38 



SCIENCE 



[N. S. Vol. LIV. No. 1384 



Mearrangements of some Tiew Jiydroxamic acids 

 related to heterooyolic acids and to diphenyl and 

 triphenylacetio acid: Laudee W. Jones and 

 Chakles D. Hued. Hydroxamie acids of thio- 

 phene and furane alpha oarboxylie acids yield 

 silver salts of their acyl derivatives which are 

 less readily rearranged than the corresponding de- 

 rivatives of benzhydroxamic acid. Diphenyl- and 

 triphenylacethydroxamio acids were also examined, 

 and it was found that an increase in the number 

 of phenyl groups occasions greater readiness to 

 rearrange. Diphenylacethydroxamie acid is formed 

 by the action of diphenylketene upon hydroxyla- 

 mine — a new type of reaction. Triphenylaeethy- 

 droxamic acid is not produced by the interaction 

 of ethyl triphenylacetate with hydroxylamine, but 

 is quantitatively formed from the acid chloride. 



The hydroxamie acid of cyclopropane carboxylic 

 add and its derivatives: Lauder W. Jones and 

 Alfred W. Scott. The monohydroxamic acid 



HaC H 



/d— CO.NHOH 



was prepared in order to determine what effect 

 the trimethylene ring would have upon the Beek- 

 mann rearrangement of this compound and some 

 of its derivatives. The hydroxamie acid is a 

 colorless solid which melts at 123°. The benzoyl 

 ester (A) C3H,— CO.NHO.CO.C.H, (m. p. 149°) 

 and the acetyl ester (B) O3H5— 00 . NHO . CO . CH3 

 (m. p. 106°), as well as the potassium, sodium and 

 silver salts of these esters were studied. When the 

 salts of (A) were heated gently, they decomposed 

 to give cyclopropane isocyanate and the corre- 

 sponding benzoates. Their relative stabilities in- 

 creased in the order given above. When the 

 salts of the alkali metals were heated with 

 water, they showed a pronounced tendency to hy- 

 drolyze, which made it diiScult to control the re- 

 action so that the usual product of rearrangement, 

 a sym-disubstituted urea, could be obtained. Un- 

 expected stability was encountered in the case 

 of the potassium salt of the acetyl ester (B) 

 which is but little decomposed at 190°. The sil- 

 ver salt of this ester, unliie silver salts, was 

 readily soluble in a mixture of alcohol and water, 

 or in water alone. 



The preparation of phenyl acetylene: John C. 

 Hessler. Nef's method of preparing phenyl 

 acetylene was to heat w-bromstyrene in a sealed 

 tube with alcoholic potassimu hydroxide. He used 

 only a email quantity of alcohol in order to mini- 



mize the yield of the by-product, phenyl- vinyl ethyl 

 ether. The writer's method is to allow the brom- 

 styrene to flow, drop by drop, upon molten caustic 

 potash contained in a flask heated in an oil bath 

 at 200 to 220*. The phenyl acetylene distills 

 over as it is formed, carrying with it only traces 

 of unchanged bromstyrene. Yield: 80 per cent, 

 of the theory of purified product. 



On a quantitative study of the Grignard reagent : 

 H. Oilman, P. D. Wilkinson and W. P. Fishel. 

 In connection with some work on the addition of 

 the Grignard reagent to ethylenic hydrocarbons, a 

 method for the quantitative estimation of this 

 reagent was found desirable. For this purpose 

 a number of methods are being investigated, among 

 them, (1) titration with iodine, (2) an indirect 

 analysis involving the determination of the mag- 

 nesium and alkyl halide actually used, and (3) 

 an extension of the Zerewitinoff method involving 

 the measurement of hydrocarbons given off when 

 the Grignard reagent is treated with a compound 

 containing ' ' active ' ' hydrogen. The first of these 

 methods, that of titration with iodine, has been 

 found unsuitable. In this connection the op- 

 timum conditions for the formation of the Grig- 

 nard reagent are being studied. 



A simple type of glass pressure bottle: E. E. 

 Read. The apparatus consists of a simple adap- 

 tation of the common soda siphon to the pur- 

 pose of a glass pressure flask. 



An indirect method of mercurization of organic 

 compounds and a method of carton linking: Mor- 

 ris S. Kharasch. The method consists of heat- 

 ing the mercury salts of carboxylic acids, which 

 lose carbon dioxide readily, the mercury then tak- 

 ing the position originally occupied by the car- 

 boxyl groups. Also, since the mercury can be 

 readily replaced by a halogen, the method enables 

 one to substitute a carboxyl group by a halogen. 

 It was also found that the mercury compounds 

 thus formed, especially those of the aliphatic 

 series, can be made to split off mercury, thus 

 linking the two carbon atoms. In the aromatic 

 series, in the case of carboxylic acids which do not 

 lose carbon dioxide readily, the mercury usually 

 orients ortho to the carboxyl g^oup. However, 

 if a negative group is present in the molecule, 

 the mercury orients itself ortho to that group, ir- 

 respective of the position of the negative group. 

 In this respect, a number of substituted benzoic 

 acids have been investigated. 



Charles L. Parsons, 

 Secretary 



