From their results concerning mainly radical chlorinations of substituted alkanes and from other literature data dealing with this subject, the authors discuss about mesomeric effects of substituents in relation with medium and reactants modifications. With the aid of a properly modified structure-reactivity correlation, it can be demonstrated that changes in reactivity of chlorinating agents or in structure of aliphatic substrates result in quantitative variation in the importance of mesomeric effects of substituents.Dans la chloration photochimique de derives aliphatiques, I'espece active, soit le chlore atomique, est tres reactionnelle, et engendre des lors, un melange de tous les isomeres inonochlores possibles dont la distribution est en relation directe avec la structure de la molCcule de depart. Les reactivites relatives des differentes positions d'une chaine aliphatique portant un groupement fonctionnel sont a la base d'une etude possible des effets de substituants.Parmi ceux-ci, I'effet inducteur joue un rble tres important en creant, dans la molecule, un gradient de densit6 Clectronique, entrainant le chlore radicalaire, denature electrophile, a se fixer aux endroits les plus riches en electrons, c'est-a-dire au voisinage d'un substituant Clectrodonneur, mais le plus loin possible d'un electrocapteur.Les travaux de notre laboratoire ont demontre quantitativement le phenombne, grtice a un traitement des resultats experimentaux par la correlation structure-reactivite (l), adaptee aux photochlorations sous la forme [l a 51 :
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