Steric hindrance deactivation

Steric hindrance to activation by carboaromatic nitro groups is well-known, but there seems to be no analogy in the chemistry of azines. The lone-pair of azine-nitrogen has a steric effect comparable " to, somewhat greater than, or somewhat less " than a hydrogen atom. It is not certain whether bulky groups such as i-butyl produce a steric distortion of the lone-pair orbital and whether activation or deactivation results. 

Tetraamination of 2,4,5,6-tetrafluoropyrimidine with dibutyl-amine involves the high reactivity of fluorine as a leaving group rather than activation by the 2,4,6-fluorines. The latter cannot account for the reactivity of the 5-fluorine since the 2,4,6-substituents undoubtedly all react first. Apparently, deactivation by the three dibutylamino groups so introduced (cf. 174) is diminished by steric hindrance to the necessary co-planarity with the ring. 

Very few graft copolymers based on poly(arylene ether)s have been synthesized, probably because of their chemical inertness. Klapper et al. reported grafting the polystyrene or polyisoprene onto the poly(ether ether ketone ketone) (PEEKK) by anionic deactivation.229 The carbonyl groups on tire backbone can be attacked by the polystyrene monoanion or polyisoprene anion (Mn about 3000). Due to the steric hindrance only about 30% of tire carbonyl groups can be reacted. 

Dimethoxybenzoylimidazolium chloride also reacts rather slowly because of steric hindrance and electronic deactivation of the carbonyl group by the two methoxy groups. The synthesis of 2,6-dimethoxybenzoyl chloride was carried out in chloroform at 90 °C in a bomb tube to give a yield of 60% after 3 h.[41... 

The reactivity of microgels resides in terminal carboxyl acid groups and in residual unsaturated dicarboxylic acid groups of the EUP-component. Due to sterical hindrance, presence of less reactive maleic acid units and deactivation of termi-... 

Electrophilic substitution at the anthraquinone ring system is difficult due to deactivation (electron withdrawal) by the carbonyl groups. Although the 1-position in anthraquinone is rather more susceptible to electrophilic attack than is the 2-position, as indicated by jt-electron localisation energies [4], direct sulphonation with oleum produces the 2-sulphonic acid (6.3). The severity of the reaction conditions ensures that the thermodynamically favoured 2-isomer, which is not subject to steric hindrance from an adjacent carbonyl group, is formed. However, the more synthetically useful 1-isomer (6.7) can be obtained by sulphonation of anthraquinone in the presence of a mercury(II) salt (Scheme 6.4). It appears that mercuration first takes place at the 1-position followed by displacement. Some disulphonation occurs, leading to the formation of the 2,6- and 2,7- or the 1,5- and 1,8-disulphonic acids, respectively. Separation of the various compounds can be achieved without too much difficulty. Sulphonation of anthraquinone derivatives is also of some importance. 

Fio. 6. Steric hindrance to dissociative chemisorption in the ortho position of toluene resulting in severe ortho deactivation. 

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