Chemistry 30A
UCLA Fall 2009
Midterm Exam II KEY
On my honor, I have neither given nor received any aid on this exam
Signature:
KEY
Name:
KEY
UCLA Student I. D. Number:
Question
Points
--------------------------------------1 (28)
--------------------------------------2 (24)
--------------------------------------3 (15)
--------------------------------------4 (18)
--------------------------------------5 (20)
--------------------------------------6 Extra Credit (5)
--------------------------------------Total
Chemistry 30A, Fall 2009
Page 1
Name: KEY
THEORY
1.
A. (4) Calculate the Double Bond Equivalents (DBE) (Degree of Unsaturation) for C12H18BrClN2O2.
DBE = #C (#H + #X)/2 + (#N)/2 +1 = 12 (18+2)/2 + 2/2 + 1 = 4
B. (4) Circle the isoprene units in abietic acid.
HOOC
HOOC
C. (4) Define stereospecific reaction using words and an example.
A reaction wherein the stereochemistry of the product is dependent on the
stereochemistry of the starting material. For example, syn dihydroxylation of cis or
trans alkenes. For example, syn hydroboration of cis or trans alkenes.
D. (4) Draw the structure of the tertiary butyl cation clearly showing its geometry and label the
hybridization at the cationic carbon.
H3C
H3C
CH3
sp2 Hybridized Carbon
Planar Structure
E. (4) What two factors contribute to the stability of tertiary butyl cation verses methyl cation?
1) Inductive release of electron density by the alkyl groups to the cation center.
2) Hyperconjugation which is overlap of an adjacent C-H sigma orbital with the
F. (4) What physical property dominates the difference in boiling points between two alkynes.
Molecular Weight
G. (4) Define a Lewis Acid.
Electron pair acceptor such as H+ or AlCl3
Chemistry 30A, Fall 2009
Page 2
Name: KEY
THEORY and NOMENCLATURE
2. (24)
A. (4) Name the following compound using IUPAC rules including absolute stereochemistry.
Br
trans,cis-(7S)-7-bromo-2,5-nonadiene
B. (4) Name the following compound using IUPAC rules including absolute stereochemistry.
F
Br
Z-(7S)-4-bromo-3-chloro-7-fluoro-3-octene
Cl
C. (4) Draw the structure of (5S)-5-bromo-4,4-dimethyl-1-nonen-6-yne.
Br
D. (4) Draw the structure of bicyclo[6.3.0]-4-undecyne.
E. (4) Name the following compound using COMMON NAMES.
(R)-1-allyl-3-methylene-1-vinyl-cyclopentane
F. (4) Calculate the Enthalpy of Reaction (Horxn) for the following reaction using the Bond
Dissociation Enthalpies (Ho) given.
Ho Data (kcal/mol):
H-H 104
H-C 101
H-I
71
I-I
36
C-I
57
C=C 90 ( only)
HI
Horxn = Sum (bonds broken) - Sum (bonds formed)
= (71 + 90) (101 + 57)
= +3 kcal/mol
Chemistry 30A, Fall 2009
Page 3
Name: KEY
MECHANISMS
3.
A. (8) Propose a detailed mechanism to explain the following transformation.
H2O H2SO4
OH
H3O+
H2O
H2O
OH
O
H
B. (7) Draw the Reaction Coordinate Diagram for the mechanism proposed in part 3A.
LABEL structures associated with each energy level.
LABEL the Free Energy of Reaction (Gorxn).
For the rate determining step LABEL the transition state and the Activation Energy (EA).
Transition
State
2o
Cation
E
Ea
3o
Cation
ROH2
Cation
Alkene
!Gorxn
Alcohol
Reaction Coordinate
Chemistry 30A, Fall 2009
Page 4
Name: KEY
REACTIONS and SYNTHESES
4. (18) Suggest reagents, starting materials or products for the following transformations.
Pay attention to Regiochemistry and Stereochemistry!
A.
OH
OH
1) OsO4
2) NaHSO3 H2O
B.
OH
Br
Br2 H2O
C.
O
1) O3 CH2Cl2
2) Me2S
O
D.
H2 Lindlar's catalyst
OR 1) Sia2BH THF 2) AcOH
OR Nao NH3
E.
H
1) Sia2BH THF
O
2) H2O2 NaOH H2O
F.
Br
1 eq Br2
Br
Chemistry 30A, Fall 2009
Page 5
Name: KEY
REACTIONS and SYNTHESIS
5. (20) Suggest reagents to accomplish the following transformations or suggest reaction products.
Pay attention to Regiochemistry and Stereochemistry!
A.
1) Nao
Br
NH3
2) 1 eq Br2
Br
B.
Me
1) BH3 THF
2) H2O2 NaOH H2O
OH
C.
1) NaNH2
Pr-I
Cl
2) H2 Lindlar's catalyst
3) Cl2 Ethyl alcohol
D.
HBr
Br
E.
1) Br2
2) 3 equiv NaNH2
3) NaNH2
Br
AND
Cl
Chemistry 30A, Fall 2009
Page 6
Name: KEY
EXTRA CREDIT
6. (5) Answer Only One Question Using Both Words and Drawings.
Explain how ozone in the stratosphere protects us.
OR
Explain how the following molecule (rhodopsin) allows us to see.
Opsin
A. Ozone in the stratosphere can adsorb a high energy photon of UVC light to give
an excited state molecule which falls apart to oxygen and an oxygen atom.
Recombination of these reforms ozone and releases heat. So there is a net
conversion of light to heat. Ultraviolet C light is responsible for damage to DNA
which results in skin cancer.
O
h!
O
O
O
O.
+"
B. Rhodopsin can adsorb a photon of light to give an excited state molecule that then
decays by isomerizing to the all trans polyene. This trans molecule interacts with
other molecules due to its different shape and this creates a chemical signal that is
relayed down the neural path to the brain.
*
h!
N
Opsin
Opsin
Opsin
Biological
Signaling
