Isobutyryl

Exceptions formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, malonyl, succinyl, glutaryl, furoyl, and thenoyl. 

The commercially important normal to branched aldehyde isomer ratio is critically dependent on CO partial pressure which, in propylene hydroformylation, determines the rate of interconversion of the -butyryl and isobutyryl cobalt tetracarbonyl intermediates (11). 

In contrast to triphenylphosphine-modified rhodium catalysis, a high aldehyde product isomer ratio via cobalt-catalyzed hydroformylation requires high CO partial pressures, eg, 9 MPa (1305 psi) and 110°C. Under such conditions alkyl isomerization is almost completely suppressed, and the 4.4 1 isomer ratio reflects the precursor mixture which contains principally the kinetically favored -butyryl to isobutyryl cobalt tetracarbonyl. At lower CO partial pressures, eg, 0.25 MPa (36.25 psi) and 110°C, the rate of isomerization of the -butyryl cobalt intermediate is competitive with butyryl reductive elimination to aldehyde. The product n/iso ratio of 1.6 1 obtained under these conditions reflects the equihbrium isomer ratio of the precursor butyryl cobalt tetracarbonyls (11). 

Treatment of the diethylketal of methyl isobutyryl ketone with morpholine did not give the above condensation product (63), but led to a mixture of di- and tetrasubstituted isomers (124 and 125). 

Cleavage of oligonucleotide from solid support and removal of A benzoyl and A isobutyryl blocking groups. 

Although /3-oxidation is universally important, there are some instances in which it cannot operate effectively. For example, branched-chain fatty acids with alkyl branches at odd-numbered carbons are not effective substrates for /3-oxidation. For such species, a-oxidation is a useful alternative. Consider phy-tol, a breakdown product of chlorophyll that occurs in the fat of ruminant animals such as sheep and cows and also in dairy products. Ruminants oxidize phytol to phytanic acid, and digestion of phytanic acid in dairy products is thus an important dietary consideration for humans. The methyl group at C-3 will block /3-oxidation, but, as shown in Figure 24.26, phytanic acid a-hydroxylase places an —OFI group at the a-carbon, and phytanic acid a-oxidase decar-boxylates it to yield pristanie add. The CoA ester of this metabolite can undergo /3-oxidation in the normal manner. The terminal product, isobutyryl-CoA, can be sent into the TCA cycle by conversion to succinyl-CoA. 

FIGURE 24.26 Branched-chain fatty acids are oxidized by o -oxidation, as shown for phytanic acid. The product of the phytanic acid oxidase, pristanic acid, is a suitable substrate for normal /3-oxidation. Isobutyryl-CoA and propionyl-CoA can both be converted to suc-cinyl-CoA, which can enter the TCA cycle. 

A simple aniline derivative acts as a prostatic antiandro-t (>n. Its synthesis involves simple acylation of disubstituted iiriiline 13 with isobutyryl chloride to give flutamide (14). 

Isobutyryl chloride Ammonia Hydrogen chloride Bromine Calcium hydroxide... 

Fig. 7-11. Separation of amino acids after derivatization with OPA and A -isobutyryl-L-cysteine. Column Superspher 100 RP-18 (4 ptm) LiChroCART 125-4, mobile phase 50 mM sodium acetate buffer pH 7.0/sodium acetate buffer pH 5.3/methanol, flowrate 1.0 ml min temperature 25 °C detection fluorescence, excitation 340 nm/emission 445 nm. Sample diluted orange juice. (Merck KGaA Application note W219189 reproduced with permission from H. P. Fitznar, Alfred-Wegener-Insti-tute for Polar and Marine Research.)...

Isobutylene, reaction with chlorosul fonyl isocyanate, 46, 52 Isobutyryl fluoride, 45, 6 Isocyanates, acyl, derivatives of, 46, 17... 

Fig. 9. Intensity of maximum polarization (100 MHz) of chloroform produced in the thermolysis (80°C) of isobutyryl peroxide (0-2 m) in hexachlorobutodiene containing bromotriohloromethane. Data of Kaptein et cU., 1971.

Iron tricarbonyl dieme complex, 57, 16 Isobutyl chloroform.ate, 59, 165 Isobutylene, 59, 164 Isobutyl fluoride, 5, 73 Isobutyryl chloride, 59, 29 Isocyanato acid chlotrides, from amino acids, 59, 200... 

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