Amylbenzene

Prepare a solution of benzyl magnesium chloride in a 2-litre three-necked flask from 24-3 g. of magnesium turnings, 600 ml. of sodium-dried ether and 126-5 g. (115 ml.) of redistilled benzyl chloride follow the experimental details given under n-Propylbenzene (Section IV,7). Cool the flask in running water or in ice water. Place a solution of 456 g. of n-butyl-p-toluenesulphonate (Section IV,198) in about twice its volume of anhydrous ether in the dropping funnel, and add it slowly with stirring, at such a rate that the ether just boils a white solid soon forms. The addition is complete after about 2 hours. Pour the reaction product 

1 litre of water and 125 ml. of concentrated hydrochloric acid contained in a 4 or 5-litre beaker the precipitated magnesium p-toluenesulphonate will ultimately pass into solution. Separate the ether layer, extract the aqueous layer with about 250 ml. of ether, and add the extract to the original ether layer. Wash the ethereal solution with about 100 ml. of water and dry it with about 10 g. of anhydrous potassium carbonate. Distil off the ether through a short fractionating column on a water bath add 5-7 g. of sodium in small pieces to the residue and reflux for about 

2 hours (in order to remove any benzyl alcohol formed by the atmospheric oxidation of the benzyl magnesium chloride). Decant the solution and distil from an air bath through a well-lagged and efficient fractionating column (compare Sections 11,15-11,17) (1) collect the fraction of b.p. 190-210°. Redistil and collect the n-amylbenzene at 198-203°, The yield is 90 g. 

PROPERTIES TECHNICAL GRADE PROPERTIES PURE GRADE TECHNICAL grade 

Comoostion. weight percent CompotitUm, weight percent  

Purity by freezing point, mot % Purity by freezing point, mol %  

Specific grevity of liquid at 60/80 F 0.B88 Spaciflc gravity ol liguid at 60/60 F irSB28 ms— 

Acidity, diftillatian raiidue neutral Acidity, distillation residue neutral neutral 

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FIGURE l.l Hydrophobic interaction and reversed-phase chromatography (HIC-RPC). Two-dimensional separation of proteins and alkylbenzenes in consecutive HIC and RPC modes. Column 100 X 8 mm i.d. HIC mobile phase, gradient decreasing from 1.7 to 0 mol/liter ammonium sulfate in 0.02 mol/liter phosphate buffer solution (pH 7) in 15 min. RPC mobile phase, 0.02 mol/liter phosphate buffer solution (pH 7) acetonitrile (65 35 vol/vol) flow rate, I ml/min UV detection 254 nm. Peaks (I) cytochrome c, (2) ribonuclease A, (3) conalbumin, (4) lysozyme, (5) soybean trypsin inhibitor, (6) benzene, (7) toluene, (8) ethylbenzene, (9) propylbenzene, (10) butylbenzene, and (II) amylbenzene. [Reprinted from J. M. J. Frechet (1996). Pore-size specific modification as an approach to a separation media for single-column, two-dimensional HPLC, Am. Lab. 28, 18, p. 31. Copyright 1996 by International Scientific Communications, Inc.. Shelton, CT.]... 

I-A1ON0-2-NAPHIH0L-4-SULE0NIC acid, 11, 72 16, 91 17, 91 Aminonaphtholsulfonic acids, coupling to form azo dyes, 16,16 p-Aminophenol, 16, 39 Aminopiperole, 16, 6 /3-Ahinopropionic acid, 16, 1 4-Aminoveratrole, 16, 4 Ammonium dichromate, 16, 74 Ammonium formate, 17, 77 Ammonium thiocyanate, 16, 74 Ammonium vanadate, 13, 1 to w-Amyl alcohol, IS, 17 hri.-Amyl alcohol, 13, 68 -Amylbenzene, 10, 4 -Amyl borate, 13, 17 -Amyl bromide, 16, 41 iso-Amyl iodide, 13, 62 n-Amyl iodide, 13, 62 n-Amybnagnesium bromide, 16, 41... 

Table 4. Retention factors k and column efficiencies N for an unretained thiourea and retained compound amylbenzene in columns packed by different methods [53] ...

The first reactions concerned (Simons and Archer, 27) alkylation of benzene with propylene to form isopropylbenzene, with isobutene to form f-butylbenzene and di-f-butylbenzene, and trimethylethylene to form amylbenzene. Later on (Simons and Archer, 28) studied these and other reactions in more detail and showed that high yields could be obtained and that the product was not contaminated with tars or other obnoxious impurities. It was shown that the products obtained with trimethylethylene were mono- and di-f-amylbenzene, that phenyl-pentane resulted from the use of pentene-2, and that cyclohexene produced cyclohexylbenzene. Cinnamic acid reacted with benzene (Simons and Archer, 29) to form /3-phenylpropionic acid and allyl benzene reacted with benzene to form 1,2-diphenylpropane. It is interesting to note that although allyl alcohol reacted with benzene to form 1,2-diphenylpropane, the intermediate in the reaction, allylbenzene, was isolated and identified. This shows that in this case the hydroxyl reacted at a more rapid rate than the double bond. Both di- and triisobutylene reacted with phenol (Simons and Archer, 30) at 0°, when using hydrogen fluoride containing only relatively small quantities of water, to form f-butyl-benzene, but diisobutylene with 70% hydrogen fluoride produced p-f-octylphenol. Cyclohexene reacted with toluene to form cyclohexyl-toluene and octene-1 rapidly reacted with toluene to form 2-octyltoluene (Simons and Basler, 31). 

FIGURE 5.11 Gradient-elution reversed-phase separation of alkylbenzenes on a Purospher Star RP-18e, 3 am, column (30x4mm i.d.). (A) Non-adjusted linear gradients, 50%-100% acetonitrile in 3min at ImL/ min and at 3mL/min. (B) Adjusted linear gradients, 50%-100% acetonitrile in 3 min at ImL/min and 50%-100% acetonitrile in Imin at 3mL/min. Conditions 40°C, detection UV, 254 nm sample B—benzene, MB—toluene, EB—ethylbenzene, PB—propylbenzene, BB—butylbenzene, AB—amylbenzene, and HB—hexylbenzene. 

Ammonolysis, 401 Ampoules, glass. 205 n-Amylamine, 413, 417 n-Amyl acetate, 383 -Amyl alcohol, 247, 249 n-Amylbenzene, 511, 517 n-Amyl borate, 305 n-Amyl bromide, 279 tao-Amyl bromide, 279 n-Amyl chloride, 273 tao-Amyl chloride, 273 tert.-Amyl chloride, 275 n-Amyl cyanide, 407, 408 Amylene, 239 n-Amyl fluoride, 272, 289 n-Amyl iodide, 288 n-Amyl nitrite, 302, 306... 

Similarly, a product believed to be n-amylbenzene was formed by the reaction of amyl chloride with benzene in the presence of aluminum chloride. It is quite probable, however, that the product reported at boiling at 185-190°C contained much. vec-amy I ben zenes and possibly even a small amount of tert- amylbenzene. In fact, isomerization often accompanies alkylation of aromatic hydrocarbons. 

Methylethylbenzene Ethylisopropylbenzene sec-Amylbenzene Trietbylbenzene Diisopropylbenzene Di-sec-amvlbenzene Dii sopropylnaphthalene Di-sec-amylnaphthalene Isopropyltetralin... 

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