Testing aromatic formation

A wide-ranging study by French researchers (IFP and Elf) on oxidation mechanisms in solvent refined, isomerized wax, and poly-alpha-olefin (PAO) base stocks oxidation was published in 1995.33 Included was the finding that in modified TFOUT tests, insolubles formation was related to aromatics content, becoming significant at about 6% CA, but surprisingly not increasing further with CA (Figure 5.19). 

Primary aromatic amines differ from primary aliphatic amines in their reaction with nitrous acid. Whereas the latter yield the corresponding alcohols (RNHj — ROH) without formation of intermediate products see Section 111,123, test (i), primary aromatic amines 3neld diazonium salts. Thus aniline gives phcnyldiazonium chloride (sometimes termed benzene-diazonium chloride) CjHbNj- +C1 the exact mode of formation is not known, but a possible route is through the phenjdnitrosoammonium ion tlius ... 

Sulphinic acids. Aromatic sulphinic acids are found in Solubility Group II. They may be detected by dissolving in cold concentrated sulphuric acid and adding one drop of phenetole or anisole when a blue colour is produced (Smiles s test), due to the formation of a para-substituted aromatic sulphoxide. Thus the reaction with benzenesulphinic acid is ... 

Hydrazides of vicinal acetylene-substituted derivatives of benzoic and azole carboxylic acids are important intermediate compounds because they can be used for cyclization via both a- and /3-carbon atoms of a multiple bond involving both amine and amide nitrogen atoms (Scheme 131). Besides, the hydrazides of aromatic and heteroaromatic acids are convenient substrates for testing the proposed easy formation of a five-membered ring condensed with a benzene nucleus and the six-membered one condensed with five-membered azoles. 

Boronic acids (69 and 70) (Fig. 45) with more than one boronic acid functionality are known to form a polymer system on thermolysis through the elimination of water.93 Specifically, they form a boroxine (a boron ring system) glass that could lead to high char formation on burning. Tour and co-workers have reported the synthesis of several aromatic boronic acids and the preparation of their blends with acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) resins. When the materials were tested for bum resistance using the UL-94 flame test, the bum times for the ABS samples were found to exceed 5 minutes, thereby showing unusual resistance to consumption by fire.94... 

The preparation of macrocyclic diimines and endocyclic enamines are represented by the procedures for the formation of 1,10-DIAZA-CYCLOOCTADECANE and N-METHYL-2-PHENYL-A2-TETRA-HYDROPYRIDINE. Other procedures representative of alkylation reactions and aromaticity (TRI-i-BUTYLCYCLOPROPENYL FLUOROBORATE) round out a volume of tested experimental procedures of general value. 

In our calculations we will first discuss our results starting with both the 2-and 3- octyl cations (the 4- octyl cation cannot form a 1,6-p-H-structure). The n-octane conversion to aromatics, as described by Davis (8), is a good test of our proposed mechanisms, for several reasons (1) his experimental observation would require the formation of approximately equal amounts of 1,2-dimethylcyclohexane (o-xylene) and ethylcyclohexane (ethylbenzene), even though in our mechanism the structure of the needed 1,6-p-H cation intermediates are quite different, and (2) the formation of to- and p-xylene requires a prior isomerization of n-octane to 2- and 3- methylheptane, and this must be a faster reaction than the dehydrocyclization (or at least competitive with it). If our mechanisms are valid, we should be able to reproduce some aspects of the above results. 

The detailed modeling of soot formation in the shock tube pyrolysis of acetylene [106] and other fuels [107] provides the central basis for the fuel-independent general mechanisms suggested here. It must be noted, as well, that a large body of work by Howard et al. [108, 109] on premixed flames with regard to formation of aromatic species provides direct tests of the proposed mechanisms and are key to understanding and modeling soot formation. 

In the meantime, all of the higher intermediates shown in Fig. 2 have been tested and numerous comprehensive surveys of this work have appeared (24, 81—83, 91, 93, 112, 113, 132). Some of these simultaneously describe the formation of secondary aromatic substances in wood, i.e. lignans, tannins, flavonoids, etc., which arise by essentially similar routes coupled with acetate metabolism. A few outstanding recent developments may bear repetition here. 

---