Alkanes

Combustion


Radical

Initiation, propagation, and termination
Bromine more selective and chooses stable tertiary radical
Substitution with halogens
Uses hv (UV) or peroxides



Alcohols

Sn1: tertiary carbon, protic solvent
Sn2: primary carbon, polar aprotic center

Oxidation: PCC (primary), CrO, KMnO, AgO
Reduction: LAH, NaBH
4


Pinacol rrg

Protection
Trmethylsilyl to cap alcohols, F deprotects

SOCl2 and PBr change alcohols for X

Mesylates and Tosylates are considered excellent leaving groups and made with alcohols

Fischer Esterification



Aldehydyes/Ketones

Nucleic addition when nucleophile attacks carbonyl

Acetal/ketal


Imine



Enamine


Haloform


Aldol condensation


Keto/enol tautomerism


Organometallic (eg. Grignard)
Li or Mg (Grignard) can be added to haloalkane and these can make R-R bonds
Wolff-Kishner Reduction

N
2
released


Clemson Reduction




Carboxylic Acids

Nuc attack


Reduction with LiAlH can convert to a primary alcohol

Decarboxylation

Beta-keto acids can do this

Hell-Volhard-Zelinsky Halogenation


Substitution and alpha positions
COOH converted to enolizable form
Halogen or some other electrophile gets attacked by double bond
Reverts back to COOH form (net: alpha H replaced by electrophile)


Acid Derivatives

Preparation
COOH +SOCl acid chloride
COOH + COOH (heat) anhydride
Acid chloride + COOH + (base) anhydride
Acode chloride + alcohol (base) ester
Acid chloride + amine amide
Acid chloride + water COOH

Nucleophilic substitution is when some Nuc basically knocks off a LG

Hoffman RRG


Transesterification


Saponification


Amide hydrolysis


Decarboxylation

Beta-keto esters beta-keto acids enols ketos
Esters to acids by hydrolysis

Acetoacetic ester synthesis

Acetoacetic ester is synthesized by claisen condensation of 2 ethyl acetates

Claisen condensation


Aldol condensation



Amines

Amide formation: amine + C=O with good LG (can be an acid derivative)

Amine rxn with nitric acid


Primary amines react with nitrous acid to yield a diazonium salt, which is highly unstable
and degradates into a carbocation that is capable of reaction with any nucleophile in
solution. Therefore, reacting primary amines with nitrous acid leads to a mixture of
alcohol, alkenes, and alkyl halides.

Alkylation
Amines with alkyl halides can substitute for polyalkylation in presence of base

Hofmann elimination

Less substituted alkene can be formed, as opposed to Zaitsevs rule

Wittig Rxn
Carbonyl + phosphorus ylide alkene
C
1
=O +Ph
3
P=C
2
C
1
=C
2