CHM 1321 Assignment 4 Answers

1) Draw the important resonance forms and show the resonance hybrid structures for the following:
(a) H 3C O C CH3 O C O CH3 H 3C + CH 3

H3 C

O C

CH3

H3 C

O (b) H 3C C CH 2 O C O

H 3C

O C

CH2

H3 C

O C

CH2

H3C

CH2

H3 C + CH2

O (c) H 3C C NH 2 O C O C O +C H3 C NH 2 +

O H 3C C NH 2 H 3C

NH 2

H 3C

NH 2

(d)

OH C CH 3 H 3C C H2 O C H C H2 CH3 O H C CH3 H 3C C H2 + H O H3 C + C H2 CH 3

H 3C

Assignment 4 - Answers
S H 2C CH H 2C CH2 + S + H 2C C H H2 C CH2

(e)

H2 C CH H 2C CH 2 H C C H

H2 C C H H 2C CH 2

(f)

HC HC

CH2 C CH H- CH 2 C HC C HC CH - C H

HC HC

H C C H

CH2

CH

HC HC

H C C H

C CH

CH2

HC HC

H C C H

CH 2

CH

HC HC

H C C H

C CH

CH 2

(g)

HC HC

H C C H

CH 2 C CH

HC HC

H C C H

C CH

CH2

HC HC

H C C H

C CH

CH 2

HC HC

H C C H

C CH

CH2

HC HC

H C C H

C CH

CH2

H + + CH2 C HC C HC CH + C + H

Assignment 4 - Answers
CH3 N H 2C CH3

(h)

CH3 N H 2C CH3

octets full - no resonance possible

(i)

CH3NO2 O N

H 3C

O N

H 3C

O + N H 3C O +

(j)

CH3COOH

H3C

O C

H 3C

O C

H 3C

O C

O + C H H 3C O +

Assignment 4 - Answers 2) For the following resonance forms, label the major and minor resonance forms, and show which ones are of equal energy. Justify your choices.
(a) H H 3C C C N Minor H3 C C C N H Major

All atoms have a full Octet. In the second structure, the negative charge is located on the more electronegative atom.

(b)

H3 C

O C

C H

H C

CH3

H 3C

Major In the Major resonance structure, all atoms have a f ull octet. In the minor and intermediate resonance forms, one carbon is lacking an octet. In the intermediate structure has less separation between opposite charges than does the minor structure.

Minor

C CH 3 H Intermediate

O C

H C

H 3C

O C

C H

H C

CH 3

(c)

H3 C

O C

O C H C H2 CH 3 H3 C

O C

C H

O C

C H2

CH3

H3 C

O C

C H

O C

C H2

CH3

Minor

Major

Major

All atoms in all structures have a full octet. In the Major (2 equivalent) resonance forms, the negative charge resides on the more electronegative oxygen atom. In the Minor resonance form, the negative charge resides on the less electronegative carbon.

(d)

H3 C

H2 C

C NH 2

NH 2

H 3C

H2 C

NH2 C NH 2

H 3C

H2 C

NH2 C NH 2

Minor

Major

Major

In the Major (2 equivalent) resonance f orms, all atoms have an octet (this criterion overides having a positive charge on a more electronegative atom). In the minor resonance form, the positively charged carbon atom is lacking an octet.

Assignment 4 - Answers 3) For each pair of ions, determine which is more stable. Justify your answer in each case. a)
H H3C C CH3
or

H H3C C OCH3

H3C C OCH3 H

Delocalization with the lone pairs of the oxygen stabilizes the second compound. b)
H H2C C C CH3 H

or

H2 H2C C C CH2 H

H2C C C CH3 H H

Delocalization with the electrons in the double bond stabilizes the first compound. In the second compound, the double bond is too far away. The CH2 carbon has no lone pairs to donate to the positively charged carbon. c)
H2C CH3 or H2 C C N H2C C N

Delocalization with the lone pairs of the nitrogen stabilizes the second compound. d)
H2 C H2C H2C C H2 C CH2 H2C H2 C CH CH C H CH2

or
CH H2C

H2 C H2C H2C C H2 C CH

CH2

Delocalization with the electrons in the double bond stabilizes the first compound. In the second compound, the double bond is too far away. The CH2 carbon has no lone pairs to donate to the positively charged carbon. 5

Assignment 4 - Answers

e)
H3C N CH3 H3C CH3 CH C CH3 H3C CH3

or
C H3C

H3C N C

CH3

Delocalization with the lone pairs of the nitrogen stabilizes the first compound. f)
O C

H3C

CH3

H3C

or

CH3CH2O

H3C

O C

Delocalization with the lone pairs of both oxygens stabilizes the first compound.

Assignment 4 - Answers 4) For the following pairs of compounds, predict which one will be the strongest acid and justify your choice.
NH2 a) vs OH

NH2

NH

(1)

OH

(2)

look at the conjugate bases: -in equation 2 the atom bearing the negative charge is more electronegative than the atom holding the negative charge in equation 1. Therefore the negative charge will be more stabilized in the conjugate base of equation 2 -this means that this conjugate base will be more stable and a weaker base than the conjugate base in equation 1 - since the conjugate base in equation 2 is weaker, the corresponding acid will be stronger So OH is the stronger acid O b) OH vs OH

R O R

R O

(1)

(2)

The conjugate base in equation 2 is stabilized by resonance. O R O R O O this conjugate base is more stabilized than that in equation 1, therefore this is the weaker conjugate base and O is the stronger acid H R O

c) Br Br

CBr3CO2H vs CH3CO2H O O Br O H H O H H H H H Br Br O O Br O O H + H (2) + H (1)

The bromines in equation 1 are more electronegative than the corresponding hydrogens in equation 2. The stronger electron withdrawing power of the bromines stabilize the conjugate base in (1) by the inductive effect. Since the conjugate base in (1) is more stable than in (2) it is a weaker base and therefore the acid in equation (1) is the stronger acid

Assignment 4 - Answers

O d) MeN NMe SH vs MeN

O NMe OH

SH

(1)

OH

(2)

-in equation 1 the atom bearing the negative charge is larger (lower in the periodic table) than the atom holding the negative charge in equation 2. Therefore the negative charge will be more dispersed in the conjugate base of equation 1 -the dispersion of negative charge in the conjugate base in equation 1 results in better stabilization of the negative charge, therefore this conjugate base will be more stable and a weaker base than the conjugate base in equation 2 - since the conjugate base in equation 1 is weaker, the corresponding acid will be stronger So O MeN NMe is the stronger acid SH O O S H O

e)

vs

O O S H R O R O H

O O S R O R O

(1)

(2)

The conjugate base in equation 1 is stabilized by resonance this stabilizes this conjugate base more than that in equation 2, therefore this is O O O O O O the weaker conjugate base and S S S R R R is the stronger acid O O O O OH S R O

Assignment 4 - Answers
f)
OH OH

vs
CF3 CH3

OH CF3

+
CF3

(1)

OH CH3

+
CH3

(2)

The flourines in equation 1 are more electronegative than the corresponding hydrogens in equation 2. The stronger electron withdrawing power of the flourines stabilize the conjugate base in (1) by the inductive effect. Since the conjugate base in (1) is more stable than in (2) it is a weaker base and therefore the acid in equation (1) is the stronge acid

Assignment 4 - Answers 5) Write equations for the following reactions using arrow notation. Predict whether the reaction will favor the starting materials or products and justify your choice.
O a) O O pKa 4 H + Br O H + Br O O + Br H pKa -4

Reaction will favor the starting materials HBr is a much stronger acid than butanoic acid (HBr has a lower pKa). This shifts the equilibrium to the left favoring the starting materials OH b) + H N + pKa 35 N

N H +

pKa 17

Reaction will favor the products oxygen is more electronegative than nitrogen. This means that the negative charge is better stabilized on oxygen than on nitrogen. Therefore is a weaker base than N O

and so the reaction must favor the products. An alternate explaination involves pKa. R-OH is a stronger acid that R2NH (ROH has a lower pKa). Therefore the reaction will favor products

c)

OH

HBr

OH

H Br pKa -4

OH2 pKa -3

Br

Reaction will favor the products HBr is a much stronger acid than oxonium (HBr has a lower pKa). This shifts the equilibrium to the right favoring the products

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Assignment 4 - Answers

d)

H + NH

H + NH

+ pKa 4

NH 2

pKa -2 Reaction favors the products

oxygen is more electronegative than nitrogen. Therefore positively charged oxygen will be less stable than a positively charged nitrogen. This means that a protonated oxygen compound like R2 OH + will be a stronger acid than the corresponding protonated nitrogen compound

e)

CF3OH

CF3CH2 O

CF3O H

CF3 CH 2O

CF3O

CF3 CH 2 OH

Reaction favors the products The f luorines are closer to the oxygen in CF 3OH than in CF3 CH 2OH. Theref ore the inductive ef fect from the electronegative fluorines will be stronger for CF3O- than for CF 3CH2 O-. This means that the negaitive charge on CF3O- will be more stabilized by the inductive ef fect that then negative charge on CF3 CH 2O-. Because CF3 O- is more stable, the reaction will favor the products. f) OH2 + H O H + Br Br

OH + BrH pKa < -4

pKa = -2

Reaction favors the starting materials HBr is a stronger acid than the alcohol (pKa is lower). Therefore the equilibrium will be shifted to the left and the starting materials will be favored

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Assignment 4 - Answers

g)

S +

S +

S +

SH

reaction favors the products The anion in PhS- is stabilized by resonance and is therefore a weaker base than the anion of cyclohexylthiol. This means that the acid in the starting materials is stronger than that in the products. This f orces the reaction to favor the products S S S S at least one resonance structure must be drawn

h)

CH 3CO2

CF3 CO 2H

CH 3CO2

CF 3CO2 H

CH3 CO2 H

CF3 CO 2

The conjugate base CF 3CO2 - is a weaker base than CH 3CO2 -. This is because the CF3 goup is a stong electron withdrawing group (inductive effect). This stabilizes the negative charge in CF3 CO 2- by dispersing the negative charge. This means that CF 3CO2 H is the strongest acid and therefore this equilibrium will lie towards the products.

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