HYDROXYOXAMIDES. PART 11. 1563 CLV1.-Hydroxyoxamides. Part 11. By ROBERT HOWSON PICKARD, CHARLES ALLEN, WILLIAM AUDLEY BOWDLER, and WILLIAM CARTER. SCHIFF AND MONS ACCHI (Anncclen, 1895, 288, 31 3) hydrolysed oxa- methane with hydroxylamine, and obtained a compoand to which they gave the name ‘‘ hydroxylamide,” and ascribed the formula, NH,*CO*CO*NH*OH. At the same time, they pointed out that it de- composed at the same temperature as, and was very similar to, the compound obtained by Holleman (Rec. truv. chim., 1894, 13, 84) by the action of hydrochloric acid on oxamidedioxime. Holleman then compared the two substances (Rec. trav. chim., 1896, 15, 148), showed that they were not identical, and suggested that they were stereoisomerides of the formula NH,*C(NOH)*CO*OH. H e gave the syn-formula t o his own compound, since this more readily explains the formation of cyanamide when it is treated with acetic anhydride.The anti-configuration was given t o Schiff and Monsacchi’s compound, as this more readily accounts for the formation of carbon dioxide and carbamide when it is heated. In 1901, it was shown by Pickard and Carter (Trans., 79, 841) that1564 PICKARD, ALLEN, BOWDLER, AND CARTER : the compounds obtained when oxamethane and the oxamates, R-NH=CO*CO,Et, are hydrolysed with hydroxylamine, react as hydr- oxamic acids, the acetyl derivatives yielding biurets and allophanates, in accordance with the reactions of hydroxamic acids described by Thiele and Picknrd (Awnden, 1899, 309, 189). Schiff (Annalen, 1902, 321, 357), however, although acknowleclging that these reactions are best explained by the hydroxyoxamide formula, NH;CO-CO*NH*O€I, or R*NH*CO*CO*NH*OH, ascribed the amid- oxime formula, NH,*C(NOH)*CO*OH, to the compound obtained by the hydrolysis of oxamethane, basing this opinion mainly on some titration experiments, which apparently showed that the compound in question behaved on titration like an amino- or amido-acid (compare Schiff, AlenaZen, 1901, 319, 59).We have reinvestigated these compounds, and now bring forward fresh evidence in favour of the Several new hydroxyoxamides have been prepared, namely, o-tolyl, 0-, m-, and p-nitrophenpl and ethyl-hydroxyoxamides, and they all give the various reactions of hydroxamic acids (compare Zoc. cit.). The ethylhydroxyoxamide is of interest as it shows that the method which has yielded the substituted biurets with an aromatic radicle will also yield those with aliphatic radicles.The latter are not obtained when ethyl allophanate is treated with aliphatic amines (Hofmann, Bey., 1871, 4, 265). One mol. of a hydroxyoxamide, when dissolved in water or alcohol, is neutralised by 1 mol. of potassium hydroxide, We were unable to repeat under very varied conditions the experiments described by Schiff (Zoc. cit.), in which hydroxyoxamide w3.s neutralised by the calculated quantity of potassium hydroxide only after treatment with formaldehyde, using phenolphthalein as indicator. When an oxamate is hydrolysed with 2 mols. of hydroxylamine, the hydroxylamine salt of the hydr- oxamic acid is first obtained, and it is possible that the hydroxyoxamide used by Schiff in his titration experiments mas contaminated with the hydroxylamine salt.Hydroxyoxamide, when neutralised with ammonia and treated with a solution of silver nitrate, yields a colourless, stable silver salt ; it is significant that in Schiff and Monsacchi’s paper it is stated that the hydroxyoxamide is crystallised from water, whereas the silver salt is only stable when prepared from a product which has been either crystallised five or six times from water or once from dilute acetic acid. Hydroxyoxamide decomposes violently at 15 So without melting, and it is noteworthy that products containing traces of the hydroxylamine salt decompose at about the same temperature. Various types of hydroxamic acids have been titrated with decinormal solutions of caustic alkalis, using phenolphthalein as the indicator, and it has been found that they all give approximately quantitative results. hydroxyoxamide ” formula.HYDROXYOXAMIDES.PART I i . 1565 The silver salts of hydroxyoxamide and phenylhydroxyoxamide, when treated with ethyl iodide, yield esters which behave as monobasic acids when titrated with caustic alkalis. It is very difficult to understand how esters with an acid reaction could be obtained from a substance having the amidoxime constitution, NH,*C(NOH)*CO,H, since the groups NH,*C(NOH)- and R*NH-C(N0H)- have a basic or neutral function, the amidoximes, C,H,*C(NOH)*NH, and C,K,*CH(OHj*~(NOH)*NH,, being neutral substances. The esters of hydroxamic acids, R.C(OH):N*OEt, on the other hand, are acid by virtue of their tautomeric hydrogen atom, b&g soluble in caustic alkalis and re- precipitated by carbon dioxide.The hydroxyoxamides, R*NH*CO*CO*NH*OH, when treated with aniline, yield anilides of the type R*NH*CO-CO*NH*C,H,, and when treated with a n alcoholic solution of phenylhydrazine form phenyl- hydrazides of the type R*NH*CO*CO*NH*NH*C,H5. These two re- actions, which are approximately quantitative, are also given by hydroxamic acids, and afford strong evidence against such formulae as NH,*C(NOH)*CO,H for hydroxyoxamide (arnidoximeoxalic acid), or CO,H*C( NOH)*NH* OH for malondih y droxamic acid (hy droxamoxime- malonic acid). Ulpiani and Ferretti (Gaxxetta, 1902, 32, i, 205) have shown that hydroxyoxamide is obtained when nitromalonamide is treated with concentrated sulphuric acid.They formulate the course of the reaction as follows : NH,*CO*CH(NO,)*CO~NH, - NX,*CO*CH,*NO, - NH,*CO*CH:NO*OH -. NH,*CO*C'(OH):NOH. This reaction affords further evidence in favour of the hydroxamic nature of these compounds, and is entirely opposed t o formulae of the type NH,*C(NOH)*CO,H. A reinvestigation of the amidoximeoxalic acid, NH,*C(NOH)*CO,H, confirms its general rroperties as described by Holleman (Zoc. cit.). It behaves as a monobasic acid when titrated with potassium hydroxide, the acidity of the carboxyl group not being masked by the NH, group as inferred by Schiff. Moreover, it forms a stable, crystalline ester which is neutral, thus differing from the esters of the hydroxyoxamides.To sum up, therefore, these hydroxyoxamides behave in all respects like typical hydroxamic acids, and there is not the slightest evidence in favour of the amidoxime constitution. E XPE R I M E N:T A L. Hydroxyoxccmide, NH,*CO*CO*NH*OH or NH,*CO*C(OH):NOH. When oxamethane is hydrolysed with hydroxylamine either in aqueous or alcoholic solution, at any temperature from 0' t o loo", a mixture of hydroxyoxamide and its hydroxylamine salt is obtained.1566 PICKAHD, ALLEN, BOWDLElt, AND CARTER: . A product, which separsted out when saturated aqueous solutions of oxamethane (1 mol.), hydroxylamine hydrochloride (2 mols.), and sodium carbonate (1 mol.) were mixed at 60°, contained NaC1=21*08; N=22.68 per cent. This analysis showed that 28.73 per cent.of the organic matter in the product was nitrogen, whereas the pure hydroxyl- amine salt of hy droxyoxamide, NH,*CO* CO*NH*OH,NH,OH, contains N = 30.65 per cent. 0.104 Gram (1 mg.-mol.) of hydroxyoxamide, after recrystallisation from dilute acetic acid, when dissolved in alcohol or water, either at the ordinary temperature or warm, nentralises approximately 10 C.C. of N/lO potassium or barium hydroxide solution, using phenol- phthalein as indicator. I n no case did the addition of formaldehyde alter the titrations, and in every case the usual coloration was given by the solution with ferric chloride, both before and after titration. Silver Xcdt.-An aqueous solution of pure hydroxyoxamide is exactly neutralised with dilute ammonia, and then precipitated with a solution of silver nitrate.The silver salt, when first precipitated, is slightly yellow, but rapidly becomes white,is quite stable when dry, and explodes when heated. Ethyl Ester, NH,* GO* C( OH):N*O* C,H,.-The silver salt suspended' in ethyl alcohol is boiled under a reflux condenser with the calculated quantity of ethyl iodide for three hours. After filtering off the silver iodide, the solution is evaporated to dryness and the resulting product crystallised from alcohol. The ester is thus obtained in star- shaped clusters of pearly lamins which melt at 178'. It is not affected by boiling water and is only slightly hydrolysed by warm solutions of hydroxylamine. 0:132 Gram (1 mg.-mol.) dissolved in water required 10 C.C. of N/10 potassium hydroxide solution for neutralisation with phenol- phthalein as indicator : 0.0712 gave 13 C.C.moist nitrogen at 15' and 752 mm. N = 21.12. C,H80,N, requires N = 2 1-2 1 per cent. Oxanzphenylhydracaide, NI3,*COoCO0NH*NH~C,H,.-An alcoholic solution of phenylhydrazine and hydroxyoxamide is boiled under a reflux condenser €or two hours. . The phenylhydrazide crystallises out from the solution on cooling, and the crystals, after successive washings with acetic acid and sodium carbonate solution and recrys- tallisation from alcohol, melt at 231O." ' Acet ylhydroxyoxamide, NH,*CO* C( OH): "0. COO CH, (Schiff and Monsacchi, Zoc. &.).-A cold aqueous solution of 0.146 gram (1 mg.- mol.) was neutralised by 11 *6 C.C. of N/ZO potassium hydroxide solution, partial hydrolysis having taken place.* Schleussner (Inaug. Diss., Munich, 189'1), gives the melting point as 230-233'. .HYDROXY OXAMIDES, PART 11. 1567 When boiled with dimethylaniline, the acetyl derivative is quanti- tatively converted into carbamide. Plienylliydrox~oxaxccmide, C,H,*NH*CO*C(OH):NOH. 0.1 80 Gram (1 mg.-mol.) of phenylhydroxyoxamide (Schiff and Monsacchi, loc. cit.) is neutralised by 10 C.C. of N/10 potassium hydroxide solution. Phenylhydroxyoxamide, when warmed with aniline, yields oxanilide, and when boiled with an alcoholic solution of phenylhydrazine yields oxanilphenylhydraxide, C ~ ~ ~ = N H * C O * C O * ~ H * N H * C ~ H ~ . ~ This crys- tallises from glacial acetic acid in clusters of stellate needles, and melts and decomposes at 228'. It is insoluble in a solution of sodium carbonate, gives Bulow's reaction, and reduces Pehling's solution : 0.2525 gave 36.7 C.C.moist nitrogen at 15' and 744 mm. N = 16.65. 'The silver salt and ethyl ester mere prepared as described under The silver salt is obtained as a white, amorphous precipitate, and The ester crystallises from alcohol in coIourless, silky needles which It is soluble in potassium hydroxide solution and is 0.208 Gram (1 mg.-mol.) dissolved in alcohol neutralised 10.1 C.C. of Cl,H1,O,N, requires N = 16.47 per cent. the analogous derivatives of hydroxyoxamide. leaves metaIIic silver on ignition. melt a t 176". reprecipitated by carbon dioxide. XI10 potassium hydroxide solution : 0.1111 gave 13.5 C.C. moist nitrogen a t 22' and 750 mm. N- 13.58. C,,,Hl,O,N, requires N = 13-46 per cent.Phenylacetylhydroxyoxamide, when boiled with pyridine, decom- poses violently, evolves carbon dioxide, and gives a .solution which, when thrown into water, yields a mixture of phenyl- and s-diphenyl- . car bamides. The three nitro-phenyl-, o-tolyl-, and ethyl-hydroxyoxamides, their acetyl derivatives, and transforma tion products have been prepared from the corresponding oxamates by analogous methods to those pre- viously described (Zoc. cit.). hy drazide. * Oxanilic acid, when treated under similar conditions, yielded only traces of1568 PICKARD, ALLEN, BOWDLER, AND CARTER : o- Nitrophenylhydroxyoxa~id~ and Derivcdues. Ethyl o-nitrophenyloxamaie, NO,- C6H4*NH*CO*C02*C2H5, is obtained by the condensation of ethyl oxalate (1 mol.) and o-nitroaniline (1 mol.). It crystallises from alcohol or acetic acid in pale yellow needles and melts at 113O : 0.1257 gave 13.4 C.C.moist nitrogen at 22' and 752 mm. N = 11.93. Cl,H1,O,N, requires N = 11 *76 per cent. o-iVitropheny Zhydroxyoxamide, NO,* C,H,*NH GO* CO* NH*OH, cry s- tallises from glacial acetic acid in silky, white needles which melt and decompose at 153O : 0.1400 gave 22.3 C.C. moist nitrogen at 18.5' and 756 mm. N = 18.24. 0.225 Gram (1 mg.-mol.) dissolved in warm alcohol neutralised 10.6 C.C. of N/10 potassium hydroxide solution. The sodium, potassium, ammonium, and hydroxylamine salts are yellow, crystalline substances, of which the last melts at 161'. The acetyl derivative, NO,*C,H,*N H*CO*C(OH) *NO*CO°CH,, crjs- tallises in colourless, silky needles from acetic acid and melts at 160'.When boiled with sodium carbonate solution, it is completely decom- posed, yielding o-nitroaniline : 0.2348 gave 32.7 C.C. moist nitrogen at 21° and 756 mm. N = 15.76 Cl,H,06N, requires N = 15.73 per cent. o-Nitrophenylbiuret, NO,* C,H,*NH*CO*NH*CO*NH,, crystallises from hot water in beautiful, long, canary-coloured needles which melt at 181O: C,H70,N, requires N = 18-66 per cent. 0.1644 gave 37.1 C.C. moist nitrogen at 25' and 764 mm. N = 25.31. C,H,O,N, requires N = 25.00 per cent. o-Nitro-ozan~tphenylhydraz~de, N02*C6H, H* CO*CO*XH NH*C,H,, crystallises from acetic acid in small, yellow needles which melt and decompose at 1 8 1 O . It reduces Fehling's solution and gives Bulow's reaction : 0.0827 gave 13.7 C.C. moist nitrogen at 25' and 757 mm.N = 18.40. C,,H,,O,N, requires N = 18.66 per cent. m-Nitrophsnylhydroxyoxamide and Derivatives. m-Nitrophenylhydroxyoxamide, NO,* C,H,*NH* COO CO*NH* OH, cry s- tallises from acetic acid in colourless, silky needles which melt and decompose at 161O :HYDROXYOXAMIDES, PART 11. 1569 0.1517 gave 24.1 C.C. moist nitrogen at 15' and 757 mm. N = 18.44. 0.225 Gram (1 mg.-mol.) dissolved in alcohol was neutralised by The hydyoxglamine salt was obtained as a jelly which became crys- It crystallises from anhydrous alcohol in lustrous, The C,H70,N, requires N = 18*66 per cent, 10 C.C. of N/10 potassium hydroxide solution. talline on shaking. silky, yellowish needles and melts and decomposes at 188'. sodium, potassium, and ammonium salts are yellow.m- Nitrophen ylncet y Zh ydroxyoxcmide, NO,*C,H;NH*CO~C(OH):NO*CO*CH,, crystallises from acetic acid in white, silky needles which melt and decompose a t 184'. It is only slightly soluble in alcohol or chloroform : 0,1482 gave 20.8 C.C. moist nitrogen a t 22' and 761 mm. N = 15.91. C,,H,O,N, requires N = 15.73 per cent. The sodium and potassium salts are yellowish, crystalline compounds. The ammonium salt crystallises from alcohol in small, yellow, prismatic needles which melt and decompose at 150'. Carbonyl di-m-nitrophenylcarbamide, CO(NH*COoNH*C,K,*NO,),, crystallises from water in golden-yellow needles. It melts and decom- poses a t 142' : 0*1038 gave 20.3 C.C. moist nitrogen at 24O and 760 mm. N=21.93. CT,,Hl2O7N, requires N = 21.64 per cent. m-Xitrophenylbiuret, N0,*C,H40NH*CO*NH~CO*NH,, separates from a mixture of water and alcohol in canary-yellow crystals melt- ing at 178".0.0672 gave 14.4 C.C. moist nitrogen at 21O and 760 mm. N = 24.40. C,H,O,N, requires N = 25.00 per cent. ElhyZ m-nitrophenylallophanate, NO,*C,H,*NH~CO*NH*CO,*C,H,, crystallises from alcohol in yellowish, silky needles, which melt at 188'. I t is soluble in potassium hydroxide solution, and is reprecipi- tated by acids : It is slightly soluble in a solution of sodium hydroxide : 0.0850 gave 13 C.C. moist nitrogen at 24' and 744 mm. N= 16.77. C,,HllO,N, requires N = 16.60 per cent. m-Nitro-oxani~henyZ/~ydraxide, NO2*C,H,*NH*CO.CO*NH.NH.C,H5, crystallises from alcohol in glistening, yellow lamina?, melts at 1 8 4 O , and reduces Fehling's solution : N = 18.48.0.0791 gave 13 C.C. moist nitrogen a t 20° and 749 mm. C,,Hl,O,N, requires N = 18.66 per cent. m-Hitro- oxanilide, NO,* C6H4' NH CO CO NH. C,H,, is obtained by VOL. LXXXI. 5 N1570 PICKARD, ALLEN, BOWDLER, AND CARTER : heating the hydroxyoxamide with aniline at 170' for four hours. It crystallises from nitrobenzeue in yellowish, prismatic needles which melt at 204': 0.1530 gave 20.6 C.C. moist nitrogen a t 24' and 756 mm. N= 15.00. C1,H,,04N3 requires N = 14-73 per cent. p- NitropAenyl~~ydroxyoxamide and Derivatives. Ethyl p-nitrophenyloxamacte, NO,*C,H,*NH*CO C0,*C,H5, crystal- 0.1813 gave 18.8 C.C. moist nitrogen at 22' and 764 mm. N=11a80. CloMlOO5N2 requires N = 11.76 per cent. p-Nitrophenylhydroxyozamide, NO,*C,H,*NH*CO*CO*NH*OH, crys- tallises in colourless needles from glacial acetic acid and melts at 182' : 0.1142 gave 18.8 C.C.moist nitrogen at 19' and 756 mm. N = 18.78. C,H,05N3 requires N = 18-66 per cent. 0.225 Gram (1 mg.-mol.) dissolved in alcohol required 9.8 C.C. of NIT0 potassium hydroxide solution for neutralisation. The hydroxylamine salt is a pale yellow, crystalline substance melt- ing at 190'. The acetyl derivative, N0,*C,H4*NH*CO*C(OH):NO*CO*CH3, crys- tallises from acetic acid in silky, white needles melting with decompo- sition a t 182' : 0.1923 gave 26.8 C.C. moist nitrogen at 22' and 756 mm. N= 15.67. lises from acetic acid in white, prismatic needles and melts at 166' : . CloH,O,N, requires N = 15.73 per cent. It is completely decomposed when boiled with dilute sodium car- bonate solution, yielding p-nitroaniline.p-Nitrophenylbiuret, N0,*CGH,.NH*CO*NH*CO*NH2, crystallises from water in pale golden-yellow needles with water of crystallisation. It melts a t 206' and is very soluble in alcohol. NO,* C6H4 NH CO NH CO, C,H,, crystallises from alcohol in white, silky needles which melt and decompose at 220° : N = 16.59. Eth y I p-nitrophenyla llophanat e, 0.0604 gave 8.8 C.C. moist nitrogen at 1s' and 751 mm. p-ffitro-oxcarti~~~enyZhydraxide, ~ 0 , ~ C , H 4 * ~ ~ ~ ~ O ~ C O ~ ~ ~ It melts CloHl,O,N, requires N = 16.60 per cent. crystallises from alcohol in flat, compact, yellow needles. and decomposes a t 217' and reduces Fehling's solution : 0.1599 gave 25.6 C.C. moist nitrogen at 15' and 750 mm. N = 18.52. C,,H,,O,N, requires N = 18.66 per cent.HYDROXYOXAMIDES, PART 11.1571 o-Tolylhydroxyoxamide and Derivatives. Ethyl o-tolyloxamate, CH,-C',R,*NH~CO*CO,*C,H,, is erroneously described in Beilstein as a substance melting a t 130' when anhydrous. Such a substance is a mixture of the oxamide and oxamate. The two are separated by extraction with ether, in which the oxamate is much the more soluble. It crystallises from dilute alcohol and melts a t 40' : N=7*18. 0.2926 gave 18.8 C.C. moist nitrogen at 21' and 748 mm. CllHI,03N requires N = 6.76 per cent. o-Tolylhydroxyoxamide, CH~*C,H,*NH*CO*CO*NH*OH, crystallises from dilute acetic acid in star-shaped clusters of needles and melts at 152' : 0.1880 gave 23.8 C.C. moist nitrogen at 20' and 756 mm. N= 14-44. C,H,,O,N, requires N = 14.44 per cent.The acetyl derivative crystallises from acetic acid in needles and 0.1133 gave 12 C.C. moist nitrogen at 19' and 754 mm. It is very easily soluble in alcohol. melts a t 125': N= 12.07. C11H,,04N2 requires N = 11 W.5 per cent. The ammonium salt crystallises from alcohol in Iustrous, silvery plates which melt with decomposition at 139". The sodium salt is a microcrystalline powder which begins to decompose a t about 120'. Ctcrbonyldi-o-tolylcarbumide, CO(NH*CO*NH*C6H,*CH,)z, crystal- lises from alcohol in needles and melts a t 190' : 0.0740 gave 11 C.C. moist nitrogen a t 19' and 756 mm. N= 17.04. C17H,,0,N, requires N = 17.17 per cent. EthyE o-toZyZaEZophanate, CH,*C,H,*NH*CO*NH*C02-C2H5, crysta1- 0.2819 gave 31 *3 C.C. moist nitrogen a t 195'and 758 mm.N = 12.65. o-Tolylbiuret, CH3* C,H,*NH*CO*NX*CO *NH2, separates f porn 0.0894 gave 17 C.C. moist nitrogen at 20' and 758 mm. N=21*67. lises From dilute alcohol in needles and melts a t 137' : C,,H,,O,N, requires N = 12.61 per cent. alcohol as a microcrystalline powder which melts at 180' : CSHl,O,N, requires N = 31 -76 per cent.1572 PICKARD, ALLEN, BOWDLER, AND CARTER : Ethylhyd.roxyoxanLide and J)e.riuativee. Ethylhydroxyoxumide, C,H,*NH*CO*CO*NH*OH, crystallises from ether in colourless lamins, melts a t 138', and is very soluble in most organic solvents. 0.132 Gram (1 mg.-mol.) of the product extracted by ether from the acidified aqueous solution of its hydroxylamine salt was neutralised by 8.6 C.C. of N/10 potassium hydroxide solution. The hydrozylarnine salt crystallises from alcohol in small, white, glistening needles melting at 156' : 0.0705 gave 16:c.c.moist nitrogen at 21' and '756 mm. N=25.65. C,H,,O,N, requires N = 25.45 per cent. The acetyl derivative,. C2H,*NH*CO-C(OH):NO*CO*CH3, crystal- lisea from acetic acid in lustrous, colourless needles which melt a t 138' : 0.1071 gave 15.5 C.C. moist nitrogen at 20' and 744 mm. N = 16.24. C,H,,O,N, requires N = 16.09 per cent. Ethylbitwet, C,H,*NH*CO*NH.CO*NH,, crystallises from water in star-shaped clusters of prismatic needles. These melt at 153' and decompose violently a few degrees higher : 0.0447 gave 13 C.C. moist nitrogen a t 22' and 748 mm. N = 33.32. C,H,02N, requires N =I 32.06 per cent. . Hydi*oxamic Acids. Omldihydroxamic Acid, (CO~NH*OH),.-0*120 Gram (1 mg.-mol.) of oxaldihydroxamic acid (Hantzsch and Urbahn, Ber., 1894, 27, 801) dissolved in warm water was neutralised by 18.6 C.C.of N/10 barium hydroxide solution. When boiled with an alcoholic solution of phenyl- hydrazine, a quantitative yield of oxaldiphenylhydrazide (m. p. 278') was obtained. Malondihydvoxamic Acid, CH,( CO*NH*OH),,-This was prepared according t o Hantzsch and Urbahn's method (Zoc. cit.), who give the melting point as 154-1.55'. H. Schiff (loc. cit.) states that the purest specimen he obtained melted at 144-145'. We found it to cryetallise from dilute acetic acid in square plates melting at 1609" (Nitrogen found, 21.08 per cent. ; calc., 20.89 per cent.) 0.134 Gram (1 mg.-mol.) dissolved in dilute alcohol neutralised 18.5 C.C. of N/lO barium hydroxide solution. * In crptallising these and similar products, it is advisable to drop the powdered ammonium or hydroxylamine salt into dilute acetic acid which has been previously warmed ; on cooling, the free acid separates out.Boiling with dilute acetic acid often decomposes these hydroxamic acids.HYDROXYOXAMIDES. PART rI. 15'73 When boiled with an alcoholic solution of phenylhydrazine, malon- dihydroxamic acid yields malondiphenylhydrazide (m. p. 186'). Benxhydroxamic Acid, C,H,*CO*N€€*OH.-O*l37 Gram (1 mg.-mol.) dissolved in alcohol gave a coloration with phenolphthalein after the addition of 5.2 C.C. of XI10 potassium hydroxide solution. This is due to the formation of the salt C,H,~C(OH):NOH,C,H,*C(OH)*NOK described by Lossen (Annalen, 1872, 161, 347).0.137 Gram (1 mg.-mol.) dissolved in alcohol was neutralised by 9.7 C.C. of N/10 barium hydroxide solution. Benzhydroxsmic acid, when boiled with an alcoholic solution of phenylhydrazine, yields benzoylphenylhydrazine (m. p. 169O). Milligram-mols. of dibenzhydroxamic acid, acetylbenzh ydroxamic acid,* benzoylpyromucylhydroxamic acid (Trans., 1901, 79, 847), and p-tolylacetylhydroxyoxamide (Zoc. cit .) were all neutralised by 9.9-10 C.C. of XI10 potassium hydroxide solution. One mg.-mol. of methyleneamidoxime-acethydroxamic acid, NH,*C(NOH)*CH,*CO*NH*OH (Modeen, Ber., 1891, 24, 3437), was neutralised by 9 C.C. of N/10 barium hydroxide solution. Oxamates of the type NRR*CO*CO,*C,H, are hydrolysed by an alcoholic solution of hydroxylamine, giving the secondary amine and oxaldihydroxamic acid.This was proved in the case of ethyl methyl- oxanilat e, I" ethyl eth y loxanila te, and ethyl pi peridy Ioxamat e. The following hydroxamic acids were prepared for the purpose of Pyr.uvyl~iaenyliiydraxone~ydroxacmic acid, comparison. CH,*C( N*NH* C,H,)*CO *NH*OH, was obtained by treating the corresponding ester with an alcoholic solution of hydroxylamine and was isolated by means of i t s lead salt. It crystallises from a mixture of ethyl acetate and benzene in white needles which melt a t 148". It is very soluble in alcohol, acetone, or ethyl acetate, but only slightly so in ether : 0.0901 gave 16.8 C.C. moist nitrogen a t 16' and 750 rum. N=21.45 0.193 Gram (1 mg.-mol.) dissolved in alcohol was neutralised by 10 C.C.of N/lO barium hydroxide solution : * Acetylbenzhydroxamic acid, when boiled with pyridine, gives a solution whioh when thrown into water, yields s-diphenylcarbamide. .t. These oxamatev mere prepared by heating ethyl oxalate (1 rnol.) and the amine (1 mol.) in an oil-bath at 150" for 4-5 hours. The products were washed with dilute sulphuric acid to free from excess of the amine, dried, and fractionated. Ethyl ethyloxsnilate, C,H,'N(C2H,)'CO'C0,'C,H,, is a pale yellow oil which boils C,Hl1O,N3 requires N = 21-76 per cent. at 215-220",1514 HYDROXYOXAMIDES. PART 11. The acetyl derivative crystallises from dilute acetic acid in colourless 0.1053 gave 16.2 C.C. moist nitrogen a t 16' and 750 mm. N=17.73. C,lH,,O,N, requires N = 17-87 per cent. The ammonium and sodium salts are soluble in alcohol, and the sub- stance is entirely decomposed by boiling with pyridine or dimethyl- aniline, needles which melt at 113'.P~enyZgZycinehyd~oxGlmic acid, C,H,*NH*CH,*CO*NH*OH. An alcoholic solution of hydroxylamine is prepared in the usual way, and when quite cool the equivalent quantify of ethyl anilino- acetate (Bischoff and Hausdorfer, Ber., 1892, 25, 2270) is added. On the addition of sodium (I mol. dissolved in alcohol), an almost quantita- tive yield of the sodium salt of the hydroxamic acid is obtained. This is filtered off, dissolved in water, and the hydroxamic acid set free by the addition of the exact quantity of dilute sulphuric acid re- quired, The white precipitate is filtered off and crystallised from dilute alcohol.The hydroxamic acid is thus obtained in the form of colourless, small, glistening plates which melt and decompose at 118' : 0.1688 gave 0.3580 GO, and 0.0923 H20. 0.2280 ,, 34.7 C.C. moist nitrogen a t 20' and 736 mm. N= 16.84. 0.166 Gram (1 mg.-mol.) dissolved in alcohol was neutralised by 10.3 C.C. of N/lO barium hydroxide solution. Phenylglycinehydroxamic acid is soluble in alcohol, but only slightly so in ether, benzene, or water. It is dissolved and decomposed by dilute mineral acids. Its aqueous solution gives the usual coloration with ferric chloride. Acety? Derivative.-The hydroxamic acid is extremely difficult to acetylate owing t o its extraordinary sensitiveness towards acids. It waR therefore dissolved in pyridineand kept cool while the calculated quan- tity of acetyl chloride was slowly added.The mixture, after standing overnight, was poured into water, and the resulting precipitate crys- tallised from alcohol. The acetyl derivative was thus obtained in the form of long, colourless, prismatic needles melting at 1079 It is insoluble in ether and has an acid reaction toward litmus : 0.1375 gave 16.5 C.C. moist nitrogen at 20' and 745 mm. N = 13.45, On neutralising an alcoholic solution with sodium ethoxide, the C = 57.84 ; H = 6.07. C,H,,O,N, requires C = 57.83 ; H = 6.02 ; N = 16.86 per cent. C,,H,,O,N,:requires N = 13.46 per cent.TEE CONSTITUENTS OF COMMERClAL CHRYXAROBIN. 1578 sodium salt is precipitated. warming its aqueous solution. ing the acetyl derivative with sodium carbonate or dilute ammonia. This salt slowly decomposes to a n oil on No better result is obtained on treat- Amidoximeoxalic Acid. 0.104 Gram (1 mg.-mol.) of amidoximeoxalic acid (Holleman, Zoc. cit.) dissolved in approximately 30 C.C. of water a t 20' required 9.4 C.C. of R/ 10 potassium hydroxide solution for neutralisation. Ethyl Eater, NH,*C(NOH)*CO,*C,H,.-The silver salt suspended in alcohol is boiled with the calculated quantity of ethyl iodide, The alcohol is then evaporated off and the oily mass extracted with ether. The ester separates from the ether in colourless, lustrous needles. These melt at 97-98O and evolve gas a t 140-170°, a t which tempera- ture entire decomposition sets in. The ester is soluble in water, alcohol, or ebher, and i t s solutions are completely neutral to litmus, and give a sienna-brown coloration with ferric chloride : 0,0963 gave 18.5 C.C. moist nitrogen a t 20' and 750 mm. N = 21.68. C,H,03N, requires N= 21.21 per cent. Some of the materials used in this research were purchased by a grant from the Research Fund Committee of the Society, for which the authors desire to express their indebtedness. MUNICIPAL TECHNICAL SCHOOL, BLACKBURN.