1014
INDUSTRIAL AND ENGINEERING CHEMISTRY
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2 0 40 60 80 100,120 140 160 Temperature - C.
FIGURE 5 . EFFECT OF ADDITIONAGENTSON COEFFICIENT OF STATIC FRICTION A. B.
C.
Menthol m-Dimethylaminophenol p.4minophenol
I
.O 6
20 40 60 80 100 J20 140 160
Temperature - C. FIGURE 6. EFFECTSOF ADDITIONAGENTSON COEFFICIENT OF STATIC FRICTION A. p-Hydroxydiphenyl E . p-Cresol
D.
u-Naphthol
F.
1,5-Dihydroxynaphthalene
E. Thymol
properties of the adsorbed film, or both. For instance, a-naphthol has very little beneficial effect while P-naphthol very greatly increases the lubricating power both at room temperature and a t elevated temperatures. The inhibition of the decrease in “oiliness” on heating may be due to the action of the addition agents as negative catalysts in the oxidation of the oil; this hypothesis is supported by the fact that most of the substances that have beneficial effects are known to act as antioxygens. The use, in lubricating oils, of addition agents that lower the coefficient of static friction a t ordinary temperatures and prevent the rise in the frictional coefficient a t higher temperatures probably has very considerable commercial advantage. The addition of these substances in the small amounts required to improve the lubricating characteristics of the oil would not add appreciably to the cost of manufacture of the lubricant nor should it in any way affect unfavorably the other characteristics of the oil. The use of oil containing
C. a-Naphthylamine D . Cyolohexanol
such addition agents should be of particular advantage in the lubrication of slow-moving machine parts or of bearings on which it is difficult to maintain continuously an excess of oil, as well as on bearings that are operated intermittently and are started and stopped frequently. The advantage would, perhaps, be less evident when the lubricant is used on bearings that are operated at high speed and with flood lubrication, although even under such conditions the addition to the oil of a substance that increases its lubricating power should be of some benefit. LITERATURE CITED (1) Hardy, chapter on “Friction, Surface Energy, and Lubrication” in Alexander’s “Colloid Chemistry,” Vol. I. Chemical Catalog Co., N. Y . , 192G. (2) Rhodes and Allen, IND.EXG.CHEM.,25, 1275 f1933). ( 3 ) Wilson and Barnard, Ibid., 14, 653 (1922). RECEIVED April 9, 1934.
The ketone was purified by distillation under reduced pressure and by two recrystallizations from ethanol. The melting point was 68” to 69” C. best yields of laurone reported in the literature are 10 SHERLOCK SWANN, JR., E. G. APPEL,AND S. S. KISTLER to The 30 per cent from lauric acid over thoria a t 400” C. (S), from lauric acid with phosphorous pentoxide ( 2 ) , and 91 per University of Illinois, Urbana, Ill. cent by heating small quantities of the acid in an iron dish N T H E first part of this communication’ it was shown that for about 4 hours. The preparation of laurone described in ketones could be prepared in excellent yield by distilling this paper gives better yields than the first two methods and the corresponding acid over thoria akrogel a t atmospheric produces laurone a t a much higher rate than the third. Besides laurone, undecylenone, CH, = CH(CH,),COor under reduced pressures. The size of the ketone which (CH2)?,CH=CH2 (melting point, 43” C.) was prepared from can be conveniently prepared is limited by the volatility of the acid and ketone. In order to extend the scope of the ethyl undecylenate in 86 per cent yield. This is a new method to higher ketones, the conversion of ethyl esters was ketone. The microanalysis in per cent is as follows: calcustudied. The esters have a much lower boiling point than lated for C2iH310: C = 82.30, H = 12.42; found: C = their corresponding acids and, therefore, may often be em- 82.39, H = 12.47. This method may be used successfully to prepare in large ployed when the use of the free acid is not feasible. quantities aliphatic ketones of high molecular weight which Ethyl laurate was chosen as a typical example. The results of its conversion to laurone are shown in the following table: were formerly obtained only with difficulty. The microanalysis was carried out by K. Eder of the RATE TEMP. ESTBR Chemistry Department of the University of Illinois. RUN OVER OF RECON-
Thoria Aerogel Catalyst: Aliphatic Esters t o Ketones
I
No. 1
2 3 4 (1
ESTER“ CATALYSTCATALYST Grams 57 57 57 57
Grarna/min. 3-4 3-4 4-6 8
The ethyl laurate was
25 to 30 mm. pressure. 1
COVERED
KETONE
VERSION
Grams % 27 61.8 92.5 39 10.0 34.8 82.5 17.0 29.6 70.0 distilled over the catalyst a t 150’ t o 160’ C .at
C. 300 360 360 360
IND. ENQ.CHEM., 26, 388-91 (1934).
Grams 20.0 4.0
LITERATURE CITED (1) Gruen, A,, Ulbrich, E., and Krczil, F., 2.angew. Chent., 39, 421 (1926). (2) Kipping, F. S., J . Chem. SOC.,57, 981 (1590). 13) Pickard, R. H., and Kenyon, J., Ibid., 99, 57 (1911). RECEIVED June 9,1934
