Dimethylethyl benzenesulfenamide

Transformations. Dialkylated A -dimethyldithiocarbamoyl-acetonitriles are transformed into ketones by W-bromosuccinimide bromination or by basic hydrolysis (eq 3), and they are hydrolyzed in acidic ethanol to produce a-mercapto carboxylates. Bromination of (1) in methanol leads to the formation of l,3-dithietan-2-ylium ion. Alkylated N,N-dimethyldithiocarbamoylacetonitriles are reductively desulfurized to a-branched nitriles with tributylstannane in the presence of a catalytic amount of azobisisobutyronitrile (eq 4).  

Related Reagents. 7V,7V-Diethylaminoacetonitrile 2-(2,6-Dimethylpiperidino)acetonitrile Lithioacetonitrile Methoxy-acetonitrile 

Yoshiro Masuyama Sophia University, Tokyo, Japan 

Preparative Methods commercially available or prepared by reacting tert-butylamine with benzenesulfenyl chloride in ether. Purification distillation at 94—95 °C/7 mmHg. 

Oxidation of Alcohols. AA(1,1-Dimethylethyl)benzenesul-fenamide is most commonly used as a catalyst for the oxidation of alcohols to aldehydes and ketones. The reaction requires the use of stoichiometric amounts of W-chlorosuccinimide (NCS) in order to convert the sulfenamide to the corresponding sulfinimidoyl chloride, which is the active oxidant in the reaction. In addition, it is necessary to perform the reaction in the presence of a base, most commonly potassium carbonate, in order to trap the HCl that is formed. The yield of the reaction is improved by the presence of a dehydrating agent, usually molecular sieves (MS). The preferred solvent for the reaction is dichloromethane. 

---

As mentioned above, the active oxidant in this reaction is 7V-(l,l-dimethylethyl)benzenesulfinimidoyl chloride, and alcohols can be oxidized to the carbonyl compounds using stoichiometric amounts of this compound. However, (V-(l,l-dimethylethyl)benzenesulfenamide and other by-products of the oxidation can be difficult to separate from the desired aldehyde or ketone, so it is generally advantageous to use the catalytic method. 

---