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ACETIMIDO-NAPHTHYL-AMIDE v. NAPH- THYL-ACETAMIDINE. ACETIMIDO-TOLYL-AMIDE v. TOLYL-ACETA- MTDINE. ACETO-ACETIC ACID CH3. CO. CH2. CO..H or CH.,.C(OH):CH.C02H. Occurrence. —In urine of diabetic patients (Geuther a. Kupstein, Fr. 14, 419 ; Deichmiiller, A. 209, 30 ; Tollens, A. 209, 36 ; Jaksch, H. 7, 487). Preparation. — The ethyl ether (4-5 g.) is mixed with water (80 g.) containing KOH (2-1 g.), and after 24 hours the liquid is acidified and shaken with ether (Ceresole, B. 15, 1327, 1872). Properties. — A thick acid liquid, miscible with water. At 100° it splits up into C02 and ace- tone. Nitrous acid gas forms C02 and iso-nitroso- acetone. Salts. — BaA'2aq. Amorphous. V.e. sol. water. Violet colour with FeCl3. — CuA'22aq. Amorphous. Ethyl Aoeto-acetate or Aceto-acetic Ether CH3.CO.CH2.CO.,Et or CH3.C(OH) : CH.CO.Et. Di-acetic ether (Geuther, J. 1863, 323), ethyl-di- acetic acid (Geuther, J. 1865, 302), acetone-car- boxylic acid (Frankland a. Duppa, A. 138, 211) (180°) (B. Schiff, B. 19, 561); (180-8° cor.) ^1-4253. EOO 51-62 (B.). S.V. 153-34 (S.). M.M. 6-501 at 16-25 (P.). Formation.— The formation of aceto-acetic ether by the saponification of cyano-acetone by alcoholic HC1 (Matthews a. Hodgkinson, B. 15, 2679) is denied by James (A. 231, 245). Preparation. —Ethyl acetate (1 kilo.), that has been carefully dried, is treated with sodium (100 g.) in small pieces. As soon as the first reaction abates it is heated with inverted condenser over a water bath for 2i hours until the sodium is dissolved. Dilute (50 p. c.) acetic acid (550 g.) I is then added, and when the liquid is cool, it is mixed with water (500 c.c.). The light oily layer is washed with a little water and fractioned. ! The yield (175 g.) is small, but much ethyl ace- tate (400 g.) is recovered (Conrad, A. 186, 214). [ Aceto-acetic ether may be still further purified C by shaking with cone, aqueous NaHS03, with which it combines. Impurities may then be ex- tracted by ether, and the compound of aceto- acetic ether with NaHS03 afterwards decomposed by K,CO3 (Elion, R. 3, 246). The formation of aceto-acetic ether may be expressed by the equation : 2CH3.C02Et + Na,,= CHvCO.CHNa.CO,Et + NaOEt + H2, the sodio-aceto-acetic ether being afterwards de- composed by the added acetic acid : CH.,.CO.CHNa.CO ,Et + HOAc = CH3.CO.CH2.C02Et + NaOAc. Sec also p. 21. Properties. — A liquid with an agreeable sweet odour. Slightly soluble in water, the liquid giving a violet colour* with FeCl3. Unlike its ethyl and acety 1 derivatives, it forms a crystalline compound with NaHSOs (indicating presence of the ketonic carbonyl group, CO). Salts. — Aceto-acetic ether behaves as a mono- basic acid. This may either be ascribed to the situation of the group CH2 between two CO groups, or else by having recourse to the formula CH3.C(OH) :CH.CO,Et, which represents a com- pound that might be expected, as a tertiary al- cohol, to possess a phenolic character. Like phenol, it gives a violet colour with FeCls. Sodio-aceto-acetic Ether CH3.CO.CHNa.CO,,Et or CH3.C(ONa):CH.CO,Et. Needles. Produced by the action of sodium or sodic ethylate upon aceto-acetic ether in the cold. Preparation. — Sodium (10 g.) is dissolved in absolute alcohol (100 g.) ; when cold, dry ether (90 g.), followed by aceto-acetic ether (56*5 g.) di- luted with ether (60 c.c.), is added. If the liquid is well stirred with a little water (2 c.c.) solid sodium acetacetic ether separates (Harrow, C. J. 33, 426). The pp. is a hydrate, which becomes dry in an exsiccator (Elion, R. 3, 240). Reactions. — (a) With iodine in ethereal so- lution it gives di-aceto-succinic ether (q. v.). — (b) Heated alone or with NaOEt it gives acetone, aceto-acetic ether, NaOAc, and sodic dehydrace- tate. — (c) With alkyl iodides it forms alkyl-aceto- acetic ethers (q. v.) : CHj.CO.CHNa.CO.jEt + B'l = Nal + CH3.CO CHB'.CO.,Et. Other iodo- bromo- and chloro- compounds act similarly. — (d) But with tri-PHENYL-METHYL BRO- MIDE Ph,CBr it forms CH3CO.C(CPh3).,CO ,Et (Allen a. Kolliker, 4.227, 110).— (e) Chloroform, in presence of NaOEt forms OXY-UVITIC ETHER : C6H2Me(OH)(CO,H)2 [1:3:4:6], the first stage probably being : 2CH3.CO.CHNa.CO,Et+ NaOEt + CHC1,= COaEt.CHAc.CH K;(COIKt).C!O.CHa + 3XuC, + HOEt (Oppenheim a. Pfaff, B. 7, 929 ; 8, 884 ; 9, 321 ; Conrad a. Guthzeit, A. 222, 249). Other SaZfs.-Al^H.A,).,. Needles [76°]. Insol. water, v. e. sol. ether, benzene or CS2. May be sublimed.— Co(CBH9Oa)2. Bed pp. Sol. hot" benzene or ether.— Cu(C,.H,,Os)2 [182°]. Green needles (from alcohol). Insol. water, v. sol. benzene, ether or CS2. Got by adding Gu(OAc)2 to a solution of aceto-acetic ether in alcohol, the calculated quantity of ammonia being also added (Conrad a. Guthzeit, B. 19, 19). — Mg(CsH.,Oa), [240°]. From aceto-acetic ether and 'magnesia-mixture.' Plates (from ether- benzene). — Hg(CljHl,Oj);j Amorphous. Formet by shaking aceto-acetic ether with HgO. — Ni(CdHaO,):;. Reactions. — 1. Boiled for a long time, or mssed through a red-hot tube, it forms dehy- Iracetic acid, C8HS04, and alcohol. 2. Boiled with alkalis it gives CO2, acetone, acetic acid and alcohol, according to the reac- tions : CH3.CO.CH.,.C02Et + 2KOH = CH3.CO.CH~ + K.,C03 + HOEt ; CH3.CO.CH2.CO.;Et + 2KOH = 2CH3.CO.OK + HOEt. 3. Decomposed by water at 150°, or by strong acids, into C0._, acetone and alcohol. 4. Action of sodium alcoholates. — (a) Heated with dry NaOEt, or with alcoholic NaOEt, ethyl acetate is got in small quantity (12 p.c. of the theoretical) (Wislicenus, A. 186, 193 ; Isbert, A. 234, 160).— (b) 50 g. heated with NaOEt (from 8-9 g. Na) and MeOH (75 g.) at 130° gives methyl acetate (7 g.) and ethyl acetate (1 g.). Similar results are obtained by using PrOH in- stead of MeOH (Isbert).- (c) At 130° with NaOPr and excess of MeOH gives methyl acetate and a little propyl acetate. — (d) Heated with alcohol at 180° it is not affected, but if a very little NaOEt be present it is completely decomposed, yielding EtOAc. Similar results are got by using PrOH and NaOPr. Resacetic Acid H-j-jOs is found in all these cases as a resinous body, not volatile with steam. It forms brown amorphous salts, NaA', KA', and NH4A', sol. water (Isbert, A. 234, 167). 5. Sodium-amalgam forms 3-oxy-butyric acid: CH3.CO.CH.,.CO.,Et + H2 = CH3.CH(OH).CH2.CO;iEt. 6. Phcnyl-hydrazine in the cold forms, as with all ketones, a phenyl-hydrazide : I \CMe.CH2.CO.,Et (?), HN' but at 100° this loses EtOH and becomes methyl- OXJ/-QUINIZINE (q. v.) (Knorr, B. 17,2032). Pseudo- cumyl-hydrazine produces the homologous hy- drazide CH3.C(NJHCliH.!Me:i).CH,.CO.!Et [78 J]. Longyellow needles (from alcohol), or thick prisms (from ether). V. sol. hot alcohol or ether, si. sol. cold alcohol or benzoline. Very unstable, and at 130°-140° changes to oxy-tetra-methyl-quinizine: XO . CH2 Me3C6H< \N — CMe (Haller, B. 18, 706). 7. Hydroxylamine forms, as with other ketones, the oxim : CH3.C(NOH).CH...CO.,Et, 0-Oximido-butyric acid, CH3.C(NOH).CH2.CO~ H ; colourless crystals, [140°], si. sol. water, alcohol or ether (Westenberger, B. 16, 2996). 8. Fuming nitric acid yields oxalic acid and OXIMIDO-ACETO-ACETIC ETHER (q. v.) (Propper, A. 222, 48). 9. Sulphuryl Chloride forms mono- or di- chloro-aceto-acetic ether, according to the pro- portions used (Allihn, B. 11, 567) : CH3.CO.CH.,.C02Et + SO.,C1.,= CH.,.CO.CHCl.CO.,Et + SO .,"+ HC1 ; CH.t.CO.CH.,.CO,Et + 2SO,C1., = CH.,.CO.CCl2.CO2Et + 2SO2 + 2HC1. 10. Bromine gives mono-, di-, tri-, and per- BROMO-ACETO-ACETIC ETHERS (Wedel, A. 219, 95). ACETO-AOET10 AOID. 19 11. Chlorine forms only ACETIC ETHEB (q. V.). 12. PhospJiorus pentachloride forms the chlo- rides of two CHLOBO-CBOTONIC ACIDS (q. v.). 13. Dry prussic acid heated with aceto-acetic ether for 3 days at 100 forms a cyanhydrin, CH3.C(OH)(CN).CH,.Cp.,Et, which is cpnverted by boiling dilute HC1 into oxy-pyrotartaric acid (G. H. Morris, C. J. 37, 7). 14. Cyanogen chloride passed into sodio- aceto-acetic ether forms CYANO-ACETO-ACETIC ETHEB (q. v.) CH1.CO.CH(CN).CO.iEt (Haller a. Held, C. R. 95, 235). 15. Ammonia, whether dry (Precht, B. 11, 1193), aqueous or alcoholic (Duisberg, A. 212, 171), produces the imide of aceto-acetic ether. Aceto-acetic ether imide C6HnN02 [34°]. (213° uncor.) at 700 mm., (1543) at 154 mm. S.G. 32 1-014. S. (cone. NH.,Aq) 1-25. Dry NH3 is greedily absorbed by aceto-acetic ether, the compound CH3.C(OH)(NH.J.CH..CC).,Et being doubtless at first formed. The liquid soon se- parates into two layers, water and the imide of aceto-acetic ether. The latter is purified by distillation (Collie, A. 226, 297). Properties.— Colourless monoclinic prisms. V. si. sol. water, .v. sol. alcohol, ether, benzene, CS2 and CHC13. Moisture greatly lowers its melting-point. It is CH3.C(NH).CH.i.C02EtorCH3.C(NH2):CH.CO?Et. Reactions. — (a) Aqueous HC1 splits it up into NH3 and aceto-acetic ether (Duisberg). — (b) Cold dilute NaOH has no action, but on warming it gives NH3,HOEt, acetone andCCy— (c) Pb(OAc)2, HgCL, ZnS04, or FeGL, also splits it into aceto- acetic ether and NH3, the latter throwing down the metallic hydrate. AgNO3 does not give any pp. — (d) Glacial acetic acid also regenerates aceto-acetic ether on boiling. — (e) Sodium amal- gam gives ^-oxy-butyric acid. — (/) Nitrous fumes passed into alcoholic solution forms nitro- so-aceto-acetic ether. A by-product C8H,,N5O5, forms plates [170°].— (g) Ac.,0 at 160° forms an acetyl derivative, C8HloAcN02 [63°] (232°), which combines with bromine, forming C6HinAcBr2N02 [140 "-Q. — (h) Paraldehyde gives di-hydro-tri-me- thyl-pyridine di-carboxylic acid, which is also formed from aceto-acetic ether, NH3, and alde- hyde.— (i) EtI at 100° forms ethyl-aceto-acetic ether and a base (c. 290°), possibly ethoxy- di - methyl - pyridine. Condensation -products : C10H13NO3 [160°]. Present in the brown resin got when CgH,,NO2 is distilled under atmo- spheric pressure. Insoluble in alcohol and ether. Boiled with KOHAq it forms oxy-di-methyl- pyridine carboxylic acid. 16. Aceto-acetic ether methyl-imide, CH3.C(NMe):CH2.CO.,Et or CH3.C(NHMe) : CH.CO,Et, (133°) at 50 mm., (215 ) at 760 mm., is formed in like manner from aceto-acetic ether and mcthyl- amine (Kuchert, B. 18, 618^, With paraldehyde and H2S04 it gives a condensation-product, C13H2304N, which forms ^rimetric crystals with blue fluorescence [86°]. \^> 17. DiethylaminctormsP-di-eihyl-amido- crotonic ether, CH.,.C(NEt2):CH.CO2Et, a liquid (160°-163°) at 20' mm. 18. Heated with aniline (1 mol.) at 120° it yields a crystalline body, C10H,,N02, which melts at 81° and is probably the anilide of acet-acetic acid CHs.C(NPh).CH2.C02H. By dissolving this substance in cold H2S04, H20 is eliminated with formation of (Py. l)-oxy-(Py. 3)-methyl- QUINOLINE (Knorr, B. 16, 2593). 19. o-PJienylene-diamine forms : C,H4(N : CMe.CHrC02Et)2. 20. o-Tolylene-diamine gives : CH3.C(iH3<^>CMe.CH2.CO,Et. (Ladenburg, B. 12, 951 ; Witt, B. 19, 2977). 21. With aldehydes (Claisen, B. 12, 345) : CH3CO.CH2.C02Et + BCOH = H,O + CH3.CO.C(CH.B).CO2Et. The bodies are mixed in molecular proportions, and HC1 is passed in at 0°. Or the bodies may be heated with Ac2O. Examples (Matthews, C. J. 43, 200) : — (a) Isobutyric aldehyde gives C10H180S (219°-222D). Oil. Smells like peppermint. Com- bines with bromine, (b) Valeric aldehyde gives CUH1803 (237°-241L). S.G. if -9612. Oil. Smells of strawberries. (c) Chloral gives CjHjCLA, (154°-158°) at 25 mm. S.G. if 1-3420. From chloral, acet-acetic ether, and Ac20 at 150°. (d) Furfural gives C,,H12O4 [62°], (188°- 189°) at 30 mm. From furfural, acet-acetic ether, and Ac2O. Easily soluble in chloroform, acetic acid, alcohol, and benzene. Large doubly-refract- ing crystals (from light petroleum and ether ). 22. Aceto-acetic ether (2 mols.) condenses with aldehyde-ammonia, forming di-hydro-tri- METHYL-PYRIDINE-DI-CARBOXYLIC ETHEB (q. V.) I 2CH3.CO.CH2.CO.,Et + CH3.CH(OH)NH2 = 3H.,O 4- CiHi!NMe3(CO2Et).i. Since the product contains three methyls and two CO2Et groups, we may assume these to be identical with the same groups in the. reacting bodies. And inasmuch as the product is not acted upon by nitrous acid gas and forms an ammonium iodide with Mel, it would seem to be a tertiary base. Nevertheless, inasmuch as methylamine and aldehyde give a similar body, the reaction may probably be represented thus : CHMe C02Et.CH 0 HC.CO.,Et Me.COH H2 HOC.Me NH Me ,CH C02Et.C MeC .CO,Et ii CMe \ (Hantsch, A. 215, 74 ; B. 18, 2579). Other alde- hydes in presence of NH3 form similar derivatives of the pyridine series (v. METHYL-PYBIDINE) . Thus cinnamic aldehyde and ammonia forms di- methyl - styryl - di - hydro - pyridine di-carboxy lio ether, H2C5NMe.,(CH:CHPh)(CO2Et)2, [148 ] (Epstein, A. 231, 3). 23. With formamide and ZnCl2 aceto-acetio ether gives di-methyl-pyridine carboxylic ether (Canzeroni a. Spica, Q. 14, 449). 24. With acetamide and A1C1, it forma CH3.C(NAc).CH2.CO.,Et [65°]. Needles. Converted by KOH into the amide of aceto-acetic ether. 25. Mixing with acetamidine hydrochloridt and dilute NaOH, and, after standing for some days, evaporating to dryness and extracting with alcohol, yields a di-methyl-oxy-pyrimidine^ c 2 20 ACETO-ACETIC ACID. CdH8N.jO [190°]. Needles. V. sol. water or alco- hol, si. sol. ether or benzene. It is probably CH3.C< CH. Propionamidine forms a homologue, methyl- ethyl-oxy-pyrimidine [160°]. Its hydrochloride forms thick prisms, C.H10N.,OHC1 [c.243°]. V. e. sol. water, v. sol. alcohol— (C;H10N2OHCl),PtCl4 [2:HT]. Prisms. (Pinner, B. 17, 2520 ; 18,2847). 26. With urea in alcoholic solution it forms /3-uramido-crotonic ether (Behrend, A. 229, 5) : MeC(OH) : CH.C02Et * NH^CO.NH., = NH.fCO.NH.CMe : CH.CO.Et + H.,O. The free ^-URAMIDO-CBOTONIC ACID, when liberated from its salts, changes at once into its anhydride, methyl-uracil : NH.CO.NH.CMe : CH.CO 27. Thio-urea (40 g.), heated with aceto-acetic ether (40 g.) slowly to 150', gives a compound CjHgN^OS (5 g.), which may be thio-methyl- uracil. It may be crystallised from water. It dissolves in alkalis and is reppd. by acids. Its melting-point lies above 300°. Its aqueous solution gives with AgN03 an amorphous pp. of C5H4Ag,N,SO (Nencki a. Sieber, J. pr. [2] 25, 72). If a little HC1 be added to an alcoholic solution of thio-urea and aceto-acetic ether, un- stable needles are formed. These are converted by alcoholic potash into potassium thio-methyl- uracil, C5H5KN.,SO (List, B. 19, 219). 28. Aceto-acetic ether (20 g.), plienyl-urea (10 g.), and ether (6 g.) at 150° react thus : C.HL.O, + C7H,N,0 = C19H,,.N,O, + H.,0. The product is an oil which is decomposed by alcoholic potash with formation of ammonia and aniline, and by boiling cone. HC1 with form- ation of CO.., alcohol, acetone, and phenyl- carbamic ether, PhNH.CO.^Et. The reactions indicate that the body CI3H, NV03 has the consti- tution NPhH.CO.N : CMe!CH2CO^Et, or perhaps ^CMe.CKj.CO.Et (Behrend, A. 233, 1). 29. Combines directly with di-phenyl-urea, in presence of a little ether at 150°, forming an oil, C^H^NX)^ This body is converted by al- coholic KOH into aniline and K2C03, and by acids into phenyl-carbamic ether and aniline. The body must be PhNH.CO.NPh.C(OH)Me.CH2.C02Et. Similar addition products are probably first formed in the case of other ureas, but H20 splits off : PhNH.CO.NH.C(OH)Me.CH.,.C02Et = H2O + PhNH.CO.N : CMe.CH.,.CO,Et. 80. p-Di-azo-tohtcnc Chloride, acting on an alcoholic solution of aceto-acetic ether, forms yellow needles of p-toluene-azo-aceto-acetic ether [188 ] C(,H4Me.N2.CH(CO.CH3).C02Et(Richtera. Miinzer, B. 17, 1929 ; v. AZO compounds). 31. Hydrazo-benzene at 100°-150° forms HOEt and a crystalline base, C,(H,4N20 (A. Miiller, B. 19, 1771). 32. Copper aceto-acetic ether is converted by COClz into an anhydride of di-acetyl-acetone di-carboxylic ether, CO(CHAc.CO;tEt)2. The anhydride may be : CH3.C - 0 - C.CHS II II CO.,Et.C-CO-C.CO,Et. [80°]. Sol. glacial HOAc, H,S04, cone. HC1, ben- zene, alcohol, or ether. NH3 converts this body into oxy-di-methyl-pyridine-di-carboxylic ether : CHj.C-NH-C.CH, II II COJ3t.C-CO-C.C02Et (Conrad a. Guthzeit, B. 19, 22). 33. Aceto-acetic ether, heated with CS.2 and PbO at 100°, forms ' thio-carbonyl-aceto-acetic ether ' CH3.CO.C(CS).CO2Et [156°-162°]. Yellow needles (from alcohol) (Norton a. Oppenheim, B. 10, 703). 34. S-jClj converts sodium aceto-acetic ether suspended in benzene into sulphido-aceto-acetio ether S(CHAc.C02Et)2 [81°] (Buchka, B. 18, 2092). 35. With succinic acid it reacts thus : CBH1003 + C,H,04 = ClaH1404 + 2H.O. The product is a crystalline acid [76°], which ia the acid ether of a dibasic acid C^Os [200°] (Fittig, B. 18, 2526). Condensation products from aceto-acetic ether. — 1. By heat: Passed through a red-hot tube it forms DEHYDKO-ACETIC ACID (q. v.) and other products (Perkins, jun. C. J. 47, 240). — 2. By hydrochloric acid : Dry HC1 at 8° forms, in four weeks, acetic ether and ' carb-aceto-acetic ether ' CgH,0O, (290°-295° uncor.). S.G. 511-136. This liquid is slightly decomposed on distillation. It gives no colour with aqueous Fe2Cl6 (Duisberg, A. 213, 179). Carb-aceto-acetic ether is also formed when aceto-acetic ether is heated with acetyl chloride at 120° (Wedel, A. 219, 116).— 3. By sulphuric acid : C,H;(OH)(CO.H).CO.O.CsH;(COiH)(CO.Et) [62°]. Got by leaving a mixture of aceto-acetic ether (1 pt.) and cold cone. H.,SO4 (2| pts.) for fourteen days and then pouring into water (Hantzsch, A. 222, 4). Needles resembling as- bestos. SI. sol. cold water, m. sol. hot water and ether, v. sol. alcohol, v. e. sol. chloroform. De- composed by heat. It is acid to litmus and, when hot, has a spicy odour. Its formation may be represented thus : 4CttHI0Os = C18H,A + 3C AOH. Reactions. — (a) Boiling alkalis form carbonate and acetate, acetone, and mesityl oxide. (6) On neutralising with alcoholic potash it decomposes thus : C.H7(OH)(COaH).CO.O.C.H,(CO,H)CO.,Et+KOH= O xO .,, the potassium salt of mesitene-lactone carb- oxylic acid being ppd. while its ether remains in solution. Mesitene-lactone Carboxylic Acid CH,.C:C(CO.sH).CMe : CH.CO.O [155°] (iso-dehydracetic acid). Fluffy crystals (from water). SI. sol. cold water, v. sol. hot water. Monoclinic prisms (from alcohol). May be sublimed. Reactions. — Distilled with lime it gives mesi- tyl oxide. Salts.— KA'?2aq. — NaA'.— NH4A'— BaA',,.— MgA'2.- CuA'.,2aq. — Ag4H;,A'7. — AgsHA':. Strong ACETO-ACETIC ACID. 21 bases convert iso-dehydraeetic acid into oxy- mesitene dicarboxylic acid, CH3.C(OH)C:C(COl!H).CMe:CH.CO,H, •which forms a stable copper salt Cu^H A"fc, but its alkaline salts readily split off COU : CaHjfOHXCO^Na)., f NaOH = C,.H8(OH)(CO,Na) + Na.CO3, forming oxy-mesitene carboxylates. These readily undergo a similar decomposition : CdH3(OH)(CO.,Na) + NaOH = Na,CO3 + CBH.,OH, probably forming ' mesitenyl ' alcohol, which at once changes to mesityl oxide. Baryta is the best alkali to use in these decompositions. Mesitene Lactone CH,.C : CH.CMe :CH.CO.O i i [51-5°] (245° cor.). From iso-dehydracetic acid by distillation, or by heating with H^SO, at 170°. Glittering tables. Very soluble in alcohol, ether, or water, sparingly so in CS2. Tastes bitter and spicy. Neutral to litmus. Separated by K2C03 from aqueous solution. Gives with Br in CS2 a bromo-derivative, C,,H7BrC02 [105°]. Converted even by water into oxy-mesitene carboxylic acid. Hence it is a 5-lactone. Oxy-mesitene Carboxylic Acid C(jHg(OH)(CO.,H) i.e. CH3.C(OH):CH.CMe:CH.C02H. From its lactone (mesitene-lactone) by boiling with water or, better, with baryta. A thick liquid, soluble in water. Its salts are amor- phous, e.g. BaA'2) CaA'2. These salts on boiling form carbonate and mesityl oxide. Mesitene-lactone Carboxylate of Ethyl C6H7(CO2Et)CO2 i.e. CHS.C: C(CO.,Et).CMe:CH.CO.O. Formed, together with its potassium salt, by the action of alcoholic KOH on the product of con- densation of aceto-acetic ether, as described above. Also from its potassium salt by EtI. Also got when aceto-acetic ether, saturated with HC1, is left at 0° for a month (Polonowska, B. 19, 2402). Oil. Reactions.— (a) Br in CS2 forms C0HsBr(CO2Et)CO., [87°]. Needles (from alcohol). — (b) NH3 passed into an alcoholic solution forms satiny plates of C(jH7(CO.^t)(CO,NH4)(ONH4) melting at [104°], giving off 2NH3 + H2O, and changing to the lactone. Warm water or cold alcohol also change it to the lactone. Cold HClAq liberates CbH,(CO;iEt)(CO.iH)(OH), which maybe extracted by ether. Small plates [76°]. Boiled with water, two-thirds are changed to lactone, and when the lactone is boiled with water, one- third becomes oxy-acid. It forms salts of the form C<jH,(OH)(CO2Et)(COzH), viz. CuA',aq, PbAUq. When the acid is boiled with alkali there is formed dehydracetic acid and its decomposition products, -mesityl oxide, acetone, and CO^ and the following decomposition also occurs : CH..C .-C. CO,Et).CMeK3H.CO.O + 3H,0 = CH1.COIH+HOEt+CH1(CO,H).CMe«H.CO.H, resulting in homomesaconic acid. Homomesaconic Acid CH2(C9,H).CMe : CH.CO^H [147°]. Small prisms (from water). V. sol. cold water, and alcohol, si. sol. ether. Not volatile with steam, but sublimes about 120°. Salts. — BaA"4 |aq. — CaA"aq. — CuA"2aq. — Ag, A".- KHA".- NH4H A". Ethyl ether Et,A". (240°-242°). Theory of the Condensation. — As acetone gives mesityl oxide C8H100 or CH,.CO.CH:C(CH.,)2, so aceto-acetic ether, if it is CH3.CO.CH.jCO,Et, should give the dicarboxylic ether of mesityl oxide, CuH,O(COJEt)2, or the acid,C6H80(CO.H),. Instead of this, it gives an isomeride of the latter, CdH,(OH)(CO.,H),, so that the group CO.CH must have changed to C(OH):C. Assuming that this group pre-exists in aceto-acetic ether, the condensation would be as follows : CH3.C( OH ) «(COilEt)H + HO.CMe tCH.CO^t = CH3.C< OH ) £!, C03Et).CMe :CH.COaEt + HaO= CH,.C :C( COaEt>.CMe rCH.CO.O +HOEt+H,0. Acetyl-aceto-acetic Ether CH3.CO.CHAc.CO,Et or CHa.C(OAc):CH.CO:JEt, di-aceto-acetic ether. (200°-205-). S.G.i^ 1-064 (James) ; ^ 1*101 (Elion). From aceto-acetic ether (65 g.), ether (50 g.) and sodium (9 g.), by adding a solution of AcCl (30 g.) in ether (50 g.) in the cold (J. W. James, A. 226, 210 ; C. J. 47, 1). Properties. — Pleasant smelling liquid, slightly decomposed on distillation. Miscible with alco- hol, ether, and benzene, hardly soluble in water, but slowly decomposed by it into acetic acid and aceto-acetic ether. Fe^Cl,, gives a raspberry-red colour, removed by S02. Salts.- Acetyl-aceto-acetic acid is a strong acid, and can expel acetic acid from its salts. — CuA'^aq: insoluble in water; [148°].— NaA' (Elion, R. 3, 255).— NiA'22aq. Reactions.— 1. NaOEt decomposes it into EtOAc and sodium aceto-acetic ether. Benzoyl-aceto-acetic Ether CH3.CO.CBzH.CO,Et From sodium aceto-acetic ether and benzoyl chloride alone (Bonne, A. 187, 1), or dissolved in ether (James, A. 226, 220 ; C. J. 47, 10). Properties. — A fairly strong acid, capable of displacing acetic acid. Salt.— CuA'2 (from benzene) [180^-190°]. Formed by shaking the ether with aqueous cupric acetate. SI. sol. alcohol or benzene, m. sol. ether. o - Nitro - benzoyl - aceto - acetic Ether. — Pre- pared as above, using nitro-benzoyl chloride. It is an oil. Boiled with dilute H2S04 it forma o-nitro-phenyl methyl ketone and also o-nitro- benzoyl-acetone in smaller quantity. Cone. KOH forms a salt CH3CO.C(CtiH4NOJK.CO;,Et (Gevekoht, A. 221, 323). Constitution of Aceto-acetic Ether. Some chemists adopt Frankland's formula for aceto-acetic ether, CH3CO.CH2.CO2Et ; others prefer Geuther's formula, CH3.C(OH):CH.C02Et ; while a third party, relying upon the results of Baeyer's researches into the constitution of the derivatives of indigo, consider that both formuliB are equally correct, or rather that at the moment of reaction the first may change into the second. Against Frankland's formula it is argued (1) That the copper salt is blue or green, whereas compounds in which copper is united to carbon (e.g. copper acetylide) are red or yellow. (2) That it does not account for the existence of acetyl and benzoyl derivatives. (3) The formation of hydro-quinone di- carboxylic ether, a body containing two hydroxyls, by the action of sodium on di-bromo-aceto-acetio 23 ACETO-ACETIC ACID. ether. This indicates the presence of hydroxyl in di-bromo-aceto-acetic ether. (4) The action of ammonia, and especially of di-ethylamine. In favour of Frankland's formula may be noted the compounds with NaHSO,, phenyl-hydrazine, and hydroxylamine. The action of sodium upon aceto-acetic ether would be represented by Franklaud's formula, thus : C Hj.CO.C H,.CO.Et + Na = CHJ.CO.CNaH.CO,Et + H. Ethyl iodide converts the product into ethyl- aeeto-aeetic ether : CH j.CO.CNaH.CO.Et + EtI = CH,.CO.CEtH.CO,Et + Nal These two reactions may be repeated upon the ethyl-aceto-acetic ether : CH,CO.CKtH.CO,Et + Na=CH,.CO.CEtNa.COaEt+H CH,.CO.CEtNa.CO,Kt + EtI = CHj.CO.CEtj.CO., Kt + Nal. Adopting Geuther's formula, the four equations become : CH,.C( OH) cCH.CO.Et + Na= CHj.C(ONa) K)H.COaEt + H CH..C( ONa) :CH.CO,Et + EtI =CH,.C(OEt) :CH.COaEt + Nal CH,.C(OEt):CHX:O,Et+Na=CHs.C(OEt):CNa.CO..1Kt+H CH,.C(OE ) !CNa.CO.,Et + Ktl = CH,.C(OEt) :CEt.CO,Et + Nal It will be seen that the third and fourth equa- tions are similar to the first and second on Frankland's hypothesis, but different in kind to the first and second if Geuther's hypothesis be accepted. Such a difference is not borne out by experiment. Thus if it be held that the action of sodium upon aceto-acetic ether depends upon its affinity for oxygen, the third equation presents a difficulty. And if we suppose that, owing to some intra-molecular change, the third equation ought to be written thus : CH3.C(OEt):CH.CO,Et+Na=CH>.C(ONa).-CEt.C0.1Et + H then by the action of acetic acid on the product we ought to get an ether CHs.C(OH):CEt.CO;!Et isomeric, not identical, with ethyl-aceto-acetic ether, CHj.C(OEt):CH.CO.jEt; but the two ethers are found to be identical (James, C. J. 47, 1). In- asmuch as the change of CH,.C(OH):CEt.CO.,Et into CH3.C(OEt):CH.COiEt would be contrary to all analogy, it is necessary, if we adopt Geuther's formula, to assume that the mode of formation of di-ethyl-aceto-acetic ether is something very different from that of ethyl- aceto-acetic ether. Again Geuther's formula would make methyl-ethyl-aceto-acetic ether, CH,.C(OEt):CMe.CO.JEt and ethyl-methyl-aceto- acetic ether, CHs.C(OMe):CEt.CO.jEt isomeric, yet this does not appear to be the case (James). It may be said that there is some improba- bility in the assumption required by Frankland's formula, of direct union between sodium and carbon, but such a union is known to occur in sodium acetylide and sodium ethide, and it is very probable in many cases, such as sodio- malonic ether, sodium nitro-ethane, and sodic barbiturate. In order that hydrogen attached to carbon may be displaceable by metals, it is necessary that very powerful chlorous groups should also be attached to the carbon, such as the nitroxyl in nitro-ethane. One carbonyl, CO, is not sufficient to produce an acid, but two are. Thus the hydrogen in the group CO-CH^CO is displaceable by metals, as in barbituric acid, XNH.COV CO ^CH.. These considerations account for the acidity of aceto-acetic ether, if we assume Frankland's formula CH3.CO.CH,.CO.OH. Although the existence of acetyl-aceto-acetic ether favours Geuther's hypothesis, yet the fact that this body is a strong acid is wholly opposed to that view, and is very much better explained by the formula CH3.CO.CH(CO.CH3).CO.OEt, since if two carbonyls can make the group CPL, acid, d fortiori three carbonyls can have a simi- lar effect. The formation of ethyl and di-ethyl-acetone from ethyl-aceto-acetic ether and di-ethyl-aceto- acetic ether respectively cannot be explained on Geuther's hypothesis. If, therefore, we have to choose between one formula and the other, the balance of evidence would iadicate CH3.CO.CH ..CO ,Et. Methyl aceto-acetate C H"SO3 i.e. CH Ac.CO.,Me (170° cor.) S.G. e 1-037 (Brandes, J.Z. 3, 25). From sodium and methyl acetate. Gives a cherry- red colour with Fe2Cl6. Boiled with acids or strong bases it gives CO2, acetone, and MeOH. Salts.— CH3.CO.CHNa.CO,Me. SI. sol. ether. — Cu(C5H.03).j2aq. Separates on adding cupric acetate and baryta water to the ether as pale green crystals, insoluble in alcohol. Iso- butyl aceto-acetate C8HM0, i.e. CH-sAc.CO.AH., (202°-206°) S.G. 2 -979; ^'932. From iso-butyl acetate and sodium. Iso-amyl aceto-acetate C9HI603 i.e. CH2Ac.C02C5Hn (223°) S.G. $.s -954. From iso-amyl acetate and Na (Conrad, A. 186, 228). Converted by Cl into an oily di-chloro-derivative (Conrad, A. 186,243) and by NH3 into the imide of aceto-acetate of iso-amyl [190°-195°] (Collie, A. 226, 319). ALKYLATED ACETO-ACETIC ETHERS. Sodium aceto-acetic ether is converted by alkyl iodides into mono-alkyl aceto-acetic ethers, CH3.CO.CXH.CO.jEt. The sodium derivatives of these are in like manner converted by alkyl iodides into di-alkyl-aceto-acetic ethers, CH.,.CO.CXY.C02Et. Such ethers are of great service in organic syntheses, for they are split up by weak alkalis into carbonic acid and mono- or di-alkyl acetones: CH3.CO.CXY.CO.,Et + 2KOH = CH3.CO.CXYH + HOEt + K.,C03, and by strong potash into mono- or di-alkyl-acetic acid and acetic acid : CH3.CO.CXY.CO.iEt + 2KOH = CH3.C02K + HCXY.C02K + HOEt. In practice the ketonic and acetic decompo- sitions both occur, at the same time, but the acetic decomposition increases with the con- centration of the alkali (Wislicenus, A. 206, 308). Preparation.— The alkyl-aceto-acetic ethers are prepared by dissolving the calculated quan- tity of sodium in 10 times its weight of absolute alcohol, cooling, adding the aceto-acetic ether and then the alkyl iodide until the liquid, which may be warmed, if necessary, is neutral to litmus. The greater part of the alcohol is then distilled off and water is added. This dissolves the Nal and the new ether rises as an oil and is fractionated (Conrad a. Limpach, A. 192, 154). A. WlTH ONE MONOVALENT RADICLE. Methyl - aceto - acetic Acid CSH80S ».«. CH3.CO.CHMe.CO.H. A thick liquid which splits up on warming into CO2 and methyl ethyl ketone (Ceresole, B. 15, 1874). Its barium salt is soluble and gives a violet colour with Fe.jCl.j. Nitrous acid forms iso-nitroso-methyl- ethyl -ketone. Methyl Ether CH3.CO.CHMe.CO.,Me ACETO-ACETIC ACID. 2.3 (177-4° cor.) S.G. 2 1-020 (Brandes, Z. 1866, 458). From sodium aceto-acetate of methyl and Mel. Smells like mint. Gives a violet-red colour with Fe2Cls. Ethyl Ether CH3.CO.CHMe.CO.,Et (186-8" cor.) (Geuther, Z. 1866, 5). S. G. s 1-009. Gives a deep blue colour with Fe2Cla. Reactions. — 1. Sodium amalgam gives an oxy-valeric acid CH3CH(OH).CHMe.CO,JI.— 2. Potash forms methyl-ethyl ketone, alcohol and KjCO,. — 3. PC15 gives chloro-methyl-crotonic acid [69-5°] (206°) (Kiicker), chloro-methyl-aceto- acetic ether, C7HnC10, (180°) S.G. ^ 1-Q93, smelling of peppermint, and di-chloro-methyl- aceto-acetic ether (210°-220°) S.G. i* 1-225 (Isbert, A. 234, 188). — 4. Sodium and cyanogen chloride form cyano-methyl-aceto-acetic ether CAcMeCy.C02Et (c. 93°) at 20 mm. S. G. 22 -996. It is a colourless liquid insol. water and alkalis (Held, C. R. 95, 522 ; Bl. [2] 41, 330). Acetyl derivative CgH,^ i.e. CMeAc./)0.2Et. Methyl-diacetyl-acetic ether (205°-220°). From methyl-aceto-acetic ether in ethereal solution and AcCl (James, A. 226, 219, C. J. 47, 1). 81. sol. water. Coloured raspberry red by Fe2Cl6. Does not pp. cupric acetate, even on addition of dilute NaOH. Ethyl-aceto-acetic acid. Methyl ether CH3.CO.CEtH.CO.,Me (189-7° cor.) S. G. ii-995 (Brandes, Z. 1866, 457), Fe2Cl6 gives deep violet colour. Cone. NH3 forms an oil C7H13N02, the imide of ethyl-aceto-acetate of methyl insoluble in water, and also silky needles [83 '•''] of a soluble amide (probably CBHnN02 see below) (Brandes, Z. 1866, 457). Ethyl ether C8HM0S i.e. CAcEtH.CO.jEt (1983 cor.) S.G. & -998 (G.) ; is -983 (F. D.) (Geuther, Ar. Ph. [2] 116, 97; Frankland a. Duppa, C.J. [2] 4, 396; Wislicenus, A. 186, 187). Preparation. — Aceto-acetic ether is dissolved in benzene and four-fifths of the calculated quan- tity of sodium added, then EtI, and the product rectified. The aceto-acetic ether recovered is treated with the remaining fifth of the sodium. Yield 70 per cent. (Wedel, A. 219, 100). Properties.— An oil. Coloured blue by Fe^Cl,.. Reactions. — 1. Reduced by sodium amalgam to an oxy-hexoic acid,CHs.CH(OH).CHEt.CO2H. 2. Boiled with baryta or weak alcoholic KOH, it gives methyl propyl ketone. — 3. Boiled with cone, alcoholic KOH, or heated with dry NaOEt, it gives n-butyric acid and acetic acid, or their ethers. — 4. Treated with NaOEt and cyanogen chloride it forms cyano-ethyl-aceto-acetic ether, CH3.CO.CEtCy.CO2Et (c. 105°) at 20 mm. S.G. 42 "976. A colourless liquid with agreeable odour. Insol. in water or alkaline solutions, miscible with alcohol- or ether (Held, C. R. 98, 522, Bl. [2] 41, 330). — 5. Bromine acting on an ethereal solution forms mono- di- and tri- BROMO-ETHYL- ACETO-ACETIC ETHER (q. v.). — 6. PC1S gives mono- and di- CHLORO-ETHYL-ACETO-ACETIC ETHER, and only one CHLORO-ETHYL-CROTONIC ACID (q. v.) (Isbert, A. 234, 183).— 7. Benzoic aldehyde ' and HC1 form some benzylidene-ethyl-aceto- ; acetic ether or cinnamoyl-ethyl-acetic ether, Ph.CH:CH.CO.CHEt.CO.,Et (210°) at 22 mm. Converted by NaOEt and EtI into cinnamoyl-di- ethyl- acetic ether. — 8. Cone, aqueous ammonia forms two amides, one soluble in water, C6H,,NO2, the other insoluble, CBH1;>NO.j. They are formed in equi-molecular quantities ; the oily insoluble amide crystallises when cooled. On distilling the soluble amide does not pass over with steam. Insoluble amide C8H15N02 imide of ethyl- aceto-acetic ether CH3.C(NH).CHEt.C02Et or CHu.C(NH,):CEt.C02Et [59;5^]. Monoclmic tablets (from alcohol), smelling of peppermint. Decomposed by water, or dilute acids, into NH, and ethyl-aceto-acetic ether (Geuther, Z. 1871, 247). Soluble amide C6HMN02 i.e. CAcHEt.CONHj [90 ]. Needles (from water, alcohol, or ether). May be sublimed. May be obtained from the preceding body by heating with water at 135°. On dry distillation it gives NH3, C02 and methyl propyl ketone. The latter body is also formed by heating it with water at 200°, with boiling aqueous HC1, with CaCl,, ZnCL, ?./),>, or PC1S (Isbert takes it to be di-ethyl ketone). Heated with dry KOH at 100° it forms butyric -and acetic acids (Isbert, A. 234, 170). Salts. - CH3.CO.CNaEt.CO,Et. Formed by adding sodium to a solution of ethyl-aceto-acetio ether in dry ether or benzene (3 or 4 vols.) (J. W. James, C. J. 47, 1). Also by shaking an ethereal solution of the ether with perfectly dry NaOH (Elion, R. 3, 234). It is amorphous. V. sol. ether. A little water added to its ethereal solu- tion forms a pp. of CH^CO-CNaEtCO-jEt aq, insol. ether or benzene, but sol. water or alcohol. Acetic acid re-converts the sodium salt into ethyl-aceto-acetic ether (v. constitution of ACETO- ACETIC ETHER). Ethyl aceto-acetic ether forms no copper compound. This is thought to favour the for- mula CH3.C(OEt):CH.CO.,Et. Iso-amyl ether CH3.CO.CHEt.CO2CsH,, (233° -236°) S.G. f?.5 '937 gives no colour with Fe2Cl6 (Conrad, A. 186, 228). Acetyl derivative CHt.CO.CAcEt.CO2Et. Ethyl-di-acetyl-acetic ether (c. 230°); (144°- 150°) at 50 mm. S.G. ^ 1-034. From CHj.CO.CNaEt.CO.jEt and AcCl (Elion, R. 3, 265). Liquid. Insol. KOHAq. Gives no colour with Fe2Cl6. Alcoholic NH3 converts it into acetamide and CH3.CO.CHEt.CO.jEt. Allyl- aceto-acetic Ether C9HU0S i.o. CH3.CO.CH(C3Hi).CO.rEt (206°) (Zeidler, A. 187, 33) (214° cor.) at 720 mm. (Perkin, C. J. 45, 540). S.G. f ?.. -982 (Z.) ; if -993 ; ff -985 (P.). From sodium aceto-acetic ether and allyl iodido (Z. ; Wolff, A. 201, 46). From aceto-acetio ether, allyl iodide, and zinc, di-allyl-aceto-acetio ether being also formed (0. Hofmann, A. 201, 77). Reactions. — 1. Fe.,Cl6 gives a crimson colour. 2. Boiling alcoholic KOH forms CO2 and allyl- acetone.— 3. Dry NaOEt at 150°-160° gives ethyl acetate and allyl-acetate. — 4. Sodium amalgam forms an oxy-heptenoic acid, CH3.C(OH)H.CH(C3H5)CO.^I. Propyl -aceto-acetic Ether C9H,gO, i.e. CH3.CO.CHPr.C02Et (209°) S.G. § -981. From aceto-acetic ether (153g.) by adding first a solu- tion of sodium (27g.) in dry alcohol (270g.) and then PrI (206g.) (Burton, Am. 3, 385). Decom- posed by aqueous KOH into C0.2, alcohol, and methyl butyl ketone. Iso-propyl-aceto-acetic Ether CBH1BOj t.«. CHj.CO.CPrH.COiEt (201°) at 758 mm. S.G. 2 •880. From sodium aceto-acetic ether and iso- propyl iodide (Frankland a. Duppa, A. 145, 78). 24 ACETO-ACETIC ACID. Coloured pale reddish-violet by Fe.^Cl^ (Demar- cay, Bl. 27, 224). Iso -butyl -aceto -acetic Ether C,0H1(jO3 i.e. Pr.CH.CHAc.CO.fEt (218°) S.G. !™ -951. From sodium aceto-acetic ether and iso-butyl iodide (Rohn, A. 190, 306). Decomposed by baryta giving methyl iso-amyl ketone and iso-butyl- acetic (hexoic) acid. Heptyl -aceto -acetic Ether C,3H2I03 i.e. CH3.CO.CH(C;Hli).CO.,Et (272°) S.G. ~7 '9324. From sodium aceto-acetic ether and heptyl iodide (Jourdan, A. 200, 105). Colourless oil. Decomposed by dilute alkalis into methyl octyl ketone and C02 ; and by cone, alkalis into acetic and n-ennoic acids. Secondary Heptyl-aceto-acetic Ether (250°- 260°). Prepared similarly from secondary heptyl iodide (Venable, B. 13, 1651). Octyl -aceto -acetic Ether C14H.,603 i. e. CHs.CO.C(C8H17)H.CO,,Et (281°) S.G. "}|£ -9354. From octyl iodide and sodium aceto-acetic ether (Guthzeit, A. 204, 1). Decomposed by alcoholic KOH into methyl ennyl ketone and decoic acid. Benzyl -aceto -acetic Ether CI3HI60S i.e. CH3.CO.CH(CH4Ph)CO.jEt (276°) S.G. J|f 1-036. From sodium aceto-acetic ether and benzyl chlo- ride (Ehrlich, B. 7, 690 ; A. 187, 12 ; Conrad, B. 11, 1056). Sodium amalgam gives exo-oxy-phenyl- valeric acid CH3.CH(OH).CH(CH.2Ph).CO,Et. Alcoholic KOH forms phenyl-ethyl methyl ketone. B. WITH TWO DI-VALENT RADICLES : Ethylene-aceto-acetic Acid. CH3.CO.C(C2HJ.CO.,H. From the ether by saponification. Liquid. Decomposed by heat or by dilute acids into tri-methylene methyl ketone .CH, CH,.CO.CH<^ | and CO,. Ethyl ctJier.-EtA' (193°-195°). From aceto- acetic ether (26g.) by adding a solution of sodium (5g.) in alcohol followed by ethylene bromide (38g.) The liquid is boiled for eight hours, filtered, and distilled. The residue is boiled for twelve hours longer with a solution of sodium (5g.) in alcohol, evaporated, and treated with water. The ether is extracted by ether and dried over K,C03 (W. H. Perkin, jun., C.J. 47,834 ; B. 16, 2136; 19, 1247). It reacts with phenyl- hydrazine, forming an oil. Ethylidene-aceto-acetic Ether. CH-.-CHiCAc.CO^Et (210°-212°) S.G. ^ 1-023 By passing HC1 into aldehyde (1 pt.) mixed with aceto-acetic ether (3 pts.) (L. Claisen a. F. H. Matthews, A. 218, 172 ; Claisen, B. 14, 345). Pungent ethereal oil. Miscible with H.2SO,. Reactions. — 1. Hot potash decomposes it, forming aldehyde. — 2. Combines with bromine. Tri-chloro-ethylidene-aceto-acetic Ether. CCla.CH : CAc.CO.jEt. S.G. ii 1-342 From chloral, aceto-acetic ether and Ac.^0 at 160 \ (Claisen a. Matthews, A. 218, 175). Thick oil. Decomposed by heat. Propylene-aceto-acetic Acid. CH..CH v I >CAc.CO.H CH/ - From the ether by saponification. Oil. Forms an amorphous silver salt, AgA'. Ethyl ether (210°-215°) at 720 mm. Aceto- acetic ether (26g.) is heated with sodium (4'6g.), dissolved in dry alcohol and propylene bromide (40g.) at 100°. After two days the tubes are opened and a fresh quantity of alcoholic NaOEt (from 4'6g. sodium) is added, and the tubes heated again at 100° (Perkin, jun., B. 17, 1443). Tri-methylene Bromide acts on aceto- acetic ether in presence of NaOEt, but the product C,HI4O, (V.D. 6-21) is not tri-methylene- aceto-acetic ether, for its boiling point (223°) and molecular magnetic rotation, 10'195, are both too high, and it does not react with phenyl- hydrazine. It is, however, the ether of a crys- talline acid which splits up on distillation into CO2 and C6H,nO, and on boiling with water into CO^and acetyl-butyl alcohol. Theacid isprobably xC(CO.,H):CMe CH/ \CH.,.CH.,.O (Perkin, jun., B. 16, 208, 1789; 19, 1247, 2557). Iso-tmtylidene-aceto-acetic Ether (CH.,).,CH.CH:CAc.CO,Et(2190-222°). From isobutyric aldehyde, aceto-acetic ether and HC1 (Claisen a. Matthews, A. 218, 174). Liquid smelling of peppermint. Iso-amylidene-aceto-acetic Ether. (CH3)2CH.CH2.CH:CAc.C02Et (237°-241°) S.G. ^ -961. From valeric aldehyde, aceto-acetic ether and HC1 (Claisen a. Matthews, A. 218, 174). Benzylidene-aceto-acetic Ether Ph.CH : CAc.CO.jEt (a-aceto-cinnamic ether), [60°] (180°-182°) at 17 mm. (295°-297°) at 760 mm. From aceto-acetic ether, benzoic aldehyde and gaseous HC1 at 0". (Claisen a. Matthews, A. 218, 177) 4 or 6 sided tables (from alcohol) ; trimetric, a : b : c = -447 : 1 : -962. Colourless oil, solidifying very slowly. V. sol. chloroform, m. sol. cold alcohol, ether, glacial acetic acid or CS._,, v. si. sol. benzoline. Insoluble in aqueous KOH. H2S04 forms a bright yellow solution which, on warming, becomes very dark red. On pouring this solution into water a white pp. is formed, and on adding NaOH this dissolves, forming a violet solution. Reactions. — Bromine in ether forms a di- bromide [97°]. This forms short needles (from benzoline). Theory of the Process. — Benzoic aldehyde probably first combines with HC1 forming Ph.CH(OH)Cl, and this reacts with aceto-acetic ether thus : Ph.CHCl(OH) 4 CH.Ac.CO2Et = H.,0 + Ph.CHCl.CHAc.CO.tEt. Two compounds of this formula may be isolated before distillation, one forms prisms [41°], the other small rhombohedra or triclinic tables [72°] (both from benzoline). They are both unstable, giving off HC1. One of them has pro- bably the formula Ph.CHCl.CHAc.C02Et and decomposes into HC1 and Ph.CH:CAc.C02Et, which recombines with HC1 forming the other Ph.Ctt,.CClAc.CO._,Et. On distillation both pro- bably give HCland benzylidene-aceto-acetic ether. Beuzylidene-ethyl-aceto-acetic Ether Ph.CH:CH.CO.CHEt.CO.,Et (205°-220°) at 22 mm. (Cinnamoyl-ethyl-acetic ether). From benzoic aldehyde, ethyl-aceto- ACETO-ACETIC ACID. 25 acetic ether, and HC1. Yield small (Claisen a. Matthews, A. 218, 184). Benzylidene-di-ethyl-aceto-acetic Ether Ph.CH:CH.CO.CEt2.CO2Et f 101°- 102"]. Formation.— (1) From the above, NaOEt, and EtI. — (2) From benzoic aldehyde, di-ethyl-aeeto-acetic ether, and HC1 (C.M.). Tri- clinic prisms (from benzoline). V. sol. ether or chloroform, m. sol. cold alcohol or benzoline. Dibromide [55°]. Furfural-aceto-acetic Ether (C,H,O)"CAc.C02Et [62-5°]. (189°) at 30 mm. From furfur-aldehyde, aceto-acetic ether, and Ac2O at 160°. (Claisen a. Matthews, A. 218, 176.) Trimetric crystals, a : b : e = '439 : 1 : -465. V. sol. alcohol, glacial acetic acid, chloroform, and benzene. M. sol. ether, si. sol. benzoline. C. WITH TWO MONOVALENT RADICLES. Di-methyl-aceto-acetic Acid CteH100, i.e. CH3.CO.CMe.,.C02H. From the ether by dissolving in cold dilute (1\ per cent.) aqueous KOH, setting aside for a day or two, then acidifying with EL,S04, ex- tracting with ether, evaporating the ether, and triturating with BaCOs. The crystalline barium salt, BaA.j', is decomposed by dilute H2S04 (Cere- sole, B. 15, 1871). Very hygroscopic crystals, which slowly split up into C02 and methyl iso- propyl ketone. The barium salt gives a brown colour or pp. with Fe2Cl6. It reduces boiling silver nitrate. Ethyl Ether CSH,4OS i.e. CH3.CO.CMe2.C02Et (184°) S.G.i^-991. From sodium methyl-aceto- acetic ether and Mel (Frankland a. Duppa, A. 138, 328). Potash or baryta splits it up into alcohol, C02, and methyl iso-propyl ketone. Methyl-ethyl-aceto-acetic Ether CHa.CO.CMeEt.CO.jEt (196° uncor.) (J.) (201° i. V.) (Wislicenus, A. 219, 308). S.G. ff.j -947. From sodium ethyl- aceto-acetic ether and Mel (Saur, A. 188, 257) ; or sodium methyl-aceto-acetic ether and EtI (J. W. James, A. 226, 209 ; C. J. 47, 1). Oil. Fe2ClK gives a violet colour. Distilled with dry NaOEt it gives ethyl acetate and ethyl methyl- ethyl-acetate (or valerate). Methyl-allyl-aceto-acetic Ether C10HI603 i.e. CH3.CO.CMe(C3Hi)CO,Et (c. 209°-2H'). From allyl-aceto-acetic ether, Mel, and NaOEt (James, C. J. 47, 3). Pleasant- smelling oil, miscible with alcohol, ether, or ben- zene. Fe2Cl8 gives no colour. The same body may be got from methyl-aceto-acetic ether, allyl iodide, and NaOEt. Methyl-propyl-aceto-acetic Ether C)0H))(O3 i.e. CHj.CO.CMePr.CO.jEt (214°) (L.K.); (216°) (J.). S.G. ^ -959 (L.K.) ; V '9575 (J.). From methyl-aceto-acetic ether, NaOEt, and PrI (Liebermann a. Kleemann, J5. 17, 918) or from propyl-aceto-acetic ether, NaOEt, and Mel (E. J. Jones, A. 226, 287). Di-ethyl-aceto-acetic acid CH3.CO.C(C.jH5)2.CO,H. Thick colourless liquid. SI. sol. water. Preparation. — Di-ethyl-acet-acetio ether is left in the cold for several weeks with 10 p.c. aqueous KOH. After removing the unaltered ether, the product is acidified and extracted with ether, and the acid purified by conversion into the barium salt, acidifying the latter, and again extracting with ether. Reactions. — It decomposes very slowly in the cold, but on heating to 60' it rapidly evolves CO2, forming di-ethyl-acetone. The latter body is also formed by distilling the barium salt. Salts. — A'Na ; easily soluble white micro- scopic crystals.— A'2Ba 2aq ; transparent prisms, rotates on water (Ceresole, B. 16, 830). Ethyl ether C10H18O., i.e. CH3.CO.CEtv,.CO.!Et (218°). S.G. 2° -974. From sodium ethyl-aceto- acetic ether and EtI (Frankland a. Duppa, A. 138, 211 ; James, A. 226, 205). From Cl.CO.,Et, Na, and EtI (Geuther a. Matthey, J. pr. [2] 6, 160). Reactions. — 1. With hot aqueous baryta it gives di-ethyl-acetone.— 2. Distilled with dry NaOEt it gives di-ethyl-acetic (hexoic) ether, acetic acid, and sodic di-ethyl-acetate.— 3. PC13 gives mono- and di-chloro-di-ethyl-aceto-acetic ether and chloro-ethyl-crotonic ether (James, A. 231, 235).— 4. With bcnzoio aldehyde and HC1 gas it forms some C6Hi.CH:CH.CO.CEt2.CO.iEtt cinnamoyl-di-ethyl-acetic ether. Crystals, [102°], (200°-205°) at 3 mm. Easily soluble in ether and chloroform, slightly in cold alcohol and in light petroleum (Matthews, C. J. 43, 205). Bromine in chloroform forms a di-bromide, [55°]. Prisms v. sol. alcohol and light petroleum. Di-allyl-aceto-acetic Ether C)2H18OS i.e. CH3.CO.C(C3H3)2C02Et (240°). S.G. ?f s -948. From sodium allyl-aceto- acetic ether and allyl bromide (Wolff, A. 201, 45). From aceto-acetic ether, allyl iodide, and zinc (0. Hofmann, A. 201, 77). Colourless oil, with faint peculiar odour. Insol. water, sol. alcohol, ether, or benzene. Boiling cone. KOHAq forms di-allyl-acetone, or methyl heptinyl ketone, and di-allyl-acetic acid. Di-propyl-aceto-acetic Ether CtyK.aQ3 i.e. CHj.CO.CPr.j.COsEt (236C). S.G. = -9585. From sodium propyl-aceto-acetic ether and PrI (Burton, Am. 3, 386). Alkalis split it up, giving di- propyl-aceto-acetic ether and di-propyl-acetone or methyl heptyl ketone. Di-isobutyl-aceto-acetic Ether Cn'R.M,OJ i.e. (PrCH^CAc.COjEt (2501-253°). S.G. ^ -947. From sodium isobutyl-aceto-acetic ether and iso- butyl iodide (Mixter, B. 7, 500). Di-n-heptyl-aceto-acetic Ether C^H^O, i.e. CH3CO.C(C,Hli),,CO,Et (332°) S.G. J"^ -891. Formed together with di- heptyl-acetic ether and methyl octyl ketone by heating sodium heptyl-aceto- acetic ether with heptyl iodide and dry alcohol for a long time (Jourdan, A. 200, 112). Decomposed by dilute alkalis into CO2 and methyl pentadecyl ketone, and by concentrated alkalis into acetic and di- heptyl-acetic (hexadecoic) acids. Di-octyl-aceto-acetic Ether C^H^O, i.e. CH,.CO.C(C8H,,)2.C02Et (264") at 90 mm. (340°-342°) at 760 mm. From octyl-aceto-acetic ether, NaOEt, and octyl iodide (Guthzeit, A. 204, 9). Decomposed by alkalis into di-octyl-acetone (methyl heptadecyl ketone) and di-octyl-acetic (heptadecoic) acid. Benzyl-methyl-aceto-acetic Acid CMHM0, i.e. CH,.CO.CMe(CH2Ph).CO?H [34°] (275°). From the ether by saponification. 81. sol. cold water. Salt : AgA'. 20 ACETO-ACETIC ACID. Ethyl etfwr-EtA' ('2<<VT). S.G. f? 1-046. Prepared by action of Mel on a mixture of benzyl-aceto-acetic acid and sodium ethylate (Conrad, B. 11, 1055). Benzyl ctfwr— PhCH,A' (53°?). Methyl hy- dro-cinnamein. Liquid. Benzyl-ethyl-aceto-acetic Ether CH3.CO.CEt(CHJPh).CO.jEt (29G°). Colourless liquid. " Di-benzyl-aceto-acetic Ether CH,.CO.C(CHJ>h).rCO,Et. From sodium benzyl-aceto-acetic ether and benzyl chloride (Ehrlich, A. 187, 24). Thick non-volatile liquid. OTHER DERIVATIVES of aceto-acetic acid will be described as acetyl derivatives.e.g'.AcETYL- GLUTABIC ETHEB, ACETYL-SUCCINIC ETHEB, &C. See also OXY-ACETO-ACETIC ETHEB, OxY-DI-ETHYL- ACETO-ACETIC ETHEB, OXY-DI-METHYL-ACETO-ACETIC ETHEB. For analogous acids see PBOPIONYL-PBOPIONIC ACID, VALEBYL-VALEBIC ACID. ACETO-BENZOYL-BENZOIC ANHYDBIDEu. BENZOYL-BENZOIC ACETIC ANHYDRIDE. ACETO-BEOMO-ACETIC ETHEB t>. BBOMO- ACETO-ACETIC ETHEB. ACETO-BBOMO-AMIDE v. ACETAMIDE. ACETO-BTJTYBIC ACID v. ACETYL-BUTYBIC ACID. ACETO-CHLORO-AMIDE v. ACETAMIDE. ACETO-CHLOBHYDRIN v. GLYCEBIN. ACETO-CHLOBHYDROSE: C14H19C1O9 i.e. C6H,Ac4O5Cl. Formed by treating 1 mol. an- hydrous glucose with 5 mol. AcCl, and purified by solution in chloroform, agitation with sodium carbonate, and evaporation. - Semifluid ; some- times crystalline. Dextro-gyrate. Bitter. In- sol. in water, slightly sol. in CS._,, easily in alco- hol, ether and chloroform. Distils in a vacuum, partly undecomposed. Gives, up all its chlorine to alcoholic silver nitrate. Reduces Fehling's solution. Reconverted into glucose by heating with water (Colley, C. R., 70, 401). H. W. ACETO-CINNAMONE v. BENZYLIDENE-ACE- IONE. ACETO-COUMARIC ACID v. COUMAKIC ACID. ACETO-CTJBCTJMIN v. CUBCUMIN. ACETO-ETHYL NITBATE C.2H40, 2C.JI.NO, (84°_86°) S.G. M 1-045. Formed by dry' distil- lation of potassium ethyl-sulphate with potas- sium nitrate. Liquid, having a sweet taste and aromatic odour. Explodes violently when heated above its boiling point. Not miscible with water. Resolved by heating with potash-lye into aldehyde and nitric acid (Nadler, A. 116, 173). H. W. ACETO-ETHYL-STJCCINIC ACID v. ACETYL- ETHYL-SUCCINIC ACID. ACETO-ETHYL-THIENONE v. ETHYL-THI- ENYL METHYL KETONE. ACETO-GLYCEBOLS v. GLYCEBIN. ACETO-GUANAMINE v. GUANIDINE. ACETO-TETBA-METHYLENE v. TETBAME- THYLENE METHYL KETONE. ACETO-METHYL-THIENONE v. METHYL- THIENYL METHYL KETONE. ACETONAMINES. Di-Acetonamine CSH,,NO i.e. CH3.CO.CH2.CMe,.NH2. Preparation. — 1. Dry ammonia-gas is passed into a flask containing boiling acetone, the con- ducting tube terminating just above the liquid ; the resulting mixture of acetone-vapour and am- monia is passed through a tube heated to 100°, and then through a condensing tube ; the distil- late is neutralised with sulphuric acid diluted with an equal volume of water, and, after re- moving the ammonium sulphate which crystal- lises out, and distilling off unaltered acetone, the liquid is evaporated to dryness and the residue exhausted with boiling alcohol. Diacetonamine sulphate then crystallises out on cooling, and may be purified by recrystallisation from alcohol (Heintz, A. 174, 154).— 2. Acetone saturated with ammonia is left to itself for three or four weeks, finely pounded oxalic acid is then added in quan- tity sufficient to form an acid salt, and a quantity of water equal to that of the acetone. The re- sulting crystalline precipitate is easily separated by boiling alcohol into insoluble ammonium ox- alate and soluble diacetonamine oxalate. A fur- ther quantity of this last salt remains in the mother-liquor, together with salts of other bases (Sokoloff a. Latschinoff, B. 7, 1384). Properties.- — Free diacetonamine, separated from either of its salts by adding strong soda-lye and agitating with ether, is a colourless liquid lighter than water, having an ammoniacal odour and strong alkaline reaction ; more soluble in cold than in hot water, mixes in all proportions with alcohol and ether ; oxidises and turns brown on exposure to the air ; forms crystalline salts with hydrochloric, sulphuric, and oxalic acids. By distillation it is for the most part resolved into NH3 and mesityl oxide CGH100, and on the other hand is easily formed by direct combination of these bodies : C8H10O + NH3 = C6H13NO. Salts. — CBH13NOHC1 crystallises from alco- hol in rhombic prisms, v. sol. alcohol, resolved by dry distillation into NH4C1 and CtiH)0O (Heintz, A. 175, 252)— (C?H13NO,HCl)?PtCl4,2H.JO crystallises from water, in which it is easily so- luble (according to Sokoloff a. Latschinoff ; also in dilute alcohol), in orange-yellow monoclinic prisms containing 2H20, which they give off in a vacuum (H.) ; under ordinary pressure (S. and L.). The normal oxalate (CBHlsNO)2C.jH.,O4 forms monoclinic tablets, very soluble in cold water, less soluble in alcohol than the acid salt. This latter C6H13NO,C,,H,04,H.,0, forms mono- clinic prisms ; very soluble in hot, less in cold, water ; easily in boiling alcohol, from which it separates out almost completely on cooling. The picrate C6H13NO,C(iH3(NO.,)30,H./), forms gold- yellow needles, somewhat sparingly soluble in cold water. Thesulphate (CgH13NO).jH2S04 forma monoclinic crystals (from alcohol). Reactions. — 1. HN02 decomposes the salts forming di-acetone alcohol and mesityl oxide : 2C6H,3NO + 2HN02 = CttH,2O2 + C6HIOO + 2N2 + 3H2O. 2. Chromic acid mixture converts it into para- formaldehyde together with formic, acetic, and amido-iso-valeric acids NH-j.CMe2.CH2.CO.jH, and a small quantity of amido-iso-butyric acid NH.,.CMe.,.CO2H (Heintz, A. 198, 45).— 3. Solid KOH forms an anhydride, CI2H24N20 [83°]. This is v. sol. alcohol, chloroform, or benzene, m. sol. ether or light petroleum. Hot water decomposes it (Antrick, A. 227, 381). It forma a salt, (C,.,H.j,N.jOHCl),PtCl4, when dry. Small prisms.— 4. An aqueous solution of diacetc- ACETUN AMINES. 27 namine hydrochloride heated for ten hours at 120 with aqueous hydrocyanic acid forms the hyclrochlorides of diacetonamine cyanhydrin and of nitrilo-diacetonamine, together with a little amido-iso-butyric acid (Heintz, A. 189, 231 ; 192, 340). — 5. Diacetonamine oxalate boiled with alcoholic solutions of aldehydes forms condensation products. — 6. Sodium amalgam reduces di-acetonamine to a secondary amido- iso-hexyl alcohol CH.,.CH(OH).CH2.CMe.,NH2. 