Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes
*Adds a halide

Addition of HX
(Mark)

HBr

Br
CH3

Addition of HX

CH3

Add two Br's anti

CH3

to alkene

ROOR

CH3

CH3

Br2

CH3

CH3

OH (Mark w/ Br as H

Br2

Forming alkene

H2O

from vicinal dihalide

H3C

*Wedges with wedges

Br

H
Br

*Anti and co planar

OH
D
Br

and anti-planar)

*Anti and co planar

Br
D
Br

(or CCl4)

Adding a Br and

to least substituted
carbon.

H H

CH2Cl2

*Adds a halide

Br H

HBr

CH3

carbon.

H H

(Anti-Mark)

to more substituted

NaI or KI

CH3

acetone

H3C

CH3

and dashes with dashes

*E2 Like!

*E1 like and it cannot

Dehydration to

H2SO4

alkene

OH

give terminal alkene

heat
*SPECIAL REACTION:

OH

Addition of OH
(direct and mark)

POCl3

dehydrates to form

heat

terminal alkene.
*CANNOT CONTROL

CH3

CH3
CH3

H3O+

CH3

STEREOCHEM!
*Low yield!

OH

*C+ formation!

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Oxymercuration/

CH3

demercuration

Notes

CH3
OH

1) Hg(OAc)2/ H2O

(Add OH from alkene

2) NaBH4

mark and antiplanar)

CH3
O CH3

CH3

SPECIAL: Adds alcohol

1) Hg(OAc)2/ CH3OH

instead to form ethers!

2) NaBH4

*Mark and antiplanar

*Complex mechanism

*Complex mechanism
*Mark and antiplanar
*WILL BE SEEING THIS
MORE IN ORGO II
*Anti-mark

Hydroboration

(Add Oh anti-mark and

CH3

syn planar)

CH3

1) BH3 / THF

2) H2O2 / -OH

Catalytic Hydrogenation

H 3C

CH3

H3 C

(Alkenes -> Alkane, Syn

D

Pt, Pd, or Ni
CH3

CH3

*Steric factors must be

payed attention to

H2

Addition of H)

*Notice Peroxide

OH

*Can use D2 instead

H3 C
H
H

*expensive
Formation of

CH3

Vicinal Diols

OsO4

(Syn)

H2O2

D
CH3

KMnO4

cold, basic

OH
CH3

*toxic
*great yield

D OH

OH
CH3
D OH

*cheaper
*safer
*poor yield

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task
Ozonolysis

Reaction
R

Notes
O

1) O3 / CH2Cl2

(double bond cleavage)

R
R

1) O3 / CH2Cl2

Warm KMnO4

2) (CH3)2S

1) O3 / CH2Cl2

2) (CH3)2S

*Can isolate the

formaldehyde.

R
H

*Can use Zn/acetic acid

instead of (CH3)2S

2) (CH3)2S

R
R

O
H

*further oxidizes to form

KMnO4

cleavage

warm

carboxylic acids
*cannot isolate the
formaldehyde

KMnO4

O
R

warm

warm

addition (formation of
cyclopropane)

R
OH

+ CO2 +

H2O

Carbene / Carbenoid

CH3

KMnO4

CH3
CH2N2

the Simmons-Smith

H3C

*stereochem is preserved
*Second reaction uses

heat

*syn

CH3

CH2I2
Zn(Cu)

reagent

CH3
D

H3C

*useful for synthesis

Formation of epoxides
from alkenes

CH3

CH3
MCPBA

ORGO II)

O
D

(ESPECIALLY IN

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes

to form ethers. You

H2O

OH

CH3

OH

2)H3O+

Formation of

H3C

CHCl3

*please look up the

Cl

Cl
CH3

mechanism so you can

CH3

KOH

H 3C

CH3

see how the carbene

is formed

CH3
Br

CHBr3
KOH

Br

*forms the nucleophile

Formation of the
acetylide anion

mechanism.

D
OH

D
H

*Please look up

CH3

1) OH

Dichlorocarbenes

*Basic are like SN2

(least substituted side)

Dibromocarbenes and

side.

will see this in Orgo II.

from more substituted

OH

H3O+
NOTE: Can use RO-

*acidic conditions opens

CH3

CH3

Opening of Epoxides

H 3C C

NaNH2

C H

H3C C

that is handy when

connecting carbons!

Uses of the acetylide

anion

*SN2 because of the

with methyl or 1o halides

H 3C C

CH3Br

C CH3

exception we learned
from before!!!!

with 2o or 3o halides

H 3C C

H3C C

Br
-

*E2 remember from last

H3C CH CH3

CH2

H3C CH

with carbonyl groups (ketones, aldehydes, and formaldehydes)

*acetylide anion attacks

HO
O
H3C C CH3

1) H3C

2) then H3O+

test!!!

H3C

partially positive carbon

C CH3

*DO NOT FORGET

then H3O+

C
H3C

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes
*Need either geminal or

Synthesis of Alkynes

Br Br

1) NaNH2 / 100oC

H3C CHCH CH3

2) H3O+

vicinal dihalides

C CH2 CH3

HC

*Look up mechanism
*NaNH2 gives terminal

Br Br

*KOH gives internal

CH2CHCH2CH3
Br
H3C C CH2 CH3
Br
Br
KOH

HC CH2 CH2CH3

200oC

Br
Halogenation of alkynes

Br2 and alkyne

H 3C

H 3C

CH3

*Stereochem cannot
be controlled

H 3C

Br

Br2
(1 eq)

Br

+
Br

H 3C
HBr and alkyne

Br

Br

HBr

*syn addition

(1 eq)

H 3C

H 3C

*Mark

H
Br

HBr
(2 eq)

Br
*Anti mark

HBr and alkyne

HBr

H 3C

ROOR

H
H 3C

Br

*syn addition

H
*Takes it all the way back

Catalytic reduction with

reactive catalyst

H 3C

CH3

H2

to alkane
*generally bad yield

Pt, Pd, or Ni

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Alkyne to Alkene:

Lindlar's catalyst

TRIPLE to DOUBLE

H 3C

Notes
*isolates an alkene with

H2 / Pd(BaSO4)

CH3

quinoline

a SYN addition of H

H 3C

CH3

CH3

*isolates an alkene with

Dissolving metal

H 3C

NaNH3

CH3

H 3C
Addition of H-OH to
alkynes

Mercuric Ion

HgSO4 / H2O

H3C CH2 C

H2SO4

an ANTI addition of H

*Mark addition

*If not terminal, you will

CH3

H3C CH2

get a mixture.

*Formation of ketone

H3C CH2 C

CH3

HgSO4 / H2O

H2SO4

C
CH2 CH3

H3C CH2

+
O
C
CH3

H3C CH2 CH2

Hydroboration

*Antimark addition

O
1) Sia2BH

H3C CH2 C

2) H2O2 / -OH

*will get a mixture if not

C
H3C CH2 CH2

terminal

*Formation of aldehyde

Oxidation of alkynes
(mild conditions)

H 3C

CH3

*Forms vicinal

KMnO4 / H2O

carbonyls

neutral / cold

*further oxidizes terminal

alkynes to form
carboxylic acid.

H 3C

KMnO4 / H2O
neutral / cold

OH
O

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task
Cleavage of Alkynes:

Reaction

Notes

Oxidation of alkyne (strong)

H 3C

*Forms H2O and CO2

C CDH2

1) KMnO4 / H2O

if terminal.

H 3C

2) -OH / heat

OH

+
O
CDH2

HO
H 3C

1) KMnO4 / H2O

2) OH / heat

H 3C

C CDH2

1) O3

H
H3C CH

from Grignard

*Same products as
previous

CDH2

H 2O

CO2

OH
*Forms from 1o, 2o, 3o,

H
H3C CH

allyl, vinyl, and aryl

MgBr

The Organolithium

Formation of alcohols

ether

Br

CO2

Mg

OH HO

2) H2O H3C

2) H2O

The Grignard Reagent

Reagent

1) O3

H 2O

OH

Ozonolysis

H 3C

*This reagent acts like

Li

H3C CH2

Br

pentane or hexane

H3C CH2

Li

1o alcohols. (Grignard and formaldehyde)

1)

*Carbon attachment
H

2) H3O+

OH

2o alcohols. (Grignard and aldehyde)

*Know this mechanism!

O

MgBr

1)

*Carbon attachment

2) H3O+

OH

3o alcohols. (Grignard and ketone)

*Know this mechanism!

O

MgBr

grignard but is stronger.

*Know this mechanism!

MgBr

carbons.

*Carbon attachment

1)
2) H3O+

OH

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task

Reaction

Notes
*Reaction goes until

Grignard and esters

OH

MgBr

completion

or acid halides

OCH3 1)

*Know this mechanism!

2) H3O

Grignard and Epoxides

(opening of epoxides)

*SN2 like (attacks least

MgBr

1)

OH

2) H3O+

*Know this mechanism!

*This is just good to

Attaching Deuterium to
carbons

substituted side)

D2O

MgBr

H 3C

Corey-House Reaction

Li

CH3Br

H 3C

CuI

CH3Li

know.

*not well understood

(CH3)2CuLi

(do not need to know

mechanism)

Br

*another way to attach

carbons.

Hydride reduction of

*reduces only

mild conditions (NaBH4 as reagent)

carbonyls

aldehydes and

OH

NaBH4

ketones.

EtOH

*use alcohols as a

NaBH4

solvent.

no reaction

EtOH

Cl
*reduces aldehydes,

strong conditions (LiAlH4 as reagent)

ketones, esters, acid

O
OH

1) LiAlH4 / ether

halides, carboxyllic

2) H3O+

acids.

OH

*Use ethers solvents

O
O

1) LiAlH4 / ether
2) H3O+

OH

OH

*Two step process

Facilitator: Chris Lovero

Organic Chemistry Reactions

Task
Raney Nickel

Reaction

Notes
*Reduces both carbonyl

H2

OH

and alkene.

Ra-Ni

Oxidation of alcohols

*any [ox] can be used

2o alcohols

Na2CrO7

*KMnO4 and NO3 can

H2SO4 / H2O

OH

be used but they are

harsh.

CrO3 / H2SO4 / H2O

acetone / 0oC
(Jones reagent)

PCC
CH2Cl2
1o alcohols

*PCC is the only one

Na2CrO7
H2SO4 / H2O

that can isolate

OH

the formaldehyde.

O
CrO3 / H2SO4 / H2O

OH

acetone / 0oC
(Jones reagent)

H
PCC

CH2Cl2

Formation of the

*RETENTION from

Tosylate Ester

OH

TSCl

OTos

where alcohol was

originally (SN2

purposes)
Formation of alkyl halide
from 3o alcohols

OH

HCl / ether
0oC

Cl

Facilitator: Chris Lovero

Organic Chemistry Reactions 10

Task

Reaction

Notes
*Basically an SN2

Formation of 1o/2o

PBr3

alkyl halides from 1o/2o

Br CH3

reaction. (Inversion

CH2Cl2

from original alcohol)

alcohols

*Can also use SOCl2

PCl3

H3C OH

CH2Cl2

Cl CH3

for Cl, but it undergoes

a special mechanism!

P / I2

CH3

CH2Cl2
Unique cleavage with

OH
CH3

HIO4

HIO4

*Vicinal diols must

CH3

be syn

OH

H
O
Formation of Alkoxide

1o or 2 o alcohols

Nao
OH

Anion

O
Ko

2o or 3o alcohols

OH
O

Williamson ether
synthesis

*Basically that SN2

Br

H 3C

exception we learned

in test 2
*Must be identical

Ethers from intermolecular

dehydration

2x CH3CH2-OH

H2SO4

CH3CH2-O-CH2CH3

140oC

Pinacol - Pinacolone

OH OH

Rearrangement

alcohols or else you

will get a mixture!!!

*Need vicinal diols

*Know mechanism

H2SO4

(methyl shift!)
Fischer Estherification

H 3C

CH2 OH

C
O

*CAN USE ACID

H3C CH2 O

+
HO

CH3

C
O

CH3

HALIDE instead of
carboxyllic acid!!!