Acetic anhydride production from ketene

Four different methods (vapour-phase acetylation using acetic anhydride, acetylation using ketene gas, liquid phase acetylation using acetic anhydride/xylene, or neat acetic anhydride) were used to acetylate pine wood chips to a variety of WPGs for the production of MUF-bonded particleboards (Nilsson etal., 1988). Composite boards were exposed to unsterile soil in fungal cellar tests. Boards made from ketene acetylated chips were not found to be resistant to decay at the maximum WPG level achieved (17 %) with a liquid acetic anhydride modification, no decay was recorded at a WPG level of c. 18 % after 12 months exposure, whereas with a vapour-phase treatment at the same WPG, evidence for decay was found. 

Uses. The lowest member of this class, ketene itself, is a powerful acetylating agent, reacting with compounds containing a labile hydrogen atom to give acetyl derivatives. This reaction is used only when the standard acetylation methods with acetic anhydride or acetyl chloride [75-36-5] do not work weU. Most of the ketene produced worldwide is used in the production of acetic anhydride. Acetic anhydride is prepared from the reaction of ketene and acetic acid. 

Acylation. Reaction conditions employed to acylate an aminophenol (using acetic anhydride in alkaU or pyridine, acetyl chloride and pyridine in toluene, or ketene in ethanol) usually lead to involvement of the amino function. If an excess of reagent is used, however, especially with 2-aminophenol, 0,A/-diacylated products are formed. Aminophenol carboxylates (0-acylated aminophenols) normally are prepared by the reduction of the corresponding nitrophenyl carboxylates, which is of particular importance with the 4-aminophenol derivatives. A migration of the acyl group from the O to the N position is known to occur for some 2- and 4-aminophenol acylated products. Whereas ethyl 4-aminophenyl carbonate is relatively stable in dilute acid, the 2-derivative has been shown to rearrange slowly to give ethyl 2-hydroxyphenyl carbamate [35580-89-3] (26). 

Production is by the acetylation of 4-aminophenol. This can be achieved with acetic acid and acetic anhydride at 80°C (191), with acetic acid anhydride in pyridine at 100°C (192), with acetyl chloride and pyridine in toluene at 60°C (193), or by the action of ketene in alcohoHc suspension. 4-Hydroxyacetanihde also may be synthesized directiy from 4-nitrophenol The available reduction—acetylation systems include tin with acetic acid, hydrogenation over Pd—C in acetic anhydride, and hydrogenation over platinum in acetic acid (194,195). Other routes include rearrangement of 4-hydroxyacetophenone hydrazone with sodium nitrite in sulfuric acid and the electrolytic hydroxylation of acetanilide [103-84-4] (196). 

The filtrate from this first batch will comprise a solution of 180 to 270 kg of unprecipitated acetylsalicylic acid (1.0 to 1.5 mols), 510 kg of acetic anhydrice (5.0 mols), 600 kg of acetic acid (10.0 mols) (obtained as a by-product in the acetylation step) and 1,200 kg of the diluent toluene. Into this filtrate, at a temperature of 15° to 25°C, ketene gas is now passed through a sparger tube or diffuser plate, with good agitation, until a weight increase of 420.5 kg of ketene (10 mols) occurs. The reaction mixture wiil now contain 180-270 kg of unprecipitated acetylsalicylic acid (1.0-1.5 mols) and 1,532 kg of acetic anhydride (15 mols) in 1,200 kg of toluene. This mother liquor is recycled to the first step of the process for reaction with another batch of 1,382 kg of salicylic acid. On recirculating the mother liquor, the yield of pure acetylsalicylic acid is 1,780 to 1,795 kg per batch. 

The production of acetic anhydride from acetic acid occurs via the intermediate formation of ketene where one mole of acetic acid loses one mole of water ... 

Since reaction of wood with acetic anhydride leads to the formation of acetic acid by-product, which must be removed from the wood, there has been some interest in the use of ketene gas for acetylation (Figure 4.4a). Ketene, for reaction with wood, is produced by pyrolysis of diketene. Provided that the wood contains no moisture, no acetic acid by-product is produced. However, ketene presents handling problems it is very toxic and explosive, and it also has a tendency to dimerize. A comprehensive series of studies of ketene-based acetylation has been performed in Latvia and this work has been reviewed by Morozovs etal. (2003). Hardwoods have been found to be more reactive to ketene than softwoods and the optimal temperature for reaction has been determined as 47 °C. Application of vacuum and treatment of wood with ammonia solution has been used to remove the excess ketene. The reaction of wood with liquid diketene was also studied, with a WPG of 35 % being obtained after reaction for 3 hours at 52 °C. 

Acetic anhydride may be produced by three different methods. The first procedure involves the in situ production from acetaldehyde of peracetic acid, which in turn reacts with more acetaldehyde to yield the anhydride. In the preferred process, acetic acid (or acetone) is pyrolyzed to ketene, which reacts with acetic acid to form acetic anhydride. A new process to make acetic anhydride involves CO insertion into methyl acetate. This may be the process of the future. 

Figure 17.14. Some unusual reactor configurations, (a) Flame reactor for making ethylene and acetylene from liquid hydrocarbons [Patton et al., Pet Refin 37(li) 180, (1958)]. (b) Shallow bed reactor for oxidation of ammonia, using Pt-Rh gauze [Gillespie and Kenson, Chemtech, 625 (Oct. 1971)]. (c) Sdioenherr furnace for fixation of atmospheric nitrogen, (d) Production of acetic acid anhydride from acetic acid and gaseous ketene in a mixing pump, (e) Phillips reactor for low pressure polymerization of ethylene (closed loop tubular reactor), (f) Polymerization of ethylene at high pressure.

A portion of the acetic acid, which is the major product, can be converted in a separate unit to acetic anhydride. Acetic anhydride may be produced from acetic acid, acetone, or acetaldehyde. With both acetic acid and acetone the initial product is ketene. The ketene is highly reactive and reacts readily... 

Hydroxylamine can be prepared from ammonia and hydrogen peroxide using a titanium silicalite catalyst in 83% yield.68 The by-product acetic acid could be recycled to acetic anhydride by pyrolyzing part of it to ketene. 

Claisen rearrangement. The quenching of the lithium enolates derived from allylic acetates results in enol phosphates, which show a higher propensity for Claisen rearrangement than ketene silyl ethers. The mixed anhydride products can be used directly to generate carboxylic acid derivatives. 

In the benzo[g]indolizine series, the ester (756) has been obtained from the isoquinolium ylide (755 R = C02Et) and cyclopentanone (which is a synthetic equivalent of cyclopentyne), acetic anhydride reacts with the ylide to afford the acetoxy-derivative (757), and the action of keten on the cyano-analogue (755 R = CN) leads to the ketone (758)/ Diphenylcyclopropenone combines with 1-methyl-3,4-dihydroisoquinoline to form the rearranged adduct (759). The benzo[e]indolizine (761) is one of the products of the thermolysis of the azide (760). Heating indoline with acrylic acid in polyphosphoric acid gives a mixture of the tri- and tetra-cyclic compounds (762) and (763). ... 

In the ketene process, acetic acid is thermally dehydrated at 750°C to ketene. The ketene is separated from by-product water and reacted with another mole of acetic acid to produce acetic anhydride. Figure 22.19 is a schematic diagram of this process. 

In the preaeuoe of potassium acetate,ketene reacts with aromatlo aldehydes to give a little J -lactono, bat the principal product ia a mixed anhydride. It has been definitely ehowni that this anhydride does not come from the reaction of keteno with the lactone whir may be formed in a first step ... 

The formation of acrylonitriles from the reaction of dihalogenomethylene-phosphoranes with aroyl cyanides has now been extended to include the use of aliphatic acyl cyanides, although the conditions need to be closely defined. Perfluoroisocyanates with diphenylmethylenetriphenylphosphorane give the expected keten-imines (28) or their rearrangement products (29). Formylation of both reactive and stable ylides has been achieved using the mixed anhydride of formic and acetic acids. ... 

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