Acetone, from carbohydrates

In 1904, Schardinger discovered the bacteriological formation of acetone from carbohydrates, and Pringsheim, in the years 1905-1909, described the reduction of carbohydrates to isopropyl alcohol and n-butyl alcohol. The subsequent work of Fernbach and Weizmann led to the development of an industry for the production of these substances by the fermentation of carbohydrates. ... 

Other Processes. Isopropyl alcohol can be prepared by the Hquid-phase oxidation of propane (118). It is produced iacidentaHy by the reductive condensation of acetone, and is pardy recovered from fermentation (119). Large-scale commercial biological production of isopropyl alcohol from carbohydrate raw materials has also been studied (120—123). 

Butyl alcohol can be obtained from carbohydrates (such as molasses and grain) by fermentation. Acetone and ethanol are also produced. Synthetic processes account for the majority of current-day production. Propylene and synthesis gas give -butyl alcohol. Isobutyl alcohol is a byproduct. 

J. D. Stevens, Isolation of aldehydo and septanoside derivatives from the acid-catalyzed reaction of D-glucose and some of its derivatives with acetone-methanol, Carbohydr. Res., 21 (1972) 490-492. 

More than seventy years ago the impressive discovery was made that bioreduction of mannitol, glycerol and starch yields butanol. Fermentations in which butyric acid, butanol and acetone are formed from carbohydrates by different bacilli (butyl bacteria) belong in this group. The term butyl bacteria as a generic name for microbes producing the genetically related substances of the four-carbon series was proposed in 1921" and has been applied since then. The approximate course of these reactions is shown by the following formulations which, however, do not explain the mechanism ... 

It may be stated at this point that the presence of a /3-hydroxy-butyrate fat in certain organisms is a matter of general biochemical importance. Usually /3-hydroxybutyric acid and the acetone bodies are derived from n-butyric acid directly. The unambiguous formation of jS-hydroxybutyric acid anhydrides from carbohydrates opens up new vistas its formation from acetaldehyde, and from pyruvic acid, through aldol intermediates can be understood without difficulty. Kirrmann s reaction, to which little attention has been paid, is at the same time an example of an oxygen shift, leading from hydroxyaldehydes to fatty acids. 

The trifluoroacetyl group, which is extremely labile towards hydrolysis, may be readily removed under mild conditions from carbohydrate mixed-esters. Thus, treatment of an acetone solution of methyl... 

An illustration of the use of the direct fermentation method is described in British Patent 4845 (1915) by C. Weizmann. In this process acetone and butyl alcohol was produced from carbohydrate material as maize, rice, wheat, oats, rye, dari, and potatoes. A culture of bacteria obtained from soil, cereals as maize, rice, flax, was used. This organism is resistant to 90-100 degrees C. for 1-2 minutes, and liquefies gelatin. It is supposed to be B. granulobaoter pectinovorium. The method used in preparing the culture was the inoculation of sterile maize mash with maize meal heated to 90-100° C. for 1-2 minutes. The mixture was allowed to ferment at about 37° C. A pronounced odor of butyl alcohol was considered the indication of the active existence of the organism desired. 

Until World War 1 acetone was manufactured commercially by the dry distillation of calcium acetate from lime and pyroligneous acid (wood distillate) (9). During the war processes for acetic acid from acetylene and by fermentation supplanted the pyroligneous acid (10). In turn these methods were displaced by the process developed for the bacterial fermentation of carbohydrates (cornstarch and molasses) to acetone and alcohols (11). At one time Pubhcker Industries, Commercial Solvents, and National Distillers had combined biofermentation capacity of 22,700 metric tons of acetone per year. Biofermentation became noncompetitive around 1960 because of the economics of scale of the isopropyl alcohol dehydrogenation and cumene hydroperoxide processes. 

Fermentative Manufacture. Throughout the years, riboflavin yields obtained by fermentation have been improved to the point of commercial feasibiUty. Most of the riboflavin thus produced is consumed in the form of cmde concentrates for the enrichment of animal feeds. Riboflavin was first produced by fermentation in 1940 from the residue of butanol—acetone fermentation. Several methods were developed for large-scale production (41). A suitable carbohydrate-containing mash is prepared and sterilised, and the pH adjusted to 6—7. The mash is buffered with calcium carbonate, inoculated with Clostridium acetohutylicum and incubated at 37—40°C for 2—3 d. The yield is ca 70 mg riboflavin/L (42) (see Fermentation). 

Acetonide formation is the most commonly used protection for 1,2- and 1,3-diols. The acetonide has been used extensively in carbohydrate chemistiy to mask selectively the hydroxyls of the many different sugars. In preparing acetonides of triols, the 1,2-derivative is generally favored over the 1,3-derivative, but the extent to which the 1,2-acetonide is favored is dependent on stmcture. Note that the 1,2-selectivity for the ketal from 3-pentanone is better than that from acetone. ... 

Weizmann A process for producing acetone and //-butanol by the fermentation of carbohydrates by bacteria isolated from soil or cereals. Later work has shown that effective bacteria are Clostridium acetobutylicum and Bacillus granulobacter pectinorum. Used in Britain in World War I for the manufacture of acetone, needed for the production of cordite. Subsequently operated by Commercial Solvents Corporation in Terre Haute, IN, and in two plants in Canada. Later abandoned in favor of synthetic processes. Invented by C. Weizmann in the University of Manchester in 1915, based on earlier work at the Pastern Institute by A. Fembach and E. H. Strange (hence the alternative name Fembach-Strange-Weizmann). The money that Weizmann obtained from royalties on this process was used in founding the State of Israel, of which he was the first president. 

It is commonly known that lipids, carbohydrates, and glycolipids are present in the Golgi apparatus (27). The determination of the components that react with the ZIO mixture was carried out by removing each component from tissues before incubation in the ZIO mixture. After lipid extraction by acetone (14), chloroform-methanol (15), or propylene oxide (27), no osmium-zinc precipitates could be detected in structures that normally reacted with ZIO. Blumcke et al. (15) summarized the nature of the lipids that react with the ZIO mixture as follows lipids and lipoproteins of cell membranes, neutral fat droplets (41), and lipid globules of type II pneumocytes and alveolar macrophages were, however, not as electron dense as the normally reactive lamellae containing highly unsaturated fatty acids. 

Fig. 37 Example of synthesis of an imino sugars starting from an achiral non-carbohydrate precursor. Reagents and conditions (a) BnOCH2(2-thienyl)CuCnLi2, THF, —78 °C 10% HC1 (b) NaOMe, MeOH, reflux HC1, i-PrOH (c) n-BuLi, PhOCOCl, THF, -78 °C (d) Pb(OAc)4, toluene, reflux (e) HC1, EtOH (f) Me4NBH(OAc)3, acetone, AcOH (g) 0s04, NMO (h) Pd(OH)2, H2.

Butanol, which at one time was an unwanted by-product in the preparation of acetone, is now the most important product of the fermentation. The building of a large new factory in Puerto Rico using 10,000 tons of molasses per annum for its production is an indication of this importance. Butanol is probably still the best solvent for cellulose nitrate lacquers. Dibutyl phthalate is certainly the most widely used plasticizer for synthetic resins, and butyl oleate, tributyl citrate and dibutyl tartrate have also been described as plasticizers. Another important use of butanol is as a source of butadiene, which serves as an intermediate in the conversion of sucrose into a synthetic rubber. Although in recent years other methods have been described for the preparation of butanol (for example, from ethyl alcohol and from acetylene), yet the fermentation of carbohydrates is still the cheapest process. 

FIGURE 21-19 Regulation of triacylglycerol synthesis by insulin. Insulin stimulates conversion of dietary carbohydrates and proteins to fat. Individuals with diabetes mellitus lack insulin in uncontrolled disease, this results in diminished fatty acid synthesis, and the acetyl-CoA arising from catabolism of carbohydrates and proteins is shunted instead to ketone body production. People in severe ketosis smell of acetone, so the condition is sometimes mistaken for drunkenness (p. 909). 

---