1765
NEW COMPOUNDS Acid
Eqter
M.
q
(cor.) C.
Vol. 63 Calcd.
Analyses, %2
H
Found
H Phenacyl 55.5-56.5 69.02 7.97 68.92 8.07 p-Phenylp henacyl 88.0-89.7 7.40 74.57 7.35 74.53 PBromophenacyl 95.0-95.8 5.93 54.02 53.81 5.81 p-Nitrobenzyl Oil a-HydroxyPhenacyl 60.0-60.5 70.54 8.54 70.29 8.42 capric PPhenylphenacyl 80.3-80.8 75.35 75.32 8.01 7.91 p-Bromophenacyl 93.0-93.5 56.09 55.86 6.54 6.54 54.5-55.5 p-Nitrobenzyl 63.12 63.16 7.63 7.80 a-HydroxyPhenacyl 63.5-64.0 71.81 71.80 9.06 9.05 p-Bromophenacyl lauric" 91.0-91.5 58.09 57.83 7.08 7.03 p-Nitrobenzyl 59.0-59.5 64.91 64.94 8.36 8.32 a-Hydroxy69.0-69.5 72.47 Phenacyl 72.87 9.46 9.40 myristic p-Bromophenacyl 95.0-95.4 59.84 7.54 59.72 7.40 p-Nitrobenzyl 66.45 66.32 8.99 67.0-68.0 8.77 a-Hydroxy69.8-70.1 Phenacyl 73.79 9.81 73.68 9.86 palmitic 61.78 96.0-96.5 p-Bromophenacyl 61.38 7.95 7.86 9.14 69.5-70.5 p-Nitrobenzyl 67.76 9.16 67.78 a-Hydroxy74.58 74.25 Phenacyl 76.4-76.8 10.00 10.12 stearic 62.52 p-Bromophenacyl 98.0-98.5 8.25 62.74 8.31 69.20 76.5-77.0 9.32 68.91 9.49 p-Nitrobenzyl The p-phenylphenacyl esters a-hydroxy-lauric, myristic, palmitic and stearic acids separated from aqueous alcohol as gelatinous masses. Repeated attempts to purify them for analysis met with failure. L
C
a-Hydroxycaprylic
their melting points are described in a previous communication.'
Some Chlorophenoxyacetic Acids
2,4-DichlorophenoxyaceticAcid.-Equimolecular quantities of 2,4-dichlorophenol (5.0 8.1 and monochloroacetic acid (2.9 9.) were heated with a slight excess (2.7 g.) of sodium hydroxide, and 15 cc. of water, until the solution ORGANIC RESEARCH LABORATORY NATIONAL OIL PRODUCTS Co. DONALD PRICE was evaporated almost to dryness. The residue was then HARRISON, N. J. RICHARD GRIFFITH dissolved in 100 cc. of hot water, the solution cooled to room temperature and acidified with hydrochloric acid. RECEIVED MARCH22, 1941 A heavy oil separated which soon crystallized. The mixture was extracted with ether, the ether extract washed a-Naphthylcyclohexaol-1 with water and evaporated t o dryness on the water-bath To an ethereal solution of a-naphthylmagnesium bro- The yield of 2,4-dichlorophenoxyacetic acid was 5.9 g. mide prepared from 50 g. of a-bromonaphthalene and 6.5 (87%); recrystallized from benzene, m. p. 138"; white odorless crystals, almost insoluble in water. g. of magnesium were added, after one hour, 100 ml. of Anal. Calcd. for CsH6O~Clz: C1, 32.08; neut. equiv., benzene and then during a fifteen minute period 25 g. of cyclohexanone dropwise with stirring. The alcohol was 221.0. Found: C1, 32.10; neut. equiv., 221. isolated in the usual way. The oil so obtained crystallized 2,4,5-Trichlorophenoxyacetic Acid.-Equimolecular after several weeks. The crystals were washed with cold quantities of 2,4,5-trichlorophenol (5.0 9.) and monopetroleum ether and then recrystallized three times from chloroacetic acid (2.4 9.) were heated with a slight excess the same solvent. The substance formed transparent, (2.2 9.) of sodium hydroxide, and 30 cc. of water, until the colorless rhomboids; m. p. 66-68", yield 40%. solution was evaporated almost to dryness. The residue Anal. Calcd. for C1BH160: C, 85.00; H, 7.96. Found: was then dissolved in 200 cc. of hot water and treated as described above. The yield of 2,4,5-trichlorophenoxyC, 85.14; H, 7.95. The preparation of this substance was previously re- acetic acid was 5.5 g. (85%) ; recrystallized from benzene, ported in the literature,' but it was not purified and no m. p. 153'; white odorless crystals, almost insoluble in water. quantitative data regarding it were given. Anal. Calcd. for CsHsOsC13: C1, 41.63; neut. equiv., (1) Sherwood, Short and Stansfield, J . Chem. Soc., 1834 (1932). 255.5. Found: C1, 41.57; neut. equiv., 256. DEPARTMENT OF CHEMISTRY THEC. B. DOLGECOMPANY OF CHICAGO UNIVERSITY CONN. ROBERTPOKORNY ILLINOIS RICHARD D. KLEENE WESTPORT, CHICAGO, RECEIVED MARCH27, 1941 RECEIVED APRIL22, 1941 (1) Price and Griffith, THIS JOURNAL, 62, 2884 (1940). (2) Microanalyses carried out by Dr. Everette I,. May of this Laboratory.
