Name:

CHEM 331

Third Hour Exam (Chapters 8 and 9)

All answers should be written on the exam in the spaces provided. Clearly indicate your answers in the spaces provided; if I have to guess as to what or where your answer is, it's wrong. Where applicable, outline the logic or mystical principle you used to arrive at your answer, as partial credit may be awarded for correct approaches. You are strongly advised to read through the entire exam before beginning. (1).. 4 pts........................._______ (2).. 4 pts........................._______ (3).. 8 pts........................._______ (4).. 6 pts........................._______ (5)..16 pts........................._______ (6)..10 pts........................._______ (7)..21 pts........................._______ (8)..16 pts........................._______ (9).. 6 pts........................._______ (10).. 8 pts........................._______ _____________________________

TOTAL (99 pts)................_______ Percentage _______

1. [4 pts] Mevacor is used clinically to lower serum cholesterol levels. How many chiral centers does Mevacor have? Circle the chiral carbons.
HO * O O

*
O

* * * * * Mevacor

8 Chiral Carbons

2. [4 pts] Draw a Fischer Projection for the following chiral, tetrahedral carbon:
OH CH2CH3 H OH H Br CH2CH3

Br

One possibility....

3. [8 pts] Stereochemistry Questions: Assign R or S to the following molecules: (a)

HO HO CH3 CH2CH3

(b)
CH2CH2Br HOH2C Br H

S (dont forget to rotate the H (lowest priority) to top or bottom

4. [6 pts] A solution of an unknown compound X (3.0 g of X per 20 mL), when placed in a polarimeter tube 2.0 dm long, was found to have an observed rotation of 1.8 . What is the specific rotation of X? . []D = /(C )(l) = (-1.8)/ (0.15 g/mL)(2.0 dm) = -6 Dont forget Concentration is g/mL and the cell path length is in decimeters (1 dm = 10 cm)

5. [16 pts] Shown below are five compounds whose molecular formula is C6H12. Base the answers to the questions below on these five structures.

a. List two isomers that would be constitutional isomers of each other C or E and any other on the list b. List two isomers that would be diastereomers of each other D and either A or B c. List two isomers that would be meso compounds. D and E have a plane of symmetry d. Isomer A has an optical rotation of +35. What is the optical rotation of isomer B? -35 e. What is the optical rotation of isomer D? D is a diastereomer of A cant tell is optical rotation 6. [10 pts] Two stereoisomers are obtained from the reaction of HBr with (3S, 4S)-4-bromo-3-methyl1-pentene. a. [4 pts] Draw the structures of the two stereoisomers that form, showing stereochemistry of the new chiral center.
Br Br Br Br Br

HBr

b. [2 pts] What is the relationship between these two stereoisomers? Same Enantiomers Diastereomers Meso compounds

c. [4 pts] One of the stereoisomers is not optically active. Circle the optically inactive compound and explain why it is optically inactive. The circled compound is a meso compound contains a plane of symmetry thus its not optically active

7. [21 pts] Draw the structure of the expected product(s) or reagent for each of the following reactions, as required. Indicate the stereochemistry of the products where appropriate. (a)
2 equiv. HCl Cl Cl

(b)
1 equiv. Br2

Br

Br

(c)
1. disiamylborane 2. NaOH, H2O2 O H

(d)
1. O3 2. Zn, H3O+

O OH

HO O

(e)

H2, Pd/CaCO3, Pb or Na or Li, NH3

(f)

H2O, H2SO4, HgSO4

(g)
H2, Pd/C

8. [16 pts] Synthesis: Devise a short sequence of reactions for the construction of the following products. Write the required reagents on each arrow and draw the intermediate product(s) that will form in your sequence to receive full credit. a. [6 pts]

1. NaNH, NH3 H 2. 1-Bromobutane

H2O, H2SO4, HgSO4

b. [10 pts]
1. NaNH2, NH3 2.
Br

1. NaNH2, NH3 2.
Br

H2, Pd/C

9. [6 pts] Name the following compounds according to IUPAC nomenclature:

Cl

6-chloro-3-ethyl-5-isopropyl-1-nonen-8-yne

10. (16 pts) Short Answers- Choose 4 of the following 6 questions. a. Explain how R and S are related to (+) and (-). R and S are designations for the configurations of mirror image chiral carbons. (+) and (-) are the optical activity in opposite directions for chiral carbons. There is no correlation between knowing R/S and the direction of the optical rotation for a chiral carbon. b. Define the term: enantiomers Compounds with the same molecular formula same connectivity, different three dimensional arrangement that are non-superimposable mirror images c. The following statement is false. Explain why. Any molecule containing a stereocenter must be chiral. Consider the Meso Compound is contains stereocenters and has a plane of symmetry therefore it cannot be chiral. d. Explain why the pKa of the proton on a terminal alkyne is 25 but the proton on a terminal alkene is 45. The hybridization of the carbons of a terminal alkyne is sp while the hybridization of the carbons of an alkene is sp2. The sp hybrid orbital is shorter and rounder due to more s character electrons in this orbital are held closer to the positively charged nucleus and are more stable as an anion (thus the proton was more acidic).