1. (14 points) (2 points each) Write your answer in the box to the right of the question.
a) Which of the following cannot be made by the reduction of a ketone or aldehyde with NaBH4 in methanol?
1) 1-butanol
2) 2-butanol
3) 2-methyl-1-propanol
4) 2-methyl-2-propanol
b) What is the product of the following reaction?
O
(1) LiAlH4
(2) H2O
OH
O
1)
3)
OH
OH
2)
4)
OH
c) Which one of the following diols would cleave into two fragments with HIO4?
1) 1,3-hexanediol 2) 2,4-hexanediol 3) 3,4-hexanediol 4) 1,6-hexanediol
d) Which of the following is the preferred conformation for epoxide ring formation in the presence of NaOH?
OH
OH
1)
OH
2)
3)
4)
OH
Br
Br
Br
Br
(CH ) CH O CH CH CH CH
3 2
2
2
2
3
e) The name of the following ether is:
1) butyl isopropyl ether. 2) isobutyl propyl ether. 3) sec-butyl isopropyl ether.
4) butyl propyl ether.
f) What is the product of the following reactions?
O
CH3COCH2CH3
2 CH3CH2CH2Li
H3O+
diethyl ether
O
OH
1) CH3CCH2CH2CH3
3) CH3CHCH2CH2CH3
OH
2) CH3CH3CCH2CH2CH3
OH
4) CH3CH3CH3CCH2CH2CH3
CH3
CH3
g) Which of the following reacts the fastest with aqueous NaOH?
1) ethylene oxide (oxirane) 2) cis-2,3-dimethyloxirane 3) trans-2,3-dimethyloxirane 4) 2,2,3,3-tetramethyloxirane
Chemistry 212
Name_______________________________
LSW S’01
Exam 2
Last, First
2. (21 points) (3 points each) Write your answer in the box to the right of the question.
a) What is the product of the following reaction?
O
1) 2 CH3MgBr
O
2) H3O+
1) HO
OH
3)
OH
OH
2)
OH
OH
4)
b) Give the product of the following reaction.
O
(1) LiAlD4
(2) H2O
OH
OH
1) CH3CH2CCH3
2) CH3CH2CCH3
H
OD
OD
3) CH3CH2CCH3
D
4) CH3CH2CCH3
H
D
c) Which of the following reagents would be used to carry out the transformation shown below?
O
?
OH
2) LiAlH4
1) NaBH4
3) H2/Pt
OH
4) PCC/CH2Cl2
d) What is the product of the following reaction?
CH3
H3C
C
H
C
OsO4, (CH3)3COOH
H
1) CH3CH=O
2) meso-2,3-butanediol
(CH3)3COH, OH3) racemic (2R,3R) and (2S,3S)-2,3-butanediol
4) cis-2,3-epoxybutane
2
Chemistry 212
LSW S’01
Name_______________________________
Last, First
Exam 2
e) Compound A, C6H12O, is readily oxidized with K2Cr2O7 in H2SO4/H2O to give compound B, C6H10O. Compound B
has four peaks in its C-13 NMR (broadband decoupling). Which one of the following fits the data for compound A?
OH
OH
CH2OH
1)
2)
HO
CH3
3)
CH3
4)
f) What is the major product of the following reaction?
CH3
NBS, benzoyl peroxide
NaOCH2CH3
CCl4, heat
CH3CH2OH
Br
CH2OCH2CH3
CH2Br
CH2OCH2CH3
CH3
Br
1)
2)
Br
3)
OCH2CH3
4)
OCH2CH3
OCH2CH3
g) What reagents and/or reaction sequence below would convert cis-3-hexene to meso-3,4-hexanediol?
1) OsO4, (CH3)3COOH, (CH3)3COH, NaOH
3) O3 followed by Zn/H2O
2) B2H6/diglyme followed by H2O2/NaOH
4) CH3CO3H followed by NaOH/H2O
3. (16 points) (4 points each) Write your answer in the box to the right of the question.
a) What is the final product of the following reactions?
(CH3)2C=CHCH2CH3
1) BH3/THF
PCC
1) CH3MgBr
2) H2O2, OH- CH2Cl2 2) H3O+
1) 2,3-dimethyl-3-pentanol 3) 2,4-dimethyl-3-pentanol
2) 2,3-diemthyl-2-pentanol 4) 2,2-dimethyl-3-pentanol
3
Chemistry 212
LSW S’01
Exam 2
b) What is the final product of the following sequence of reactions?
(CH3)2CHOH
PBr3
Mg
1)
diethyl ether
1) (CH3)2CHOCH2CH2OH
Name_______________________________
Last, First
O
2) H3O
PCC
+
CH2Cl2
3) (CH3)2CHCH2CHO
O
2) (CH3)2CHCCH3
4) (CH3)2CHCH2CO 2H
c) Benzene reacts with 2-methyloxirane in the presence of AlCl3 to give a product with a formula of C9H12O.
Identify the product.
O
+
AlCl3
C9H12O
CH3
OH
OH
OH
1)
OH
2)
3)
4)
d) Which synthetic pathway below gives a racemic mixture of the following deuterated compound with little isomeric
impurities?
H
D
+ enantiomer
OH
O
1) cyclopentene
CH3COOH
1) LiAlD4
2) H2O
2) cyclopentene
3) cyclopentene
4) cyclopentene
1) BD3/THF
2) H2O2, NaOH
D2/Pt
DCl
Br2, hv
NaOH
CCl4
H2O
H2O, CH3OH
heat
4
H
Chemistry 212
LSW S’01
Name_______________________________
Last, First
Exam 2
4. (15 points) Use the following information to identify Compound X, which has an empirical formula of C8H9ClO.
a) The Mass Spectral Data in mass/e-, for the major peaks show:
22% at 156 and 11% at 158, which indicates ___________________________
22% at 139 and 11% at 141, which indicates ___________________________
12% at 121, which indicates _________________________
The molecular formula of compound X is:__________________________
b) The IHD of compound X is:
c) The infrared spectrum of compound X has:
Large broad peak at 3500 nm, which indicates _________________
Strong peaks at 3030 nm, which indicates _________________
Medium peaks at 2870 nm, which indicates __________________________
d) The λmax in the UV of compound X is near 356 nm, but after shaking with a sodium hydroxide solution the λmax
of the compound shifts to 478 nm. This indicates that the chemical is probably
e) The proton NMR of compound X, has the following peaks.
Chemical shift
Peak
# of H’s
Probable group
δ 2.75ppm
triplet
(2H)
δ 3.69ppm
triplet
(2H)
δ 7.02ppm
doublet
(2H)
δ 7.50ppm
doublet
(2H)
δ 8.41ppm
broad singlet
(1H)
I believe the structure of Compound X is:
5
Neighboring group
Chemistry 212
Name_______________________________
LSW S’01
Exam 2
Last, First
5. (8 points) Choose two (2) of the following. (You will be graded on the first two with answers unless you place an X on one.
Indicate the best method of synthesis for two of the following from the indicated starting materials.
a) Synthesize 3-methyl-1-hexanol from 1-bromobutane.
b) Synthesize isopropyl methyl ether from any halogenated hydrocarbons, and any other inorganic materials.
c) Synthesize
O
from any halogenated alkene.
6
Chemistry 212
Name_______________________________
LSW S’01
Exam 2
Last, First
6. (12 points) Choose three (3) of the following. (You will be graded on the first three with answers unless you place an X on one.
Indicate the best reagent for the indicated conversions. (Indicate the stereochemistry if necessary)
a)
O
CH2OH
?
CH
b)
c)
d)
7
Chemistry 212
Name_______________________________
LSW S’01
Exam 2
Last, First
7. (10 points) Choose two (2) of the following. (You will be graded on the first two with answers unless you place an X on one.
Indicate the major organic product for the following reactions. (Indicate the stereochemistry if necessary)
a)
O
NaBH4
CH3OH
HBr
1) Mg, Et2O
PCC
2) H2C=O
CH2Cl2
3) H3O
+
b)
c)
8
Chemistry 212
Name_______________________________
LSW S’01
Exam 2
Last, First
8. (8 points) Predict the major product and propose a mechanism for the reaction shown below.
HBr (xs)
O
9. (8 points) Propose a method to purify a mixture of p-ethylbenzoic acid, 3-phenylpropanol, and p- propylphenol. Indicate
how each species would be recovered with high purity, (you may draw a detailed flow chart or write this in
paragraph form.
9