Download Summary of Reactions Which Will Appear on Exams

Summary of Reactions Which
Will Appear on Exams
1. COMBUSTION OF HYDROCARBONS (ALKANES/ALKENES/ALKYNES, etc)
CxHy + (x + y/4)O2
xCO2 + y/2H2O + heat
C10H20 + 15O2
10CO2 + 10H2O
(this is the only reaction you will need to balance;
for all others only the organic product(s) required)
2. FREE RADICAL HALOGENATION OF ALKANES
light or
heat
R-X + H-X
R-H + X-X
X = Cl, Br
light
CH3-Cl + H-Cl
CH4 + Cl2
heat
CH3-CH3 + Br2
CH3-CH2-Br + H-Br
(you need to know the mechanism)
3. HYDROGENATION OF ALKENES
H
H
C
C
R
R'
CH3
CH3
metal catalyst
(Ni, Pt or Pd)
H2
metal catalyst
(Ni, Pt, Pd)
H
H
H
C
C
R
H
R'
H
H
CH3
H2
CH3
cis product
syn-addition
of hydrogen
4. ADDITION OF HX TO ALKENES
H
R"
C
H
H-X
C
R
R'
H
X
C
C
R"
R
R'
X = Cl, Br, I
X = OH, H2SO4 catalyst required (hydration)
Markovnikov addition (you need to know the mechanism)
5. ADDITION OF X2 TO ALKENES
H
H
C
H
X-X
C
R
R'
X
X
C
C
R
H
R'
X = Cl, Br
X
CH3
CH3
X-X
anti-addition
of halogen
X
CH3
CH3
trans product
6. DIHYDROXYLATION OF ALKENES
H
H
C
C
R
KMnO4
cold, NaOH
R'
CH3
KMnO4
cold, NaOH/H2O
H
OH
OH
C
C
R
R'
OH
OH
CH3
CH3
H
CH3
cis product
syn-addition
of OH groups
7. OXIDATIVE CLEAVAGE OF ALKENES
H
R"
C
C
R
KMnO4
in H2O, H+
H
R"
C
R'
+
O
O
C
R
R'
a ketone
an aldehyde
further
oxidation
HO
C
R
O
a carboxylic acid
8. FREE RADICAL POLYMERIZATION OF ALKENES
CH2=CH
heat
R'O-(CH2-CH)-(CH2-CH)n-etc
+ R'O-OR'
R
R
R
(you need to know the mechanism--in packet)
9. HYDROGENATION OF ALKYNES
R
C
C
metal catalyst
(Ni, Pt or Pd)
H
1H2
R
H
C
R'
syn addition
C
R'
cis product
10. HALOGENATION OF ALKYNES
X2
R
C
C
R
C
R'
X
X = Cl, Br
X
anti addition
C
R'
trans product
11. HX ADDITION TO ALKYNES
R
H-X
R
C
C
H
C
H
C
X
X = Cl, Br, I
(you need to know the mechanism)
H
Markovnikov addition
12. HYDRATION OF ALKYNES
R
H2O
R
C
C
H
H
C
H2SO4
HgSO4
catalysts
R
CH3
C
C
HO
H
O
an enol
(unstable)
a ketone
Markovnikov addition
13. ALKYLATION OF TERMINAL ALKYNES
_
NaNH2
R
C
C
R
H
C
C
Na+ + R'CH2X
R
C
C
CH2R'
or
(or CH3X)
(X=Cl, Br, I)
(2o or 3o alkyl halides do not work)
(R
C
14. HALOGENATION OF CONJUGATED DIENES
1
2
3
4
CH2=CH-CH=CH2
X2
1
2
3
4
1
2
3
4
CH2-CH-CH=CH2 + CH2-CH=CH-CH2
X
X = Cl, Br
X
X
X
1,4-addition
1,2-addition
15. HX ADDITION TO CONJUGATED DIENES
1
2
3
4
CH2=CH-CH=CH2
H-X
1
3
4
1
2
3
4
CH2-CH-CH=CH2 + CH2-CH=CH-CH2
H
X = Cl, Br
2
X
1,2-addition
H
X
1,4-addition
C
CH3)
16. ELECTROPHILIC AROMATIC SUBSTITUTION
E
reagents
X
X
halogenation
Cl2/FeCl3 or AlCl3 (cat) E = Cl
Br2/FeBr3 or AlBr3 (cat) E = Br
nitration
HONO2/H2SO4(cat)
E = NO2
sulfonation
HOSO3H
E = SO3H
Friedel-Crafts alkylation
R-Cl/AlCl3 (cat)
E=R
O
Friedel-Crafts acylation
R
O
C
Cl
/AlCl3 (cat)
E = C-R
(you need to know the mechanism and the
directing effects of various substituents "X")
17. AROMATIC SIDECHAIN OXIDATION TO BENZOIC ACIDS
CH-R
X
R'
KMnO4
H2O, heat
CO2H
X
R, R' = alkyl or H
18. AROMATIC RING REDUCTION TO CYCLOHEXANES
R
3H2
Pt cat
high pressure
R
19. REDUCTION OF NITRO GROUPS TO ANILINES
NO2
NH2
Fe
HCl
X
X
20. CONVERSION OF SULFONIC ACIDS TO PHENOLS
SO3H
OH
NaOH
300 oC
X
X
+
then H3O
21. REDUCTION OF CARBONYL COMPOUNDS TO ALCOHOLS
NaBH4
ethanol
O
C
R
H
aldehydes
O
or
LiAlH4, ether;
then H3O+
primary alcohol
OH
NaBH4
ethanol
C
R
R-CH2OH
R'
ketones
O
LiAlH4, ether;
then H3O+
C
R
OR'
esters
or
LiAlH4, ether;
then H3O+
C
R
R'
H
secondary alcohol
R-CH2OH
+
R'OH
primary alcohol
(you need to know the mechanism of aldehyde and
ketone reductions but not esters)
22. OXIDATION OF ALCOHOLS TO CARBONYL COMPOUNDS
O
R-CH2OH
CrO3
or Na2Cr2O7
C
R
R-CH2OH
primary alcohol
(PCC = pyridinium
chlorochromate)
H
aldehyde
O
CrO3
or Na2Cr2O7
C
R'
R
H
CrO3
or Na2Cr2O7
C
R
R'
ketone
secondary alcohol
OH
OH
carboxylic acid
C
R
C
R
O
PCC
R
C
H
aldehyde
primary alcohol
OH
O
R'
no reaction
R"
tertiary alcohol
(You need to know the mechanism of oxidation of
alcohols to aldehydes and ketones with CrO3)
23. CONVERSION OF ALCOHOLS TO ALKYL HALIDES
R-OH
R-OH
SOCl2
PBr3
R-Cl
R-Br
24. WILLIAMSON ETHER SYNTHESIS
R-O-CH2R'
R'CH2-X
Na or
NaH
_
R-O
R-OH
Na+
+
or
R-O-CH3
CH3-X
X = Cl, Br, I
(2o or 3o alkyl halides usually do not work in this reaction)
25. POLYMERIZATION OF EPOXIDES
base cat
(B)
O
H2C
CH
R
R
B-(CH2-CH-O)n-CH2-CH-O-etc
R
(you need to know the mechanism--in packet)
26. ACID/BASE REACTIONS OF CARBOXYLIC ACIDS, PHENOLS AND AMINES
NaHCO3
or NaOH
O
O
C
C
R
OH
HCl or H2SO4
R
O- Na+
NaOH
(but not NaHCO3)
ArO- Na+
Ar-OH
HCl or H2SO4
HCl
R3NH+ Cl-
R3N
NaOH
27. ALKYLATION OF AMINES
N ••
R'
R'''CH2X
R
R'
R
+
N
X+
R"
or
R
R"
CH3X
(1o, 2o or 3o)
R, R', R" = alkyl, H, aryl
CH2R'''
R'
X = Cl, Br, I
N
X+
CH3
R"
a quaternary ammonium salt
(2o or 3o alkyl halides usually do not work in this reaction)
Ph
H
Ph
CH3CH2I
N ••
H
CH3
N
+
Ph
INaOH
•• N
CH2CH3
CH3
a quaternary
ammonium salt
(only if there
is at least one H
on the nitrogen)
CH2CH3
CH3
28. SYNTHESIS OF GRIGNARD REAGENTS AND ORGANOLITHIUM COMPOUNDS
ether
R-X
+
R-Mg-X
Mg
Grignard reagent
R-X
+
2Li
alkane
solvent
X = Cl, Br, I
R-Li
+
LiX
29. REACTIONS OF GRIGNARD REAGENTS AND ORGANOLITHIUM COMPOUNDS
R-Mg-X
H2O
or
R-H
R-Li
O
R-Mg-X
CO2
R-COH
or
then H3O+
R-Li
R
O
R-Mg-X
then H3O
C
R'CH
R'
aldehyde
R-Li
O
R-Mg-X
+
or
H
2o alcohol
R
then H3O+
OH
C
R'CR"
R'
ketone
R-Li
OH
+
+
or
a carboxylic acid
R"
3o alcohol
(you need to know the mechanism--in packet)
30. ELIMINATION OF ALKYL HALIDES TO ALKENES
H
X
C
H
H
R
H
NaOH
C
C
R'
R
H
X = Cl, Br, I
(you need to know the mechanism)
C
+ NaX
R'
31. HYDRATION OF ALDEHYDES AND KETONES
H2O
acid or base
catalyst
O
HO
OH
C
RCH
R'
H
HO
OH
aldehyde
O
H2O
acid or base
catalyst
C
R'CR
R'
ketone
R
(you need to know the mechanism--in packet)
32. REACTIONS OF ALDEHYDES AND KETONES WITH ALCOHOLS
O
R"OH
base
catalyst
RCH
HO
OR"
C
R'
H
HO
OR"
a hemiacetal
aldehyde
O
R"OH
base
catalyst
C
R'CR
ketone
O
2R"OH
acid
catalyst
RCH
a hemiketal
R'
R
R"O
OR"
C
R'
H
an acetal
aldehyde
O
2R"OH
acid
catalyst
R"O
C
R'CR
ketone
OR"
R'
a ketal
R
(you need to know the mechanism--in packet)
33. CYANOHYDRINS FROM ALDEHYDES AND KETONES
O
HO
HCN
NaCN
CN
C
RCH
R'
H
HO
CN
aldehyde
O
HCN
NaCN
R'CR
C
R'
ketone
R
(you need to know the mechanism--in packet)
34. REACTIONS OF ALDEHYDES AND KETONES WITH AMINES AND DERIVATIVES
O
+
C
R
NZ
H+ cat
Z-NH2
C
R
H
H
aldehyde
O
+
C
R
NZ
+
H cat
Z-NH2
C
R
R'
R'
ketone
Z = OH, NHPh, alkyl, aryl
(you need to know the mechanism--in packet)
35. OXIDATION OF ALDEHYDES TO CARBOXYLIC ACIDS
Ag+1
NH4OH
O
O
C
R
C
H
O
R
OH
O
Cu+2
C
R
(Tollens
oxidation)
Fehling or
Benedict
oxidation
C
H
R
OH
36. SYNTHESIS OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES
O
O
+
C
R
SOCl2
C
OH
R
Cl
O
O
2
+
C
R
O
C
SOCl2
R
OH
C
O
R
37. HYDROLYSIS OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES
O
O
H2O
C
+ HCl
C
R
Cl
R
O
O
C
C
R
O
OH
O
H2O
2
C
R
R
OH
38. REACTION OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES WITH ALCOHOLS
O
O
R'OH
C
R
+ HCl
C
Cl
R
OR'
an ester
O
C
R
O
O
R'OH
+
C
C
O
O
R
R
OR'
C
R
OH
39. FISCHER ESTERIFICATION OF CARBOXYLIC ACIDS TO ESTERS
O
O
+
+
C
R
H cat
R'OH
+ H2O
C
R
OH
OR'
(must remove water)
an ester
(you need to know the mechanism)
40. HYDROLYSIS OF ESTERS TO CARBOXYLIC ACIDS AND ALCOHOLS
O
O
+
H cat
+ H2O
C
R
R
+
C
R
OR'
O
O
C
C
+ NaOH
R'OH
+
OH
O
HCl
_
O Na
R
OR'
R'OH
+
R
(you need to know the mechanisms for both of these)
41. AMINOLYSIS OF ESTERS TO AMIDES
O
O
heat
+ HNR"2
C
R
R
OR'
R" = H, alkyl, aryl
+
C
NR"2
an amide
C
R'OH
OH
42. REACTIONS OF GRIGNARD REAGENTS AND ORGANOLITHIUM COMPOUNDS
WITH ESTERS TO FORM TERTIARY ALCOHOLS
2 R"-Mg-X
O
+
or
C
R
OH
then H3O+
R
2 R"-Li
OR'
+
C
R'-OH
R"
R"
(you need to know the mechanism)
43. REACTION OF CARBOXYLIC ACID CHLORIDES AND ANHYDRIDES WITH AMINES
O
O
C
R
+ HNR'2
Cl
C
R
NR'2
an amide
O
O
C
C
R
O
O
+ HNR'2
O
+
C
R
R
NR'2
R' = H, alkyl, aryl
44. HYDROLYSIS OF AMIDES
HCl
H2O
heat
O
O
C
R
NR'2
R
NaOH
H2O
heat
O
OH
O
C
R
+ HNR'2
C
C
NR'2
R
_
O
(you need to know the mechanism)
+ HNR'2
+
Na
C
R
OH