1 Classification reactions Nitriles

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. 

The nitrogen-containing groups, other than the amino, that are commonly met are the amide, nitrile, iniide, nitro. and azo. As a general procedure, individuals of the first three types are subjected to hydrolysis and those of the last two are converted into reduction products. Definite instructions for these reactions have already been given in connection with the Classification Reactions, page 146, and they will therefore not be repeated here. 

The 1,3-dipolar cycloaddition of organic azides with nitriles could give rise to two regioisomers. Since organic azides are Type II 1,3-dipoles on the Sustmann classification (approximately equal HOMO-LUMO gaps between the interacting frontier orbital pairs) the reactions could be dipole HOMO or LUMO controled and the regioselectivity should be determined by the orbital coefficients for the dominant HOMO-LUMO interaction. Such systems show U-shaped kinetic curves in their... 

Classification and Organization of Reactions Forming Difunctional Compounds. This chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and olefin. Reactions that form difunctional compounds are classified into sections on the basis of the two functional groups of the product. The relative positions... 

NIOSH REL (NitrUes) CL4mg/mV15M DOT CLASSIFICATION 6.1 Label Poison SAFETY PROFILE Poison by ingestion, skin contact, inhalation, intraperitoneal, and subcutaneous routes. Readily decomposes to HCN and acetone. Keep cool and do not store for long periods. Combustible when exposed to heat or flame. To fight fire, use CO2, dry chemical, alcohol foam. Vigorous reaction with H2SO4. When heated to decomposition it emits toxic fumes of CN . See also NITRILES, HYDROCYANIC ACID, and ACETONE. 

The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases in the length of carbon chains for example, the reactions f-BuOH f-BuCOOH, PhCHgOH PhCOOH, and PhCH=CHCH20H PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated ketones, aldehydes, esters, acids, and nitriles have been placed in Sections 74D and 74E (Alkyls from Alkenes), respectively. 

There are several areas of uncertainty regarding the literature classification of phosgene chemistry. The most common classification is based on the nature of the reaction center and usually lists the reagents, or the products of reaction (isocyanates, carbonates, carbamates, ureas, chloroformates, acid chlorides, isonitrUes, nitriles, carbodiimides, etc.) [1, 2]. 

---