2312 usually three) columns, and by comparing the fragmentation pattern in the mass spectrum. In the gas chromatograph-mass spectrometer combination, a Varian Aerograph, Model 204-2, was connected by a low volume heated line, fed through an effluent stream splitter, to the helium concentrator of a Perkin-Elmer-HitachiR M U 6-D. Synthesis of cu,cu,a-Trideuterio-o-xylene. A solution of 2.65 g (0.0175 mole) of methyl o-toluate and 0.6 g of lithium aluminum deuteride (Metal Hydrides) in 10 ml of ethyl ether was stirred at reflux for 12 hr. Work-up with aqueous acid gave 2.14 g (0.0172 mole) of a white solid, mp 31-33” (lit.18 o-methylbenzyl alcohol mp 34”). The crude dideuterio alcohcl(1 g) was added to 20 ml of cold, freshly distilled thionyl chloride, and the solution was slowly warmed to the boiling point and refluxed until gas evolution ceased. Excess thionyl chloride was removed on a rotary evaporator, and small portions of pentane were added and removed under vacuum to flush out the remaining traces of thionyl chloride. The resulting clear oil was dissolved in 20 ml of dry tetrahydrofuran and stirred (18) “Handbook of Chemistry and Physics,” 32nd ed, Chemical Rubber Publishing Co., Cleveland, Ohio, 1950, p 806.
at reflux under nitrogen with 0.26 g of lithium aluminum deuteride. The reaction mixture was acidified, and the product o-xylene was extracted into a known volume of pentane. Comparison of the gas chromatogram of this solution with a standard mixture indicated that 0.76 g of the deuterated o-xylene was present (theory, 0.88 g). The o-xylene was isolated by preparative gas chromatography to ensure purity of the sample. Analysis by mass spectroscopy at reduced ionization voltage showed the o-xylene to be 98% dJ and 2 % d?,with no detectable amounts of d, or do.
Acknowledgments. The support of this research by the National Science Foundation (GP-3496) is gratefully acknowledged. The mass spectrometer used in this investigation was purchased under a National Science Foundation Research Instrument Grant. Mr. John S. Wishnok and Mr. Charles I. Barta participated in the development of the oxygen lamp and in measuring its spectral output.
Photochemistry of Sodium 9-Anthroate in Aqueous Solution’ Anne W. Bradshaw and 0. L. Chapman Coiitributionf r o m the Department of Chemistry, Iowa State University of Science and Technology, Ames, Iowa 50010. Received November 5, 1966 Abstract: The photochemistry of sodium 9-anthroate in aqueous solution has been investigated. Earlier reports that irradiation of sodium 9-anthroate in the presence of air gives photodimer and anthraquinone have been con-
firmed, and carbon monoxide, 10,lO’-bianthrone, and anthracene have also been isolated. In degassed solutions sodium 9-anthroate gives anthrol anion and carbon monoxide. Air oxidation of the anthrol anion is responsible for formation of anthraquinone and 10,lO’-bianthrone. The photochemical isomerization of sodium 9-anthroate to anthrol anion is considered to be analogous to the photoisomerization of 9-nitroanthracene.
R
ecent investigations of vinyl2v3 and ary12s4 nitro compounds have uncovered photochemical rearrangements in which the nitro group isomerizes to a nitrite ester which then gives rise to products. Irradiation (A
