NOTES
2556
Vol. 61
TABLE I to pursue the investigation further and, therefore, SOLUBILITY OF SILICON TETRAFLUORIDE AT ROOM TEM- wish to relinquish the problem to others who may PERATURE (27-33 ") AND TOTAL PRESSURE OF 750-760 M M . Solvent
Methyl alcohol, absolute Methyl alcohol, 94% by wt. Ethyl alcohol, absolute Ethyl alcohol, 96.1% by wt. Ethyl alcohol, 95% (U.S. P.) Ethyl alcohol, 94.3% by wt. Ethyl alcohol, 92.6y0 by wt. Ethyl alcohol, 91.0% by wt. Isopropyl alcohol, 98% %-Butylalcohol, 98% (U.S. P.) Amyl alcohols (fusel oil) Glycol, c. P. Diethylene glycol, c. P. Glycerol, c. P. Acetone, c. P. anhyd. Acetic acid (glacial) Pyruvic acid, tech. (3845%)
Wt. % of cc. solvent SiFd in soh.
G.SiFd100
.. .. 57.2 60.8 61.4 61.5 63.4 63.9 39.4 30.4 20.9
32.8 39.0 36.4 37.8 38.1 38.1 38.8 39.0 28.2 23.4 17.3 26.2 17.6 5.7 3.1 1.1 4.4
be interested in it.
TENNESSEE VALLEY AUTHORITY DEPARTMENT OF CHEMICAL ENGINEERING WILSONDAM,ALABAMA RECEIVED MAY8, 1939
Occurrence of the Syringyl Radical in Plant Products BY EINARWEST,A. S. MACINNES, JOSEPH L. MCCARTHY AND HAROLD HIBBERT
It has now been shown that treatment of jute fiber, rye straw and corn stalks with a 2% solu.. tion of hydrogen chloride in anhydrous ethanol, .. according to the method described for the ethan.. olysis of spruce and maple woods,l gives rise to 3.2 1.1 typical ethanolysis products, namely, ethanol .. lignin and a mixture of volatile oils. The yields In addition to these quantitative data, it was of ethanol lignin and volatile oils are of the same found that silicon tetrafluoride is sparingly soluble order of magnitude as those obtained from spruce and maple woods. The presence of the syringyl in benzene and trichloroethylene, and insoluble in radical has been established in the volatile carbon tetrachloride at room temperature. oils from each of these fibers. Thus, following On the addition of 9% by weight of water to the the procedures previously describedP2a-ethoxysaturated solution in 95% alcohol (U. S. P.), a propiosyringone as the p-nitrobenzoate (m. p. gelatinous precipitate of hydrated silica was 141-142'), syringoylacetaldehyde as the monoformed. However, when the original solution semicarbazone (m. p. 207-208') , and syringaldewas subjected to vacuum distillation at room hyde as the 2,4-dinitrophenylhydrazone(m. p. temperature, silicon tetrafluoride was evolved 235-235.5')) were isolated. Mixed melting points until a solution containing approximately 26.5% with authentic specimens showed no depression. of the gas remained, which corresponds to a mole These, and previous results with hard woods,1'2 ratio of alcohol to silicon tetrafluoride of approxwould seem to point to the presence of syringyl imately 6:l. On adding an equal volume of water derivatives in the lignin constituents of all angioto the residual solution from the vacuum distillasperms, for example as indicated in corn and rye tion, no precipitate formed, possibly because the (monocotyledons) and in jute and maple (disilicon tetrafluoride had combined chemically with cotyledons). the ethyl alcohol. Subsequent addition of a solBrickman, Pyle, McCartby and Hibbert, THIS JOURNAL, 62, uble barium salt precipitated 95% of the fluorine 868(1)(1939). (2) Hunter, Cramer and Hibbert, ibid., 61, 516 (1939); Pyle, as pure barium fluosilicate. This reaction offers a convenient method for preparing barium Brickman and Hibbert, i b i d . , 61, 2198 (1939). DIVISION OF INDUSTRIAL AND CELLULOSE CHEMISTRY fluosilicate of high purity. MCGILLUNIVERSITY RECEIVED JUNE 30, 1939 When saturated solutions in glycol were dis- MONTREAL, CANADA tilled in a vacuum at room temperature, 50 and -~ 100' , the residual solutions contained fluorine equivalent to 26.2, 24.5, and 2.8% silicon tetra- Reaction of p-Fluorophenol with Benzene and Aluminum Chloride fluoride, respectively; on addition of water to BY ARTHUR W. WEST ON^ AND C. M. SUTER them, a precipitate was formed in each case. The above information is of interest in that Recently it was found2 that in the deethylation such solutions in organic solvents may furnish of p-fluorophenetole with aluminum chloride in the basis for the synthesis of organic fluorine benzene solution a by-product was obtained in compounds as well as a means of preparing pure ( I ) Sharp snd Dobme Post-Doctorate Fellow 1938-1939. fluorine salts. However, the authors do not plan (2) Stater, Lawson and Smith, THISJOURNAL, 61, 163 (1939).
