OPTICAL ACTIVITY OF TARTRAMIDE AND ITS DERIVATIVES. 1349 CXXX.--The InJIuence of Various Xubstituents on the Opticul Activity of Tartramide. By PERCY FARADAY FRANKLAND and ARTEUR SLATOR, M.Sc., Ph.D. THIS research forms a part of the systematic investigation which is being carried out by one of us on the rotatory power of optically active amides and their substitution products (see P. F. Frankland, F. M. Wharton, and H. Aston, Trans., 1901, '79, 266). In t h i s part of the investigation, various substituted amides, (CH*OH),(CONHR), of tartaric acid have been prepared and their rotation observed in solution, the primary object being t o ascertain the influence on optical rotation of the various radicles 11. Some of these amides have been prepared before, but with the exception of the toluidides and anilide their rotations have not been determined. P.A. Guye and A. Babel (Arch. Xci. phys. nat., 1899, [ iv], '7, 34) have published determinations of the anilide and toluidides in pyridine solutions of 5 per cent. concentration, but the figures given differ considerably from those recorded in t h i s paper, and these discrepancies are discussed later (p. 1352). The following is the general method of preparation : the amine (2 mols.) is heated with tartaric acid or methyl tartrate (1 mol.) either directly .or in alcoholic solution. The yields are good, and the resulting amides are purified by crystallisa- tion from a suitable solvent until the melting point is constant. I n general, the amides are white, somewhat insoluble substances, usually crystsllising in needles or flat plates ; they melt a t high temperatures, undergoing more or less decomposition.The methyl ester was obtained by th.e method of preparation described by P. F. Frankland and F. W. Aston (Trans., 1901, 79, 517); when distilled in vcicuo and crystallised from benzene and ligroin, it had a rotation ago' = + 7 . 7 9 O . The aromatic amides, which were only slightly soluble in the com- moner solvents at the ordinary temperature, dissolved fairly readily in cold pyridine. The amide and the hydrazide were the only two derivatives which wero practically insoluble in pyridine, and their rotations were determined in aqueous solution. The compounds were recrystailised until they were optically constant, and the rotations were then determined at various concentrations by means of a Laurent half-shadow polarimeter.The length of the tube was usually 100 mm. for strong solutions and 300 mm. for dilute solu- tions ; the tube was surrounded by a water-jacket with an arrangement for obtaining a constant temperature, and the rotations, except where otherwise stated, were determined a t 20'.1350 FRANKLAND AND SLATOR: THE INFLUENCE OF VARIOUS The pyridine used for the rotation was Kahlbaum’s gereinigt,” which was dried with lime or caustic potash and distilled, This base is a remarkably good solvent for many organic substances and, as has been shown (W. R. Innes, Trans,, 1901, 79, 261) by ebullio- scopic observations, the compounds are not associated in solution. The molecular weight of tartaric p-toluidide as determined by the rise in boiling point of pyridine solutions was 331, 330, and 354 with concentrations of 1.23, 2.42, and 3.67 grams per 100 grams of the solvent, the normal molecular weight being 328.Pyridine is a strongly dissociating solvent as compared with other organic liquids, and its effect on the specific rotation of optically active substances at various concentrations has not hitherto been determined. It will be seen that for lorn concentrations the specific rotation is in most cams constant. Ethyl tartrate in pyridine solution (now being examined by one of us) gives a specific rotation which is almost constant up to 10 per cent. This constant is about 8 times as large as the specific rotation of the pure ester, andako several timeslarger than that determined in any other solvent (alcohol, water, &c.), even at the highest dilution, In the case of the amides, again, it is noticeable that, water and alcoholic solutions generally give lower rotations than pyridine solutions, Most of the amides of d-tartaric acid have very high positive rota- tions, and the appended list (p.1367) gives a comparison of their mole- cular rotations. Tartramide has a positive molecular rotation of nearly 160’ in water solution and about 210’ in methyl alcohol solution. With the exception of the phenylhydrazidc, the substituted amides hitherto examined have a higher molecular rotation. Aromatic groups (such as toluidide, anilide, naphthylamide) raise the rotation very con- siderably, whereas the effect of the aliphatic radicles (such as ethyl- amide and methylamide) is smaller.The dextro-influence of the anilide and toluidide groups is a3 follows : p-toluidide == m-toluidide > anilide > o-toluidide. The o-toluidide is considerably lower than the others. It is noticeable that in the substitution of hydroxy-groups by benzoyl and the three toluyl groups it has been found that the dextro-influence is in the order p-toluylxn-toluyl > o-toluyl, whilst the relative position of the benzoyl group varies in different substances (P. F. Frankland, Trans,, 1899, 75, 345). The same order is noticed in the isomeric toluidides as given above, whilst the m-toluidide and anilide have almost identical molecular rotations. The B-naphthylsmide has a much higher rotation than the a-compound.There is a resemblance in constitution between an a- and an ortho- compound, and also between a p- and either a para- o r a meta- compound, and this similarity is brought out in the rotation of theseSOBbTlTUENTS ON THE OPTICAL ACTIVITY OF TARTHAMIDE. 1351 amides. Thus the a-naphthylamide is more soluble, has a lower melt- ing point., and a lower rotation than its P-isomeride, and, similarly, the o-toluidide is more soluble, has a lower melting point and a lower rotation than the para-compound. The ethylamide and methylamide have almost identical molecular rotations in pyridine, but in water the former has a slightly higher rotation, The influence of these two groups is in the positive direction, but is not nearly so great as that of the aromatic groups previously discussed above.Tartaric hydrazide has a slightly higher molecular rotation than tarharnide ; the phenylhydrazide, however, unexpectedly exhibits a much lower rotation than either of the former compounds, but, on the other hand, the hydrazones have extremely high rotations, thus : [ hl];2p'. Tartramide ....................... -@-CO*NH, ............... + 15s' 1 I Tartaric hydrazide ............... ......... 170 Tartaric phenylhydrazide ...... -(&CO*NH*NH*C,H, ... < 80 554 I Tartaric benzylidenehydrazone . -&CO*NH*N:CH*C,H, . 1 Tartaric f urf urylidenehy drazone &-CO*NH*N: CH*C,H,O 73 6 I Tartaric acetophenonehydrazone -@-CO*NH*N:C<CH3 I . 1 C6H5 397 The great influence on the rotation brought about by the introduction of the benzylidene, f urfurylidene, and acetophenone residues respectively is doubtless an example of the phenomenon which has recently been attracting much attention, namely, the powerful rotatory effect of a double linking, either between two carbon atoms or between an atom of carbon and an atom of nitrogen (Eykman, Ber., 1891, 2 4 , 1278; Binz, Zeit.phgsikal. Chem., 1893, 12, 723 ; Forster, Trans., 1899, '75, 1149; Walden, Zeit. physikccl. Chern., 1896, 20, 569; Haller and Muller, Compt. rend., 1899, 128, 1270; 129, 1005; Haller and Minguio, Compt. rend., 1900, 130, 362 ; -Rupe, Annalen, 1903, 327, 157; Ber., 1903,36, 2796 ; Haller, Cornpt. rend., 136, 1222). It is wortby of note that the tartaric hydrazones may be capable of existing in two (or even three) geometrically isomeric forms, and, as these isomerides would doubtless differ considerably in rotation, it is obvious that a strict comparison of .the rotations observed is hardly warrantable until these compounds have been more fully investigated from this point of view.1352 FRANKLAND AND SLATOR: THE INFLUENCE OF VARIOUS I n order t o ascertain the influence of a benzene ring united through a side chain, the benzylamide of tartaric acid has been prepared. It is interesting to note that this amide ranks with the fatty amides and has a molecular rotation slightly higher than the methyl- and ethyl- amides, and not nearly so high as the aromatic amides, thus confirm- ing the rule previously enunciated with respect to distance from the asymmetric carbon atom. This was also previously found to be the case in the substitution of hydroxyl radicles, in which the phenacetyl group ranks rather with the aliphaticradicles than with the aromatic ones.Thus we have a uniform resemblance between acetyl, phenacetyl, benzoyl, and toluyl groups, replacing the hydrogen of the hydroxyl group, and the ethylamide, benzylamide, anilide, toluidide, and other groups replacing the hydroxyls of the carboxyl groups. As already mentioned, the rotations of the anilide and tolu- idides observed by Guye and Eabel differed considerably from the values obtained in the present communication. Our results were verified by observations of the rotatory power of specimens of the anilide and toluidides prepared from the ester of tartaric acid and the corresponding aromatic amine.Fresh preparations of these amides, made by Miss M. B, Thomas, afforded a further confirmation of our results. The following table gives a comparison of tlhe different values" ob- tained : Botations i n Pysidine Xolutions. [a]iO" ~ 1 : ~ ~ 0 - Anilide ............ 246 246 249 259 p-Toluidide ............ 242 241 243 240 0- ,, ............ 199 203 205 . 239 nz- ,, ............ 224 226 228 233 ), ,, ............ 218 Amide. Slator. Miss 1 honas. bliss Thomas. Guye. The first specimen of the m-toluidide was prepared from Kahl- baum's m-toluidine, the second from K6nig's specially pure base. It is remarkable that the density of Guye and Babel's 5 per cent. solutions (about 0.966) is so considerably smaller than that determined by Miss Thomas 2nd ourselves (about 0*994), and even smaller than that of pure pyridine itself (about 0.980). By correcting for the maniFestly erroneous density of the pyridine solutions given by Guye and Babel, their rotations for the anilide and m-toluidide become practically the same as ours, whereas their rota- * These values are independent of the concentration of the solutions.SUBSTITUENTS ON THE OPTICAL ACTIVITY OF TARTRAMIDE.1353 tions for the ortho-compound are materially higher, and for the para- isomeride lower, than our own observations for the corresponding compounds. Besides the amides described, two of the imide compounds have been prepared, namely, tartranil and tartaric p-toluil, Estimations of the rotations have been taken in pyridine and methyl alcohol solutions.As we should expect, the toluil has a higher rotation than the anil, although they are not so high as the corresponding toluidide and anilide. Ladenburg (Bey., 1896, 29, 2710) describes two imides, namely methyl and ethyl tartrimide, which have respectively molecular rota- tions of + 281O and + 261O in 7.3 per cent. aqueous solution. I n these cases, the imide compound has a slightly higher molecular rotation than the corresponding amides in aqueous solution, but, inasmuch as the etliylimide has a lower molecular rotation than the methylimide, it suggests th st with aromatic radicles the rotation should be still lower, as witb tartranil in aqueous solution we have actually found t o be the case, Walden (Zeit. physikul. Chem., 1895, 1'7, 248) similarly found malanil :and malic P-naphthimide t o have lower rotations than the amides.The comparatively low rotation of all these imides is re- markable in view of the fact that they contain a cyclic grouping, which is generally attended with a high rotation. If only one series of compounds, the amides, for example, be pre- pared from tartaric acid, only the comparative rotatory influences of the various amide groups in the molecule m i l l be obtained. Similarly, by preparing amides of acetyltartaric acid, another series is obtained, and it will be possible to judge whether the acetyl group has in any way a constant influence and whether the amide groups have the same comparative influences as in the foregoing series. So far, we have only one acetyl derivative, the rotatory power of which has been determined.Others have been prepared, but their rotations are as yet unknown. The o-toluidide of acetyltartaric acid, which has been prepared by acetylating the o-toluidide, gives a lower molecular rota- tion than any of the other compounds described in this paper excepting the phenylhydrazide. The diminution in rotation which we have observed on acetylating tartaric o-toluidide is what would be anticipated from the known reIationship between the rotations of the tartaric esters and their diacetyl derivatives. Similarly, inasmuch as it has been shown by Purdie and Irvine (Trans., 1901, '79, 957) that the dextro-rotation of the tartaric esters is enhanced by replacing the >CH*OH groups by >CH=OMe, we should anticipate that the dextro-rotation of tartramide would be1354 FRANKLAND AND SLATOR: THE INFLUENCE OF VARIOUS exceeded by that of dimethoxysuccinamide, and this is aotually found to be the case.A survey of these relations is conveniently obtained by means of the following data : E thy1 dime t hoxysuc- Ethyl diace ty 1 tartrate Dimethoxysuccinamide Tartaric o-toluidide Tsrtramide (aqueous Diacetyltartarico-toluid- Ethyl tartrate (liquid) 15.8 cinate (liquid) ...... + 2 10.6' (liquid) ............... + 919' (aqueous solution), .. 166-2 (pyridine solution) ... + 667.0 solution).,. ............ 158.0 ide (pyridiae solution) + 80.0 Ex P E RIM ENTA L. Tartmmide, This substance slowly crystallised in well-defined needles from a methyl alcoholic solution of methyl tartrate which had been saturated with dry ammonia at the temperature of a mixture of ice amd salt, a further crop of crystals being obtained by removing ammonia from the mother liquor in a vacuum desiccator.The amid6 melted at 195O with decomposition. 0.1307 gave 21.3 C.C. moist nitrogen at 20.3' and 759.7 mm, N 5 18.63. C4H,04N, requires N = 18.92 per cent. Tartramide is insoluble in chloroform, benzene, ligroin, acetone, ether, and cold pyridine; it is slightly soluble in alcohol and dissolves more readily in water. At; 12', 100 grams of methyl, ethyl, and isobutyl alcohols dissolve respectively_O*l987, 0.0355, and 0.0152 gram of tartramide. Rotations were taken in aqueous and in methyl alcohol solutions, but owing to the insolubility of the substance very dilute solutions had to be used.The rotation in aqueous solution remained unaltered after 31 days, and on heating the solution from 14-30' no variation in rotation was observed; [ Q ] ~ at 14', 20°, and 30' was found to have the values + l07', l06', 107', respectively. Rotations in Water. Per cent. Density solution =p. a~oe(Z= 1). d 20°/49 [ a ]ioo. [ M ]Eon. 1 *305 + 1.394' 1.0031 + 106.5' + 158' 0.077 0'083 0.9984 I08 160SUBSTITUENTS ON THE OPTICAL ACTIVITY OF TAHTRAMIDE. 1355 notations in Methyl Alcohol. Per cent. Density solutioii=p. u2p"(Z= 1). d 20°/4". c a 1;:. [MI;:. 0.1797 0.207' 0.7997 + 144' 213O 0.0807 0*090 0.7930 141 208 Tartvanilide (Polikier, Bev., 1891, 24, 2959). This compound was prepared by slowly adding 1 part of dry tartaric acid to 5 parts by weight of boiling aniline.A white mass (aniline hydrogen tartrate} a t first separated, but soon redissolved, and when all the tartaric acid had been added the con- tents of the flask suddenly solidified to a mass of yellowish-white, pearly plates. These crystals, which were rendered colourless by washing successively with dilute hydrochloric acid and a small quantity of alcohol, were found t o be insoluble in water, only very slightly soluble in benzene, ligroin, chloroform, glacial acetic acid, and nitro- benzene, but dissolving readily in cold pyridine ; when recrystallised from methyl alcohol, they melted at 250' with decomposition. 1, 0.2003 gave 16.7 C.C. moist nitrogen a t 21° and 746.9 mm. N = 9.32. 2. 0.2012 ,, 0*1001 H,O and 0.4725 CO,. C = 64.06 ; H= 5-53. 3. 0.2002 ,, 0 0994 H,O ,, 0.4691 CO,.C = 63.90; H=5.52. C,,H,,0,N2 requires N = 9.33 ; C = 64.00 ; H = 5.33 per cent. Rotcctions in Pyvidine. Per cent. Density solution =p. n*fio(Z= 1). d 20'14". [ U ] y . [ M go". 5,421 + 13-26' 0-9920 + 246.5' + 740' 1.820 4.39 0.9825 245.6 737 This anilide was also prepared from methyl tartrate and aniline, and was purified by crystallisation from alcohol. This specimen gave the following data: p=3*100; ar(Z= 1) = +7*535O; cl 2Oo/4O == These results were confirmed by rotations obtained from another specimen made from the acid.* Traces of water in the pyridine solu- tion were found to affect the rotation appreciably (to 3 or 4 per cent.), and the following results were obtained from the specially dried solvent : 0.9854; [a]? = +246*7'; [M]2,0" = +740°.* This specimen was independently prepared and examined by Miss M. B. Thomas,1,356 FllANKLAND AND SLATOR : THE INFLUENCE OF VARIOUS Per cent. Density sdution =p. uD (I= 1). d '20"/4" [ u l D . [MID. 2.289 + 5-54' 0.9847 + 245.9' 738' i 4.05 9.86 0.9877 246-4 739 A t 20' d 15"/4". At 15' 4.05 10.03 0-9936 249.3 74s The rotation diminishes slightly with increase of temperature, as Rotation in Methyl Alcohol.-p = 0.0803 ; ar(Z= 1) = + 0.127' ; shown by the above numbers. d 20'14' =0.792 ; [a]y = -+ 200'; [ M]2,0" = + 600'. Zbytccric p-l'oluidide, ( C,H7*NH*CO),*( CH*pH),. This substance can be prepared by heating p-toluidine hydrogen tnr- trate (1 mol.) with toluidine (1 mol.) (Bischoff, Ber., lS90, 23, 2049), but is more rwdily obtained by heatingp-toluidine (2 mols,) and tartaric acid (1 mol.) for about 10 hours in an oil-bath at 180-185'.The mixture of reagents did not fuse and the reaction was rather slow. The p-toluidide, which remained after extracting the product successively with boiling water, dilute hydrochloric acid, and alcohol, was crystallised from a mixture of alcohol and pyridine and then melted at about 240' with decomposition. This substance is slightly soluble in ethyloand methyl alcohols, and still less so in chloroform, acetone, carbon disulphide, and water ; it dissolves in hot aniline, hot nitrobenzene, strong sulphuric acid (without blackening), and also in pyridine. 0.2863 yielded 21.0 C.C. moist nitrogen at 14.6'and 751 mm. N = 8.51. CI,H,,O,N, requires 8.56 per cent. Rotations in Pyridine.The first preparation, which bad possibly slightly racemised, gave a constant rotation [a]?= + 2 3 8 O in solution of from 112 to 7 per cent, strength. With it later preparation, which was subsequently shown to be non-racemised, the following data were obtained: 4 per cent. solution, ~$'(i! = 1) = + 9.54' ; d 20'/4' = + 0,9863 ; [ a]y = + 242' ; [ M]2,0"= + 793'. A preparation made from methyl tartrate and p-toluidine and purified as before gave the following result : 3.885 per cent. solution, ar(Z = 1) = + 9-23'; d 20°/4'= + 0.986 ; [a]?= + 241O ; [M]r = + 790'. As a comparatively high temperature was used in the foregoing pre- paration from tartaric acid, it was considered necessary to prove more conclusively the absence of racemisstion i n the product. The specimenSUBSTITUENTS ON THE OPTICAL ACTIVITY OF TARTRAMIDE.1357 of amide was, therefore, hydrolysed with hydrochloric acid at 120-125O for 5 hours, and the rotation of the resulting tartaric acid measured. The tartaric acid, which was separated in the form of its lead salt, was liberated from this substance by the action of hydrogen sulphide and finally obtained from the filtered solution by evaporation. A blank experiment was performed by heating some tartaric acid in hydrochloric acid solution in a sealed tube under conditions similar to those employed in the hydrolysis tube. The following rohtions were obtained with 10 per cent. tartaric acid solutions ( I = 2.962) : Pure tartaric acid (calcu- Pure tartaric acid (used lated) ............ ) * * ......+4"15' in preparations). ........ + 4'1 2' 1st hydrolysis ............ + 3'59' 2nd 8 , ............ + 4" 3' >, ,, (blank experi- ment) ..................... + 4" 2' From these results, it is probable that the foregoing specimen of p-toluidide was not appreciably racemised, but that a slight racemisa- tion took place during hydrolysis. A later observation of the rotatory power of this amide gave the following results : Temp. solution =p. a D ( l = 1 )a Density. la], [ M I D Per cent. 20' 4.502 + 10.70" 0.987 + 241' + 790 15 ?, 10-87 0.994 243 796 Tartaric 0-To Zuidide. Tartaric acid (1 mol.) and o-toluidine (2 mols.) were heated together for about 8 hours in a flask placed in an oil-bath at 160'. The impure product was boiled with water to get rid of tartaric acid, and the residual di-o-toluidide, when crystallised from 70 per cent.alcohol, separated in acicular plates and melted at 184-185'; it was slightly soluble in hot benzene, carbon disulphide, and other common solvents, easily soluble in pyridine, and also in hot alcohol. 0,2694 gave 19.8 C.C. moist nitrogen at 15" and 739.5 mm. N=8*38. C,,H,,O,N, requires N = 8.56 per cent. Rotufions in, Pyridine. This toluidide was also prepared from the methyl ester ; it melted a t 189", and when the two specimens were dried the rotations of both VOL. 1,xxxIrr. 1 T13.35 FRANKLAND AND SLATOR: THE INFLUENCE OF VARIOUS were found to agree, recently distilled pgridine being used as the solvent. Per cent. Temp. solution =p. a& = 1). Density. [MID. 20' 3.012 + 5.90' 0.9845 +199' +653' 20 4.994 10.02 0.9868 203 667 15 4-994 10.18 0.9936 205 673 Tcwtai*ic m- Toluidide. Tartaric acid (1 mol.) and Kahlbaum's purest m-toluidine (2 mols.) were heated in a flask placed in an oil-bath at 160' for about 8 hours.The whole became liquid and after a time resolidified owing to the separation of ditoluidide. The product, when purified by the method employed for its 0- and p-isomeridep, crystallised from alcohol in needles, and its solubility lay between those of the other two isomerides; it melted a t 184'. 0*2309 gave 17.1 c.c, nitrogen at 16.5' and 750 mm. C,,H,,O,N, requires N = 8.56 per cent. Rotations in P@dine.-The substance is very soluble in pyridine, and in a 2 per cent. solution i t gave [.ID = + 224.0', and 224%' after recrystallisation, this constancy indicating the purity of the specimen.N=8.50. Per cent, Density solution =p. uio"( i! = 1). d 20"/4". [a]?,"". Br I?. 15.93 + 36.03' 1.012' -I- 223.6' + 733' 0.8665 2.13 0.978 225.3 739 Xpecimen prepwed fvom tlte methyl estev (m. p. 184') gave : Per cent. Density solntion=p. U ~ ~ ' ( Z = 1). d 20"/4". [ u]","". [ M ]:o". 2-009 + 4.34' 0.9822 +220° +722O Specially purified m-toluidine from Messrs Kanig (Leipzig) gave specimens of di-m-toluidide having the following rotatory power : Preparedfiom Tartaric Acid (m. p. 182-183'). Pp_r cent. Density solution=p. a2p"(Z= 1). d 20"/4". [ u ] y . [ M]io*. 2.121 + 4.571' 0.9824 +219O +720° 1.705 3.599 0,9822 215 705SUBSTITUENTS ON THE OPTICAL ACTIVITY OB' TARTRAXIDE. 1359 Pvepared from Methyl Tccrti*ate (in.p. l82O). Per cent. Density solution =p. ay(Z = 1). d 20"/4". [ n pa. [ M];o". 2.153 + 4-55' 0.9329 + 2 1 7 O +710° 6.65 14-37 09934 218 713 Another specimen prepared from Kah1b;tum's nz-toluidine gave the following results : Per cent. Temp. solntioii =p. aioo(Z= 1). Density. [a]':. [>I]:'. 20" 4.772 +10*64' 0.9875 + 2 2 6 O +740° 15 4.772 10-80 0.994 228 747 Tartccric a. Nccp?t,th,yZamitle, (CH*OH),(CO *NH*C,,H7),. a-Naphthylamine (2 mols.) and powdered tartaric acid (1 mol.) were heated in a n oil-bath at 170' for 5 hours. The brown product was extracted with boiling dilute hydrochloric acid, and the residue, when crystallised from a mixture of pyridine and alcohol, separated i n fine needles, often in large clusters. When washed with alcohol and recrystallised from the above mixture, it melted at 213-2149 The a-naphthylamide is insoluble i n the common solvents except pyridine and hot acetic acid, and dissolves t o a less extent in alcohol.0.1531 gave 9.4 C.C. moist nitrogen at 14' and 739.7 mm. N =7*03, C,,H200,N, requires N = 7.02 per cent. Rotations in Pyridine. Per cent. Density solution =p. az*(Z = 1 ). d 20"/4". [ a]',"". [ M 1':'. 3%06 (recryst.) 3-71 0*991 98.4 394 3.378 +3,28" 0.988 +9S.3' 3-393' 6.560 6.56 0-997 100.3 40 1 1.303 1.25 0.983 97.6 390 Tccrta?.ic ,8-iVapht?qZamide, (CHOH),( GO NH*C,,H7),. F-Naphthylamine (2 11101s.) and tartaric acid (1 mol.) were heated €or about 6 hours at 160-170' in an oil-bath. The product was boiled with water and dilute hydrochloric acid, the residue being treated with warm alcohol t o extract coloured matter and then crystal- lised from pyridine.The compound crystallises in plates melting at 279'; it is insolnble in the common solvents, with the exception of alcohol and pyridine; in the former of these, it is slightly soluble, and 4 T 21360 FRANKLAND AND SLATOR: THE INFLUENCE OF VARIOUS dissolves readily in the latter. It differs from the a-compound in crystalline form, has a much higher rotation and melting point, and is much less soluble. 0.2362 gave 14.2 C.C. moist nitrogen a t 14.2' and 742.6 mm. N = 6-90. C,4H200,N, requires N = 7-02 per cent, Rotations in Yyridine. 3% s t Xpe c imen. Per cent. Density solution =p. ay(Z = 1). d 20"/4". [ a J',"". [ M ]iO". 1-339 + 3.83O 0.984 + 291' + 1163' 2.129 5.96 0.984% 284 1138 * A different specimen of pyridine. Second Xpecimen.Per cent. Density solution =p. a?(Z=l). d 20"/4". [a JE'J". [ q o . 0.7373 + 2.1 lo 0.9798 +29Z0 + 1169' 1,185 3.359 0.982 289 1155 The P-naphthylamide mas also prepared from methyl tartrate. After purification and recrystallising, the following rotations mere obtained : Per cent. Density solution=p. a~oo(Z=l). d 20"/4". r.l;Oo [ M 1 5 1,316 + 3-764' 0.9808 + 292' + 1167O 0.5505 1.566 0.9795 290 1162 Tart uric Methylanzide, (CH* OH),( CO*NH* CH,),. An attempt was made to prepare this compound by warming a mixture of methyl tartrate with a 33 per cent. solution of methyl- amine ; the product, after crystallisation from alcohol and benzene, melted at 187-189', and combustion pointed t o its being the methyl- amine salt of a substituted tartramic acid, (CH*OH),(CO*NH* CH,)(CO*O*NH,-CH,).0.1860 gave 23.1 C.C. moist nitrogen a t 11*5'and755 mm. N = 14-68. 0.2045 ;, 25-1 C.C. ,, 9 3 95O ,, 754.6 mm. N = 14.64. C,H1,O,N, requires N = 14.43 per cent. This substance gives no precipitate with silver nitrate, but, on boiling the solution, silver. is precipitated.SURSTITUENTS ON THE OPTICAL ACTIVITY OF TARTRAMIDE. 1361 The diamide was obtained by distilling the gaseous amine (dried with lime) into a cooled solution of methyl tartrate in anhydrous methyla5ed spirit. After a short time, the amide separated and was recrystallised from alcohol, the melting point being 189'; it gave no precipitate of silver when boiled with silver nitrate solution. The amide is easily soluble in water and pyridine, insoluble in cold alcohol, benzene, ethyl acetate, and carbon disulphide.0.1980 gave 26.6 C.C. moist nitrogen at 14' and 756 mm. C,H1,0,N2 requires N = 15.95 per cent. The compound gave a- specific rotation in a 3 per cent. pyridine solution of -I- 158*0°, and t 158*6O in the same solvent after recrystal- lisntion from alcohol. Rotatiorbs in Pyridine. N= 15.72. Per cent. Density solution =pa a:""( Z = 1). d 20"/4'. [a J',"". 1 M lioO 2.988 + 4.65O 0,985 + 158.0' + 278' 2932 (recryst.) 4-60 0*989* 158.6 279 7.679 12.16 1.000 158.3 279 1.433 2.21 0.981 157-2 277 0,684 1.045 0.980 155.9 2 74 * A .different specimen of pyridine. IZotutions in Water. Per cent. solution =p. 0 994 2.325 3.041 (After boiling)* 7.475 7.7 74 10.35 a y ( Z = l ) .+ 1-44' 3.334 4.235 4.245 10.31 10.84 14.59 Density d 20"/4". 1.001 1-005 1.006 1-006 1.018 1.020 1.027 [u Jy. + 144.7' 142.7 138.5 138.8 135.5 136.7 137.3 I ; o . 255O 25 1 244 244 239 241 242 * Part of the solution was tar9d, boiled, cooled, and made up to the original weight ; the rotation of this boiled solution was practicaIly identical with that of the original, showing that there is no birotation. Furtaric Et hy Zamide, ( CH OH),( CO N H C,H,), , A mixture of ethylamine (2 mols.) and methyl tartrate (1 mol.) in anhydrous alcoholic solution slowly deposits the ethylamide on cooling. After distilling off the alcohol, more crystals were obtained, the totaI jield being 75-80 per cent. The amide, when recrystallised from ethyl acetate and a small quantity of alcohol, was obtained in white,1.362 FRANKLAND AND SLATOR: THE lNFLUENCE OF VARIOUS glistening, felted needles melting at 210--211°; i t is easily soluble in water and pyridine, fairly soluble in alcohol, less so in ethyl acetate and benzene, and dissolves in acetic acid.0.1958 gave 24.1 C.C. moist nitrogen at 15" and 735 mm. N = 13.93. C,H,,O,N, requires N = 13.76 per cent. The specimen obtained from the first crystallisation had a specific rotation of + 137.1' and when recrystallised gave + 137.9". The remaining rotations were determined with the latter specimen. Per cent. solution =pa 3 *87 1 3,761 5.030 2.401 1.049 Per cent. solution =p. 1.390 1 *905 3.943 7-468 Rotcctions in Pyridine. D cnsity a:')"( Z = 1 \. d 20"/4". [a];O. + 5.25" 0.989 + 137.1" 5.1 25 0.988 137.9 6.83 0,9936 136.6 3-26 0,985 137.8 1.395 0.982 135.7 Rotations in ruler.Density a:oo( I = 1). d ZOO/,". [a]:oo. + 1.790' 1*001 128.6" 2.396 1.002 125-5 4.990 1.007 125.7 9.53 1-017 125.5 [ M 1,"'. + 280" 281 279 281 277 [ M IF'. + 262" 25 6 256 25 6 Tccrta& Benxylande, (C H *OH),( CO NH* CH,C6H5>,. Methyl tartrate (1 mol.) and benzylamine (2 mols.) in alcoholic solution were allowed to react in the cold, when the benzylnmide separated in white, glistening plates. On recrpstallisiltion from hot alcohol, it separated either in plates or needles according to the conditions. The amide is easily soluble in pyridine and insoluble in water; i t melts at 199". N = 8.63. 0.2767 gave 21.1 c,c. moist nitrogen at 14" and 73 1 mm.C,,H,,,O,N, requires N = 8 -5 6 per cent. Rotations in Pyridine Solution. Per cent. Density solution =p. aF*(l= 1). d 20"/4". [a]:U". [M ]io'. 5,497 t 4.983" 0.9911 + 91*5' + 300' 3.46 I 3.1 23 0.9861 91.5 300 1.022 0.932 0.9802 (93.0) (305)SUBSl!ITOENCS ON THE OPTICAL ACTIVITY OF TARTRANIDE. 1363 Tartaric Phenylhydraxide, (CH*OH),*(CO*NH*NH *C,H5)2. This compound has been prepared by heating methyl tartrate with phenylhydrazine, and was crystallised from alcohol or from glacial acetic acid (Bulow, Anncclen, 1886, 236, 195; Fischer and Pasamore, Ber., 1889, 22, 2734). I n alcoholic solution, tartaric acid and phenyl- hydrazine form diphenylhydrazine tartrate, in distinction to aniline and the toluidines, which form only the mono-salt. The phenyl- hydrazide can be prepared by heating either the above-mentioned salt or a mixture of phenylhydrazine with an alkyl tartrate or the free acid ; when recrystallised from pyridine and water, it melted and decomposed at about 231O.0.1877 gave 28.2 C.C. moist nitrogen a t 13.7Oand 744 mm. N = 17.33. The specific rotation [ a17 of different specimens varied considerably (from 16' to 24'). These inconsistences are possibly due to traces of anilide, which would greatlyaffect the rotatory power. We can only conclude from these figures that the value of [MI:' for the phenyl- hydrazide is many times smaller than that of the anilide or the toluidide, being probably (80'. We hope soon to be able to obtain more accurate information as to the rotatory power of this compound, which is being further examined by one of us.C1,H,,O,N, requires N = 17.02 per cent. Tartaric Hydraxide, (CH*OH),(CO*NH*NH,),. This compound was prepared as described by Von Rothenburg (Ber., 1893, 26, 2057). An alcoholic solution of hydrazine hydrate, prepared by the interaction of caustic potash and hydrazine hydro- chloride dissolved in alcohol, when treated with methyl tartrate, slowly deposited the hydrazide, which was collected and dried. This compound was insoluble in pyridine, slightly soluble in alcohol, and readily dissolved in water, giving a neutral solution, from which i t had a tendency to separate as an oil. The determinations of rotatory power were made on the substance so obtained without recrystallising. Like the amide, it is insoluble in the common solvents except water.It differs from the amide in being much more soluble in water, and the aqueous solution when shaken up with benzaldehyde, forms a benzylidine derivative.1364 FRANKLAND AND SLATOK : THE INFLUENCE OF VARIOUS Rotutioiza in Water. Per cent. Density solution=p. U ~ ~ ~ ( Z = ~ ) . d 20"/4". [a]2,0". [ ni y. 2.0'54 + 2*206O 1.0058 +97*1° + 173' 3.264 3.146 1.0105 95 *4 170 6.552 6.41 1.0257 95.4 170 Turtaric Benxylidenehydvaaide, (CH*OH),(CO*NH*N:CH*C,H,),. This substance, which is described by Ton Rothenburg (Zoc. cit.), is obtained on shaking up an aqueous solution of the hydrnzide with benzaldehyde; it is slightly soluble in alcohol and more so in pyridine. It was recrystallised from pyridine and gave white, lustrous plates melting a t 230' with decomposition.Rotations ;n Yyridilte. Per cent. Density solution =p. uioo(Z= 1). d 20"/4". [ a ] y . [ M]to6. 03826 +0600° 0.9788 f160.2' +567O 0,922 1.411 0,9802 156-1 553 1.834 2.826 0,9829 156.8 555 Twtaric Fugfur ylideneh ydmzide, (CH OH),( COO NH * N : CH C,H,O) On shaking up a cold, not too dilute, aqueoils solution of the hydrazide of tartaric acid with freshly distilled furfuraldehyde, this compound was precipitated ; this was filtered off, thoroughly washed with water, and recrystallised from pyridine and alcohol, when it crptallised in small, irregular plates, melting at about 204O, which tend to become brown, 0,1395 gave 20.4 C.C. moist nitrogen a t 155'and 746.5 mm. N = 16.77. C,,H,,O,N, requires N = 16.82 per cent. The rotations in pyridine solution were not very constant, owing, After the first crystallisation, the probably, to slight decomposition.following results were obtained : Per cent. Density solution=p. a~@'(Z=l). d 20'14.. [ a ]',". I I","". Oms418 + 1*82O 0*9802 + 220.6' + 737" 3.054 6.64 0*9890 219.9' 735SUBSTITUENTS ON THE OPTICAL ACTIVlTY OF TARTRAMIDE. 1365 2'arta& Bydyaxone of Acetophenone, (CH* OH),(CO*NH*N:CMe C,H,),. Acetophenone reacts with tartaric hydrazide, forming a hydrazouo having similar properties to the above-descri bed aldehydic hydrazones. The new hydrazone was recryetallised from a mixture of pyridine and alcohol and melted at about 232'. P1478 gave 18.9 C.C. of moist nitrogen at 185'and 750 mm. N = 14-54. C,oH,204N, requires N = 14.7 per cent. A 0.747 per cent.solution in pyridine gave the following data : 1) = +0*760"; d 2Oo/4' == 0.9814 ; [a]y = + 104'; [M]2,0" = + 397". Y'artranil, (CH*OH),(CO),:NC,H,.-One part of tartaric acid was heated for 4 hours at 180' with 2 parts of aniline in an open flask on the oil-bath. The mass mas extracted with boiling water and the aolu- tion concentrated until crystallisation took place. The crystals were dissolved in methylated spirit and decolorised with animal charcoal ; they somewhat resembled tartranilide in appearance and melted with decomposition at 225". The compound is soluble in water, alcohol, and pyridine, but only t o a very slight extent in the other common solvents; 100 grams of water and methyl alcohol dissolve 1.3079 and 3.8315 grams of tl.e tartranil respectively at 20'.0.1994 gave 9.4223 CO, and 0.0790 H20b C = 67.76 ; €€= 4.40. 0.2004 ,, 0.424'7 CO, ), 0.0791 H20, C=57&80; H=4*39. CloH,04N requires C = 57-97 and I1 = 4'35 per cent.. Rotations in (1) Jifccter, (2) Methyl Alcohd, and (3) Pgridine, Per centb bolution =p. 1, 045964 2, 1.3049 1.6393 3.2258 3. 0.693 4.760 1 m.2346 u',"'( I -L 1). + 0.6s' 1 *29 1-36 1-70 3.31 0.88 6'28 Density cl 2 0 "/ 4 ', 1-0003 0'7980 O~SOOl 0*807'r 0-9827 0.9950 1-ooai [ a ] y + 114' 104 131 130 127 131 132 [ M]EOo. =i- 236" 216 270 268 263 271 272 VOL. LXXXIII, 4 s1366 OPTICAL ACTIVITY OF TARTRAMIDE AND ITS DERlVATIVES. Tartaric p-Toluil, (CH*OH),(CO),:N*C,H,.CH,. The toluidine hydrogen salt was made by warming together p-toluidine (1 mol.) and tartaric acid (1 mol.) until they melt and resolidify, this salt being then heated for about 7 hours in an oil-bath a t 2004 The toluil was extracted from the slightly charred mass with boiling water, and, after repeated crystallisation from water, melted at 235O with decomposition ; it was soluble in alcohol and pyridine, insolubh in chloroform, benzene, and most of the other organic solvents.0.2205 gave 12.6 C.C. of moist nitrogen at 14O-and 737 mm. N=6-52. CllHl104N requires C = 59.73 ; H = 4.98 ; N = 6.35 per cent. 0.2254 gave 0,4943 CO, and 0.1008 H,O. C = 59.81 ; R = 4.97. Rotations in (1) Methyl Alcohol, (2) Pyidine. Per cent. solution =p. u y ( I = I). 1. 1.976 + 1.87" 1.1'77 1.187 1,064 1.091 1-93 3,136 1.36 2.180 2. 6.317 10 *43 Density Id 20"/4", [4y. CMl~o', 0.7963 126.7 280 017962 128.7 284 0,9971 165-6 366 0.9838 165.2 365 0.9818 163.3 36 1 0.7996 + 1 18*3O 3- 261O Acetyltartaric o-Toluidide, (CH*O*CO CH,),(CO*NH* C, E€t)2. The 0-toluidide of tartaric acid can be acetylated by acetic anhydride (Bischoff, Bey,, 1890, 23, 2050), but more easily by warming with acetyl chloride. When hydrochloric acid was evolved only very slowly, the excess of acetyl chloride was distilled off and the residue extracted with a small quantity of alcohol. The main part of the acetyl com- pound which remained in the residue was crystallised from glacial acetic acid; it separated in a colloidal form from tbe solvent and was slightly coloured. On washing with ether, the colour was removed, although on drying the substance it again became slightly yellow. The substance, which dried to a fine powder and melted at 2294 wits fairly soluble in hot chloroform, alcohol, glacial acetic acid, but less SO in benzene-; it was easily soluble in pyridine, but insoluble in water. 0.2595 gave 1 5 5 C.C. of nitrogen at 12%O and 750 mm. N= 6-98. C,,H,,O,N, requires N = 6.81 per cent,SLMPLIFICATION OF ZEISEL'S METHOD, 1367 Rotations in Pyridine. Per cent. Density solution =p. aioo(l = 1). d 20'14". [a]","". [M12,0". 5.237 + 1.016O 0.9891 + 19.61" 80.8 5,315 (recryst.) 1.036 0.9895 19.7 81.2 2.594 0.432 0.9830 16.94 69.8 4.492 0.844 0.9872 19.0 78.4 S u m m a r y of R o t a t i o n s . [ M yo . Solvent. [ M]Zoo. Solvent. n f \ P Methyl Methyl Amide. Pyridine. Water, alcohol. , Amide. Pyridine. Water. alcohol. Tartramide ...... - 1-158" +210" Hydrazide ......... -- +170" - Anilide ............ -I- 739" p-Toluidide ...... 793 o-Toluidide ...... 667 rn-Toluidide ...... 730 a-Nnphthylamide 400 8-Naphthylamide 1160 Ethylamide ...... 279 Benzylarnide ...... 300 Phenylhydrazide ( < 80) Methylamide ... 278 Benzylidene hydrazide ... +554" - - Furfurylidene hydrazide ...... 736 - - Hydrazone of acetophenone 397 - - Tnrtranil ......... 272 216 268" Tartaric p-To!nil 366 - 280 Diacetyltartaric o-tolnidide ... 80 - - THE UNIVERSITY, BIRMINGHAM.