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Facilitator: Chris Lovero Organic Chemistry II Reactions 1

Task Reaction Notes


Symmetrical
ethers through
R OH H2SO4
R O R
*cannot be unsymetrical

(you will get mixtures!)


dehydration of 1o x2 140oC
alcohols

Cleavage of ethers O CH3 Br *can also use HI, HCl,


HBr
byvstrong acids
+ H3C Br etc

* vinyl or aryl do not get

cleaved (NO SN2 ON

SP2)
HBr

O Br HO

Autoxidation *basically forms


R R R peroxides.... which
O2 (xs)
R O H R O O OH + R O O H EXPLODE!
slow
R R R

MCPBA CH3 CH3 *epoxide will form along


MCPBA
O the more substituted

CH3 CH3
alkene

*SN2 like
Intramolecular OH NaOH O
Williamson Br *forms O- that attacks

halogenated C
OH
NaOH H3C O
H3C
Cl

Opening of *activate the O first


CH3 CH3
Epoxides *weak Nu are good
H3O+ OH *more substituted side
O
H2O OH attacked
D D

*SN2 like (least subs)


CH3 OH
1)-OH so strong Nu and base
CH3
O *Grignard reagent and
2)H3O+ D acetylide anion can
D OH work tooo
Facilitator: Chris Lovero Organic Chemistry II Reactions 2
Task Reaction Notes

Free Radical *Low T: more stable TS


Halogenation
CH3 CH3
NBS *High T: more stable
Expanded Br
hv 0oC compound
CH3 CH3

NBS

60oC
transition state
CH3 CH3
. CH3

CH3
. CH3 CH3

Br

Conjugated *in this example we will examine the *Low T: more stable TS
Systems case of HBr
*High T: more stable

compound
H2C CH2
*NOTE: If more than one
H3O+
HBr conjugated system
Br2
possibly exists, examine

the transition states of

HBr / 0oC HBr / 40oC


each one and do the

reactions with the more


H H
stable transtion states!

H2C
Br Br

transition state

+ +

D = donating group W = withdraw group *1,2 or 1,4 adduct


Diels-Alder
Reaction *know endo rule
D D
heat *Diene and Dienophile
+ *Know Stereochem
W W *PRACTICE THIS!!!

D D
W
heat
+
W
Facilitator: Chris Lovero Organic Chemistry II Reactions 3
NOTE: FROM HERE, YOU HAVE TO KNOW YOUR META, ORTHO, AND PARA DIRECTORS
Task Reaction Notes
*X = Cl or Br
Halogenation of X
Benzene X2, FeX3 or

(I2 / CuCl2)

Nitration of *H2SO4 acts as a


NO2
Benzene HNO3
catalyst

H2SO4 heat

*REVERSIBLE DUE TO
Sulfonation SO 3H
(fuming sulfuric) SO3 / H2SO4 ENTROPY

heat

SO 3H
+ H2SO 4
+ H2O

*watch rearrangement!
Friedel-Crafts
Alkylation *no strong deactivators
R
RCl (no strong W grps)

AlCl3 *no amino groups

*watch for polyalkylation

Friedel-Crafts O *no strong deactivators


O
Acetylation (no strong W grps)
Cl R R *no amino groups

AlCl3

Gatterman-Koch O *no strong deactivators


Formation (no strong W grps)
(forming CO / HCl H
benzaldehyde) *no amino groups
AlCl3 / CuCl

Clemmensen O *avoid using this


Reduction reactant in the presence
Zn(Hg)
R R of alkenes, alkynes,
HCl
alcohols and amines.
Facilitator: Chris Lovero Organic Chemistry II Reactions 4
Task Reaction Notes
*Do not confuse with
Reduction of Nitro
group into Amino Zn, Sn, or Fe Clemmenson Red.
Group
HCl
NO2 NH2

W = withdraw group X = leaving grp (halide) Nu = nucleophile *need Strong W groups


Nucleophilic
Aromatic ortho and/or para to
X Nu
Substitution of Aryl Nu (2eq) leaving group.
Halides: W W W W
heat, pressure *Nu can be OH-, RO-,
Addition /
NH3.
Elimination
*NOTE: If - OCH3 is the
W W
Nu, only need 1 eq

Nucleophilic X OH *occurs when Strong W


Aromatic group is not O/P
Substitution of Aryl 1) NaOH (2eq) / 340oC / 2500 psi

Halides: 2) H3O+
*formation of benzyne

in mechanism
Elimination /
Addition X NH2 * Nu can be OH-, RO-,

-
NH2 NH2.
NaNH2 /
+ *will get a mixture (like
NH3 (l) second example)

CH3 CH3 CH3

*8 different stereochems
Chlorination of Cl
Benzene actually occur
3 Cl2 / heat Cl Cl *this particular molecule

pressure is the commercial

Cl Cl compound Rid

Cl (lice killer)

Catalytic
Hydrogenation
3 H2 / 1000 psi / 100oC

Ru or Rh (Pt,Pd,Ni also)

Birch Reduction W *withdraw groups ->


W
sp3

0 0 *donating groups ->


Na or Li
D D sp2
NH3(l) / ROH
Facilitator: Chris Lovero Organic Chemistry II Reactions 5
Task Reaction Notes
Side Chain Rxn: CO2H
*Can use either reagent
Oxidation (CH2)n *Does not work for bulky

KMnO4/H2O groups.

O
OH-/100oC
HO2 C CO2 H

CO2 H

Na2Cr2O7 / H2SO4

heat (no rxn)

*If aromatic ring is


Halogenation of Cl
side chains CH2CH3 Cl2 / light activated, use NBS
+ instead of Br2
Cl
*Pay attention to Temp
54% 44%
Br2 (or NBS) / light (if it's low or high)

*WILL EXPLAIN THIS


Br
BETTER IN CLASS

Nucleophilic Subs major! *SN1 or SN2 or E2?


*SN1 CH2 Br +
of Benzylic CH3OH Depends on conditions!
Halides
heat *Resonance form that
+
does not disrupt the

CH2 OCH3 aromaticity is more

stable

I
NaI
Br *SN2
acetone

CH3CH2O-
*E2
Na+
-
Rxns of phenols NaOH O *2nd rxn is Fischer
similar to alochols Estherification

*3rd rxn is only one that


O R
RCO2H is different!
OH
O
or RCOCl

PBr3 OH
(no rxn)
Facilitator: Chris Lovero Organic Chemistry II Reactions 6
Task Reaction Notes
Oxidation of *This reaction forms a
Na2Cr2O7
Phenols to HO OH D-A dienophile!
O O
Quinones
H2SO4

Formation of *Phenoxide anion can


OH 1) NaOH
Salycilic Acid OH O
react with the weak
2) CO2
OH electrophile because it
+
3) H3O is so strongly activated.

2o alcohols *any [ox] can be used


REVIEW: Na2CrO7
Oxidation of *KMnO4 and NO3 can
alcohols H2SO4 / H2O be used but they are

O harsh.
OH CrO3 / H2SO4 / H2O

acetone / 0oC

(Jones reagent)

PCC

CH2Cl2

1o alcohols H *Only use PCC because

PCC Jones reagent will


OH O
yield carboxyllic acid
CH2Cl2

REVIEW:
Cleavage of H3C CH3 H3C CH3
Alkenes by 1) O3
Ozonolysis O + O
H CH3 2) (CH3)2S H CH3

REVIEW: R H R *Really know the

Hydration of H2O / H2SO4 mechanism now


CH3
Alkynes and how the enols
HgSO4 HO H O
R H tautomerize.

1) Sia2BH R H H
RCH2
2) H2O2 / OH- O
H OH

either
1 mixture of ketones
R R
reagent
Facilitator: Chris Lovero Organic Chemistry II Reactions 7
Task Reaction Notes
Dithiane Synthesis *Dithiane will be given
of Aldehydes and O *BuLi =
Ketones 1) BuLi H3O+
S S S S CH3(CH2)2CH2-Li
2) R - X
HgCl2
R H
H H R H *Halide must be methyl

or 1o
1) BuLi

2) R1 - X

O
H3O+
S S 1
1 HgCl2 R R
R R

Ketones from *2 eq because first


Carboxylic Acids
O 1) R1 - Li (2eq) O
is used to make salt
+ 1
R OH 2) H3O R R

Ketones from O
Nitriles 1) R1-MgX
R C N 1
2) H3O+ R R

Aldehydes from *lithium aluminum tri(t-butoxy)hydride


Acid Chlorides
O LiAlH(OtBu)3
O
*Rosenmund Reduction
R Cl
R H
H2 / Pd / BaSO4 / S

*Make sure you know


Ketones from
Acid Chlorides O how to form Gilman
O
(R1)2CuLi Reagent (refer to Corey-
1
R Cl R R House in previous rxn

sheet)

Wittig Reaction: *Know how to prep the


H H
phosphorous ylide!
Ald and Ketones
H
ONLY *trans is more stable
O (Ph)3 P C
because you want

H + bulky groups to be

furthest away from

each other.
H maj
H
Facilitator: Chris Lovero Organic Chemistry II Reactions 8
Task Reaction Notes
Aldehydes and *Aldehydes or
Ketones: O OH
- unhindered ketones
CN
Formation of R C CN
Cyanohydrins *will use this as a
R H HCN
H reagent in the future.

O OH
NaCN
H3CH2C C CN
H3CH2C H H+
H
*non AQ favors reactant
Aldehydes and
Ketones: Addition O RNH2 *AQ favors product
of 1o Amines C N R
C
H+

Wolf-Kishner O
*avoid halogens and
Reaction NH2NH2 other good LGs.

KOH/DMSO (Use Clemmensen

instead)

Aldehydes and (H3C)2N


Ketones: Addition O (CH3)2NH
of 2o Amines
H3O+

Acetal Formations
"protected
carbonyls" OEt
CH3 2(CH3CH2OH)
CH3
H+
O EtO

*aldehyde protected
*easier to just use
OH OH
before ketone because
O HO CH 3
+
1) OH OH /H it is more reactive

H 2) CH3MgBr H

O 3) H3O+ O

O -
O CH 3

H
H
O O
O O