CHEMISTRY 341

Final Exam December 13, 1999 NAME KEY

Problem 1 Problem 2 Problem 3 Problem 4 Problem 5 Problem 6 Problem 7 Problem 8 Problem 9

15 pts 12 pts 18 pts 15 pts 32 pts 32 pts 10 pts 10 pts 16 pts TOP 10 reasons Scott wanted to be the organic SI Guy . . . 10. 9. 8. 7. 6. 5. 4. 3. 2. To learn more Organic Chemistry To make fun of Fergie To find out how to synthesize Viagra It's too cold to golf So someone would actually listen to him talk He is a sadist Where else could he find friends? Organic is where it's all happenin' He's a chemistry geek

Problem 10 15 pts Problem 11 12 pts Problem 12 12 pts Given 1 pts 1

and the number 1 reason Scott wanted to be the organic SI Guy . . . 1. To pick up women

TOTAL

200 pts

Words of Wisdom from the SI Guy . . . #1) #2) #3) There are 3 ways to get something done - 1. Do it yourself. 2. Pay someone to do it. 3. Forbid your children to do it. There are 3 types of people in this world - 1. Those that can count. 2. Those that can't. English is totally overdid.

If you need scrap paper or more room, use the back of the test pages. Please read through each problem carefully. Enter your answers in the spaces provided.

Chem 341

Final Exam

13 December 1999

1. Name the following structures (IUPAC) or provide the structure that corresponds to the name for the following. (15 points)
a) 1-(2-methylpropyl)-1,4-cyclohexadiene

Cl b) (R)-2-chloro-3-ethylpentane

c)

(R)-2,4-dimethyl-2-hexene

Br Br d) a meso form of 2,3-dibromobutane Br or Br

e)

trans-hept-4-en-2-yne

2. Circle the most stable molecule in each pair below. (12 points)

CH3 Br CH3 CH3

CH3 Br

CH3 H H CH3 CH3 CH3

CH3 H3C H H CH CH3 3

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OH

Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

3. Circle all of the following pairs which represents resonance forms. (18 points)

O (a)

OH (b)

O (c)

OH

OH

OH O (d) N O N (e) OH

(f) H O

N N N H

N N N

4. What is the relationship between the following pairs of molecules? (15 points)
check one identical
OH HO Cl Cl HO OH

enantiomers diastereomers constitutional isomers

conformers

X
HO Br Cl OH

X
Cl CH3 C C HO H H N H OH CH3 CH3 Br OH H C C HO CH3 H H N

HO

HO

OH

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Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

5. Fill in the boxes for the major organic products of the following reactions. Indicate stereochemistry clearly where necessary. (32 points)

O O OH 1) BH3 2) H2O2, NaOH

1) HBr (1 eq) 2) (CH3)2CuLi H2 Lindlar catalyst 1) NaNH2 2) 1-bromo-2-methylpropane Cl

O3 then + Zn, H3O Cl 1) HCl (1 eq) 2) HBr (1 eq) Br

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Cl2 (excess) Cl Br Cl

H2 Pd/C
Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

6. Fill in the boxes for the major organic products of the following reactions. Indicate stereochemistry clearly where necessary. (32 points)

OH O O OH

Br 1) BH3 2) H2O2, NaOH HBr 1) Hg(OAc)2 2) NaBH4 KMnO4 H3O+

1) OsO4 2) NaHSO3

OH

OH

OH or Br

NBS, light

Cl2, H2O

H2 Pd/C

Br Cl

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OH
Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

7. The two tosylates shown below react differently under identical reaction conditions. One will undergo a facile SN2 reaction while the other will easily eliminate via an E2 mechanism. Draw the structure of the major product for each reaction. (10 points)
OCH3 CH3

OTos CH3

NaOCH3 DMSO

OTos CH3

NaOCH3 DMSO CH3

8. The following substitution reaction is described by the accompanying reaction diagram. Show on the diagram with arrows, the activation energy for the rate determining step and G. (10 points)

OTos CH3

Some nucleophile

substitution product

G G reaction progress

(a) Does the reaction take place by a SN1 or a SN2 mechanism? (b) Check the box for the statement that is true about the reaction. A racemic mixture of enantiomers will be produced.

SN1

A mixture of two diastereomers, both racemic will be produced.

A mixture of two diastereomers, both chiral will be produced. A single stereoisomer will be produced.
page 6 of 10 Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

9. Fill in the missing structure or reagents where necessary. (16 points)

OH PBr3 Br 1) Mg 2) D O 2 D

Tos-Cl base

OTos

NaCN HMPA

CN

10. Starting from ethynyl benzene, synthesize the molecule shown using any other reagents you need. More than one step will be necessary. Show all reagents and intermediate structures along the way. (15 points)

H2 / Lindlar or Li / NH3

(CH2=CH)2CuLi

Br HBr

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Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

11. Below is the IR and 1H NMR spectra for an unknown compound with a molecular formula C5H10O. In the 13C NMR, four resonances appear at 210, 45, 22, and 16 ppm.

(a) The IR stretching frequency at 1720 cm-1 corresponds to what functional group? (4 points)

Carbonyl (Ketone)
(b) What is the structure of this molecule? (8 points)
O

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Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

12. A molecule with the molecular formula C7H7Br displays the following mass spectrum.

(a) How many units of unsaturation are present? (3 points)

(b) What is the structure of the base peak at m/e 91? (3 points)

or

(c) What is the structure of the molecule? (3 points)

Br

(d) Briefly explain why there are two peaks at m/e 170 and 172 of nearly equal amounts. (3 pts)

Bromine exists in nature as roughly a 50:50 mixture of two isotopes which are 2 mass units different. 79 Br and 81Br

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Prof. Gregory R. Cook

Chem 341

Final Exam

13 December 1999

USEFULL DATA Infrared Correlations: C-H stretches: alkanes alkenes alkynes alcohols carbonyl alkyne nitrile 2850 - 2960 cm-1 3020 - 3100 cm-1 3300 cm-1 3400 - 3650 cm-1 1680 - 1750 cm-1 2100 2260 cm-1 2210 - 2260 cm-1 medium/strong medium strong (sharp) broad/strong strong medium medium

O-H stretch: C=O stretch: CC triple bond: CN triple bond

1

H NMR Correlations: (alkanes) (adjacent to sp2 carbon) (Y = O, N, Br, Cl, etc) (alkenes) (benzene rings) (aldehydes) (acids) 0.5 - 1.5 ppm 1.5 - 2.5 ppm 2.5 - 4.5 ppm 4.5 - 6.5 ppm 6.5 - 8.0 ppm 9.5 - 10.0 ppm 11.0 - 12.0 ppm

C-H allylic Y-C-H C=C-H sp2 aromatic O=C-H CO2H

13

C NMR Correlations: (alkanes) (Y = O, N, Br, Cl, etc) (alkenes) (benzene rings) (esters) (aldehydes, ketones) 10 - 60 ppm 40 - 80 ppm 100 - 150 ppm 120 - 160 ppm 175 - 200 ppm 200 - 220 ppm

C Y-C C=C sp2 aromatic O=C-O O=CR2

Atomic Weights C H O Cl Br 12 1 16 35 (75%), 37 (25%) 79 (52%), 81 (48%)

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Prof. Gregory R. Cook