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Aliphatic Organic Synthesis
Aliphatic Organic Synthesis
R H Major C Br
H C H Haloalkane H H
R C H
H C Br H Minor R H C Br H C Br H
Electrophilic addition
HBr
C
n
H R C
C H O Expoxethane ROH H H C H
H H Alcohol R C
H R C OH
H C OH H Diol
OR OH Ether
Reactions of Alkenes.
1. Alkene C2H4 +Br2 Reagent: Conditions: Type: Mechanism:
H C H Br Br C
AS P192
H H H C Br
H C Br H
2.
Alkene
haloalkane 3
AS P192
H H H C H
H C Br H
H3C H
H H H
H Br
H3C H
H H H3C H C
+
H C H H H
H Br
Br Secondary Carbocation
3.
Alkene
Alcohol
AS P193
RCH2CH2OH H2O/H3PO4 cat. Or H2SO4 cat. 3000C/ 60 atm Electrophilic addition Required.
H H O O O O H H C H H C H H O O S O O
H H C H
H C H O HO S O O H + OH2 H C H H C H O H
H2SO4
4.
Alkene C2H3R +O2 Reagent: Conditions: Type: Mechanism: O2 Ag cat. 250oC Oxidation Not required.
Epoxyethane RCHOCH2
AS P196
H C R C
H H R
H C O
H C H
5.
Alkene
Alkane 5
AS P195
RCH2CH3
Reactions of Epoxyethane
6. Epoxyethane Diol AS P197
RCHOHCH2OH
Not required.
H H C OH H
OH2
C OH
7.
AS P197
Not required.
H H C OH H
ROH
C OR
Reactions of Alkanes
8. Alkane RC2H5 +Cl2 Haloalkane RCH2CH2Br 7 AS P192
Cl
Cl
Cl
Cl
Cl
CH3
HCl
+ +
CH3
CH3
Cl
Cl
CH3Cl
Cl
Cl Cl CH3
+ + +
Cl CH3 CH3
H R C
H C O H
H H Alcohol
Nucleo Sub
H C
H H H Conc NH3 heat in a sealed tube H Br R C C Nucleo Haloalkane H Sub H amine Nucleo KCN, alocoholic Sub Solution, reflux H H C CN
+
NH2
H2 / LiAlH4
C H
Reduction H R C H H C H NH2
Hydrolysis
H /H2O, reflux H R C H H C H C OH O
amine
Carboxylic acid
Reaction of Haloalkanes
9. Haloalkane RCH2CH2Br +NaOH Alcohol RCH2CH2OH AS P209
Br H OH
H C H
H C H OH
10.
Amine RCH2CH2NH2
A2 P88
H C H
H N H NH3
+
H H H C H
H C H N
H H
NH4Br
11.
Haloalkane RCH2CH2Br + KOH Reagent: Conditions: Type: KOH in ethanol Heat under reflux Elimination
Alkene RCH2CH2
AS P212
10
Mechanism:
Required.
H R C H
H C H OH Br H C H C H H
12.
Haloalkane RCH2CH2Br +KCN Reagent: Conditions: Type: Mechanism: KCN in ethanol Heat under reflux
Nitrile RCH2CH2CN
A2 P90
H R C H
H C H CN Br R
H C H
H C H CN
Reaction of Nitriles
13. Nitrile RCH2CH2CN Amine RCH2CH2CH2NH2 A2 P90
11
H2, Ni cat
H R C H
H C H CN
H C H
H C H N
H H
4[H]
C H
14.
H Cl
+ H2 O
C H
12
Reaction of Alcohols
H R C H H C H C OH O
Carboxylic acid
H+/
reduction
H R C H
H C C
H Aldehyde
H+/
Cr2O 72(aq),
reflux
NaBH4
H R C
H C O H H+ or OH- (aq)
H H 1o Alcohol
H H
H R C H
H C H Ketone
H C
OH 2o Alcohol
15.
1o Alcohol RCH2CH2OH Reagent: Conditions: Type: Mechanism: H H C H 16. 1o Alcohol RCH2CH2OH Reagent: Conditions: Type: Mechanism: H H C H H C H O H K2Cr2O7/H2SO4 HUR Oxidation Not required. H C H O H K2Cr2O7/H2SO4 Heat under distillation Oxidation Not required.
Aldehyde RCH2CH2CHO
AS P223 A2 P62
[O] H
H C H
H C H CHO
AS P223 A2 P62
[O] H
H C H
H C H COOH
17.
Alkene RCHCH2
AS P227
14
H O H H
+
H C H + O H H H
H C H
H C+ H
C H
H C H C
H H
18.
A2 P67
H C H
H C H O C
+H
O R
C H
19.
Haloalkane RCH2CH2X
Type: Mechanism: H H C H H C H
16
RCHOHCH3 + [O] Reagent: Conditions: Type: Mechanism: H R C H C H K2Cr2O7/H2SO4 Heat under Reflux Oxidation Not required
RCOCH3
[O] R
H C O
H C H H
OH H
17
O OH
X
H Ketone R C H H C H C R' H+/ Cr O 2(aq), reflux 2 7 O R reduction
oxidation H C H H C H H+/ C
Aldehyde H C OH CN
OHCN R H
H C H
H C H
Cr2O72(aq), reflux
Hydroxynitrile
LiAlH4ether oxidation H R C H H C H O H
2o Alcohol
1o Alcohol
Reactions of Aldehydes
21. Aldehyde RCH2CHO Reagent: Conditions: Type: Mechanism: K2Cr2O7/H2SO4 Heat under Reflux Oxidation Not required 18 Carboxylic acid RCH2COOH A2 P63
CHO
[O] H
H C H
H C H COOH
A2 P63
Mechanism:
H H C H H C H
H C H
H C H OH
23.
A2 P64
H R C CN OH
CN
19
Reactions of Ketones
24. Ketone RCOCH3 Reagent: Conditions: Type: Mechanism:
H R C O H H O H C H H R
A2 P66
H R C
H C H
OH H
20
21
NAE H R C H H C H Ester O cat R'OH/concH2SO4 reflux H H O O Esterification NAE C R C C C H+(aq)/ H2O OH R H H NAE Carboxylic acid reduction H2O NAE CH3 CH3 C
O C O Acid Anhydride
LiAlH4ether H R C H
oxidation H C H O H
1o Alcohol
25.
Carboxylic acid 22
1oAlcohol
A2 P63
RCH2COOH Reagent: Conditions: Type: Mechanism: H R C H H C H COOH LiAlH4, ether r.t.p. Reduction Not required
RCH2CHOH
H R C H
H C H OH
26.
Ester RCH2COOR
A2 P67
ROH, Conc. H2SO4 Cat Heat under reflux Esterification Not required
O C OH
R'
O C OR'
23
Reactions of Esters
27. Ester RCH2COOR Reagent: Conditions: Type: Mechanism: H+/H2O Heat under reflux Hydrolysis Not required Carboxylic acid RCH2COOH A2 P67
O C OR'
O C OH
24
O R C Cl
NAE
H2 O Alkaline r.t.p.
O R C OH Carboxylic acid
25
Mechanism:
O R C Cl OH
Required
O R C OH Cl R C OH O
29.
Ester RCH2COOR ROH, Conc. H2SO4 cat r.t.p. Nucleophilic addition elimination reaction Required
O C OR Cl
A2 P67
O R C OR
30.
Acid chloride RCH2COCl Reagent: Conditions: Type: Mechanism: Conc. NH3 r.t.p.
26
O R C Cl NH3 H R
O C N H
+
O Cl H Cl R C NH2
27
O R C OR Ester
NAE Conc.NH3
H2 O
CH3
C OH
CH3
C OH
32.
1o amide RCH2CONH2
A2 P67
NH3
CH3
C NH2
CH3
C OH
33.
Ester RCH2COOR
A2 P67
Mechanism:
Not required
O CH3 CH3 C O C O O O
R'OH
CH3
C OR'
CH3
C OH
34.
30