Isobutyraldehyde

Synonyms isobutanal 2-methyl-1-propanal isobutyric aldehyde isobutyl aldehyde 2-methyl propionaldehyde valine aldehyde 

Isobutyraldehyde is used in the synthesis of cellulose esters, resins, and plasticizers in the preparation of pantothenic acid and valine and in flavors. 

Colorless liquid with a pungent smell bp 64.5°C (148.1°F) mp -66°C (-86.8°F) density 0.794 soluble in water (11 g/lOOmL), ether, acetone, and chloroform. 

Isobutyraldehyde is a moderate skin and eye irritant the effect may be slightly greater than that of n-butyraldehyde. An amount totaling 500 mg in 24 hours produced severe skin irritation in rabbits 100 mg caused moderate eye irritation. 

The toxicity of isobutyraldehyde determined on test animals was very low. Exposure to 8000 ppm (23,600 mg/m ) for 4 hours was lethal to rats. 

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An example of such recychng in a parallel reaction system is in the Oxo process for the production of C4 alcohols. Propylene and synthesis gas (a mixture of carbon monoxide and hydrogen) are first reacted to ra- and isobutyraldehydes using a cobalt-based catalyst. Two parallel reactions occur ... 

Ethyl acetate [141-78-6] is produced commercially by the Tischenko condensation of acetaldehyde using an aluminum ethoxide catalyst (60). The Tischenko reaction of acetaldehyde with isobutyraldehyde [78-84-2] yields a mixture of ethyl acetate, isobutyl acetate [110-19-0] and isobutyl isobutyrate [97-85-8] (61). 

Rhodium Ca.ta.lysts. Rhodium carbonyl catalysts for olefin hydroformylation are more active than cobalt carbonyls and can be appHed at lower temperatures and pressures (14). Rhodium hydrocarbonyl [75506-18-2] HRh(CO)4, results in lower -butyraldehyde [123-72-8] to isobutyraldehyde [78-84-2] ratios from propylene [115-07-17, C H, than does cobalt hydrocarbonyl, ie, 50/50 vs 80/20. Ligand-modified rhodium catalysts, HRh(CO)2L2 or HRh(CO)L2, afford /iso-ratios as high as 92/8 the ligand is generally a tertiary phosphine. The rhodium catalyst process was developed joindy by Union Carbide Chemicals, Johnson-Matthey, and Davy Powergas and has been Hcensed to several companies. It is particulady suited to propylene conversion to -butyraldehyde for 2-ethylhexanol production in that by-product isobutyraldehyde is minimized. 

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Other examples are glycine — formaldehyde, alanine — acetaldehyde, valine — isobutyraldehyde, phenylalanine — phenylacetaldehyde, and methionine — methional (106). Products such as dried skim milk, dried eggs, and dehydrated vegetables and fmits are particularly susceptible to deteriorative flavor changes ascribed to this reaction (Table 10). 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

Manufacture. Commercial preparation of neopentyl glycol can be via an alkah-cataly2ed condensation of isobutyraldehyde with 2 moles of formaldehyde (crossed Canni22aro reaction) (2,8). Yields are - 70%. 

Manufacture and Processing. 2,2,4-Trimethyl-l,3-pentanediol can be produced by hydrogenation of the aldehyde trimer resulting from the aldol condensation of isobutyraldehyde [78-84-2]. 

Esters. The monoisobutyrate ester of 2,2,4-trimethyl-1,3-pentanediol is prepared from isobutyraldehyde ia a Tishchenko reaction (58,59). Diesters, such as trimethylpentane dipelargonate (2,2,4-trimethylpentane 1,3-dinonanoate), are prepared by the reaction of 2 mol of the monocarboxyhc acid with 1 mol of the glycol at 150—200°C (60,61). The lower aUphatic carboxyHc acid diesters of trimethylpentanediol undergo pyrolysis to the corresponding ester of 2,2,4-trimethyl-3-penten-l-ol (62). These unsaturated esters reportedly can be epoxidized by peroxyacetic acid (63). 

Methyl Isoamyl Ketone. Methyl isoamyl ketone [110-12-3] (5-methyl-2-hexanone) is a colorless Hquid with a mild odor. It is produced by the condensation of acetone and isobutyraldehyde (164) in three steps which proceed via the keto-alcohol dehydration to 5-methyl-3-hexen-2-one, and hydrogenation to 5-methyl-2-hexanone. 

Isobutyraldehyde is commonly available as a by-product of propylene/Oxo hydroformylation. Methyl isoamyl ketone is used as a solvent for ceUulose esters, acryHcs, and vinyl polymers. It is available in the United States from Eastman (Kingsport, Tennessee) (47) and Union Carbide (South Charleston, West Virginia) and was priced at 1.42/kg in October 1994. 

Propylene-Based Routes. The strong acid-catalyzed carbonylation of propylene [115-07-1] to isobutyric acid (Koch reaction) followed by oxidative dehydration to methacrylic acid has been extensively studied since the 1960s. The principal side reaction in the Koch reaction is the formation of oligomers of propylene. Increasing yields of methacrylic acid in the oxydehydration step is the current focus of research. Isobutyric acid may also be obtained via the oxidation of isobutyraldehyde, which is available from the hydroformylation of propylene. The -butyraldehyde isomer that is formed in the hydroformylation must be separated. 

For example, HRh(CO)2L2, after dissociation of CO, goes on to generate -butyraldehyde as shown ia Figure 4 (13,14). A similar cycle could be written for isobutyraldehyde. 

The largest oxo producers ia Western Europe are BASE, Hbls, and Hoechst (formerly Ruhrchemie), representing 50—51% of the total regional capacity of 2.527 x 10 metric tons. These companies have the broadest spectmm of products ranging from and adehydes to alcohols and acids. However the primary products are n- and isobutyraldehyde, at combiaed capacities of 1.08 x 10 t. The -butyraldehyde goes principally iato the manufacture of 2-EH. 

Factors affecting the accumulation of ansamitocins P-2, P-3, and P-4 in JSbocardia sp. C-15003 have been studied (246) the addition of isoleucine, propionate, ptopionaldehyde, or -ptopyl alcohol to the fermentation medium resulted in the increased production of P-2 the addition of valine, isobutyrate, isobutyraldehyde, or isobutyl alcohol increased the production of P-3, reaching more than 90% of the total ansamitocins produced and the addition of leucine, isovalerate, isovaleraldehyde, or isoamyl alcohol increased the production of P-4. 

Butyra.Idehydes. Normal and isobutyraldehydes are produced from propylene by the oxo or hydroformylation process (see Oxo process). 

Racemic pantolactone is prepared easily by reacting isobutyraldehyde (15) with formaldehyde ia the presence of a base to yield the iatermediate hydroxyaldehyde (16). Hydrogen cyanide addition affords the hydroxy cyanohydria (17). Acid-cataly2ed hydrolysis and cyclization of the cyanohydria (17) gives (R,3)-pantolactone (18) ia 90% yield (18). 

The principal commercial source of 1-butanol is -butyraldehyde [123-72-8] obtained from the Oxo reaction of propylene. A mixture of n- and isobutyraldehyde [78-84-2] is obtained in this process this mixture is either separated initially and the individual aldehyde isomers hydrogenated, or the mixture of isomeric aldehydes is hydrogenated direcdy and the n- and isobutyl alcohol product mix separated by distillation. Typically, the hydrogenation is carried out in the vapor phase over a heterogeneous catalyst. For example, passing a mixture of n- and isobutyraldehyde with 60 40 H2 N2 over a CuO—ZnO—NiO catalyst at 25—196°C and 0.7 MPa proceeds in 99.95% efficiency to the corresponding alcohols at 98.6% conversion (7,8) (see Butyraldehydes Oxo process). 

Commercial isobutyl alcohol is made almost exclusively from the hydrogenation of isobutyraldehyde obtained by the hydroformylation of propylene. However, this alcohol is also commonly obtained as a coproduct in the Eischer Tropsch synthesis of methanol (16,17). 

Historically, isobutyl alcohol was an unwanted by-product of the propylene Oxo reaction. Indeed, isobutyraldehyde the precursor of isobutyl alcohol was occasionally burned for fuel. However, more recentiy isobutyl alcohol has replaced -butyl alcohol in some appHcations where the branched alcohol appears to have preferred properties and stmcture. However, suppHes of isobutyl alcohol have declined relative to overall C-4 alcohols, especially in Europe, with the conversion of many Oxo plants to rhodium based processes which give higher normal to isobutyraldehyde isomer ratios. Further the supply of isobutyl alcohol at any given time can fluctuate greatly, since it is the lowest valued derivative of isobutyraldehyde, after neopentyl glycol, methyl isoamyl ketone and certain condensation products (10). 

The principal industrial appHcation for isobutyl alcohol is as a direct solvent replacement for 1-butanol. It is also used as a process solvent in the flavor and fragrance, pharmaceutical, and pesticide industries. The maximum employment of isobutyl alcohol was in the mid-1980s when it had a distinct price advantage over 1-butanol (10). More recently, however, with increased demand for other value added derivatives of isobutyraldehyde, the price differential between isobutyl and -butyl alcohols has diminished resulting in a switching back by some consumers to 1-butanol. 

The two isomeric butanals, n- and isobutyraldehyde, C HgO, are produced commercially abnost exclusively by the Oxo Reaction of propylene. They also occur naturally ia trace amounts ia tea leaves, certain oils, coffee aroma, and tobacco smoke. 

Catalytic oxidation of isobutyraldehyde with air at 30—50°C gives isobutyric acid [79-31-2] ia 95% yield (5). Certain enzymes, such as horseradish peroxidase, cataly2e the reaction of isobutyraldehyde with molecular oxygen to form triplet-state acetone and formic acid with simultaneous chemiluminescence (6). 

Many commercially important isobutyraldehyde derivatives are prepared through aldol and/or Tischenko condensation reactions. For example, isobutyraldehyde undergoes the aldol reaction to form isobutyraldol (2,2,4-trimethyl-3-hydroxypentanal [918-79-6]) which, when hydrogenated, gives 2,2,4-trimethyl-1,3-pentanediol (TMPD) [144-19-4],... 

Isobutyraldehyde also undergoes consecutive aldol and Tischenko condensations to give 2,2,4-trimethyl-l,3-pentanediolmonoisobutyrate [25265-77-4] (Texanol, Filmer IBT), alternatively prepared by the esterification of TMPD with isobutyric acid. 

Neopentyl glycol (2,2-dimethyl-1-propanol [126-30-7]) another important iadustrial derivative of isobutyraldehyde, is obtained from the aldol reaction product of isobutyraldehyde with formaldehyde followed by hydrogenation. 

Isobutyraldehyde reacts with aqueous ammonia at 0—10°C to give hexahydro-2,4,6-ttiisopropyl-r-ttiazine, (4) (18), whereas under refluxing conditions the enea2omethine [5339-41-3] (5), is formed (19). Isobutyraldehyde condenses with two mole equivalents of urea in the presence of an acid catalyst to give isobutyUdenediurea [2224-20-6] (IBDU), (6) a slow release fertiliser (20). 

About 69% of the total 1988 U.S. consumption of isobutyraldehyde, went into the production of isobutyl alcohol and isobutyraldehyde condensation and esterification products. The other principal isobutyraldehyde derivative markets (as a percentage of total 1988 U.S. isobutyraldehyde consumption) are neopentyl glycol (15%) isobutyl acetate (6%) isobutyric acid (5%) isobutyUdene diurea (2.5%) and methyl isoamyl ketone (1.7%). 

Trimethyl-l,3-pentanediol (TMPD), the hydrogenated aldol condensation product of isobutyraldehyde, is a modifying agent in alkyd resins (qv), high sohds coatings, and moisture-set inks. 

The monoisobutyrate ester of TMPD, Texanol, or Filmer IBT, formally an isobutyraldehyde trimer, is prepared in a single step from isobutyraldehyde or, alternatively, by the esterification of TMPD with isobutyric acid. This monoester is most commonly employed as a coalescing agent for latex-based paints and water-based ink formulations. 

The principal markets for neopentyl glycol (NPG), the hydrogenated, crossed aldol condensation product of isobutyraldehyde and formaldehyde, are in water-borne and alkyd-surface coatings. 

Isobutyl isobutyrate, the Tischenko condensation product of two molecules of isobutyraldehyde, is a slow evaporating ester solvent that has been promoted as a replacement for ethoxyethyl acetate. Although produced primarily by the acetylation of isobutyl alcohol, some isobutyl acetate is produced commercially by the crossed Tischenko condensation of isobutyraldehyde and acetaldehyde. Isobutyl acetate [110-19-0] is employed mainly as a solvent, particularly for nitrocellulose coatings. 

Isobutyric acid, the simple oxidation product of isobutyraldehyde, is employed in the esterification of TMPD to form the mono- and diesters of TMPD. Some isobutyric acid is also used in the production of isobutyronittile, an organo-phosphate pesticide precursor. 

Isobutyhdene diurea (IBDU), a slow release fertilizer, is formed from isobutyraldehyde and two moles of urea. 

Methyl isoamyl ketone (MIAK), a product derived from the aldol condensation of isobutyraldehyde and acetone, is used principally as a solvent for lacquers, ceUulosics, and epoxies. 

The earhest commercial route to -butyraldehyde was a multistep process starting with ethanol, which was consecutively dehydrogenated to acetaldehyde, condensed to crotonaldehyde, and reduced to butyraldehyde. In the late 1960s, production of -butyraldehyde (and isobutyraldehyde) in Europe and the United States switched over largely to the Oxo reaction of propylene. 

The earhest modification of the Oxo process (qv) employed cobalt hydrocarbonyl, HCo(CO)4, as catalyst. The reaction was carried out in the Hquid phase at 130—160°C and 10—20 MPa (1450—2900 psi) to give a ratio of n- to isobutyraldehyde of between 2 1 to 4 1. / -Butyraldehyde, the straight-chain isomer and the precursor of 2-ethylhexanol, was the more valuable product so that a high isomer ratio of n- to isobutyraldehyde was obviously advantageous. 

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