Alcohols
Electrophilic Aromatic Substitutions Halogenations
X2 / (AlCl3 or FeBr3) [x=Cl;Br;Fl]
Iodination
I2 / CuCl2
Iodobenzene
Nitration
cHNO3 / cH2SO4
Nitrobenzene
Sulfonation
SO3 / H2SO4
Benzenesulfonic Acid
Alkylation
X-R / Lewis Acid
1. Polyalkylation 2. No rxn EW; aryl; vinylic 3. Rearrangement
Acylation
X-CO-R / Lewis Acid
O R
Reduction Nitrobenzene
π―π ππ π) ππ, π―πͺπ π)πΊππͺππ π) ππ, π― + ; ; ; ; π·π π― + π) π΅ππΆπ― π)π―π) π) πΆπ― β
NO 2
NH2
Aniline
π―π
Aryl Alkyl Ketones
;
π·π ,πͺ
ππ
O
π―+
R
R
Alky benzene Benzene
π―π πΉπ,πͺ;π¬ππΆπ―
;
π―π π·π;π¬ππΆπ―
βP Cylcohexane; cis product Rhodium more effective
Oxidation or Degradation of side chain Alky group on benzene Free Radical Bromonation Preparing dienes from Benzene
π²π΄ππΆπ π―ππΆ,ππππ
;
π΅ππͺπππΆπ π―ππΆ,ππππ
π΅π©πΊ ; ππ π―ππΆπ πο΅; πͺπͺππ
;
π²ππͺπππΆπ
Benzoic Acid
π―ππΆ,ππππ
π΅π©πΊ π·ππͺπΆπ π, πͺπͺππ
Radical initiator
π³π, π΅π― π¬ππΆπ― Non-conjugated diene
Nucleophilic Aromatic Substitution Addnβ/eliminatio n [w/ EW] Bimolecular displacement Benzyne= Elimination/Addn β
π. βπΆπ― π. π―ππΆ
π. ) π΅ππΆπ―; π―ππΆ; β π» β πΆ π) π―ππΆ +
;
Substituting X for OH Meininheim complex intermediate
π² + π΅π―π β π΅π―π
Substituting X for OH Substuting X for NHs Benzyne Intemediate
Alcohols Oxymercuration/ demercuration
π)π―π π¨π π, π»π―π, π―ππ π) π΅ππ©π―π
Markovnikov
Hydroboration
π) π©π―π, π»π―π π) π―πππ, βπΆπ―
AntiMarkovnikov
Alcohols to alky group (Cl, Br) SN1
HBr or HCl
πΊππͺππ
SN2
πππππ πππ
/ 2 step rxn
π·π©ππ
; πππππ πππ;inversion/concert rxn
Good substrate 3ο° cation, benzyl and allylic cation For 1ο° or 2ο° alcohols
Reduction Family A=Aldehydes and ketones Aldehydes
π) π΅ππ©π―π, π¬ππΆπ― π) π³ππ¨ππ―π, π¬ππΆπ― ; π) π―ππ + π) π―ππ +
Ketone
π) π΅ππ©π―π, π¬ππΆπ― π) π³ππ¨ππ―π, π¬ππΆπ― ; π) π―ππ + π) π―ππ +
Primary alcohol NaBH4 is milder used more LiAlH4 is very strong Secondary alcohol
Reduction of Family B=carboxylic acids, esters and electronegative groups Carboxylic Acids Esters
π) π³ππ¨ππ―π, π¬ππΆπ― π) π―ππ + π) π³ππ¨ππ―π, π¬ππΆπ― π) π―ππ +
Primary alcohol Primary alcohol
Grignard Reagent O.M. organo-metallic cmpds (R-MgX) Family A/ Nucleophilic addition Ketones Aldehydes
π) πΉπ΄ππΏ; π¬ππΆπ― π) π―ππ + π) πΉπ΄ππΏ;π¬ππΆπ― π) π―ππ+
3ο° alcohol With the exception of formaldehyde 2ο° alcohol
Grignard Reagent O.M. organo-metallic cmpds (R-MgX) Family B/ Nucleophillic substitution; nucleophillic addition Esters Carboxylic acid
π) πΉπ΄ππΏ; π¬ππΆπ― π) π―ππ +
3ο° alcohol And 1ο° alcohol No alcohol
X2 / (AlCl3 or FeBr3) [x=Cl;Br;Fl]
Iodination
I2 / CuCl2
Iodobenzene
Nitration
cHNO3 / cH2SO4
Nitrobenzene
Sulfonation
SO3 / H2SO4
Benzenesulfonic Acid
Alkylation
X-R / Lewis Acid
1. Polyalkylation 2. No rxn EW; aryl; vinylic 3. Rearrangement
Acylation
X-CO-R / Lewis Acid
O R
Reduction Nitrobenzene
π―π ππ π) ππ, π―πͺπ π)πΊππͺππ π) ππ, π― + ; ; ; ; π·π π― + π) π΅ππΆπ― π)π―π) π) πΆπ― β
NO 2
NH2
Aniline
π―π
Aryl Alkyl Ketones
;
π·π ,πͺ
ππ
O
π―+
R
R
Alky benzene Benzene
π―π πΉπ,πͺ;π¬ππΆπ―
;
π―π π·π;π¬ππΆπ―
βP Cylcohexane; cis product Rhodium more effective
Oxidation or Degradation of side chain Alky group on benzene Free Radical Bromonation Preparing dienes from Benzene
π²π΄ππΆπ π―ππΆ,ππππ
;
π΅ππͺπππΆπ π―ππΆ,ππππ
π΅π©πΊ ; ππ π―ππΆπ πο΅; πͺπͺππ
;
π²ππͺπππΆπ
Benzoic Acid
π―ππΆ,ππππ
π΅π©πΊ π·ππͺπΆπ π, πͺπͺππ
Radical initiator
π³π, π΅π― π¬ππΆπ― Non-conjugated diene
Nucleophilic Aromatic Substitution Addnβ/eliminatio n [w/ EW] Bimolecular displacement Benzyne= Elimination/Addn β
π. βπΆπ― π. π―ππΆ
π. ) π΅ππΆπ―; π―ππΆ; β π» β πΆ π) π―ππΆ +
;
Substituting X for OH Meininheim complex intermediate
π² + π΅π―π β π΅π―π
Substituting X for OH Substuting X for NHs Benzyne Intemediate
Alcohols Oxymercuration/ demercuration
π)π―π π¨π π, π»π―π, π―ππ π) π΅ππ©π―π
Markovnikov
Hydroboration
π) π©π―π, π»π―π π) π―πππ, βπΆπ―
AntiMarkovnikov
Alcohols to alky group (Cl, Br) SN1
HBr or HCl
πΊππͺππ
SN2
πππππ πππ
/ 2 step rxn
π·π©ππ
; πππππ πππ;inversion/concert rxn
Good substrate 3ο° cation, benzyl and allylic cation For 1ο° or 2ο° alcohols
Reduction Family A=Aldehydes and ketones Aldehydes
π) π΅ππ©π―π, π¬ππΆπ― π) π³ππ¨ππ―π, π¬ππΆπ― ; π) π―ππ + π) π―ππ +
Ketone
π) π΅ππ©π―π, π¬ππΆπ― π) π³ππ¨ππ―π, π¬ππΆπ― ; π) π―ππ + π) π―ππ +
Primary alcohol NaBH4 is milder used more LiAlH4 is very strong Secondary alcohol
Reduction of Family B=carboxylic acids, esters and electronegative groups Carboxylic Acids Esters
π) π³ππ¨ππ―π, π¬ππΆπ― π) π―ππ + π) π³ππ¨ππ―π, π¬ππΆπ― π) π―ππ +
Primary alcohol Primary alcohol
Grignard Reagent O.M. organo-metallic cmpds (R-MgX) Family A/ Nucleophilic addition Ketones Aldehydes
π) πΉπ΄ππΏ; π¬ππΆπ― π) π―ππ + π) πΉπ΄ππΏ;π¬ππΆπ― π) π―ππ+
3ο° alcohol With the exception of formaldehyde 2ο° alcohol
Grignard Reagent O.M. organo-metallic cmpds (R-MgX) Family B/ Nucleophillic substitution; nucleophillic addition Esters Carboxylic acid
π) πΉπ΄ππΏ; π¬ππΆπ― π) π―ππ +
3ο° alcohol And 1ο° alcohol No alcohol
