Your C342 Team: Part I

Prof. Martha G. Oakley

Prof. Laura C. Brown

This course will be team taughtwe will manage the entire course as a team, including lectures, quizzes and exams

Part 2: Your Associate Instructors

Toolika Agrawal 2nd Year Grad Cook Lab

Ryan Bell Ist Year Grad Student

Emily Rigsbee 1st Year Grad Student

Brittany Witherspoon 1st Year Grad Student

C342 Organic Chemistry II

A Challenging Course

Understanding

Time Many of life's failures are people who did not realize how close they were to success when they gave up. ~ Thomas Edison

Discussions: Attend Any You Like

You may attend more than one discussion per week, if space You may earn up to 10 bonus points over the semester for 4 attending office hours (max 1 per week)

OFFICE HOURS
We will hold 12 office hours weekly beginning next week Professor Oakley will hold office hours this week from 3:00-4:00 on Tuesday and from 4:00 to 5:05 on Thursday, Simon Hall (across from Jordan), Room 320B. Professor Brown will hold office hours this week on Monday 9-10 am and Wednesday from 12:20-1:20 in Chemistry A112 Regular office hours begin next week.
5

Grading
Quizzes (see syllabus for dates) best 3 out of 4 (100 pts) Early quizzes available only for university sanctioned events, etc. Exams 3 x 2 hr exams; Tues evenings (150 pts each) Final Exam (300 pts) Drop lowest exam or of final grade, whichever is lowest YOU ARE RESPONSIBLE FOR READING THE SYLLABUS

Grading Cutoffs
The instructors do not grade on a curve (A) understands the material well and can apply it creatively to new situations. Cutoff for an A- no higher than 90%. (B) Good, solid understanding of the material Cutoff for a B- no higher than 75% (C) Major gaps in understanding Cutoff for a C- no higher than 60%. (D or F) Still larger gaps
7

Active Learning
You should be thinking during class We will do lots of problem-solving in class We will call on students to help us work problems You should be trying to work the problem at the same time as the student who has been called on You get a bonus point every time you participate right or wrong There are no other ways to earn bonus points, except for discussion attendance

Courtesy in Class
This is a large room and there are a lot of people in it. Whispering in class makes it difficult for others to hear the lectures This class costs a lot of money! Lecture attendance is optional in this course Should you choose to attend lecture, we expect you to be courteous to us and to your classmates If we are slowed or cannot continue because of noise, you are responsible for all the material we would have covered without the noise.
9

Review of Organic Chemistry I

Work practice problems on Oncourse (Resources, Practice Problems for Quiz 1) Read Chapter 4.2-4.6 (Review) Work problems 4.3, 4.16, 4.17, 4.18, 4.19, 4.22, 4.29, 4.30, 4.31

10

Lewis Structures and Formal Charge

11

B. Write a Lewis structure for diazomethane (CH2N2) and assign each atom a formal charge (connectivity as shown)

12

II. Curved Arrows

B. Move from electron source to electron sink source: sink: ________ __________ charge or _____________ _____________

charge or partial

13

III. Resonance
A. Provide appropriate curved arrows to show how to generate additional resonance structures (if possible)

14

B. How many resonance structures can you draw for the benzyllic cation (5 possible)? Show the electron flow between each one.

15

IV. Curved Arrows in Reaction Mechanisms

16

17

V. Following Electron Flow in Reactions You Haven't Seen Before

A. Thioester Claisen Condensation
O + S CH2 S O CH3

Note: I will give you either the arrows or the products

18

continued
O S
-O

CH3 S

19

A.

B.

20

Provide Arrows
Provide mechanistic arrows, indicating the direction of electron flow, for the following one-step transformation. Hint:number your carbons. Where are bonds broken or formed?

O H

H O

O H O N H O H H H N

21

Which of these groups of mechanistic arrows is correct? Why? Electron source? Sink?
H N
+HN

CO2H N H O CH3

H H N

CO2H O CH3

N+ H

N H

H N
+HN

CO2H N H O CH3

H H N

CO2H O CH3

N+ H

N H

VI. Nomenclature
You should be able to write structures from IUPAC or common names Examples: 1. isopropanol (2 propanol) 2. cis 3-hexene (Z-hexene)

3. tert-butanol (2,2-dimethylethanol)

4. trans-2-butene (E-butene)

5. n-butylamine (1-butyl amine)

23

VII. Thermodynamics and Equilibrium

(1) Gravitational

(2) Electrical

(3) Chemical 24

Free Energy is a Combination of Enthalpy and Entropy G = H TH If G < 0, reaction is product-favored If G >0, reaction is reactant-favored In other words: If G < 0, reaction is thermodynamically favorable (higher to lower energy) If G >0, reaction is is thermodynamically unfavorable (lower to higher energy)
25

Example of an Exothermic Reaction. Where does the energy come from? Consider the reaction H2(g) + Cl2 (g) --> 2 HCl

26

27

Estimating Reaction Enthalpy from Bond Enthalpies

OH
Enol tautomer

O
Keto tautomer

These molecules are a special kind of isomer of one another called tautomers (molecules that differ by the placement of a double bond and a proton).

28

C=O C-O: C=C C-C:

29

OH

Bonds broken:

Bonds formed:

Enthalpy of reaction:

30

Practice: Predicting Entropy Changes

1. CO2 (s) ----> CO2 (g) 2. 2CO + O2 (g) ----> 2 CO2 (g) 3. Ag+(aq) + Cl-(aq) ----> AgCl (s) 4. CO2 (g) ---> CO2 (aq) 5.

+ H2

31

Chemical Equilibrium

Concentrations of products and reactants at equilibrium are CONSTANT. Equilibrium is DYNAMIC; the rates of the forward and reverse reactions are equal. Equilibrium concentrations are independent of the direction of approach (same reaction, same temp). 32

How do we know equilibrium is dynamic?

Equilibrium Reaction: CH3COOH (aq) + H2O (l) Acetic acid CH3COO- + H3O+ acetate

At equilbrium, add a tiny amount of radioactive sodium acetate: C*H3COOGet labeled acetic acid: C*H3COOH How can this happen?

33

Direction of Approach Doesnt Matter

Figure 14.1

N2(g) + 3H2 (g)

2NH3(g) 34

A brief look at kinetics

The rate of a reaction depends on the concentration of the reactant(s) and a constant that is characteristic for the reaction. For example, isomerization of butene:

Rateforward = kforward [cis-butene] Ratereverse = kreverse [trans-butene] What happens to the concentrations of cis and trans butene as we approach equilibrium?

35

How do these rate constants relate to the equilibrium constant Kc?

At equilibrium, Rateforward = Ratereverse

Thus: kforward [cis-butene]eq = kreverse [trans-butene] eq Rearranging: kforward kreverse

=

[trans-butene] eq [cis-butene]eq

36

Writing Equilibrium Constant Expressions

For the reaction aA + bB cC + dD Keq = --------------------

Only consider substances whose concentrations change as the reaction occurs. Should we consider: A) B) C) D) E) Pure solids Pure liquids Gases Solutes in dilute solutions (the stuff thats dissolved) Solvents in dilute solutions

37

Shifting a Chemical Equilibrium: Le Chateliers Principle

If a system is at equilibrium and conditions are changed so that the system is no longer at equilibrium, the system will

Example: isomerization of butene. Keq = 1.5 at 600 K

Remove 1/2 of cis butene at equilibrium. What happens?

38

Figure 14.6

Can drive a reaction to completion by removing one of the products. Acid-Catalyzed Esterification of Carboxylic Acids
O OH OH H2SO4 O O

+ H2O propyl acetate 0 mmol 0mmol .67 mmol .67mmol

39

init. 1 mmol 1 mmol eq. .33 mmol .33 mmol

The concentrations of reactants and products at equilibrium are dictated by the difference in free energy between them:

At room temperature, For example calculate Keq for following reaction: N2(g) + 3H2 (g) G =-32.90 kJ 2NH3(g)

Or to estimate, Keq =

40

A word about arrows

Irreversible Reactions:
O O OH
heat

O
+ CO2 (g)

OH OH

NH3

OH

NH4

Keq ~ 1016

Acid-Catalyzed Esterification of Carboxylic Acids Reversible Reactions:

O OH OH H2SO4 O O

+ H2O propyl acetate Keq = 4

init. 1 mmol 1 mmol 0 mmol 0mmol Note: your book uses .33 mmol arrows only when the reaction is actually at eq. .33 mmol equilibrium .67 mmol .67mmol

equilibrium. This is technically correct but not very useful pedagogically. We will use reversible arrows to indicate that both forward and reverse reactions are occurring.

41

VIII. Acid-Base Reactions and pKas

H-A + H2O H3O+ + AKa = [H3O+ ][A- ] [HA]

Normally written in simplified form:

H-A H+ + AOr

H-A+

H+ + A

Ka is simply the equilibrium constant for this reaction:

42

Arrow pushing for acid-base reactions:

Why is this wrong?

43

Directionality of Acid-Base Reactions

?

In which direction does the equilibrium lie?

44

Which is the stronger acid, HA or HB? Stronger base?

Acidity and pKa

Define pKa: [H+ ][A- ] Ka = [H-A] If Ka = 10-7, what is pKa? 7 So, the higher the Ka, the stronger or weaker the acid?

So, the higher the pKa, the stronger or weaker the acid?

If the pKa values differ by 1 unit, by how much do Kas differ? 46

Acid-Base Equilibria
In which direction does the equilibrium lie? Is Keq < 1 or > 1? Keq=

47

Where K = Ka

Ka =

[H+ ][A- ] [H-A]

Acid H-Cl O

Review from Organic Chemistry I

Conjugate Base pKa Ka

OH acetic acid H O H

NH3+

Note:

NH4+ NH2 O

49

50

Structure and Acidity

NH3
Conj base? pKa?

H 2O

HF

38

16

H C C H
Conj base? pKa?

H C N:

name?
25 9

OH OH O O

OH

How about within a column of the periodic table?

H-I H-Br H-Cl H-F CH3OH CH3SH

O OH
v.

OH

OH

OH

4.8

15.9

10

15

53

What about this series?

H H H H H H

H3C CH3

54

Review Effects Inductivefrom C341

O OH I O OH Br O OH Cl O OH

name? pKa 4.8 3.2 2.9 2.6 As halogen electronegativity increases, pKa _____________
O OH Cl Cl Cl OH Cl

O OH Cl

O OH Cl

pKa 4.8

2.9

1.5

0.7

Inductive effect falls off rapidly with distance:

O OH Cl O OH Cl O OH Cl O OH

_________ ______________ _________ ______________ 4.8 4.5 4.0 2.8

Example 16.2. Pick the stronger acid in each pair.

O OH

v.

O OH

name?

OH

OH

OH

NO2

NO2

10
Explain:

8.4

7.2

57

Which is the most acidic proton in this molecule? Next? Least? O O

When the acid is neutral, consider the stability of the conjugate base. The more stable (less reactive) the conjugate base, the more reactive the acid, lower pKa. 58

How to decide which atom is most basic?

Draw resonance structures for each form:

59

acid O OCH3 H

conjugate base O OCH3

pKa

-6.5

Why is the protonated ester more acidic than the protonated amide? Hint: think about resonance structures.

H O NH2

O NH2 -0.5

60

List the five structural factors important for determining the pKa of an acid:
1) 2) 3) 4) 5)

61

IX. pKas and Substitution Reactions

A. Which molecule is more likely to react via an SN2 mechanism? SN1? Predict products?

62

63

64