COMMUNICATIONS TO THE EDITOR
1382
VOl. 57
67 g. of the anilide. Reaction of the acid anilide steam-bath. At the end of an hour the material with phosphorus pentachloride followed by re- in the flask is recrystallized from hot water. duction of the product by stannous chloride and Using this method as it stands, repeated preparahydrogen chloride in absolute ether yielded the tion shows large amounts of tars which obliterate new phenanthrene aldehyde 1-phenanthraldehyde much of the yield. Oxidation of the catechol (m. p. 110-111'; yield, 65%). These reactions must also be repressed for greater yields. To now make it possibletopreparemany 1-substituted carry out this purpose the following method was phenanthrene derivatives hitherto difficult to used. Fifty grams each of monochloroacetic acid, obtain, and we are engaged in the preparation of such compounds. Reduction of the aldehyde catechol, and freshly distilled phosphorus oxychloto the carbinol (m. p. l65"), followed by a ma- ride were mixed together in a one-liter shortlonic ester condensation with the carbinol bro- necked flask fitted with reflux condenser and a mide (m. p. 97") gave P-( 1-phenanthry1)-propionic tube through which sulfur dioxide was passed. acid (m. p. 189-189.5'); experiments on the cycli- A tube was attached to the end of the reflux conzation of this acid are not yet complete. denser to lead away hydrogen chloride gas evolved The excellent researches of Cook and co- in the reaction, and the sulfur dioxide. After the workers [Cook, Dodds, Hewett and Lawson, flask was filled with the sulfur dioxide from a tank, Proc. Roy. Soc. (London), 114, 278 (1934)l have heating was started, a steady stream of gas always shown that oestrogenic property is possessed by a flowing. At the end of an hour heating was variety of polycyclic compounds; and we are stopped, the purple crystals of crude chloroacetohaving the keto-cyclopentenophenanthrenesand catechol crystallized from hot water, decolorized derivatives tested for this property. We have with acid, Norite and sodium sulfite, and again also prepared three 1-hydroxy-1-alkyl-l,2,3,4-crystallized. The light violet tinged crystals were tetrahydrophenanthrenes (111)in crystalline state washed with absolute alcohol, and finally ether. in which the alkyl group R is methyl (m. p. 86- The yield was 53.6 g., m. p. 173". Without these S6.5'), ethyl (m. p. 57-57.5') and n-propyl (m. p. modifications, namely, the sulfur dioxide atmos86-87',) ; these compounds likewise are being phere and freshly distilled phosphorus oxychlotested for oestrogenic activity. ride, the yield was 8.3 g. R
OH
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COLUMBIA UNIVERSITY HENRYD. HOBERMAN NEWYORKCITY RECEIVED JUNE15, 1935 THE RAMAN SPECTRUM OF RUBBER
Sir: It has been previously reported that the Raman (111) effect is exhibited by rubber as a continuous scatThe physiological tests are being made by Dr. tering together with the presence of broad bands James Bradbury' at the University of Michigan [Franklin and Laird, Phys. Rev.,36, 147 (1930); Hospital. The details of the experiments will Busse, J. Phys. Chem., 36, 2862 (1932)l. Busse be published later. attributed this result to the viscosity of the soluCHEMISTRY LABORATORY W. E. BACHMANN tions or to the possibility that the rubber groups UNIVERSITY OF MICHIGAN ANN AUBOR,MICHIGAN respond to a wide range of frequencies. However, RECEIVED JUNE 13, 1935 viscous solutions of polysterol in carbon tetrachloride give a line spectrum [Signer and Weiler, THE PREPARATION OF Helv. Chim. Acta, 15, 649 (1932)]. As to the MONOCHLOROACETOCATECHOL second explanation, this does not seem to be the Sir: nature of the Raman effect [Bar, Helv. Phys. In the synthesis of adrenaline according to the Acta, 4, 369 (1931); B&, 2. Physik, 79, 455 method of Stolz [Ber., 37,4149 (1904)l the prepa- (1932)J. The Raman effect has been investiration of monochloroacetocatechol is necessary. gated extensively for terpenes other than rubber. Chloroacetic acid, catechol and phosphorus oxyThe bands and continuous background for chloride are mixed together and refluxed on the rubber appear to be due to fluorescence of im-
