Primary alkyl physical properties

Alkyl orthophosphate triesters, 79 41 terteAlkyl peroxycarbamates, decomposition of, 78 486 Alkyl peroxyesters, 78 478-487 chemical properties of, 78 480 487 physical properties of, 78 480 primary and secondary, 78 485 synthesis of, 78 478-480 synthetic routes to, 78 479 tert-Alkyl peroxyesters, 78 480 84, 485 as free-radical initiators, 74 284-286 properties of, 78 481-483t uses of, 78 487 Alkylperoxy radical, 74 291 Alkyl phenol ethoxylates, 8 678, 693 ... 

Carlier fundamental studies of autoxidations of hydrocarbons have concentrated on liquid-phase oxidations below 100 °C., gas-phase oxidations above 200°C., and reactions of alkyl radicals with oxygen in the gas phase at 25°C. To investigate the transitions between these three regions, we have studied the oxidation of isobutane (2-methylpropane) between 50° and 155°C., emphasizing the kinetics and products. Isobutane was chosen because its oxidation has been studied in both the gas and liquid phases (9, 34, 36), and both the products and intermediate radicals are simple and known. Its physical properties make both gas- and liquid -phase studies feasible at 100°C. where primary oxidation products are stable and initiation and oxidation rates are convenient. 

The existence of such an inner salt is well established by the physical properties of many amino acids and by the chemical reactions of the higher alkylated amino derivatives formed by converting the primary amine group into secondary and tertiary alkyl amine groups. 

The use of dialkylsulfate, R SO, and base to alkylate lignin produces a product in which the aromatic and primary and secondary, aliphatic alcohols (109,110) are alkylated. Some tertiary aleohol groups may escape alkylation (111). These products are extensively hydrophobic since almost all of the acidic alcohol groups are now capped as ethers and all carboxylic acid groups have been converted to esters. Unless other ionic functional groups are present, these products dissolve only in nonpolar or organic solvents and have the physical properties of a thermoplastic. 

Because there are only primary and tertiary hydrogen atoms in 146, the relative percent of 149 is 9/10 x 1 and the relative percent of 93 is 9/10 x 5.2. The percent of 149 is therefore 0.9/(0.9 -t- 0.52) = 0.9/1.42 = 0.63 x 100 = 63%. The percentage of 93 is 0.52/(0.9 -i- 0.52) = 0.52/1.42 = 0.37 x 100 = 37%. The mixture of two chlorinated products is predicted to be a ratio of 63 37, 63% of 149 and 37% of 93. These alkyl chlorides are isomers, and they should have different but quite similar physical properties, so they may be difficult to separate. The difference in rate between primary and tertiary is only a factor of five, so reaction is not selective for one product because the radical intermediate is not very selective for one type of hydrogen atom over another. In other words, there will be a mixture and no product is favored to a great extent over the other. 

The synthesis, physical and chemical properties of sulphamides have been the subject of various reviews down through the years333-338. Sowada339 has summarized the three main synthetic routes in the preparation of sulphamides as follows (a) reaction of primary amines (alkyl or aryl) with sulphuryl chloride (b) reaction of primary amines with chlorosulphonic acid (c) reaction of primary amines (alkyl, cycloalkyl and aryl) with sulphamide. 

Most organic azides do not possess the properties required for primary explosives and generally can be characterized by low physical and chemical stability (lower alkyl azides, sulfuryl azide explode even spontaneously [8, 11]), high sensitivity to mechanical stimuli (lower aUcyl azides, acyl azides e.g., carbonyl diazide explode on contact with a glass rod [30]), low thermal stability (e.g., cyanogen azide, l,3,5-triazido-2,4,6-trinitrobenzene, dicyanamid azide, esters of azidoacetic acid [8]), or sensitivity to light [127]. 

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