claim: 1. Method of preparing,arx acetoacetyl aro3 0 mati c acid amide, which comprises reacting dike tene ar@d a priinary amin ' e selected from the grou p c I onsisting of the aromatic mono amines havi ng more than six carbon atoms in their molecule s, the aromatic poly amines, and the substitute d aromatic mono and poly amilines, in the 35 pres ence of. a solvent inert to the reactants, separatin g from. the reaciion mixture the solid products thus formed, removing the'refrom excess reacta nts, and reegvering the resultant acetoacetyl ami de. 40 2. Method of preparing an acetogcetyl aromati c acid wnide, wliieh comprises reflusing dike tene and a primary amine selected from the grou p consisting of the aromatie mono amines havi ng more than six carbon atoms in their mole- 45 cide s, the aromatie poly amlnes, and the substitute d aromatic mono and poly -amines, In the pres ence of a solvent Inert to the reactants, separati ng from the reaction mixture the solid prodformed, removing therefrom excess re- 50 ucts thus acta nts, and recovering the resultant seetoacetyl ami de. S. Method as defined in claim 1, wherein acetone Is employed as the said solvent. 4. Method of preparing bis-aeetoacetyl o-toli5 5 dine , which comprises heating and reacting diketent with o-tolidine in solution in an inert solvent for the reactants, and sepamting from the reswta nt reaction mixture and recovering the bisacet oacetyl o-tolidine thus produced. 60 5. Method. for preparing bis-acetoacetyl. benzidine , which comprises heating -and reacting diketene with benzidine in solution in an inert solvent for the reactants, and sepamting from the result- 65 a.nt reaction mixture axid recovering the biga6et oacetyl benzidine thus produred. 6. Method for preparing a'substituted acetoacet auffide, which comprises reacting diketene and a compound selected from aniline derivatives 70 in which there is directly attached to a7 carboix, ato m of the benzene ring a radical selected from the group consistft of hydroxyi, nitro. amino snd alkoxy, radicals, in the prew=e of a solvent Inert to the reactants, and reroverwt from the

resultant reaetion mixture the subgtituted acetoacetaniude thus produced. 7. Method for preparing a hydro7.y acetoacetanllide, which comprises heating and reacting diketene and a primary amino phenol iii the presence of a volatfle solvent for the reactants which is inert thereto, and recovering from the result@6nt reaction mixture the hydroxy acetoacetaxande thus produced. 8. As a cheniic6l compound, para-hydroxyacetoacetanilide, being a solid melting at between 88@ and 90' C., and being soluble in alcohols, ketones, esters and water, gnd only slightly soluble in ethers and chlorinated solvents. 15 9. Method for producing an acetoacetyl aroMatic amide, which comprises reacting. diketene and a primary amine selected from the,group consisting of the aromgtic monoamines havin . g more than six carbon atoms in their'molecules, 20 the arombtic polyaniines, and the substituted aromatic amines in which there is directly attached to at least one carbon atom of a benzene ring a radical selected from the group consis-ting -of hydroxyl, nitro, and alkoxy -radicals, in the 25 presence of a solvent-inert to the reactants, and recovering from the resultant reaction mixture the acetoacetyl aromatic amide thus produced, I 10. Method for preparijig an acetoacetyl aromatic aniide, which comprises reacting diketene 30 and a para primary diamino derivektive of an %aromatic hydrocarbon having two benezene nuclei directly united in its molecule, in the presence of an inert solvent for the reactants, and thereafter recovering from the reswtant reaction mix35 ture the acetoacetyl aromatic, amide thus produced. 9,152,786 11. Method for preparing an aretoacetyl aromatic amide, which comprises reacting diketene and a Para primau diamino diphenyl, in the presence of an inert solvent 'for -the reaetb6nts,' and'thereafter recoveri@ fro@n -the resultant reaction mixture the acetoacetyl aromatic amide thus @roduced. 12. Method for preparing.an acetoacetyl aromatic nmide, which comprises reacting diketene and a para primary diamino dialkyl diphenyl, 10 in the presence of an inert solvent for the reactants, and thereafter recovering from the resultant reaction mixture the acetoacetyl aromatic amide thus produced. 13. Method for preparing para-hydroxy aceto- 15' acetanilide, whicli comprises heating and reacting diketene and para aniino phenol in the presence of a volatile soivent for the reactants which is inert thereto, and recovering from the resuliant reaction mixture the pam-hydro:@@y aceto- 20 acetanilide thus prgduced. 14. Method for producing an acetoacetyl aro@ matic amide, which comprises slowly introducing diket6ne in srnall successive portions into an agitated solution in an Inert volat:Ue solvent of 25 a primary amin6 selected f;,or4 the gr6up consikting of the aromatic mono'aniines having more than si)i carbon atoms in their molecules, the aromatic poly amines, and, the substituted aro. matic amines in whith-there is directly attached 30 to at least one carbon atom of a benzene ring a radical selected from the@ groui@ consisting of hy@ droxyl,'nitro, and alkoxy radicals,and recovering from the resultant reaction mixture the acetoacetyl aromatieamide thus produced. ALBERT B. BOESIR, JR.

Patento . d Apr. 4. 1939 2,vl52p786 UNITED 'STATES PATENT OFFICE PSWAM'nOl,f OF ACETOACEum,mmm&,no -ACED AMMES Alber& B. Bome, Jr.. Pittsburgh, Pa. asdsnor to Carbide and Carb@on ChemicaLs a c @of New York No Dramin. APPUestion July 9, 1930, serba NO..891778 .14 ClaimL (CL 260-562) This invention relates to the production of acetoacetyl aromatic acid ainides by reacting diketene with an aromatic primary mono- or polyaniine or substituted aromatic primary amine, in the presence of an inert volatile solvent for the reactants, and preferably a medium or a lowboiling inert solvent in -which the acetoacetyl ardmatic amide is quite soluble when bot, such as acetone, dioxan, benzeile and toluene. 10 The production of acetoacetanilide by reacting anihne and dikeiene already Is known; and the process therefor is covered iii'U. S. Patent 1,982,675 issued December 4, 1934, to George H. Law. It has now been discovered that by reacting 1 r) diketene with the higher. primary aromatie monoamines, primaty aromatic poly-amines, and with substituted prima ry aromatio mono- and polvamines, under conditions where the speed and violence of the.reaction and the temperaturie of 20 the reaction mixture is at all times under coritrol it Is readily possible to produce acetoacetic ilcia amides from such a-mines and substituted amlnes in very satisfactory yields. According to the invention, diketene and such 2r) a primary aromatic amine or substituted amine are slowly reacted in the presence of a solvent for the reactants which ig lnirt with respect to each, and in which the(resultant amide is soluble. Preferably the diketen -e- is introdu@ed slowly into 30 an agitated solution of the amine in the Inert solvent, at an elevated temperature which is desirably around the boiling point.or refluxin@ point thereof. After completion of the reaction, the solvent Is removed by distiuation, and the aceto35 acetic acid amide Is separated from any unreacted amine and recovered. Thus, notwithstanding the powerful polymerization tendency of diketene, and the high chemical reactivity of primary mono- and poly-amines and substituted 40 amines, in6luding those derived from aromatic hydrocarbons containing in their molecules two or more, ititerconnected benzene nuclei, either condensed or uncondensed,'It is possibl ei--by utilwng the 'Present inventionr-to prepare from 45 these compounds. valuable gcetoacetyl aromatic amides with good yields and efaciencies. 'of Bis-para-arnine derivatives diphenyl aAd its hoinologues, amino iupbenylmethane,@ a and p. n and their homologues, and arafti amines such as benzylamine and its homo@. logues, exemplify aromatic- an-dnes -wl2ich reswt 'With Wketene to yield thM aCet4MZetyl amiden. The folaowing eumples wrve to illustrate the u invention: EXMPLI 1 Pre@aration of W- . acetoacetyl orthotolidine A solution of 212 grams (1 mol) of orthotolidine in 2100 cc. of acetone was heoted under reflux to a the boiling point of acetone, and 176 grams (1.05 niol) of diketene was slowly added over a period of 15 minutes while constantly stirring the mixture. After approximately an hour the reaction pr6duct began to separate. Refluxing wM 10 continued for 3 hours and the'reaction mixture, a fr6e-flowing crystal,line slush, was then allowed to stand overnight, and the crystallized product was separated by filtration. There thus waslobtained 245 gr4ms of bis-acetoacetyl oithotoiidine -15 w hich melted at 203' to 204' C. The futrate was c oncentrated to half its original volume by distil lation,' cooled, and a further 29 grams of the bl s-acetoacet5ri orthotolidine, melting p6int 20211 t O 203' C., was obtairied. On further concentrat ion, an additional 63 @ grams of bisacetoacety, 2 0 or thotolidine, melting point 2010 to 2020 C., was o btained which was separated by filtration and w ashed with acetone. Thus a yield of diacetoacetyl tolidine of 88.7% w as secured, based upon the orthotolidine, with 2 6 a diketene efficiency of 84.9% based upon dia cetoacetyl tolidine. Acetone was removed by di stillation from the mother liquor from the final fil tration and the residue treated with 200 ce., 3 0 of, a 5% aqueous sodilirn hy&oxide solution. The caustic alkali-insoluble material, consisting chiefly of diacetyl orthotolidine, was separated by filtration. 7he futrate was then acidined with 25 cc.. of concentrated hydrochloric acidi and the 35 precipitated dia@etoacetyl orthotolidine separated on a filter, !washed, and air dried. There was obtained an additionai 8 grams of somewhat iinpure diacetoacetyl orthotolidine wliieh melted at 1950 to 2000 C., increasing the total yield to 90.8%. As acidifying agents, other.acids, such as sulfuric 40 or acetic, may be used. The reaction Involved is indicated by the equa. tion: 'BIN Nut+20EIgOOCII.C.0 ---o 45 H* (o-ToUdim) (Dn*m) 50 cuscOcutdoNH >NHO06HI OCHS EEI Beu=e. toluene imd Otha womauc by&ocar. U@

2- bons, dioxan, and other low or medium-boiling lr-ert solvents may be used in place of the acetone. The use of acetone as the solvent Is much preferred from a production viewpoint. The solubii!ty of the orthotoiidine'in acetone is far greater than in toluejle, etc. Moreover, wben using acetone as a solvent, the reaction may be conducted at a low temperature, around 56' C., with good yields, wwle eliminating to a large extent the 10 formation of byproducts. EXLWLE 2 Preparation of bis-acetoacetyl benzidine To a solution of 36.8 grams of benzidine (bis15 paradiamino-diphenyl) in 400 cc. of acetone was added slowly 35.3 grams of diketene. The solution t@en was heated under reflux with agitation for 4 hours, during which time a crystalline reaction product, diacetoacetyl benzidine, separated 20 out. The niixture was cooled to room temperature and filtered. Thus ther e was;obtained 57 grams of pui-e diacetoacetyl benzidine which melted with decomposition at 2331 C. The ace,tone extract was evaporated, and yielded 10.6 25 grams of a caustic alkali-insoluble material. The residue was suspended in, 100 cc. of warm acetone, and the resulting suspension filtered while warm' There.was obtained 4.6 grams of acetone-insoluble diacetyl bclnzidine, melting at from 325' to SD 3300 C. Concentration of the acetone flltrate Yielded 4.2 grams of monoacetyl benzidine, melting at from 193' to 195, C. The percentage conversion of the benzidine was 80%; and the yield of the bis-acetoacetyl benzidi . ne rn the basis of 3r) the amount of benzidine that reacted was 97.5%. I EIAWLE 3 Production of acetoacet-alpha-naphthylamide To a cold solution of 8.4 grams of diketene 40 in 50 cc. of dioxan was added in the cold a solution of 14.3 grams of alpha-naphthylamine in 50 cc. of dioxan. After .24 hours the odor of diketene had disappeared, and a portion of the reaction product had crystallized from the solu45 tion. Addition of petroleum ether caused a further,- precipitation. The crystallized reaction ptoduct was separated by flltration of the mixture, washed with petr(>leum ether, and then was 50 recrystallized from benzene. A yield of over 9001o was obtained of the acetoacet-alphanaphthylaniide in the form of almost colorles,$ needles which melted at 1181 to 1201 C. By introducing diketene to a refluxing solution of the@'alpha-naphthylaniine, in dioxan, the reaction may be completed in a shorter,time. The equation for the reaction may. be writte as fouows: NE3 CIISCOCH2CONH 60 OECSCOCH=C=O 65 Aljb ll%ph. (Diket6ne) (Acetoaeet. alph&- naphthylsmi de) ExAzwLz 4 Under, conationg substantially Identical 'with 70 @those recited j@i Example 3, supra, but usi'ng beti@naphthylamine,instead of alphanaphthylamlne, a yield of o,ver 90% of aceto-adet-betanaphthylamide, melting at 1000 tb 1020 C., was produced ec6idi 76 The acetoacetyl aromatic acid amides, of the invention are in general used in the dyestuff Industry as Intermediates for the production of dyes of the Hansa yellow type. They also, under ring closure in the presenre of dehydrating agents, form hydroiiymethyl quinoline derivatives. Di- 5 aceto-@acetyl tolidine, knov@n as:Naphthol AS-G, is a commercially important dyestuff component. The following examples illustrate the production of substituted acetoacetanjlides in acdordance with the invention; 10 ExAlOLE 5 Para-hydroxy acetoacetanilide To a refluxing solution of 10.9 grams of paraamino-phenol in 150 cc. of @ acetone 8.4 grams of diketene was add@d dropwise. After reflu2dng the niixture for one hour, the acetone was removed by distillation, leaving 19 grams of viscous residue which slowly crystallized upon cooling. This product was purified by recrystallization 20 from water after treatment of the water solution with decolori@zing carbon. The reaction product, para-hydroxy acetoacetanilide, was recovered in th& fo@m of colorless needles which melted at be25 tween 88' and 90, C. This product is soliible-in alcohols, ketones, esters and water, but only slightly soluble in ethers, chlorinated solvents,. and aromatic and aliphatic hydrocarbons. It has the apparent structure designated by the for mula .30 iio iDOCHiCOCIEls Para-hydroxy acetoacetanwd.e formed by the reaction of one mole of diketene 35 with one of the aniine. EXAZOLig 6 Para-nitroacetoacetanilide To a refluidng solution of 50 grams of para40 nitroaniline in 600 cc. of acetone 33.4 grams of diketene were added dropwise. After refluxing. the solution for 4 hours, the acetone was distmed off, and the resultant crystauine residue was treated with a dilute solution of - the theoretical 45 amount of. sodium hydroxide for dissolving the resultant amide. The unreacted para-nitroaniline then was separated by flltration..'The flltrate was neutralized with. dilute hydrochloric 50 acid, whereupon para-nitroacetoa6etanilide precipitated. This was filtered off, washed with water, and air-d#ed, giving 9, yield of 659'o thereof. Vlhen recrystau!zed.from water it occurred as a pale yelloo . crystalline compound which melted at 1241 to 124.5' C. It has the apparent structu cated by th re mdi e formula NHOOCHSCOCHS 60 Para-nitroacetoacetaniffde 65 and is formed by the reaction of equimolecular proportions of the reactants. EXAWLZ 7 70 Pard-ethoxy acetoacetanitide To a refluxing solution of 34 grams of paraphenetidine in 250 cc. of,. acetone was added slowly 21 grams 6f diketene. The heat developed by the reswtant reaction was sumelent to keep jr,

the soiutioli gmt1y refluxing without extemal BPPUcatiOn Of heat. When addition of the diketene was completed, the acetone was removed by distiuation. The residue solidified upon coolIng; and it was purffled by reerYstaUization from a mixture of ethyl acetate and petroleum ether. Thus were obtained 48 gram of para-ethoxy neetoacetaniude, oceurring as colorless needles melting at between 1010 and 1020 C., and correio sponding to a yield of around 87.4%. This product has the apparent structure COCHICOCH3 15 Pan-etboxy awtoamtanflide and results from the interaetion of equiinolecular- proportions of the reactants. EXAMLI 8 20 Ortho-methozy acetoacetanilide FoRowing the procedure described in Example 7 and using 31 gra= of ortho-anisidine and 21 gra= of diketene there were obtained 45 grams in rm 26 Of ortho-metho3ck acetoacetgmilide the fo of colorless platelets, which melt at between 85and 860 C., corresponding to a yield of around 87%. 7he compound has the apparent structure NRCOCHiCO-CH3 so CH$ 35 Ortho-raetb@.y mtomt@.Wd. ENAWLE 9. Diwetoacetyl meta-phenvlene diamine To a refluxing solution of 27 grams of met40 phenylene diamine in 250 cc. of acetone 47 grams of diketene were added dropwise. Thereafter the acetone solution was eoncentrated and cooled, whereupon an alinost quantftative yield of 4,5 diacetoacetyl ineta-phenylene diamine crystal lized out and was filtered off and airdried. 'Upon recrystarization from glacw@ acetic -acid, it occurred as a@ oblorless eiystaulnei compound that melted at betweezi 1071@ and 108' C. and was soluble In water, alcohols, keton'es, esters, and 50 ethers, but was practically insoluble in chlorinated solvents and In aromatic and aliphatic hydrocarbons. It has the apparent structure NUCOCIISCOCHNECOOHICOCHS so yl -ewpbmylene di=ine V.,V&mm 10 DiacetoacetVi p.ard-phenyle,ne diamine 65 Upon adding 46.2 grams of diketene Slowly to a refluxing solutioxx of 27 grams of Pam-phenylene diamine In 375 dc. of acetone ai2 biitial yield of 52 grams of diacetoacetyl Para-phenylene diamine separated mpidly from solution, which was 70 repamted by filtration from the reaction.mixture after cooung the latter. The fatrate upon further concentration yielded an additional 12 -grams of this produet, thereby providing a total yield of 92.5%; after purification by recrystauization with 75 water It ocem as a lustrous pearl gm MatalUne compound which welts at between 176- and 178* C. and hgz the apparent structure NEC30CHiCOCHs 5 COCHsCOCH3 10 Dimtbawtyl para-@henylone diamine it win.be understood that the method of the Pre sent Invention Is not limited. to the production of the particular acetoacetyl aromattc amides spe cificauy recited in the specifleation. On the 15 cont rary, the method may be utilized for the produet ion of acetoacetyl anudes from other aromati c priiiiary mono- and poly-amines of simple and condensed aromatic hydrocarbons, and from othe r substituted aromatic mono- and PO'Y- 20 B y the expression "higher arom6,tic mono min es" aPP6axing-in the accompanying cla-Ims Is Intended to designate those primary amines havi ng more thaii 6 carbon atoms in their inoie 25 Cule s. T he inventioii is s'useeptible of modification withi n the scope of the appended claims. I