Butanol synthesis

Isobutyl alcohol [78-83-1] forms a substantial fraction of the butanols produced by higher alcohol synthesis over modified copper—zinc oxide-based catalysts. Conceivably, separation of this alcohol and dehydration affords an alternative route to isobutjiene [115-11 -7] for methyl /-butyl ether [1624-04-4] (MTBE) production. MTBE is a rapidly growing constituent of reformulated gasoline, but its growth is likely to be limited by available suppHes of isobutylene. Thus higher alcohol synthesis provides a process capable of supplying all of the raw materials required for manufacture of this key fuel oxygenate (24) (see Ethers). 

Asymmetric Hydroboration. Hydroboration—oxidation of (Z)-2-butene with diisopinocampheylborane was the first highly enantioselective asymmetric synthesis (496) the product was R(—)2-butanol in 87% ee. Since then several asymmetric hydroborating agents have been developed. Enantioselectivity in the hydroboration of significant classes of prochiral alkenes with representative asymmetric hydroborating agents is shown in Table 3. 

Methyl vinyl ketone can be produced by the reactions of acetone and formaldehyde to form 4-hydroxy-2-butanone, followed by dehydration to the product (267,268). Methyl vinyl ketone can also be produced by the Mannich reaction of acetone, formaldehyde, and diethylamine (269). Preparation via the oxidation of saturated alcohols or ketones such as 2-butanol and methyl ethyl ketone is also known (270), and older patents report the synthesis of methyl vinyl ketone by the hydration of vinylacetylene (271,272). 

Because they are similar, the aLkanolamines often can be used interchangeably. However, cost/perfomiance considerations generally dictate a best choice for specific appHcations. AMPD is manufactured in very low volumes for use as a reagent in certain medical diagnostic tests, although some is used in certain cosmetic products. 2-Ainino-1-butanol is used primarily as a taw material for the synthesis of ethambutol [74-55-5] an antituberculosis dmg. The first step in the synthesis of this dmg is the resolution of AB into its optical isomers because only (i)-2-amino-l-butanol, [5856-62-2] is utilized in this synthesis. 

An example of a specialty olefin from an amyl alcohol is Phillips Petroleum s new process for 3-methyl-1-butene (used in the synthesis of pyrethroids) from the catalytic dehydration of 3-methyl-1-butanol (21,22). The process affords 94% product selectivity and 94% alcohol conversion at 310°C and 276 kPa (40 psig). 

Furalazine, Acetylfuratrizine, Panfuran-S. Heating nitrovin in butanol or dimethylformamide at 100—130°C affords furalazine, 6-[2-(5-nitro-2-furanyl)ethenyl]-l,2,4-triazine-3-amine (34). An improved synthesis originates with 5-nitro-2-furancarboxaldehyde and acetone, proceeds through 4-(5-nitro-2-furanyl)-3-buten-2-one followed by a selenium dioxide oxidation to the pymvaldehyde hydrate, and subsequent reaction with aininoguariidine (35). Furalazine, acetylfuratrizine (36), and the A[-A/-bis(hydroxymethyl) derivative, Panfuran-S, formed from the parent compound and formaldehyde (37), are systemic antibacterial agents. 

Studies of the synthesis of quiaolines usiag transition-metal catalysts and nonacidic conditions (55) have determined that mthenium(III) chloride is the most effective of a wide range of catalysts. The reaction between nitrobenzene and 1-propanol or 1-butanol gives 65 and 70% yields of 2-ethyl-3-methylquiQoline [27356-52-1] and 3-ethyl-2-propylquiQoline, respectively. 

A fermentation route to 1-butanol based on carbon monoxide employing the anaerobic bacterium, Butyribacterium methjlotrophicum has been reported (14,15). In contrast to other commercial catalytic processes for converting synthesis gas to alcohols, the new process is insensitive to sulfur contaminants. Current productivities to butanol are 1 g/L, about 10% of that required for commercial viabiUty. Researchers hope to learn enough about the bacteria s control mechanisms to be able to use recombinant DNA to make the cells produce more butanol. 

Butane, 2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)-catalyst in homogeneous asymmetric hydrogenation, 6, 781 Butane-1,4-dioic acid, 2,2-di(indolyl)-synthesis, 4, 226 Butanenitrile, 4-hydroxy-dihydropyran synthesis from, 3, 769 Butanoic acid, -y-aryl-y-amino-synthesis, 1, 433 1-Butanol... 

Early examples of enantioselective extractions are the resolution of a-aminoalco-hol salts, such as norephedrine, with lipophilic anions (hexafluorophosphate ion) [184-186] by partition between aqueous and lipophilic phases containing esters of tartaric acid [184-188]. Alkyl derivatives of proline and hydroxyproline with cupric ions showed chiral discrimination abilities for the resolution of neutral amino acid enantiomers in n-butanol/water systems [121, 178, 189-192]. On the other hand, chiral crown ethers are classical selectors utilized for enantioseparations, due to their interesting recognition abilities [171, 178]. However, the large number of steps often required for their synthesis [182] and, consequently, their cost as well as their limited loadability makes them not very suitable for preparative purposes. Examples of ligand-exchange [193] or anion-exchange selectors [183] able to discriminate amino acid derivatives have also been described. 

The major use of sec-butanol is to produce MEK by dehydrogenation, as mentioned earlier. 2-Butanol is also used as a solvent, a paint remover, and an intermediate in organic synthesis. 

The second major discovery regarding the use of MTO as an epoxidation catalyst came in 1996, when Sharpless and coworkers reported on the use of substoichio-metric amounts of pyridine as a co-catalyst in the system [103]. A change of solvent from tert-butanol to dichloromethane and the introduction of 12 mol% of pyridine even allowed the synthesis of very sensitive epoxides with aqueous hydrogen peroxide as the terminal oxidant. A significant rate acceleration was also observed for the epoxidation reaction performed in the presence of pyridine. This discovery was the first example of an efficient MTO-based system for epoxidation under neutral to basic conditions. Under these conditions the detrimental acid-induced decomposition of the epoxide is effectively avoided. With this novel system, a variety of... 

A second paper161 describes the use of the same base in either THF or t-butanol for the elimination of a-acetoxy phenyl sulphones as outlined in equation (68), in essence a reaction sequence very similar to the Julia olefin synthesis (Section III.B.3) except in the method by which the sulphonyl group is finally removed. 

The aqueous layer remaining after extraction with n-butanol was acidified (to pH 1) by the addition of 50% sulfuric acid, giving a precipitate of adipic acid which was collected by filtration, washed with 120 parts of water in two equal portions, and dried at 110° C. The crude adipic acid obtained was recrystallized from twice its weight of water to provide adipic acid in 90.2% yield, which was pure enough to be used in the synthesis of adiponitrile. 

Hydroformylation is an important industrial process carried out using rhodium phosphine or cobalt carbonyl catalysts. The major industrial process using the rhodium catalyst is hydroformylation of propene with synthesis gas (potentially obtainable from a renewable resource, see Chapter 6). The product, butyraldehyde, is formed as a mixture of n- and iso- isomers the n-isomer is the most desired product, being used for conversion to butanol via hydrogenation) and 2-ethylhexanol via aldol condensation and hydrogenation). Butanol is a valuable solvent in many surface coating formulations whilst 2-ethylhexanol is widely used in the production of phthalate plasticizers. 

Clay-supported heteropoly acids such as H3PW12O40 are more active and selective heterogeneous catalysts for the synthesis of MTBE from methanol and tert-butanol, etherification of phenethyl alcohols with alkanols, and alkylation of hydroquinone with MTBE and tert-butanoi (Yadav and Kirthivasan, 1995 Yadav and Bokade, 1996 Yadav and Doshi, 2000), and synthesis of bisphenol-A (Yadav and Kirthivasan, 1997). 

The synthesis of aldehydes from alkenes known as hydroformylation using CO and hydrogen and a homogeneous catalyst is a very important industrial process [204]. Today, over seven million tons of oxoproducts are formed each year using this procedure, with the majority of butanal and butanol from propene. To further increase the efficiency of this process it can be combined with other transformations in a domino fashion. Eilbracht and coworkers [205] used a Mukaiyama aldol reaction as a second step, as shown for the substrate 6/2-63 which, after 3 days led to 6/2-65 in 91% yield via the primarily formed adduct 6/2-64 (Scheme 6/2.13). However, employing a reaction time of 20 h gave 6/2-64 as the main product. 

Synthesis of 2-butanol by the nickel-catalyzed hydrogenation of 2-butanone ... 

A novel reaction for the synthesis of 4-amino-substituted quinolines 80 or 4-quinolones 81 was reported. Reaction of various ketones, such as 82 and 83, with o-oxazoline-substituted anilines 84 and 85 in the presence of a catalytic amount of /Mol ucncsul tonic acid (p-TSA) in dry w-butanol led to 80 and 81, respectively <06T9365>. To the authors surprise, the reaction of acetophenones 82 lead to a different outcome than that of the cyclic or acyclic ketones 83 containing more than one carbons a to the ketone. 

Raghavan and coworkers have reported on the preparation of 4-hydroxybenzoic add esters (parabans) possessing antimicrobial activity by esterification of 4-hydroxybenzoic acid (Scheme 6.153) [299]. Optimum results were obtained using the alcohol (1-butanol) as solvent in the presence of catalytic amounts of zinc(II) chloride or p-toluenesulfonic acid (pTsOH) under atmospheric conditions. After 5 min of microwave irradiation at 120 °C, ca. 40% conversion to the ester was observed. Related studies on the synthesis of long-chain aliphatic esters have been described by Mariani and coworkers [300]. 

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