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Textbook: “Organic Chemistry”, John McMurry, 9th, 2016

강의자료(PPT): university web disk (ID, PW : orchem)
(원서교재 필독: 시험의 약 10%는 원서 이해 정도를 평가할 예정임)

Lecture Schedule:
Week Content
1-7 1-7장, 과제-1
8 7장, 중간시험
9-14 8-11장, 과제-2
기말시험
15

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주의 사항
1. 정시에 과제 미 제출: - 20%
2. 채점에 오류가 발견되지 않은 상황에서 학점 (변경) 관련 상담 불가!

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3
◼ What is organic chemistry, why have so many
people studied it, and why should you study it?

The answers to these questions are all around you:

1. Living things are made of organic chemicals.
2. Lots of industrial products are organic materials.

Ex) proteins, DNA, foods, medicines, clothes, shoes,

tables, computers, plastic containers, many electronic
devices, cables, rubbers, etc.

⇒Thus, anyone with a curiosity about life, living things,

plastics, rubbers and fibers must have a basic
understanding of organic chemistry.

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 What are organic compounds?

◼ In mid-1700s, “Organic compounds” referred to compounds

from living sources (mineral sources were “inorganic”). Organic
compounds were considered to have some vital force as they
were from living sources. It was thought that it could not be
synthesized in laboratory

1816, Chevreul found that soap can be separated into several

organic compounds which he termed fatty acids

◼ In 1828, however, Wöhler showed that it was possible to

convert ammonium cyanate (inorganic salt) into urea (organic
substance).
 What are organic compounds?

◼ Nowadays, so many organic compounds are designed and

synthesized in the laboratory.

☞ There was no fundamental difference between organic and

inorganic compounds. The only distinguishing characteristic
of organic chemicals is that all contain the element carbon.

☞ Organic chemistry is the study of carbon compounds!

 Why is carbon special?
Carbon shares 4 valence electrons and forms 4 covalent bonds.
Carbon atoms can bond to one another to form long chains and rings.
→ Carbon can form immense diversity of compounds, from simple methane
to very complex DNA.

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# Other elements commonly found in organic compounds:
H, N, P, O, S, F, Cl, Br, I, etc.
 1-1 Atomic Structure: The Nucleus
◼ Structure of an atom
◼ Nucleus
- Positively charged, and consists of protons and neutrons
- very small (~ 10-14 - 10-15 m in diameter), but very dense and
contains essentially all the mass of an atom

◼ Electron
- Negatively charged.
- has negligible mass and move around the nucleus

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# Electron density increases steadily toward the nucleus.
Atomic Number and Atomic Mass

◼ Atomic number (Z) : number of protons in an atom’s nucleus

◼ Mass number (A) : number of protons and neutrons
◼ Atoms of a given element have the same atomic number
◼ Isotopes: atoms with the same atomic number but different
mass numbers (different numbers of neutrons)

◼ Atomic mass (or atomic weight) of an element : weighted

average mass in atomic mass units (amu) of an element’s
naturally occurring isotopes
Ex)
H: 1.008 (1H, 2H, 3H),
C: 12.011 (12C, 13C): (12×0.9889) + (13.0034×0.0111) = 12.011
N: 14.0067 (14N, 15N)
O: 15.9994 (16O, 17O, 18O)
Cl: 35.453 (35Cl, 37Cl)
Br: 79.909 (79Br, 81Br)
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 1-2 Atomic Structure: Orbitals
◼ Quantum mechanics describes electron energies and locations by a
wave equation
◼ Wave function (ψ) : solution to a wave equation
◼ Each wave function is an orbital.

◼ A plot of ψ2 describes where an electron is most likely to be.

→ You can think of an orbital as looking like a photograph of the
electron taken at a slow shutter speed.
→ The orbital would appear as a blurry cloud indicating the region of
space around the nucleus where the electron has been.

The electron cloud has no a specific boundary, but for practical

purposes, an orbital represents the space where an electron spends
90-95% of its time.
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 Shapes of Atomic Orbitals for Electrons

There are four different kinds of orbitals: s, p, d, and f

s and p orbitals: most important in organic chemistry
s orbitals: spherical, with the nucleus at center
p orbitals: dumbbell-shaped, with the nucleus at middle

d orbitals:
dxy, dyz, dxz, dx2-y2: cloverleaf-shaped
with the nucleus at center
dz2: elongated dumbbell-shaped
with a doughnut around its middle
dz2
Orbitals and Shells

◼ Orbitals are grouped in shells of increasing size and energy

◼ Each orbital can be occupied by two electrons
1st shell: one 1s orbital (2 electron)
2nd shell: one 2s orbital and three 2p orbitals (8 electrons)
3rd shell: one 3s, three 3p, and five 3d orbitals (18 electrons)

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Figure 1.4 The energy levels of electrons in an atom.

 p-Orbitals

◼ - There are three mutaully perpendicular p orbitals, px, py, and pz, of
equal energy
◼ The two lobes of a p orbital are separated by a region of zero
electron density, a node(마디)
◼ The two orbital regions separated by the node have different
algebraic signs, + and -, in the wave function.

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1-3 Atomic Structure: Electron Configurations
◼ Ground-state electron configuration
- a list of orbitals occupied by an atom’s electrons

◼ Rules:
1. Lowest-energy orbitals fill first: 1s → 2s → 2p → 3s → 3p → 4s
→ 3d (aufbau (“build-up”) principle)

2. Electron spin can have only two orientations, up  and down .

Only two electrons can occupy an orbital, and they must be of
opposite spin (Pauli exclusion principle).

3. If two or more empty orbitals of equal energy are available,

electrons occupy each with spins parallel until all orbitals have
one electron (Hund's rule). 14
# Eight electrons (an electron octet) in an atom’s outermost shell, or valence
shell, impart special stability to the noble (or inert) gas elements in group 8A of
periodic table: (He (2); Ne(2+8); Ar(2+8+8); Kr(2+8+18+8).

# The chemistry of main-group elements is governed by their tendency to take on

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the electron configuration of the nearest noble-gas (Ex: Na → Na+ + e-).
1-4 Development of Chemical Bonding Theory

◼ Carbon always has 4 bonds (C is tetravalent!)

◼ The 4 bonds of carbon have specific spatial directions.
→ atoms surround carbon as corners of a tetrahedron:

A dashed line indicates

a bond behind the page

A wedge indicates a
bond coming forward

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Figure 1.6 A representation of a tetrahedral carbon atom

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 Why do atoms bond together?
⇒ Because the resulting compound is more stable than the
separate atoms
How can bonds be described electronically?
The chemistry of many main-group elements is governed by their
tendency to take on the electron configuration of the nearest noble gas.

Alkali metals (M → M+ + e-)

halogens (X + e- → X-): M+X- (electrostatic attraction: ionic bond)
→ Ionic bonds as a result of electron transfer
Ex: NaCl (Na+Cl-)

How do elements closer to the middle of the periodic table form bond?
Ex) carbon (6C):
They bond to other elements, not by gaining or losing electrons, but by
sharing them. Such a shared-electron bond is called a covalent bond.

The collection of atoms held together by covalent bonds is

called a molecule. 18
 Electron-dot structures:
a simple way of indicating covalent bonds (or Lewis structures)

The electron-dot structures show valence electrons of an atom as dots

Hydrogen has one dot (1s1): H·
Carbon has four dots (2s2 2p2):

◼ Atoms with one or three valence electrons form one or three bonds
(Ex: H-H, BH3, etc.)

◼ Atoms with four or more valence electrons form as many bonds as

they need electrons to fill their valence shells to reach a stable octet
EX-1:
Carbon has four valence electrons (2s2 2p2), forming four bonds (CH4)

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 Ex-2: O

◼ Oxygen has six valence electrons (2s2 2p4) and forms

two bonds (H2O)

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Ex-3: N

◼ Nitrogen has five valence electrons (2s2 2p3) and

forms only three bonds (NH3)

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Line-bond structures:
a simpler way of indicating covalent bonds (or the
Kekulé structures)

1) A two-electron covalent bond is indicated as a line drawn

between atoms.
2) Lone pairs of nonbonding valence electrons are often not shown,
although it’s still necessary to keep track of them mentally.
◼ Valence electrons that are not used for bonding are called
nonbonding electrons, or lone-pair electrons :

Ex: Nitrogen atom in ammonia (NH3)

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# Summary on electron-dot and line-bond structures

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Problem 1-5 What are likely formulas for the following
substances?
(b) AlH? (c) CH?Cl2 (e) CH3NH?
H
H
H
Al H Al H H Al H

Problem 1-6 Write line-bond structures for the following substances,

showing all nonbonding electrons:
(a) CHCl3 (b) H2S (c) CH3NH2 (d) CH3Li

Problem 1-7 Why can’t an organic molecule have the formula C2H7 ?

C C C C
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1-5 The Nature of the Chemical Bond: VBT

Two models to describe covalent bond formation :

1. Valence Bond Theory (VBT): 원자가 결합 이론
2. Molecular Orbital Theory (MOT): 분자 오비탈 이론

Each model has its strengths and weaknesses, and chemists tend to
use them interchangeably depending on the circumstances.

However, VBT is more easily visualized,

so most of the descriptions in this book derive from VBT.

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 VBT:

◼ Covalent bond forms when two atoms approach each other closely
so that a singly occupied orbital on one atom overlaps a singly
occupied orbital on the other atom
→ Electrons are paired in the overlapping orbitals and are attracted
to nuclei of both atoms

Ex) Hydrogen molecule (H2):

H–H bond results from the overlap of two singly occupied 1s orbitals:
The H-H bond is cylindrically symmetrical
It has a circular cross section
The bond is formed by head-on overlap of two atomic orbitals 26
→ “sigma (s) bond”
Bond Energy

◼ The reaction 2 H· → H2 releases 436 kJ/mol

◼ The product (H2) has 436 kJ/mol less energy than two H atoms:
→ The H–H bond has a bond strength of 436 kJ/mol.
(1 kJ = 0.2390 kcal; 1 kcal = 4.184 kJ)

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 Bond Length is an optimum distance between nuclei
that leads to maximum stability

If too close, they repel because both nuclei are positively charged.
If too far apart, bonding is weak.

⇒ Every covalent bond has both a characteristic bond strength

and bond length. 28
1-6 sp3 Hybrid Orbitals and the Structure of
Methane
◼ Carbon has 4 valence electrons (2s2 2p2): can form four bonds
to hydrogens.

→ Are there two different kinds of C-H bonds in methane?

No! All C–H bonds are identical !! (tetrahedral)

C
H
H
H
How can we explain this?
→ C atom uses four sp3 hybrid orbitals to form 4 C-H bonds !!
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sp3 hybrid orbitals:
one 2s orbital and three 2p orbitals combine to form four equivalent,
unsymmetrical about the nucleus, tetrahedral orbitals
(s+p+p+p = four sp3 orbitals)

Four sp3 hybrid orbitals are oriented to

the corners of a regular tetrahedron ! 30
 The Structure of Methane

◼ sp3 orbitals on C overlap with four 1s orbitals of H atom to form four

identical C-H bonds

- Bond angle (each H–C–H): 109.5° (the tetrahedral angle)

because four sp3 orbitals on C are tetrahedrally oriented
.

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 1-7 sp3 Orbitals and the Structure of Ethane

◼ Two sp3 orbitals overlap to form a C-C s bond.

◼ Three sp3 orbitals on each C overlap with H 1s orbitals to form six
C–H bonds
◼ All the bond angles are near the tetrahedral value of 109.5o. 32
1-8 sp2 Orbitals and the Structure of Ethylene

H H
C C
H H
◼ sp2 hybrid orbitals:
- 2s orbital combines with two 2p orbitals, giving three sp2 hybrid
orbitals (s+p+p = three sp2 orbitals)
- sp2 orbitals are in a plane with120° angles
◼ Remaining p orbital is perpendicular to the plane 33
 ◼ Two sp2-hybridized orbitals overlap to form a s bond (head-on overlap)
◼ p orbitals overlap side-to-side to form a pi () bond
→ sp2–sp2 s bond and 2p–2p  bond result in sharing four
electrons and formation of C=C bond (bond strength: C=C > C-C)

Electrons in the s bond are centered between nuclei, but electrons in

the  bond occupy regions on either side of a line between nuclei 34
☞ bond strength: s bond >  bond
 Structure of Ethylene

H H
C C
H H

◼ H atoms form s bonds with four sp2 orbitals

◼ H–C–H and H–C–C bond angles: ~ 120°

◼ C=C bond: shorter and stronger than the C-C bond in ethane
→ C=C bond length: 133 pm (ethane C–C: 154 pm)
→ C=C bond strength: 611 kJ/mol (ethane C-C: 376 kJ/mol)

# The C=C bond is less than twice as strong as the single bond
because the  bond is not as strong as the s bond.

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Problem 1-10 Draw a line-bond structure for propene, CH3CH=CH2.
Indicate the hybridization of the orbitals on each carbon,
and predict the value of each bond angle?
H H H

H C C C H

Problem 1-11 Draw a line-bond structure for 1,3-butadiene,

CH2=CH-CH=CH2. Indicate the hybridization of the orbitals
on each carbon, and predict the value of each bond angle.

H H H H

H C C C C H

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1-9 sp Orbitals and the Structure of Acetylene
H C C H

◼ Carbon 2s orbital hybridizes with a single p orbital, giving two sp

hybrids (s+p = two sp orbitals)
◼ two p orbitals remain unchanged
→ sp orbitals are linear, 180° apart (on x-axis)
→ two p orbitals are perpendicular to the sp orbitals
(on the y-axis and the z-axis) 37
 Orbitals of Acetylene

◼ The two sp hybrid orbitals from each C form a sp–sp s bond

◼ The pz orbitals from each C form a pz–pz  bond by sideways overlap
and py orbitals overlap similarly to form a py–py  bond
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Bonding in Acetylene

◼ Sharing of six electrons forms CC

◼ Two sp orbitals form s bonds with H atoms

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In general,
Bond strength: sp3C-H < sp2C-H < spC-H
Bond length: sp3C-H > sp2C-H > spC-H

→ How would you explain these observations ? 40

 1-10 Hybridization of Nitrogen and Oxygen
◼ Elements other than C can also have hybridized orbitals

◼ 1. Ammonia (NH3) (N: 1s2, 2s22p3)

- N’s orbitals (s+p+p+p) hybridize to form four sp3 orbitals
- One sp3 orbital is occupied by two nonbonding electrons, and
three sp3 orbitals have one electron each, forming bonds to H
- the lone pair of electrons occupies more space than the N-H bond:
(bond angle: H-N-H < 109.5)

2. Methylamine:

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(bond angle: H-N-H < H-N-CH3) Why?
 Hybridization of Oxygen in Water

◼ Oxygen atom (1s2, 2s22p4) is sp3-hybridized

→ It forms only two covalent bonds, leaving two lone pairs

H–O–H bond angle: 104.5°

# Repulsion between electrons:
nonbonding-nonbonding > nonbonding-bonding > bonding-bonding

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 P- and S-containing bonds
◼ They are the third-row analogs of nitrogen and oxygen, and the bonding
in both can be described using hybrid orbitals.

However, because of their positions in the

third row, they can expand their outer-shell
octets and form more than the typical number
of covalent bonds.
For example, P often forms
five covalent bonds, and
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S often forms four.
Problem 1-14 Identify all nonbonding lone pairs of electrons
in the following molecules, and tell what geometry you
expect for each of the indicated atoms.
(a) The oxygen atom in dimethyl ether,
H3C O CH3

(b) The nitrogen atom in trimethylamine,

H3C N CH3

CH3
(c) The phosphorous atom in phosphine, PH3

(d) The sulfur in the amino acid methionine, H3C S CH2CH2CHCOH

NH2

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 1-11 Describing Chemical Bonds:
Molecular Orbital Theory (MOT)

◼ VBT:
- uses hybrid atomic orbitals to account for geometry
- assumes the overlap of atomic orbitals to account for electron
sharing

◼ MOT:
- MOT describes covalent bond formation as arising from a
mathematical combination of atomic orbitals (wave functions) on
different atoms to form molecular orbitals, because they belong to the
entire molecule rather than to a individual atom.

- Just as an atomic orbital, a MO describes a region of space in a

molecule where electrons are most likely to be found.

- Like an atomic orbital, a MO has a specific size, shape, and energy

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◼ H2 molecules:
There are two ways in combining two singly occupied 1s atomic orbitals
to form two MOs

(1) Additive combination (부가적인 조합)

- lower in energy than the two atomic orbitals
- a bonding MO (결합성 분자오비탈) because electrons in this MO
spend most of their time in the region between the two nuclei, thereby
bonding the atoms together.

(2) Subtractive combination (상쇄적인 조합)

- higher in energy than the two atomic orbitals
- an antibonding MO (반결합성 분자오비탈) because any electrons it
contains can’t occupy the central region between the nuclei, where there
is a node, and can’t contribute to bonding. The two nuclei therefore repel
each other.

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# Just as bonding and antibonding s MOs result from the head-on
combinations of two s atomic orbitals in H2,
bonding and antibonding  MOs result from the sideways combination
of two p atomic orbitals in ethylene

◼ The  bonding MO: combining p orbital lobes with the same

algebraic sign
◼ The  antibonding MO: combining p orbital lobes with the
opposite signs
◼ Only bonding MO is occupied by electrons

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 1-12 Drawing Chemical Structures
H H
..........
H
1. Electron-dot (전자 점) structures
(Lewis structures) .. ..
H C C H H
C
H
H

2. Line-bond (선 결합) structures H H C C H

(Kekule structures) H C C
3. Condensed (간결) structures CH3
H H

CH3CH2CHCH3 or CH3CH2CH(CH3)2
4. Skeletal (골격) structures
Rules for skeletal structures:
(1) C atoms aren’t usually shown. A carbon atom is assumed to be at
each intersection of two or three lines (bonds) and at the end of each
line. Occasionally, a C atom might be indicated for emphasis or clarity.
(2) H atoms bonded to C aren’t shown. Since C always has a valence of
4, we mentally supply the correct number of H atoms for each carbon.
(3) Atoms other than C and H are shown
49
 One further comment
◼ Such groupings as –CH3, -OH, and –NH2 are usually written with the
C, O, or N and the H atom second.
◼ But, the order of writing is sometimes inverted to H3C-, HO-, or H2N-
if needed to make the bonding connections in a molecule clearer.
 Homework
26, 27, 28, 29, 36, 42, 47, 50, 51

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