Reduction alkaline media

Azoxybenzene is readily prepared by reduction of nitrobenzene in an alkaline medium with dextrose or sodium arsenite ... 

Reduction. These hydroxybenzaldehydes can be reduced by catalytic hydrogenation over palladium or platinium to yield the corresponding hydroxybenzyl alcohols, but the electrolytic reduction in an alkaline medium gives the coupling product l,2-bis(4-hydroxyphenyl)ethane-l,2-diol in very good yield from 4-hydroxybenzaldehyde (49—51). 

Two different sets of experimental conditions have been used. Buu-Hoi et al. and Hansen have employed the method introduced by Papa et using Raney nickel alloy directly for the desulfurization in an alkaline medium. Under these conditions most functional groups are removed and this method is most convenient for the preparation of aliphatic acids. The other method uses Raney nickel catalysts of different reactivity in various solvents such as aqueous ammonia, alcohol, ether, or acetone. The solvent and activity of the catalyst can have an appreciable influence on yields and types of compounds formed, but have not yet been investigated in detail. In acetic anhydride, for instance, desulfurization of thiophenes does not occur and these reaction conditions have been employed for reductive acetylation of nitrothiophenes. Even under the mildest conditions, all double bonds are hydrogenated and all halogens removed. Nitro and oxime groups are reduced to amines. 

Support for this suggestion comes from many quarters. Reduction of the jS-carboline anhydro-bases with sodium and alcohol or with tin and hydrochloric acid gives the 1,2,3,4-tetrahydro derivatives, as does catalytic reduction over platinum oxide in an alkaline medium. On the other hand, catalytic reduction with platinum oxide in acetic acid results in the formation of the 5,6,7,8-tetrahydro-j3-carbolinium derivatives (see Section III,A,2,a). It should be noted, however, that reduction of pyrido[l,2-6]indazole, in which the dipolar structure 211 is the main contributor to the resonance hybrid, could not be effected with hydrogen in the presence of Adams catalyst. 

An additional means of eliminating hydrogen ions as quickly as they are produced during reduction is to carry out precipitation in an alkaline medium. The following set of equations represents this particular case ... 

The reductive cleavage of the N-O bond in the isoxazolidine 162 unmasks the 1,3-amino alcohol moiety. Thus, isoxazolidines can be viewed as direct precursors of 7-amino alcohols. The reductive cleavage of the cycloadduct proved difficult. W2 Raney-Ni and nickel boride were both ineffective. In contrast, nickel-aliminium alloy in an alkaline medium efficiently reduced the N-O bond at room temperature in the presence of a base (Equation 27) <1997TA109>. 

If the reduction takes place in an alkaline medium, products derived from two molecules of nitrobenzene are formed. In these products the unaltered portions of the nitrobenzene molecules are united by means of nitrogen atoms. These substances are ... 

Most reactions with hydrazine are carried out with aldehydes and ketones in the presence of alkali. The reduction proper is preceded by formation of hydrazones that decompose in alkaline medium at elevated temperatures to nitrogen and compounds in which the carbonyl oxygen has been replaced by two hydrogens. The same results are obtained by alkaline-thermal decomposition of ready-made hydrazones of the carbonyl compounds. Both reactions are referred to as Wolff-Kizhner reduction [280]. 

Direct preparation of azo compounds in good yields is accomplished by treatment of nitro compounds with lithium aluminum hydride [576], with magnesium aluminum hydride [577], with sodium bis(2-methoxy ethoxy)aluminum hydride [575], with silicon in alcoholic alkali [331] or with zinc in strongly alkaline medium [578], Hydrazobenzene was obtained by controlled hydrogenation of nitrobenzene in alkaline medium (yield 80%) [572] and by reduction with sodium bis 2-methoxyethoxy)alumium hydride (yield 37%) [544],... 

In an acidic medium, a PEMFC fed with ethanol allows power densities up to 60 mW cm to be reached at high temperatures (80-120 °C), but this needs platinum-based catalysts, which may prevent wider applications for portable electronic devices. On the other hand, in an alkaline medium, the activity of non-noble catalysts for ethanol or ethylene glycol oxidation and oxygen reduction is sufficient to reach power densities of the order of 20 mW cm at room temperature. This opens up the hope of developing SAMFCs that are particularly efficient for large-scale portable applications. 

Reticuline (38), one of the most important intermediates in the biosynthesis of opium alkaloids, has been synthesized in racemic form (Scheme 7) (78). 6-Methoxy-7-benzyloxyisoquinoline (39), prepared from O-benzylisovanillin via a modified Pomeranz-Fritsch isoquinoline synthesis, was treated with benzoyl chloride and potassium cyanide to obtain Reissert compound 40. Alkylation of the anion generated from 40 with 3-benzyloxy-4-methoxybenzyl chloride gave the corresponding 1-substituted Reissert compound 41 which was hydrolyzed in alkaline medium to 1-benzylisoquinoline derivative 42. Quatemarization of 42 with methyl iodide followed by sodium borohydride reduction and debenzylation led to ( )-reticuline (38) in about 25% overall yield from 39. 

The reduction of aromatic nitro compounds with glucose and other carbohydrates in an alkaline medium has been a much neglected reaction procedure (see, for example, Bigelow and Palmer [46, Note 7]). The reaction has much to... 

The reduction of arsenic compounds to arsine by nascent hydrogen may also be effected in alkaline medium thus in the presence of caustic alkali with zinc,10 aluminium11 or sodium amalgam,12 and also in ammonia or ammonium chloride with zinc.13... 

The tetraphenylallene system represents a particularly elegant confluence of chemistry, electrochemistry, and EPR. The carbanion of 1,1,3,3-tetraphenyl-propene is formed spontaneously in alkaline medium. Or it can be formed by the two-electron reduction of 2-ethoxy-1,1,3,3-tetrapheny 1-prop- 1-ene (at 2.2 V) or of tetraphenylallene (at -2.11 V). The tetraphenylallyl radical is then produced by anodic oxidation of the carbanion at -0.95 V. Its EPR spectrum was obtained using the two-stage flow cell described earlier [37]. 

On reaction with zinc dust in alkaline medium, naphthalic acid is subjected to reductive dimerization with so-called deoxynaphthalic anhydride 366 as the result (13CB1484). The formation of diarylnaphthalides 371 on... 

---