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Why is para-aminobenzoic acid more acidic than ortho-aminobenzoic acid?
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Posted by
Malcolm Holley
Why is para-aminobenzoic acid more acidic than ortho-aminobenzoic acid?
The problem in ortho-aminobenzoic acid is that the acidic hydrogen of carboxylic group is H-bonded with the lone pair of nitrogen in amino group. As a result it is more difficult to extract it compared to that in para-aminobenzoic acid since the H-bond must also be broken during acid-base reaction. Para-aminobenzoic acid does not have a H-bond due to the distance between the two groups.
I would like to add that since the hydrogen of the $\ce{-COOH}$ group is more acidic and $\ce{N}$ has a lone pair. This is why H-bond occurs with $\ce{-NH2}$ group as electron donor and not the other way round.
Also, I presume that by ortho effect you intended to tell that due to repulsion of $\ce{-NH2}$ group $\ce{-COOH}$ group would go out of the plane. However, as we have seen, it is difficult as it is already H-bonded with the nitrogen atom and moving out of the plane would put strain into the H-bond. Moreover, the repulsion by $\ce{-NH2}$ group is not too intense so it would (in most part) avoid the strain.
The problem in ortho-aminobenzoic acid is that the acidic hydrogen of carboxylic group is H-bonded with the lone pair of nitrogen in amino group. As a result it is more difficult to extract it compared to that in para-aminobenzoic acid since the H-bond must also be broken during acid-base reaction. Para-aminobenzoic acid does not have a H-bond due to the distance between the two groups.
I would like to add that since the hydrogen of the $\ce{-COOH}$ group is more acidic and $\ce{N}$ has a lone pair. This is why H-bond occurs with $\ce{-NH2}$ group as electron donor and not the other way round.
Also, I presume that by ortho effect you intended to tell that due to repulsion of $\ce{-NH2}$ group $\ce{-COOH}$ group would go out of the plane. However, as we have seen, it is difficult as it is already H-bonded with the nitrogen atom and moving out of the plane would put strain into the H-bond. Moreover, the repulsion by $\ce{-NH2}$ group is not too intense so it would (in most part) avoid the strain.
The problem in ortho-aminobenzoic acid is that the acidic hydrogen of carboxylic group is H-bonded with the lone pair of nitrogen in amino group. As a result it is more difficult to extract it compared to that in para-aminobenzoic acid since the H-bond must also be broken during acid-base reaction. Para-aminobenzoic acid does not have a H-bond due to the distance between the two groups.
I would like to add that since the hydrogen of the $\ce{-COOH}$ group is more acidic and $\ce{N}$ has a lone pair. This is why H-bond occurs with $\ce{-NH2}$ group as electron donor and not the other way round.
Also, I presume that by ortho effect you intended to tell that due to repulsion of $\ce{-NH2}$ group $\ce{-COOH}$ group would go out of the plane. However, as we have seen, it is difficult as it is already H-bonded with the nitrogen atom and moving out of the plane would put strain into the H-bond. Moreover, the repulsion by $\ce{-NH2}$ group is not too intense so it would (in most part) avoid the strain.
The problem in ortho-aminobenzoic acid is that the acidic hydrogen of carboxylic group is H-bonded with the lone pair of nitrogen in amino group. As a result it is more difficult to extract it compared to that in para-aminobenzoic acid since the H-bond must also be broken during acid-base reaction. Para-aminobenzoic acid does not have a H-bond due to the distance between the two groups.
I would like to add that since the hydrogen of the $\ce{-COOH}$ group is more acidic and $\ce{N}$ has a lone pair. This is why H-bond occurs with $\ce{-NH2}$ group as electron donor and not the other way round.
Also, I presume that by ortho effect you intended to tell that due to repulsion of $\ce{-NH2}$ group $\ce{-COOH}$ group would go out of the plane. However, as we have seen, it is difficult as it is already H-bonded with the nitrogen atom and moving out of the plane would put strain into the H-bond. Moreover, the repulsion by $\ce{-NH2}$ group is not too intense so it would (in most part) avoid the strain.
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