2-Phenyl-2-chloropropane

Poor Hammett a correlations are often obtained for reactions in which a positively charged centre is formed that can resonate with an electron donating substituent, because of the additional resonance transmission for these substituents This phenomenon is illustrated by the solvolysis of substituted 2-phenyl-2-chloropropane (Figure 5). Scheme 6 shows how a transition structure may obtain extra stabilisation by resonance interaction between carbenium ion and 4-methoxy and 4-dimethylamino groups. In these cases there is no effect on the energy of the reactant molecules. 

Figure 5 Solvolysis of substituted 2-phenyl-2-chloropropane. , a for meta substituents k, a for para substituents O, a for para substituents...

Sodium borohydride efficiently reduces organic halides, especially if they can form stable carbonium ions. For example, icrl-cumyl chloride (2-phenyl-2-chloropropane) and benzhydryl chloride are converted into cumene (82 /o) and diphenylmethane (72" ), respectively. The following conditions are used for the reduction of these compounds 50°C reaction temperature, 1-2 hr reaction time, 65 vol% diglyme, 0.5 mole of the organic halide, 4.0 mole of sodium borohydride, and 1.0 mole of sodium hydroxide (added in order to minimize the hydrolysis of sodium borohydride). The use of DMSO as a solvent has also been reported. 

Replacement of one of the phenyl groups by an alkyl group of similar bulk, on the other hand, alters the biologic activity in this series. Alkylation of phenylacetonitrile with isopropyl bromide affords the substituted nitrile, 136. Treatment of the anion prepared from 136 with strong base with 2-dimethylamino-l-chloropropane gives isoaminile (137). It is of note that alkylation of this halide, isomeric with that used in the early methadone synthesis, is apparently unaccompanied by isomer formation. Isoaminile is an agent with antitussive activity. 

Phenyl toloxamine o-Benzylphenoxy-/3-chloropropane Benproperine 4-Benzylplperldine Ifenprodil tartrate 1 -Benzyl-4-piperidone Fentanyl Pipamperone Tinoridine... 

The fact that 3-chloro-and 3-acetoxy-l,2-propanediol give,398 respectively, 2-acetoxy-l,3-dichloropropane and l,2-diacetoxy-3-chloropropane with 2-acetoxy-2-methylbutanoyl chloride suggested that the regiospecificity is controlled by steric factors, but electronic factors may assume a dominant role in certain cases. Thus, 1-phenyl-... 

Oxitol, see 2-Ethoxyethanol Oxitol acetate, see 2-Ethoxyethyl acetate 2-Oxobornane, see Camphor Oxocyclohexane, see Cyclohexanone Oxolane, see Tetrahydrofuran Oxomethane, see Formaldehyde Oxybenzene, see Phenol 1,1 Oxybisbenzene, see Phenyl ether l,l -Oxybis(2-chloroethane), see Bis(2-chloroethyl) ether Oxybis(chloromethane), see s/m-Dichloromethyl ether 2,2 -Oxybis(l-chloropropane), see Bis(2-chloroisopropyl) ether... 

The potassium salt of 7-methyl-3-phenyl-2,4-dioxo-l,2,3,4-tetrahydropyrido[2,3- pyrimidine-5-carboxylate 153 was condensed with l-bromo-3-chloropropane or 1,4-dibromobutane in anhydrous DMF at room temperature to afford the A-l-alkyl derivatives 154 and 155, respectively <1994FA499>. The corresponding A-l-piperazinylalkyl derivatives of 153 were also prepared in more than 40% yield. Debenzylation of 6-benzyl-3-methylpyrido[4,3-,7 pyrimidine 156 by Pd/C-catalyzed hydrogenolysis in AcOH gave the analogue 157 <1994JHC1569>. 

Problem 15.49 Convert cinnamaldehyde, C6H5—CH=CH—CH=0, to l-phenyl-l,2-dibromo-3-chloropropane, C6H5CHBrCHBiCH2Cl. ... 

Dehydrohalogenation of l-phenyI-2-chloropropane, or dehydration of l-phenyl-2-propanol, could yield two products l-phenylpropene or 3-phenyl-propene. Actually, only the first of these products is obtained. We saw earlier (Secs. 5.14 and 5.23) that where isomeric alkenes can be formed by elimination, the... 

DBA-DLD. See Dibenzylamine DBB. See 1,4-Dibromobutane DBBP. See Dibutyl butyl phosphonate DBCP. See 1,2-Dibromo-3-chloropropane DBDA. See N-(1,3-Dimethylbutyl)-N -phenyl-p-phenylenediamine... 

Na-methoxide added to a soln. of 7-chloro-l,3-dihydro-5-phenyl-2H-l,4-benzo-diazepin-2-one in anhydrous dimethylformamide, stirred and heated 0.5 hr. on a steam bath, cooled to 30, treated with l-bromo-3-chloropropane, and stirred 66 hrs. at 20° -> 7-chloro-l-(3-chloropropyl)-l,3-dihydro-5-phenyl-2H-l,4-benzodiazepin-2-one. Y 86%. L. H. Sternbach et al., J. Med. Ghem. 8, 815 (1965). 

N-phenyl a-naphthyl amine 1,2-epoxy-3-chloropropane Methacrylic 87)... 

A suspension of 2,3-dihydro-2-phenyl-l,5-benzothiazepin-4(5H)-one in isopropanol added to a stirred soln. of Na-methoxide in isopropanol, refluxed 20 min., cooled to 40°, treated with l-bromo-3-chloropropane, and refluxed 5 hrs. 

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