Post on 09-Jan-2017
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
C - Br
Reactivity for halogenoalkane • Carbon bond to halogen – F, CI, Br, I • High electronegativity on halogen gp • High reactivity – due to polarity of C+- CI -
C - Br ᵟ+ ᵟ-
electron
Electron deficient carbon
OH ..
ᵟ- ᵟ+
Nucleophilic Substitution rxn
CH3CH2CI + OH- → CH3CH2OH + CI-
H H
׀ ׀
H - C – C – CI
׀ ׀
H H
+ OH- ᵟ+ ᵟ-
H H
׀ ׀
H - C – C – OH + CI-
׀ ׀
H H
H Br H
׀ ׀ ׀
H - C – C – C – H
׀ ׀ ׀
H H H
CH3CHBrCH3 + OH- → CH3CHOHCH3 + Br-
+ OH-
H OH H
׀ ׀ ׀
H - C – C – C – H + Br-
׀ ׀ ׀
H H H
ᵟ+ ᵟ-
Nucleophilic Substitution Electrophilic Addition
vs Reactivity of Alkene - High reactivity - Unstable bond bet C = C - High reactivity – Weak pi bond overlap bet p orbital - Unsaturated hydrocarbon – ᴨ bond overlap
C = C Electron rich π electron
ᵟ- ᵟ-
H ᵟ+
C = C ᵟ- ᵟ-
E ᵟ+
E+ Electron deficient Nu
ᵟ-
ᵟ-
Nucleophile – Lone pair electron – Donate electron pair - Lewis Base
H H ׀ ׀
C = C
׀ ׀ H H
CH2=CH2 + Br2 → CH2BrCH2Br
+ Br – Br ᵟ- ᵟ+
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
vs
CH2=CH2 + HCI → CH3CH2CI
H H ׀ ׀
C = C
׀ ׀ H H
ᵟ- + H – CI
ᵟ+
H H ׀ ׀
H - C – C – H
׀ ׀ H CI
Electrophilic Addition rxn
ᵟ-
Electron rich region
Electrophilic Substitution rxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br ᵟ+
+ NO2+
ᵟ+
Electrophilic Substitution
vs
C = C Electron rich π electron
ᵟ- ᵟ-
ᵟ+
C = C ᵟ- ᵟ-
E ᵟ+
E+ Electron deficient
E ᵟ+
H H ׀ ׀
C = C
׀ ׀ H H
CH2=CH2 + Br2 → CH2BrCH2Br
+ Br – Br ᵟ- ᵟ+
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
vs
CH2=CH2 + HCI → CH3CH2CI
H H ׀ ׀
C = C
׀ ׀ H H
ᵟ- + H – CI ᵟ+
H H ׀ ׀
H - C – C – H
׀ ׀ H CI
Electrophilic Addition rxn
E
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
ᵟ+ + H E
+ H
Electron rich region
H Br
+ HBr
C6H6 + HNO3 C6H5NO2 + HCI
AICI3 dry ether
warm/conc H2SO4
H NO2
Reactivity of Alkene - High reactivity - Unstable bond bet C = C - High reactivity – Weak pi bond overlap bet p orbital - Unsaturated hydrocarbon – ᴨ bond overlap
Reactivity of Benzene (Unreactive) - Delocalization of electron in ring - Stability due to delocalized π electron - Substitution instead of Addition
C6H6 – no reaction with brown Br2(I)
ethene decolourize brown Br2(I)
Benzene –stable (unreactive) toward addition rxn
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
H
Electrophilic Addition
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
C - Br OH .. ᵟ- ᵟ+
Nucleophile Electrophile
ᵟ+
C = C ᵟ-
Nucleophile – Lone pair electron – Donate electron pair - Lewis Base
Organic Rxn
Addition rxn Substitution rxn
Nucleophilic Substitution
Free Radical Substitution
Electrophilic Substitution Electrophilic Addition rxn
Free radicle
CI CI
CI CI . .
:
Radical (unpair electron)
uv radiation
H H ׀ ׀
C = C
׀ ׀ H H
+ Br – Br
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
ᵟ+
ᵟ-
H H
׀ ׀
H - C – C – CI
׀ ׀
H H
+ OH-
H H
׀ ׀
H - C – C – OH + CI-
׀ ׀
H H
ᵟ- ᵟ+ H
E + + H
E ᵟ+
H H
׀ ׀
C = C
׀ ׀
H H
H H
׀ ׀
H - C – C – H
׀ ׀
CI CI
H H
׀ ׀
H - C – C – H
׀ ׀
H CI
H H
׀ ׀
H - C – C – H
׀ ׀
H OH
Add HCI
CI2 / UV
H H
׀ ׀
H - C – C – CI
׀ ׀
H H
H H
׀ ׀
H - C – C – OH + CI-
׀ ׀
H H
H H
׀ ׀
H - C – C – NH2 + CI-
׀ ׀
H H
H H
׀ ׀
H - C – C – CN + CI-
׀ ׀
H H
NH3
OH-
CN-
H
׀
H - C – H
׀
H
H
׀
H - C – CI + H
׀
H
CI2 → 2 CI•
CH3• + CI2 → CH3CI + CI•
CI• + CH4 → HCI + CH3•
H
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
C - Br OH .. ᵟ- ᵟ+
Nucleophile Electrophile
H ᵟ+
C = C ᵟ-
Nucleophile – Lone pair electron – Donate electron pair - Lewis Base
Free radicle
CI CI
CI CI . .
:
Radical (unpair electron)
uv radiation
H H
׀ ׀
C = C
׀ ׀
H H
H H
׀ ׀
H - C – C – H
׀ ׀
CI CI
H H
׀ ׀
H - C – C – H
׀ ׀
H CI
H H
׀ ׀
H - C – C – H
׀ ׀
H OH
Add HCI
CI2 / UV
H H
׀ ׀
H - C – C – CI
׀ ׀
H H
H H
׀ ׀
H - C – C – OH + CI-
׀ ׀
H H
H H
׀ ׀
H - C – C – NH2 + CI-
׀ ׀
H H
H H
׀ ׀
H - C – C – CN + CI-
׀ ׀
H H
NH3
OH-
CN-
H
׀
H - C – H
׀
H
H
׀
H - C – CI + H
׀
H
CI2 → 2 CI•
CH3• + CI2 → CH3CI + CI•
CI• + CH4 → HCI + CH3•
Alkene – Addition rxn Halogenoalkane – Substitution rxn Alkane - Radical substitution
H OH
׀ ׀
H - C – C – H
׀ ׀
H H
H O
‖ ׀
H - C – C – H
׀
H
H O
‖ ׀
H - C – C – OH
׀
H
H O H
׀ ‖ ׀
H - C – C – C – H
׀ ׀
H H
H OH H
׀ ׀ ׀
H - C – C – C – H
׀ ׀ ׀
H H H
H OH H
׀ ׀ ׀
H - C – C – C – H
׀ ׀ ׀
H CH3 H
Alcohol – Oxidation rxn
10 alcohol 20 alcohol 30 alcohol
carboxylic acid aldehyde ketone
no reaction
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
Reactivity of Alkene - High reactivity - Unstable bond bet C = C - High reactivity – Weak pi bond overlap bet p orbital - Unsaturated hydrocarbon – ᴨ bond overlap
C = C Electron rich π electron
ᵟ- ᵟ- Br ᵟ+
H H ׀ ׀
C = C
׀ ׀ H H
+ H – Br ᵟ- ᵟ+
H H ׀ ׀
H - C – C – H
+ ׀ H
Electrophilic Addition
Symmetrical Alkene
HBr polar
CH2=CH2 + HBr → CH3CH2Br
: Br-
H H ׀ ׀
H - C – C – H
׀ ׀ H Br
CH2=CH2 + Br2 → CH2BrCH2Br
Electrophilic addition to symmetrical alkene
H H ׀ ׀
C = C
׀ ׀ H H
+ Br – Br ᵟ+ ᵟ-
Br2 non polar : induced dipole due to C=C
H H ׀ ׀
H - C – C – H
+ ׀ Br
: Br-
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
carbocation
carbocation
Heterolytic fission
Heterolytic fission
CH2=CH2 + Br2/H2O → CH2BrCH2Br
H H ׀ ׀
C = C
׀ ׀ H H
+ Br – Br
Heterolytic fission
ᵟ+ ᵟ-
H H ׀ ׀
H - C – C – H
+ ׀ Br
: Br-
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
H H ׀ ׀
H - C – C – H
+ ׀ Br
: OH- from
H2O
H H ׀ ׀
H - C – C – H
׀ ׀ Br OH
H H ׀ ׀
C = C
׀ ׀ H H
H H ׀ ׀
CH3 – C = C – CH3
+ H – Br
H H ׀ ׀
H - C – C – H
׀ ׀ H Br
+ H – Br
H H ׀ ׀
CH3 – C – C – CH3
׀ ׀ H Br
only 1 product
H CH3
׀ ׀
H – C = C – H
Asymmetrical Alkene
+ H – Br
H CH3
׀ ׀
H – C – C – H
׀ ׀
H Br
H CH3
׀ ׀
H – C – C – H
׀ ׀
Br H
carbocation
2 product
H H ׀ ׀
C = C
׀ ׀ H H
+ H – Br ᵟ- ᵟ+
H H ׀ ׀
H - C – C – H
+ ׀ H
HBr polar
CH2=CH2 + HBr → CH3CH2Br
: Br-
H H ׀ ׀
H - C – C – H
׀ ׀ H Br
CH2=CH2 + Br2 → CH2BrCH2Br
Addition to symmetrical alkene
H H ׀ ׀
C = C
׀ ׀ H H
+ Br – Br ᵟ+ ᵟ-
Br2 non polar : induced dipole due to C=C
H H ׀ ׀
H - C – C – H
+ ׀ Br
: Br-
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
carbocation
Heterolytic fission
Heterolytic fission
CH2=CH2 + Br2/H2O → CH2BrCH2Br
H H ׀ ׀
C = C
׀ ׀ H H
+ Br – Br
Heterolytic fission
ᵟ+ ᵟ-
H H ׀ ׀
H - C – C – H
+ ׀ Br
: Br-
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
H H ׀ ׀
H - C – C – H
+ ׀ Br
: OH- from
H2O
H H ׀ ׀
H - C – C – H
׀ ׀ Br OH
H CH3
׀ ׀
H – C = C – H + H – Br
H CH3
׀ ׀
H – C – C – H
׀ ׀
H Br
H CH3
׀ ׀
H – C – C – H
׀ ׀
Br H
Addition to asymmetrical alkene
CH2=CHCH3 + HBr → CH3CHBrCH3 or CH2BrCH2CH3
major
minor
CH3 CH3
׀ ׀
H – C = C – CH3 + H – Br
CH3 CH3
׀ ׀
H – C – C – H
׀ ׀
H Br
CH3 CH3
׀ ׀
H – C – C – H
׀ ׀
Br H
major
minor
✓
✓
Markovnokov rule - Hydrogen/electrophile add to carbon with most H2 bonded - Due to stable carbocation intermediate formed
R
׀
R – C +
׀
R
H
׀
R – C +
׀
R
H
׀
H – C +
׀
R
H
׀
H – C +
׀
H
30 carbocation
> > >
20 carbocation 10 carbocation
H CH3
׀ ׀
H – C ← C – H
׀ +
H
H CH3
↓ ׀
H – C → C – H
+ ׀
H
+ H – Br ᵟ- ᵟ+
: Br-
: Br-
2 alkyl gp – positive inductive effect – push electron to carbocation (more stable)
Heterolytic fission H CH3
׀ ׀
H – C = C – H
Addition to asymmetrical alkene
CH2=CHCH3 + HBr → CH3CHBrCH3
major
minor
CH3 CH3
׀ ׀
H – C = C–CH3 + H – Br
CH3 CH3
↓ ׀
H – C → C ← CH3
+ ׀
H
CH3 CH3
׀ ↓
H – C ← C – CH3
׀ +
H
major
minor
✓
✓
Markovnokov rule - H add to carbon with most H2 bonded - Due to stable carbocation formed
R
׀
R – C +
׀
R
H
׀
R – C +
׀
R
H
׀
H – C +
׀
R
> >
H CH3
׀ ׀
H – C – C – H
׀ ׀
H Br
H CH3
׀ ׀
H – C – C – H
׀ ׀
Br H
1 alkyl gp – positive inductive effect – push electron to carbocation (less stable)
ᵟ+ ᵟ -
: Br-
CH3 CH3
׀ ׀
H – C – C – CH3
׀ ׀
H Br
3 alkyl gp – positive inductive effect – push electron to carbocation (more stable)
: Br-
2 alkyl gp – positive inductive effect – push electron to carbocation (less stable)
CH3 CH3
׀ ׀
H – C – C – CH3
׀ ׀
Br H
30 carbocation
most stable
10 carbocation
least stable
H CH3
↓ ׀
H – C → C – H
+ ׀
H
H CH3
׀ ׀
H – C ← C – H
׀ +
H
>
20 carbocation – greater positive inductive effect - more stable/lower charge density carbocation
CH3 CH3
↓ ׀
H – C → C ← CH3
+ ׀
H
>
CH3 CH3
׀ ↓
H – C ← C – CH3
׀ +
H
30 carbocation – greater positive inductive effect - more stable/lower charge density carbocation
H CH3
׀ ׀
H – C ← C – H
׀ +
Br
H CH3
↓ ׀
H – C → C – H
+ ׀
Br
+ Br – CI ᵟ- ᵟ+
: CI-
: CI-
2 alkyl gp – positive inductive effect – push electron to carbocation (more stable)
Heterolytic fission H CH3
׀ ׀
H – C = C – H
Addition to asymmetrical alkene
CH2=CHCH3 + BrCI → CH2BrCHCICH3
major
minor
CH3 CH3
׀ ׀
H – C = C–CH3 + I – CI
CH3 CH3
↓ ׀
H – C → C ← CH3
+ ׀
I
CH3 CH3
׀ ↓
H – C ← C – CH3
׀ +
I
major
minor
✓
✓
Markovnokov rule - H add to carbon with most H2 bonded - Due to stable carbocation formed
R
׀
R – C +
׀
R
H
׀
R – C +
׀
R
H
׀
H – C +
׀
R
> >
H CH3
׀ ׀
H – C – C – H
׀ ׀
Br CI
H CH3
׀ ׀
H – C – C – H
׀ ׀
CI Br
1 alkyl gp – less positive inductive effect – (less stable)
ᵟ+ ᵟ -
: CI-
CH3 CH3
׀ ׀
H – C – C – CH3
׀ ׀
I CI
3 alkyl gp – positive inductive effect – push electron to carbocation (more stable)
: CI-
2 alkyl gp – less positive inductive effect – (less stable)
CH3 CH3
׀ ׀
H – C – C – CH3
׀ ׀
CI I
30 carbocation
most stable
10 carbocation
least stable
H CH3
↓ ׀
H – C → C – H
+ ׀
Br
H CH3
׀ ׀
H – C ← C – H
׀ +
Br
>
20 carbocation – greater positive inductive effect - more stable/lower charge density carbocation
CH3 CH3
↓ ׀
H – C → C ← CH3
+ ׀
I
>
CH3 CH3
׀ ↓
H – C ← C – CH3
׀ +
I
30 carbocation – greater positive inductive effect - more stable/lower charge density carbocation
EN CI higher
EN CI higher
ᵟ-
Electron rich region
Electrophilic Substitution rxn
C6H6 + Br2 C6H5Br + HBr
+ Br-Br ᵟ+
+ NO2+
ᵟ+
Electrophilic Substitution Electrophilic Addition
vs
C = C Electron rich π electron
ᵟ- ᵟ-
ᵟ+
C = C ᵟ- ᵟ-
E ᵟ+
E+ Electron deficient
E ᵟ+
H H ׀ ׀
C = C
׀ ׀ H H
CH2=CH2 + Br2 → CH2BrCH2Br
+ Br – Br ᵟ- ᵟ+
H H ׀ ׀
H - C – C – H
׀ ׀ Br Br
vs
CH2=CH2 + HCI → CH3CH2CI
H H ׀ ׀
C = C
׀ ׀ H H
ᵟ- + H – CI ᵟ+
H H ׀ ׀
H - C – C – H
׀ ׀ H CI
Electrophilic Addition rxn
E
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
ᵟ+ + H E
+ H
Electron rich region
H Br
+ HBr
C6H6 + HNO3 C6H5NO2 + HCI
AICI3 dry ether
warm/Conc H2SO4
H NO2
Reactivity of Alkene - High reactivity - Unstable bond bet C = C - High reactivity – Weak pi bond overlap bet p orbital - Unsaturated hydrocarbon – ᴨ bond overlap
Reactivity of Benzene (Unreactive) - Delocalization of electron in ring - Stability due to delocalized π electron - Substitution instead of Addition
C6H6 – no reaction with brown Br2(I)
ethene decolourize brown Br2(I)
Benzene –stable (unreactive) toward addition rxn
Electrophile - Electron deficient - Accept lone pair - Positive charge - Lewis Acid
H
+ Br – Br ᵟ- ᵟ+
Cyclohexene (Addition) vs Benzene (Substitution)
✓
Positive charge distributed in benzene ring (carbocation intermediate)
Benzene highly unreactive to addition rxn
: Br- +
+ Br – Br
+ Br – Br AICI3 dry ether
Benzene undergo substitution rxn
Cyclohexene undergo addition rxn
Benzene undergo electrophilic substitution (Bromination)
Loss H+ enable aromatic ring to reform
Br - Br
Br Br
Benzene undergo electrophilic substitution (Nitration)
+NO2
NO2 NO2
Positive charge distributed in benzene ring (carbocation intermediate)
Loss H+ enable aromatic ring to reform C6H6 + HNO3 C6H5NO2
Conc H2SO4
50C
Conc HNO3 + H2SO4 produce NO2+ electrophile
+
H
Reactivity of Benzene (Unreactive) - Delocalization of electron in ring - Stability due to delocalized π electron - Substitution instead of Addition
Electrophilic Substitution
H
E ᵟ+
+ + H
E
Electron rich region
C6H6 + Br2 C6H5Br + HBr AICI3 dry ether
H
+ Br-Br ᵟ+
+ HBr Br
✓
OH O
‖ ׀
CH3-C–CH3 + [O] CH3- C– CH3
H
׀
CH3-CH2-OH + [O] CH3- C = O
Reduction rxn Oxidation rxn
MnO4- /H
+
K2Cr2O7/H+
10 Alcohol – Oxidised to Aldehyde and Carboxylic acid
20 Alcohol - Oxidised to Ketone
MnO4- /H
+
K2Cr2O7/H+
MnO4- /H
+
K2Cr2O7/H+
Oxidation vs Reduction rxn
O
‖
CH3-COH
Oxidation of Alcohol Acidified dichromate(VI)/permanganate(VII)
Reduction carbonyl (C = O) Sodium borohydride (NaBH4)
Lithium aluminium hydride (LiAIH4) / dry ether
O
‖
CH3-COH CH3CHO CH3CH2OH
O OH
׀ ‖
CH3-C–CH3 CH3- C– CH3
[H-] [H-]
NaBH4 NaBH4
Carboxylic acid reduced to aldehyde / alcohol
NaBH4
[H-]
Ketone reduced to alcohol
Hydride ion (nucleophile) :H-
produce
hydride ion / :H-
O
‖
CH3-COH CH3CH2OH
Carboxylic acid reduced alcohol
[H-]
LiAIH4 dry ether with acid
stronger reducing agent
Sn / conc HCI / reflux
Nitrobenzene reduced to phenylamine
NH3+ NO2
NH2
NaOH
phenylammonium
ion
reducing agent
Convert benzene to phenylamine
Convert propanoic acid to propanol
Convert ethanal to ethanol
O
‖
CH3CH2 COH CH3CH2CH2OH [H-]
stronger reducing agent
LiAIH4 dry ether / acid
CH3CHO CH3CH2OH [H-]
NaBH4
50C
NO2
conc HNO3 + H2SO4 Sn / conc HCI / reflux
NH3+
NaOH
NH2
׀ ׀ C - C –OH ׀ ׀
O ‖ C – C – C
O ‖ C – C – H
O ‖ C – C – OH
O ‖ C –C – C– O – C – C
No reaction
1o alcohol
[O]/Cr2O7/H+
Aldehyde
Ketone
Carboxylic Acid
Free radical substitution
CI2/ UV
Halogenoalkane
Alkane
2o alcohol
[O]/ Cr2O7/H+
[O]/ Cr2O7/H+
3o alcohol
[O]/ Cr2O7/H+
Substitution
warm / OH-
Alcohol
Alcohol Alkene
Elimination
100C /Conc alcoholic OH-
Alkane Halogenoalkane Dihalogenoalkane
Condensation
Ester
Addition
Polymerisation
X
׀ ׀ C – C – CI ׀ ׀
׀ ׀ C = C ׀ ׀
׀ ׀ ׀ ׀ C – C – C – C ׀ ׀ ׀ ׀
׀ ׀ C – C ׀ ׀ H CI
׀ ׀ C – C ׀ ׀ CI CI
׀ ׀ C – C ׀ ׀ Br Br
׀ ׀ C – C ׀ ׀
׀ ׀ C – C – OH ׀ ׀
Start here
PolyAlkene
׀ ׀ C – C ׀ ׀ H H
[H]/ NaBH4 [H]/ NaBH4
[H]/ NaBH4
oxidation
reduction
oxidation
oxidation
reduction
reduction
conc HNO3 / H2SO4
50C
NO2
Sn / conc HCI / reflux
NH3+
NaOH
NH2
C – C = C – C → C – C – C – C ‖
O
Synthetic routes
C –C –C – I → C – C – C-H ‖
O
Two steps 1 - Addition of H2O 2 - Oxidation alcohol to ketone
Two steps 1 – Substitution with OH- to alcohol 2 - Oxidation alcohol to aldehyde
But-2-ene to Butanone 1-iodopropane to propanal
1-chloropropane to propanoic acid
C –C –C –CI → C – C–COOH
Three steps 1 – Substitution with OH- to alcohol 2 - Oxidation alcohol to aldehyde 3 - Oxidation aldehyde to carboxylic acid
C – C = C – C
C – C – C – C ׀ ׀
H OH
C – C – C – C ‖
O
H2O /300C
H2SO4 catalyst [O] oxidation
K2Cr2O7/H+
C – C – C – I C – C – C – H ‖
O
C – C – C–OH
warm NaOH
SN2
[O] oxidation
K2Cr2O7/H+
C – C – C – CI C – C – COOH
C – C – C–OH C – C – C – H ‖ O
warm NaOH
SN2
[O] oxidation
K2Cr2O7/H+
Propane to propanoic acid
C –C –C → C –C –COOH
C – C – C C – C – COOH
C – C – C–CI C – C – C–OH
[O] oxidation
K2Cr2O7/H+
reflux
Warm NaOH
SN2
Free radical
substitution
UV / CI2
Three steps 1 – Free radical substitution to halogenoalkane 2 – Substitution with OH- to alcohol 3 – Oxidation alcohol to carboxylic acid
[O] oxidation
K2Cr2O7/H+
reflux
Synthetic routes Propane to propyl propanoate
Butene to butanone
Three steps 1 – Addition HBr 2 – Substitution with OH –
3 – Oxidation of alcohol to ketone
Four steps 1 – Free radical substitution/UV 2 – Substitution with OH -
3 – Oxidation alcohol to carboxylic acid 4 – Esterification with conc acid
Ethene to ethanoic acid
C – C
׀ ׀
H OH
C – C – H ‖
O
C – COOH
Three steps 1 – Addition using H2O 2 - Oxidation alcohol to aldehyde 3 – Oxidation aldehyde to carboxylic acid
Ethanol to ethyl ethanoate
C – C-OH → C–COO–C–C
C – C – O – C – C
‖
O
C–C–OH
C – COOH
Esterification
Ethanol + ethanoic acid
Conc H2SO4
Two steps 1 – Oxidation alcohol to carboxylic acid 2 – Esterification with ethanol/conc acid
C = C → C – COOH
Free radical
substitution
UV / CI2
C–C–C–CI
C – C – C
C–C–C–OH Warm NaOH
SN2
C–C–COOH [O] oxidation/reflux
K2Cr2O7/H+
C – C – C – O – C – C – C
‖
O Esterification
Propanol + propanoic acid
Conc H2SO4
C – C = C – C C – C – C – C ‖ O Addition HBr
C – C – C – C ׀ ׀
Br H Warm NaOH
SN2
C – C – C – C ׀ ׀
OH H
[O] oxidation
K2Cr2O7/H+
[O] oxidation
K2Cr2O7/H+
reflux
C – C = C – C → C – C – C – C ‖
O
C = C
H2O /300C
H2SO4 catalyst
[O] oxidation
K2Cr2O7/H+
[O] oxidation
K2Cr2O7/H+
reflux
C – C – C → C – C – C –O–C–C–C ‖
O
Synthetic routes
Benzene to phenylamine
Ethanoic acid to ethyl ethanoate
Two steps 1 – Reduction to alcohol 2 – Esterification with ethanoic acid/conc acid
C – COOH
C–C–OH
Three steps 1 – Nitration substitution of benzene 2 – Reduction of nitrobenzene 3 – Addition NaOH
Ethanoic acid to ethanol
C – C
׀ ׀
H OH
C – C – H ‖
O
C – COOH
Two steps 1 – Reduction acid to aldehyde 2 - Reduction aldehyde to alcohol
C – COOH → C –COO–C–C
C – C – O – C – C
‖
O
Reduction [H-]
LiAIH4 dry ether
acid
Esterification
Ethanol + ethanoic acid
Conc H2SO4
Ethane to Ethanol
C – C → C–C-OH
C – C
C – C – CI
Two steps 1 – Free radical substitution/UV 2 – Substitution with OH-
NO2
NH2
NH2
NH3+
conc HNO3
conc H2SO4 50C
Sn / conc HCI / reflux
NaOH
C – COOH → C – C-OH
Reduction [H-]
NaBH4
Reduction [H-]
NaBH4
Free radical
substitution
UV / CI2
C – C
׀ ׀
H OH
warm NaOH
SN2