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SECOND SBRIBS— 189N9 
 
 VOLUME iV . SBCTXOKm 
 
 MATHPMATiCAL. PHYSICAL AND CH2MI0AL BCWNCE* 
 
 
 THE f AtlTOMEftlSM OF 
 
 Oxymcthykne and Fomiyl Compounds 
 
 By CHAS. G. L. WOLF, B.A.. M D. 1^9 4| 
 
 Demonstrator of Practicia Chemistry, McQiU University 
 
 'fa 
 
 FOR SALB BY 
 
 J HOPE 4 SONS, OTTAWA ; THE COPP-CLARK CO.. TORONTO 
 
 BERNARD QUARITCH, LONDON. ENGLAND 
 
 '898 
 
CH^. a. L. WDLF, 1894. 
 
 Section III., 1898. 
 
 191] 
 
 Teanb. R. S. C.' 
 
 'Y.—The Tautomerism of Oxymethylene and Formyl Compounds. 
 By Chas. G. L. Wolf, B.A., M.D. 
 
 Demonstrator of Practical Chemistry, McGill University. 
 (Communicated by Dr. Ruttan and read May 25, 1898.) 
 
 Of the different kinds of isomerism which are found in organic com- 
 plexes, that perhaps which has excited the greatest amount of interest in 
 the last five years has been Tautomeric. 
 
 Tautomerism may be defined as the property which metameric bodies 
 may possess of reciprocal transformation, the change being due to a 
 certain part of the molecule being labile, and under different conditions 
 of having a tendency to select one or other part of the complex as its 
 place of junction. 
 
 The word Tautomerism, derived from the Greek ravros, the same, 
 is not perhaps the most suitable name etymologically that could be chosen,, 
 but as it is the name which has been longest in use, it is still retained to 
 denote this property. Of the other names which have been suggested 
 since the publication of Laar's papers, the more important are : Desmo- 
 tropism, Morotropism, Pseudomerism and Tropomerism. 
 
 Desmotropism, suggested by Jacobson (JiCyuos) ; 
 
 Merotropisra, bj' Michael {Mepos) ; 
 
 Pseudomerism, by Laar (ipsuSffs") ; 
 although having in special cases some significance, are scarcely to be 
 commended, because of the implication that one of the tautomeric com- 
 pounds is the more stable. In the case of ethyl formyl phenyl acetate 
 the stability of the two isomei-s is practically alike, so that, in this case 
 a definition of this kind does not exactly apply. 
 
 Claisen has made the suggestion that the word Tropomerism 
 (Tps(peiv) should be used, but he did not insist upon it, on the ground 
 that there are already too many designations for the property. 
 
 The first important contribution to the subject was that of Conrad 
 Laar, who in his first paper, and especially in his second, attempted very 
 successfully to give a classification of those molecular arrangements 
 which would be capable of existing in isomeric modifications dependent 
 on the shifting of a part of the molecule from one position to another. 
 He divides tautomers according to the number of atoms over which the 
 labile part would move. 
 
 The first classification divides the groups into two : (1) Dyads or 
 artiads, and (2) triads or perissads. From the combination of these one 
 is able to obtain still more complex groups capable of tautomerism. 
 
 Sec. III.. 1898. 5. 
 
 il 
 
92 
 
 ROYAL SOCIETY OF CANADA 
 
 The dyad type is naturally a restricted one, and consists of two 
 polyvalent atoms bound together with more than a single bond, to the 
 one or other of which the labile hydrogen or other group may be attached. 
 Hydrocyanic acid is an example of this class. The formula can be repre- 
 sented in two ways : 
 
 N 
 
 In . 
 
 Hydrocyanic acid, 
 and for the methyl derivatives ; 
 
 N 
 
 Methylcyanide. 
 
 N— H 
 
 Isohydrocyanic acid, 
 
 N-CH, 
 
 D 
 
 Methyl isocyanide. 
 
 Nef here assumes a divalent carbon for the formula of hydrocyanic acid, 
 because of the great addition capacity of potassium cyanide. 
 
 A second dyad type is that to which the benzol sulphinic acids be- 
 long. They contain a grouping which may react as 
 
 ' 0-H O 
 
 I or 11 
 
 0=S-Ph 0=SH 
 
 Ph 
 
 The sodium salts of this acid react with alkyl iodides according to the 
 first formula ; the ethyl ester of carbonic acid gives, on the other hand, 
 the sulphinic esters corresponding to the second type. 
 
 The triads consist of three polyvalent atoms jomed together. The 
 middle atom must bo at least trivalent, and the other two divalent. 
 
 Laar divides the triads into six classes. It would be beyond the 
 limits of this paper to go into a detailed description of the ditterent forms 
 in which triads present themselves, except in so far as the oxymethylene 
 compounds are considered. The following table gives a list of the com- 
 binations in which the elements group themselves : 
 
 TRIAD TYPES— I. 
 
 1_ 
 Class I Group I _x-C-0 
 
 H 
 
 Group II —N— 0^=8 
 
 H 
 Group III _N-C=N- 
 
 and -N = C-0 
 
 k 
 
 and — X=C— S 
 
 and -N=C-N 
 
fWOLP] 
 
 OXYMETHYLENE AND FORMYL COMPOUNDS 
 
 93 
 
 Group IV... 
 
 s-c=o 
 
 1 
 
 
 ^ 
 
 Group v.... 
 
 . -N-C = N-C=0 
 
 k 
 
 Class II Group I 
 
 .. O-U 
 
 Mixed and termin- 
 al carbon atoms. 
 
 i 
 H 
 
 1 1 
 
 Group II... 
 
 1 
 .. -N-C = C 
 
 H 
 
 Group III... 
 
 1 1 
 H-S-C=C- 
 
 Ferissad . . . 
 
 .. 0-C=C-C=N 
 
 1 
 
 
 i 
 
 ■Class III Group I 
 
 ..-Lc=L 
 
 Unsaturated hy- 
 drocarbon chain. 
 
 1 
 
 H 
 
 Class IV Group I... . 
 
 0-N=N— 
 
 Chains without 
 carbon. 
 
 Group II 
 
 1 
 H 
 
 .. -N-N=N- 
 
 j 
 
 
 i 
 
 Class V Group I 
 
 1 
 0-N=C- 
 
 1 
 
 Middle nitrogen 
 and terminal car- 
 bon atoms. 
 
 Group II 
 
 1 
 H 
 
 . . -N-N=C- 
 
 1 
 
 
 i 
 
 Class VI 
 
 ..-cLnJ- 
 
 Two carbon atoms 
 bound together 
 by nitrogen. 
 
 i 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 and 
 
 s=c-o 
 
 -N=C— N=C-0 
 
 k 
 
 o=c~c- 
 
 i 
 
 I I 
 
 -N=C-C 
 
 k 
 
 s=c-c- 
 
 k 
 
 I i I 
 
 0=C-C=C-N- 
 
 I 
 H 
 
 I I I 
 
 c=c-c- 
 
 ! I 
 
 H 
 
 0=N— N- 
 I 
 H 
 
 -N=N-N- 
 I 
 H 
 
 0=N-C— 
 
 A 
 
 -N=:N-C- 
 
 I 
 H 
 
 -C = N-C— 
 I 
 H 
 
 The oxymethylene compounds belong to Laar's second class of triads, 
 in which besides a middle carbon atom, one has at one end another atom 
 of the same kind. To this class belong the ketones, aldehydes and the 
 phenols, which may be represented by the tautomeric groups. 
 
 I 
 
 — c=o 
 
 Keto or aldo form. 
 
 =c 
 
 II 
 
 — C— OH 
 Enol form. 
 
04 ROYAL SOCIETY OF CANADA 
 
 Although Polok and Thumraol have attempted to prove that the 
 tautomer of acetaldohyde, the simplest member of the group except for 
 maldehyde, exists, it is somewhat doubtful if such is the case. 
 
 The alkyl derivatives corresponding to these compounds ai-e however 
 known, for example ; 
 
 H C=0 
 
 Butyric aldehyde. 
 
 H,c.c,ir5 
 
 cii,.c=o 
 
 Methyl propyl ketojie. 
 
 IIC'OC.H, 
 Vinyl Ethyl Ether. 
 
 CH, 
 
 CH3C— OCJI^ 
 Isopropenyl ethyl ether. 
 
 Isomerides are more difficult to obtain in these cases whore the labile 
 part is a hydrogen atom, for the presence of a difficultly movable group 
 Lch as ethyl, by increasing the stability of the molecvde, favours he 
 formation of two compounds of tautomeric structure. That the ethyl 
 trroup itself can be labile is best shown by Claisen's expermcnt ot long 
 continued heating of isoacetonhenon phenyl ether, which changes mto 
 phenyl propyl ketone. The ketone, as one would expect, is the more 
 
 stable compound. , 
 
 The extreme mobility of the hydrogen, as compared with complex 
 groups in cases of this kind, is not to be wondered at, when one sees that 
 it plays the same part in dissociation processes in solution. 
 
 The most important compound which has displayed tautomeric 
 phenomena is ethyl aceto acetate, to which since its simultaneous dis- 
 covery in 1863 by Geuther, and Frankland and Duppa, two formul^ 
 have been ascribed, which are known respectively as the Geuther and 
 Frankland formuUe. Geuther viewed it as a /i oxycrotonic ester, having 
 
 the structure 
 
 CH,-C=CH-COOC,H, 
 
 in 
 
 while Frankland'B formula was that of the otetyl derivative of aeetic 
 
 Gstcr 
 
 CH,CO'CH,COOC,H, 
 
 This ester, on account of the numerous syntheses to which it has been 
 applied, had been the subject of the most thorough study. Many of the 
 derivatives of this most interesting compound are to be described as 
 belonging to the first formula. On the other hand, the physical proper- 
 ties of the compound are only concordant with the second. 
 
 I 
 
[woif] 
 
 OXYMETHYLENE AND FORMYL COMPOUNDS 
 
 9B 
 
 It is thoroforo necessary to assumo if one wishes to bring the two 
 formuiie into concordanco, that although the ester itself is the carboxylic 
 ester of acetone, it is capable of reacting as its tautomor, giving deriva- 
 tives of the oxycrotonic ester. 
 
 Chemical reactions used alone for proving the constitution of a com- 
 pound of this kind, are apt to lead to difficulties which cannot be explained 
 away by any hard and i'ast rule. 
 
 To the second class of Laar belong the ketones, aldehydes and phenols, 
 and also the acids and their esters. 
 
 =CH 
 
 I 
 110—0=0 
 
 = 011 
 C,H,0-O = 
 
 =C 
 
 II 
 
 HO— 0— on 
 
 =0 
 
 CaiijOo— on 
 
 The possibility is therefore present that ethyl malonate may act in a 
 luutomeric sense, and. indeed, Michael has suggested that the sodium 
 derivative of raalonic ester may be represented by the formula, 
 
 OOOC^Hs 
 HC-ONa 
 0OC.,H, 
 
 whereas the free ester certainly has the formula, 
 
 oooojr, 
 
 / 
 
 iicii 
 
 0000,11^ 
 
 The closely allied dicarboxyglutaconic ester, on the other hand, appears 
 to have the enol I'ormula in the I'ree state, and would possess the second 
 of the following two constitutions : 
 
 /COO0.,H, 
 0000.11, 
 
 II 
 
 II 
 
 jj(i, , ooocjr, 
 
 \COO0.JL 
 
 /C00CJI5 
 
 l?\cooc,ii, 
 
 OH 
 O-OOOCJI. 
 
 Ion " 
 
 This would be an example which, compared with acetic ester, would 
 tend to prove the law of Olaisen, that the enol form is the moro likely 
 
96 
 
 ROYAL SOCIETY OF CANADA 
 
 to bo produced tho more negative the groups combined to the methono 
 group in question. Hence, 
 
 y 
 
 COOColL 
 
 ^\COOC,II, 
 
 "COH 
 OC,H, 
 
 Dicarboxvptlutiiconii' ester. 
 
 cooaH, 
 
 CH, 
 COCH, 
 
 Acetoivcetic ester. 
 
 The grounds for this as8uini>tion arc the formation of a lactone, the 
 cthoxypyrone dicarooxylic ester on heating (presupposing tho presence 
 of a hydroxyl group), and also the ferric chloride reaction and the 
 absorption capacity for electrical oscillations of high frequency, the 
 significance of both of which will be explained later. 
 
 The investigation of tautomeric compounds is thus confined to sub- 
 stances which have a double bond and a hydrogen atom in a certain 
 position relative to this bond. Many substances have been obtained 
 which are tautomeric in the sense that certain derivatives obtained by 
 chemical reactions, and which should have been identical, have been found 
 to differ. Such, for instance, to take a simple example, is benzamide ; 
 this substance, and other acid amides, as Tafel and Enoch show act 
 with alkyl iodides according to two formuhv, giving in the one case oxygen 
 derivatives or oximido esters ; in the other true nitrogen esters, which 
 may be represented by the following : 
 
 Cell-Cv, 
 
 
 Here one has a compound which, like ethyl acetoacetate, is homogeneous, 
 but whose silver salt reacts in a different manner from its sodium salt,, 
 
 with the same reagent. 
 
 Benzamide is a representative of compounds which far outnumber tho 
 second class of isomerides, which is more directly connected with this paper. 
 
 These are the compounds which not only yield tautomeric deriva- 
 tives, but can themselves exist in two forms which can be represented by 
 tautomeric formula;. 
 
 On account of the extreme lability of the hydrogen atom, these 
 isomers are much more difficult to obtain. The following table will give 
 a rim-nii of these compounds : 
 
 ACETVLDIBENZOYLMETHANE. 
 
 Claisen, Ann. d. Chem., 291, 25. 
 
 ^C (0H).CH3 
 -CO.CoHo 
 CO.CsHs 
 
 or 
 
 Solid, M.P. 80-85°. 
 
 ^CO.CHa 
 
 HC-^ CCCfiHs 
 
 CO.CeHB 
 
 Solid, M.P., 107-110°. 
 
[WOLP] 
 
 OXYMETHYLENE AND FORMYL COMPOUNDS 
 
 97 
 
 TRIHKNZOYr.MKTHANK. 
 
 ClalHen, eheiida. 
 
 C(On).CBH» ^i.w.v«ris 
 
 C»-CO.C,,H„ or OH CCCnHj 
 
 \co.c„n„ " co.c«n., 
 
 Solid (before melting) Solid, M.P., 222-226", 
 chiuiniiiK to li. 
 
 MK^ITYhOXYUOXAKKSTEU. 
 
 ( ■Metliyl ester and free acid). 
 
 Claisen, ebendii. 
 
 CO. CH : C (CH^lj 
 
 CH : C OH). COOCsII, 
 
 a 
 
 M.P., 21-22 . 
 
 or 
 
 CO. CH : C (CH:,»a 
 CH... CO. COOCjHr, 
 
 Solid, M.P., r)0-flO\ B.F., 20O-2(B'', 
 
 FOHMYM'IIKNYI.AIETIC KSTKH. 
 
 Wislicenus, Ann d. Cliem. 291, 147 
 
 DiOXYl'YHIDlNIJlLAIUiOXYUC KSTKR. 
 
 (luthzL'it, Ann. d. Chem. 285, 35. 
 Ber. d. deutsch. Cheni. Ges. 26, 
 2795. 
 
 DlArKTYLSUtCINIC KSTEK. 
 
 Similarly, Dilienzoylauccinic 
 
 ester. 
 Knorr, Ann. d. Chem. 293, 70. 
 
 CdHj 
 
 .C:CH(OH) 
 
 Fluid, B.P., i:«° b. 15 mm. 
 
 C,,H». 
 COOC..H,,' 
 
 ICH.CHO 
 
 3 
 
 Solid, M.P. ca. 70. 
 
 CH 
 
 CH' 
 
 COOC^Hs 
 
 C : C (OH)-,^^ 
 
 \C - C (OH)/' 
 
 COOC.jHj 
 Solid, M.P., 109' 
 
 COOCoHr, 
 
 -CH CO^ 
 
 \c 
 
 CO 
 
 NH 
 
 COOCjH, 
 Solid, M.F., 179° 
 
 CHa . C (OH) : C . COOC..H5 
 
 CHa . C (OH) : C . COOCaHu 
 
 a 
 
 Fluid. 
 
 CH, . CO . CH . COOC0H5 
 
 I 
 CH3 . CO . CH . COOC..H5 
 
 Solid(''^^-P-'^"- 
 ^°""l} M.P.. (58°. 
 
98 
 
 ROYAL SOCIETY OF CANADA 
 
 Ester ok J. Wislicenl 5. 
 
 Hagemann and Callenbacli. 
 
 Ber. d. deutsch. chem. Ges. IK), (i39. 
 
 CH;,.C: 
 
 rC.COOCoH, 
 
 (2) 
 
 CH .C (OH), 
 
 CH, . CUn^ 
 
 ,C H - CO 
 
 ,CH.COOC,Hr, 
 
 CH3.C 
 
 --CH, . CH,/ 
 
 (1) Fluid, B.P., 150-152° at 22 mm 
 
 (2) Fluid, B.P., 148-152° at 22 mm 
 
 DiBENZOYLMETHANE. 
 
 Wislicenus, Lowenheim & Wells. 
 Ber. der siiehs. Akad. (SitzunR v.) 
 1, March, 18<)7. 
 
 _^C(0H).C„H5 ^, CO.CiH,, 
 
 CH-^^ CH, 
 
 CO.C«H, CO.C„H, 
 
 Solid, M.P., ll-o-lS". Solid, M.P., 77-5-7&° 
 
 Phenylnitromethane. 
 
 Hantzscb & Soi\uli:ze. Berd. d. 
 
 deutsch. Ges. 29, 6!)i), 
 
 2251. " Ref^ trav. 
 
 chim. U <5fi, 30.5. 
 
 CoHv CH = N;: 
 
 (Iso-Ph.) 
 Solid, M.P., 84°, 
 
 ^O 
 -OH 
 
 CuHr,. CH,. NO, 
 Fluid. 
 
 It will now bo necessary to go into the grounds for assuming that 
 the differences in the compounds are due to tautomeric change and not to 
 any other form of isomerism which plays apart in organic chemistry. 
 
 The proofs may be divided into two sections ; physical and chemical. 
 
 Of the two classes, that one which is the more likely to give certain 
 results is the first, for it assumes that in the process of physical examina- 
 tion no change will take place in the compounds under investigation. In 
 the case of chemical reaction, one can never be certain that substances, 
 especially those which are su.-^ceptible to change, will not undergo under 
 the influence of heat, or cold, solvents, foreign substances in proximity, 
 etc., changes which will render the results, if not valueless, at least .un- 
 certain. 
 
 The physical methods which lend themselves to the constitutive ex- 
 amination of substances are few in number, but they have in this direc- 
 tion been exceedingly useful. They are ; 
 
 1. The determination of the molecular refraction. 
 
 2. The determination of the molecular magnetic rotation. 
 
 3. The determination of the molecular volume. 
 
 4. The selective absorption. 
 
 f). The absorption for electric oscillations. 
 
 The first three of these methods are mainly the result of the repre- 
 sentative work of Briihl, W. II. Perkin, sr., and of I. Traube. They are in 
 contradistinction to the latter two, quantitative, and admit in many cases 
 of an accurate judgment being made of the constitution of a compound. 
 They rest on the assumption that the molecular properties of organic 
 substances are the sum of their atomic functions. The spectromclric; 
 investigations of Briihl, who has determined the molecular refVactions of 
 
[WOLF] OXYMETHYLENE AND FOR.MYL COMPOUNDS 99 
 
 a very great number of substances u^ing the foimula of Lorenz and 
 
 Lorentz, and the numbers of Conrady, li = g=^} Where R is the 
 
 molecular refraction, a^i the refractive index, and d the density, and w the 
 molecular weight, snow that in substances of the formyl and oxymethy- 
 leno types, the former possess, in consequence of the lack of a double 
 bond, a much lower molecular refraction that f'ould be accounted for by 
 any errors of observation. The dispersion would also appear to stand in 
 close relation with the constitution of thos- substances. 
 
 Perkin's woik on the influence of the constitution of substances on 
 the rotation which polarized light undergoes when passing through 
 layers of substances in a strong magnetic field, has led to like results. 
 
 The selective absorption of substances has been another property 
 which has been made use of for determining the presence or absence of 
 hydroxyl groups in substances suspected to contain them, and the recent 
 extremely interesting results of Spring wouhl tend to show that there is 
 a detlnite relation between this group and the colour of liquids observed 
 
 in long layers. 
 
 The investigation cf the molecular solution volume which is dependent 
 on the determination of the specilic gravity of solutions, is also a most 
 useful method for the ditfercntiation of isomers of the tautomeric type, 
 and as Wislicenus remarks, it would be of much value, considering the 
 behaviour of these compounds in soluti^.n. to determine quantitatively by 
 this method, to what extent the dissociating caj-acity atVects the compound, 
 and, perhaps^ although open to doubt, one might obtain results agreeing 
 to some extent with those obtained by colorimetric means. 
 
 The last method is that of Dnvde. who in the course of an investiga- 
 tion into the dielectric constants of organic bodies, has shown that com- 
 pounds containing hydroxyl display an anomalous absorption for electric 
 oscillations of a detinite period, but of high frequency. 
 
 The writer 1ms hail the advantage of examining some of the sub- 
 stances which are described in this paper in an apparatus constructed by 
 Prof. Drude. and has been able to confirm resvUts obtained chemically 
 
 by this means. 
 
 The method, which is a beautiiul qualitative one, possesses the ail- 
 vantao-e of giving immediate negative or i.osiiive results, of being easily 
 used ami of requiring but small quantities of the substance under exami- 
 nation. The original papers will be found in Wiedemann's Annalen, (iO, 
 500, and in I he r.crichte der deutscheii chemischen (iesellschaft, 30, 940. 
 ' In contradistinction to the methods above described are the chemical, 
 which, although giving results of the utmost value, arc not attended with 
 the same surety. 
 
100 
 
 ROYAL SOCIETY OF CANADA 
 
 The reagents which are principally concerned in this paper are those 
 which will dilFcrcntiate the formyl group : 
 
 HC=0 
 
 L 
 
 from the oxymethylene group, 
 
 H 
 
 HC— OB 
 
 II 
 HC— 
 
 or, in other words, reagents reacting on hydroxyl, but not on the aldo 
 group. Of these, the first is acetic anhydride. This reacts, as is well 
 known, with hydroxyl comjwunds, giving an acetate according to the 
 general formula : 
 
 =C.OH + (CoH^OO = =C.0C2E,0, + CH3COOH. 
 
 The demand that this method makes for a temperature exceeding 
 100° is suiRcient to render it untrustworthy, and, as with formyl phenyl 
 acetic ester and oxymethylene phenylacetic ester, as with most of the 
 compounds on which it has been tried, identical acetates have been 
 obtained. 
 
 Hydroxylamine and phenylhydrazine have been used to determine 
 the presence of aldehydes or of ketones. That these are of smaller value 
 than one would be led to expect at first sight will be shown in the experi- 
 mental part of this paper, and this is undoubtedly due to the formation 
 from the two tautomers of identical addition products, which on losing 
 water give the same derivative. There is, however, a reagent, which, 
 unlike the amines, seems to have the selective power sought for, and this 
 is phenyl isocyanate or carbanil, suggested by Goldschmidt, and investi- 
 gated further by Michael, which combines with hydroxyl, amide and 
 imide groups, giving respectively urethancs and substituted ureas. 
 
 = C . OH + CJr.NCO= 
 
 CO . CONHC„H, 
 
 = C . NH2 + C,H,NCO= = C . NH CONHCA 
 
 With ketones, however, the substance does not react This has proved 
 to be the case with oxymethylene phenylacetic ester, which gives the 
 corresponding carbanilic acid ester, whereas the ketone compound does 
 not form an additive product with this substance. 
 
 The most general reagent which hus been used for the recognition of 
 hydroxyl in groups closely allied to the oxymethylene combination, has 
 been ferric chloride. This test, which is dependent on the formation of 
 
[wolf] OXYMETHYLENE AND FORMYL COMPOUNDS 101 
 
 a red or blue colour with an aqueous solution of ferric chloride ditteren- 
 tiatcs the group. 
 
 —CO — CII — CO- and - CO.CH . COOC„H, 
 
 from their hydroxyl tautomers, and hence is displayed by ft diketones 
 and ft ketonic esters as acoto acetic ester. This colour is due to an un- 
 stable compound, of which that of Claisen has been analysed. And in 
 the last journal of the Chemical Society, Morrel and Crofts report the 
 isolation of a similar compound from ketophenylparaconic methyl ester 
 by the action of an anhydrous ethereal solution of ferric chloride. 
 
 That the reaction is due to the enol form and not to that of the aldo 
 of keto modification, is shown by the fact that phenols and substances 
 such as salicylic ester display an analogous behaviour. 
 
 This agrees with the results obtained by the treatment of the two 
 forms of formylphenylacetic ester with ferric chloride. That form 
 whose physical properties, molecular refraction, rotation, etc., point to 
 its pjsse.'^sing the enol formula, gives an intense coloration with this re- 
 agent. On the other hand, that having the formyl configuration does 
 not react except after long standing, during which time, owing to the 
 catalytic action of the electrolyte, a tautomeric transformation has taken 
 place. 
 
 One of the most interesting applications of this reaction will be 
 spoken of m the experimental part of this paper. It is the use of a 
 colorimetric method to determine to what extent the tendency towards 
 enolization or aldolization is exerted in media which have different dis- 
 sociation capacities, and although those experiments have not yielded 
 strictly quantitative results, the information they have aftbrded has 
 thrown much light on the tendency of the substances to establish an 
 equilibrium of the two isomers more or less rapidly, according to the 
 nature of the solvents. 
 
 The method briefly described is this : A weighed quantity of sub- 
 stance under examination is dissolved in a definite amount of the various 
 solvents, e.g., methyl alcohol, ethyl alcohol, benzol, ether or chloroform, 
 and after being allowed to stand for a certain time, aliquot parts are 
 diluted with alcohol, a single drop of ferric chloride solution added, and 
 the colour compared in the very convenient colorimeter of Duboscq. 
 They are also compared with a fresh alcoholic solution of the compound. 
 According as the substance has been changed to the enol. or to the aldol 
 form, one gets a deepening of the colour or the reverse. 
 
 It has been shown by Wislicenus, in the case of oxymethylene phenyl 
 acetic ester, that the a form tends to become converted to the keto deri- 
 vative, shown by a lessening of the intensity of the colour, while in the 
 case of the ft compound, a solution after standing has not the same inten- 
 sity of colour as that observed with a fresh solution. 
 
i 
 
 102 
 
 ROYAL SOCIETY OF CANADA 
 
 Belonirinflr to the same class as the ferric chloride reaction are the 
 compounds which arc formed by substances containing the enol complex 
 with the alkali metals, and with copper and silver. All those substances 
 containing a labile hydrogen atom, with the exception of Laai''s class III., 
 give compounds with the metals. 
 
 It is now of interest to know how far the metals possess the same 
 capacity as the hj'drogen to give tautonieric compounds. It is well 
 known that the dissociation constants of weak organic acids are not so 
 large as these of the corresi)onding salts. It would, therefore, bo expected 
 that on account of the extreme lability of those atoms, the isolation of 
 tautomers would be much more difficult. As yet, isomers of this kind 
 have been obtained in relatively few cases, one of which is to be found 
 with oxymethylene phenyl acetic ester. 
 
 The determination of the constitution is also much more complex, as 
 there are at present no physical methods to guide as in the case of the 
 original substances. 
 
 When the a t'orni of oxymethylene phenyl acetic ester is dissolved 
 in ether, and the mixture treated with metallic sodium, one obtains a 
 sodium derivative which must be regarded as 
 
 NaO : CII : C • C,U^- COOaH^ 
 
 This gives immediately on acidification the liquid ester, and shows the 
 intense coloration with ferric chloride.. If, however, one allows a solu- 
 tion of the sodium compound in water to stand for even a minute before 
 acidification, one obtains not the ^ form, but crystals which are in every 
 way characteristic of the form, and which give no coloration with 
 the ferric chloride solution. 
 
 This would show, that starting with the a ester one obtains a sodium 
 derivative of that ester which, on solution in water, is so excessively un- 
 stable that inside of sixty seconds a tautomeric change takes place, con- 
 verting the whole of the enol form to the keto form, which can therefore 
 but have the constitution 
 
 IIC=0 
 
 cji, c . Na . cooaiij 
 
 The remarkable behaviour of ethyl formyl phenyl acetate in alkaline 
 solution towards acids under different conditions, and towards carbon 
 dioxide must here be noticed, as it bears very directly on some of the 
 results obtained in this paper. 
 
 If one dissolves indifferently either the <r or /i ester in dilute (normal) 
 alkali, one obtains a solution which, according to the foregoing, must be 
 regarded as the sodium derivative of the fi form, because when an excess 
 of acid is added there occurs an immediate precipitation of the aldo-ester. 
 
[W01.F] OXYMETHYLENE AND FORMYL COMPOUNDS 103 
 
 If, however, the acid be added slowly and in small portions, one 
 obtains at first the a ester, and finally a point is reached where the fi 
 ester is also thrown down. If carbon dioxide be led into the solution, 
 one also gets as a first precipitation the oily ester and afterwards a crop 
 
 of the ciystals. 
 
 This would be explained by the assumption of a state of equilibrium, 
 which in the first part of the reaction is disturbed by the precipitation of 
 the less acid or a ester, which under slow acidification is again formed at 
 the expense of the /i compotind. When, however, acidification takes 
 place quickly, no time is given for the establishment of equilibrium, 
 hence the oxyraethylene derivative is precipitated at once. 
 
 The (i sodium compound of ethyl formyl phenyl acetate reacts with 
 copper sulphate or acetate, giving two derivatives which are fairly stable, 
 and which correspond to the a and (i modications. The latter is the 
 less stable, and by allowing it to stand in the exsiccator, changes in the 
 course of a few hours into the a modification. Here, also, without the 
 use of a solvent one must assume a shifting of the copper atom from the 
 formyl complex into the oxymethylene type. 
 
 From the behaviour of the sodium and copper derivatives of the 
 formyl phenyl acetic ester in the solid state and in solution, one might 
 naturally expect that by acting on these in a medium with small or large 
 dissociation capacity, one would obtain with alkyl and acyl iodides 
 compounds differing according to the position of the substituting groups. 
 
 As one may imagine in the case of a solution of a sodium compound 
 in water, the sodium atom will be in great part dissociated, and there 
 may be to a large extent a condition of partial freedom of the organic 
 part of the molecule. In consequence of this, one has the substituting 
 group entering at the position which from nature it has a tendency to 
 
 select. 
 
 On the other hand, if one uses a medium like absolute ethor, which 
 allows of very little, if any dissociation, one will get direct sub-stitution ; «.e., 
 a substiuition oc.urring at the situation lately occupied by the metal. 
 That this occurs will be shown in the case of formyl ])ropionic ester. 
 
 Conversely it follows that by starting with a compound of definite 
 configuration one can by no means be sure that the derivatives obtained 
 by alkylizing or acylizing will have the same structural peculiarities 
 which characterized the original substance. 
 
 Since writing the above, two papers have appeared by Robert Schiff 
 on the " Tautomeric Forms of Aceto Acetic Ester and similar compounds." 
 By taking different samples of acetoacetic ester, and condensing them 
 with benzal aniline in the presence of tracv.- *' piperidine, or of sodium 
 athelate, he has obtained benzal aniline additic.i priuiucts of aceto acetic 
 ether, which belong to the enol form of that ether, and also to the ketol 
 form. It would appear that the formation of oxymethylene compouMds 
 
104 
 
 ROYAL SOCIETY OF CANADA 
 
 by means of sodium ethylate, would in the highest degree tend to the 
 formation of enol derivatives, and it is quite possible, could one perform 
 this condensation with substances having a ketolizing action, that the 
 tautomeric substituted acetic esters would be produced. 
 
 It would appear from Schitf' s results that the influence of piperidine 
 and sodium ethylate on the condensation of substituted acetic esters with 
 bcnzal aniline is a general one, and it would be of interest to learn to 
 what extent such syntheses can be accomplished in the oxymethylene 
 
 series. 
 
 EXPERIMENTAL PART. 
 
 OXYMETHYLENE BENZYL CYANIDE. 
 
 Oxymethylene benzyl cj-anide was prepared, according to Claisen's 
 method, by condensing benzyl cyanide with amyl formic ester in absolute 
 ethereal solution by means of metallic sodium in the form of wire. The 
 sodium salt was deconn.posed by means of acetic acid, and the compound 
 recrystallized from alcohol ; it forms white needles, melting at 166°. 
 
 An attempt was made to pre])are the sodium salt by acting on the 
 cyanide with metallic sodium in absolute ether; no reaction took place, 
 even after the mixture was allowed to stand some weeks. The compound 
 was prepared by adding the calculated quantity of sodium ethoxide to a 
 solution of the cyanide in absolute alcohol. The compound comes out as 
 a white amorphous powder, of which more is obtained on adding absolute 
 ether. 
 
 0-3282 gram of sodium salt gave 0-1392, NaaSo,, 
 calculated for CJI^NONa 13-77%, 
 
 found, 13-74%. 
 
 Preparation of the Benzyl Comjwund. 
 
 In order to examine the behaviour of the sodium compound under 
 different conditions of dissociation, it was benzoylated in aqueous solution 
 and in ethereal suspension. For this purpose 55 grams of the dry salt 
 were suspended in ether, and after being cooled with ice, 4-6 grams of 
 benzoyl chloride were slowly added, the mixture being well stirred. No 
 rise of temperature was observed. The mixture was allowed to stand 
 over night in a cool place, and at the end of this time the sodium chloride 
 and unchanged sodium compound tiltered off and extracted ten times 
 with ether. The ether evaporated and left a crystalline mass smelling 
 strongly of benzoyl chloride. The residue was crystallized, first from 
 ethyl acetate, and finally twice from dilute alcohol. 
 
 The melting point remained constant during alcohol crystallization • 
 M.P. 117°-118°. 
 
[wolf] 
 
 OXYMETHYLENE AND FORMYL COMPOUNDS 
 
 lOS 
 
 O'lfiOO gram of substance gave 0-475(5 CO2 and 00644 HjO. 
 0-3222 " " " 15-4 CC8. moist nitrogen at 18°, and 
 
 741 mm. pressure. 
 
 C,gHi,NOo requires C = 77-10°, H=4-41°, N = 5-62°; 
 found 0^77-26°, H=4-44°, N^5-41°. 
 
 Action of Benzoyl Chloride on the Sodium Compound in aqueous solution. 
 
 5-5 grams of the sodium compound were dissolved in 50- ccs, of water 
 in a stoppered flask, and the solution cooled externally by means of ice. 
 4*6 grams benzoyl chloride were then added gradually, the mixture being 
 shaken constantly for two hours. At the end of this time the precipitate 
 which had fallen had agglutinated to a soft mass. Dilute sodium hydrate 
 solution was then added till the acid reaction had disappeared, and the 
 soft mass farther rubbed with the alkali till all smell of the acid chloride 
 was no longer evident. The solid was then separated by means of the 
 pump, Avoll washed with water, and recrystallizedfrom ethyl acetate and 
 from dilute alcohol. 
 
 This presented the same characteristics as the compound obtained 
 previously, coming down as short thick prisms, melting at 117°. 
 
 0-1988 gram substance gave 0-5642 gram CO2 and 0-07U4, H,0. 
 
 0-2612 " " " 12-65 ccs. moist nitrogen at 17° and 735 
 
 mm. 
 
 Calculated for CioHuNOo. C=77-10°, 11=4-41°, N=5-44° ; 
 
 found, C=77-3!1°, H=4-43°, N=5-48°. 
 
 Hence oxymethylene benzyl cyanide gives but one acyl derivative on 
 being benzoylated in absolute ether and in water. 
 
 Colorimetric Estimations. 
 
 0-2 gram of oxymethylene benzoyl cyanide was dissolved in 10 ccs. 
 each of methyl alcohol, absolute ether and benzol. This was allowed to stand 
 for 24 hours, and at the end of this time 2 ccs. ci the solution taken and 
 diluted to 10 ccs. with absolute alcohol and a single drop of ferric chloride 
 solution added, and the coloured solutions examined in the Duboscq color- 
 imeter. It will not be necessary here to give details of the colorimeter 
 readings, which were carefully controlled by duplicate experiments. The 
 results, however, would show that if one can take the lessening of colour 
 as a criterion of the amount of ketolization occurring in dissociating 
 media, the relation of the amount of aldo compound in alcohol to that 
 in methyl alcohol was as 1 to 1'5321. 
 
 In the case of benzol and ether, the amount of ketolization was so 
 small that no difference could be detected between the amounts obtained 
 from the fresh solution of the oxymethylene ester and that to be found 
 after the substance had stood in a solvent for 24 hours. 
 
106 
 
 ROYAL SOCIETY OF CANADA 
 
 The Copper Salt of Oxymethylene Benzyl Cyanide. 
 
 1-45 gram of oxyraothylone bonzol cyanide was dissolved in 15 ecs. 
 of alcohol, and 10 ccs. of a 10" solution of copper acetate added. There 
 appeared to be a salt formed, so excessively soluble that it was immedi- 
 ately dissolved. Later on an amarphous dark green powder was pre- 
 cipitated ; this was separated and proved to be a basic salt of oxymethy- 
 lene benzyl cyanide. It is insoluble in ether, alcohol and water, and gave 
 on bonzoylating the same benzoyl ether previously obtained. 
 
 li 
 
 OXYMETHYLENE CAMPHOR. 
 
 Oxymethylene camphor was prepared according to Claisen's direc- 
 tion, and further purified by distillation with steam. It forms a white 
 crystalline mass, melting at 80°. The action of phenyl isocyanate on this 
 compound has been jireviousiy investigated, and the coloration with 
 ferric chloride was indicative of the enol form. 
 
 That the aldol compound of methylene camphor is not produced in 
 a manner to be isolated is shown by the following experiments : 
 
 The sodium compound was dissolved in water, and the solution 
 divided into two portions, one of which was made acid with dilute sul- 
 phuric acid, the other with carbon dioxide ; both operations were con- 
 ducted in the cold. It appeared at first that the compound precipitated 
 by means of the gas possessed a lower molting point than that obtained 
 by sulphuric acid. This was found not to be the case on carefully repeat- 
 ing the experiment. The intensity of colour given by equal amounts of 
 ferric chloride and of the respective compounds, was in all cases the same. 
 Claisen's observation that the melting point of oxymethylene camphor is 
 much depressed by traces of moisture, appears therefore to be correct. 
 The influence of carbon dioxide on the alkaline compound was next 
 investigated : 
 
 The solution was made as cold as possible, and a slow stream of the 
 gas led into the mixture. After a part of the oxymethylene camphor 
 had been precipitated, the compound was filtered off quickly and carbon 
 dioxide again passed in. Both these samples proved to be identical in 
 melting point, ferric chloride reaction, etc. 
 
 A jiortion of the sodium compound was dissolved in iced distilled 
 water, and ice cold dilute sulphuric acid added, and the mixture shaken 
 out immediately with ether. 
 
 The ether solution was made up to 5 ccs., divided into two portions 
 of 2i CCS., and one portion evaporated on the water bath. After evapo- 
 ration, both tests were made up to the same bulk, and a drop of ferric 
 chloride solution added to each. 
 
 i 
 
Iwolf] OXYMETHYLENE AND FORMYL (OMroUNOS 107 
 
 Absolutely no ditVeroiico in the two toKts could be obsevveii. 
 
 This would show that evrn under the most tiivouniblo cundilions 
 aldolization in this eompourd does not take place. 
 
 That the aldol compound docs exist in a state of e(|uilibrium in solu- 
 tit)n together with the oxymethylene compound, is shown by the follow- 
 ing eolorimetrie estimations : 
 
 Two grums of the oxymolhyleno camphor were dissolved in methyl 
 aleohol, ether, and in benzol ; allowed to stand for 24 hours, and at the 
 end of this time 2 ccs. of eaeh were made up to 10 ccs., mixed wi'h a 
 single drop of ferric chloride solution, and compared in the colorimeter. 
 
 The intensity of colour was inversely to the dissoi-iating ca|>aeity of 
 the solvents. The colour produced by ether and benzol was practically 
 alike ; that by ethyl alcohol was about half as strong, and methyl alcohol 
 was again weaker. 
 
 KxHYIi OXVMETHYLENE PROPIONATE. 
 
 Oxyniethylene propionic ester was prepared according to the direc- 
 tions of W. Wislioenus. by condensing formic ethyl ester and propionic 
 elh}-! ester in absolute ether by means of metallic sodium. 
 
 The compound is volatile with ether vapcuir, and hence gives small 
 yields, which can be increased by using a long Jlempel's column or other 
 similar device for distilling oflf the ether. 
 
 It boils at 142° at ordinary pressure. The sodium compound is 
 easdy prepared by treating the ester with sodium wire in ab.'^olute ether. 
 It forms a yellowish white solid, which was dried in vacuo. 
 
 P)rp(ir<ition of Ester Xo. 1. 
 
 Instead of benzoylating this com])ound with benzoyl chloride, the p. 
 nitro benzoyl chloride was used in order to get the melting point of the 
 benzoatc as higli us ])ossible. 
 
 1-85 gram of p. nitro benzoyl chloride was dissolved in 5(1 grams 
 absolute other, and after cooling with ice, 152 gram of the tinely pow- 
 dered sodium compound was added. The reaction takes jjlaco quickly, 
 and at tho end of 24 hour.s is at an end. The mixture was then filtered 
 through a paper cone in a Soxhlet tube, and exhausted with ether. This 
 left tho sodium chloride in the cone, the ether dissolving out the benzoate. 
 The benzoate was recrj-stallized three times from alcohol, and forms long 
 slightly yellow needles, melting at 120°-121°. 
 
 0- 158(1 gram substance gave 0-::{24() gram CO, aiul (l-lKUi II^O. 
 
 0'13;i2 gram substance gave (II.) ccs. moist nitrogen at 19" and 
 G4T mm. 
 
 Calculated for C,., II,, NO,. 
 
 C = 55 91X, II = \'^:rfo, X = -y^\%. 
 
 found, C = 56-11%, U = 4-49%, N = 5-22;^. 
 
 Sec. III., 1898. (). 
 
108 ROYAL SOCIETY OF CANADA 
 
 Pre/xtrafion of Exter N<>. II. 
 
 1-52 ^vii\n of tho sodium coiiipoiiiul of oxynu'thyU-no propionic 
 ethyl os,ti"i- was dissolved in 50 ecH. of wnlef, and ufter euulinir 1-52 frrams 
 of p. iiitro benzoyl ehloi-idu and u few drops of sodium hydrate solution 
 added. The mixture was tlien shaken eon.-tantly for six hours. The 
 ester whieh was jireeiiiitatcd was tillered oil liy means of the pump and 
 reerystullized three limes from alcohol. It had a meltini,' jioinl at least 
 20 degrees highei than iho ester obtained fiom the ethereal solution, it 
 melted con.slantly at U(r-142°, ami givi's the following results on analy- 
 sis : 
 
 0-2142 gram gave 0-4408 gram (XK and 0822 gram ILO. 
 
 0-:5000 gram gave 14-0 ccs. moist rntrogen at lit" and 747 mm. 
 
 Culculuted iorC,, 11 „ NO,,. 
 
 C = 55-91%, U = 4-05%, N = 501%. 
 
 found, C = 50-10%, 11 = 4-20%, N = 5-20% 
 
 It was now of importance to see which of the two compounds was 
 the labile one, and if one Avere the nuire stable, to see it a slutting ol the 
 benzoyl group could be etfected. In order to do this one gram of each 
 was introduced into a small tube, the ends sealed, and both heated for an 
 hour in the vapour of dijdienylamine. B.l'. :{10°. Both charred, and on 
 exlracliiig the charred residues with alcohol no crystalline ]U'oducts were 
 obtained. 
 
 The substances were next distilled in vacuum, and in which tliey 
 boil without dec(tn\iiosition, lienzoatt No. 1 boils at about 215°-217° at 
 15 mm., l)Ut did not apjiear to be changed, as the melting point remained 
 the same as before (120°). 
 
 The desired etVeet was jjrodneed by heating the two substances in 
 closed tubes in a batli of sulphuric acid at 2l5"--250° for live minutes. 
 After rccrj'stallization both melted sharply at 140°. 
 
 If one assumes that the two isomers are not stereoisomerie in the 
 sense of fumaric and nuileie acids, and are not to be represented by the 
 fornuihe 
 
 11C0UC-(V,11.N02 
 
 II 
 
 ciijC-coocyi, 
 
 but by the tautomeric forinuhe 
 11-C-00C-C,H,N02 
 CH3CCOOC2IIJ 
 
 CUI,NO..C-UO-("Il 
 
 II 
 
 .cjIjUCouCjH; 
 
 11 C : 
 ClljC-COOCoII, 
 OCC.H.NOj 
 
[ wolf] 
 
 OXYMF/rilYLKNE AND FORMYL COMPOUNDS 
 
 109 
 
 it follows lliat tlie olmiigo of ono of tliese substuiices into the other must 
 bo the lesult of tho (shifting of the heavy benzoyl group iron\ ono part 
 of the molecule to the other in an analogous manner to CUUson's example 
 of isopropenyl ethyl ester. 
 
 One cannot, of course, fix either of the tiuitomeric configurations to 
 the formula of ono or of the other of those compounds, but it is safe to 
 conclude that tho isomerism is tautomeric and not stereoisomeric. 
 
 Ox\'mothyleno propionic ester was examined with Professor Drude's 
 apparatus for anomalous absorption, and the results obtained by this 
 method prove conclusively that tho ester had the enol contiguration, as 
 the absorption for electric oscillations was of the most marked type. 
 
 OXVMETIIVLENE SUCCIMC KsTEH. 
 
 Oxymethylcno succinic ester was prcpaivd according to tho direction 
 oi' Wislicenus, by treating ethyl succinate with ethyl formate in the 
 presence of sodium in absolute ethereal solution. 
 
 The reaction docs not pi'occH'd smoothly, and must bo carefully 
 watched, for if the mi.Kture lie made too cold tli(! reaction does not take 
 place readily, and, on the other hand, if the tomporaiuvo rise, the mix- 
 ture boils, and large ([uantities of succinylosuccinic ester are formed. 
 
 O.xymclhylene succinic ester is ;in oil boiling at 1;;')° at a pressure of 
 20 mm. 
 
 The action of p. nitro heii:ot/l rhloride on oxi/methylene, surri7uf ester. 
 
 If the sodium compound of oxymethylene succinic ester be bonzoy- 
 latod according to the ordinary SchottonBaum mn method, the vield is 
 by no means good, so that one proceeds in the following way : 
 
 The ester is dissolved in the calculated quantity of normal sodium 
 hydrate in a small stopperi'd flask, and covered with a layer of other. 
 (Jiie molecule of p nitro benzoyl chloride is then added, also a few drops 
 of .sodium hy<lrate solution, the flask is then continuously shaken for an 
 hour, at tlus end of which lime the bottle is tilled with a mass of silky 
 needles. These are filtered olV and recrysfallizeil Irom dilute alcohol. 
 The compound melts sharply at HH". It gavt; the following numbers of 
 analysis : 
 
 0-22()0 gram gave ()-452tJ gram CO., and ()01)82 gram ILO. 
 
 (t'27-l:2 gram gave 10 4 ccs. moist nitrogen at 22° and 751 mm. 
 
 C,„ II,. NO, requires C = 54 70 ;/. II = 4 82%, N = 3'1»S%. 
 
 found, C = 54-»)l:;„ II = 4'82%, N = 4'13r„. 
 
 The oxymethylene succinic ester was also bcnzoylated in ethereal 
 solution. For this ])urposo 202 grams of the esttsr were dissolved in 
 ab.solule ether, and to this 0-2.'i gram of .sodium wire added. After the 
 ester had been completely converted into tho sodium derivative, the cal- 
 
no 
 
 ftOYAL SOCIKTY OF CANADA 
 
 ciiluled iiiiaiility ot'ji. iiitvol bi'iizoyl clilorido wum added, mid th« mixture 
 iiUowod to Htand lor sotno dayn. Alter tiltering from tlic Hodium cblonde 
 the ethereal solution was evaporated, and the residue crystallized from 
 alcohol several times. 
 
 The meltiiit,' point of the comi»oiiiid was identical with that of the 
 preceding, namely, 1(14°. 
 
 It gave the following mnnbei-soii analysis : 
 
 ('„ 11„ NO. requires C = 54 70%, U = 4-82%. 
 
 found, (' = .i4-9!ty„ II = 4-80x. 
 
 The Preparation of the Copper Cumpoirml. 
 
 404 grams of oxymethylene succiidc ester were dissolved in a little 
 alcohol, and 19!t gram of cuprie acetate in a 10% solution in water 
 added. On strongly cooling the mixture the copper compound is pre- 
 cipitated in splendid long green silky needles, which on crystallization 
 fiom alcohol melt at V.VA°-rA5°. 
 
 OM^Ul gram gave, on ignition. 0545 gram Cu O. 
 
 Calculated for C,s Hjb 0^ Cn. 
 Cu = 13-54%. 
 
 found. 13-25%. 
 
 The colorimetric estimations of oxymethylene succinic ester were 
 cuiricd on in exactly the same way us with the previous compounds. 
 The ditference in colour after the solutions were allowed to stand was so 
 marked that no comparison could be made. In the case of oxymethylene 
 alcohol, the ketolization appeared to have gone so far that with ferric 
 chloride scarcely any colour could be observed. 
 
 Oxymethylene succinic ester shows nuirked absorption for electric 
 oscillations when exanuned with Drude's apparatus. This result was in 
 accordance with the chenncal results obtained above. 
 
 The Relation of Oxvmetiiyf.ene SrcciNtc Kster to Aconic Acid. 
 
 Oxymethylene succinic ester bears a close relation to aconic acid, 
 which has been investigated by Kekuld, Heers, Swarts and Meilly. 
 
 lieittcr, in an investigation of the methyl ester of aconic acid, has 
 shown that this ester reacts with phenyl hydrazine, giving two com- 
 ]iounds melting at 107° and 178° respectively. 
 
 The formula whicdi he ascribes to the first is that of a hydrazone- 
 hydra/ideof the hy])othetical (;a\ i 'v onic acid: to the second, a hydra- 
 zone-dihyra/.ide of the .same cornp'-Tjcl. 
 
 The following experiments v.-o '.;• tend to show that in the action of 
 phenyl hydrazine on oxymethylene succinic ester, two substances are 
 
 I 
 
[woir] 
 
 oxymethyi;ene and foh.myi. comi^ounds 
 
 111 
 
 formed. Ono has a multiiig point ol' llO^ana srives aiutlytical resulls 
 a^rt't'iii^ with thu pyrazolono Ibrmiiiii 
 
 NC.II, 
 
 0(; N 
 
 COO(Uf,(!H.,II(' — cir 
 
 Oxyinuthylone 8ucciiiif ostcr on Ireatmont with extern of phenyl hy- 
 drazine, or treatini,' tho pyrazolone with another molecule of the same re- 
 agent, a splittin^r of tlie jiyrazolone ring takes place with the formation 
 of tho hydrn/.onedihydiazido of formyl succinic acid. 
 
 Tho compound melting at 1()7° was not obtained. 
 
 It is now of interest, considering that oxymethylcne succinic e.ster is 
 the ' .;i ' corresponding to tho lactonic aconic acid, to investigate the 
 action of phenyl hydrazine on this former sub.stance, for in this way it 
 was that some light might be thrown upon the constitution of aconic 
 acid, which has been variously represented by the following constitu- 
 tions : 
 
 COOU 
 HC = C — CH,, 
 
 I I 
 O - CO 
 
 H,C 
 
 rooH 
 
 C = OH 
 
 I I 
 
 O — CO 
 
 4 grams of formyl succinic ester wore mixed with two grams of 
 phenyl hydrazine freshly distilled. The mixture immediately became 
 hot and turned deep red. It did not solidify in a freezing mixture. It 
 was then boated for some hours on the water bath, and tinally in a paral- 
 tin bath at IG0°. On cooling and adding a very little ether, the mass .set 
 perfectly solid. Thesubstance was recrystaliizcd from low boiling petrolic 
 ether, and then from alcohol by dissolving at TO'' and placing the solu- 
 tion in tho freezing mixture. Tho sub.stance melted at 110°. It gave 
 tho following numbers on analysis : 
 
 Oi27;{ gram gave 0-29GJ gram CO., and O-OC.J-l gram IL.O. 
 
 OiOTC gram gave IT'l ccs. moist nitrogen at 2'.'," and 750 mm. 
 
 Calculated for C„ ll,^ No O,, 
 
 C = 6}Ul%, II = .')(;9%, X = 11-34%. 
 
 found, C = C:{-41%. II = 570,^. N = ll-.3!)%. 
 
 It is, therefore, tho pyrazolone ester of J jibcnyl jiyrazolone, 4 acetic 
 acid. 
 
 An attempt was made to obtain the acid corresponding to the pyra- 
 zolone ester by bydrolyzing the ester, but no dclinile compound could bo 
 isolated. 
 
 In order to ascertain whether by the treatment oi" the pyrazolone 
 osier with excess of phenyl hydrazine a sjilitting of the ring could bo 
 
112 ROYAL SOCIETY OF CANADA 
 
 effected svitli tl>o formation of the hydrazone-hydrazide, a quantity of 
 the i^yrazolone, melting at 110°, was treated with phenyl hydrazine at 
 1(]0- in a parattin bath. On erystallizing, a compound was obtained, the 
 melting point of which was found to be U)0', and gave the following 
 numbers on analysis : 
 
 0-22IJ8 gram gave 0-5-t90 gram CO.;, and 01038 gram H^O. 
 U0G97 gram gave 12-8 ccs. moist nitrogen at 23° and 74G mm. 
 Calculated for C,;, IL4 N, O.. 
 
 C = (](!':J4%, II = f>-r^%- N = 20-19%. 
 found, C = MOl%. II = 5-32y„, S = 20'4G%. 
 
 The Kime compound was prepared by treating oxymethylene succinic 
 osier with two molecules of phenyl hydrazine, whicdi gave the same com- 
 p„uml melting sharply at 190°. and a nitrogen determination gave a nitro- 
 gen content of 20'r)r)t,. 
 
 It is therefore evi.lent that the jiyrazolone obtained by the treatment 
 ..foxymethvlene succinic e.ster with one molecule of i)henyl hydrazine, 
 on the addition of an.aher mclecule of the reagent, splits according to 
 the following : 
 
 ll.C. CH., COOC, li- 
 
 ne 
 
 \;o 
 
 CHoCONII XHC.ll, 
 C = X.NH C\ H, 
 
 II I +2C„ 11. Nil. NIL,= I 
 
 It vl eU ■ CII.CONIINHCJI, 
 
 Lriviii'r the hvdrazone-hvdrazide of formyl succinic ester, 
 
 Kxt^ERlMENTS WITH FnR.MYL PhENVI. AcETIC EsTER. 
 
 As formyl phenyl acetic ester shows such a marked tendency 
 towards kelolization in dissociating media, it is of interest now to ascer- 
 tain what etlect substituted hydrazines would have on solutions of the 
 ester which had been allowe.l lo stand lor .some lime. For this purpose 
 a qnantilv of formyl phenyl acetic e.ster was heated at Hf for some hours 
 in order to eonvert'it completely into the enol form and one gram of the 
 ester was dissolved in 50 ecs. respectively of methyl alcohol and of 
 benzol. After 24 hours standing the calculated quantity of phenyl 
 hydrazine freshly distilled was added and the nii.xture allowed to stand 48 
 hours. On the addition of the reagent, the methyl alcohol solution be- 
 came slightly coloured, the benzol solution inside of ten minutes was a 
 deep yellow .'and on standing 24 hours the colour of the methyl alcohol 
 solution was deep yellow, while that of the benzol was deep green. There 
 appeared to be in the benzol drops of water deposited. 
 
 The solvents in both eases were distilled off at the room temperature, 
 by ].lacing the receivers connected with the Hasks containing them in a 
 freezing mixture, and evacuating. The methyl alcohol solution left a 
 
[wolf] OXYMETHYLENE AND FORMYL COMPOUNDS 113 
 
 palo yellow mass which became fluid at the temperature of the room, and 
 set in the freezing mixture. 
 
 The benzol solution giivo 11 scmi-erystaliine green mass which re- 
 mamed solid at the room tempenituro. The benzol solution when allowed 
 to stand for some time deposited crystals which, when Hltere.l olV and 
 dried on a porous tile, melted at 192°. 
 
 Both the residues above mentioned on being exposed to air for 48 
 houre turned red. It appeared to be impossible to isolate from either oi' 
 the.se residues a deHnite crystalline i)roduct, although the benzol residue 
 was to a large extent crystalline. 
 
 The behaviour of the residues dissolved in concentratcnl sulphuric 
 acid was quite similar. They dissolved with a decq) red colour. A crys- 
 tal of potassium bichromate makes the colour markedly deejier. 
 
 The methyl alcohol i-esidue was heated in a test tube over a free 
 flame. A lively reaction ensued and alcohol was given off. The oil set to 
 a cry.stalline mass. This was dissolved in alcohol and water added, an.l 
 comes down again as a light [)rown substance identifled with the 1-4 
 methyl phenyl pyrazolone melting at 1!)2^ not sharp. It was also i,leii- 
 tiried by the pyrazolone reaction wilh sulphuric acid and fenic chloride. 
 
 The benzol residue gave a similar yield of the same comi)uuiid. 
 
 The Action of p. hrn)a}ih.c)njl Hijdrazinr. 
 
 2 grams of formyl pli.nyl acetic ester were dissolved in KlO ccs. of 
 methyl alcohol an.l lOi) ccs. „f b.Mi/.ol n'spectively. and alloweil lo .stand 
 24 hours. After this time the calculated (|iiantity of the liydra/,ine was 
 adiled and the mixture allowed to stand at oiMinary Icniperalniv. After 
 a lap.se of 12 hours the iien/.ol .solution hail I'ccoiue turbid, and alter L't 
 hourw had deposited a somewhat large ([uantity of crystals. Tlie.se were 
 filtered otfand the solution evuiioraled in vacuo at the onlinarv tempera- 
 ture. 
 
 The crystals so obtained al'tei- crystallization from aleoli.il in whirli 
 they are sparingly .soluble, melted witii decoin|iosition at 2J.') ' and irave 
 the |»yrazolone reaction. 
 
 Tlie solution on evajioration ly^ww a semi .soliil nuiss, which was|ilaced 
 on porous plates and washed with .1 little alcohol and reerystallizt'd frotn 
 alcohol, ill which it is (piite soluble when hot and only sliglitlv.so when 
 cold Ithasidsoa melting point of 2;");)". It gave (he following num- 
 bers on analysis : 
 
 0-I0;50 gram gave O'OiibJ gram AgHr. 
 Calculated for, (",. ir,, N.,Hr()Hrr=25-4h;;. 
 found, nr~2r)-.'](i%. 
 
 The methyl alcohol solution on being treated in the .same wav gave a 
 yellow paste which did not solidify l)ut stitlened in the freezin^r mixture. 
 
J14 ROYAL SOCIETY OF CANADA 
 
 On lu.alin. to lOO^ on tl.- water butl, it ,.ave a dry 3-"-;;«^^ f'f^ 
 ^:':Z>^^ with difficully i.. aicol..! and was -.THtaU.^ i^- U. It 
 also nu-lU-d ul :t^y\ U ;;ave tl.o iblluwing number, om analysis . 
 
 111".)!;-) .Main i;ave OlltlO K'"^'" A^-'Bi'. 
 
 Culculaledh.rC, 11„N, l^i-OHr = U5 41%. 
 
 round, J}r = •24-52%. 
 
 1, i.s hen.e il.c 1-4. id.ei.yl p. bmrnphenyl pyrazolone. 
 
 (JONCI.CSIONS. 
 
 1 ] ho suhs.an... nnesligaled iu thin paper were uxy.nethylene ben- 
 .vl evauide, oxvnM.l'nyleuc ean.pbo.-. oxymethylene propion.c es er and 
 ox V etbvle e sue.-inu. es.er. It ha. been denH.nslraled that altb.agh 
 ullu e elumgc can be detected in soluli..,, in Home cases the cljango 
 ;;oinr<>f"l'l-e.:ily largo clitncnsions, the compounds are only capable ot 
 I'xistiu"- in the enol nioditication. 
 
 ' ■■^Oxvnunhvlene propionic e.ter is the only one of these compounds 
 which .nv;. isonieri. acvl derivatives, the lower melting o,ie ts capab eon 
 h 'anng at a high tcmpJrature of transformation .nto the h.ghcr melttng 
 
 """f Oxvmethylene phenyl acetic ester docs not give ison^ric con. 
 pounds on^.eing treated with phenyl hydraz.ne in medta ot dtflerent dis- 
 
 ^^'^■*1";^;;;:Ttb:;.odtK.ts ..rmed .. the treatment of form^ s^etnic 
 e.tcr with pbenyl hydrazine, is identical with that obtained by Keitter 
 
 tnim inetlivl acoiiale. ,. ,■ . 
 
 1 ,,„,: i.ere to thank I'rofe.ssor W. Wislicenus lor his kindne,-s in 
 ,H.,w>ng the experimental part of this work to be presented to th,8 
 MHiety. and alM. for the help which he extended me during the oourse of 
 
 ''"Tinicnd to study the therai-eutic action of the tautomeric com- 
 pounds which have been presented in this paper, and experiments have 
 already been coinincnced in this direction. 
 
[ woi.f] 
 
 OXYM ETHYLENE AND FORMYL COMPOUNDS 
 
 113 
 
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 in- 
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