558 EDELEANU SOME DERIVATIVES OF XLII.-Xonze Derivatives of Phennylmethacrylic Acid. By L. EDELEAXU P1i.D. IN the Berichte for 1887 (p. 616) I described some derivatives of phenylmethacrylic acid and phenylisobutyric acid and I have since obtained some further derivatives. PuranitrophenyZisobutyric A c i d C,H,(NQ2)*CH2.CH(CH,).COOH. Phen-j-lisobutyric acid obtained by Conrad and Bischoff’s method, is gradua11S added in small portions to six times its weight of nitric acid sp. gr. 1.52. On pouring the mixture into cold water the nitro PHEN YLMETHACRYLIC ACID. 559 acid is precipitated and after several crystallisations from alcohol forms small prisms melting at 121". I t is rzadily soluble in alcohol and acetic acid but only very slightly in benzene and light petroleum.Analysis gave-ClO-bNO4- I. 11. - C 57-42 5 7-45 H . . . . 5.26 5.43 N . . . . . . 6.70 - 6.88 0 . . . . 30-62 -- -The acid forms salts with the alkalis and with barium and strontium, all of which dissolve readily in water. The silver salt is very insoluble. Its analysis gave dried at loo" 34% per cent. Ag. CloHl,NO, requires 34-21 per cent. Ag. Oxidation with permanganate yielded an acid which was identified as paranitrobenzoic acid. Along with the paranitrophenylisobutyric acid of melting point 121" is an acidPrhich remains liquid at the ordinary temperature and could not be crystallised even on cooling to a low temperature. It forms salts which resemble those of paranitrophenylisobutyric acid but they are less stable. The silver salt contains 1 mol.H,O and is decom-posed at 100" ; dried over sulphuric acid it gave 32.49 per cent. Ag ; theacid C,oH,,N04 + OH requires 32.33 per cent. On oxidation this acid yields orthonitrobenzoic acid. The liquid acid is therefore, orthoni trophenylme thacrylic acid. In order if possible to obtain this nitro-acid in a crystalline state, I nitrated the methyl salt C6H5*CHz*CH(CH3).COOCH,; it is a liquid boiling at 232". Analysis gave-CllHl,% C . . . . . . 74.16 H 7-86 74.35 7.90 This was dropped slowly into fuming nitric acid sp. gr. 1.54 pre-cipitated by much water and crystallised from ether. The product separated in long prisms melting at 76" easily soluble in ordinary solvents. The analysis shows that in this case it is converted into a dinitro-derivative.The results were as follows:-C11Hl2N,O,. I. IT. - C . . . . . . 49.25 49.26 H 4-59 - . . . . 4.48 N 10.45 - 10.45 0 35.82 - -560 SOME DERrVATIVES OF PHENYLMETHACRYLIC ACID. On warming this nitro-derivative with sulphuric acid for a few minutes and diluting with water the acid is liberated and forms colourless six-sided prisms somewhat flattened. It melts a t 89" and is very soluble in ordinary solvents. Analjsis gave-C,,HlONZO,. I. 11. C 47.24 47.09 -H 3.92 4-1 1 N . . 11-02 - 11.20 O . . . . . . 37.80 ---Nitroami~7ophenylisobutyric Acid, is obtained from the dinitro-acid by reduction with ammonium sulphide. It crystallises from hot water in bright-red plates which melt a t 138". MOZ*CsH3( NHZ) CHz*CH(CHS)COOH, Analysis gave :-CIOH,2N@.4.I. Jr. - c 53.57 53-40 H 5.36 5.48 N 12-50 -0 . . 28.57 -12.68 - -AmidomethyZhydrocarbosty1.i1 C,HlZN,O. On boiling the nitroamidophenylisobutyric acid with ammonium sulphide for two hours a substance was obtained which no longer dissolved in ammonia. It crystallised from water in slender needles which melted a t 216", and dissolved with great difficulty in alcohol and light petroleum. Analysis gave-c 10HIZNZO * I. Ir. - c 66.18 68.30 H 6-82 7.01 N 15-91 - 15.95 o 9.09 - --The formation oE this compound leads to the conclusion that one of the nitro-groups in this d~nitrophenylisobu.tyr~c acid is ortho to the fatty part wllilst the second nitro-group is either para or meta. An experiment in which paranitro~henylis~butyric was heated with fuming nitric acid produced the same diuitro-acid as above described. The second nitro-group is therefore in the para-position to the methane residue SATURATED AND UNSATURATED BIBASIC ACIDS. 561 The following formulaa may therefore be given as expressing the constitution of these four compounds :-CH2.CH (CH3) .COOCH3 CH2'CH(CH3) 'COOH PI \/ NO2 NO2 Paraorthodinitrophenyliso-butyric acid. 0 Methyl paraoythodinitrophenyliso-butyrate. CH2*CH (CH3) CO OH CH,.CH(CH3)\ /\ NH-/" \/ NH2 I IN* \/ NH2 Paramido-orthonitrophenylisobutyric Paramidomsthylhydrocarbo -acid. styril. Chemical Laboratory, Artit 1 ery Co I leg e Woo lw ich