--%>

What is ortho effect?

Orthosubstituted anilines are generally weaker bases than aniline irrespective of the electron releasing or electron withdrawing nature of the substituent. This is known as ortho effect and may probably be due to combined electronic and steric factors.

The overall basic strength of ortho, meta and para substituted anilines, however, depends upon the electron,-donatingelectron-withdrawing resonance effect as well as inductive effect as discussed below:

(a) If the substituent has electron withdrawing inductive (-I) as well as resonance (-R) effect. Then all the substituted anilines are weaker bases with ortho isomer being the weaker base. Then m-isomer in this case is relatively stronger base because R-effect does not operate at m-positive. For example, basic strength of o, p, m-nitro anilines are given as follows:

(b) If the substituent has electron donating inductive (+I) as well as electron donating resonance (+R) effect, then among the substituted anilines, the ortho substituted anilines are weaker bases than aniline whereas p- and m- isomers are relatively stronger bases. However, the p-isomer is still stronger than m-isomers. This is clear from the basic strength of toluidines as given below:

(c) If a substituent has electron donating resonance effect (+R) but electron withdrawing inductive effect (-I), the overall basic strength depends upon the relative predominance of R-effect or I-effect.

(i) When a substituent has strong (+R) effect and weak (-I) effect (For example, -OCH3 group). At meta-position it exerts only (-I) effect causing base weakening effect. Among o- and p-isomers, ortho isomer is weaker base than aniline due to ortho effect while para-isomer is stronger base than aniline due to dominance of + R effect. The basic strength of o-, p- and m-anisidines are as under:

Similar trends are observed in amino-phenols with any ortho aminophenol is stronger base than aniline due to stabilization of o-hydroxy anilinium ion because of intramolecular H-bonding. The basic strengths of aminophenols are as under:

-NH2 group has much stronger (+R) effect and much weaker (-I) effect than -OH group and -OCH3 groups. The decreasing order of basic strengths of phenylenediamines is as given below:

(ii) when the substituent has a weak +R effect but a strong -I effect Chloro group (-Cl) is common example. Since -I- effect outweighs the +R effect, therefore, all the three o-, m- and p- chloroanilines are weaker bases than aniline. However, due to ortho-effect, o-chloroaniline is the weakest base. Further in p-chloroaniline is the weakest base. Further in p-chloroaniline both +R only the -I effect operates; therefore, p-chloroaniline is relatively stronger base than m-chloroaniline. Thus, the basicity of o-, m- and p- chloroanilines relative to aniline follows the sequence as given below:

   Related Questions in Chemistry

  • Q : Non-ideal Gases Fugacity The fugacity

    The fugacity is a pressure like quantity that is used to treat the free energy of nonideal gases.Now we begin the steps that allow us to relate free energy changes to the equilibrium constant of real, nonideal gases. The thermodynamic reaction 

  • Q : Molal elevation constant of water The

    The boiling point of 0.1 molal aqueous solution of urea is 100.18oC  at 1 atm. The molal elevation constant of water is: (a) 1.8    (b) 0.18   (c) 18    (d) 18.6Answer: (a) Kb

  • Q : Can protein act as the buffer Can

    Can protein act as the buffer? Briefly comment on that statement.

  • Q : What are haloalkanes and haloarenes and

    Alkyl halides or haloalkanes are the compounds in which a halogen is bonded to an alkyl group. They have the general formula RX (where R is alkyl grou

  • Q : Relationship between Pressure and

    The pressure-temperature relation for solid-vapor or liquid vapor equilibrium is expressed by the Clausis-Clapeyron equation.We now obtain an expression for the pressure-temperature dependence of the state of equilibrium between two phases. To be specific,

  • Q : What are heterogenous catalysis? Give

    When the catalyst exists in a different phase than that of reactants, it is said to be heterogeneous catalyst, and the catalysis is called heterogeneous catalysis. For example, SO2 can be oxidized to SO3

  • Q : How haloalkanes are prepared from

    Alkyl halides can be prepared from alkanes through substitution and from alkenes through addition of halogen acids or through allylic substitution.    From alkanesWhen alkanes are treated with halogens, chlo

  • Q : Problem on moles of solution The number

    The number of moles of a solute in its solution is 20 and total no. of moles are 80. The mole fraction of solute wil be: (a) 2.5 (b) 0.25 (c) 1 (d) 0.75

  • Q : Water under pressure problem-henry law

    Can someone help me in going through this problem. The statement “When 0.003 moles of a gas are dissolved in 900 gm of water under a pressure of 1 atm, 0.006 moles will be dissolved under the pressure of 2 atm", signfies: (a)

  • Q : Unit of molality Select the right

    Select the right answer of the question. The unit of molality is: (a) Mole per litre (b) Mole per kilogram (c) Per mole per litre (d) Mole litre