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Naming
Molecule Alkane Alkene Alkyne Alcohol Alkyl Halides Suffix -ane -ene -yne -ol Group -yl -enyl -ynyl -hydroxyl -fluoro -chloro -bromo -iodo Examples
OH
Cl
Bimolecular: Rate = k[substrate][nucleophile] One step mechanism 1o substrates are most reactive Strong nucleophilic reagents (-ve charge) Flip in stereochemistry (S ! R or R ! S) Aprotic polar solvents (DMSO, DMA, DMF)
Unimolecular: Rate = k[substrate] First step = slow rate determining step Carbocation intermediate (Hydride or Methyl shifts possible for 2o substrates ) 3o substrates are most reactive Good leaving groups Weak nucleophilic reagents (R-OH and F-) Racemic products () (50% S & 50% R) Protic polar solvents (R-OH)
Reactions - Elimination
E2 (Second Order)
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Bimolecular: Rate = k[alkyl halide][base] One step mechanism Strong Base reagents (RO-) Simple bases (Zaitsevs rule) vs. Bulky bases (Hoffmans rule)
E1 (First Order)
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Unimolecular: Rate = k[alkyl halide] First step same as SN1 Weak Base reagents (ROH) Outcompeted by SN1 at room temperature
Reactions - Predictions
Identify the type of reaction, and predict what the product will be.
Br
a)
I
CH3OH
?
3 )3
c)
Cl
Br
Na+ -OCH2CH3
K+ -OCH(CH
b)
d)
H 2O
Reactions - Alcohols
Reduction (Nucleophilic Addition)
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Oxidized
O OH O O
Weak Strong
R-MgBr (Grignard) R-Li (Organic Lithium) Nucleophile / H2O or H3O+ NaBH4 (weak) LiAlH4 (strong) PCC (weak) CrO3, H2SO4 / H2O (Jones Reaction - strong) SOCl2 PBr3 TsCl NaH Na(s) H2SO4 H3PO4
OH
Oxidation
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OH
OH
Reduced
Electrophile / Pyridine
NaOR ROH
Alcohol
Alkene
Reactions - Alkenes/Alkynes
Reaction Name Hydrohalogenation Oxi-Deoxymercuration Hydroboration-Oxidation Halogenation Hydrogenation Alkene Reagent Alkyne Reagent Type of Addition HX
1) Hg(OAc)2, THF, H2O 2) NaBH4 1) BH3, THF 2) H2O2 / OH-
2HX
1) HgSO4 2) H2SO4, H2O 1) BH3, THF 2) H2O2 / OH-
Markovnikov (X) Markovnikov (OH) Anti-Markovnikov (OH) ANTI (Xs) SYN (Hs)
X2
H2 Pt or Pd/C
2X2
2H2 Pt or Pd/C
MOST OF THESE MAKE RACEMIC MIXTURES YOU NEED TO DRAW THE CORRECT STEREOCHEMISTRY!!!
Double Elimination (Strong base or 2NaNH2) Cis-Hydrogenation (Lindlars Catalyst) Trans-Hydrogenation (Na(s), NH3(l) / NH4Cl) Acetylide Anion Formation (NaNH2 or BuLi)
Other Reactions
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3o Alcohol (or 2o with heat) SN1 with HBr Gilman Reagent: 1o RX + R2CuLi ! R-R
Organic Synthesis
a)
1) BH3, THF 2) H2O2 / OHPCC LiCH3 PBr3 !
Br
b)
Br
Mg ether 1)Acetone 2) H2O H2SO4 H2 Pd/C
c)
O OH
1) Li+ -AlH4 2) H3O+ Tosyl Chloride NaOCH2CH3 Pyridine HOCH2 CH3