Org

ganic Chem
mistry Crassh Course
Examkrackers MCAT Com mprehensive Co
ourse, Charles Feng
http://fenguin.net/mcat fenguin@gmail.
f .com (224) 5332-0039

EL
LECTROPHILE E: ATTRACTS ELECTRONS (a.kk.a. Lewis acid))
Generally a cation or has an in
ncomplete octtet

Acids (HX), alkyl halides (RX)

Halogens (F2, Cl2, Br2, I2)
Carbonyls (C
C=O), acyl halid des (RC=OX
X)
Organometaallic compounds (Hg(OAc)2)
Carbonyl carrbons of carbo onyls

NUCLEOPHILE:: DONATES ELE ECTRONS (a.k.a. Lewis base)

Generally an anion or has a fre
ee pair of electrons

Water (H2O),, alcohols (RO

OH), thiols (RSSH)
Ammonia (N NH3), amines (N NH2R, NHR2, NR R3)
Compoundss with pi bondss (alkenes, alkyynes)
Halogen anions (Br, Cl, ettc)
Alpha carbons of carbonylls (b/c keto-en nol tautomerism
m)
Grignard reaagents (RMgX X)
Ylides (PC)

EL
LECTROPHILIC ADDITION
Pi bond attacked by electrrophile

Halogenation
C=C + X2 XCC
CX
Generally atttacks opposite
e sides due to formation
f of bromonium/ch
b hloronium triaangle

Hyydrohalogenaation
H XCCH
C=C + HX
Generally follows Markovnnikov (H attach
hes to C w/ mo
ost Hs)
With HBr & peroxide:
p anti-Markovnikov

Hyydration
C=C + H2O HOC
CCH
Generally follows Markovnnikov w/ carbo
ocation rearran
ngement
With Hg(OAcc)2, NaBH4: Markovnikov, no carbocation re
earrangementt
With BH3, H2O2: anti-Marko
ovnikov

Caarbonyl Halogenation
CC=
=O + X2 + acid/base
a XCC=OO
=O + 3 X2 + base O C=O + HCX3
H3CC=

HCX3 is called a haloform

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 Org
ganic Chem
mistry Crassh Course
Examkrackers MCAT Com mprehensive Co
ourse, Charles Feng
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f .com (224) 5332-0039

EL
LECTROPHILIC SUBSTITUT TION
Electrophile replaces grou
up (usually hyd
drogen)

Aromatic substiitution
Aromatic sysstem binds to electrophile

NUCLEOPHILICC ADDITION
Nucleophile attacks one siide of pi bond,, pi bond breaks

Grignard Reaction
RMgX + C=O RCOH
RMgX + C=N RCNH
Basically you MgX as R:
u can treat RM
Also works with
w CN, S=O, N=O

Caarbonyl Reducction
NaB H4 + C=O HCOH
BH4 or LiAlH
LiAlH4 is the stronger redu
ucing agent

Accetalization/Ke
etalization
C ROCOH
ROH + C=O
R
OH + RO COH R
ROCOR
=O HOC
H2O + C= COH
ROCOH is a hemiketal/hhemiacetal (deepending on whether
w originaal C=O was an ketone or aldehyde)
ROCOR is a ketal/acetal
Can use a dio
ol (HOROH) to protect carrbonyls, formin
ng a ring whic h can then be changed backk to carbonyl by acid

Keeto-Enol Tauto
omerization
CC=O
C + accid/base C=CO
Left is keto, right
r is enol

Aldol Addition
C2=C = HO-C
C1O + C3=O C3C2C1=O
O
Aldol Condensaation
C2C1=O + acid/base C3=C2C
HO-C3C C1=O
Creates an enal
e

W
Wittig Reaction
P+C + C=O C
C=C
Ylide: sometthing with adjaacent positive and negative charges
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 Org
ganic Chem
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Examkrackers MCAT Com mprehensive Co
ourse, Charles Feng
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f .com (224) 5332-0039

onjugate Addiition
Co
C=C N NucCCC=O
CC=O + Nuc
Can have 1,4
4 and 1,2 addittions for a alph
ha/beta-unsatu
urated carbon
nyl

namine/Imine Formation
En
N 2/NH2R HOCN
O=C + NHR NR2/HOCNHR
HOCNR
H 2 + acid C
C=CNR2
HOCNHR
H + acid C
CC=NR
Double bond
d between carrbons = enamiine; double bo
ond between C and N = imin
ne

W
Wolf-Kishner Re
eduction
R2C=O
O + H2NNH base R2C
H2 + acid + b CH2

NUCLEOPHILICC SUBSTITUTION
Nucleophile attacks carbon bonded to le
eaving group, replaces it

SN
N1 vs. SN2
Nucleophile: weak nucleop phile = SN1, strrong = SN1
Substrate: ste
erically hinderred substrate = SN1, unhindeered = SN2
Solvent: polaar solvent = SN
N1, nonpolar = SN2
Speed: SN1 depends
d on su
ubstrate, SN2 depends
d on substrate and nu
ucleophile
Stereochemisstry: SN1 creattes racemic, SN
N2 has inversio
on of configuraation
Skeleton: SN1 has rearrang gement, SN2 doesnt

n
Decarboxylation
O=C OH O=CCH3 + CO2
CCH2COO
Reactant nee
eds to be a beta-keto acid

Nucleophilic Accyl Substitution

n
/ 5 RCOCl (acyl chloride)
RCO? + SOCl2/PCl3/PCl
RCO?
R + RCOOH RCOOCOR (acid anhydride)
RCCO? + ROOH RCOOOR (ester)
RCO? + H2O RCOOH H (carboxylic acid)
RCOO? + RNHH2 RCONHR (amide)
Accetoacetic Este
er Synthesis
RCOCH2COOC2H5 + RX RCOCHRCCOOC2H5
R COOC2H5 + acid R
RCOCHR RCOCH2R + CO2

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 Org
ganic Chem
mistry Crassh Course
Examkrackers MCAT Com mprehensive Co
ourse, Charles Feng
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f .com (224) 5332-0039

Alkylation
NH3 + RX RNNH2
NRH2 + RX R2NH
NR2H + RX R3N
NR3 + RX R4N+
Hofmann Elimin
nation
R4N+ + heaat alkenee + NR3
Creates the least
l substituted alkene (Hofmann producct)

Hofmann Degraadation
NH2 + base + X2 + waater RN
RCO NH2

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