90 EEDSON ON SOME DERIVATlVES OF V111.- Ox some Derivcdiues of Plmiylacetic Acid. By P. PHILLIPS B EDSON D.Sc. Assistant Lecturer and Demonstrator in Chemistry a t the Owens College. FOE our knowledge of the derivatives of phenylacetic acid we arc: chiefly indebted t o Radziszewski (Bet-. 2 207) who first investigated the conditions under which substitution may take place either in the aromatic nucleus or in the side-chain. My investigation of some of the derivatives of this acid has led to results differing somewhat from those of t h e above-mentioned chemist. I here propose to give an account of these results together wit,h some further particulars rela-tive to the bromonitrophenylacetic acids &c. the study of which I undertook whilst in Bonn a t the proposal of Professor Kekule ant1 burg’s prism but Ladenburg throws doubts on Gmcbc’s proof of the sjmmetri-cal character of naphthalene PHEXYLACETIC ACID.91 short notices of which have already appeared in anotller Journal ( R e r 10 530 and 16.57). Nitro-del.ivativ~s.-Phenylacetic acid when nitrated yields two iso-meric nitro-derivatives viz. the para- and the ortho- the former constituting the chief portion of the yield. The method of separating these two acids by the different solubilities of their barium salts does not give satisfactory results. If however tlhe acid prepared from the less soluble salt be crystallised repeatedly from a hot mixture of alco-hol and water an acid is obtirinecl crystallising in long needles, and melting a t 150-151" wliich proves t o be paranitrophenylacetic acid.(1.) PnrnnitropheiiyZncetic a c i d is soluble in hot water from which it crystallises in long yellowish-white brittle needles ; it is sparingly soluble in cold water and easily in alcohol and ether. Its analyses gave the following results :-I. 0.3066 gram yielded 0.5978 gram COz and 0.1109 gram H,O. 11. The " NOz " was determined by Limpricht's method (Uer. 11, 35) 10 C.C. of stannous chloride solution diluted to 250 C.C. gave a solution 10 C.C. of which required 10.83 C.C. of iodine solution. 1 C.C. of iodine solution contained 0.01108 gram I = 0.000667 gram NO?. 0.2132 gram of acid heated with 10 C.C. SnCIz solution diluted to 250 c.c. gave a solution 10 C.C. of which required 7-64 C.C. of iodine. 25 X (10.83 - 7-63) x 0.000667 = 0.005336 gram KO2, Found.I. 11. C - = 96 53.03 52-16 HY . . . . . . . . - 7 3-86 4-01 NO = 46 25.41 - 25.0.2 - -- - 0 . . . . . . . . = 32 17.67 - -___ 181 100*00 This acid when oxidised by a mixture of potassium bichromate and sulphuric acid yielded paranitrobenzoic acid m. p. 230" ; the combus-tion of which gave the following numbers :-0 3064 gram yielded 0.5682 gram COz and 0.088 gram H,O. Calculated for C6 ff jNO,CO,H. Found. C 50.29 50.52 H . . . . . . . . . . 2-39 3-16 Methyl purni7it,.o~heiL~7acetnte C,Hf,.P\T0,.CH2C0,CH3 crjstallises from alcohol in yellowish-white plates by slow evaporatioii of the aIcohoIic solution it is obtained in thick striated plates ; it melts a t 54-55" 92 EEDSOS OX SOME DERIT'ATIVES OF Ethyl paranitrvplieuSlacctat~ crystallises from dilutc alcohol i n thin, shiiiiig leaflets nieltiiig at 62-6 i'.Tlic Z ~ l n r i z ~ ? ~ ~ suZf is obtained in I;reautiful light ello ow transparent (.i*,vstds bj- allowing the aqucoiis solution to cvaporate slowly. These (*rystals apim~r to be six-sided plates ; as o n exposure to s i r they c~rffortwe and bec'ome opaque their esact crj-stalline form could not be tl9xxmiinerl. Tlie crystals quickly dried between filter-paper gave results (I) corresponding t o t h e formula 13a(CsT-I,N0~)~ + 7HZO ; v hilst tlie air-dried opaque crystals gave results (11) for the formula I. 0-5358 gram heated at l l O - l l . ~ o l o s t 0,113 gram and gave lh(CJ1&OJL + 2&0. 0.1951 grain 13uS01. Cdcnlatcd for IJa(C'*H~ZCo,)> + m'J0.Found. 1h . . . . . . . . . . 21.99 2 1-45 11,o. . . . . . . . . . 20.22 21.08 11. 0.2912 gram heated at 10G--11Oo lost 0.0214 gmm and gave ci.i28S gram BaS04. Calculated for 13a(c&To4)2 + 21120 Found. Ih 2 5 . i O 25 92 lI,O . . . . . . . . 6 . i 5 7-34 The arlwoiis solution of thc barium salt gives with lead acetate wlutim a wliitc precipitate which partially dissolves wheii boiled and ~~ec~ybtallises on coo;iiig ; with silver nitrate solution a while curdy 1)recipitate soluble in aiumotiia and nitric acid arid firially with ferric chloride a brownish precipita:e. duction of the psranitro acid by tin and hjdrochloric acid ; it crystnl-libes from Lot aqueous solutions in white lustrous leaflcts which 1,econie brown on exposure to air and melt s t 199-200" with decom-Imiition.Ylic analysis of this acid gave the following numbers :-0 2 3 3 i gram gave 0.5432 gmm C 0 2 and 0.129 grain water. I;on lld. c,. . . . . . . . 96 G2.57 63.08 H . . . . . . I 5-96 6.06 N . . . . . . . . 14 0.27 -0,. . . . . . . . 32 21-20 - - -151 100.00 ( 2 . ) O,-tl~ci.iiit,.o~l~e?l~Zacetic acid. - The alcoholic mo tlier-liquors €ro1:1 tlie crjstallisatiori of the Paranitl.o-d~riv~tive wlicn conceiitrate PIIENTLACETIC ACin. 93 yield a body crystallising in white opaque tufts of needles melting. it'' 112 -117'. A similar product is ohtained by decomposing the niorck soluble barium salt with hydrocliloric ncicl. By allowing the solntion of this body in inethSl or ethyl alcohol to evnpomte slowly large well-formed crystals separate out yliich were collcctcil and recrystallised from alcohol.By this means a fcw grams of thcse crystals wero obtained melting a t 137-133". When crystnllisecl from hot water, in which they arc sparingly soluble white shininq needles sepnrntc out at first and on standiny minute crystals appear having n form similar to the lnrqer oms. Coth the needles and the minute crgstals melt a t 137-138". The combustion of the acid crystallised from water gave the follow-ing results :-0.302 gram Sielded 0.585 'gram CO and 0.11% gram H,O. Calculated for C,FTZ;ZCO2H. Foun (1. c $3.03 52-64 H . . . . . . . . 3-86 4-13 This acid when oxidised by boiling with n solution of potassium permangannte yields orthonitrobenzoic acid subliming i n white needles and melting a t 141-143O.Moreover upon redaction i t is converted into osindol which was recognisccl by its melting point, 120° and its reaction with nitrous acid. From these facts I concluclc that the second nitro- acid in. p. 137 -188" is ol.tlionit7.o~lien~~~cetic ccrid. For the following description and ineasurcments of the crystals of orthonitrophenylncctic acid I am i n d e b t d to Mi Baker. Orth on 2roph englncetic Acid. Monoclinic. Fig. 1. OP + I' mPcn ; tabiilar thro-rigli OP. , 2. OP + P c&m in eqnilibrinrn together with 0312,). c i K c = 1.0 0.5%; L = 9 7 O li'. . Found. Calculated. OP +P = 51" 45' 51" 4.")' mPm + P . . = 108 9 108 13 OP 03Pm = 97 1 7 97 1 7 +P +I' (in clino-diagonal) . . . . = 94 28 94 2s mP2 cnF2 (in ortho-diagonal) .. . . = 81 lt; 81 ( 9.2 EEDSON ON SOME DERIVATIVES O F Barium orthonitrophenylacetate crystallises from its aqueous solu-tions in white lustrous scales which are more easily soluble in water than the crystals of the corresponding salt of the para-acid. The analysis of this salt shows its formula to be BR(C,&NO~)~ + 2H20 ; the water cannot be directly determined as the salt is decomposed at 100-110". 0.495 gram gave 0.2121 gram BaS04 i.e. 2.5.17 per cent. Ba wliilst Ba(C,H,NO,)? -+ 2H,O requires 25.70 per cent. Ba. Aqueous solutions of this barium salt give no immediate precipitate with s,lution of lead acetate; on standing however the lead salt separates out in tufts of fine needles. Silver nitrate and ferric chloride give reactions similar t o those with the solutions of the salt of the para-acid .( 3. ) Rnmo- c7ey iv n lives .-B ro mo ph en y 1 acetic ac id was prep are d by an application of Barth and Weselky's method for such cases viz. by treating plienylacctic acid and mercuric oxide suspended in water, with the calculated quantity of bromine in small quantities a t the same time cooling by immersion in water. The reaction which takes place is expressed by the following equation :-2C7H7C02H + HgO + 2Br2 = 2C7H6Brco2H + HgBr2 + 2H20. After the completion of the reaction an excess of caustic soda is added and the filtrate from the mercuric oxide acidified with hydro-chloric acid ; the bromo-acid separates out as a white crystalline pre-cipitate and after washing with cold water is crystallised from hot dilute alcohol.The chief portion separates ont from this solution as a slightly colourcd oil which on standing soIidifies to a crystalline mass; some also crystallises out in tufts OF white needles both por-tions melting at 76". The alcoholic mother-li ynors on concentration jield an acid having a somewhat higher melting point. This latter portion is converted into the barium salt either by boiling its aqueous solution with barium carbonate or with baryta-water aiid in urhich ease the excess of barium is removed by precipitation with carbonic :xcid. The concentrated aqueous solutions of this salt yield a white crystalline deposit formed of opaque nodular masses ; these deposits were crystnllised from hot water and finally decomposed by hydro-chloric acid.Pacrabro??zoz~hen2JZacetic Acid.-The acid thus obtained is dissolved in hot water from which solution il separates on cooling in long flat lustrous needles resembling the crystals of benzoic acid and melting a t 114-115". I t s analysis shows it to be a monobromophenylacetic acid and its melting point is the same as the parabromol?llen~Iacetic acid prepared by Loring Jackson and W. Lowery (Bey. 10 1210) from parabronibenzyl bromide PHENPLACETIC ACID. 95 The analysis gave the followiiig results :-I. 0.256 gram gave 0.4188 gram C02 and 0.0786 gram H,O. 11. 0.23136 gram gave 0.198 gram AgBr and O.CO65 gram Ag. Found. I. IT. C,. . . . . . . . . . = 96 44.65 44.GO -H; . . . . . . . . = 7 3.25 3.39 -Br . . . . . . . . = 80 37.20 __ 37.14 - - 0,.. . . . . . . . . 64 17-90 247 100.00 -O ~ t l r o b ~ o ~ n o ~ l i ~ ~ ~ ~ ~ l a c e t i c Acid.-The mother-liquors coctaiuing the mere soluble barium salt which on further evaporation Iield no crystalline deposit, were precipitated with a solution of lend awtate, and the white precipitate so formed d t e r mashing with cold water was boiled with dilute sulphuric acid. The filtrate from tlie lead sulphate OIL cooling yielded crystals of an acid which after several crystal-]isations from hot water is cbtained in tlie form of long lustrous flat needles melting a t 103-104" the analysis of which gave the follow-ing results :-I. 0.2104 gram gave 0.8436 gram C 0 2 and 0*0.%4 gram H,@. 11. 0.257 gram gave 0.2148 gram AgBr and 0.0066 gram Ag. Found. Calculated.I. Ir. C . . . . . . . . . . . . 44.65 44.33 -H i . . . . . . . . . . . . 3-25 3.04 -o* . . . . . . . . . . . . 17-90 100~00 Br . . . . . . . . . . . . 37.20 - :ji.43 - --These results together with the fact that when this acid is oxidised hy boiling with a solution of potassium permanganate orthobromo-bellzoic acid is formed melting at 143-144" prove this acid to bt: orthobromophenylacetic acid. The orthobromobenzoic acid gave the following results for the bromine determination ; 0.1932 gram gave 0.1754 gram AgBr and 0.0027 gram Ag giving 39.24 per cent. Br, whereas the formiila CGH,< C02H requires 39.83 per cent. Br. Orthobromplie~iylacetic mid may be obtained in well-formed crys-tals by the slow evaporation of its solution in glacid acetic acid for the following description of which I am indebted to 31r.Baker :-H 9 ci BEDSOS O S SOJlE DERIVATIVES O P 0 rt /LO Z 1.0 nip 7 e ) I y 7n c e t i c it c id. System monoclinic ti 6 1 = 1.000 0.657 1.767; L = XI" 44 . Forms obscrvecl WP . OP . mP00 . Roo . +Pm. . -P. Calciilat rd. Foi 1111 1. mP COP (in ortho-tlingonal) . . . . 112" ;;i' 112" 2i' . . . . . . . . . . . . . . . . OP mP-00 (L) 99 44 99 44 UP =+P ca . . . . . . . . . . . . . . . . 142 51 142 4C: COP -I' . . . . . . . . . . - . . . . . . . . . 163 6 163 1 5 UP %W . . . . . . . . . . . . . . . . . . . . 110 40 110 5-1. OP COP C?5 23 95 2-c From the ahovc experiments bromine in the cold acts on phenyl-acetic acid in a similar mamer to nitric acid producing para- 2nd ortho-derivatives in each case the melting point of the " para " is about 13" higher than that of the " ortho." Furtlier these results show that the parabromphenylacetic acid described by Radziszewski (Zoc.cit.) melting a t 76" is a mixture of the two isoiiierides. A similar remark may be made with regard to the para- and ortho-nitro-phenylacetic acids clescrihed by the same chemist the former melting a t 114" and the latter a t 98". In one of the recent numbers of the Be7.7i7ze~ Bericlite (12 17'64), Maxwell publishes a description of paranitrophen3.lncetic acid to which he attributes the melting point 151*.5-1.52" which agrees toler-ably Tell with my determinatioc as does the description of the methyl- and ethyl-ethers of this acid. The barium saltis described as anhydrous and ergstallising in needles a difference probably due to the method of preparation.(4,) Bihi.omo-Jcl.;v~tives.-To prepare a bibronio-acid crude bromo-phenylacetic acid (m. p. 5G") was sealed up in a strong glass vessel with the calculated qnantitp of bromine and exposed for several niontlis to the action of sunlight. Thus a brownish liquid was pro-duced and on opening the vcsscl quantities of hydrobromic acid were given off. The product after mashing several times with water, was converted into the methpl-ether xs all attempts to obtain a crys-talline product by crystallisation from alcohol had proved futile, yielding n yellowish viscous mass only. The methyl-ether when dis-tilled under reduced pressure chiefly came over at 220-230' ; thi PHENYLACETIC ACID.47 portion was saponified by boiling with caustic potash. The potassium salt decomposed with hydrochloric acid and an acid obtained which crystallises from water in white shining needles melting a t 114-115". But a small quantity of this acid was obtained ; the bromine deter-mination shows it to be ;L bibromophenylacetic acid. 0.276 gram gave 0,3521 gram AgBr and 0.0022 gram Ag which corresponds to 54-78 per cent. Br whilst C,H,Br,CH,CO,H requires 58-42 per cent. Br. Together with this acid other acids are formed but in quantities nsufficient for analysis. (5.) Broi,ioi~itl.o-derivatl:ves.-Short notices of the preparation and separation of two bromonitrophenylacetic acids and the corresponding hromamido-derivatives have already appeared (Ber. 10 530 and 1637).The following is a more detailed account of these acids and also of a third isomeride. As in the preparation of these acids I used a bromophenylacetic-acid melting at 76" the formation of three bromonitro-acids is not astonishing as the bromo-acid contained both the para- and ortho-derivatives ; it renders doubtful however the constitution attributed to the bromonitrophenylacetic acid melting a t 167-169". 3 0 , Parabromorn etanitrophen. y lace tic acid C B,' R r crptallises 'CH,CO,, from its hot aqueous solutions in small flat greenish-yellow needles, melting at 113-114". It dissolves in hot water but is almost in-soluble in cold water and is easily soluble in alcohol and ether. The analysis of this acid gare the following results :-I.0,3005 gram gave 0.4076 gram CO and 0.0735 gram H20. 11. 0.252 gram gave 0.1736 gram AgBr and 0.0055 gram Ag. 111. The " NO " determination was made by Limpricht's method, 0.2123 gram gave 0.036768 gram NO,. Found. I 11. 111. < '-- - C8 56 36.92 36.97 H - - 6 2.30 2.66 NOz . . . . 46 17-68 .- - 17-31 Br . . . . . . 80 30.76 - 30.90 -0 2 32 13-34 - - -260 100.00 This acid when oxidised by potassium bichromate and sulphuric acid yields parabromometsnitrobenzoic acid melting at 197-199", described by Hiibner Ohly and PhiIipp (Liebig's dnnaben 143 248). Its analysis gave the following results :-YOL. XXXVIT. 98 BEDSON ON SOME DERIVATIVES OF I . 0.2675 gz:am gave 0.3391 gram CO and 0.05485 gram H,O. 11. 0.289 gram gave 0.3635 gram CO and 0.0577 gram H,O.111. 0.3 gram gave 0.221 gram AgBr and 0.0057 gram Ag. Found. 11 I. I I. Ill' c , - - 84 34.14 34.54 34.29 -H . . . . . . - - 4 1-62 2.23 2.21 -N . . . . . . - 14 5.69 64 26.03 0 4 . . . . . . -246 100~00 - - -_ - -BY - 80 39-52 - - 32.7:3 - - - -- -__ Barium parabromometani trophenylacetate Ba( C,H,BrNOa) + H20, crystallises in yellowish plates or needles united in concentric groups is soluble in waker but less soluble than the salt of the 2-bromitro-acid. The ana,lpsis of this salt gave the following results : 0.569 gram heated a t 110-120" lost 0.154 gram and gave 0.1969 gram BaS04 corresponding to 2.70 per cent. H,O and 20.33 per cent. Ba whilst the formula requires 2.79 per cent. H,O and 20.35 per cent. Ra. A dilute solution of the barium salt gives with silver nitrate a white curdy precipitate soluble in nitric acid with copper acetate a bright blue precipitate and witth lead acetate a white precipitate, which dissolves on boiling.The methyl ether forms yellowish-white needles usually grouped together melting a t 40-41". Its ethyl ether has only been obtained as an oily liquid. NH, Para~rornometamidop~en~jlacetic m i d C,H,/Rr olhined by the rediiction of the nitro-acid with tin and hydrochloric acid crystal-lises from water in white silky needles which colour slowly on ex-posiire t n the air. It is less soluble in water than the a-bromamido-acid but is easily soluble in alcohol and chloroform and sparingly in ether. It melts a t 133-134'. I t s analysis gave the following result :-0.2156 gram gave 0.3315 gram CO and 0.0714 gram H,O.\CH?CO,H Calculated for C6H,NH,.Br.CH2C0,H. Found. C 41.73 41.92 H 3.47 3.66 Its hydrochlorate C,H,BrNCO2H.HC1 + H,O crystallises in whit PHESPLACETIC ACID. 99 needles united in concent.ric groups becoming red on exposure t o the air. It is soluble in cold water. The analysis of this salt gave the following results* :-I. 0.2636 gram gave 0.1282 gram AgCl and 0.0041 gram Ag. 11. 0-2208 gram gave 0.275 gram CO and 0.084 gram H,O. 111. 0.333 gram gave 0.2168 gram of AgBr. Found. Calculated. I. 11. 111. C . . - 33.96 - . . . . . . . . . . . . 33.72 - 4.21 - H 3-86 Br 28.12 - - 27.68 C1 . . . . . . . . . . . . 12.47 12.51 - -a-BI.o.l~zo1Lit)"@~~?~e?L~lacetic acid crystall ises from water in yellowish-white branching needles melting at 167-169'.It is easily soluble in alcohol and ether is insoluble in cold water but soluble in hot water, and less soluble in a mixture of alcohol and water than the isomeric acid already described. The following are the results of its analy-s1s :-I . 0.303 gram yielded 0.4106 gram CO and 0.0776 gram H20. 11. 0.5884 gram yielded 0.7955 gram CO and 0.1354 gram H20. 111. 0.5335 gram yielded 0.3861 gram AgBr and 0.004 gram Ag. IV. 0.2172 gram by Limpricht's method gives 0.037852 gram (' NO,." Found. c - Calculated. I. 11. In. IV. C . . - . . . . . . . . . . 36.92 36.93 36.86 -H - . . . . . . . . . . 2.30 2.83 2.54 -31.32 - Br . . . . . . . . . . 30.76 NO,. - . . . . . . . . . 17.68 0 . . . . . . .. . . 13.34 - -- - 17-42 - - - -100~00 The barium salt Ba(C8H,BrN04)2 + 4H,O forms yellow transpa-rent needles united to form concentzic groups is soluble in hot water, less solubfe in cold and more soluble khan the salt of the isomeride already described. The following results confirm the above formula : -0.4718 gram heated at 110-115" lost 0.046 gram and gave * I n I tphe chlorine waB determined by adding silver nitrate to the aqueous solu-tion of the hydrochlorate ; in 111 the substance heated with lime &c. gave a mix-ture of silver chloride and bromide and the amount of the lat,ter determined by sub-tracting the silver c'hloride given by the chlorine determination. H 100 BEDSOS OX SOMI3 DERIVATIT'ES OF 0.1501 gram BaS04 ; or 9.74 per cent. H,O and 18.69 per cent.Ba the formula requiring 9.99 per cent. H20 and 18.84 per cent. Ba. The aqueous solutions of the barium give with silver nitrate and lead acetate solution similar reactions to those of the isomeric acid ; copper acetate however gives a green precipitate. The methyl-ether forms transparent slightly yellow flat shining needles; it melts a t 66-68". The ethyl-ether forms yellowish needles. a-BromaImidophelz?tlacelic acid is obtained by reducing the corre-sponding a-nitro-acid with tin and hydrochloric acid ; it crystallises from Kater in white brittle needles which redden.on exposure to the air and melt a t 167" a decomposition taking place at the same time. It is soluble in alcohol and chloroform but sparingly soluble in ether. Its analysis gave the following results :-I.0.2006 gram gave 0.3055 gram CO and 0.0684 gram HZO. 11. 0.2276 gram gave 0.1692 gram AgBr and 0.0099 gram Ag. Found. - CalcuIated. I. 11. C . . . . . . . . . . . . 41.73 41.52 -H . . . . . . . . . . . . 3.47 3.78 -Br 34.78 - 34-88 The hydrochlorate of a-bromamidophenylacstic acid, C8H,BrN02HC1 + H20, crystallises from water in long white needles which become red on exposure to the air ; it is more soluble in water than the hydrochlorate of the isomeric acid already described. Its analysis gave the following results :-I. 0.2404 gram gave 0.302 gram CO and 0.0892 gram H,O. 11. 0.220 gram gave 0.1065 gram AgCl and 0.0034 gram Ag. 111. 0.2029 gram gave 0.1319 gram AgBr. IV. 0.9059 gram heated in a current of dry air at 90-100" lost 0.0574 gram.' Calculated for Found .CGH3Br.NH2CH2CO2H.HC1 + 7 -_1___7 H,O. I. 11. 1x1. IV. 34.23 - - - c 33.74 H 3.86 4.11 - - -27.64 - Br 28.12 C1 12.4'7 - 12.45 -H20 6.32 - --6.35 - - I The salts of t'his acid with the alkalis are easily soluble in water PHENYLACETIC ACID. 101 their solutions give a dark green precipitate with copper acetate of tlie copper salt. /3-Brornonitrophenylacetic Acid.-Together with the above two bromo-nitrophenylacetic acids a third is formed ; it was separated from the yellow crystalline mass obtained by extracting with chloroform the mother-liquors from the nitration of the bromophenylacetic acid. This extract was dissolved in glacial acetic acid and the solution allowed to evaporate slowly thus an acid was obtained crystallising in small transparent yellow prisms.It melts a t 162" and when crystallised from hot water it forms long colourless needles having the same melting point. By reduction with tin and hydrochloric acid, it is converted into a bromamidophenylacetic acid which crystallises from water in white leaflets becoming brown on exposure to the air ; it melts at 186". Its hydrochlorate is less soluble in water than that of either of the above isomerides. But a small quantity of these two acids has been obtained ; the analysis of the bromamido-acid gave the following results :-I. 0.213 gram yielded 0.324 gram CO and 0.072 gram H,O. 11. 0.2385 gram gave 0.1821 gram AgBr and 0.0061 gram Ag. Found. Calculated ioi. r h \ C,IIB.13r.NHf.CiI,C0,H I. I r. - C . . . . . . . . . . . . 41-7s 41-45 H . . . . . . . . . . 3.47 3 . i 5 Br . . . . . . . . . . 34.78 - ;;$*2'3 -From the parabromomctamidophenylacetic acid and the a- brom-amidlo-acid I have attempted to obtain the amidophenylncetic acids by means of tlie action of sodium amalgam on tlie aqueous solutions of these acids ; the results of this action are however not very satisfac-tory. Some further clue to the constitution of the above bromonitro-phenyl acet,ic acids I hope to obtain by the preparation of the nitro-paramidophenj lacetic acids and from which by means of the diazo reaction t o prepare the corresponding br~inonil~o-deriv~ttIvcs