The Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

σ
log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has
a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl
hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly
linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl
hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the
discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

σ
rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst
but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl
ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1
ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

O
Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O
Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5
any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

O
acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

O
log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

σ
log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has
a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl
hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly
linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl
hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the
discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

σ
rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst
but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl
ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1
ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

O
Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O
Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5
any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

O
acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

O
log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2OThe Hammett plot for hydrolysis of the acid chlorides of benzoic acids

in aqueous acetone is very odd indeed. Hammett plots need not be perfectly

linear to give useful information, but this one is clearly made up

of two intersecting straight lines. This might look like disaster at fi rst

but, in fact, it tells us something rather important. The right-hand part

of the curve, where the more electron-withdrawing substituents lie, has

a slope of +2.5: just what we should expect for rate-determining attack

of water on the carbonyl group. As we go to less electron-withdrawing

substituents, the rate of the reaction suddenly starts to increase as we

pass the para-chloro compound and the left-hand part of the curve has

a slope of –4.4.

What can this mean? If the reaction becomes faster as we pass the

discontinuity in the curve—and it gets faster whether we go from right

to left or left to right—there must be a change in mechanism. If there is

a choice between two mechanisms, the faster of the two will operate.

Mechanism 1 is the rate-determining nucleophilic attack by water on

the carbonyl group.

The new mechanism goes faster for more electron-donating substituents

and has quite a large negative ρ value, suggesting the formation of

a cation in the rate-determining step. This mechanism (mechanism 2)

must surely be the SN1-like preliminary formation of an acylium ion by

loss of chloride ion.

Ar Cl

Ar OH

acetone

log k

ArCOCl

hydrolysis

p-Cl

ρ = – 4.4 ρ = + 2.5

H2O

Ar Cl

log k

ArCOCl

hydrolysis

rate by

mechanism 1

ρ = – 4.4

ρ = + 2.5

any compound reacts at

the faster of the two mechanisms

H2O