Facilitator: Chris Lovero Organic Chemistry Reactions 1

Task Reaction Notes

H H
H CH
3
HBr
H
CH
3
Br H
H
H
Addition of HX
(Mark)
*Adds a halide
to more substituted
carbon.
H H
H CH
3
HBr
ROOR
H
CH
3
H Br
H
H
Addition of HX
(Anti-Mark)
*Adds a halide
to least substituted
carbon.
Br
2
CH
2
Cl
2
(or CCl
4
)
Add two Br's anti
to alkene
*Anti and co planar
CH
3
D
CH
3
Br
Br
D
Adding a Br and
OH (Mark w/ Br as H
and anti-planar)
CH
3
D
CH
3
Br
OH
D
Br
2
H
2
O
Forming alkene
from vicinal dihalide
*Anti and co planar
Br
Br
CH
3
C H
3
H
H
NaI or KI
acetone
H
CH
3
H
C H
3
*Wedges with wedges
and dashes with dashes
*E2 Like!
Dehydration to
alkene
OH
*E1 like and it cannot
give terminal alkene
H
2
SO
4
heat
OH
POCl
3
heat
*SPECIAL REACTION:
dehydrates to form
terminal alkene.
Addition of OH
(direct and mark)
CH
3
CH
3
CH
3
CH
3
OH
*CANNOT CONTROL
STEREOCHEM!
*Low yield!
*C+ formation!
H
3
O
+
Facilitator: Chris Lovero Organic Chemistry Reactions 2
Task Reaction Notes
Oxymercuration/
demercuration
(Add OH from alkene
mark and antiplanar)
*Complex mechanism
*Mark and antiplanar
CH
3
D
CH
3
H
OH
D
1) Hg(OA
c
)
2
/ H
2
O
2) NaBH
4
Hydroboration
(Add Oh anti-mark and
syn planar)
*Anti-mark
*Notice Peroxide
CH
3
D
CH
3
D
OH
H
1) BH
3
/ THF
2) H
2
O
2
/
-
OH
SPECIAL: Adds alcohol
instead to form ethers!
CH
3
D
CH
3
H
O
D
CH
3 1) Hg(OA
c
)
2
/ CH
3
OH
2) NaBH
4
*Complex mechanism
*Mark and antiplanar
*WILL BE SEEING THIS
MORE IN ORGO II
CH
3
C H
3
D
CH
3
CH
3
C H
3
D
C H
3
H
H
H
2

Pt, Pd, or Ni
Catalytic Hydrogenation
(Alkenes -> Alkane, Syn
Addition of H)
*Steric factors must be
payed attention to
*Can use D
2
instead
Formation of
Vicinal Diols
(Syn)
CH
3
D
CH
3
D
OH
OH
CH
3
D
OH
OH
CH
3
D
OsO
4
H
2
O
2
KMnO
4
cold, basic
*expensive
*toxic
*great yield
*cheaper
*safer
*poor yield
Facilitator: Chris Lovero Organic Chemistry Reactions 3
Task Reaction Notes
Ozonolysis
(double bond cleavage)
*Can use Zn/acetic acid
instead of (CH
3
)
2
S
*Can isolate the
formaldehyde.
1) O
3
/ CH
2
Cl
2
2) (CH
3
)
2
S
R
R R
R
O
R
R
O
R
R
+
1) O
3
/ CH
2
Cl
2
2) (CH
3
)
2
S
H
R R
R
O
H
R
O
R
R
+
1) O
3
/ CH
2
Cl
2
2) (CH
3
)
2
S
H
R H
R
O
H
H
O
R
R
+
Warm KMnO
4

cleavage
KMnO
4
warm
R
R R
R
O
R
R
O
R
R
+
H
R R
R
O
OH
R
O
R
R
+
H
R H
R
O
R
R
+
KMnO
4
warm
KMnO
4
warm
CO
2
O H
2 +
*further oxidizes to form
carboxylic acids
*cannot isolate the
formaldehyde
Carbene / Carbenoid
addition (formation of
cyclopropane)
CH
3
D
CH
2
N
2
heat
CH
3
D
D
H CH
3
C H
3
CH
2
I
2
Zn(Cu)
D
H
CH
3
C H
3
*syn
*stereochem is preserved
*Second reaction uses
the Simmons-Smith
reagent
Formation of epoxides
from alkenes
*useful for synthesis
(ESPECIALLY IN
ORGO II)
CH
3
D
CH
3
D
O
MCPBA
Facilitator: Chris Lovero Organic Chemistry Reactions 4
Task Reaction Notes
Opening of Epoxides
NOTE: Can use RO
-

to form ethers. You
will see this in Orgo II.
*acidic conditions opens
from more substituted
side.
*Basic are like SN2
(least substituted side)
*Please look up
mechanism.
H
3
O
+
H
2
O
CH
3
D
O
CH
3
D
OH
OH
CH
3
D
O
1)
-
OH
2)H
3
O
+
OH
OH
D
CH
3
Formation of
Dibromocarbenes and
Dichlorocarbenes
CH
3
D
D
H CH
3
C H
3
CHCl
3
KOH
CH
3
D
Br
Br
CHBr
3
KOH
D
H
CH
3
C H
3
Cl Cl
Formation of the
acetylide anion
C H
3
C C H C H
3
C C
-
NaNH
2
*forms the nucleophile
that is handy when
connecting carbons!
Uses of the acetylide
anion
with methyl or 1
o
halides
C H
3
C C
- CH
3
Br
C H
3
C C CH
3
*SN2 because of the
exception we learned
from before!!!!
with 2
o
or 3
o
halides
C H
3
C C
- C H
3
CHCH
3
Br
*E2 remember from last
test!!! C H
3
CH CH
2
with carbonyl groups (ketones, aldehydes, and formaldehydes)
C H
3
C CH
3
O
C H
3
C C
-
1)
2) then H
3
O
+
C H
3
C
C
C H
3
C CH
3
O H
*acetylide anion attacks
partially positive carbon
*DO NOT FORGET
then H
3
O
+
*please look up the
mechanism so you can
see how the carbene
is formed

Facilitator: Chris Lovero Organic Chemistry Reactions 5
Task Reaction Notes
Synthesis of Alkynes
*Need either geminal or
vicinal dihalides
*Look up mechanism
*NaNH
2
gives terminal
*KOH gives internal
1) NaNH
2
/ 100
o
C
2) H
3
O
+
C H
3
CHCH CH
3
Br Br
CH
2
CHCH
2
CH
3
Br Br
C H
3
CCH
2
CH
3
Br
Br
C H CH
2
CH
2
Br
Br
CH
3
KOH
200
o
C
C H
3
C C CH
3
C H C CH
2
CH
3
Halogenation of alkynes
Br
2
and alkyne
C H
3
C C H
Br
2
(1 eq)
Br
C H
3
H
Br
Br
Br H
C H
3
+
*Stereochem cannot
be controlled
HBr and alkyne
C H
3
C C H
HBr
(1 eq)
HBr
(2 eq)
H
Br H
C H
3
Br
Br
*Mark
*syn addition
HBr and alkyne
C H
3
C C H
HBr
ROOR
H
H Br
C H
3
*Anti mark
*syn addition
Catalytic reduction with
reactive catalyst
C H
3
C C CH
3
H
2

Pt, Pd, or Ni
*Takes it all the way back
to alkane
*generally bad yield
Facilitator: Chris Lovero Organic Chemistry Reactions 6
Task Reaction Notes
Alkyne to Alkene:
TRIPLE to DOUBLE
*isolates an alkene with
a SYN addition of H
H
2
/ Pd(BaSO
4
)
quinoline
C H
3
C C CH
3
CH
3
H H
C H
3
Lindlar's catalyst
Dissolving metal
C H
3
C C CH
3
NaNH
3
H
H CH
3
C H
3
*isolates an alkene with
an ANTI addition of H
Addition of H-OH to
alkynes
Mercuric Ion
CH
2
C C H C H
3
HgSO
4
/ H
2
O
H
2
SO
4
HgSO
4
/ H
2
O
H
2
SO
4
C
O
CH
3
CH
2
C H
3
CH
2
C C CH
3
C H
3
C
O
CH
2
CH
2
C H
3
CH
3
C
O
CH
3
CH
2
CH
2
C H
3
+
*Mark addition
*If not terminal, you will
get a mixture.
*Formation of ketone
Hydroboration
CH
2
C C H C H
3
1) Sia
2
BH
2) H
2
O
2
/
-
OH
C
O
H CH
2
CH
2
C H
3
*Antimark addition
*will get a mixture if not
terminal
*Formation of aldehyde
Oxidation of alkynes
(mild conditions)
C H
3
C C CH
3
KMnO
4
/ H
2
O
neutral / cold
O
O
C H
3
C C H
KMnO
4
/ H
2
O
neutral / cold
O
OH
O
*Forms vicinal
carbonyls
*further oxidizes terminal
alkynes to form
carboxylic acid.
Facilitator: Chris Lovero Organic Chemistry Reactions 7
Task Reaction Notes
Cleavage of Alkynes:
*Forms H
2
O and CO
2
if terminal.
C H
3
C C
Oxidation of alkyne (strong)
1) KMnO
4
/ H
2
O
2)
-
OH / heat
O
OH C H
3
C H
3
C C H
1) KMnO
4
/ H
2
O
2)
-
OH / heat
O
OH
O H
2
CO
2
+ +
CDH
2
+
O
O H CDH
2
Ozonolysis
1) O
3
2) H
2
O
C H
3
C C CDH
2
O
OH C H
3
+
O
O H CDH
2
C H
3
C C H
O
OH
O H
2
CO
2
+ +
1) O
3
2) H
2
O
*Same products as
previous
The Grignard Reagent
CH C C H
3
Br
H
Mg
ether
CH C C H
3
H
MgBr
*Forms from 1
o
, 2
o
, 3
o
,
allyl, vinyl, and aryl
carbons.
The Organolithium
Reagent
CH
2
Br C H
3
Li
pentane or hexane
CH
2
Li C H
3
*This reagent acts like
grignard but is stronger.
Formation of alcohols
from Grignard
1
o
alcohols. (Grignard and formaldehyde)
MgBr
O
H H
1)
2) H
3
O
+
OH
*Know this mechanism!
*Carbon attachment
2
o
alcohols. (Grignard and aldehyde)
MgBr
O
H
1)
2) H
3
O
+
OH
*Know this mechanism!
*Carbon attachment
3
o
alcohols. (Grignard and ketone)
MgBr
O
OH
*Know this mechanism!
*Carbon attachment
1)
2) H
3
O
+
Facilitator: Chris Lovero Organic Chemistry Reactions 8
Task Reaction Notes
Grignard and esters
or acid halides
*Reaction goes until
completion
*Know this mechanism!
MgBr
O
OCH
3
1)
2) H
3
O
+
OH
Grignard and Epoxides
(opening of epoxides)
O
1)
2) H
3
O
+
OH
MgBr
*SN2 like (attacks least
substituted side)
*Know this mechanism!
Attaching Deuterium to
carbons
C H
3
MgBr
D
2
O
C H
3
D
*This is just good to
know.
Corey-House Reaction
CH
3
Br CH
3
Li (CH
3
)
2
CuLi
Li
CuI
+
Br
*not well understood
(do not need to know
mechanism)
*another way to attach
carbons.
Hydride reduction of
carbonyls
mild conditions (NaBH
4
as reagent)
O
NaBH
4
EtOH
OH
O
Cl
NaBH
4
EtOH
no reaction
*reduces only
aldehydes and
ketones.
*use alcohols as a
solvent.
strong conditions (LiAlH
4
as reagent)
O
OH
1) LiAlH
4
/ ether
2) H
3
O
+
OH
O
O
1) LiAlH
4
/ ether
2) H
3
O
+
OH
+
OH
*reduces aldehydes,
ketones, esters, acid
halides, carboxyllic
acids.
*Use ethers solvents
*Two step process
Facilitator: Chris Lovero Organic Chemistry Reactions 9
Task Reaction Notes
Raney Nickel
*Reduces both carbonyl
and alkene.
H
2
Ra-Ni
O
OH
Oxidation of alcohols
2
o
alcohols
OH
Na
2
CrO
7
H
2
SO
4
/ H
2
O
CrO
3
/ H
2
SO
4
/ H
2
O
acetone / 0
o
C
(Jones reagent)
PCC
CH
2
Cl
2
O
*any [ox] can be used
*KMnO
4
and NO
3
can
be used but they are
harsh.
1
o
alcohols
OH
Na
2
CrO
7
H
2
SO
4
/ H
2
O
CrO
3
/ H
2
SO
4
/ H
2
O
acetone / 0
o
C
(Jones reagent)
PCC
CH
2
Cl
2
O
OH
O
H
*PCC is the only one
that can isolate
the formaldehyde.
Formation of the
Tosylate Ester
OH
TSCl
OTos
*RETENTION from
where alcohol was
originally (SN2
purposes)
Formation of alkyl halide
from 3
o
alcohols
OH
HCl / ether
0
o
C
Cl
Facilitator: Chris Lovero Organic Chemistry Reactions 10
Task Reaction Notes
Formation of 1
o
/2
o
alkyl halides from 1
o
/2
o
alcohols
*Basically an SN2
reaction. (Inversion
from original alcohol)
*Can also use SOCl
2

for Cl, but it undergoes
a special mechanism!
PBr
3
CH
2
Cl
2
C H
3
OH
Br CH
3
Cl CH
3
I CH
3
PCl
3
CH
2
Cl
2
P / I
2
CH
2
Cl
2
Unique cleavage with
HIO
4
OH
CH
3
OH
H
HIO
4
O
CH
3
H
O
*Vicinal diols must
be syn
Williamson ether
synthesis
Br C H
3
O
-
O
*Basically that SN2
exception we learned
in test 2
Pinacol - Pinacolone
Rearrangement
OH OH
H
2
SO
4
O *Need vicinal diols
*Know mechanism
(methyl shift!)
Fischer Estherification
C H
3
CH
2
OH
+
C
O
O H
CH
3
H
+
C
O
O
CH
3
CH
2
C H
3
*CAN USE ACID
HALIDE instead of
carboxyllic acid!!!
Formation of Alkoxide
Anion
OH
1
o
or 2
o
alcohols
2
o
or 3
o
alcohols
OH
O
-
O
-
Na
o
K
o
Ethers from intermolecular
dehydration
2x CH
3
CH
2
-OH CH
3
CH
2
-O-CH
2
CH
3
H
2
SO
4
140
o
C
*Must be identical
alcohols or else you
will get a mixture!!!