Tert-Butyl benzene chloride

In an alternative procedure 26 g. of anhydrous ferric chloride replace the aluniiniuni chloride, the mixture is cooled to 10°, and the 50 g. of tert.-butyl chloride is added. The mixture is slowly warmed to 25° and maintained at this temperature until no more hydrogen chloride is evolved. The reaction mixture is then washed with dilute hydrochloric acid and with water, dried and fractionally distilled. The yield of tert.-butyl benzene, b.p. 167- 170°, is 60 g. 

Sometimes acylium ions lose carbon monoxide to generate an ordinary carbonium ion. It will be recalled that free acyl radicals exhibit similar behavior at high temperatures. Whether or not the loss of carbon monoxide takes place seems to depend on the stability of the resulting carbonium ion and on the speed with which the acylium ion is removed by competing reactions. Thus no decarbonylation is observed in Friedel-Crafts reactions of benzoyl chloride, the phenyl cation being rather unstable. But attempts to make pivaloyl benzene by the Friedel-Crafts reaction produce tert-butyl benzene instead. With compound XLIV cyclization competes with decarbonylation, but this competition is not successful in the case of compound XLV in which the ring is deactivated.263... 

Dinilro-l-(2-methyl-2-nitropropyl)-benzene, (CH )2.C(N02).CH2.C6H3(N02)2, crysts, mp 68 9° was prepd by reaction or 2,4 dinitrobenzyl chloride with Na salt of 2-propanenitronate (Ref 3) and eso-Trinitro-(tert-butyl)-benzene, (CH3)3C.C6H2(N02)3, yel wh ndls(from ale),... 

A suspension of aluminum chloride (66.5 g, 0.5 mole) in benzene (390 g, 5 moles) is rapidly stirred at 20-30° while tert-buty alcohol (74 g, 1 mole) is added dropwise. The mixture is set aside overnight and then poured on crushed ice and hydrochloric acid. The benzene layer is separated and the aqueous layer is washed with ether. The united benzene-ether solutions are evaporated and the residue is fractionated through a 30-cm column, giving tert-butyl-benzene (65-70%), b.p. 168-170°/740 mm. 

Step 1 Once generated by the reaction of tert butyl chloride and aluminum chloride tert butyl cation attacks the TT electrons of benzene and a carbon-carbon bond is formed... 

A) The preparation of [H-chloroethoxyjchloromethyl]phosphonic acid Acetaldehyde (1.1 mol) and hydroxymethylphosphonlc acid (1 mol) in 500 ml of benzene are saturated with hydrogen chloride gas at 10°C to 15°C. The mixture is aged at 25°C for 24 hr, the solvent distilled out in vacuo and the residue flushed three times with benzene to remove all traces of hydrogen chloride. The residue is taken up in benzene (500 ml), treated with tert-butyl hypochlorite (0.8 mol) and azobisisobutyronitrile (0.8 mm) at 40°C until titration shows the absence of hypochlorite and the solution is then evaporated to yield [(1-chloro-ethoxy)chloromethyll phosphonic acid in the form of an oil. 

The cyclic diazastannylene 1 has been found to be very suitable for this type of reaction 1S5) (cf. also Sect. 4.1). In Eqs. (43) and (44) the chlorine atoms of the Lewis acids are transferred to the divalent tin atom resulting in the formation of 57 and 76 and tin(II) chloride, the latter being insoluble in benzene. In (45) the solubility of the produced compounds is again important because SnS precipitates from the solution thus, the equilibrium is shifted to the right (in Eqs. (43)-(45) R denotes tert-butyl). 

Oxidative coupling of 2-bromo-4,6-di-im-butylphenol (202, Scheme 51) with potassium hexacyanoferrate(III) in a two-phase system consisting of aqueous potassium hydroxide and benzene affords the dibenzofuranone 203 by the mechanism indicated.The dibenzofuranone 203 is a convenient source of 1-dibenzofuranol (205). On boiling with isopropanol, compound 203 provides the tetra-tert-butyl-l-benzofuranol 204, which may be de-butylated by treatment with aluminum chloride in toluene. 1-Dibenzo-furanol (205) is also obtained by direct treatment of the dibenzofuranone 203 with aluminum chloride in toluene. With boiling methanol, however, compound 203 supplies the methoxy analog 206, which on mild debutylation affords 4-methoxy-1-dibenzofuranol (207). ... 

The adduct could also be synthesized from preformed benzophenone. Thus, 5.2 mmoles of benzophenone reacted in 25 ml. of DMSO (80% )-tert-butyl alcohol (20%) containing 5.7 mmoles of potassium tert-butoxide to give a 93% yield of the adduct in 15 minutes at 25°C. The DMSO-benzophenone adduct was also isolated by benzene extraction of the hydrolyzed and acidified oxidates of benzhydryl chloride, benzhydryl bromide, benzhydryl amine, diphenylacetonitrile, and 1,1-diphenylace-tone in DMSO (80% )-tert-butyl alcohol (20% ). 

NEOPHYL CHLORIDE [Benzene (chloro-tert-butyl)-]... 

In a thoroughly dry 500-ml., three-necked, round-bottomed flask fitted with a mechanical stirrer, dropping funnel, and a Y-tube containing a caldum chloride drying tube and a thermometer (Note 1) are placed 24.2 g. (26 ml., 0.20 mole) of a-phenyl-ethylamine (Note 2) and 50 ml. of dry benzene (Note 3). The solution is cooled in an ice-salt bath to 5°, and a solution of 44.5 g. (50 ml., 0.41 mole) of feri-butyl hypochlorite2 (Note 4) in 50 ml. of dry benzene (Note 3) is added at such a rate as to maintain the temperature below 10° (Note 5). After the addition of the tert-butyl hypochlorite solution is complete, the reaction mixture is stirred at room temperature 1-4 hours (Note 6). 

Dicyclopentadiene was used as another difunctional agent for the synthesis of an oligomeric AO from 4-methylphenol [120] (after tert-butylation, AO 99 was obtained) or diphenylamine [121]. Polymeric aromatic amines for application in rubber stabilization were obtained in the presence of acid catalysts from diphenylamine and l,4-bis(l-hydroxy-l-methylethyl)benzene or 1,4-diisopropylbenzene [122] or from iV,A -diphenyl-l,4-phenylenediamine and a,to-p-xylylenedi-chloride [123]. Polymerization of 2,2,4-trimethyl-1,2-dihydroquinoline in the presence of protic or Lewis adds [1] is very important commerdally. Oligomeric product 100 is an effective AO and AF agent for rubbers. 

A suspension of 66.5 g. (0.5 mole) of aluminum chloride in 390 g. (5.0 moles) of benzene is stirred rapidly and held at 20-30° while 74 grams (1.0 mole) of tert-butyl alcohol is added dropwise. The mixture is allowed to stand overnight and then is poured into a mixture of crushed ice and hydrochloric acid. The benzene layer is separated, and the aqueous portion is extracted with ether. The combined ether and benzene solutions are evaporated, and the residue is fractionally distilled through a 30-cm. column, giving a 65-70% yield of teri-butylbenzene boiling at 168-170°/740 mm. 

Substituted oxazolidin-5-one derivatives, which are prepared from N -protected a-annino dicarboxyhc acids and paraformaldehyde, are employed for dual protection of the a-annino and a-carboxy groups in the synthesis of P-aspartyl and y-glutamyl esters (Scheme 4).Py For this purpose the oxazolidinone derivatives are synthesized by treatment of the Z amino acids with paraformaldehyde in a nnixture of acetic anhydride, acetic acid, and traces of thionyl chloride or by azeotropic distillation of the Z amino acids with paraformaldehyde and 4-toluenesulfonic acid in benzene. The resulting heterocychc compounds are readily converted into the tert-butyl esters with isobutene under acid catalysis. Esterification is achieved with tert-butyl bromidet or with Boc-F.P l Finally, the oxazolidinone ring is opened by alkaline hydrolysis or catalytic hydrogenolysis to yield the tert-butyl esters. 

Dichlorocyclopropanes have been converted to l,l-bis(phenylsulfanyl)cyclopropanes in good yield under phase-transfer conditions using sodium hydroxide as base, benzene as organic solvent, and tetrabutylammonium bromide or benzyltriethylammonium chloride as catalyst. Typically, ler/-butyl 2,2-bis(phenylsulfanyl)cyclopropanecarboxylate (3) was obtained in 71 /o yield from tert-butyl 2,2-dichlorocyclopropanecarboxylate by this method. ... 

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