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Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium As Catalysts

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Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium As Catalysts K. K. GEORGIEFF I Research Laboratories, Shawinigan Chemicals, Ltd., Shawinigan Falls, Quebec, Canada Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium as Catalysts Reduction in costs, hazards, and time of re- action makes this process commercially attractive 1NDUSTRIAL production of acetylacetone ester, length of time required to complete The yields with methyl acetone, which by the Claisen condensation of acetone the reaction, and effect of temperature on had been dried with acetic anhydride, and aliphatic acetate esters, using sodium yield are lacking. This information is were identical to those obtained with or sodium alkoxide as catalyst, has been given in the present article. The amount chemically pure synthetic mixtures of the made economically impossible by the of by-product acetoacetic ester produced same composition. hazards of the reaction, the low yields, in the author’s experiments was small as The inert diluent materially affected and the great length of time required compared to that divulged in the patent. the yield, but the amount was not crit- for reaction of the last few per cent of the This was probably due to a difference in ical within wide ranges of concentra- sodium, because of coating of the par- the amount of diluent used, although the tion. Best results were obtained with ticles. The latter disadvantage has, to a slightly different order of adding the re- medium boiling hydrocarbons such as small extent, been alleviated by use of so- agents may have had a minor effect. toluene. Isohexane gave somewhat called “sodium sand.” Within recent lower yields, while Varsol (a commercial years, dispersed sodium of 1- to 20- petroleum fraction, boiling point 154’ micron particle size has become commer- Sodium Alkoxide as Catalyst to 175’ C.) gave much poorer results. cially available and it was conjectured The use of sodium ethoxide and meth- When prepared in isohexane, the sodium that its use might solve many difficulties. oxide was first investigated. The over- methoxide was granular and the par- Therefore, experimental work was car- all reactions on which the yields were ticles were about the same size as the ried out on both dispersed sodium and based are expressed by the following original sodium; that prepared in tolu- sodium alkoxide prepared from sodium equations : ene was somewhat gelatinous. This dif- sand, to make a valid comparison. ference in physical form, as well as the Published yields of acetylacetone are CHsOH + Na + CH30Na + l/zHz slightly higher reaction temperature pos- not directly comparable because dif- CHa.CO.OCH3 CHa.CO.CH8 * + + sible in toluene, probably accounts for ferent ratios of reagents have been used, CH30Na = CH,.C(ONa)=CH.C0.CH3 the higher yields. With Varsol as dilu- but all have been low on sodium or so- 4- 2CH30H ent, reactions of sodium with methanol dium alkoxide (7-3, 6, 7, 77). Some CH3.C(ONa)=CH.CO.CH3 + CH3- and of acetone with methyl acetate were authors (I, 77) state that 2 gram-atoms sluggish. Treatment of the Varsol first of metallic sodium are required per mole with concentrated sulfuric acid and then of product, in contrast to 1 gram-mole of To make a direct comparison with pre- with sodium, followed by distillation, sodium ethoxide. However, in this in- viously published work (Z), a mole ratio made no difference. vestigation, 1 gram-atom of sodium was of ester-acetone-sodium alkoxide of Increasing the ratio of ester to the found equivalent to 1 gram-mole of so- about 4.07 : 1 : 1 was used in most experi- other reactants increased the yields based dium alkoxide. The advantages of using ments. Ethyl and methyl acetates gave on sodium and acetone (Table I). The dispersed sodium in the preparation of about the same yield, based on alkoxide. yields given are based on the amount of ethyl acetoacetate have been described by The yield was only slightly lower when acetylacetone recovered on distillation. Frampton and Nobis (5). Since com- the acetone and ester were added to- The total loss in the conversion of the pletion of this work, a patent (4)was is- gether to the sodium methoxide than sodium salt to free acetylacetone and in sued on the preparation of acetylacetone when acetone alone was added to the the distillation may be as high as 5 to from ethyl acetate, acetone, and dis- ester and catalyst. However, part of this 6%. This is indicated by comparison be- persed sodium. However, considerable difference was due to the lower tempera- tween the amount of free diketone re- doubt exists as to how the yield figure ture used. This is economically im- covered on distillation and the amount of was derived, and experimental data on portant, as it permits the use of cheap dry sodium acetyl acetonate originally particle size of the sodium, amount of commercial “methylacetone” as raw ma- produced, as determined by the copper diluent, yields based on acetone and terial, after removal of alcohol and water. method of analysis (70). VOL. 49, NO. 7 JULY 1957 1067 I I I I I tate I I I Ac I I I I I I I I I I I I I I I I The yields on ester Iz'ere 50 to Sl%, toluene or xylene \vas added to a mis- The total reaction time was about 2 but much of the loss was mechanical. ture of acetone, methyl acetate, and hours. one for preparation of the dis- In one run with ethyl acetate, the high diluent for safety as 1141 as economy in persed sodium and another for the boilers formed (including ethyl acetoace- using methyl acetone. After a small por- Claisen condensation. This compares tate and tar) accounted for not more than tion of the sodium had been added, an with 24 hours if small pieces of sodium 14.7y0 of the ester consumed. even if it induction period of several minutes oc- are used (6) and 40 to 50 hours by the ivere assumed that they were derived curred. The reaction then proceeded sodium alkoxide route starting with entirely from it. with a rapid liberation of heat and had to sodium sand. be cooled rapidly, otherivise it might have The yields increased with rise in the Dispersed Sodium as Catalyst gotten out of control. However, by add- maximum reaction temperature up to ing several per cent of crude reaction mix- about 70". But in contrast to the results The over-all reaction may be repre- ture from a previous run, this induction of Frampton and Sobis (5) on the prep- sented by the equation : period was reduced and the hazard de- aration of ethyl acetoacetate, higher creased. In the experiments reported in temperatures (up to 92") obtained by Table 11, less sodium acetoacetonate operating under pressure gave no in- CHI*CO.OCHa T CH3.CO.CHa + than that needed for maximum safety crease in yield. The temperature at Na -+ CHa.C(ONa)=CH.CO.CH3+ was added, to minimize its effect on the which the sodium was added did not ap- CH30H $. '/zHz final equilibrium. On completion of ad- pear to affect the yield appreciablv, dition of sodium (20 to 25 minutes), the within the range of 5' to 35". In all runs: the sodium dispersed in mixture was heated for 30 minutes. Medium boiling aromatic hydrocar- Table I. Preparation of Acetylacetone Using Sodium Alkoxide as Catalyst Ester- A41cohol Acetone- Max. Re- Na AIkoxide Di lu en t Temp. of Yield, Yo coveled, Charge, Acetate Amount, Reaction, 011 0 11 % of Coni- Moles Ester Compound O c. alkoxide acetone Theoryh ments 12.18 :3:3 Ethyl Isohexane 150 62-63 56.0 74.8 85.4 c 12.23 :3 :3 Methyl Isohexane 155 57 56.7 83.6 85.6 560 47 54.6 .,. ... 1 Toluene 565 59 60.1 ... ... d 12.3 :3:3 Methyl Toluene 1000 59 61.6 79.2 75.7 d* Varsol 910 60 52.4 58.7 78.0 de 6:3:3 Methyl Toluene 975 63 48.0 55.0 71.5 d a During acetone-ester condensation. Includes alcohol origmally charged to form alkoxide. Acetone added to estei-alkoxide mixture. Acetone-ester mixture added to methoxide. e Commercial methyl acetone used. 7 068 INDUSTRIAL AND ENGINEERING CHEMISTRY ACETYLACETONE PREPARATION Table II. Preparation of Acetylacetone Using Dispersed Sodium I) Preformed Na Acetyl Maximum Temaerature. ___Ardnnnte - - - .. - c. Yield, % HZRe- MeOH Added to During After On On covered, Recovered, Charge", Diluent Na addn. Na addn. Na acetone % Theory % Theory Mole yo Xylene 26-34 26 50.5 69.6 75.5 ... ... 22-27 72 71.4 77.8 86.6 ... ... 16-20 74 69.5 75.6 79.4 ... 1.7 Toluene 25-30 69 67.5 74.2 69.3 ... 0.7 5-6 81.2 68.0 74.1 76.9 73.0 0.7 14-20 92.0 68.4 74.0 80.0 88.6 0.7 Cumene 23-28 70 60.4 62.8 68.4 96.4 0.95 Based on Na used. bons were the most satisfactory diluents. Toluene and xylene gave approximately the same results, but cumene appeared to give lower yields. The results are summirized in Table 11. In all runs, the molar ratio of methyl acetate-acetone-sodium was 8.2 : 2 : 2 and the total weight of diluent was about 950 grams except in the case of cumene, which was 535 grams. The yields on methyl acetate were 45 LO 55%, but again mechanical losses were relatively high. Methuds of Recovery The first method tried was to evapo- rate the volatiles from the sodium salt, treat the salt with aqueous acetic acid, extract the acetylacetone with ethyl ace- tate, and distill the extract.
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