1 ’-Chloro- 1-methyl-benzene Chloride

We note that while tin reagents have often been employed for the organoboron halides/ the use of organostannanes as starting materials can also be applied to the synthesis of heavier group 13 derivatives. In the context of polyfunc-tional Lewis acid chemistry, this type of reaction has been employed for the preparation of ort/ o-phenylene aluminum derivatives. Thus, the reaction of 1,2-bis(trimethylstannyl)benzene 7 with dimethylaluminum chloride, methylaluminum dichloride or aluminum trichloride affords l,2-bis(dimethylaluminum)phenylene 37, l,2-bis(chloro(methyl)aluminum)phenylene 38 and 1,2-bis(dichloroalumi-num)phenylene 39, respectively (Scheme 16). Unfortunately, these compounds could not be crystallized and their identities have been inferred from NMR data only. In the case of 39, the aluminum derivative could not be separated from trimethyltin chloride with which it reportedly forms a polymeric ion pair consisting of trimethylstannyl cations and bis(trichloroaluminate) anions 40. 

Benzyl Chloride a>- Cblorotoluene or l -Chloro l-methyl-benzene, CgHg.CH. Cl col liq with pungent odor, d 1.00 at 20/20, fr p -39°, bp 179.4° misc with ale, eth or chlf insol in w. Other props and various methods of prepn are discussed in Ref 1 its toxicity, fire expln hazards are given in Ref 2... 

Benzene carboxaldehyde. See Benzaldehyde Benzenecarboximidamide, 4,4 -[1,6-hexanediylbis (oxy) bis-. See Hexamidine Benzenecarboxylic acid. See Benzoic acid Benzene chloramine. See Chloramine-B Benzene chloride. See Chlorobenzene Benzene, 1-chloro-2-isocyanato-. See2-Chlorophenyl isocyanate Benzene, 1-chloro-3-isocyanato-. See3-Chlorophenyl isocyanate Benzene, 1-chloro-4-isocyanato-. See4-Chlorophenyl isocyanate Benzene, 2-chloro-4-isocyanato-1-methyl-. See 3-Chloro-4-methylphenyl isocyanate Benzene, (chloromercuho)-. See Phenylmercuric chloride Benzene, chloromethyl-. See Monochlorotoluene... 

A mixture of a-(p-nitrophenyl) allyl chloride, 2 moles of triethylamine, and benzene refluxed 4 hrs. a-chloro-/ -methyl-p-nitrostyrene. Y 92%. G. Cigna-rella et aL, Tetrahedron 20, 1057 (1964). 

A soln. of l-(3,4-dichlorophenyl)-3-isopropyl-3-(2-propynyl)urea and PGI5 in benzene refluxed 4 hrs. 2-chloro-3- (3,4-dichlorophenyl) -l-isopropyM-methyl-imidazolium chloride (Y 76.8-95%) dissolved in water and made slightly alkaline with 20%-NaOH 3-(3,4-dichlorophenyl)-l-isopropyl-4-methyl-2-imid-azolone (Y 91%).—Otherwise inaccessible 1,3-disubst. 2-imidazolones can easily be prepared by this method. F. e. s. P. J. Stoffel and A. J. Speziale, J. Org. Ghem. 27, 3079 (1962) cf. J. Org. Ghem. 28, 2917 (1963). 

Metalation. Benzene reacts with alkaH metal derivatives such as methyl or ethyUithium ia hydrocarbon solvents to produce phenyUithium [591 -51 -5], CgH Li, and methane or ethane. Chloro-, bromo-, or iodobenzene will react with magnesium metal ia ethereal solvents to produce phenyHnagnesium chloride [100-59-4], C H MgCl, bromide, oriodide (Grignard reagents) (32). 

Polarization is found in reactions involving chlorides. 1,1-Dichloro-2,2-dimethylcyclopropane (26) reacts with lithium ethyl in benzene-ether solution (40°) giving mainly l-chloro-2,2-dimethylcyclopropane (27 X = H) and 3-methyl-l,2-butadiene (28) both of which are polarized (Ward et al., 1968). If n- or t-butyl lithium are used in the reaction, the butene produced by disproportionation shows only net polarization. 

The first step is the preparation of the P-ketoester easily accessible by condensation of methylisopropylketone with dimethylcarbonate in benzene in the presence of sodium hydride. Chlorination of this 3-ketoester with sulfiiryl chloride in dichloromethane occurred smoothly at room temperature affording the methyl 2-chloro-3-oxoalkanoate free from side products. The acidic splitting of the latter with 50 % sulfuric acid under reflux gives a yield of 70 % pure product, free from the isomeric form (eqn. 3). 

Chloro-3-hydrox34oluene, see p-Chloro-ro-cresol 2-Chloroisopropyl ether, see Bis(2-chloroisopropyl) ether p-Chloroisopropyl ether, see Bis(2-chloroisopropyl) ether Chloromethane, see Methyl chloride (Chloromethyl)benzene, see Benzyl chloride Chloromethyl bromide, see Bromochloromethane Chloromethyl ether, see sym-Dichloromethyl ether (Chloromethyl)ethylene oxide, see Epichlorohydrin (2-Chloro-l-methylethyl) ether, see Bis(2-chloroisoprop-yl)... 

The Friedel-Crafts alkylation of aromatic compounds by oxetanes in the presence of aluminum chloride is mechanistically similar to the solvolyses above, since the first step is electrophilic attack on the ring oxygen by aluminum chloride, followed by a nucleophilic attack on an a-carbon atom by the aromatic compound present. The reaction of 2-methyloxetane and 2-phenyloxetane with benzene, toluene and mesitylene gave 3-aryl-3 -methyl-1-propanols and 3-aryl-3-phenyl-l-propanols as the main products and in good yields (equation 27). Minor amounts of 3-chloro-l-butanol and 4-chloro-2-butanol are formed as by-products from 2-methyloxetane, and of 3-phenyl-l-propanol from 2-phenyloxetane (73ACS3944). 

---