1. (2 points each) Write your answer in the box to the right of the question.
1) Which of the following has the largest Keq for the formation of the hydrate (as shown below)?
O
R
+ H2O
R'
O
1) CH3CCH3
HO OH
Keq
R
R'
O
O
O
2) CH3CCH2Cl
3) CH3CCHCl2
4) CH3CCCl3
2) Identify the reagents needed to carry out the following conversion.
O
?
HC CCH2CH2CH3
A) H2 /Lindlar Pd followed by H2 SO4/H2 O
C) H2 O, HgSO4/H2 SO4
CH3CCH2CH2CH3
B) O3 followed by H2 O
D) LiAIH4 followed by H2 O
3) What is the product of the reaction below?
CHO
NaCN, ethanol
then dil. HCl
Br
OH
H
CN
CN
1)
H
OH
H
H
2)
Br
OH
Cl
3)
Br
Cl
H
4)
Br
CN
4) The compound shown to the right is the hemiacetal formed between:
OH
CH3CH2 CH OCH(CH3)2
A) propanal and 2 –propanol
C) acetone and 1-propanol
B) 2 -methylpropanal and ethanol
D) ethanal and 2 -methyl-1-propanol
5) What is the product of the reaction of butanal with excess methanol and catalytic sulfuric acid?
O
1) CH3CH2CHCH
O
2) CH3CH2CH2COCH3
OCH3
3) CH3CH2CH2CH2OCH3
6) What is the product of the following reaction sequence?
4) CH3CH2CH2CH(OCH3)2
Organic Chemistry
212 LSW S’01
EXAM 3
(1) P(C 6H5)3
CH3CH2CH2Br
cyclopentanone
(2) CH3Li
CH2CH2CH3
CH=CHCH3
1)
Name________________________
Initials
2)
CH2CH2CH3
CHCH2CH3
3)
4)
7) What is the product of the following Baeyer-Villiger oxidation reaction?
O
O
C6H5COOH
CHCl3
O
1)
O
2)
OCH3
H3C
O
O
3)
O
4)
OH
CH3
OH
8) What is the product of the reaction below?
O
(CH3)2CHCH2CH
1)
+
Br2
2)
H
O
O
O
Br O
acetic acid
H
3)
Br
4)
Br
Br
Br
9) Which of the following optically active compounds racemizes in dilute KOH/CH3 OH solution?
O
H CH3 O
1)
3)
H3C
C6H5
O
H3C C6H5 O
2)
4)
H CH3
10) Benzalacetone is the crossed aldol condensation product formed between benzaldehyde and acetone.
Which of the following is the structure of benzalacetone?
O
1) C6H5CH=CHCCH3
2) C6H5CH=C(CH3)2
O
O
2) C6H5CCH=CHCH3
4) C6H5CH2CCH=CH2
11) What is the product of the following reaction?
2
Organic Chemistry
212 LSW S’01
EXAM 3
O
Name________________________
Initials
O
1) NaOEt, EtOH
H
O
2) CH3I
H3C OH O
O
H
1)
H
3)
CH3
O
O
2) H3C
O
4)
H
OH
CH3
H
12) Which of the following reagents can convert cyclohexanone to N-ethylcyclohexylamine as shown below?
NHCH2CH3
O
?
A)
B)
C)
D)
CH3 CH2 NH2 and H2 /Pt
LiAlH4 followed by H2 O and then CH3 CH2 Br
CH3 CH2 Br and NH3
CH3 CH=O and NH3
(3 points each) Write your answer in the box to the right of the question.
13) The compound shown below is the cyclic hemiacetal of:
H3C
OH
O
CH2CH3
A) 5-hydroxyheptanal
C) 6-hydroxy-3 –heptanone
B) 5-hydroxy-2 -heptanone
D) 6-hydroxyheptanal
14) Which synthetic method below correctly does the following conversion?
CHO
CHO
?
Br
A)
B)
C)
D)
(1) Mg, diethyl ether
(1) LiAID4, diethyl ether
(1) HOCH2 CH2 CH2 OH, H+
(1) HOCH2 CH2 OH, H+
D
(2 ) D2 O
(2 ) D2 O
(2 ) Mg, diethyl ether
(2 ) DCl
15) Identify the missing reagent for the reaction below.
3
(3 ) D2 O
(3 ) H2 O, H+
(4) H2 O, H+
Organic Chemistry
212 LSW S’01
EXAM 3
Name________________________
Initials
NH2
+
N
CH3
N
CH3
?
NH2
O
OH
1)
O
2)
3)
O
4) H3C C H
OH
16) What is the product of the following intramolecular aldol condensation reaction?
O
KOH, CH3OH
H
H
heat
O
O
O
1)
CHO
CHO
2)
3)
4)
17) Identify the starting reagent needed to make the following cyclic ketone by an intramolecular aldol condensation reaction.
O
NaOH, H2O
?
heat
O
1)
CH3
O
H3C
O
3)
CH3
H
H3C
O
O
O
2)
4)
H3C
O
H
H
O
18) Identify the starting reagents needed to make the following compound by a mixed aldol condensation.
?
O
KOH, CH3OH
CH=CCCH2CH3
CH3
A)
B)
C)
D)
benzaldehyde (C6H5CH=O) and 3 -pentanone
benzaldehyde (C6H5CH=O) and 2 -pentanone
acetophenone (methyl phenyl ketone) and 2 -butanone
acetophenone (methyl phenyl ketone) and butanal
(4 points each) Write your answer in the box to the right of the question.
4
Organic Chemistry
212 LSW S’01
EXAM 3
Name________________________
Initials
19) The Robinson annulation reaction is shown below. Identify the missing reagent in the first step.
O
O
CH3
+
?
KOH, CH3OH
CH3
Al[OC(CH3)3]3
benzene, heat
O
O
O
O
1) H2C=CHCCH3
3) H2C=CHCH2CH
O
O
2) CH3CH=CHCH
4) CH3CCH2CH3
20) What is the product of the reaction sequence below?
A)
B)
C)
D)
1) BH3/THF
PCC
(C 6H5)3P=CH2
2) H2O 2, OH-
CH2Cl2
DMSO
2 -methyl-1-hexene
2 ,3 -dimethyl-2 -pentene
2 -methyl-2 -hexene
3 -methyl-1-hexene
21) (9 points) Choose three of the following. Predict the major organic product of the following reactions.
A)
O
CH3CH2CH
NaOH, H2O
o
O C
B)
O
+
HN(CH3)2
C)
O
O
+
H
NaOH
Ethanol, H2O
D)
O
O
+ CH3CH2Br
22) (9 points) Choose three of the following. Provide the reagents required for each of the following transformations.
5
Organic Chemistry
212 LSW S’01
EXAM 3
Name________________________
Initials
A) 3-pentanone Æ 3-methylpentanol
B) (E)-3,4-dimethyl-3-hexene Æ 2-butanone
C) 1-decanol Æ decanal
23) (8 points) Choose two of the following. Provide brief explanations for the following observations.
A) When left overnight in 17O isotopically labeled water, H217O, unlabelled formaldehyde is found to have
incorporated the 17O isotope.
B) The dipole moment of diphenylcyclopropenone (µ = 5.1 D) is substantially larger than that of
benzophenone (µ = 3.0 D).
C) The β carbon of an α,β- unsaturated ketone is less shielded than the corresponding carbon of an alkene.
Typical 13C NMR chemical shift values are near 110 ppm for a simple alkene, while the 13C NMR
chemical shift values are closer to 130 ppm for an α,β-unsaturated ketone.
24) (6 points) Choose one of the following. Synthesize the following compounds from the indicates starting materials.
6
Organic Chemistry
212 LSW S’01
EXAM 3
O
A) All carbons from ethanol (CH3CH2OH) Æ
Name________________________
Initials
O
H
CH3
B)
OH
+
C6H5CH=CCH2OH
OH
CH3CHCH3
CH3
25) (8 points) Propose a mechanism for the following reaction.
O
O
Cl
KH, THF
(78% yield)
room temp.
Cl
H3C
26) (8 points) Use the following information to identify compound X.
7