View
- Term
- Definition
- Both Sides
Study
- All (41)
Shortcut Show
Next
Prev
Flip
CHEM 3332: EXAM 2
Halogenation of Benzene
|
X2, FeX3 or I2/CUCl2
Adds an X (Br or Cl)
|
Nitration of Benzene
|
HNO3 and H2SO4 heat
Adds Nitro Group (NO2)
H2SO4 acts as catalyst
|
Sulfonation (fuming sulfuric)
|
Reversible due to entropy, concentrated acid
Adds SO3H group
SO3/H2SO4 and heat
Reversible: benzene + H2SO4 = benzenesulfonic acid + H20
|
Desulfonation
|
-Diluted acid
-Benzenesulfonic acid + H2O + H2SO4 = benzene + SO3
|
Friedal-Crafts Alkylation
|
Adds an R group
NO RXN: NH2, NHR, NR2
RCl and AlCl3
|
Limitations of Friedal-Crafts Alkylation
|
Remember carbocation rearrangement
No strong deactivators (withdrawing groups)
No amino groups (NH2, NHR, NR2)
Be careful polyalkylation (alkyl groups are activators) Can't stop at mono sub
|
Acyl Group
|
-COR
|
Friedal-Crafts Acetylation
|
Solves problems of Alkylation
Attaches acyl group (COR)
Catalyst AlCl3
|
Advantages of FC Acetylation
|
No polyacylation
No carbocation rearrangement
Disadvantage: No amino groups and strong deactivators
|
The acyl chloride
|
SOCl2
Turns carboxylic acid into necessary acyl chloride reagent
|
Gatterman-Koch Formation (Form benzaldehyde)
|
Forms benzaldehyde
CO/HCl and AlCl3/CuCl
No strong deactivators or amino groups
|
Clemmenson Reduction
|
Reduces Acetophenone to Carbon chain (reduces aldehydes and ketones to carbon chain)
Zn(Hg) and HCl
No alkene, alkyne, alcohol, amine
|
Reduction of Nitro group into Amino group
|
NO2 -> NH2
Zn, Sn, or Fe and HCl
|
Activating Substituent
|
Ring more reactive (faster)
ALWAYS Ortho/Para directors
Electron donating group
(Negative, wants to start a fight, make a reaction)
Electron pair on atom bonded to ring
|
Deactivating Substituent
|
Ring less reactive (slower)
Meta directors are always deactivating
Electron withdrawing group
(Positive wants to stop the reaction)
+ charge or partial + on atom bonded to ring
|
Addition/ Elimination
|
AED (Addition, elimination, deactivating group)
Withdrawing group ortho/para to leaving group
Nu (2 eq) heat, pressure
Nu (OH-, RO-, NH3,), OCH3- 1 Eq
|
Elimination/ Addition
|
(EAND) No Deactivating/W Group O/P
Form benzene in mechanism
Nu = OH-, RO-
NH2 = mixture
1) NaOH (2 eq)/ 340/ 2500 psi
2) H3O+
NaNh2/ NH3 (I)
|
Chlorination of Benzene
|
3 Cl2 / heat
Pressure
8 diff stereochem
6 Cl around a hexane
|
Catalytic Hydrogenation
(3H2 / 1000 psi / 100) and
Ru or Rh (Pt, Pd, Ni)
|
Benzene -> cyclohexane
|
Birch Reduction
|
Na or Li and NH3(I) / ROH
Withdraw = sp3
|
Side Chain Oxidation
|
KMnO4 / H2O and OH-/100
Na2CrO7 / H2SO4 and heat
Oxidizes to carboxylic acid
|
Halogenation of side chains
|
Cl2/ light (mix of Cl on side chain)
Br2/light (Br added to carbon closest to benzene ring)
Aromatic activated use NBS
|
Nucleophilic Subs of Benzylic Halides
|
SN1, SN2, E2 depend on conditions
CH3OH/heat = SN1
NaI/acetone = SN2
CH3CH2O- / Na+ = E2
|
Rxns of phenols similar to alcohols
|
NaOH turns OH to O-
RCO2H or RCOCl (fischer estherification)
PBr3 = No RXN
|
Oxidation of Phenols to Quinones
|
Na2Cr2O7 and
H2SO4
Forms Diels Alder
|
Formation of Salicylic Acid
|
From phenol
1) NaOH
2) CO2
3) H3O+
|
Oxidation of Alcohols (Secondary)
|
Na2CrO7 and H2SO4/H2O
Jones (CrO3/H2SO4/H2O acetone)
PCC and CH2Cl2
|
Oxidation of alcohols (primary)
|
PCC/ CH2Cl2
Isolates aldehyde
Jones forms carboxylic acid
|
Cleavage of Alkenes by Ozonolysis
|
1) O3
2) (CH3)2S
|
Hydration of alkynes
|
H2O/ H2SO4 and HgSO4 (Hungry ketone)
1) Sia2BH
2) H2O2 /OH- (Silly aldehyde)
|
Dithiane Synthesis of Aldehydes and Ketones
|
1) BuLi
2) R - X
3) H3O+ and HgCl2
BuLi = CH3(CH2)2CH2Li
Halide must be methyl or primary
|
Ketone from Carboxylic Acid
|
1) R' - Li (2 eq)
2) H3O+
(first make
salt)
|
Ketone from nitrile
|
R-CN -> ketone
1) R' - MgX
2) H3O+
|
Aldehydes from Acid Chlorides
|
LiAlH(OtBu)3
H2/Pd/BaSO4/S
Replaces Cl with H
|
Ketones from Acid Chlorides
|
(R')2CuLi
Replaces Cl with R' group
|
Aldehydes and Ketones: Formation of Cyanohydrins
|
-CN and HCN
NaCN and H+
Attaches a CN
|
Aldehydes and Ketones: Addition of primary amines
|
RNH2 and H+
Non-aq favors product
Aq favors reactant
|
Acetyl formation
|
2(CH3CH2OH) and H+
|
1. Carboxylic acids to acyl chlorides
2. Alcohols to acyl halides
|
1) SOCl2
2) SOCl2 (if R-OH)
or (COCl)2 (benzoic acid)
|
Addition of Hydrides
|
1. LiAlH4 (adds an H to ketone)
2. H3O+ (protonates)
|
Catalytic Hydrogenation
|
H2, Raney Ni
Reduces everything (even double bonds)
|