STUDY: This review does not cover all material relevant to the midterm!

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

Reactions - Nucleophilic Substitution

SN2 (Second Order)
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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)

SN1 (First Order)

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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

Modified SN2 (1o & 2o)

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Reduced

Electrophile / Pyridine

Williamson Ether Synthesis (SN2 nucleophile formation)

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NaOR ROH

Acid Catalyzed Hydration / Dehydration

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Alcohol

!""E1 (1o) / E2 (2o + 3o) Markovnikov"

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!!!

Further Alkyne Reactions

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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