March, 1948
NEW COMPOUNDS
One crystallization from benzene and several from methanol elevated the melting point to 151.5-182". Anal. Calcd. for C11H&140n: C1, 41.23. Found: 41.02, 41.18. OF CHEMISTRY DEPARTMENT C. A. BUEHLER UN,IVERSITB OF TENNESSEE BURTONP. BLOCK KVOXVILLE16, TESSESSEE RECEIVED DECEXBER 10, 194.7
533
30 ml. of glacial acetic acid was heated for six hours on a steam-bath. The silver chloride was removed by filtration and the solvent evaporated under diminished pressure. The acetate boiled a t 161-162' (13 mm.); n16D 1.5033; d2"4 0.9536. Anal. Calcd. for C18H~802:C, 78.19; H, 10.21. Found: C, 78.15; H, 10.44. Hydrolysis of the acetate yielded 2,4,6-triisopropylbenzyl alcohol, m. p. 83-84°.4 REYNOLD C. FUSON THEKOYESCHEMICAL LABORATORY J. WAYNEKNEISLEY UNIVERSTTY OF ILLINOIS NORMAN RABJOHN IJRBANA, ILLINOIS M. L. WARD RECEIVED NOVEMBER 23. 1945
Derivatives of sym-Trialkylbenzenes 2,4,6-T~iethylbenzonitrile.-A mixture of 60 g. of 2,4,6ethylbromobenzene,' 5.0 g. of cuprous cyanide and 60 ml. of pyridine mas heated under reflux for eleven hours, allowed to cool somewhat arid poured into 400 nil. of dilute ammonium hydroxide solution. The nitrile was extracted with a mixture of benzene and ether. The solution was Derivatives of 8-Chloroquinoline~ washed with water and with dilute ammonium hydroxide solution, dried over calcium chloride and distilled. The 8-Chloroquinoline 7.0-g. portion of picric nitrile boiled a t 150-151° (24 mm.); T Z ~ O D 1.5201; dZ54 acid (containing 10%Picrate.-A water) was dissolved in 90 ml. of 0.9366; yield 6457. benzene. The solution was dried over anhydrous sodium -4naZ. Calcd. for CI?HI?S: C, 83.37; H, 9.15. Found: sulfate, filtered, and added to a solution of 4.5 g. of 8C, 53.23: H. 9.12. chloroquinolineZin 25 ml. of benzene. The yellow precipi.Dillingham a n d ReidZmade this compound by another tate was collected, washed with benzene, and dried. The method; they reported the boiling point as 108.5' (2 yield was 10.5 g. (977,); m. p. 178-180". A sample was tnm.) arid the density as d"j4 0.9356, but did not include recrystallized from ethanol (70 ml./g.) for analysis, m. p. an analysis. 178-180". 3,5-Dinitro-2,4,6-triethylbenzonitrile.-Two grams of Anal. Calcd. for ClsHgOrN4Cl (392.7): C, 45.88; H. 2,4,6-triethylbenzonitrilewas added slowly to 20 ml. of 2.31. Found: C, 45.50; H, 2.11. fuming nitric acid which had been cooled to 0". The Thiourea Addition Compound of 8-Chloroquino1ine.mixture mas allowed t o stand for thirty minutes in an ice- This compound was obtained during an attempted prepabath and was then poured into 200 ml. of water. The ration of 8-quinolinethiol from 8-chloroquinoline via the product was recrystallized from methanol; m. p. 69isothiuronium salt. A solution of 1.64 g. of S-chloro70.5'; yield 1.5 g. quinoline in 15 ml. of absolute ethanol was boiled under Anal. Calcd. for C1,H,50&3: C, 56.30; H, 5.41. reflux with 0.76 g. of thiourea for fifteen minutes; the Found: C, 56.21; H, 5.57. thiourea gradually dissolved. On cooling, the clear solu1-Ethyl-2,4,6-triisopropylbenzene.-2,4,6-Triisopropyl- tion deposited 1.0 g. (38%) of colorless needles, m. p. 131benzyl chloride was coupled with methylmagnesium iodide 132'. (The same result was obtained when the reaction according to the method described for 4-t-butyl-2,6-di- mixture was boiled five hours.) The addition compound methylbenzyl ~ h l o r i d e . ~ 1,2-Di-(2,4,6-triisopropyl- (0.8 g.) was recrystallized from ethanol for analysis; rephenyl)-ethane4 was obtained in 63%, yield. The alkyla- covery 0.6 g., colorless needles, m. p. 132-133'. The compound gave positive sodium-fusion tests for nitrogen, tion product, 2,4,0-triisopropylethylbcnzene,boiled a t halogen and sulfur, but was completely inert to hot alco101-103" (5 mm.); n Z 01.4927. ~ Anal. Calcd. for C17H28: C, 87.85; H, 12.15. Found: holic silver nitrate. This showed that it was not the desired 8-quinolineisothiuronium chloride, but an isomeric C, 88.21; H, 12.04. Ethyl 4-t-Butyl-2,6-dimethylbenzyl Ether.-This com- addition-compound of 8-chloroquinoline and thiourea. Anal. Calcd. for C I O H ~ ~ N ~(239.7): SCI C, 50.08; H pound was produced in an attempt to reduce 4-t-butyl-2,6dimethylbenzyl chloride. To a solution of 15 g. of sodium 1.21. Found: C, 49.78: H, 4.31. hydroxide pellets in 220 ml. of 95nc ethanol was added 25 (1) This work was done under a contract recommended by the g. of the chloride. Three grams of aluminum powder was Committee on Medical Research betneen the Office of Scientific added slowly, with stirring, and the mixture heated under Research and Development and the L-niversity of Rochester. reflux for three hours. The ether, isolated in the usual (2) Clam and Scholler, J . p r a k t . Chew!., (2) 48, 1.10 (1893). way, boiled a t 120-126.5" (7 m m . ) ; n z a 1.5008; ~ yield DEPARTMENT OF CHEMISTRY is%. OF ROCHESTER Anal. Calcd. for C15H~40:C, 81.75; H , 10.98. Found: THEUNIVERSITY ROCHESTER, KEWYORK G. E. MCCASLAND C, 82.02; H, 11.03. RECEIVED JANUARY 17, 1946 Ethyl 2,4,6-TriisopropylbenzylEther.-This compound was produced in an attempt to reduce 2,4,6-triisopropylbenzyl chloride by a procedure similar to that used with 4-t-butyl-2,B-diinethylbenzyl chloride. The product, isolated in the usual manner, boiled a t 132-134" (6 mm.); SOME HYDROXYPEROXIDES nZoD1.4928. The peroxides shown in Table I have been synthesized' A n a l . Calcd. for CisHauO: C, 52.38; H , 11.52. Found: in an anhydrous ethereal solution. Hydroxy dicarbethoxyC, 52.05; H, 11.
