Chapter 13

--halogenalkanes
一 Introduction
塑料之王
teflon-PTFE

Flame retardants （阻燃）

and anaesthetics(麻醉剂)
fire extinguisher（灭火器）
non-stick lining of pans (不粘锅)

isoflurane https://zhuanlan.zhihu.com/p/143293657

plastic

extinguisher bromochlorodifluoromethane-1211
bromotrifluoromethane-1301
 Chapter 13 halogenlkanes
一 Introduction
① General formula (with a single halogen atom) CnH2n+1X

C4H9Br C3H7Cl C3H7I

P212
 Chapter 13 halogenlkanes
一 Introduction
① General formula (with a single halogen atom)

CnH2n+1X

② Bond polarity

C-F
Trend in bond polarity
C-Cl
C-Br
C-I
Intermolecular force
Van der Waals’ force, Dipole-dipole force

P212
 Chapter 13 halogenlkanes
一 Introduction
① General formula (with a single halogen atom)

CnH2n+1X

② Bond polarity
Less polar
（electronegativity difference decrease down group7）

draw a diagram to show the polarity of halogen alkane

Intermolecular force
Van der Waals’ force, Dipole-dipole force

P212
 Chapter 13 halogenlkanes
一 Introduction
① General formula (with a single halogen atom)

CnH2n+1X

② Bond polarity
Less polar
（electronegativity difference decrease down group7）

draw a diagram to show the polarity of halogen alkane

Intermolecular force Solubility

Van der Waals’ force
Insoluble in water (?)
Dipole-dipole force

P212
 Chapter 13 halogenlkanes
一 Introduction
① General formula (with a single halogen atom)

CnH2n+1X

② Bond polarity
C-F
Trend in bond polarity
C-Cl
C-Br Less polar
C-I

C-X bond enthalpy

Trend in bond strength

Weaker

P212
 Chapter 13 halogenlkanes
一 Introduction
① General formula (with a single halogen atom)

CnH2n+1X

② Bond polarity
Less polar
（electronegativity difference decrease down group7）

draw a diagram to show the polarity of halogen alkane

Intermolecular force Solubility

Van der Waals’ force
Insoluble in water (?)
Dipole-dipole force
Boiling point Trend:
with increased chain length
going down the halogen group
P212
一 How does halogenalkane react!
C-X bond polarity
(X has larger electronegativity than C)

Draw a diagram to show the polarity of haloalkane

CH3Br

Ø (C be Attacked by)Nucleophile: electron pair donor

H2O H2 OH- NH3 C=N-

P213-214
一 How does halogenalkane react!
C-X bond polarity
(X has larger electronegativity than C)

Draw a diagram to show the polarity of haloalkane

CH3Br

Ø (C be Attacked by)Nucleophile: electron pair donor

Negatively charged, has lone pair (NH3 OH- CN-)

P213-214
一 How does halogenalkane react!
C-X bond polarity
(X has larger electronegativity than C)

C-X bond enthalpy

P213-214
一 How does halogenalkane react!
C-X bond enthalpy
Trend in bond strength

Weaker

Bond enthalpy high, difficult to break ?

C-X bond polarity

(X has larger electronegativity than C)

(C be Attacked by)Nucleophile: electron pair donor

Negatively charged, has lone pair
(NH3 OH- CN-)

P213-214
 02
Nucleophilic
substitution
Nucleophile
Leaving group
(离去基团)

C-X bond is polar

Curly arrows: show how electron pairs move

P214
一 Nucleophilic substitution-example
aqueous sodium hydroxide(NaOH) OH- as nucleophile

ethanol

Outline the mechanism:

①CH3CH2Cl + NaOH
② CH3CHBrCH3 + KOH

Curly arrows: show how electron pairs move

P212-213
一 Nucleophilic substitution-example
Cyanide ion (KCN) cynide ions in aqueous ethanol
important chemical
reaction to increase the
length of carbon chain

Propanenitrile

Outline the mechanism:

① CH3CH2Cl + KCN
② CH3CHBrCH3 + NaCN

Curly arrows: show how electron pairs move

P212-213
一 Nucleophilic substitution-example
aqueous sodium hydroxide(NaOH) OH-

ethanol

Cyanide ion (KCN) cynide ions in aqueous ethanol

important chemical
reaction to increase the
length of carbon chain

Propanenitrile

Curly arrows: show how electron pairs move

P212-213
一 Practice
一 Nucleophilic substitution-example

Ammonia (in excess NH3)-Why?

2 + NH4Cl

Curly arrows: show how electron pairs move

P216
一 Practice

(c)Outline the mechanism of reaction 2

 negatively charged and
一 Nucleophilic substitution? lone paired electrons
nucleophile
① with aqueous alkali, OH–(aq)
condition

ethanol

② with cyanide ions, CN– (in ethanol)

increase the length

of carbon chain

propanenitrile

③ with ammonia, excess NH3 (in ethanol)

+
ethylamine

Curly arrows: show how electron pairs move

一 hydrolysis: 水解 breakdown by water

H2O is a less effective nucleophile than OH-

OH- is negatively charged

We can investigate the rate of hydrolysis using

aqueous silver nitrate solution. The water in the
silver nitrate solution acts as the nucleophile

Reflux (回流) apparatus for

hydrolysis of a halogenoalkane.
 Substitution ?
C13 Q2 Q4 Q7ai b Q8 Q10c
一 Nucleophilic substitution?
① halogenalkane+nucleophile→alcohol
nucleophile in aqueous alkaline
solution

一 Free radical substitution? alkane + halogen→halogenalkane

② UV light/Sun light/ high Temperrature

free radical
 消除反应
一 Elimination reactions in halogenalkanes
① halogenalkane + base→alkene
OH- + CH3CH2Br → CH2=CH2 + H2O +Br-
no water present

Collect gas
over water

② condition: ethanoic/ in ethanol, hot

Curly arrows: show how electron pairs move

P217-218
 消除反应
一 Elimination reactions in halogenalkanes
① halogenalkane + base→alkene
② condition: ethanoic/ in ethanol, hot Symmetric
molecules
③ Name and outline the mechanism （NaOH act as a base）

OH- + CH3CH2Br → CH2=CH2 + H2O +Br-

Curly arrows: show how electron pairs move

P217-218
 消除反应
一 Elimination reactions in halogenalkanes
halogenalkane + base→alkene
symmetric
molecules
base
④ isomeric products formed

Asymmetric
molecules

WHY?
H can be removed from more
than one carbon atom

P217-218
 消除反应
一 Elimination reactions in halogenalkanes
halogenalkane + base→alkene

base
④ isomeric products formed

WHY?
H can be removed from more
than one carbon atom

P217-218
一 Example
 11.3 Isomerism
一 Isomers：Compounds with the same molecular formula but
whose atoms are arranged differently
Stereoisomer: Compounds with the same structural formula with atoms
arranged differently in space

E/Z isomerism contain C=C and.....

stereoisomerism
optical isomerism

u Explain the origin of the E/Z isomer shown.

The C=C double bond can not rotate.
2 different atoms or group of atoms on each carbon atoms of C=C bond.
has no E/Z isomer, because two same atoms on one
carbon atom of C=C

P192-193
 一 E/Z isomers • The C=C double bond can not rotate.
• 2 different atoms on each carbon atoms of C=C bond.

Highest priority atoms are on opposite side for E isomer

Highest priority atoms are on the same side for Z isomer

2. CIP priority rules

P44
 一 E/Z isomers • The C=C double bond can not rotate.
• 2 different atoms on each carbon atoms of C=C bond.

u Whether the following compounds have E/Z isomer, E or Z?

P44
 11.3 Isomerism
一 Isomers：Compounds with the same molecular formula but
whose atoms are arranged differently
different arrangement of hydrocarbon chain

chain isomerism
different positions of the same functional group
Structural positional isomerism
Different functional group

isomerism Functional group isomerism

E/Z isomerism
stereoisomerism
optical isomerism

Structural: Compounds with the same molecular formula but different

structural formulae.
Stereo-: Compounds with the same structural formula with atoms
arranged differently in space
P192-193
 消除反应
一 Elimination reactions in halogenalkanes
halogenalkane + base→alkene

(ii) State the role of KOH in this reaction

(iii) Name the other procut in this reaction.

State why this reaction can form several different products,

(iv) Can it form any by-product besides alkenes?

 一 Substitution or Elimination reactions
halogenalkanes

OH- as nucleophile OH- as base

alcohol alkene

factors:
① condition：T and solution
② types of halogens: primary secondary tertiary

P218
 一 Substitution or Elimination reactions

Substitution factors

condition halogen concentration

OH- as nucleophile alcohol aqueous primary low

halogen secondary
alkanes
OH- as base alkene ethanol, hot tertiary high

Elimination

isomeric product WHY?

H can be removed from more
than one carbon atom
一 CFCs: halogenalkanes containing both chlorine and fluorine atoms

• 氟氯烃(CFCs)如：CHF2Cl
• the use of CFSs e.g, CHF2Cl will destroy
UV
overall equation: 2O3 → 3O2
initiation: CHF2Cl → ·CHF2 + Cl·
propagation: Cl· + O3 → ClO·+ O2 Cl·作为catalyst
ClO· + O3 →2O2 + Cl·

• CFCs will be replaced by HFCs (hydrofluorocarbons), WHY?

→ because it does not contain C-Cl bond
 一 CFCs: halogenalkanes containing both chlorine and fluorine atoms

臭氧O3 2O3 → 3O2

① CFCs（such as CF3Cl will produce Cl· under UV light）

UV
(initiation) ·

② O3 will decompose to O2 (Cl· as a catalyst)

UV
Equation 1 Cl· +O3→ ClO· + O2
(propagation)
Equation 2 ClO· +O3→ Cl· + 2O2

③ C-Cl is weaker than C-F

④ how to avoid ?
Use HCFs (without C-Cl bond)
https://www.youtube.com/watch?v=aU6pxSNDPhs ozone depletion
P209
一 Practice
一 CFCs: halogenalkanes containing both chlorine and fluorine atoms
一 Summary Wb C13 Q5 Q6(biv 不写) Q7ci
C14 Q10a b c
• halogenalkanes
u general formula
u name
Ø solubility
• physical property Ø boiling point
Ø bond polarity (polar)

Name reagent condition product

• reactions KOH in aqueous aqueous alcohol
solution

nucleophilic KCN in ethanol / nitrile

substitution
ammonia in excess NH3 amine
ethanol
elimination KOH in ethanoic hot, ethanol alkene
solution