Reduction and Hydrolysis of Nitriles

Hydrolysis of nitriles normally requires quite harsh conditions and long reaction times [101,102]. Applying microwave irradiation for this type of re- 

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Allyl bromides may be converted to j8,y-unsaturated ketones by reaction with nitrile oxides followed by reduction and hydrolysis of the resulting oxime (Scheme... 

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

Methods of synthesis for carboxylic acids include (1) oxidation of alkyl-benzenes, (2) oxidative cleavage of alkenes, (3) oxidation of primary alcohols or aldehydes, (4) hydrolysis of nitriles, and (5) reaction of Grignard reagents with CO2 (carboxylation). General reactions of carboxylic acids include (1) loss of the acidic proton, (2) nucleophilic acyl substitution at the carbonyl group, (3) substitution on the a carbon, and (4) reduction. 

A number of biotransformations have been accomplished by rhodococci, including, for example, the hydrolysis of nitriles including polyacronitriles (Tauber et al. 2000), and the reduction of the conjugated C=C double bond in 2-nitro-l-phenylprop-l-ene (Sakai et al. 1985). 

The chiral cyanohydrins also lead directly to a-hydroxy acids by hydrolysis (sequence B) [69] and to protected a-hydroxy aldehydes by first hydroxyl group protection, followed by reduction of the nitrile and hydrolysis of the intermediate imine (not shown) (sequence C) [114]... 

Copper-catalysts promoted with i) other group VIA or VIIIA metals and ii) alcaline or alcaline earth elements (IA or IIA) are used for selective hydrogenation of various organic compounds (1). Moreover Cu(Co) Zn-Al catalysts were extensively studied for the synthesis of methanol and of light alcohols (2,3). More recently, due to the development of fine chemical processes, detailed studies of copper catalysts were carried out in order to show, like for noble metals, the effect of supports (SMSI), of promoters and of activation-on metal dispersion or reduction, on alloy formation... For example modified copper catalysts are known for their utilization in the dehydrogenation of esters (4-6), in the hydrolysis of nitriles (7), in the selective hydrogenation of nitriles (8), in the amination of alcohols (9)... 

Confalone demonstrated another route through a C-C bond-forming process to form the 19-membered ansa-ring. Closure of this ring was designed so that a dipolar cyclo-addition could be utilized between a simple terminal olefin and nitrile oxide (-C=N -> 0 ), which was provided from a nitroalkane precursor such as 8. A macrolactam ring was cyclized in the form of the isoxazoline product 9. The maytansine model 10 was obtained after reduction and hydrolysis into a P-oxyketone followed by cyclization of the carbamate ring. 

Lactonization Isomerization Oxidation of alcohols to aldehydes ketones Reduction of aldehydes and ketones to alcohols Oxidation of amino groups to nitro groups Hydrolysis of nitriles to amides and caibo Q lic acids Functional group alteration... 

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