Acetone condensation

Bisphenol A. One mole of acetone condenses with two moles of phenol to form bisphenol A [80-05-07] which is used mainly in the production of polycarbonate and epoxy resins. Polycarbonates (qv) are high strength plastics used widely in automotive appHcations and appHances, multilayer containers, and housing appHcations. Epoxy resins (qv) are used in fiber-reinforced larninates, for encapsulating electronic components, and in advanced composites for aircraft—aerospace and automotive appHcations. Bisphenol A is also used for the production of corrosion- and chemical-resistant polyester resins, polysulfone resins, polyetherimide resins, and polyarylate resins. 

A Hquid-phase isophorone process is depicted ia Figure 4 (83). A mixture of acetone, water, and potassium hydroxide (0.1%) are fed to a pressure column which operates at head conditions of 205°C and 3.5 MPa (- 500 psi). Acetone condensation reactions occur on the upper trays, high boiling products move down the column, and unreacted acetone is distilled overhead ia a water—acetone a2eotrope which is recycled to the column as reflux. In the lower section of the column, water and alkaH promote hydrolysis of reaction by-products to produce both isophorone and recyclable acetone. Acetone conversion is typically ia the range 6—10% and about 70% yield of isophorone is obtained. Condensation—hydrolysis technology (195—198), and other Hquid-phase production processes have been reported (199—205). 

Feedstock Reactions Catalyst References Acetone Condensation-hydrogenation (bifunctional catalysis) Pd on sulfonated PS-DVB [6] Methanol, Raffinate II Condensation, hydrogenation Pd on sulfonated PS-DVB [61] Dioxygen dissolved in water Hydrogenation Pd on sulfonated PS-DVB [8]... 

This paper investigates the acetone condensation reaction in the vapour phase over a CsOH/Si02 solid based catalyst over a range of reaction temperatures using hydrogen and deuterium as carrier gases. 

Figure 2 Reaction profile for acetone condensation over Cs/Si02 at 573 K.

Figure 3 Yields of products formed for acetone condensation reaction as a function of temperature.

Table 2 The molecular ions observed during acetone condensation reactions under H2 and D2.

Figure 4 Mechanism for the formation of various species during acetone condensation under H2 conditions over CsOH/Si02.

Figure 5 Proposed mechanism for acetone condensation reaction under deuterated conditions.

It has been mentioned that the mixture of trimethyl-D-fructoses from the acid hydrolysis of hexamethyl-di-D-fructose anhydride III, which are now known to be the 3,4,6- and 1,4,6-trimethyl-D-fructoses, shows a specific rotation near that of pure 3,4,6-trimethyl-D-fructose it is to be inferred accordingly that these two trimethyl-D-fructoses do not differ greatly in rotation. Montgomery76 has synthesized 1,4,6-tri-methyl-D-fructose and found its rotation in chloroform to be [a] d = + 29.7°, a value approximating that of 3,4,6-trimethyl-D-fructose (+ 27.7° in the same solvent). Pertinent also are the respective rotations of the acetone condensation products from these two trimethyl-D-fructoses. Montgomery found that 3,4,6-trimethyl-D-fructose under-... 

In a 1-1. three-necked flask equipped with a dry ice-acctone condenser and a sealed mechanical stirrer is placed 700 ml. of commercial, anhydrous, liquid ammonia. To the stirred ammonia is added a small piece of potassium metal. (Caution1 Care should he exercised in handling potassium metal, since it is extremely reactive and it ignites on contact with water, atmospheric moisture, or alcohol. It should he manipulated under toluene or xylene, and blotted with filter paper before addition.) After the appearance of a blue color a few crystals of ferric nitrate hydrate (ca. 0.1 g.) are added, followed by small pieces of freshly cut potassium metal until 7.0 g. (0.18 g. atom) has been added. After all the potassium has been converted to the amide (Note 7), 24.9 g. (0.154 mole) of sodio-2-formyl-6-methylcyclohexanone is added carefully through a powder funnel (Note 8). After 1 hour a solution of 28.2 g. (0.21 mole) of w-butyl bromide (Note 9) in 50 ml. of anhydrous ether is added dropwise from an addition funnel. The mixture is stirred for 3 hours, and then the dry ice-acetone condenser is replaced by a water condenser. A steam bath is placed under the flask, and the ammonia is evaporated (Caution ) as 400 ml. of anhydrous ether is added. When the... 

The mechanism of the reaction is undoubtedly as follows when the sulfuric acid and acetone are in contact for long periods of time, several molecules of the acetone condense to form aldol condensation products. These do not break down into mesitylene until the temperature is raised in the second part of the experiment. 

The mandelic acid-acetone condensation product is added in small portions to about 1800 cc. of liquid ammonia (Note 2) contained in two silvered i-l. Dewar flasks. Each flask is fitted with... 

The crude product contains varying quantities of sodium carbonate and sodium sulfate, which are difficult to remove. These impurities are insoluble in liquid ammonia consequently the crude compound can be ammonolyzed without further purification. The mandelic acid-acetone condensation product may be purified by recrystallization from absolute alcohol it then melts at 45°. 

The solubility of the mandelic acid-acetone condensation compound in liquid ammonia at its boiling point is approximately 10 g. per 100 cc. 

A 1-1. three-necked flask is fitted with a dry ice-acetone condenser, a glass stirrer, and a glass stopper (Note 1). Potassium amide is prepared in 400 ml. of liquid ammonia from 8.0 g. (0.20 g.-atom) of potassium metal (Note 2). The glass stopper is replaced with an addition funnel containing 32.1 g. (0.300 mole) (Note 3) of 2,(>-hitidine dissolved in about 20 ml. of anhydrous ether. The lutidine solution is added to the amide... 

Gas-Phase Acetone Condensation over Hydrotalcite-like Catalysts 55... 

The potential for M02N to function as a base catalyst has been demonstrated by Bej and Thompson in a study of acetone condensation. Isophorone, which is known to be produced from a base catalysed pathway, was a product... 

Grignard reagents other than vinylmagnesium bromide may be used in this general procedure. The initial use of a Dry Ice-acetone condenser, is then not required. Use of the THF solvent provides a distinct advantage over the method recently described in detail4 in which ether is used as a solvent, since fewer steps are required. 

The kinetic data for phenol—acetone condensation to bisphenol A [reaction type (E)] in the liquid phase at 91°C over sulphonated ion exchanger [385] were best represented by the equation... 

Lactamide has been prepared by the action of gaseous ammonia on ethyl lactate 3 and from lactic anhydride 4 and gaseous ammonia. It has been made also by the action of ammonia gas on lactide.5 The amide was obtained in excellent yields by treatment of the acetone condensation product of lactic acid with ammonia.6 Amides have been prepared by the reaction of liquid ammonia with esters at temperatures varying from — 330 to... 

The procedure described in the foregoing is followed until evaporation of the acetone solution to a syrup. Water (2.3 L) is added, and the mixture is distilled under reduced pressure at 60-70°C to 1600 mL to remove acetone and acetone condensation products. Tbe final alkaline aqueous misture is adjusted to pH 2 with concentrated hydrochloric acid and heated 4 h at 40°C with constant stirring. The hydrolysate is neutralized to pH 8 with... 

Because proanthocyanidins are susceptible to oxidation, the amount of time the flask is left on the rotary evaporator should be limited to the time necessary to remove the acetone. This is most easily determined by observing the rotary evaporator condenser. Because water has a higher surface tension than acetone, condensation of water is observed as fogging of the condenser portion of the rotary evaporator. 

---