July 8, 1921] 



SCIENCE 



35 



tertiary butyl alcohol. Analytical data show its 

 composition to be CuHuO^Br,. 



Trihalog en-methyl reactions. IV. Tetrachloro- 

 suc<yinie acid: Howard Waters Doughty and 

 Benjamin Freeman. Tetrachlorosuccinic acid ia 

 formed by the action of trichloroacetic acid on 

 copper dust in benzene solution. It is a hygro- 

 scopic solid which is not very stable, being easily 

 hydrolyzed. The aniline salt (m. p. 149°) and 

 ethyl ester (b. p. 156°/13 mm.) are described. 

 Ammonium trichloroacetate reacts vigorously with 

 copper in aqueous ammonia, losing two atoms of 

 chlorine per molecule. This action also takes 

 place still more vigorously with cadmium and 

 zinc, but not with silver. 



Spiro-pyrimidines. II. Cyclohexane-l, 5-spiro- 

 pyrimidities : Arthue W. Dox and Lester Todes. 

 Cyclohexane-l, l-dicarboxylie ester, prepared by 

 condensation of 1, 5-dibromopentane with ethyl 

 malonate, condenses with urea and with guanidine 

 to form oyclohexane-1, 5-spiro-pyrimidines. These 

 products are very similar in their properties to the 

 corresponding cyclobutane-1, S-spiro-pyrimidines 

 previously described by the Writers. In certain 

 respects they resemble also the dialkylbarbituric 

 acids, but differ from the latter in having a car- 

 bon atom common to two rings. 



Spiro-pyrimidines. III. Cyclopropane-1, 5-spiro- 

 pyrimidines: Arthxjb W. Dox and Lester Yoder. 

 Cyclopropane-1, l-dicarboxylie ester, prepared by 

 condensation of ethylene bromide and ethyl malo- 

 nate, might be expected to condense with urea 

 and substituted ureas and yield spiro-pyrimidines 

 analogous to those obtained from cyclobutaue- 

 aud cyclohexane-l, l-dioarboxylic esters. Condensa- 

 tions with urea and with guanidine were readily 

 effected, but the products were invariably amor- 

 phous, insoluble substances of great stability. 

 Analyses showed the same percentages of nitrogen 

 as those calculated for the simple spiro-derivatives. 

 It is probable that the cyclopropane ring opens 

 and two or three molecules unite to form a 

 cyclobutane or cyclohexane nucleus with two or 

 three barbituric acid groups attached. The poly- 

 mer obtained from urea could not be hydrolyzed 

 by long boiling with concentrated hydrochloric 

 acid. Hydrolysis by means of sodium hydroxide 

 gave an acid which lost carbon dioxide on heating, 

 with formation of a crystalline acid, of melting 

 point 151° and neutralization equivalent 86. 



Pyrimidines from dialkylmalonio esters and ben- 

 samidine: Arthxir W. Dox and Lester Todeb. 

 In the presence of sodium ethylate at 70-75°, di- 



alkylmalonio esters condense with benzamidine to 

 form derivatives of tetrahydropyrimidine. The 

 dialkyl-malonio esters used were the dimethyl, di- 

 ethyl, dibutyl, diisoamyl, and dibenzyl. These all 

 gave white products. The corresponding mono- 

 alkyl derivatives were bright yellow. The latter 

 may therefore be regarded as possessing the tauto- 

 meric enol structure. 



An electrocliemic-al study of certain reversible 

 reductions: J. B. Con ant and H. M. Kahn. 



The reactivity of the chlorine atom in the nitro- 

 benzyl chlorides: J. B. Conant and S. S. Negus. 



The 1 . 4-addition of phosphenyl chloride : J. B. 

 Conant and S. M. Pollack. 



A comparative study of ring stability: Nao 

 Uyei and Oliver Kamm. 



Investigation of isomerism in the diphenyl series : 

 J. H. Waldo, C. S. Palmer and O. Kamm. Fix- 

 ation of the benzene nuclei in diphenyl derivatives 

 according to the Kaufler-Cain theory leads to the 

 possibility of optical isomerism in the case of cer- 

 tain diphenyl derivatives. Salts of diphenyl-0- 

 carbsxylic acid with optically active bases were 

 subjected to crystallization but there was found 

 no conclusive evidence of this type of isomerism. 

 The investigation has been extended also to ben- 

 zidine derivatives, particularly to benzidine di- 

 sulfonie acid. The negative results obtained fail 

 to support the recently proposed theories con- 

 cerning the structure of the diphenyl derivatives. 



The action of hydrogen sulphide upon tri-nitro- 

 toluene: F. J. Moore and E. H. Huntress. In 

 this reaction Cohen and Dakin observed the for- 

 mation 2-6-di-nitro 4- tolyl hydroxylamine which 

 when boiled with hydrochloric acid yielded a color- 

 less solid which they assumed to be the amine, 

 but later denied this without further characterizing 

 it. They subsequently obtained the true amine 

 by the addition of hydriodic acid. The observa- 

 tion that the above hydroxylamine yields this 

 same compound when treated with silver nitrate 

 raised the suspicion that it might be the azoxy 

 compound. This accounts for the oxygen which 

 ought to have been evolved in the original equation 

 of Cohen and Dakin^ for we have shown that 2-6 

 dinitro-4-tolyamin6 is formed at the same time. 



The constitution of the secondary product in the 

 sulphonation of cinnamic acid: F. J. Moore and 

 EuTH M. Thomas. The principal product of the 

 reaction is para-sulpho-cinnamic acid. With this 

 is formed an isomer whose barium salt is much 

 more soluble. This has hitherto been variously de- 



