M-Butyl chloride

Apparatus and procedure Closely similar to the preparation of tert.-Ci,H3MgCl, cyclohexyl-MgCl and cyclopentyl-MgCl (see Exp. 2). The yield (estimated from the results obtained from reactions with this reagent) is at least 90%. Here, too, it is essential to use M-butyl chloride which is free from butyl alcohol. 

Unlike bromine trifluoride (vide infra), chlorine monofluoride is capable of substituting fluorine for chlorine without catalysts in compounds eliminating chlorine via the intermediate formation of stable carbocations. Chlorine is easily replaced by fluorine at — 50 to — 10 C in /m-butyl chloride and at the secondary carbon atom in 1.2-dichloropropane and 1,2,3-tri-chloropropane.107... 

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 M-butyl chloride boiling at 76-80°. 

The three mixtures will likely be (1) water and M-butyl chloride, (2) water and fx-butyl bromide, and (3) n-butyl bromide and saturated aqueous sodium bromide. 

In the case of isobutane, we get almost four times as much m-butyl chloride (37%) as we would get (10%) if the 1° and 3° hydrogen atoms were equally reactive. The order of reactivity of the hydrogens then must be... 

In a 250 ml. separatory funnel place 25 g. of anhydrous feri.-butyl alcohol (b.p. 82-83°, m.p. 25°) (1) and 85 ml. of concentrated hydrochloric acid (2) and shake the mixture from time to time during 20 minutes. After each shaking, loosen the stopper to relieve any internal pressure. Allow the mixture to stand for a few minutes until the layers have separated sharply draw off and discard the lower acid layer. Wash the halide with 20 ml. of 5 per cent, sodium bicarbonate solution and then with 20 ml. of water. Dry the preparation with 5 g. of anhydrous calcium chloride or anhydrous calcium, sulphate. Decant the dried liquid through a funnel supporting a fluted Alter paper or a small plug of cotton wool into a 100 ml. distilling flask, add 2-3 chips of porous porcelain, and distil. Collect the fraction boiling at 49-51°. The yield of feri.-butyl chloride is 28 g. 

Solvent Effects on the Rate of Substitution by the S l Mechanism Table 8 6 lists the relative rate of solvolysis of tert butyl chloride m several media m order of increasing dielectric constant (e) Dielectric constant is a measure of the ability of a material m this case the solvent to moderate the force of attraction between oppositely charged par tides compared with that of a standard The standard dielectric is a vacuum which is assigned a value e of exactly 1 The higher the dielectric constant e the better the medium is able to support separated positively and negatively charged species 8olvents... 

Benzylic halides resemble allylic halides m the readiness with which they form carbocations On comparing the rate of S l hydrolysis m aqueous acetone of the fol lowing two tertiary chlorides we find that the benzylic chloride reacts over 600 times faster than does tert butyl chloride... 

In a 5-I. round-bottom flask, fitted with a stirrer, separatory funnel and a reflux condenser to the upper end of which a calcium chloride tube is attached, is placed 150 g. of magnesium turnings. A small crystal of iodine (Note i) and about 100 cc, of a mixture of 822 g. (6 moles) of M-butyl bromide and 2 1. of anhydrous ethyl ether are added. As soon as the reaction starts, 350 cc. of anhydrous ether is added and the remainder of the -butyl bromide solution is dropped in at such a rate that the mixture boils continuously. The time of addition (one and one-half hours) may be decreased by cooling the flask externally. Stirring is started as soon as enough liquid is present in the flask. 

Bls(p-fluorophenyl)butyl chloride 4-(4-Chloro-o ,a,a-trifluoro-m-tolyl)-4-piperidinol... 

A mixture of 24 partsof 4,4-bis(p-fluorophenyl)butyl chloride, 20.9 partsof 4-(4-chloro-aXX,a-trifluoro-m-tolyl)-4-piperidinol, 135 partsof sodium carbonate, a few crystals of potassium iodide in 600 parts of 4-methyl-2-pentanone is stirred and refluxed for 60 hours. The reaction mixture is cooled and 150 partsof water is added. The organic layer is separated, dried, filtered and evaporated. The oily residue is crystallized from diisopropylether, yielding 4-(4[Pg.1172]

The method described is successfully used for the alkylation and aralkylation of ethyl and /-butyl phenylacetate.3 The alkylation of ethyl phenylacetate with methyl iodide, M-butyl bromide, benzyl chloride, and a-phenylethyl chloride affords the corresponding pure monoalkylation products in 69%, 91%, 85%, and 70% (erythro isomer) yields, respectively. The alkylation of /-butyl phenylacetate with methyl iodide, M-butyl bromide, a-phenylethyl chloride, and /3-phenylethyl bromide gives the corresponding pure monoalkylated products in 83%, 86%, 72-73%, and 76% yields, respectively. 

Certain of the monoalkylated ethyl phenylacetates have been further alkylated with alkyl and aralkyl halides to produce the corresponding disuhstituted phenylacetic esters.4 Ethyl 2-phenyl-propanoate has been alkylated by methyl iodide to give pure ethyl 2-methyl-2-pheny]propanoate in 81% yield. Similarly, the alkylations of ethyl 2-phenylhexanoate with methyl iodide, M-butyl bromide, and benzyl chloride gave the corresponding pure dialkylated products in 73%, 92%, and 72% yields, respectively. 

The products in such cases contain complexes between M-butyl-magnesium chloride and the particular alkoxide employed. With the stated Low proportions of alkoxides, these complexes broadly resemble the alkoxide-free materials, but increased proportions of the alkoxide component give complexes having generally decreased chemical reactivity (see references 3 and 4). 

In order to obtain compounds with Ti-O-P and Zr-O-P units, the hexaethoxy-derivative, NsPaCOEOg, was treated with titanium and zirconium tetrachlorides. In each case, hygroscopic solids of the type NaPaCOEOiOaMCU (M = Ti or Zr) and ethyl chloride were obtained. The degree of polymerization of these solids was 1.6—1.8, and on the basis of their i.r. and n.m.r. spectra, two alternative structures, (46) and (47), were proposed. In an alternative route to the same type of compound, N3P3CI6 was treated with tetra-n-butoxytitanium in o-xylene. Butyl chloride was liberated and a solid was obtained which has been assigned the structure (48). Its thermal decomposition was studied by differential thermal analysis. 

Hartsough, D. S. and Merz Jr., K. M. Potential of mean force calculations on the SN1 fragmentation of tert-butyl chloride, J.Phys. Chem., 99 (1995), 384-390... 

To prepare a THF solution of butylmagnesium chloride from butyl chloride, the procedure described by Olah and Arvanaghi (Olah, G. A. Arvanaghi, M. Org. Synth., Coll. Vol. VI11990, 451) for the preparation of 2-phenylethylmagnesium... 

Attempts to obtain alkylcarbonium complexes by dissolving alkyl chlorides (bromides) in liquid Lewis acid halides (stannic chloride, titanium (IV) chloride, antimony pentachloride, etc.) as solvent were unsuccessful. Although stable solutions could be obtained at low temperature with, for example, t-butyl chloride, the observed N.M.R. chemical shifts were generally not larger than 0 5 p.p.m. and thus could be attributed only to weak donor-acceptor complexes, but not to the carbonium ions. The negative result of these investigations seems to indicate that either the Lewis acids used were too weak to cause sufficient ionization of the C—Cl bond, or that the solvating effect of the halides... 

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. 

TABLE 7. Butyllithium in the presence of butyl chloride, bromide and iodide (0.50 M initial concentrations) half-hves ti/2 (in hours) as a function of the solvent benzene (BNZ) or diethyl ether (DEE) at ambient temperature ... 

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