylcarbinol ; with benzoyl chlooride, triphenylcarbinol and a little benzoic acid ; with b e n d , phenylbenzoin, triphenylcarbinol and benzoic acid , and the same products are obtained by the action of brombenzene and sodium upon benzil. Phenylbenzoin, (C,H,), C ( O H ) CO C,H,, is insoluble in water, readily soluble in ether, alcohol or hot ligroin, crystallizing from the latter in radiating needles, m. p. 87'. It is decomposed into benzhydrol and benzoic acid b y the action of methyl alcoholic potash. A blood-red color is produced when its solution in concentrated sulphuric acid is warmed, indicating dissociation into diphenylmethylene and other products. Heated for three hours at 240' in a stream of oxygen, in a long tube, it gave tetraphenylethylene, benzoic acid and benzo-
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Review of .4inericait Chemical Research.
phenone. The Action 0f'Bt.onzbenzene a d Sodium on Benzpinacone gives triphenylcarbinol and benzhydrol. Sodium phenyl reacts with CO, to give a good yield of benzoic acid; with chlorcarboizic ethev, it gives triphenylcarbinol and only a small amount of benzoic ether. The r 4 ~ t i o i zof Brombeizzene aiid Sodizrm o x Benzoic Ether results in the formation of triphenylcarbinol, triphenylmethane, benzophenone, and occasionally benzoic acid also. The Action of a-B),oinizaphthale)ie aizd Sodium oft Beizaojheizoiie gives benzoic acid, naphthalene and n-N~$/zt_lild~hei~'lcar6inol. The latter is also formed by the action of brombenzene and sodium upon a-naphtylphenylketone. I t melts at I 35', is insoluble in water or ligro'iti, but easily soluble in ether or alcohol. The Action qf $-B~oi)zfolrie?te and Sodiitnt 011 Be~im$heno~ic gives a poor yield of $-tolyldiphezlylmethane. This same substance was also prepared by the action of brombenzeiie and sodium on $-tolylphenylketone. No #-tolyldiphenylcarbinol appears to be formed in either case.-Thc L'.1Tfi0i201Sodiiitiz 012 Ketones.-It is shown that the experimental results are best explained by the hypotheses and formulas of Nef. The A c f i o i ~of Sodi2~112012 Benzophenoize gives heuzpinacone and benzhydrol. The Actioiz of Sodium aizd C02o n Reii~ophci20?1egives benzilic acid. O I L the Isomei-ic Dia c e ~ l d i o , ~ ~ , s f i l b e )-Thiele's zes. lower melting isomer is shown to be identical with Xef's diacetyl dioxystilbene. When pure it melts at I I ~ ' , not at 110' as given by Thiele. 11. T.BOGERT.
The Action of Zinc on Triphenylchlorrnethane. (Second paper). BY JAVES F. NORRIS. Am. Chem. J . , 29, 609-616. T h e first paper upon this subject by Norris arid Culver (Am. C h e m J . 29, 129 (1go3)), was criticized by Gomberg (Zbid., April 1903). T h e present paper is a reply to Gornberg. The author is of the opinion that Goniberg's article was evidently writteri after a very hasty reading of the experimental evidence submitted, that his criticisms are not well founded, and that his explanations of the results obtained by Xorris and Culver are not in accord with the facts. Data in support of the author's position are gireii in full, classified under the headings : [I) Action of Sodium ; ( 2 ) Is the Reaction Quantitative? ; j'( Action of 'Zinc i l ~ Ethyl Acetate ; (4) A4bsorptionof Oxygen ; and ( 5 ) Yield of the Peroxide. I n conclusion the author says : I believe that not a single point brought out by Gomberg has a bearing on our experiniental work and conclusions.'' 34. T. BOGERT. Upon the Structure of the Starch ilolecule. BY F. E. HALE. School ojMi72es Quart., 24, 14j-171.--A review of the results secured by the various investigators who have worked in this field, and the development of a constitutional formula for the starch molecule based upon these data. T h e author believes the structural formula which he proposes to be "an appropriate graphical
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representation of the facts concerning starch, because it explains so many results of starch hydrolysis ; molecular size, intermediate production of maltodextrins, dextrins with or without reducing power and of various rotatory powers, hydrolysis by acid, alkali, or other reagents, hydrolysis of amidulin by iodine, a possible explanation of the formation of the red and blue iodides, condensation into larger bodies and into insoluble starch cellulose, and a residue not easily attacked by diastase. It brings into harmony the results of Brown and Heron, Brown and Morris, Herzfeld, Musculus and Griiber, Bondonneau, Lintner and Dull, Scheibler and Mittelmeier, Lintner, O'Sullivan, Johnson, Mylius, Girard, and many others, including a portion of Syniewski's work." (The formula is too extensive to permit of reproduction here.) M. T. BOGERT.
Further Consideration of Isocinnamic Acid. BY A. MICHAEL W. W. GARNER. Ber. d. chem. Ges., 36, goo-go8.-It has been shown in a previous paper that when an alcoholic solution of P-bromallocinnamic acid is boiled with zinc dust, there is formed, in addition to the ordinary and the allocinnamic acids, a very small amount of a lower melting substance (m. p. 36') which was regarded as a third stereomeric cinnamic acid ( " isocinnamic acid " ), and which agreed in many respects with the isocinnamic acid obtained by Liebermann from cocoa nibs. As it was possible that the authors' isocinnamic acid might be made up of hydrocinnamic and allocinnamic acids, a mixture of these two was prepared and found to resemble it closely in properties. T h e work has not been completed because recent attempts to prepare the substance in quantity have failed. T h e authors, therefore, agree with Liebermann that the existence of isocinnamic acid " as a chemical individual has not as yet been conclusively demonstrated, although certain facts have been observed for which a satisfactory explanation is still lacking. EXPERIMENTAL. By reducing P-bromallocinnamic acid with zinc dust and alcohol and separating the acids formed by the different solubility of their barium salts in methyl alcohol, small amounts of low melting acids were obtained (m. p . 36'-38', 43'-45', etc.). Salts of Isocinnamic A n Z - A n i l i n e salt ; needles (from ligroin), m. p. 83', giving allocinnamic acid (m. p. 68') when decomposed with sodium carbonate solution. B a r i u m salf ; leaflets, easily soluble in water. Calcium salt ; its aqueous ,solution on acidifying gives S a l f s of Aiiocinzamic Acid.-Barium an acid melting a t 38'-39'. salt ; crystallizes from water in prisms. Calcium salf ;fine needles, behaves in a peculiar manner with acetone. S a l f s of Hydrocinnamic Acid-The properties of the barium and calcium salts are recorded. Mixture of allo- and hydrocinnamic acids. These acids were mixed in various proportions and the melting-points of the mixtures are tabulated. A mixture containing about 73 per cent. of the allo and 27 per cent. of the hydro acid melts a t 37'-38'. AND
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Review of American Chemical Research.
A mixture of 69 per cent. allo and 31 per cent. hydro acid was converted into barium salt, which, dried and pulverized, dissolved completely in an equal weight of methyl alcohol, and when acidified yielded a product melting a t 36'. T h e defectioz of h p 3 0 c i m a m i c atzd nllocinizamic acids when present together can be accomplished by changing the allo to the ordinary cinnamic acid, the latter being almost insoluble in ligroin, while hydrocinnaniic acid dissolves easily in this solvent. Isociiinaiiiic acid when treated thus gives results almost identical with those obtained from a mixture of allo- and hydrocinnamic acids. I t is also possible to determine allocinnamic acid in presence of hydrocinnaniic by titration with potassium permanganate solution under suitable conditions. A combustion of isocinnamic acid (froin /3-bromallocinnamic) gave figures agreeing more closely with those calculated for a mixture of 80 per cent. allo acid with 2 0 per cent. hydrocinnamic than with the theory for isocinnamic acid. M.T. BOGERT. On Tetraphenylmethane. BY pvl. GOMBEKG A N D H. IV.BERGER. Bey. d. chenz. Ges., 36, ro88-1ogz.--In 1697, Goniberg publishecl an article upon the preparation of tetraphenylinetliane from triphenylmethanazobenzene. A further study of this hydrocarbon ivas contemplated, to establish its character more satisfactorily, and certain work was done in this direction. The preparation of tetraphenylmethane recently by Ullniann and hliinzhuber, hon-ever, and the identity of their product with thatobtained by Goniberg, renders a continuation of this work unnecessary. The authors, in discontinuing this line of investigations record the experiments already carried out. EXPEKIXENTAL. Tyi#htwpl?1zef/zane/~drazobe7zzeiie, (C,H,),CNHKHC,H,, is best prepared by the action of triphenylchlormethane upon phenylhydrazine in absolute ether solution, the yield of crude product being 90 per cent. of the theory. From hot absolute alcohol, it separates i n nearly colorless crystals, in. p. I 36'-137 '. Tr2#/ze1zyl?)zefhnizazobetrzeiie, (C,H,),C.N : N.C,H,.-The hydrazo body is best oxidized by dissolving it in ether atid passing in nitrous vapors. Evaporation of the ether leaves the azo compound iii beautiful yellow crystals melting with decomposition at 113'-I 14'. I n several cases, quantitative yields were secured. Tefra#henylimt/zam.-Tlie finely pulverized azo body, mixed with threeor four volumes of pure dry sand, is added carefully to a distilling flask kept at 100' on the oil-bath, and through which a current of carbon dioxide is kept constantly passing. The tetraphenylmethane is extracted from the mass with benzene, the yield being usually only 2 to j per cent. Recrystallized from benzene, it becomes snow-white, and melts at 281.5'-282~ (uncorr.). I t is identical with the product obtained by Ullmann and Munzhuber. Nilro derivative.-By dissolving tetraphenylmethane in cold fuming nitric acid, a trinitro derivative is obtained which, when crys-
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tallized froni benzene and then from ethyl acetate, forms faint Reduced with zinc dust, yellow crystals melting a t about 330’. a fuchsine-colored solution results, apparently showing the same absorption spectrum as the dye-stuff prepared from triphenyln.ethane. M. T. BOGERT.
BIOLOGICAL CHEMISTRY. The Influence of Formaldehyde on the Action of Certain Laking Agents and on Coagulation of Blood. BY CHARLES Physiol.,9 , 187-rg8.-Coagulation CLACDEGUTHRIE. Am. 1. is retarded in blood drawn into solutions of formaldehyde in proportion to the amount of formaldehyde present in the resulting mixture. Formaldehyde in sufficient amount prevents coagulatioii indefinitely, but the amount necessary to do this varies with different aninials of the same species. I n eight experiments, seven dogs and one rabbit being used, the amount necessary t o prevent coagulation ranged from I part of formaldehyde to 66.6 parts of blood to I : 400, and gave an average of I : 1 8 5 . 5 . Amounts of formaldehdye, too small to prevent coagulation, prevent the clot from advancing beyond a delicate jelly-like stage, for a period proportionate to the amount of formaldehyde present. T h e onset of spontaneous laking a t room temperature js not markedly delayed by small quantities of formaldehyde, but, once begun. it proceeds much more slowly than in normal blood. Rabbit’s blood plus formaldehyde, in the proportion of I : 1000, is moderately laked by dog’s serum. Large amounts prevent laking. Dog’s serum plus formaldehyde in the proportion of I : 2 0 0 0 or less, still retains its power of laking rabbit’s corpuscles, the amount of laking depending on the proportion of formaldehyde added. Serum from blood drawn from a dog after injection of formaldehyde in the proportion of I : 1500, lakes rabbit’s corpuscles as energetically as serum from blood drawn before the injection. Mixture of formaldehyde bloods and sera, containing more than enough formaldehyde to prevent biological laking, are rapidly and strongly laked by water or sapotoxin solution in 0 .g per cent. sodium chloride solution. Spectroscopically, no obvious change js discoverable in the haemoglobin when formaldehyde is added to blood in the proportion of I : 166, after a period of four days, or after the action of smaller amounts for longer periods of time. Blood can be well preserved for a number of days a t room temperature by adding potassium oxalate in sufficient amount to prevent coagulation, and formaldehyde in the proportion of I : 1000 : 500 or more, to retard F. P. UNDERHILL. laking and putrefaction. The Artificial Method for Determining the Ease and the Rapidity of the Digestion of neats. BY HARRY SANDS GRINDLEY AND TIMOTHY MOJONNIER. Studies U?ziz~. / h h o i s , I, No.
