Author Institution: Department of Chemistry, The College of Wooster, Wooster, Ohi

List, Ellis W., Jr.

Reinheimer, John D.

The Ohio Journal of Science

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26 WARREN T. JOHNSON AND CARL E. VENARD Vol. 57THE OXIDATION OF 0-AROYL PROPIONIC ACIDSBY SODIUM HYPOCHLORITE1JOHN D. REINHEIMER AND ELLIS W. LIST, JR.2Department of Chemistry, The College of Wooster, Wooster, OhioAs part of a general study of the applicability of the Friedel and Crafts Reactionto qualitative organic chemistry, the oxidation of /3-aroyl propionic acids has beeninvestigated. The jS-aroyl propionic acids have been recommended as derivativesof aryl hydrocarbons by Reinheimer and Taylor (1954). If these acids could beoxidized to the corresponding benzoic acid, a second derivative of the originalhydrocarbon would become available.MATERIALS AND METHODSProcedures for the oxidation of a keto containing side chain without simul-taneously oxidizing other side chains generally require the use of hypochlorite.Several procedures were recommended in the literature. Zaki and Fakim (1942)used an alkaline NaOBr solution. This procedure was not regarded as suitable,for the reagent was expensive and had to be prepared immediately before use.Fieser and Bradsher (1936) used NaOCl in an acid solution. They noted thatchlorination of the benzene ring occurred if the ring were sufficiently activated.While the aromatic rings in this series of aroyl propionic acids were not highlyactivated, this chlorination reaction might possibly interfere. Short, Strombergand Wiles (1936) were able to avoid ring chlorination by the use of alkaline hypo-chlorite solution. An adaptation of their procedure was employed.The details of the modified procedure of Short, Stromberg and Wiles are asfollows: An oxidizing solution was prepared by dissolving 2 gm. of NaOH in40 ml. of 5.25 percent NaOCl and diluting to 100 ml. with water. One gm. ofthe /3-aroyl propionic acid was dissolved in 100 ml. of the NaOCl solution andwas warmed in a water bath for 20 to 30 minutes. After the reaction mixturehad been refluxed for an additional one-half hour, the hot solution was filteredand cooled to room temperature. The acid product was precipited by bubblingin sulfur dioxide for 4 to 5 minutes. The crude derivative was separated byfiltration, washed several times with cold water and finally recrystallized fromethanol or an ethanol water mixture.Presented at the Sixty-Fourth Annual Meeting of the Ohio Academy of Science, Delaware,Ohio, April, 1955.2Taken from a portion of the Independent Study Thesis, submitted by Ellis List to theCollege of Wooster, in 1955.THE OHIO JOURNAL OF SCIENCE 57(1): 26, January, 1957.No. 1 OXIDATION OF PROPIONIC ACIDS 27The yields which are reported in table 1 were taken on material that wasdried for 24 hours in a vacuum dessicator; all melting points reported were takenwith a calibrated thermometer.DISCUSSION AND RESULTSThe results of this oxidation procedure are collected in table 1 and table 2.In table 1 /3-keto acids and their oxidation products are listed according to theboiling point of the parent hydrocarbon from which they were derived. Theoxidation products provide satisfactory derivatives of the original hydrocarbonTABLE 1Oxidation products of aroyl propionic acids of aromatic hydrocarbonsAromaticHydrocarbonsB.P. M.P. of Aroyl Crude°C Propionic YieldAcid, °C %M.P.°C DerivativeObserved LiteratureBenzeneTolueneEthyl Benzenem-Xyleneo-XyleneCumenen-PropylbenzeneMesitylenetert-Butylbenzenesec-Butylbenzenen-ButylbenzeneTetralinPhenylcyclohexane/3-MethylnaphthaleneDiphenylNaphthaleneAcenaphtheneFluorene8011113513914215315816416917318220623732*70*80*95*115*116.5-17.5127.0-28.5107.0-08.5112.0-13.0130.0-31.0139.5-41.5120.5-22.5109-09.5123.5-2595.5-96.5111-12.5121-22136-36.5165-66183.5-85172-73209-210212-13646957749173596082548260967766827852.8.7.6.0.3.8.3.4.2.6.1.9.6.9.1.2121.7(lx)180.5-81(2x)lll-12(lx)125.1-26.6(2x)165.9-65.9(lx)116.6-18.0(lx)141.4-41.9(lx)148-50(lx)164.1-65.2(3x)92.5-93.5(lx)101-102(lx)152.2-53.0(3x)191.5-93.5(3x)228.5-30.5(2x)223.5-24.5(lx)182-83(lx)217-17.5(lx)Sublimes121.7 (Beilstein, 1926)180 (Beilstein, 1926)110-11 (Beilstein, 1926)126 (Beilstein, 1926)166 (Beilstein, 1926)116-18 (Beilstein, 1926)140-41 (Beilstein, 1926)147-49 (Beilstein, 1926)164 (Beilstein, 1926)91-92 (Marvel, 1943)102.5-03 (Beilstein, 1926)154 (Heilbrun, 1953)198 (Bordroux, 1938)228-30 (Heilbrun, 1953)224 (Beilstein, 1926)182-82.5 (Beilstein, 1926)217 (Beilstein, 1926)Sublimes(Beilstein, 1926)*Melting point.(x) represents the number of recrystallizations.TABLE 2Oxidation products of aroyl propionic acidsOriginal AromaticHydrocarbon Usedsec-ButylbenzeneEthyl benzeneMesitylenen-Butylbenzenem-XyleneBenzenen-PropylbenzeneTetralintert-ButylbenzeneTolueneo-XylenePhenylcyclohexaneCumene/3-MethylnaphthaleneNaphthaleneDiphenylAcenaphtheneFluoreneM.P. °C ofKeto Acid95.5-96.5107.5-08.5109-09.5111-13.5112-13116.5-17.5120.5-22.5121-22123.5-25127.5-28.5130-31136-36.5139.5-41.5165-66172-73187.5-88209-10212-13M.P. °C ofOxidation Product92.5-93.5111-12148-50101-02125.1-26.6121.7141.4-41.9152.2-53164.1-65.2180.5-81165.4-65 9191.5-93.5116.6-18228.5-30.5182-83223.5-24.5217-17.5Sublimes over 26028 JOHN D. REINHEIMER AND ELLIS W. LIST, JR. Vol. 57for: a) the procedure is simple and the yields are fair to good; b) the productsare generally pure, so that only one or two recrystallizations are required to obtaina sharp melting point; c) the melting points are high, and the melting point dif-ference between successive members of the series is sufficient for positive identifi-cation; d) the melting point of the product is considerably different from that ofthe reactant in all but two cases.The data obtained from the oxidation of this series of keto acids may bearranged to show that the keto acids may also be identified by means of themelting points of the oxidation products. This arrangement is presented intable 2, in which the keto acids are listed according to melting point. The oxida-tion products are suitable as derivatives of the keto acids for essentially the samereasons as presented above.SUMMARYThe oxidation of /3-aroyl prop ionic acids was successful in 17 of 18 trials. Thesubstituted benzoic acids obtained are recommended as suitable derivatives forboth the original hydrocarbon and the /3-aroyl propionic acids.LITERATURE CITEDBeilstein. 1926. Handbuch Der Organischen Chemie, 4th Edition, Vol. 9. Julius Springer &Sons, Berlin.Bodroux, D. and R. Tomasin. 1937. Synthesis of p-cyclohexylbenzyl alcohol and p-cyclohexylbenzoic acid. Comp. Rend. 205: 991-993.Fieser, L. F. and C. K. Bradsher. 1936. The orientation of p-methoxydiphenyl in the Friedeland Crafts reaction. Jour. Amer. Chem. Soc. 58: 1738-1741.Heilbrun, I. and H. M. Bunsbury. 1953. Dictionary of Organic Compounds. Oxford Press,New York.Marvel, C, R. Frank and E. Prell. 1943. Optically active acyl peroxides. Preparation,decomposition, and use as catalysts for vinyl polymerization. Jour. Amer. Chem. Soc.65: 1647-1652.Reinheimer, J. D. and Sylvia Taylor. 1954. The Friedel and Crafts reaction in qualitativeorganic chemistry. II. Aroyl propionic acids of aromatic hydrocarbons. Jour. Org. Chem.196: 802-805.Short, W. F., H. Stromberg and A. E. Wiles. 1936. Syntheses in the phenenthrene series.Jour. Chem. Soc. 1936: 319-322.Zaki, A. and H. Fakim. 1942. Preparation of some p-alkyl substituted benzoic acids. Jour.Chem. Soc. 1942: 307-308.

The Oxidation of Aroyl Propionic Acids by Sodium Hypochlorite

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The Oxidation of Aroyl Propionic Acids by Sodium Hypochlorite

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