Chemistry*
233* Chapter*9*Problem*Set*
!
Nomenclature*
1) Provide!the!IUPAC!name!for!each!of!the!alkyne!containing!compounds!below.!
Cl
!
!
2) Provide!the!IUPAC!name!for!each!of!the!enyne!compounds!below.!
!
3) Provide!the!common!name!for!each!compound!below.!
!
Br
!
!
!
!
!
Page 1 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
Structure*and*Properties*of*Alkynes*
4) For!each!indicated!carbon!atom!determine!its!hybridization.!
H
!
!
5) The!smallest!cycloalkyne!that!has!been!isolated!and!stored!is!cyclooctyne.!Explain!why!alkynes!do!
not!exist!in!smaller!rings.!
!
!
!
!
!
6) Consider!phomallenic!acid!C!(shown!below),!an!inhibitor!of!bacterial!fatty!acid!synthesis.!
!
a. Circle!the!most!acidic!position.!
!
b. What!is!the!shortest!CUC!single!bond?!
!
c. How!many!sp!hybridized!atoms!are!present!in!the!
!
O
C
molecule?!
!
d.
For!the!bonds!indicated!with!arrows,!determine!
!
HO
the!orbitals!that!make!up!the!bond.!
!
!
!
7) Rank!the!compounds!in!each!series!below!from!most!acidic!(1)!to!least!acidic.!
!
NH 3
H 3C CH 3
H 3C
H
H 2C CH2
!
!
N
NH
NH
!
8) Rank!the!compounds!below!from!most!basic!(1)!to!least!basic.!
O
NH 2
NH 3
!
F
!
!
!
9) Draw!the!products!from!the!acid!base!reaction!shown!below.!Label!the!nucleophilic!site!in!the!
product.!Show!curved!arrows!to!demonstrate!the!flow!of!electrons.!
!
+
Li
!
!
10)Show!how!the!nucleophile!generated!above!would!react!with!iodoethane.!
!
!
!
!
!
!
Page 2 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
Reactions*and*Mechanisms*
11)Predict!the!product(s)!for!each!halogen!addition!below.!
!
HBr
(xs)
HCl
(2 equiv)
HCl
(1 equiv)
Ph
HBr
(xs)
HBr
(xs)
HBr
(1 equiv)
Ph
!
!
12)Predict!the!products!for!each!halogenation!reaction!shown!below.!
!
Br 2
(2 equiv)
Cl2
(1 equiv)
Ph
Br 2
(1 equiv)
Cl2
(2 equiv)
!
!
!
!
Page 3 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
13)Draw!the!electron!pushing!mechanism!for!the!reaction!shown!below.!
Ph
Br
HBr
(2 equiv)
Br
Ph
!
!
!
!
!
!
!
!
!
!
!
!
!
14)Draw!the!electron!pushing!mechanism!for!the!reaction!shown!below.!
Ph
Br
Br 2
(1 equiv)
Ph
Br !
!
!
!
!
!
!
!
!
!
!
!
!
15)Draw!the!electron!pushing!mechanism!for!the!acid!catalyzed!tautomerization!of!(Z)U2UpentenU2Uol.!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
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Page 4 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
16)Draw!the!ketone!form!for!the!following!enol!tautomers!
!
Ph
OH
OH
H
OH
!
!
17)Predict!the!products!for!the!acid!and!mercury(II)!catalyzed!hydration!reactions!shown!below.!
!
OH
HgSO 4
H 2SO 4
H 2O
H 2SO 4
H 2O
H 2SO 4
H 2O
Ph
HgSO 4
H 2SO 4
H 2O
HgSO 4
H 2SO 4
H 2O
!
!
18)Draw!the!electron!pushing!mechanism!for!the!acid!catalyzed!hydration!reaction!below.!
Ph
!
!
!
!
!
!
!
!
!
!
!
Ph
O
H 2SO 4
H 2O
Ph
Ph
!
Page 5 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
19)Draw!the!electron!pushing!mechanism!for!the!mercury(II)!catalyzed!hydration!reaction!below.!
H
HgSO 4
H 2SO 4
H 2O
O !
This mechanism is
!
written slightly
!
different than how we
!
did it in class. You can
!
write it either way.
!
!
!
!
!
!
!
!
20)Predict!the!products!for!the!hydroborationUoxidation!reactions!shown!below.!
!
1. BH 3•THF
2. NaOH, H 2O2
1. BH 3•THF
2. NaOH, H 2O2
1. BH 3•THF
Ph
2. NaOH, H 2O2
1. BH 3•THF
2. NaOH, H 2O2
1. BH 3•THF
2. NaOH, H 2O2
!
!
21)Determine!the!necessary!reagents!to!carry!out!each!of!the!interconversions!shown!below.!
!
O
!
!
!
!
O
!
Page 6 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
22)Predict!the!products!for!the!alkyne!reduction!reactions!shown!below.!
!
H2
Pd/C
H2
Lindlar Cat.
Na
NH 3(l)
H2
Lindlar Cat.
Ph
H2
Lindlar Cat.
Na
NH 3(l)
!
!
23)Predict!the!product!for!each!alkylation!reaction!below.!
!
1. NaNH 2
2. CH 3Br
1. BuLi
2. CH 3Br
1. NaNH 2
2.
H
*
*
*
*
*
*
H
I
1. NaNH 2
2. CH 3CH2Br
3. NaNH 2
4. PhCH 2Br
!
Page 7 of 8!
Chem.!233!–!Chapter!9!Problem!Set!
Synthesis*
24)Provide!the!missing!reagents!in!the!synthetic!sequence!shown!below.!
Br
O
H
+ en
O
O
!
!
25)Provide!a!reasonable!synthesis!for!each!of!the!following!compounds!using!the!provided!starting!
material.!
!
?
H
H
H
H
H
?
O
Ph
?
H
H
O
Cl
?
H
Cl
H
Cl
Cl
?
H 3C
H
!
26)Challenge!Synthesis!
!
HO
Br
!
!
Page 8 of 8!