Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task

Reaction

Symmetrical
ethers through
dehydration of 1o
alcohols

R OH

H2SO4

x2

140oC

O CH3

Cleavage of ethers
byvstrong acids

Notes

*cannot be unsymetrical

O R

(you will get mixtures!)

Br

HBr

*can also use HI, HCl,

H3C

Br

etc
* vinyl or aryl do not get
cleaved (NO SN2 ON
SP2)

HBr

Br

HO
*basically forms

Autoxidation

R
R O

O2 (xs)

R O

slow

R O O

MCPBA

CH3

Intramolecular
Williamson

Br

EXPLODE!

CH3

*epoxide will form along

the more substituted

CH3

alkene

*SN2 like

NaOH

OH

peroxides.... which

CH3

MCPBA

O OH

*forms O- that attacks

halogenated C

OH
NaOH

H3C

H3C

Cl
Opening of
Epoxides

CH3

CH3
H3O+

O
D

H2O

CH3

OH

2)H3O+

*weak Nu are good

*more substituted side
attacked

D
OH

1)-OH

OH

*activate the O first

*SN2 like (least subs)

so strong Nu and base

CH3
D
OH

*Grignard reagent and

acetylide anion can
work tooo

Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task

Reaction

Free Radical
Halogenation
Expanded

Notes
*Low T: more stable TS

CH3

NBS
hv 0oC

CH3

CH3

*High T: more stable

Br

compound

CH3

NBS
60oC

transition state
CH3

CH3

CH3

CH3

CH3
CH3

Br
Conjugated
Systems

*Low T: more stable TS

*in this example we will examine the

case of HBr

*High T: more stable

compound

CH2

H2C

*NOTE: If more than one

H3O+

HBr

conjugated system

Br2

possibly exists, examine

the transition states of

HBr / 40oC

HBr / 0oC

each one and do the

reactions with the more

stable transtion states!

H2C
Br

Br

transition state
+

Diels-Alder
Reaction

D = donating group

+
*1,2 or 1,4 adduct

W = withdraw group

heat

*know endo rule

*Diene and Dienophile

*Know Stereochem

W
D

D
heat

+
W

*PRACTICE THIS!!!

Facilitator: Chris Lovero

Organic Chemistry II Reactions

NOTE: FROM HERE, YOU HAVE TO KNOW YOUR META, ORTHO, AND PARA DIRECTORS
Task

Reaction

Halogenation of
Benzene

Notes
*X = Cl or Br

X2, FeX3 or
(I2 / CuCl2)

Nitration of
Benzene

NO2

HNO3

*H2SO4 acts as a
catalyst

H2SO4 heat

Sulfonation
(fuming sulfuric)

SO 3H

SO3 / H2SO4

*REVERSIBLE DUE TO
ENTROPY

heat

SO 3H

H2SO 4

H2O

*watch rearrangement!

Friedel-Crafts
Alkylation

RCl

*no strong deactivators

(no strong W grps)
*no amino groups

AlCl3

*watch for polyalkylation

Friedel-Crafts
Acetylation

*no strong deactivators

(no strong W grps)

Cl

*no amino groups

AlCl3

Gatterman-Koch
Formation
(forming
benzaldehyde)

Clemmensen
Reduction

CO / HCl

*no strong deactivators

(no strong W grps)

*no amino groups

AlCl3 / CuCl

*avoid using this

O
Zn(Hg)

HCl

reactant in the presence

of alkenes, alkynes,
alcohols and amines.

Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task

Reaction

*Do not confuse with

Reduction of Nitro
group into Amino
Group

Zn, Sn, or Fe

W = withdraw group

X = leaving grp (halide)

NH2
*need Strong W groups

Nu = nucleophile

ortho and/or para to

Nu

Nu (2eq)

Clemmenson Red.

HCl

NO2

Nucleophilic
Aromatic
Substitution of Aryl
Halides:

Notes

leaving group.

heat, pressure

*Nu can be OH-, RO-,

Addition /
Elimination

NH3.

*NOTE: If - OCH3 is the

Nu, only need 1 eq

Nucleophilic
Aromatic
Substitution of Aryl
Halides:
Elimination /
Addition

OH

*occurs when Strong W

group is not O/P

1) NaOH (2eq) / 340oC / 2500 psi

*formation of benzyne

2) H3O+

in mechanism

* Nu can be OH-, RO-,

NH2
NaNH2 /

NH2

NH3 (l)

NH2.

*will get a mixture (like

second example)

CH3

CH3

CH3

Chlorination of
Benzene

*8 different stereochems

Cl

actually occur

Cl

Cl

3 Cl2 / heat
pressure

*this particular molecule

is the commercial

Cl

Cl

compound Rid
(lice killer)

Cl
Catalytic
Hydrogenation

3 H2 / 1000 psi / 100oC

Ru or Rh (Pt,Pd,Ni also)

Birch Reduction

*withdraw groups ->

sp3

Na or Li

NH3(l) / ROH

*donating groups ->

sp2

Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task

Reaction

Side Chain Rxn:

Oxidation

Notes
*Can use either reagent

CO2H

(CH2)n

*Does not work for bulky

KMnO4/H2O
O

groups.

OH-/100oC

HO2 C

CO2 H
CO2 H

Na2Cr2O7 / H2SO4

(no rxn)

heat

Halogenation of
side chains

*If aromatic ring is

Cl
CH2CH3

Cl2 / light

activated, use NBS

+
Cl

54%

44%

Br2 (or NBS) / light

instead of Br2
*Pay attention to Temp
(if it's low or high)
*WILL EXPLAIN THIS

Br

BETTER IN CLASS

Nucleophilic Subs
of Benzylic
Halides

major!

*SN1

CH2 Br

CH3OH

*SN1 or SN2 or E2?

Depends on conditions!

heat

*Resonance form that

does not disrupt the

CH2 OCH3

aromaticity is more
stable

NaI

*SN2

Br

acetone
CH3CH2O-

*E2

Na+

Rxns of phenols
similar to alochols

NaOH

*2nd rxn is Fischer

Estherification
*3rd rxn is only one that

OH

RCO2H

O
O

or RCOCl
PBr3

OH

(no rxn)

is different!

Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task

Reaction

Oxidation of
Phenols to
Quinones

HO

Notes
*This reaction forms a

Na2Cr2O7

OH

H2SO4

Formation of
Salycilic Acid

*Phenoxide anion can

1) NaOH

OH

OH

2) CO2
3) H3O

REVIEW:
Oxidation of
alcohols

D-A dienophile!

2o alcohols

react with the weak

OH

electrophile because it

is so strongly activated.

*any [ox] can be used

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

OH

*Only use PCC because

Jones reagent will

yield carboxyllic acid

CH2Cl2

REVIEW:
Cleavage of
Alkenes by
Ozonolysis

H3C

CH3

H2O / H2SO4

CH3
O

2) (CH3)2S

CH3

REVIEW:
Hydration of
Alkynes

H3C

1) O3

CH3

*Really know the

R
CH3

HgSO4

HO

1) Sia2BH

2) H2O2 / OH-

mechanism now
and how the enols

tautomerize.

H
RCH2

either
reagent

OH

mixture of ketones

Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task
Dithiane Synthesis
of Aldehydes and
Ketones

Reaction

Notes
*Dithiane will be given

O
1) BuLi

S
H

2) R - X

HgCl2

*BuLi =

H3O+

CH3(CH2)2CH2-Li
*Halide must be methyl
or 1o

1) BuLi
2) R1 - X

S
R
Ketones from
Carboxylic Acids

O
R

Ketones from
Nitriles

S
R

H3O+

HgCl2

2) H3O

Aldehydes from
Acid Chlorides

*2 eq because first
is used to make salt

1) R1-MgX

R C N

1) R1 - Li (2eq)

OH

2) H3O+

*lithium aluminum tri(t-butoxy)hydride

LiAlH(OtBu)3

O
R

*Rosenmund Reduction

Cl

H2 / Pd / BaSO4 / S

*Make sure you know

Ketones from
Acid Chlorides

O
R

(R1)2CuLi

Cl

how to form Gilman

Reagent (refer to Corey-

House in previous rxn

sheet)

Wittig Reaction:
Ald and Ketones
ONLY

*Know how to prep the

phosphorous ylide!

(Ph)3

*trans is more stable

P C

because you want

bulky groups to be
furthest away from
each other.

H
H

maj

Facilitator: Chris Lovero

Organic Chemistry II Reactions

Task
Aldehydes and
Ketones:
Formation of
Cyanohydrins

Reaction
O
R

*Aldehydes or

OH

unhindered ketones

CN

R C CN

HCN

*will use this as a

reagent in the future.

OH

O
H3CH2C

Notes

NaCN

H3CH2C C CN

H+

H
*non AQ favors reactant

Aldehydes and
Ketones: Addition
of 1o Amines

RNH2

Wolf-Kishner
Reaction

*AQ favors product

C N R

H+

*avoid halogens and

NH2NH2

other good LGs.

KOH/DMSO

(Use Clemmensen
instead)

Aldehydes and
Ketones: Addition
of 2o Amines

(H3C)2N

(CH3)2NH
H3O+

Acetal Formations
"protected
carbonyls"

CH3

OEt
CH3

2(CH3CH2OH)
H+

EtO

*aldehyde protected
*easier to just use

OH OH

1) OH

HO

before ketone because

CH 3

OH /H

it is more reactive

2) CH3MgBr

3) H3O+

CH 3

H
O

H
O