Isovaleraldehyde

The systematic application of both antithetic steps will now be exemplified with the admittedly trivial synthesis of 3-methylbutanal (isovaleraldehyde). Functional group operations would yield the following alternative target molecules ... 

Prior to 1975, reaction of mixed butenes with syn gas required high temperatures (160—180°C) and high pressures 20—40 MPa (3000—6000 psi), in the presence of a cobalt catalyst system, to produce / -valeraldehyde and 2-methylbutyraldehyde. Even after commercialization of the low pressure 0x0 process in 1975, a practical process was not available for amyl alcohols because of low hydroformylation rates of internal bonds of isomeric butenes (91,94). More recent developments in catalysts have made low pressure 0x0 process technology commercially viable for production of low cost / -valeraldehyde, 2-methylbutyraldehyde, and isovaleraldehyde, and the corresponding alcohols in pure form. The producers are Union Carbide Chemicals and Plastic Company Inc., BASF, Hoechst AG, and BP Chemicals. 

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. 

A number of improvements have been made in these syntheses. For example, the use of ethanoHc ferric chloride and zinc chloride produces a good yield of 2-isopropylquinoline [17507-24-3] from isovaleraldehyde (46). The purification of 2-methylquinoline is facHitated through precipitation. A cmde quinaldine—hydrochloride and zinc chloride complex is prepared and then treated with aqueous base (47). 

All attempts failed to prepare 5-nitrotetrahydro-l,3-oxazine derivatives irom nitromethane, ammonia and formaldehyde, acetaldehyde, or isovaleraldehyde. ... 

The optically active 1,3-/ram-substitutcd tetrahydro-/f-carboline 3 is obtained predominantly on treatment of the imine 2, derived from L-tryptophan and isovaleraldehyde, with A-benzyl -oxycarbonyl-L-prolyl chloride145. 

Methane, ethene, ethane, propene, acetaldehyde, methyl formate, butene, acetone, furan, dimethyl sulfide, isoprene, isobu-tyraldehyde, diacetyl, methylfuran, and isovaleraldehyde... 

C7H4N2O2S 2719-30-4) see Astemizole isovaleraldehyde (C5H10O 590-86-3) sec Bulizide isovaleric acid... 

Isopropyl glycidyl ether Isopropylamine 4,4 -lsopropylidenediphenol Isovaleraldehyde... 

Treated with ZnBr2 followed by enamines, phenyl thioethers 829 derived from aryl aldehydes are converted to (l-(phenylthio)alkyl ketones or aldehydes 830 in moderate to good yields (Equation 19). Enamines used in these syntheses are (1) morpholine enamine derived from diethyl ketone, (2) diethylamine enamine of propiophenone, (3) piperidine enamine derived from isovaleraldehyde, and (4) pyrrolidine enamine of cyclohexanone <2000H(53)331>. 

Cobalt hydroformylation of butadiene produced low yields (24%) of an equimolar mixture of n- and isovaleraldehyde (40). It has been established that the cobalt hydrocarbonyl adds to form a stable 7r-allyl complex (93, 94). 

Isopropyl-5-methylcyclohexanol, m 12 Isovaleraldehyde, ml81 5-Keto-l,7,7-trimethylnorcamphane, c3... 

Isotropic properties, silicon, 22 482, 483t Isotropic soap phase, 22 726 Isovaleraldehyde. See also 3-Methyl butanal... 

Irradiation of 1,1-dimethylallene and aliphatic aldehydes afforded 2-methyleneoxe-tanes 51 and 52 with low regioselectivities [47]. In contrast, ethoxyallene reacted with isovaleraldehyde at the internal C=C bond with complete regioselectivity to give 53 as a 2 1 mixture of diastereomers. 

Isovaleraldehyde was purchased from Aldrich Chemical Company, Inc., and distilled at atmospheric pressure before use. 

Isopropylacrylaldehyde oxime, 2453 f Isopropyl vinyl ether, 1957 f Isovaleraldehyde, 1958 Limonene, 3337... 

Isovaleraldehyde org chem (CH3)2CtfCtf2CtfO A colorless liquid with an applelike odor and a boiling point of 92°0, soluble in alcohol and ether used in perfumes and pharmaceuticals and for flavoring. T-so val-3r al-d3,hTd ... 

Raffinate-II typically consists of40 % 1-butene, 40 % 2-butene and 20 % butane isomers. [RhH(CO)(TPPTS)3] does not catalyze the hydroformylation of internal olefins, neither their isomerization to terminal alkenes. It follows, that in addition to the 20 % butane in the feed, the 2-butene content will not react either. Following separation of the aqueous catalyts phase and the organic phase of aldehydes, the latter is freed from dissolved 2-butene and butane with a counter flow of synthesis gas. The crude aldehyde mixture is fractionated to yield n-valeraldehyde (95 %) and isovaleraldehyde (5 %) which are then oxidized to valeric add. Esters of n-valeric acid are used as lubricants. Unreacted butenes (mostly 2-butene) are hydroformylated and hydrogenated in a high pressure cobalt-catalyzed process to a mixture of isomeric amyl alcohols, while the remaining unreactive components (mostly butane) are used for power generation. Production of valeraldehydes was 12.000 t in 1995 [8] and was expected to increase later. 

The first natural product synthesis that utilized the Stetter reaction was reported by Stetter and Kuhhnann in 1975 as an approach to aT-jasmone and dihydrojas-mone (Scheme 21) [93]. Thiazolium pre-catalyst 74 was effective in catalyti-cally generating the acyl anion equivalent with aldehydes 144 and 145, then adding to 3-buten-2-one 146 in good yield. Cyclization followed by dehydration gives cii-jasmone and dihydrojasmone in 62 and 69% yield, respectively, over two steps. Similarly, Galopin coupled 3-buten-2-one and isovaleraldehyde in the synthesis of ( )-rran5-sabinene hydrate [94]. 

The previously discussed reductions by yeast of isovaleraldehyde to isoamyl alcohol, of p-xyloquinone to p-xylohydroquinone and of sodium thiosulfate to hydrogen sulfide have also been accomplished with Bacterium coli and Bacterium lactis aerogenes. Phytochemical reduction of d,l-valeraldehyde (methylethylacetaldehyde) with Termobacterium mobile Lindner Pseudomonas Lindneri) takes a practically quantitative course and yields an amyl alcohol containing 17 % excess of the dextrorotatory component. Cahill achieved especially favorable results by the reduction of isovaleraldehyde with growing bacteria instead of with their mass cultures. 

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