Tert-Butyl bromide benzene

Ethereal methyl1ithiurn (as the lithium bromide complex) was obtained by the submitters from Aldrich Chemical Company Inc. The checkers used 1.19 M methyl1ithiurn-lithium bromide complex in ether supplied by Alfa Products, Morton/Thiokol, Inc. The concentration of the methyllithium was determined by titration with 1.0 M tert-butyl alcohol in benzene using 1,10-phenanthroline as indicator. The submitters report that ethereal methyllithium of low halide content purchased from Alfa Products, Morton/Thiokol, Inc., gave similar results. 

Stage 1 Preparation of 2-Phenyl-2-Methoxy-Ethyl Bromide - 1.3 mols of tert-butyl hypo-bromite is added slowly and with agitation to a mixture of 107 grams (1 mol) of vinyi-benzene (styrene) and 250 mi of methanol (99%), kept at -10°C. When the addition of the reactant is finished, the mixture is allowed to return to ambient temperature, it is washed in water and dried on anhydrous NajS04. Rectification is effected in vacuo in order to obtain a colorless liquid BP,j = 113°C, BPj.j = 84°C, = 1,5429, yield = 76%. 

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% ). 

Markl, Lieb and Martin were also able to add arynes 112 to 2.4,6-tiiphenyl-X -phosphorins the yields are better with 2.4.6-tri-tert-butyl-X -phosphorin. Here again 1,4 addition takes place with the formation of the 1-phosphabarfelenesiii. The arynes were generated either from 2-fluorophenylmagnesium bromide or penta-chlorophenyl-lithium. The reaction of the more nucleophilic 2.4.6-tri-tert-butyl-X -phosphorin with benzene-diazonium carboxylate also leads to 1,4 addition. The structure of the benzo-phosphabarrelenes 113a-d is supported by analytical and spectroscopic data (Table 16). 

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. ... 

Allyl bromide added drop wise with stirring to a soln. of tetramethylammonium di-tert-butyl phosphate in boiling dimethoxyethane, refluxed 3 hrs., the crude intermediate triester dissolved in benzene and trifluoroacetic acid, allowed to stand 18 hrs. at room temp. allyl phosphate. Y 83% as the anilinium salt. -This method appears to be particularly suited to the phosphorylation of polyfunctional halides containing no acid-labile groups. F. e. s. A. Zwierzak and M. Kluba, Tetrahedron 27, 3163 (1971). 

Obtained by a selective one-step synthesis from 2-tert-butyl-5-methylphenoxymag-nesium bromide (1 mol) and anhydrous monomeric glyoxal (1 mol) in boiling benzene for 20 h (25%) [5059]. 

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