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Acid dissociation constants of acetoacetanilide (AAAH); acetoacet-o-toluidide (AATH); 2,4-acetoacetxylidide (AAXH); acetoacet-o-chloroacetanilide (CAAAH); acetoacet-o-anisidide (OAAAH); benzoylacetanilide (BAAH) and benzoyl-m-nitroacetanilide (NBAAH) have been determined potentiometrically in 50 per cent ethanolic media and at a fixed ionic strength (0·1) over the temperature range 12 to 42°C. From these results, the values of the free energy change (ΔG), enthalpy change (ΔH) and entropy change (ΔS) have been calculated for the ionization process. The values of pKm (minimum pKa values at temperature θ°C) have also been calculated.

Uranyl complexes of the type [UO2L2B], where L is the enolate of acetoacetanilide, and B a monodentate base like pyridine, picoline, aniline or N-substituted aniline, have been synthesised and characterised by analysis, conductance and magnetic measurements, thermal, IR and NMR spectral studies. The order of thermal stability and features of IR spectra of the series have been explained. Pentagonal bipyramidal structure has been assigned for the complexes based on the NMR spectral evidence.

A series of aldehydo sugars was subjected to condensation reactions with active methylene compounds. Acetylacetone was condensed with 2,4-O-benzylidene-3,5-O-dibenzoyl-D-ribose (1), 2,4:3,5-O-dibenzylidene-D-ribose (6), 2,3,4,5-tetraacetyl-D-ribose (7), and 2,3,4,5,6-pentaacetyl-D-glucose (9) to yield 3-ylidene-2,4-pentanedione derivatives 2, 11, 12, and 13, respectively. Sugar derivatives 1 and 6 were also condensed with benzoylacetone to give 14 and 18, with acetoacetanilide to give 16 and 19, with malononitrile to give 17 and 20, and with alpha-(gamma-butyrolactonylidene)triphenylphosphorane to give 21 and 22, respectively. Condensation of 1 with dibenzoylmethane gave 15. The double bond in compounds 2 and 11 was saturated by hydrogenation to give 23 and 24. All alpha, beta-unsaturated carbonyl compounds obtained exhibited antiviral activity and cytotoxicity. Compound 11 was found to have the most significant and selective antiviral activity against herpes simplex virus.

Iron (III) complexes of the type Fe(R−L)3, where R−L is a Schiff base derived from a β-diketone L, (acetoacetanilide, AN; acetoaceta-p-toluidide, AP and benzoylacetone, BA) and primary amines RNH2 (ammonia, methyl amine or ethyl amine) have been synthesised and characterised by analysis, magnetic moment, electronic, infrared and Mossbauer spectra.

Six polymeric complexes have been isolated with the octadentate ligand having ON-ONNO-NO donor atoms. All the complexes have high melting points, are insoluble in common organic solvents and amorphous. The cobalt(II), nickel(II) and copper(II) complexes are found to be pseudo-octahedral whereas a tetrahedral structure is suggested for zinc(II), cadmium(II) and mercury(II) complexes. The characterisation is made on the basis of analysis, conductance, magnetic susceptibility, i.r. and electronic spectral data.

The electron impact and the hydrogen and methane chemical ionization mass spectra of 5,6-dihydro-2-methyl-1,4-oxathin-3-carboxanilide, the sulfoxide and sulfone derived therefrom, and 2-(2-hydroxyethylthio)-acetoacetanilide enol have been determined. All four compounds show abundant molecular ions in the electron impact spectra and abundant [MH]+ ions in the methane chemical ionization spectra (along with the expected [M + C2H5]+ and [M + C3H5]+ ions), but relatively low [MH]+ ion signals in the hydrogen chemical ionization spectra. From high resolution mass measurements and metastable transitions determined by metastable ion refocusing, electron impact fragmentation mechanisms have been established. For 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide-4-oxide and 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide-4,4-dioxide the major fragmentation mode involves loss of the anilino radical from [M]+, followed by loss of C2H4. Fragmentation to form the aniline molecular ion increases in importance with increasing oxidation state of the sulfur. In the chemical ionization of these three compounds fragmentation of [MH]+ proceeds in a similar fashion by loss of neutral aniline and by formation of protonated aniline. The electron impact mass spectrum of 2-(2-hydroxyethylthio)acetoacetanilide is dominated by the molecular ion and the aniline molecular ion. However, in the chemical ionization mass spectra characteristic fragment ions involving loss of water and loss of aniline from [MH]+, as well as protonated aniline, are observed and serve to characterize the compound.

Whereas acetoacetanilide (II) reacted with α-cyano- and α-benzoylcinnamonitrile derivatives Ia-e to give hexa-substituted pyridines III and V, it reacted with α-carboxamido- and α-thiocarboxamidocinnammonitrile derivatives If-h to afford penta-substituted pyridines VI. One mole of acetonedicarboxylic acid dianilide (VII) reacted with two moles of each of α-cyano- and α-thiocarboxamidocinnamonitriles Ia,b,f,g to yield the dipyridyl ketones VIII and IX, respectively. On the other hand, α-benzoyl- and α-ethoxycarbonylcinnamonitriles Ic,d,i,j reacted with VII in equimolecular ratio to give the pyran derivaties X and XI, respectively. Several schemes were proposed to illustrate reactions steps. The structures of the synthesized compounds were proved by chemical and spectral methods.

Acid dissociation constants of acetoacetanilide abbreviated (AAA); Orthocarboxy-phenylhydrazoacetoacetanilide (o-CPHAAA); and orthocarboxy-phenylhydrazo-parachloro-acetoacetanilide (o-CPH-p-Cl-AAA) and chelate stability constants of the corresponding anions with Cu+2, Ni+2, CO+2, Zn+2, Mn+2, and Cd+2 ions are reported. The infra-red spectra of o-CPHAAA and o-CPH-p-Cl-AAA ligands and their chelates for copper and nickel are discussed.

Acid dissociation constants, p K ∗ , of a series of benzoylacetarylamides (Ia-h) and acetoacetanilide (IId) have been determined spectrophotometrically in 60 vol.% ethanol-water medium. The p K ∗ values of both Id and IId were similarly determined in 50 vol.% dioxane-water medium. The stability constants, log βn, of the ferric chelates with such ligands have also been determined. The effects of substituents in the keto anilides on the equilibria are discussed. Both values of p K ∗ and log βn were linearly correlated with Hammett substituent constant, σ. The equations of the straight lines obtained are: p K ∗ = 9.48 − 0.933 σ (r = 0.979); log β1 = 9.60 − 1.693 σ (r = 0.989); log β2 = 16.05 − 2.265 σ, (r = 0.957); log β3 = 19.02 − 1.657 σ, (r = 0.939). The values of the stability constants of ferric chelates of Id and IId indicate that the former ligand (Id) forms weaker complexes than the latter (IId) with iron(III) irrespective of the nature of the solvent, contrary to what has previously been reported.

Square planar mixed ligand complexes of the type [CuLL′] where L = 5-chlorosalicylaldehyde and L′ = acetoacetanilide, have been synthesized on treatment with ammonia. Amine exchange of the above Schiff base complexes has been carried out on treatment with different amines. The reaction with ethanol amine is quite interesting compared to other amines. It reacts with 5-chlorosalicylaldehyde to form a Schiff base, while the β-diketone part is removed in the complex formation. All the complexes were characterized by elemental analysis, spectral studies, magnetic measurement, TLC, and conductane.

Enolisation of acetoacetanilide (AAAH) acetoacet ortho-toluidide (AATH), 2, 4-acetoacetxylidide (AAXH), acetoacet-ortho-chloroanilide (CAAAH), acetoacetortho-anisidide (OAAAH), benzoyl-acetanilide (BAAH) and benzoyl-meta-nitro-acetanilide (NBAAH) have been studied in different solvents of varying polarities, ranging from chloroform (z=63.2) to methanol (Z=83.6) by ultraviolet spectroscopic methods. The low percentages of enol contents in formamide, dimethylformamide and dimethylsulphoxide, may be due to the formation of charge transfer complexes of these solvents with the diketones. Free energy of tautomerisation has also been calculated. The substituents on the phenyl group attached to the nitrogen have no effect on enolisation.

A series of twelve monosubstituted benzoylacetanilides have been prepared by condensation of acetoacetanilide with substituted benzoylchlorides. IR and UV spectral data are presented and discussed. The benzoyl CO stretching frequencies were correlated with σ+ (\barv=34.97σ++1705; r=0.983). The effect of substituents in the benzoyl moiety on the keto-enol equilibrium, has also been investigated. The data were correlated by the equation: logK=0.865σ+−0.615; r=0.988.

α-(2-Nitro-4-methylphenylazo)-acetoacetanilid zahlt unter dem Namen Hansagelb G®1 ) zu den wichtigsten Gelbpigmenten. Die Aufklarung seiner Struktur mit Hilfe der Rontgenkristallstrukturanalyse gelang auf dem Umweg uber das isomorphe α-(2-Nitro-4-chlorphenylazo)-acetoacetanilid. Das Molekul wird durch intramolekulare Wasserstoffbruckenbindungen in der energetisch gunstigsten Konformation festgehalten. Hierbei entsteht ein planares Resonanzsystem, welches den Farbstoffcharakter der Verbindung bewirkt. α-(2-nitro-4-methylphenylazo)-acetoacetanilide is one of the more important yellow pigment dyestuffs. Its molecular structure has been determined by means of X-ray diffraction analysis of the isomorphous α-(2-nitro-4-chlorophenylazo)-acetoacetanilide. The molecule is stabilized in the energetically most favourable conformation by intramolecular hydrogen bonds. This results in the formation of a planar resonance system to which the dyestuff properties of the compound are ascribed.

A. o-Anisidine diazotized is coupled with 2-naphthol, 3-hydroxy-2-naphthanilide, acetoacetanilide, or 1-phenyl-3-methyl-5-pyrazolone, to obtain azo-dyes. Each of the azo-dyes is chloromethylated in acetic acid solution by paraformaldehyde and dry hydrogen chloride gas in the presence of zinc chloride anhydride as a catalyst to obtain chloromethyl compounds.B. 2-Methoxy-5-hydroxymethylaniline synthesized by using o-nitroanisole as a starting material, is diazotized, it is coupled, with 2-naphthol, 3-hydroxy-2-naphthoanilide, acetoacetanilide, or 1-phenyl-3-methyl-5-pyrazolone, to obtain diazo-compounds. Each of the diazo-compounds is chlorinated in chlorobenzene solution by phosphorus pentachloride for conversion of the hydroxymethyl group into the chloromethyl group obtaining chloromethyl compounds.C. We confirmed that the chloromethyl compounds obtained by the method A and each of the corresponding compounds obtained by the method B are identical. We also succeeded to ccnfirm the positions of chloromethyl group obtained by the method A.

Acetoacetanilide and its derivatives have been examined as chelating agents for divalent metal ions in 50%(v/v) and 75%(v/v) aqueous dioxan. Acid dissociation constants were determined potentiometrically and values related to electronic effects of substituents. Stability constants of the Be(II), Co(II), Ni(II) and Cu(II) chelates were related to acid dissociation constants and to the metal.

The solubilities of acetanilide, acetoacetanilide, and the p -methyl, p -ethoxy, p -hydroxy, and p -amino derivatives of acetanilide were determined in aqueous sucrose solutions. The solubilities of all solutes were found to change significantly with changes in the concentration of sucrose solutions. The solubility curves indicate the changes probably involve solvent polarity, as indicated by dielectric constant of the solvent, and decrease in the activity of water. The solubility changes obtained for acetanilide and the several para derivatives were found to show a fair correlation with respect to the magnitude of solubility in water. This indicates a possibility of predicting solubility changes for the remainder of the compounds if the solubility change for one of the compounds is known.

The red compound obtained by coupling diazotised 2-nitro-4-toluidine and acetoacetanilide at higher temperatures has been shown by the X-ray crystal-structure analysis of its dibromo-derivative to be α-(4-methyl-2-nitrophenylazo)acetanilide. A three-dimensional analysis using 1061 structure amplitudes was refined to R= 9·9%. The molecule is planar and the configuration of the carbon atom to which coupling occurs is trigonal. There is the unconfirmed possibility of two intramolecular hydrogen bonds.

Acetoacetanilide, benzoylacetanilide and their derivatives have been examined in ultraviolet region in a series of solvents covering a broad polarity range e. e. from chloroform (Z, 63.2) to methanol (Z .83.6). Transition energies and oscillator strengths have been calculated and transition energy (ET) has been plotted against Z-values, a new empirical measurement of solvent polarity. A linear relationship was observed between the transition energy and Z-values for π π* and n π* transitions. These transitions are identified as charge transfer (c-t) transitions and with the solvents having carbonyl oxygen and sulphur atom a c-t complex formation has been suggested. Strong electron-donating substituents on phenyl group of the nitrogen atom also showed a weak to moderate n π* transitions. These substituents have no influence on the position of the λmax in the same solvent. Stabilization energy of the excited state of these ligands and hence the dipole moments of the excited states have been calculated in comparison with pyridinium iodide. Solvent sensitivities of these ligands have also been calculated.

An organic reagent viz. acetoacetanilide has been found out which precipitates beryllium quantitiatively aboveph 5.5. The complex, Be(C12H10O2N)2, containing 2.49% Be can be weighed directly after drying. Beryllium can be precipitated from solutions containing aluminium and iron by masking these foreign elements with EDTA. A method has also been described for the determination of beryllium content in beryl.

Solutions of niobium and tantalum pentachlorides in methanol react with salicylaldehyde, acetoacetanilide, benzoylacetanilide, 2-hydroxyacetophenone, 0-hydroxybenzophenone, and benzoylacetone, to produce crystalline compounds with the stoichiometry MCl 2 (OCH 3 ) 2 L. Molecular weight data indicate the compounds are monomeric. The complexes are diamagnetic. They react slowly with atmospheric moisture and decompose in methanol, benzene, and carbon tetrachloride solutions as indicated by conductance and spectral changes. Proton magnetic resonance, ultraviolet, visible and infrared spectra are reported. The NMR spectra suggest the complexes have a trans -dichloro structure.

Insoluble azo compounds were prepared from 2-methyl-5-chloroaniline (Fast Red KB base), 2-methyl-4-chloroaniline (Fast Red TR base), 2-meteoxy -5-chloroaniline (Fast Red RC base), 4-nitroaniline (Fast Red 2G base), 2-methoxy-5-: nitroaniline (Fast Scarlet R base), and 3-nitroaniline (Fast Orange R base) as diazo components and 3-hydroxy-2-naphtho-o-anisidide (Naphtol AS-OL) and 3-hydroxy-2-naplitho-o-phenetidide (Naphtol AS-PH) as coupling components, and chloromethylation of the azo compounds has been attempted. Chloromethylat-ion of the azo compounds was possible by treating the azo cornpounds in glacial acetic acid with dry hydrogen chloride and paraformaldehyde or dichloromethyl ether, using anhydrous zinc chloride or phosphoric acid as a catalyst.Phosphoric acid was ineffective as a catalyst for formation of azo compounds from o-anisidine as a diazo comonent and 2-naphthol, 3-hydroxy-2-naphthanilide (Naphtol AS), acetoacetanilide, and 1-phenyl-3-methyl-5-pyrazolone as coupling components as reported in the first series of this report but the phosphoric acid was effective as a catalyst in the preparations of azo compounds in this report. Only one chloromethyl group was introduced in all cases and the position of its entrance was confirmed to be the para position of methoxy group in aryl ring of hydroxynaphtho-o-anisidide and para position of ethoxy group in aryl ring of hydroxymaphtho-o-phenetidide.

We describe a sensitive and precise high-pressure liquid chromatographic method in which acetoacetanilide is used as the internal standard to simultaneously determine acetaminophen and phenacetin in plasma. Therapeutic as well as toxic concentrations can be determined on as little as 0.1 ml of plasma. Sample preparation is rapid and chromatography is complete in 5 min. Quantitation is accurate at 0.5 mg/liter concentration for both drugs. Day-to-day precision within 5% is attainable. Of 36 other drugs tested, only theophylline interfered, with the determination of acetaminophen.

N-Ethylacetoacetamide and acetoacetanilide were enantioselectively converted into the corresponding (S)-3-hydroxy compounds by alginate- or polyurethaneimmobilized bakers’ yeasts, while without immobilization the yield of the yeast-mediated reaction was very low.

Sixteen complex compounds of composition [MLX2] and [M′L]X2 where M=CoII; M′=CuII, CdII, or HgII; X=Cl, Br, I, NO3, SCN or ClO4; L=N,N′-bis(acetoacetanilide) ethylenediamine have been synthesized. The complexes of the first category are octahedral and the latter type are either square planar or tetrahedral as inferred from analysis, conductance, magnetic susceptibility, i.r. and electronic spectral data and molecular weight measurement.

Ten complexes of composition [Co2L2X4] (X=Cl, Br, NO3 or ClO4); [Cu2L2(NO3)4]; [Zn2L2X4 (X=Cl, SCN or ClO4); [CuCl2L] and [ZnBr2L] have been synthesized, where L is the ONNO tetradentate ligand,N,N′-bis(acetoacetanilide)-1,3-diaminopropane. The complexes have been characterised by elemental analysis, conductance, magnetic susceptibility, molecular weight and i.r., and electronic spectral measurements.

Antimony(V) Chloride, Acetoacetanilide At room temperature acetoacetanilide and antimony(V) chloride form a 1:1-(1) and a 1:2-adduct (2). These adducts react to the heterocycles C10H10Cl4NO2Sb (3) and C10H9Cl5NO2Sb (4). 3 exists in solution in two stereoisomers. The Free Energy of Activation for the transformation of the isomers is estimated.

Mossbauer spectra of tris(acetoacetanilide) iron(III) show a doublet consistent with the suggested distorted octahedral structure for the compound.

Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt Manuscript received 8 June 1979, revised 5 July 1980, accepted 7 August 1980 Interaction of acetoacetanilide(la) or its hydroxy derivative(Ib) with aromatic (or heterocyclic) aldehydes gave the corresponding \(\alpha \beta\)-unsaturated ketones(II). The reac­tion of alcoholic solution of (II) with hydrazine hydrate or hydroxylamine in a basic catlyst gave the corresponding pyrazoline or isoxazoline derivatives.

Department of Chemistry, Himachal Pradesh University, Summer Hill, Simla-171 005 Manuscript received 14 November 1983, revised 30 July 1984, accepted 19 January 1985 Monochloro-d.chloro- and trichloro-titanium(IV) naphthoxides when refluxed with acetoacetanilide (acanH) in appropriate molar ratios in benzene form compounds of composition, Ti(OC10H7)2.2acan, TiCl(OC10H7).2acan, Ti(OC10H7)3.acan, TiCl(OC10H7)2.acan, and TiCI(OC10H7). Based upon elemental analyses, conductance, cryoscopic and infrared spectral studies, their structures have been proposed

Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt Manuscript received 27 June 1980, accepted 10 March 1981 Interaction of acetoacetanilide (Ia) or its hydroxy derivative (Ib) with aromatic or heterocyclic aldehydes gave the corresponding α, β-unsaturated ketones(II). The reaction of alcoholic solution of(II)with thiourea in a basic catalyst gave the corresponding pyrimidinethione derivatives(III). Fusion of (III) with amines, active methylene, and methyl compounds gave the corresponding condensation products IV, V and VI.

A series of new diamagnetic cobalt(Ill) mixed ligand complexes having general formula [Co(AA)(tn)2]n+ (where AA = biguanide, picolinic acid, acetoacetanilide, benzoylacetanilide,m-nitrobenzoylacetanilide, acetylacetone,N-benzoylphenylhydroxylamine and malonic acid, tn = trimethylenediamine and n = 1–3) have been synthesized and characterized by elemental analysis, conductance measurements, electronic spectra, i.r. spectra, equivalent weight and magnetic measurements. The electronic spectra are typical of octahedral cobalt(III) complexes. The effect of cationic charge and the nature of the ligands on the Rf values of the complexes have been determined by paper chromatography.

Department of Chemistry, G. M. College, Sambalpur-768 004 Manuscript received 22 July 1983, revised 21 March 1984, accepted 17 June 1984 Mixed ligand complexes of cobaU(II), copper(ll) and zinc(II) with acetoacetanilide and some other nitrogen donor ligands of compositions [MX(acacN)B], [MX(acacN)-(H2O)3], [MX(acacN)B2H2O] and [MX(acacN)B2], where M-CoI I, Cul l, Znl I; X- Cl-, Br-, N\(O^-_2\);, CI\(O^-_4\) ; acacN- acctoacetanilide anion ; B- pyridine, \(\gamma\)-picoline, quinoline, have been prepared, The compounds have been characterised on the basis of analytical, conductance, magnetic susceptibility, ir and electronic spectral data. The thermal decompositions of a few cobalt( II) and copper(II) complexes were studied by DTG and DTA techniques.

Chemistry Department, Faculty of Science, M. S. University of Baroda, Baroda 390 002 Manuscript received 20 October 1978, revised 31 March 1979, accepted 6 June 1979 Mixed ligand complexes of the type [CuLL'], where LH=salicylaldimine or 2-OH-acetophenoneimine and L'H=acetoacetanilide or derivatives have been synthesised. These complexes undergo amine exchange over the Schiff base on treatment with methylamine, ethylamine and ethanolamine. The complexes have been characterised by elemental analyses, TLC, conductance, magnetic moment and spectral studies, &nbsp

From 150 to 900 \(\mu\)g of copper (II) have been extracted aqueous solutions maintained at \(p\)H 7.1 to 8.0 into 10 ml of chloroform in one step using acetoacetanilide as complexing agent and have been deter­mined spectrophotometrically in these extracts at 340 \(m\mu\), using reagent blank or pure chloroform as re­ference. In addition to the advantage of one step extraction, the possibility of the estimation of the metal ion in the presence of appreciable amounts of Ni2+, Co2+, Mn2+, Zn2+,Hg2+,Mg2+, Pb2+, Ca2+, Ba2+, Bi3+, Al3+ and F1- has been found to be very convenient. Thus copper has been determined in alloys like brass, white metal etc., without the separation of the former ions with high degree of accuracy.

Some complexes are investigated in solution by spectrophotometric methods, using a Coleman Universal Spectrophotometer, Model 14. I Chelate formation between iron(III) and acetoacetanilide (AAA) has been studied using the continuous variation, spectrophotometric titration and straight-line methods. The chelate has a violet colour and is stable between pH 2.3-3.2. The chelate has a maximum absorption at 560 mμ and the composition corresponds to one of a metal ion per one chelating molecule. The stability has been calculated by 4 methods and the average value of the dissociation constant is Kc ≈ 4 × 10-3. The molar absorption coefficient at λ = 560 mμ is 1234. The complex was found to obey Beer's law in the concentration range 1–80 mμ of Fe3+/ml. and AAA may be employed as a reagent for the colorimetric determination of iron(III). Other common metallic ions do not interfere. II Chelate formation between cupric ions and NAH and INA has been studied using the continuous variation, spectrophotometric titration and straight-line methods. The nature of these complexes is discussed and it is concluded that the composition corresponds to one of metal ion per two chelating molecules. The chelate Cu(INA)2 has a green colour and is stable for over 12hr. It is undoubtedly a very promising reagent for cupric ions. The chelate has a maximum absorption at 680–720 mμ. The stability has been calculated and the average value is Kc ≈ 1.64 × 10-5.

Three types of acetoacetanilide chelates of titanium (IV) have been isolated—the trichloro mono­-(acetoacetanilidato)-titanium (IV), dichloro-bis (acetoacetanilidato) titanium (IV), and the monochloro tris (acetoacetanilidato) titanium (IV). The monobromo-and the monoiodo tris-(acetoacetanilidato) titanium (IV) chelates have been also isolated. Addition compounds of titanium (IV) halides with acetoacetanilide have been prepared and characterised. Infrared spectral data on acetoacetanilide chelates of titanium (IV) are also presented.

1,3-Dialkyl-5-formyluracil reacts with ethyl acetoacetate, acetylacetone, benzoylacetone, acetoacetamide and acetoacetanilide under phase transfer catalytic conditions to provide exclusively the annulation products: 6-substituted-1,3-dialkyl-7-hydroxyquinazolines or/and also 4-hydroxybenzamide derivatives. Similar reaction with cyanoacetamide provides 6-cyano-7-hydroxy-1,3-dimethylpyrido[2,3-d]pyrimidine. The reaction mechanism prevailing in these reactions has been rationalized.

Monosodium derivatives of acetoacetanilide and benzoylacetanilide are synthesized and characterized. The effect of conjugate chelation on carbonyl stretching frequency has been studied by comparing the infrared and ultraviolet spectra of acetoacetanilide and benzoylacetanilide, and their monosodium derivatives. Ultraviolet spectra suggest structural differences between the monosodium derivatives and the corresponding enolates.

A kinetic and mechanistic study of oxidative coupling reactions of N,N-bis-(2-hydroxyethyl)-p-phenylenediamine with m-phenylenediamines, phenols, and acetoacetanilide is described. The reactions involve the rapid establishment of an equilibrium between N,N-bis-(2-hydroxyethyl)-p-benzoquinone di-imine and a hydroxy-amine intermediate (3). Competition between direct coupling of N,N-bis-(2-hydroxyethyl)-p-benzoquinone di-imine and hydrolysis to p-benzoquinone monomine via(3) with subsequent coupling leads to a mixture of two dye products. The relative yields are dependent on pH and coupler concentration. Kinetic evidence for the formation of the intermediate (3) is presented.

Acetonedicarboxylic acid reacts with acetic anhydride to give acetonedicarboxylic anhydride (I), its α-acetyl derivative (II), and its α,α′-diacetyl derivative (III). With aniline, compounds (I) and (II) reacted to give acetoacetanilide and 3,5-dioxo-4-carboxyhexanilide (IVb), respectively; compound (III) yielded the anils (IXa) and (Xa). Compound (IXa) isomerised in concentrated sulphuric acid to carboxyanilinodehydroacetic acid (XV) which resembles anilinodehydroacetic acid (XII) in several aspects. Compounds (IXa), (Xa), and (XV) underwent similar transannular rearrangements when heated.