Acetoacetanilide

Submitted by Jonathan W. Williams and John A. Krynitsky. Checked by Nathan I., Drake and Joseph Lann. 

In a 500-cc. round-bottomed, three-necked flask fitted with a reflux condenser, dropping funnel, and a mercury-sealed stirrer (Note 1) is placed a solution of 46 g. (0.5 mole) of dry aniline in 125 cc. of pure dry benzene. Stirring is started, and a solution of 42 g. (0.5 mole) of ketene dimer (p. 64) in 75 cc. of pure dry benzene is added dropwise over a period of half an hour. The reaction mixture is then heated under reflux on the steam bath for one hbur. After the major portion of the benzene has been removed by distillation from the steam bath, the remainder is removed under reduced pressure. The residue is dissolved in 500 cc. of hot 50 per cent aqueous alcohol from which the aceto-acetanilide separates on cooling. The mixture is cooled to 0° before filtration. A second crop of crystals can be obtained by adding 250 cc. of water to the mother liquor and cooling again (Note 2). The total yield of product, m.p. 82-83.5°, is 65 g. (74 per cent of the theoretical amount). Further purification by recrystallization from 300 cc. of 50 per cent alcohol yields 55 g. of a product which melts at 84-85°. 

A simpler seal (p. 40, Note 1) of rubber tubing lubricated by glycerol is satisfactory. 

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Hydroxylepidlne (II) Is readily prepared by cyclisation of acetoacetanilide (I) with concentrated sulphuric acid ... 

Acetoacetanilide is an inexpensive commercial product. If necessary, it may bo recrystallised from 50 per cent, ethanol m.p. 84-85°. 

Pigment YeUow 12 [6358-85-6] 21090 diarjlide coupling of tetra2oti2ed 3,3 -dichloro-ben2idine with acetoacetanilide... 

Conra.d-Limpa.ch-KnorrSynthesis. When a P-keto ester is the carbonyl component of these pathways, two products are possible, and the regiochemistry can be optimized. Aniline reacts with ethyl acetoacetate below 100°C to form 3-anilinocrotonate (14), which is converted to 4-hydroxy-2-methylquinoline [607-67-0] by placing it in a preheated environment at 250°C. If the initial reaction takes place at 160°C, acetoacetanilide (15) forms and can be cyclized with concentrated sulfuric acid to 2-hydroxy-4-methylquinoline [607-66-9] (49). This example of kinetic vs thermodynamic control has been employed in the synthesis of many quinoline derivatives. They are useful as intermediates for the synthesis of chemotherapeutic agents (see Chemotherapeuticsanticancer). 

Of these dyes, Acid Yellow 151 (37) still has the greatest market among the yellows. As reported by USITC, production had increased to 1989 tons in 1985 from 706 tons in 1975. It is produced by coupling diazotized 2-amino-l-phenol-4-sulfonamide to acetoacetanilide followed by metallizing with cobalt to obtain a 1 2 cobalt complex. Acid Orange 24 (38), which is sulfanilic acid coupled to resorcinol to which diazotized mixed xyUdines have been coupled, is an unsymmetrical primary diasazo dye with a bihinctional coupling component. 

DlsaZO Pigments. The diaiylide yeUows and oranges also known as benzidines are derivatives of benzidine coupled to two moles of substituted acetoacetanilide. Benzidine Yellows AAMX, AAOT, AAOA, and HR (PY 13, 14, 17, and 83) ate examples (Fig. 1). Yellows AAMX and AAOT are used in flexible vinyls. AAOA also colors polyethylene and polypropylene. These three differ only slightly in shade. Benzidine YeUow HR is redder. 

KNORR Quinoline Synthesis Quinoline synthesis by cyclization of acetoacetanilides. 

Acetic Acid Acetic anhydride Acetoacetanilide Acetone cyanhydnn Acetyl chloride Acrolein Acrylonitrile Alcohols Alkaloids... 

From Table 3, it can be seen that the reactivity of acyl acetanilide, such as BAA or AAA, is higher than that of the other reductant reported from our laboratory, i.e., acetanilide (AA), N-acetyl-p-methylaniline (p-APT), acetylacetone (AcAc), and ethyl acetoacetate (EAcAc). Moreover, the promoting activities of derivatives of acetoacetanilide were affected by the ortho substituent in benzene ring, and the relative rate of polymerization Rr) decreased with the increase of the bulky ortho substituent to the redox reaction between Ce(IV) ion and substituted acetoacetanilide. 

Table 3 Effect of Acetoacetanilide and Its Derivatives on AAM Polymerization Initiated by Ce(IV) Ion in Aqueous Media at 25.0°C...

Methylene coupling components with carbonyl groups in a,a-positions are very important, particularly acetoacetanilide derivatives (Scheme 12-40, X=NHAr), for the production of yellow monoazo dyes and pigments (Hansa Yellows see Zollinger, 1991, p. 180). 

In the azo coupling reaction of acetoacetanilide (Dobas et al., 1969b) the reaction steps of Schemes 12-71 and 12-72 constitute a steady-state system, i.e., Arx [B] < Ar [HB+] == 2[Ar —NJ] A 2 — 0 with a fast subsequent deprotonation (Scheme 12-73). As with nitroethane, this reaction is general base-catalyzed because the ratedetermining step is the formation of the anion of acetoacetanilide (Scheme 12-71). In contrast to the coupling of nitroethane, however, the addition of the diazonium ion (Scheme 12-72) is rate-limiting. The overall kinetics are therefore between zero-order and first-order with respect to diazonium ion and not strictly independent of [ArNJ ] as in the nitroethane coupling reaction. 

These are the only ranges of precursor products in the Colour Index that are still commercially significant. Azoic dyes have a close formal relationship to those monoazo pigments derived from BON acid or from acetoacetanilides (section 2.3.1) and some are chemically identical with them, although they are used in a totally different way. Azoic components are applied to produce insoluble azo dyes within the textile substrate, which is almost always cotton. Corresponding azoic components for the dyeing of cellulose acetate, triacetate and polyester fibres were once commercially important, but are now obsolete because of environmental hazards and the time-consuming application procedure. 

Benzidine is an aromatic diamine that can be tetrazotised and coupled to two molecules of a coupler such as acetoacetanilide. This gives a yellow disazo pigment that can be regarded as a double molecule of the monoazo pigments described above. The possibilities of making a... 

Table 2.4 Typical group 1 azo pigments made from acetoacetanilides...

The influence of mixed coupling on the properties of Cl Pigment Yellow 12 has been studied recently [12]. Carboxy- or sulpho- substituted derivatives of acetoacetanilide were evaluated as co-coupling components and analysis revealed that the state of the crystal and the particle size were changed and new diffraction peaks were observed. When these modified pigments were treated with a fatty amine such as stearylamine, the hydrocarbon chains enclosed the anionic groups in the co-coupler so that properties such as flowability, wettability and dispersibility in nonpolar solvents were greatly improved. 

The chemically most simple diarylide yellow pigment is made from bisdiazo-tized 3,3 -dichlorobenzidine and acetoacetanilide. This pigment exhibits high tinctorial strength, a property which is particularly useful for process printing inks, for which other diarylide yellow pigments were later developed. 

Nicotinic acid amide p-Substituted acetoacetanilides 5-Nitrosalicylate... 

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