LACTONIC ESTEaS DEB;IVED FROM PHENACYL BROMIDE Em. 2721 CCCLXXII.-Lactonic Esters derived from Phenucyl Bromide by Condensation with Ethyl Sodiomalonate and Analogc~us Substances. By RAMONI MOBAN RAY and J~ANENDRA NATH RAY. THE primary object of this work uix. the preparation of m-sub-stituted tetrahydronaphthalenes was not achieved. o-Benzoylbenzoic acid is readily convertible into anthraquinone. It was hoped therefore that phenacylmalonic ester under suitable conditions would pass into a tetrahydronaphthalene derivative. In presence of 6% aqueous potassium hydroxide however the reaction followed another course the lactone I (R=H) being formed, which gave benzoic acid on oxidation. OH 0 /\ PhE YO (1.1 Phl-g2:k2Et H HC--CR*CO,Et (R=H Me Et COMe CKPh or CHMe2.) Lactones of type I were also formed in the reactions between phenacyl bromide and the sodio-derivatives of malonic benzyl-malonic isopropylmalonic acetyhalonic and benzoylmalonic esters.Varying quantities of acetophenone also were produced, due to reduction of phenacyl bromide. Phenacyl bromide ethyl cyanoacetate and sodium ethoxide reacting in molecular quantities in alcoholic solution gave ethyl diphenacykyunoacetate (COPh*CH2),C(CN)*C0,Et but when dry ethyl sodiocyanoacetate (2 mols.) was heated for several hours with phenacyl bromide (1 mol.) suspended in dry benzene a sub-stance m. p. 125-127" was obtained which is believed to be the mono-substitution product. This could not be converted into a tetrahydronaphthalene derivative under a variety of conditions./ EXPERIMENTAL. The reactions of phenacyl bromide with the following substances were examined. With Ethyl Sodiomalonate.-The sodio-derivative (prepared from 0.7 g. of sodium and 5 C.C. of ethyl malonate) in cooled absolute alcohol (30 c.c.) was shaken vigorously with phenacyl bromide (6 g.). After 10 minutes the mixture now neutral was poured into much water ; by extraction with ether ethyl phenacylmalonate waa obtained as an oil (8 g.) d 1-2. The crude ester was shaken in the cold with 6% potassiu 2722 umomc ESTERS DERIVED FBOM PHENACYL BROMIDE ETC. hydroxide solution (65 c.c.). The red semi-solid mass that had separated after 12 hours was crystallised from rectified spirit the lactone (I ; R= H ) of a-carbethoxy- y-hydroxy- y-phenyl- A@-propene-carboxylic acid being obtained in colourless needles m.p. 105" (Found C 67.6. C13H1206 requires C 67.2%).* By keeping the lactone (1 g.) for 12 hours in a minimum of cold alcohol saturated with dry ammonia the corresponding umide, CloH,02*CO*NH, was obtained in long needles m. p. 153-154" after crystallisation from dilute alcohol (Found N 7-1. C,,%03N requires N 6.9%). "he lactone (1 g.) was oxidised with NjlO-sulphuric acid (50 c.c.) and N/10-potassium permanganate (excess) on the boiling-water bath. Ether extracted benzoic acid from the product after the usual treatment. With Ethyl Sodiocyunomtate.-An alcoholic solution of the reactants (1 mol. of each) was heated on the water-bath for 6 hour and then poured into water. The precipitate formed was removed after 12 hours; the filtrate gave nothing to ether.By fractionally crystaking the precipitate from 50% alcohol ethyl diphenucyl-cyunoacetate m. p. 141" (Found N 4.3. C,lHl,O,N requirea N 4.0%) was obtained together with a small quantity of a sub-stance m. p. 125-127". With Ethyl AcetylsodiTlomte.-Ethyl acetylmalonate was pre-pared by treating " molecular " sodium (1 atom.) with ethyl malonate in ice-cold dry ether and warming the mixture with acetyl chloride (1-25 mols.) a t 33" for an hour. The product after decom-position with a small quantity of water was shaken with ether. The dried extract was fractionated; the portion b. p. 125-128'117 mm. was pwe acetylmalonate (yield 60%). Ethyl acetylmalonate (4 c.c.) was added to alcoholic sodium ethoxide (0.46 g.of sodium in 25 c.c.); the mixture was treated with 4 g. of phenacyl bromide and after a few minutes warmed a t 50-55" for 4 hour. Ether extracted from the product diluted with water the lactone (I ; R=CO*CH3) of ethyl a-acetyl-y-hydroxy-y-phenyl- A@-propenecarboxylic acid which crystallised from alcohol and ether in needles m. p. 135-136" (Found C 65-6. C15H14O5 requires C 65.7%). As ethyl acetylmalonate is easily decomposed into ethyl aceto-acetate by alkali the compound m. p. 119-120" prepared from phenacyl bromide and ethyl sodioacetoacetate was compared with the preceding lactone; it depressed its m. p. With Ethyl Sodioethylmahte.-The reaction was carried out as * The humidity of the air (cu. 80%) d e determinations of hydrogen almost impossible !I!HE SYSTEM CH3.C0.0.CH3+H,0 O H 3 * 0 H + ~ C O * O H . 2723 in the case of ethyl sodiomalonate. The lactone produced (I ; R=Et) crystallised from alcohol in needles m. p. 134-135" (Found C 69.3. C1,H,,04 requires C 69.2%). With Ethyl SodiobenzyZmaEonate.-The Zuctone (I; R=CHJ?h) obtained crystallised from alcohol in flat needles m. p. 125" (Found : C 73.8; H 6.2. C&E€,,O requires C 74.5; H 5.6%). With Ethyl SodioisopropyZmal.-The constituenfs in mole-cular proportions were boiled in alcoholic solution on the water-bath for 1 hour. The product on dilution with water deposited the lactone (I; R=CHMe,) which crystallised from alcohol in needles m. p. 151" (Found C 69.7; H 6.5. C,,H,,O requhy C 70.1 ; H 6.5%). Our thanks are due to Sir P. C. Riiy for his interest in this work. COLLEGE OF SCIENCE CALCrma. [Received September 3rd 1925.