Benzaldehyde secondary alcohol formed from

N,N-Dialkylformamide or ethyl formate" and Grignard reagents have been used with some success however, the former reaction is complicated and frequently produces tertiary amines as the chief product, and the latte forms secondary alcohols by further reaction of the aldehyde. Substituted benzaldehydes have been prepared from aryllithium compounds and N-methylformanilide in good yields. ... 

The instability of some compounds under further irradiation is especially remarkable. We found that at first the secondary photo roduct is formed from the primary product and therefore has to be considered as a final product. Under these conditions benzaldehyde, the primary photoqrroduct of toluene, produces benzyl alcohol in the presence of H2O2. The addition of oxygen considerably accelerates the degradation rate, whereas the formation of phenols and hydroxylated biphenyls as well as the dimerization reactions under extended irradiation will increase. At X> 290 nm under normal conditions, we found in experiments with xylenes in aqueous H2O2, transformation rates up to 60% whereas in the corresponding reaction in dark no transformation occurred (Table 2). 

Reduction of aldehydes generates primary alcohols ketones are formed by reducing secondary alcohols. This is usually an enzymatic readion. For example, benzyl alcohol arises from benzaldehyde (see Section 8.2.2.1.2). 

The difference between primary and secondary kinetic effects can be elucidated by using the oxidation of benzyl alcohol by nicotinamide adenine dinucleotide (NAD+) as an example (Scheme 10.1 (A)). This reaction is catalyzed by alcohol dehydrogenase (ADH), and has been extensively studied [10, 21-27]. In this reaction, the hydrogen at position is transferred from benzyl alcohol to NAD+, forming benzaldehyde and reduced nicotinamide (NADH), making the primary position. Conversely, is retained upon reaction, making this the secondary position. 

Benzaldehyde is reduced about 400 times faster than acetophenone in isopropanoT (Chapter 6) While amines react with acetic anhydride quite rapidly at room temperature (reaction complete in a few hours), alcohols react extremely slowly in the absence of a base (Chapter 10) Secondary and tertiary amides are difficult to hydrolyse but a similar mechanism is successful with only a little water and plenty of a strong base (Chapter 10) Acyclic hemiacetals form relatively slowly from an aldehyde or ketone plus an alcohol, but their rate of formation is greatly increased either by acid or by base (Chapter 11). 

---