Acetonyl acetone

Acetanyl acetone, a diketone, is a water-white liquid with an agreeable odor. It is completely soluble in water, almost entirely soluble In such substances as toluene, kauri gum and rosin, and only partly soluble in raw linseed oil, shellac, dewaxed dammar and ester gum. It has been suggested as an intermediate In the manufacture af rubber accelerators, dyes, inhibitors, insecticides, and pharmoceuticals and for the preparotlr of derivatives of thiophene, furan and pyrrole. It may also be employed in tanning hides and skins. 

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This sequence is equally applicable to keto esters. Thus, condensation of guanidine with ethyl acetoacetate gives the pyrimidone, 134. Elaboration as above gives the pyrimidine, IJ5 acylation with the sulfonyl chloride (88) followed by hydrolysis yields sulfamerazine (107). Reaction of guanidine with beta dicarbonyl compounds gives the pyrimidine directly. Condensation of the base with acetonyl acetone affords the starting amine for sulfadimidine (108). ... 

This explanation is supported by the nature of the products formed in secondary reactions. The acetonyl radicals are considered to dimerize or to abstract hydrogen from the parent molecule forming, respectively, acetonyl acetone and acetone. 

Comp proplnt consisting of AN 73-69, cellulose acetate ca 5 2,4-dinitrodiphenylether 3 acetonyl acetone dioxime 2-3 finely divided C 1-5%) I)E.F.Morello et al, USP 2942962 (I960) CA 54, 25830 (I960) [Addn of an aromatic amine (DPhA or dinaphthyl-amine) to proplnts of USP 2942961 renders them less susceptible to gassing at elevated temps. 

In a similar manner, by using a-nionochloracetone, tho y-diketone, acetonyl acetone, is obtained after hydrolysis16 ... 

By the same reaction this can be obtained from acetonyl acetone ... 

Reactions proceeding more than once in the transformation of a substrate can be more effective than a single process If the reaction in question is a condensation of an N nucleophile with a carbonyl compound, the combination of the of two such reactions—allows for the synthesis of heterocycles like, the two depicted in Figure 9.27. The synthesis of quinoxaline (B) from glyoxal dihydrate (A) and orfho-phenylene diamine consists of two imine formations. Somewhat more complicated is the synthesis of dimethylpyrrole D from acetonyl acetone (C) and ammonia. After the formation of the first imine, an imine enamine isomerization occurs. A condensation followed by another imine — enamine isomerization leads to the product. 

SJ. R. McNesby et al., iTnVi., 76, 823, 1416 (1954), found acetonyl acetone, (CITsCOCIl2)2, mass-spectrometrically but were unable to find CH COC2H6 in the pyrolysis at temperatures from 466 to 524 C. 

SYNS ACETONYL ACETONE a, 3-DIACETYLETHANE 1,2-DIACETYLETHANE 2,5-DIKETOHEXANE... 

ACETONYL see ADA725 ACETONYL ACETONE see HEQ500 3-((X-ACETONYLBENZYL)-4-HYDROXYCOUMARIN seeWAT200... 

The main products are CH4, CO and ketene. Some C2H6, C2H4, CO2, H2 and traces of carbon are also formed. In addition, McNesby et could detect very small amounts of isobutene, acetonyl acetone and acetyl acetone at 500 °C. 

It seems to be well-established that methane and ketene are formed in the main reaction, while carbon monoxide, ethylene and other products, produced in trace amounts, are probably the result of the ketene decomposition. Ethane and acetonyl acetone are chain termination products (see later), while the precursor of acetyl acetone is probably the radical formed in the reaction of the acetonyl radical and the ketene. 

Relatively more attention had been paid to the study of the sensitized thermal decomposition of acetone. In the temperature range 350-400 °C, Rice et al investigated the decomposition of acetone sensitized by dimethyl mercury. The a-mount of acetonyl acetone formed was equal to that of dimethyl mercury decomposed, indicating the absence of chains. At higher temperatures, however, sensitized chain decomposition has been observed. According to Kodama and Takezaki ,... 

Less detailed investigations were carried out with other added substances such as for instance oxygen, ethylene oxide, trimethyl amine, ethers, acetyl acetone, acetonyl acetone, etc.. The results are, however, contradictory and inconclusive. 

McNesby et al could not detect methyl ethyl ketone at 500 °C, but found ethane and acetonyl acetone among the products. If ethane formation was the main termination step the decomposition should be order, while termination by the formation of acetonyl acetone gives an overall order of between 1 and i, depending on the relative rates of the elementary reactions. Experimental results clearly show that, at low pressures, the reaction order is f rather than 1. 

Methyl ethyl ketone was detected in experiments above lOO C. Acetonyl acetone has not been identified in the products so far. Actually, not more than a small amount of this compound is expected to be formed, since (i) the acetyl radical is unstable at higher temperatures, and (ii) the rate of formation of acetonyl radical is slow at lower temperatures. The formation of biacetonyl was observed in the investigation of the reaction between CH3 and acetone . Brin-ton ° has succeeded in detecting biacetonyl also among the products of acetone photolysis in the temperature range 200-475°C. Most of the evidence on the formation of biacetonyl in the photolysis of acetone is, however, based on material bal-ance and hence is only of secondary importance. 

Neglecting the acetonyl acetone formed, and utilizing the material balance, Mandelcorn and Steacie determined a value of 0.7 + 0.3 for the ratio kjg, while Noyes and Dorfman s value for this ratio was between 0.5 and 1.6. By direct measurement of all the products, Brinton ° obtained 0.5 0.05 for the same ratio in the temperature range 200-435 °C. These values, being almost independent of the temperature, are all close to that (0.5) expected theoretically for radical recombination reactions. 

Tetramethylbenzo [c]thiophene (Table V) is obtained in 42% yield when 2,5-dimethylthiophene is condensed with acetonyl acetone in anhydrous hydrofluoric acid [Eq. (4)].63 Its structure has... 

D.56) 2,5-Hexanedione, hexane-2.5-dione, acetonyl acetone, diacetonyl 110-13-4]... 

ACETONYL ACETONE (110-13-4) Combustible liquid (flash point 174°F/79°C cc). Contact with strong oxidizers may cause fire and explosions. Attacks some plastics, coatings, and rubber. 

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