Primary, secondary and tertiary compounds

The chemical properties of primary and secondary nitro compounds differ considerably from those of tertiary nitro compounds. This is due to the presence of active hydrogen atoms in the first two. The difference appears most clearly when nitro compounds are treated with alkalis. As long ago as 1872 Meyer [48,48a] observed that certain nitroparaffins were soluble in sodium hydroxide solutions. In 1888 Michael [49], and later Nef [50], suggested that the salt formed in the 

Experimental evidence of the existence of aci-forms has soon been provided. In 1895 Holleman [51] found that m- nitrophenylnitromethane yielded a yellow salt, which under the influence of hydrochloric acid was converted initially into a yellow substance having a high electrical conductivity. After some time, the product changed into a colourless substance, showing no electrical conductivity. The aci-structure was assigned to the yellow substance, and that of a pseudoacid to the colourless one. 

This observation was confirmed by Hantzsch and Schultze [52] in 1896 with phenylmtromethane. The aci-form of phenylnitromethane is a crystalline product. Its melting point is 84°C. It charges spontaneously into the normal, liquid form. Aci-forms differ from the normal ones in that they turn brown-red with ferric chloride. 

Thus the anion of the aci-form of nitroparaffins can be written in two ways Ilia and Illb 

However, these structures were in doubt for a number of years. Strong evidence for criticizing them was given in 1927 by Kuhn and Albrecht [53], They reported that optically active D- and L-2-nitrobutanes can be converted into their optically active sodium salts and then regenerated without complete racemization. This was confirmed by Shriner and Young [54] who found that 2-nitrooctane behaves similarly. Subsequently the structures la and Ha for the aci-forms and Ilia and Illb for the aci-anion appeared to be excluded as they cannot correspond to dissymmetric configurations. If they were correct, the regenerated nitro compounds should be racemic. 

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Fig. 10. Increments in C-C distances, referred to that in ethane, as present in primary, secondary, and tertiary compounds. Values for A (C-C) and the range of enors are listed in Table 17...

Classifying molecules primary, secondary and tertiary compounds... 

The classification into primary, secondary and tertiary compounds can also be applied to amides. Secondary and tertiary amides are named rather like amines, in that the other alkyl group attached to the nitrogen atom is prefixed by an N for example, N-methylethanamide (Figure 10.43) is a secondary amide, whereas N,N dimethylpropanamide, CH3CH2CON(CH3)2, would be a tertiary amide. 

Special methods are available for particular classes of compounds, Hinsberg s method of separating primary, secondary and tertiary amines (p. 249)-... 

The lower members of other homologous series of oxygen compounds— the acids, aldehydes, ketones, anhydrides, ethers and esters—have approximately the same limits of solubility as the alcohols and substitution and branching of the carbon chain has a similar influence. For the amines (primary, secondary and tertiary), the limit of solubility is about C whilst for the amides and nitriles it is about C4. 

Formic acid forms esters with primary, secondary, and tertiary alcohols. The high acidity of formic acid makes use of the usual mineral acid catalysts unnecessary in simple esterifications (17). Formic acid reacts with most amines to form formylamino compounds. With certain diamines imida2ole formation occurs, a reaction that has synthetic utiHty (18) ... 

Amines are derivatives of ammonia in which one or more of the hydrogens is replaced with an alkyl, aryl, cycloalkyl, or heterocycHc group. When more than one hydrogen has been replaced, the substituents can either be the same or different. Amines are classified as primary, secondary, or tertiary depending on the number of hydrogens which have been replaced. It is important to note that the designations primary, secondary, and tertiary refer only to the number of substituents and not to the nature of the substituents as in some classes of compounds. 

This intermediate attacks compounds containing a variety of functional groups, such as primary, secondary, and tertiary amino nitrogen atoms, carboxyl groups, and sulfhydryl groups (10). 

Rather similar was the paper [PolG36a] which also derives asymptotic formulae for the number of several kinds of chemical compounds, for example the alcohols and benzene and naphthalene derivatives. Unlike the paper previously mentioned, this one gives proofs of the recursion formulae from which the asymptotic results are derived. A third paper on this topic [PolG36] covers the same sort of ground but ranges more broadly over the chemical compounds. Derivatives of anthracene, pyrene, phenanthrene, and thiophene are considered as well as primary, secondary, and tertiary alcohols, esters, and ketones. In this paper Polya addresses the question of enumerating stereoisomers -- a topic to which we shall return later. 

Non-aqueous titrations have been used to quantify mixtures of primary, secondary and tertiary amines,5 for studying sulphonamides, mixtures of purines and for many other organic amino compounds and salts of organic acids. 

Consider now a series of compounds A, that react with two reagents, Bi and B2. A good example is the reactions of alkyl radicals (the A, s are R") with BrCCl3 (B ) and CCI4 (B2). The radicals considered are planar, tt radicals that are primary, secondary, and tertiary, but not bridgehead.21 The scheme is... 

The dienone, which is prepared essentially as described by Benedikt7 and Calo,8 monobrominates a wide range of primary, secondary, and tertiary aromatic amines almost exclusively in the para-position. The procedure described is of general synthetic utility for the preparation of para-brominated aromatic and heteroaromatic amines in high yields and frequently in a high state of purity. The submitters have used this technique to para-brominate many compounds in quantities... 

The reaction of diazo compounds with amines is similar to 10-15. The acidity of amines is not great enough for the reaction to proceed without a catalyst, but BF3, which converts the amine to the F3B-NHR2 complex, enables the reaction to take place. Cuprous cyanide can also be used as a catalyst. The most common substrate is diazomethane, in which case this is a method for the methylation of amines. Ammonia has been used as the amine but, as in the case of 10-44, mixtures of primary, secondary, and tertiary amines are obtained. Primary aliphatic amines give mixtures of secondary and tertiary amines. Secondary amines give successful alkylation. Primary aromatic amines also give the reaction, but diaryl or arylalkyl-amines react very poorly. 

All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyl dioxirane." Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone, various peroxyacids," MeRe03/H202,"" Oxone ," ° tcrt-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds, and sodium perborate." ... 

In classical organic chemistry, nltrosamlnes were considered only as the reaction products of secondary amines with an acidified solution of a nitrite salt or ester. Today, it is recognized that nitrosamines can be produced from primary, secondary, and tertiary amines, and nltrosamides from secondary amides. Douglass et al. (34) have published a good review of nitrosamine formation. For the purposes of this presentation, it will suffice to say that amine and amide precursors for nitrosation reactions to form N-nitroso compounds are indeed ubiquitous in our food supply, environment, and par-... 

A series of palmitoylethanolamine-derived inhibitors has been described in the literature as FAAH inhibitors [77, 78]. This study explored the effect of shortening the chain length and replacement of the ethanolamine head group with primary, secondary and tertiary amide alternatives. Of the compounds synthesised and tested, two compounds gave reasonable affinities for FAAH inhibition, palmitoyl-isopropylamide (63) (IC50 = 13/rM) and palmitoyl-allylamide (64) (IC50 = 3.4/rM). Both these compounds had little affinity for either CBi or CB2 receptors. 

Amongst the secretions of specialised exocrine complexes, the ancillary products which act as sticky compounds are large, often proteinaceous, molecules. Their primary, secondary and tertiary structures being inherently complex are now seen as ideal informational vehicles — alone or in combination with volatile molecules. Much recent work (Sec. 3.2, below) has identified them as the key components involved in close range transmission, and in intra-nasal peri-receptor events. Proteins are semiochemically implicated when their selective removal or presentation alters responsiveness (Belcher et al., 1990 Mucignat-Caretta et al, 1995). 

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