3장 유기반응의 성질: 알켄
•Naming alkenes
•Electronic structure of alkenes
•Isomerism in alkenes
-cis-trans isomerism
-E,Z isomerism
•Organic reactions
-kinds of organic reactions
-Reaction mechanisms
-Energy diagrams
Alkene & alkyne
• 향료, 비타민 등 천연물에서 많이 발견
3.1 알켄(unsaturated HC)의 명명
1. Find the longest chain containing the double bond,
and name it.
2. Number the carbon atoms in the chain, giving the
double bond the lowest number.
3.1 알켄(unsaturated HC)의 명명
3. Number the substituents and write the name.
a. Name the substituents alphabetically.
b. Indicate the position of the double bond.
c. Use the suffixes –diene, -triene, etc. if more than one double
bond is present.
3.1 알켄(unsaturated HC)의 명명
4. Cycloalkenes are named in a similar way, but the
double bond is placed between C1 and C2, and the
substituents receive the lowest possible numbers.
IUPAC은 1993년에 명명 규칙을 바꾸었다.
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관용명
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3.2 알켄의 전자구조
• Carbon atoms in a double bond are sp2-hybridized.
• Free rotation does not occur around double bonds.
3.3 Isomerism in alkenes: Cis-trans isomerism
• A “di”substituted alkene can have substituents either
on the same side of the double bond (cis-) or on
opposite sides (trans-).
• These isomers don’t interconvert because free rotation
about a double bond isn’t possible.
3.3 Isomerism in alkenes: Cis-trans isomerism
• Cis-trans isomerism doesn’t occur if one carbon in the
double bond is bonded to identical substituents.
3.3 Isomerism in alkenes: Cis-trans isomerism
• Cis – is less stable than trans- : steric strain (입체스트레인)
3.4 Isomerism in alkenes: E, Z isomerism
• E,Z system for “tri-”substituted alkenes
– E isomer (entgegen): two groups of higher priority are on
opposite sides of the alkene double bond.
– Z isomer (zusammen): two groups of higher priority are on
the same side of the alkene double bond.
3.4 Sequence rules for E, Z isomers
(Cahn-Ingold-Prelog rule)
1. For each double bond carbon, rank the substituents by
atomic number.
3.4 Sequence rules for E, Z isomers
2. If a decision can’t be reached, look at the second or
third atom until a difference is found.
3.4 Sequence rules for E, Z isomers
3. Multiple-bonded atoms are equivalent to the same
number of single-bonded atoms.
3.5 Kinds of organic reactions
• 어떤 종류의 반응인가? 어떻게 반응하는가?
• 4가지 형태의 유기반응
– Addition (첨가반응)
– Elimination (제거반응)
– Substitution (치환반응)
– Rearrangement (전위반응)
제거
첨가
첨가반응
• 두 반응물이 서로 첨가되어 새로운 단일 생성물이
생성되는 반응
제거반응
• 단일 출발물질이 생성물 2개로 갈라지는 반응.
치환반응
• 두 반응물이 부분을 교환하여 새 생성물 2개를 생성하는
반응.
전위반응
• 단일 반응물이 결합과 원자들을 다시 구성하여 다른
이성질 생성물을 생성하는 반응.
3.6 How Reactions Occur: Mechanisms
• In a clock the hands move but the mechanism behind
the face is what causes the movement
• In an organic reaction, we see the transformation that
has occurred. The mechanism describes the steps
behind the changes that we can observe
• Reactions occur in defined steps that lead from
reactant to product
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3.6 Reaction mechanisms
• A “reaction mechanism” describes the bonds broken and formed
in a chemical reaction, and accounts for all reactants and
products.
• 전자들의 움직임에 관한 자세한 설명
• The electrons involved in a reaction are usually π electrons or
electron lone pairs.
3.6 Reaction mechanisms
• 결합의 형성 및 절단은 대칭적 혹은 비대칭적으로 일어날 수 있다.
• 대칭적 절단- 균일성(homolytic) : 라디칼 반응
• 비대칭적 절단-불균일성 (heterolytic) : 극성 반응
Indicating Steps in Mechanisms
• Curved arrows indicate breaking
and forming of bonds
• Arrowheads with a “ half” head
(“ fish- hook” ) indicate homolytic
and homogenic steps (called
‘ radical processes’ )
• Arrowheads with a complete
head indicate heterolytic and
heterogenic steps (called ‘ polar
processes’ )
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3.6 Reaction mechanisms
• Polar reaction : electrons move in pairs.
– heterolytic bond breaking, heterogenic bond formation
• Radical reactions : single electron movement
– homolytic bond breaking, homogenic bond formation
3.7 Mechanisms of polar reactions
• Polar reactions occur as a result of partial positive and
negative charges within molecules.
• “electronegativity differences”
3.7 Mechanisms of polar reactions
• “electron-rich” sites in one molecule react with “electron-poor”
sites in another molecule.
• Nucleophile : a compound with an electron-rich atom
• Electrophile : a compound with an electron-poor atom
3.8 Addition of HCl to Ethylene
• HCl adds to the π part of C- C double bond
• The π bond is electron- rich, allowing it to function as a
nucleophile
• H- Cl is electron deficient at the H since Cl is much
more electronegative, making HCl an electrophile
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3.8 Addition of HCl to ethylene
• “Electrophilic addition”
3.9 Describing a Reaction: Transition States
and Intermediates
• The highest energy point in a reaction step is
called the transition state
• The energy needed to go from reactant to
transition state is the activation energy (∆G‡)
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• If a reaction occurs in
more than one step, it
must involve species that
are neither the reactant
nor the final product
• These are called reaction
intermediates or simply
“ intermediates”
• Each step has its own free
energy of activation
• The complete diagram for
the reaction shows the
free energy changes
associated with an
intermediate
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3.9 Energy diagram and transition states
• Reaction energy diagram
• Transition state
• Activation energy, Eact
• intermediate
3.10 Energetics and catalysis
• Reactions occur
spontaneously if the
energy of the products
is less than the energy
of the reactants.
• The rate of a reaction
can’t be predicted by
the difference in energy
between reactants and
products.
• A catalyst can change
the rate of a reaction
but can’t change the
energy difference
between reactant and
product.
