chapter 22 hw: co h d€¦ · nomenclature 1.!give the name for each compound (iupac or common...
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CHAPTER 22 HW: CO2H DERIVATIVES
NOMENCLATURE
1. Give the name for each compound (IUPAC or common name). Use R/S naming where needed.
Structure
Name
Structure
Name
2. Give the name for each ester.
Structure
Name
3. Give the name for each amide.
Structure
Name
Cl
O Br
OCH3
O
OO O
O O
O
OO
O
O
O
F NH2
OFO
N
H
N
O
Br
CH3
H3C
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4. Give the name for each compound, using cis/trans, E/Z or R/S naming where needed.
Structure
Name
Structure
Name
Structure
Name
SPECTROSCOPY
5. For each pair of isomers (A+B, then C+D), give two methods that IR spectroscopy can be used to distinguish between the isomers. Give specific wavenumbers where their IR spectra would differ.
6. Acetic anhydride has two strong signals in its IR spectrum, at 1827 and 1755 cm-1. What do these signals specifically represent?
BrO
O O
Br O
O O
O
O
O
NH2F N
O
CH3
O
O
O
O
O
I ClOCH3
ClCl
ON
O
OO
OH
O
CH3A B
NCH3
O
CH3
NH2
O
C D
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7. In each set are listed wavenumbers for the carbonyl stretching modes in each compound’s IR spectrum. Explain in detail why in each set, one carbonyl absorbs IR at a higher wavenumber than the other. Hint: draw resonance structures. a. Acetyl chloride v = 1799 cm-1, Ethyl acetate v = 1743 cm-1
b. Butanoic acid v = 1717 cm-1, Butanamide v = 1660 cm-1
8. Predict which carbonyl would absorb infrared radiation at a higher wavenumber. Explain in detail, using appropriate structures.
9. The 1H NMR of DMF has 3 signals at 2.93, 3.03 and 8.00 ppm. Explain why 3 signals are observed.
O
O
O
O
H NCH3
O
CH3DMF
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10. Predict the number of signals expected in both the 1H and 13C NMR spectra of each compound.
1H NMR:
1H NMR:
13C NMR: 13C NMR:
REACTIVITY TRENDS
11. Explain the trends in reactivity toward nucleophilic acyl substitution, using appropriate structures with your answer. a. Acetyl bromide is more reactive than methyl acetate.
b. Acetic anhydride is more reactive than methyl acetate.
c. Ethyl acetate is more reactive than N-methylacetamide.
O
NH2 N
O
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ACID HALIDE AND ANHYDRIDE REACTIONS
12. Draw the curved arrow mechanism for each reaction.
13. Give all organic and inorganic products of these reactions.
a.
O
Clexcess
NH3
O
NH2
b.O
O
O CH3OH
N
O
OCH3
a. H2OO
Cle.
O
O
OH2O
b.OH
O
Cl
py.f.Ph
O
O
O
PhOH
py.
c.
Br
OCH3CH2OH
py.g.
NH2O
O
O
NH2O
Cl
d.h.
excess
CH3CH2NHCH3
O
O
O
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CARBOXYLIC ACID REACTIONS
14. Give the curved arrow mechanism for each reaction.
15. Give the major organic product of these reactions.
16. The Fischer esterification reaction does not always produce good yields. What specific methods can
be used to drive the reaction to completion?
a.O
OH
S OH
OO
+
para-toluenesulfonic acid ( p-TsOH)
CH3OHO
OCH3
b. p-TsOH
HO OH
O
O
O
a.CH3CH2OH
H2SO4OH
Oc.
H2SO4
OHOH
O
b.cat. H+
Ph OH
O
OHd.
CH3OH
p-TsOHOHO
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17. What reagents are needed to synthesize each compound using a Fischer Esterification reaction?
ESTER REACTIONS
18. Give the curved arrow mechanism for each reaction.
a.O
OCH3
b. O
O
a.O
OOH
O
O+
H2O
KOH
OCH3
O
H2O
H2SO4OH
O
+ CH3OHb.
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19. Give the major organic product of these reactions.
20. Explain why ester hydrolysis using acid generally has an equilibrium constant of ~1, while ester
hydrolysis using base has an equilibrium constant greater than 1.
21. Give the curved arrow mechanism for this reaction.
22. Complete the sequence by filling in the necessary reagents for each synthetic step.
a.NaOH (aq)
OCH3
Oc.
KOH
H2O
OEtO
b.H2O
H2SO4O Ph
Od.
H2O
p-TsOH
OO
a.
b. H+, H2O
O
OCH3
OHMgBr
OH
O
Cl
O
OCH3
O OH
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COMBINED REACTIONS
23. Give the major organic product of these reactions.
AMIDE AND NITRILE REACTIONS
24. Give all organic and inorganic products of these reactions.
a.SOCl2
OH
Of.
O
OHHO
H2SO4
O
Ob.
H2O
H2SO4 g.OCH3
O
H2ONaOH
c.O
OH CH3CH2OH
H2SO4h.
OH H3C
O
OH
H2SO4
d.
O
OH b. CH3NH2
a. SOCl2
OHO
OHi.
p-TsOH
e.O O
H2ONaOH
j.O
O
H2O
H2SO4
a.
O NH2
con. NaOH
H2Oc. N
Ocon. H+
H2O
b.CN con. H+
H2O, heatd. CN
con. NaOH
H2O, heat
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25. Give the curved arrow mechanism for each reaction.
a.con. NaOH
H2O+ NH3
NH2
O
O
O
b.NH
Ocon. H+
H2OHO NH3
O
C con. NaOH
H2O, heatc.
O
O + NH3
N
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26 continued
HYDRIDE REACTIONS
26. Give the major organic products of these reactions. Assume excess inorganic reagent in each.
d.
CH3
CN
con. H+
H2O, heat
CH3
O
OH + NH4+
a.a. LiAlH4
b. H+, H2O
O
Of.
a. DIBAL-H
b. H+, H2O
O
O
b.a. LiAlH4
b. H+, H2ONH2
Og.
O
CNa. LiAlH4
b. H+, H2O
c.a. DIBAL-H
b. H+, H2ONH2
O
h.
a. LiAlH4b. H+, H2O
O
OCH3
d.CN a. DIBAL-H
b. H+, H2O i.NH2
O
OHO
a. LiAlH4b. H+, H2O
e.OH
O a. LiAlH4b. H+, H2O
j.a. DIBAL-H
b. H+, H2OCN
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SYNTHESIS
27. Devise a synthesis than converts 3-bromo-1-propene into 3-butenoic acid.
28. Design a synthesis to perform the following transformations, showing all reagents and synthetic intermediates (no mechanisms are necessary). a.
b.
c.
Br
O
OH
O
OH N
BrHO
O OO
CO2H
CO2H
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d.
e.
f.
g.
NH2
O
H
N
NH2
O
O
OH
OCH2CH3
O
O
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h.
i.
O
OCH3
O
O
O