91 1X.-The Action of Sodium Alcoholute on Aonidcs. By JULIUS B. COHEN, Ph.D., and WILLIAM H. ARCHDEBCOX, B.SC., The Yorkshire College. AT the meeting of the British Association in 1894 (Brit. Assoc. Bepoyts, p. 625) a communication was read by one of us on the constitution of the amides, containing a brief reference to the action of sodium methoxide on acetanilide. As this action appeared to us to have an important bearing on the constitution of the amides, we have studied it more fully, and now bring before the Society the results which we have obtained. If, to a solution of acetanilide in dry ether, powdered sDdium meth- oxide is added in molecular proportion, it dissolves ; but aEter the lapse of a few minutes, a voluminous crystalline compound is deposited, filling the liquid.This substance has the formula C,H,*NH*C O*CH3,CH3*ONa. Similar compounds have been prepared with ortho- and para,-aceto- toluidide and a- and p-acetonaphthnlide on the one hand and with sodium methoxide and ethoxide 011 the other. Benzanilide and form- anilide form similar compounds. With formylphenylhydrazide, however, no additive compounds are formed ; but the sodium appears to displace the hydrogen in the amido-groups. In the case of benz- amide, a fine granular compound is obtained, which appears to be a mixture of the alcoholate additive compound with sodium benznmide. With propionanilide, bntyranilide, diphenylacetamide, and ethyl- acefanilide no definite compounds have so far been obtained by this method. I n the case of propionanilide and bntyranilide such corn- pounds appear to exist in solution ; for if R little ether be added to either of fhese substances, sufhient to dissolve a fraction of the whole, the addition of the sodium alcoholate will at once produce a clear solution ; on evaporating the ether under diminished pressure.nothing separates out until the greater portion of the ether has gone, when crystals of the unchanged nnilide are deposited. Acetanilitle Sodium Metl~yZoxide, C6H,*NH.CO*CH,,CH3*ONa.-l.33 grams of acetanilide is dissolved in dry ether (complete solution is not necessary) and 0.54 gram of finely powdered sodium methoxide is added ; on shaking, a clear solution is obtained, but very soon n, pasty magma of needle-shaped crystals forms. The crjstals are collected, washed with ether, and di-ied over sulphuric acid in a vacuum.The substance forms a white, apparently amorphous mnss. It gave the following results on analysis. H 292 COHEN AND ARCHDEACON: THE ACTION OF I. 0.2455 gave 0.0942 Na2SOd. Na = 12.47. 11. 0.4359 ,, 0.1695 ,, Na = 12.59. 111. 002620 ,, 16.1 C.C. dry nitrogen at 13" and 770 mm. N=7.45, IV. 0.1890 ,, 0.372 COz and 0.1115 H,O. C = 56.98 ; H = 6-55. CgH,,NaN02 requires Na = 12.17 ; N = 7.40; C = 57.14; H = 6-35. I n some of the subsequent determinations, the sodium has been estimated by decomposing the compound with water and titrating with decinormal osalic acid, using phenolphthale'in as indicator. The above compound is quickly decornpofled by water and alcohol and also by boiling ether and acetone, which dissolve out the acet- anilide. It is also decomposed by acid chlorides, forming the methylic salt of the acid, sodium chloride, and acetanilide according to the equation C~HPNH.CO*CH,CH,.ON~ + *R'COCI = C6&aNH-CO*CH3 + NaCl + CH3*COOR'.If acetyl chloride is added to the calculated quantity of the sub- stance suspended in ether, meth;ylic acetate, sodium chloride, and acetanilide are formed; the latter was identified by decomposing it, with potash, into acetic acid and aniline, and by a nitrogen estimation. 0.1905 gave 17.5 c.a. moist nitrogen at 752 mm. and 16'. N == 10.48. CsHgNO requires N =3 10.37 per cent. From 2 grams of the sodium methoxide compound and 1.79 gram of benzoyl chloride, 1 gram of methylic benzoate, and 1.29 gram of acetanilide were obtained.On heating the compound in a stream of dry hyvdrogen for four hours to loo", methylic alcohol distils together with a little aniline ; the aniline was identified by converting it into the plstinochloride and analysing it. (C6H,*NH2)2,H2PLC16 requires P t = 32.66 per cent. Benzoyl chloride acts similarly. 0.294 gave 0.0955 Pt. The residue consisted for the most part of sodium acetanilide. 0.231 gave 15 C.C. moist nitrogen at 759 mm. and 13'. .CgHl2NNa0 requires N = 7.40 per cent. Further, the sodium acetanilide obtained in this way was treated with benzoyl chloride, when benzanilide, melting at 160°, is formed. The substance was analysed with the following result. 0.1745 gave 11.3 C.C. moist nitrogen at 21' and 760 mm. C1,H,,NO requires N = 7.11 per cent. The action of iodine on the sodium methoxide compound suspended in ether gives rise to a number of products, among which phenyl- carbarnine, acet-anilide, and iodoform were identified.Ethylic iodide yields ethyl methyl ether and acetanilide. Pt = 32.48. N = 7.65. N = 7-38,SODIUM ALCOHOLATE ON AMIDES. 93 The following compounds have been prepared in a manner similar to acetanilide sodium methoxide. Where the amide is but slightly soluble in ether, the sodium a.lcoholate has been added to the snb- stance suspended in the ether, well shaken, and then filtered or decanted. The clear filtrate, on standing, deposits crystals of the new compound. Acetanilide sodium ethoxide, (1,Ha*NH*CO*CH,.C2Hs.01\+a.-The preparation of this compound is identical with that of the sodium methoxide compound, and the substance is not distinguishable from the latter.0.283 required 13.9 C.C. decinormal oxalic acid. The following results were obtained on analysis. Na = 11.3 per cent. 0.2345 ,, 11.7 $ 9 9 ) Na = 11.4 ,, Cl0Hl4NO2Na requires Na = 11.6 per cent. Payace to to luidide sodium met h 0;. ide, C H3* C ,H4*NH*C 0 C H3, C H3*0 Na . Prepared as above from paracetoluidide, gave on analysis. 0,113 required 5.6.5 C.C. oxalic acid. Na = 11.74 per cent. CIoH,4N02Na requires Na = 11.33 per cent. Orf hoacetotoluidide sodium methoxide, CH3* C6Ha'NH.C 0*CH3, CH3* ONa, CloRI4NO2Na requires Na = 11-33 per cent. cr-Acetona,hthaZide sodium methoxide, CloH.I.NH.CO*CH3,CH,*ONa. 0.1705 required 7.8 C.C. oxalic acid. Na, = 10.52 per cent, This substance crystallises in brilliant, needle-shaped crystals.0.2875 required 11.6 C.C. oxalic acid. Na 9.3 per cent. C13H14N02Na requires Na = 9.6 per cent. Paracetotoluidide sodium ethoxide, C H3* C 6H4*NH* C 0 4 H3, C2H5* ONa 0.176 gave 0.0566 Na2S04. 0.1413 required 6.5 C.C. oxalic acid. Na = 10.4 per cent. Na = 10.6 per cent. Cl1HlaO,Na requires Na = 10.6 per cent. Od~oacet~toluidide sodizcm e t h x i d e , CH3*C6H4*NH*C 04 H3, C2H5*ONa. 0.1335 gave 0.0440 NhSO,. C11H16N02Na requires Nrt = 10% per cent. a-Acetonaphthulide sodium ethoxide, Cl,,H7*NH*CO*CH3,C2H5*OZITa. 0,4035 required 15% C.C. of oxalic acid. C I P H ~ ~ N O ~ N ~ requires Na = 9.1 per cent. /3- Acetonaph ta Zide sodium ethoxide, C loH,*NH* C 0*CH3, C2H5*ONa. 0.346 gave 0.1 Nhs04. CI4Hl6NO2Na requires Na = 9.1 per cent.Na = 10.6 per cent. Na = 9.0 per cent. Na = 9.3 per cent.94 COHEN AND ARCHDEACON: THE ACTION OF Benzanilide sodium ethoxide, C6H5*xH*C o*c, H5, C2H6*ONa. 0.3040 required 12.1 C.C. oxalic acid. Na = 9.1 per cent. C I ~ H , ~ N O ~ N ~ requires Na = 8.7 per cent. Formanilide sodium ethoxide,( C6H5.NH*C OH),, C2H6.0Na.-If sodium metboxide in molecular proportion is added to formanilide dissolved in ether, crystalline nodules of the new compound are deposited on the sides of the flask and the contents eventually become nearly solid. The following are the results of two analyses of the sodium et hoxide compound. The same thing occurs with sodium ethoxide. 0,398 required 13.1 C.C. oxalic acid, Na = 7.8 per cent. 0.296 ,, 9.6 ,, ,7 N = 7.5 ,, C6H5*NH*COH,C2H5*ONa requires Na = 12.2 per cent.(C6H5.NISI.COH)2,C2H~~Na ,, Na = 7-4 ,, From this it would appear that in the case of formanilide, 2 mols. This might take place in the combine with 1 mol. of the alcoholate. Action of Sodium Ethoxide on Benzamide. In this case, a fine granular precipitate is obtained, which appa- i*ently has a constant composition, but this does not correspond with that of any definite compound. It might be a mixture of equal quantities of the additive compound and sodium benzamide. The action is evident,ly of a different order from that previously described. Three different preparations gave the following results. I. 0.196 required 12 C.C. oxalic acid; Na = 14.1 per cent. TI. 0.1785 ,, 11.1 C.C. ,, Na = 14.3 ,, 111. 0-1945 ,, 12 ,, 7 7 Na = 14.2 ,, C6H5*CO-N~z,CeH,*ONa requires Na = 12.1 per cent.C6H5*COoNHNa requires Na = 16.1 per cent. Action of Sodium Ethoride and Sodium LWethoxide on Diphenyl- acetanxide. Diphenylacetamide dissolves readily in ether, but on the addition of the alcoholate very little of the latter appears to pass into solu- tion; the clear filtrate gives only a slight, flocculent deposit on standing, and on evaporation in a vacuum, unchanged diphenyl- ace t amide separates.SODIUM ALCOHOL-!TE ON AMIUES. 9 5 Action of Sodium Ethoxide and Methoxide on Ethy1nt:etanilide. The same result was obtained as in the case of diphenylacetamide. On the addition of sodium methoxide to the ethereal sohition of the amide, none of the alcoholate appeared to dissolve. Sodium etlioxide was rather more soluble ; b u t in neither case did the ethereal solu- tion, on standing or on evaporation, give any indication of a crystal- line additive compound. Action of lSlodium Ethoxide on Fos..my~henylhydl.cceide.On adding sodium ethoxide to formylphenylhydrazide a yellow solution is obtained, from which an orange-yellow compound is deposited; in the dry state this is of a light ochre colour. 0.0788 gave 0.0623 of NaJ3Oa; Na = 25.6 per cent. C7H,N20Na2 = 25.5 per cent. Apparently, this substance has the formula C,H,*NNa*NNa*COH. The formation of additive compounds of the acetyl derivatives of aniline, the toluidines, and naphthylarnines with sodium methoxide and ethoxide would indicate the presence of an unsaturated group in these amides. Claisen has shown that such additive compounds are formed i n the case of the ethereal salts, and that numerous condensations of these salts with compounds containing the group C‘H2*C0 occur in this manner according to the following equations.I I 0 /ONa -C? + Na.0C2Hj = -C-OC,H,; ‘OR \OR ONa + C2Ho*OH + &OH. ONa 1 1 -CLOC,H, + CH2*C0 = -C< \OR ‘Q-QO Applying this idea to the acetyl derivatives we may have the addition of the sodium alcoholate taking place in one of the following ways. PormuIa I. R’*NH*Y:O + Na*OC2H, = R’*NH*$l<ON2a OC Hj. , CH3 CH3 Formula 11.96 EWAN : THE ELECTROLYTIC CONDUCTIVITY The second formula is the one which appears to us to agree best with the properties of the substance. We have shown that alcohol is given off from the additive compound of acetanilide with sodium methoxide on heating, and that sodium acetanilide is formed.This reaction is confirmed by the experiments of Seifert (Bey., 1885, 18, 1358), who prepared fiodium acetmilide by evaporating to dryness an alcoholic solution of sodium ethoxide and acetanilide. Moreover, there is no doubt, considering the formation of alkyl- anilides by the action of akylic iodides on sodium acetanilide, that the sodium atom is attached to the nitrogen atom. The formation of this sodium compound from acetanilide, sodium methoxide, by heat- ing it, would be difficult to explaiu by the first formula. This being the case, it would appear probable that acetanilide itself has thd formula CsHo-N: C (OH)*CH,. The fact that diphenylacetamide and ethylacetanilide do not appear to form analogous cornpounds is then easily explained, for these two compounds contain no replaceable hydrogen, and cannot therefore form a hydrosyl group. We do fiot, of course, lose sight of the possibility of a tautomeric change taking place at the moment of formation of these addition compounds, for, as Claisen has pointed out, questions of tautomerism cannot be satisfactorily decided where chemical changes are involved. An attempt to solve the problem by the electrical conductivity of the acid amides, kindly undertaken for us by Dr. Ewnn, is desci-ibed by him in another communication.