W-Butyl Chloride

The major part of the w-amyl benzene distils at 199-201°. A careful fractionation of the distillate that comes over around 75° yields 24 g. (26 per cent of the theoretical amount) of w-butyl chloride boiling at 76-80°. 

Hollabaugh and Chessick (301) concluded from adsorption studies with water, m-propanol, and w-butyl chloride that the surface of rutile is covered with hydroxyl groups. After evacuation at 450°, a definite chemisorption of water vapor was observed as well as of n-propanol. The adsorption of -butyl chloride was very little influenced by the outgassing temperature of the rutile sample (90 and 450°). A type I adsorption isotherm was observed after outgassing at 450°. Apparently surface esters had formed, forming a hydrocarbonlike surface. No further vapor was physically adsorbed up to high relative pressures. 

Aromatic sulfides analogous to thiophenols constitute a group of molecules that fulfils the structural conditions necessary for the observation of FET (Sec. 2.4), i.e. they exhibit a low barrier to rotation about the Qp2 S bond. Thus, the torsion motions of the substituents can be accompanied by considerable fluctuation of the electrons in the highest molecular orbitals with two extreme examples of conformers, planar and vertical. The presence of two radical cation conformers was deduced as primary products of the bimolecular free electron transfer (FET) from aromatic sulfides PhSCH2Ph, PhSCHPhj, and PhSCPhg to w-butyl chloride radical based on the nanosecond pulse radiolysis experiments. ... 

As we can see in some cases this reaction yields a single alkene, and in other cases yields a mixture. w-Butyl chloride, for example, can eliminate hydrogen only from C-2 and hence yields only 1-butene. jec-Butyl chloride, on the other hand, can eliminate hydrogen from either C-1 or C-3 and hence yields both 1-butene and 2-butene. Where the two alkenes can be formed, 2-butene is the chief product this fact fits into a general pattern for dehydrohalogenation which is discussed in Sec. 5.14. 

The very rapid oxidation of phenols by solvent radical cations can be expected to yield phenol radical cations as the first products. These species are short-lived, except in highly acidic solutions, and were not observed in the microsecond pnlse radiolysis experiments described above. They were detected, however, in frozen matrices and with nanosecond pulse radiolysis Gamma irradiation of phenols in w-butyl chloride or in l,l,2-trichloro-l,2,2-trifluoroethane (Freon 113) at 77 K produced phenol radical cations, which were detected by their optical absorption and ESR spectra . Annealing to 133 K resulted in deprotonation of the radical cations to yield phenoxyl radicals. Pulse radiolysis of p-methoxyphenol and its 2,6-di-fert-butyl derivative in w-butyl chloride at room temperature produced both the phenol radical cations and the phenoxyl radicals. The phenol radical cations were formed very rapidly k = 1.5 x 10 ° M s ) and decayed in a first-order process k = 2.2 x 10 s ) to yield the phenoxyl radicals. The phenoxyl radicals were partially formed in this slower process and partially in a fast process. The fast process of phenoxyl formation probably involves proton transfer to the solvent along with the electron transfer. When the p-methoxy group was replaced with alkyl or H, the stability of the phenol radical cation was lower and the species observed at short times were more predominantly phenoxyl radicals. 

Isomerization is observed with higher alkyl halides, as in Friedel-Crafts reactions isopropylphosphonic dichloride is stated to be the sole product from n-propyl chloride,190,191 and terf-pentyl chloride undergoes C-C fission, yielding the tert-butyl acid.193 On reduction by lithium tetrahydroaluminate the phosphonic chloride formed from w-butyl chloride gives a primary phosphine that is shown by 31P-nuclear magnetic resonance to consist of n- and sec-butylphosphine in the proportions 5 95 and the product from n-octyl chloride was similarly shown to contain all four position isomers.194... 

The long-known alfin polymerization of butadiene recently has also become important industrially. The alfin catalyst is so called because it originally resulted from the transformation of an alcohol and an olefin (e.g., sodium isopropylate and alkyl sodium). Commercially, the best means of producing the catalysts is to proceed from isopropanol, sodium, and w-butyl chloride ... 

Besides methanol, many other polar and non-polar modifiers have also been used to successfully improve the separation in SFC. These modifiers include acetone, acetonitrile, acetic acid, butane, butanol, w-butyl chloride, carbon tetrachloride,dioxane, ethanol, formic acid, heptane, hexane, -hexylamine, methylene chloride, nitromethane, propanol, proprionitrile, tetrahydrofiiran, toluene, triethanolamine, trifluoroacetic acid, trifluoroethanol, trimethyl phosphate, and water. 

Look up the density of w-butyl chloride (1-chlorobutane). Assume that this alkyl halide was prepared instead of the bromide. Decide whether the alkyl chloride would appear as the upper or the lower phase at each stage of the separation procedure after the reflux, after the addition of water, and after the addition of sodium bicarbonate. 

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