Butyl alcohol from carbohydrates

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. 

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. ... 

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. 

Hydroalkoxylation reactions refer to the addition of an alcohol over an insaturation. This highly atom economical process is potentially a straightforward and clean access to ethers, and the reaction is successfully applied at the industrial level for the production of MTBE (methyl terf-butyl ether) and ETBE (ethyl tert-butyl ether) from isobutylene and methanol or ethanol. If this transformation is well known with activated olefins (reaction referred to a Michael addition), a real challenge is the synthesis of ethers from unactivated olefins. Veiy few reactions involving carbohydrates or polyols have been reported to date and most of them involve isobutylene as this substituted olefin is prompt to generate stabilized carbenium ion under acidic conditions. Dimerization reactions of the alcohol or isobutylene are the main side reactions that have to be avoided in order to reach high selectivities into the desired ethers. ... 

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. 

The total yield of 201 was increased and the synthesis time reduced by extracting [nC]butyric acid from its lithium salt by dry 0.1% HCl/He gas mixture and carrying out its pyrolysis at 530 °C over glass beads (equation 104). The relative reactivity of 201 to primary, secondary and tertiary alcohols (equation 105a, b, c) has been found to be as 1 0.4 0.1, respectively. Several bioactive compounds have been labelled with [nC]propyl ketene, such as carbohydrate compounds193 and IV-butyl compounds, for instance /V- 11 C]butyryl THPO, 202, and some phorbol esters192, 203, 204 and 205. 

By means of an ETHOS MR oven, Nuchter et al. [33] accomplished scaling-up of a microwave-assisted Fischer glycosylation to the kilogram scale with improved economic efficiency. In batch reactions, carbohydrates (o-glucose, o-mannose, d-galactose, butyl o-galactose, starch) were converted on the 50-g scale (95-100% yield, from 95 5 to 100%) with 3-30-fold molar excesses of an alcohol (methanol, ethanol, butanol, octanol) in the presence of a catalytic amount of acetyl chloride under pressure (microwave flow reactor, 120-140 °C, 12-16 bar, 5-12 min) or without applying pressure (120-140 °C or reflux temperature, 20-60 min). Furano-sides are not stable under these reaction conditions. 

Fembach and Strange (1911) were issued the British patents 15,203-15,204 on Acetone and high alcohols (amyl, butyl, or ethyl alcohols and butyric, propionic or acetic acid) from starches, sugars, and other carbohydrates. In 1913, the first plant for the production of butanol from potatoes began in... 

Fernbach A, Strange EH (1911) Acetone and higher alcohols (amyl, butyl or ethyl alcohols and butyric, propionic or a< ic acid) from starches, sugars and other carbohydrates. British Patent 15203-15204 Fischer RJ, Helms J, Dii P (1993) Cloning, sequencing and molecular analysis of the sol operon of Clostridium acetobutylicum, a chromosomal locus involved in solventogenesis. J Bacteriol 175 6959-6969 Fond O, Jansen NB, Tsao GT (1985) A model of acetic acid and 2,3-butanediol inhibition of the growth and metabolism of Klebsiella oxytoca. Biotechnol Lett 7 727-732... 

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