Organic Chem 222

Instructor: Professor Manashi Chatterjee Office: 1313 B HN Telephone: (212) 772-5377 Email: chatterjeehunterchemistry@gmail.com Office Hours: Tuesday: 4:00 pm 5:00 pm and Wednesday: 3:00 pm 4:00 pm Also by email appointment. Please include CHEM 22204

in the subject line

Lecture:Tuesday and Friday 1:10 PM - 3:00PM, North Bldg 118 4 Credit Course (Lab is a separate course) ~4 hr lecture + 1 Recitation (50 min)
2014 by John Wiley & Sons, Inc. All rights reserved.

About your Instructor

ACEDAMIC POSITIONS
Organic Chemistry Lecturer (August 2008 August 2013)

Department of Chemistry University of Nebraska, Lincoln (UNL)

Lincoln, Nebraska, USA

Organic Chemistry Lecturer (July 2006 July 2008)

Department of Chemistry & Biochemistry Instructional Division University of California, Los Angeles (UCLA); Los Angeles, California, USA

2014 by John Wiley & Sons, Inc. All rights reserved.

EDUCATIONAL BACKGROUND
University of Edinburgh Scotland, UK
Post-doctoral Fellow

University of Saskatchewan Saskatoon, Canada

Ph.D. (Organic Chemistry)

Indian Institute of Technology (IIT)

Bombay, India

M.Sc. (Organic Chemistry)

2014 by John Wiley & Sons, Inc. All rights reserved.

 2014 by John Wiley & Sons, Inc. All rights reserved.

Recitation Instructors
Ahmad Altiti Patricia Gonzalez

Nirav Kapadia
James McNamara Guangli Yang

2014 by John Wiley & Sons, Inc. All rights reserved.

Textbook and Course Materials

T. W. Graham Solomons & Craig B. Fryhle, Organic Chemistry, Eleventh Edition, John Wiley & Sons is required.
A PRS transmitter i-clicker-2

Sapling Learning (online HW access code)

Molecular models are highly recommended

2014 by John Wiley & Sons, Inc. All rights reserved.

Grading
Grades will be based upon: 700 points Clicker questions 50 pts (total clicker points will be scaled to 50 pts) Electronic Homework (Sapling) 70 pts (total Sapling points will be scaled to 70 pts) Quizzes (4x 20) 80 pts

Midterms (3 x 100)
Comprehensive Final

300 pts
200 pts

2014 by John Wiley & Sons, Inc. All rights reserved.

Missed Exams: In any class this large, there will be emergencies that cause students to miss exams. In the event of a verified emergency (medical or death in family), the student is to contact Professor Chatterjee by email and in person as soon as you get back. If, in my judgment, the excuse is valid I will substitute your final exam percentage for the test grade. If you miss more than one test, meet with me ASAP to discuss your options. I may require you to bring a Proof to document your absence. There will be no make up exams

2014 by John Wiley & Sons, Inc. All rights reserved.

Peer Instruction (PI) using i-clickers

Interactive Engagement Versus Traditional Methods Interactive teaching strategies move students from passive listeners to intellectually engaged learners who take an active responsibility for participating in and monitoring their own learning

2014 by John Wiley & Sons, Inc. All rights reserved.

Conceptual Questions are posed to the students Various scenarios are possible regarding Students spend several minutes thinking about the question Students Vote Students discuss the question with their peers defending their answer and trying to reach consensus. Students Vote again

2014 by John Wiley & Sons, Inc. All rights reserved.

Remember that the first vote reflects YOUR knowledge there should be no talking before the first vote.
Remember that the second vote reflects knowledge of YOU & YOUR PEERS. There should be lots of talking before the second vote. the

This talking should be focused on scientific reasoning the why you think a certain answer is correct convince them that your answer is correct. Politely critiquing the reasoning of your peers or asking them to explain something more fully or in a different way is appropriate. You ultimately want to reach consensus. You need to be sitting near a peer you may need to get up and move!
2014 by John Wiley & Sons, Inc. All rights reserved.

Goal & Objectives:

Students will develop an understanding of 1. Bonding and three-dimensional structure of carbon based compounds. 2. Nomenclature of organic compounds 3. Organic chemical reactions and their mechanisms.
2014 by John Wiley & Sons, Inc. All rights reserved.

Chapter 1
The Basics Bonding and Molecular Structure

2014 by John Wiley & Sons, Inc. All rights reserved.

Table of Contents
1. 2.

3.
4. 5. 6. 7. 8.

Life & the Chemistry of Carbon Compounds Atomic Structure Chemical Bonds: The Octet Rule How to Write Lewis Structures Formal Charges and How to Calculate Them Isomers How to Write and Interpret Structural Formulas Resonance Theory

2014 by John Wiley & Sons, Inc. All rights reserved.

Organic Chemistry
The branch of chemistry that deals with carbon compounds. Biomolecules (lipids & fats, proteins, carbohydrates) fabrics wood and paper products plastics Medicinals / drugs / detergents 15

Friedrich Whler (31 July 1800 - 23 September 1882) was a German chemist, best-known for his synthesis of Urea, but also the first to isolate several chemical elements. Urea is widely used in Whler is regarded as a pioneer in organic fertilizer chemistry as a result of him (accidentally) as a convenient source synthesizing Urea in the Whler synthesis of nitrogen in 1828. This synthesis was a landmark in the history of science which disproved and undermined the Vital Forces which was believed for centuries, by showing that organic compounds could be synthesized from inorganic materials. Wohler also prepared urea, a constituent of urine, from ammonium cyanate NH4(NCO) in the laboratory without the help of a living cell. Whler was a co-discoverer of beryllium, silicon, and silicon nitride (Si3N4); hard ceramic. Silicon nitride bearings are used in the main engines of the NASAs Space shuttles. 2014 by John Wiley & Sons, Inc. All rights reserved.

In this chapter we will consider:

What kinds of atoms make up organic molecules

The principles that determine how the atoms in organic molecules are bound together
How best to depict organic molecules
2014 by John Wiley & Sons, Inc. All rights reserved.

1. Life & the Chemistry of Carbon Compounds

Organic chemistry is the chemistry of compounds that contain the element carbon. Carbon, atomic number 6, is a second-row element
If a compound does not contain the element carbon, it is said to be inorganic (there are

some exceptions)

2014 by John Wiley & Sons, Inc. All rights reserved.

Carbon compounds are central to the structure of living organisms and therefore to the existence of life on Earth. We exist because of carbon compounds Although carbon is the principal element in organic compounds, most also contain hydrogen, and many contain nitrogen, oxygen, phosphorus, sulfur, chlorine, or other compounds
2014 by John Wiley & Sons, Inc. All rights reserved.

Organic Compounds
O
H H CH3CH2CH CHCH2CONH O N S CH3 CH3 COONa

O O H5C6 N H C6H5 O O OH H5C6 O

O H NCH3 HO

O OH

HO O O O CH3

2-Pentenylpenicillin

CH3O

Taxol

Codeine

Organic chemistry is the chemistry of carbon compounds.

Chapter 1

20

There are two important reasons why carbon is the element that nature has chosen for living organisms:

Carbon atoms can form strong bonds to other carbon atoms to form rings and chains of carbon atoms Carbon atoms can also form strong bonds to elements such as hydrogen, nitrogen, oxygen, and sulfur
2014 by John Wiley & Sons, Inc. All rights reserved.

Because of these bond-forming properties, carbon can be the basis for the huge diversity of compounds necessary for the emergence of living organisms

2014 by John Wiley & Sons, Inc. All rights reserved.

Credit for the first synthesis of an organic compound from an inorganic precursor is usually given to ___. a) Berzelius b) Arrhenius c) Kekule d) Wohler d) Lewis

2014 by John Wiley & Sons, Inc. All rights reserved.

2. Atomic Structure
Compounds made up of elements combined in different proportions Elements made up of atoms Atoms positively charged nucleus containing protons and neutrons with a surrounding cloud of negatively charged electrons

2014 by John Wiley & Sons, Inc. All rights reserved.

Each element is distinguished by its atomic number (Z)

Atomic number = number of protons in nucleus

2014 by John Wiley & Sons, Inc. All rights reserved.

1.1 Describe the structure of an atom.

a. Neutrons and protons are in the nucleus; electrons are in orbitals. b. Neutrons and electrons are in the nucleus; protons are in orbitals. c. Electrons and protons are in the nucleus; neutrons are in orbitals. d. Electrons are in the nucleus; neutrons and protons are in orbitals.

2A. Isotopes

Although all the nuclei of all atoms of the same element will have the same number of protons, some atoms of the same element may have different masses because they have different numbers of neutrons. Such atoms are called isotopes

2014 by John Wiley & Sons, Inc. All rights reserved.

Isotopes
12 6

14

C 6

protons but different number of neutrons. Mass number is the sum of the protons and neutrons in an atom.

Isotopes are atoms with the same number of

Chapter 1

28

Examples
12C 13C 14C

(1)

(6 protons 6 neutrons)

(6 protons 7 neutrons)

(6 protons 8 neutrons)

(2)

1H

2H

3H

Hydrogen (1 proton 0 neutrons)

Deuterium (1 proton 1 neutron)

Tritium (1 proton 2 neutrons)

2014 by John Wiley & Sons, Inc. All rights reserved.

1.2 Define isotopes.

a. Atoms with the same number of neutrons, but a different number of electrons. b. Atoms with the same number of protons, but a different number of electrons. c. Atoms with the same number of protons, but a different number of neutrons. d. Atoms with the same number of neutrons, but a different number of protons.

2B. Valence Electrons

Electrons that surround the nucleus exist in shells of increasing energy and at increasing distances from the nucleus. The most important shell, called the valence shell, is the outermost shell because the electrons of this shell are the ones that an atom uses in making chemical bonds with other atoms to form compounds The number of electrons in the valence shell (called valence electrons) is equal to the group number of the atom
2014 by John Wiley & Sons, Inc. All rights reserved.

e.g. Carbon is in group IVA Carbon has 4 valence electrons

e.g. Nitrogen is in group VA Nitrogen has 5 valence electrons

e.g. Halogens are in group VIIA F, Cl, Br, I all have 7 valence electrons

2014 by John Wiley & Sons, Inc. All rights reserved.

1.3 Counting Valence Electrons

You can always calculate the number of valence electron by analyzing the electronic configuration. Look at phosphorus. Or, for Group A elements only, just look at the group number (Roman numeral) on the periodic table.

1.3 How many valence electrons does carbon have?

a. Three valence electrons b. Four valence electrons c. Five valence electrons d. Six valence electrons e. Seven valence electrons

1.3 Answer
a. Three valence electrons b. Four valence electrons c. Five valence electrons d. Six valence electrons e. Seven valence electrons Carbon has an electronic configuration of 1s22s22p2 and thus, only has four electrons in its outer shell.

1.3 What is the electronic configuration for Al? (Z:13)

a. 1s22s22p6 b. 1s22s22p63s1 c. 1s22s22p63s2 d. 1s22s22p63s23p1

1.4 What is the electronic configuration for Ca+2? (Ca atomic number is 20)

a. 1s22s22p63s2 b. 1s22s22p63s23p6 c. 1s22s22p63s23p64s2 d. 1s22s22p63s23p64s24p2

1.5. What is the electron configuration of an oxygen ion with a single positive charge and what neutral atom shares the same electron configuration?

A. 1s22s22p3, nitrogen B. 1s22s22p3, fluorine C. 1s22s12p4, nitrogen D. 1s22s12p4, fluorine

3. Chemical Bonds: The Octet Rule

Ionic (or electrovalent) bonds are formed by the transfer of one or more electrons from one atom to another to create ions Covalent bonds result when atoms share electrons
2014 by John Wiley & Sons, Inc. All rights reserved.

Octet Rule In forming compounds, they gain, lose, or share electrons to give a stable electron configuration characterized by 8 valence electrons

When the octet rule is satisfied for C, N, O and F, they have an electron configuration analogous to the noble gas Ne
2014 by John Wiley & Sons, Inc. All rights reserved.

Electronic Configurations

Electronic configuration of carbon

The aufbau principle states to fill the lowest energy orbitals first. Hunds rule states that when there are two or more orbitals of the same energy (degenerate), electrons will go into different orbitals rather than pairing up in the same orbital.

Chapter 1

Recall: electron configuration of noble (inert) gas # of e-s in outer shell H [1s2] 2

Ne 1s2[2s22p6]
Ar 1s22s22p6[3s23p6]

8
8

2014 by John Wiley & Sons, Inc. All rights reserved.

3A. Ionic Bonds

Atoms may gain or lose electrons and form charged particles called ions

An ionic bond is an attractive force between oppositely charged ions

2014 by John Wiley & Sons, Inc. All rights reserved.

Na 1s2 2s2 2p6 3s1

give 1 e- to

Cl 1s2 2s2 2p6 3s2 3p5

(1 e- in outermost shell) (7 e- in outermost shell)

ionic bonding

Na 1s2 2s2 2p6 8

Cl 1s2 2s2 2p6 3s2 3p6 8

2014 by John Wiley & Sons, Inc. All rights reserved.

3B. Covalent Bonds & Lewis Structures

Covalent bonds form by sharing of electrons between atoms of similar electronegativities to achieve the configuration of a noble gas

Molecules are composed of atoms joined exclusively or predominantly by covalent bonds

2014 by John Wiley & Sons, Inc. All rights reserved.

1.6 Identify the compound with ionic bonding.

a. CH4 b. NaBr c. CH3Cl d. CH3OH

Electronegativity (EN)

The intrinsic ability of an atom to attract the shared electrons in a covalent bond Electronegativities are based on an arbitrary scale, with F the most electronegative (EN = 4.0) and Cs the least (EN = 0.7)
2014 by John Wiley & Sons, Inc. All rights reserved.

element (EN) Li (1.0) Na (0.9) K (0.8) Rb (0.8) Cs (0.7) Be (1.6) Mg (1.2)

H (2.1) .. B (2.0) C (2.5) Si (1.8) N (3.0) P (2.1) O (3.5) S (2.5) F (4.0) Cl (3.0) Br (2.8) I (2.5)

...

.. ..

2014 by John Wiley & Sons, Inc. All rights reserved.

Electronegativity and Bond Polarity

Electronegativities can be used to predict whether a bond will be polar. Since the electronegativity of carbon and hydrogen are similar, CH bonds are considered to be nonpolar.

Is the sharing of electrons in molecules always equal? non-polar bond

Which element is more electronegative?

Y
increasing polarity of bond

DEN = 0

X
X X X

Y
Y Y Y

DEN = 0.3
DEN = 0.6

ENY > ENX

polar bond

DEN = 0.9

0 < EN < 1.5

DEN = 1.2

Direction of electron migration

1.7 How does electronegativity change on the periodic table?

a. Increase from left to right; increase from top to bottom. b. Increase from left to right; increase from bottom to top. c. Increase from right to left; increase from top to bottom. d. Increase from right to left; increase from bottom to top.

Bond

D electronegativity

Bond type

C-H

________________

______________

N-H

________________

______________

O-H

________________

______________

C-O

________________

______________

NaCl

________________

______________

C-O is often written with partial charges. Write the correct partial charges on C and O in C-O bond

1.8 List the following atoms in decreasing electronegativity.

a. C > Br > O > F b. F > O > C > Br c. F > O > Br > C d. F > C > O > Br

Select the most electronegative element from the list below. a) H b) O c) N d) B e) C

2014 by John Wiley & Sons, Inc. All rights reserved.

Polar Covalent Bonds

Covalent bonds are either polar or nonpolar:

Nonpolar covalent bonds: bonded atoms share electrons evenly Polar covalent bonds: one of the atoms attracts electrons more than the other How strongly an atom attracts shared electrons

Electronegativity:

Klein, Organic Chemistry 1e

Polar Covalent Bonds

Electrons tend to shift away from lower electronegativity atoms to higher electronegativity atoms.

The greater the difference in electronegativity, the more polar the bond.

Klein, Organic Chemistry 1e

1.9. Which of the indicated bonds are polar covalent bonds?

a. b. c. d. e.

1, 2, 3, 4, 5, 6, 7 1, 3, 5, 6 1, 3, 4, 7 3, 5, 6, 7 1, 3, 4, 5, 6

Heterolysis

A B

heterolytic bond cleavage

A + B
ions

Homolysis

A B

homolytic bond cleavage

A + B
radicals

2014 by John Wiley & Sons, Inc. All rights reserved.

Example

:Cl.
[Ne] 3s2 3p5

. Cl:
[Ne] 3s2 3p5
covalent bonding

: :

: :

:ClCl:
2014 by John Wiley & Sons, Inc. All rights reserved.

: : : :

Ions, themselves, may contain covalent bonds. Consider, as an example, the ammonium ion
H H N H H

N H

H+

(ammonia) (3 bonds on N)

(ammonium cation) (4 bonds on N with a positive charge on N)

2014 by John Wiley & Sons, Inc. All rights reserved.

4. How to Write Lewis Structures

Lewis structures show the connections between atoms in a molecule or ion using only the valence electrons of the atoms involved For main group elements, the number of valence electrons a neutral atom brings to a Lewis structure is the same as its group number in the periodic table

2014 by John Wiley & Sons, Inc. All rights reserved.

If the structure we are drawing is a negative ion (an anion), we add one electron for each negative charge to the original count of valence electrons. If the structure is a positive ion (a cation), we subtract one electron for each positive charge In drawing Lewis structures we try to give each atom the electron configuration of a noble gas

2014 by John Wiley & Sons, Inc. All rights reserved.

Bonding

involves the valence electrons or outermost shell (or highest shell) electrons

for group A elements - the group number tells how many valence electrons
How many valence electrons on N?

Group 5A 5 valence electrons

Bonding

Lewis dot structures show the valence electrons around at atom and for most molecules and compounds a complete octet for the elements
N

Al

most monatomic ions have an electron configuration of noble gases

F

1s22s22p5

+ e- F

1s22s22p6 Ne

Bonding Patterns
Valence electrons # Bonds
4 3 2

# Lone Pair Electrons

0 1 2

C N O

4 5 6

Halides
(F, Cl, Br, I)

7
Chapter 1

66

Lewis Structures
CH4
Carbon: 4e 4 H@1 e ea: 4 e 8e

NH3
H H C H H
Nitrogen: 5e 3 H@1 e ea: 3 e 8e

H N H H

H2O
Oxygen: 6e 2 H@1 e ea: 2 e 8e

Cl2
H O H
Chapter 1

2 Cl @7 e ea: 14 e

Cl Cl

Examples Lewis structure of CH3Br

(1)

Total number of all valence electrons:

Br

4 + 1 x 3 + 7 = 14
2014 by John Wiley & Sons, Inc. All rights reserved.

H H C H Br

: :

Br:
remaining 6 valence electrons

8 H valence electrons
2014 by John Wiley & Sons, Inc. All rights reserved.

(2)

Lewis structure of methylamine (CH5N)

Total number of all valence electrons: C H N

4 + 1 x 5 + 5 = 14

2014 by John Wiley & Sons, Inc. All rights reserved.

H H C H N H
2 valence electrons left

H
12 valence electrons

2014 by John Wiley & Sons, Inc. All rights reserved.

Double and Triple Bonds

Chapter 1

72

Chapter 1

74

1.10 Which of these substances contain both covalent and ionic bonds? a) NH4Cl b) H2O2 c) CH4 d) HCN e) H2S

2014 by John Wiley & Sons, Inc. All rights reserved.

1.11 How many bonding pairs of electrons are in NH2OH?

a. One pair of electrons b. Two pairs of electrons c. Three pairs of electrons d. Four pairs of electrons

1.13 How many nonbonding pairs of electrons are in NH2OH?

a. One pair of electrons b. Two pairs of electrons c. Three pairs of electrons d. Four pairs of electrons

1.14 How many bonds (pairs of electrons) are in CH2=CH2?

a. Two bonds b. Three bonds c. Four bonds

d. Five bonds e. Six bonds

Which type of bonding is present in the compound CH3Li? a) Ionic bonding b) Covalent bonding c) Hydrogen bonding d) Ionic and Covalent bonding e) Ionic, Covalent, and Hydrogen bonding

Which of the following is the Lewis structure for CH3CH2O2H?

a)

H H C H

H C H
H O C H H O H

b)

H H C H H
H C H O

H O C
H C H O H

c)

d)

C H

e) None of these choices.

4A. Exceptions to the Octet Rule Elements in the 2nd row in the periodic table usually obey the Octet Rule (Li, Be, B, C, N, O, F) since they have one 2s and three 2p orbitals available for bonding Elements in the 3rd row in the periodic table have d orbitals that can be used for bonding and may not obey the Octet Rule

2014 by John Wiley & Sons, Inc. All rights reserved.

Examples
Cl P Cl Cl Cl Cl Cl P Cl Cl Cl Cl Cl P Cl Cl Cl

Cl

(PCl5)

Phosphorus pentachloride

F Si F F

2F F

m.p. = 179oC

(SiF62-)
2014 by John Wiley & Sons, Inc. All rights reserved.

Some highly reactive molecules or ions have atoms with fewer than eight electrons in their outer shell
F F B F

2014 by John Wiley & Sons, Inc. All rights reserved.

Which of the following is(are) not possible Lewis Structure(s) for C2H6O?
a

b c