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23 Cards in this Set
- Front
- Back
- 3rd side (hint)
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NBS in CCl4, heat |
- Allylic radicals & carbocations are resonance stabilized (multiple possible products) - 6-member ring substrate with 2 double bonds --> look to make benzene |
2 things to keep in mind |
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Diels-Alder |
- Concerted process - Endo adduct - kinetically controlled - Exo adduct - thermo controlled |
3 things remember |
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Claison Rearrangement |
- Heat - Ether with 3 carbons and a double bond -O-C-C=C - will find H suitable to reestablish aromaticity |
3 things to remember |
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UV Spectroscopy |
- HOMO & LUMO --> more conjugated pi bonds = less energy between MOs - Wavelength absorbed = lambda max - Base value of 217nm + 30nm for each pi bond |
3 things to remember |
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Aromatic Heterocycles |
- Pyridine (basic) - Pyrrole (not basic) - Furan (charged resonance) - Thiophene (charged resonance) |
4 (w/ note) |
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Aromatic Ions |
Cyclopentadienyl Anion - 5 member w/ neg charge - conjugate acid pKa 16 Cycloheptatrienyl Cation - 7 member w/ pos. Charge 8 member ring - 3 pi bonds w/ -2 charge 3 member ring - 1 pi bond w/ positive charge
3 member with |
4 rings # carbons and charge |
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Alkyl Benzene Oxidation (rgnts + 3 things) |
H2CrO4, H2O Or KMnO4, NaOH, H2O |
- need at least 1 benzylic hydrogen - only benzylic carbon remains - forms benzoic acid (benzylic carboxylic acid) |
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Birch Reduction |
Na in NH3(l), CH3CH2OH |
- Benzene reduced to 2 pi bonds - Donating groups = not reduced - withdrawing groups = reduced |
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Electrophilic Bromination (rgnts + 2 things) |
Br2, FeBr3 |
- Adds Br to benzene - H attached to same carbon as Br is removed by Fe(-1)Br4 |
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Electrophilic Chlorination (rgnts + 2 things) |
Cl2, AlCl3 |
- Adds Cl to benzene - H attached to same carbon as Cl is removed by Al(-1)Cl4 |
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Friedel Crafts Alkylation (rgnts + 3 things) |
R-Cl, AlCl3 |
- Tendency for polyalkylation - Primary alkyl halide will rearrange via carbocation intermediate - Not possible with strong withdrawing group |
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Friedel Crafts Acylation (rgnts + 3 things) |
Cl-C(=O)-CH3, AlCl3 |
- Stops after 1 acylation - Acylium ion stabilized by resonance - Not possible with strong withdrawing group |
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Nitration |
HNO3, H2SO4 |
- NO2 = super electrophile |
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Sulfonation |
SO3, H2SO4 |
Reversible by adding: H2SO4, H2O, heat |
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Clemmenson Reduction |
Zn(Hg), HCl |
- Used along with F-C Acylation as 2 step alkylation avoiding carbocation rearrangement |
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Gatterman-Koch Formylation (rgnts + 2 things) |
CO, HCl, AlCl3, CuCl |
- Forms benzylic aldehyde - Not possible in presence of strong withdrawing group |
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Nitro-Amine conversion |
Zn, HCl |
- Can't nitrate a ring containing an amine group |
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Allylic Bromination |
Exs. NBS, CCl4, heat |
Can be used to form C-X3 group to minimize products of Elimination-Addition reactions |
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Addition-Elimination |
- LG on benzene - Resonance withdrawing group ortho/para to LG |
the criteria! |
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Elimination-Addition |
- Benzyne intermediate may result in many products - Strong inductive effects select for anion intermediate w/ lone pair closer to induction |
2 things to keep in mind |
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Iodation |
I2, CuCl2 |
Iodated benzene product |
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Benzyne creation |
1. Br2, FeBr3 2. SO3, H2SO4 3. I2, CuCl2 4. H2SO4, H2O, heat 5. Mg in dry THF |
- Mg implants w/ halogen of lesser electronegativity |
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Diazonium salt |
Carboxylic acid group & N2 group |
Benzyne + CO2 + N2 |
