CHEM 3332: EXAM 2
41 Cards in this Set
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Halogenation of Benzene
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X2, FeX3 or I2/CUCl2
Adds an X (Br or Cl)
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Nitration of Benzene
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HNO3 and H2SO4 heat
Adds Nitro Group (NO2)
H2SO4 acts as catalyst
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Sulfonation (fuming sulfuric)
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Reversible due to entropy, concentrated acid
Adds SO3H group
SO3/H2SO4 and heat
Reversible: benzene + H2SO4 = benzenesulfonic acid + H20
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Desulfonation
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-Diluted acid
-Benzenesulfonic acid + H2O + H2SO4 = benzene + SO3
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Friedal-Crafts Alkylation
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Adds an R group
NO RXN: NH2, NHR, NR2
RCl and AlCl3
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Limitations of Friedal-Crafts Alkylation
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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
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Acyl Group
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-COR
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Friedal-Crafts Acetylation
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Solves problems of Alkylation
Attaches acyl group (COR)
Catalyst AlCl3
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Advantages of FC Acetylation
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No polyacylation
No carbocation rearrangement
Disadvantage: No amino groups and strong deactivators
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The acyl chloride
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SOCl2
Turns carboxylic acid into necessary acyl chloride reagent
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Gatterman-Koch Formation (Form benzaldehyde)
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Forms benzaldehyde
CO/HCl and AlCl3/CuCl
No strong deactivators or amino groups
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Clemmenson Reduction
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Reduces Acetophenone to Carbon chain (reduces aldehydes and ketones to carbon chain)
Zn(Hg) and HCl
No alkene, alkyne, alcohol, amine
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Reduction of Nitro group into Amino group
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NO2 -> NH2
Zn, Sn, or Fe and HCl
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Activating Substituent
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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
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Deactivating Substituent
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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
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Addition/ Elimination
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AED (Addition, elimination, deactivating group)
Withdrawing group ortho/para to leaving group
Nu (2 eq) heat, pressure
Nu (OH-, RO-, NH3,), OCH3- 1 Eq
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Elimination/ Addition
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(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)
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Chlorination of Benzene
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3 Cl2 / heat
Pressure
8 diff stereochem
6 Cl around a hexane
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Catalytic Hydrogenation
(3H2 / 1000 psi / 100) and
Ru or Rh (Pt, Pd, Ni)
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Benzene -> cyclohexane
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Birch Reduction
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Na or Li and NH3(I) / ROH
Withdraw = sp3
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Side Chain Oxidation
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KMnO4 / H2O and OH-/100
Na2CrO7 / H2SO4 and heat
Oxidizes to carboxylic acid
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Halogenation of side chains
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Cl2/ light (mix of Cl on side chain)
Br2/light (Br added to carbon closest to benzene ring)
Aromatic activated use NBS
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Nucleophilic Subs of Benzylic Halides
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SN1, SN2, E2 depend on conditions
CH3OH/heat = SN1
NaI/acetone = SN2
CH3CH2O- / Na+ = E2
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Rxns of phenols similar to alcohols
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NaOH turns OH to O-
RCO2H or RCOCl (fischer estherification)
PBr3 = No RXN
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Oxidation of Phenols to Quinones
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Na2Cr2O7 and
H2SO4
Forms Diels Alder
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Formation of Salicylic Acid
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From phenol
1) NaOH
2) CO2
3) H3O+
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Oxidation of Alcohols (Secondary)
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Na2CrO7 and H2SO4/H2O
Jones (CrO3/H2SO4/H2O acetone)
PCC and CH2Cl2
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Oxidation of alcohols (primary)
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PCC/ CH2Cl2
Isolates aldehyde
Jones forms carboxylic acid
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Cleavage of Alkenes by Ozonolysis
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1) O3
2) (CH3)2S
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Hydration of alkynes
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H2O/ H2SO4 and HgSO4 (Hungry ketone)
1) Sia2BH
2) H2O2 /OH- (Silly aldehyde)
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Dithiane Synthesis of Aldehydes and Ketones
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1) BuLi
2) R - X
3) H3O+ and HgCl2
BuLi = CH3(CH2)2CH2Li
Halide must be methyl or primary
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Ketone from Carboxylic Acid
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1) R' - Li (2 eq)
2) H3O+
(first make
salt)
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Ketone from nitrile
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R-CN -> ketone
1) R' - MgX
2) H3O+
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Aldehydes from Acid Chlorides
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LiAlH(OtBu)3
H2/Pd/BaSO4/S
Replaces Cl with H
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Ketones from Acid Chlorides
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(R')2CuLi
Replaces Cl with R' group
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Aldehydes and Ketones: Formation of Cyanohydrins
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-CN and HCN
NaCN and H+
Attaches a CN
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Aldehydes and Ketones: Addition of primary amines
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RNH2 and H+
Non-aq favors product
Aq favors reactant
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Acetyl formation
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2(CH3CH2OH) and H+
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1. Carboxylic acids to acyl chlorides
2. Alcohols to acyl halides
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1) SOCl2
2) SOCl2 (if R-OH)
or (COCl)2 (benzoic acid)
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Addition of Hydrides
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1. LiAlH4 (adds an H to ketone)
2. H3O+ (protonates)
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Catalytic Hydrogenation
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H2, Raney Ni
Reduces everything (even double bonds)
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CHEM 3332: EXAM 2