ALDEHYDES AND KETONES

Aldehyde STRUCTURE

C R = H, alkyl, aryl
R H

Ketone
O
R and R' = alkyl or aryl
C R and R' cannot be hydrogen!
R R'
NOMENCLATURE
 IUPAC Nomenclature of Ketones

• Choose the longest continuous carbon chain that

contains the carbonyl carbon

• Number from the end of the chain closest to the

carbonyl carbon

• Ketone ending is -one

Do the ketones section of Organic Nomenclature

program!
 EXAMPLES
O

C CH2
CH3 CH2 CH3

2-Pentanone O

CH3 C CH2
CH2 CH CH3

CH2
CH3
4-Ethyl-3-hexanone
 O

CH CH3

CH3

3-Isopropylcyclopentanone
or 3-(1-Methylethyl)cyclopentanone
 KETONES
Common, or Trivial, Names
• Name each group attached to the carbonyl group as an
alkyl group

• Combine into a name, according to the pattern:

alkyl alkyl’ ketone

NOTE: This is not all one word!

 Example of Common Names
O

C CH2
CH3 CH2 CH3

Methyl propyl ketone O

CH3 C CH3
CH2 CH2

Diethyl ketone
 SPECIAL CASES
O O
C C
CH3 CH3
dimethyl ketone diphenyl ketone

acetone benzophenone

A common laboratory O
solvent and cleaning
agent C CH3

methyl phenyl ketone

KNOW
THESE acetophenone
 IUPAC Nomenclature of Aldehydes

• Choose the longest continuous carbon chain that contains

the carbonyl carbon

• Number from the end of the chain closest to the carbonyl

carbon (carbon #1!)

• Aldehyde ending is -al

Do the aldehydes section of Organic Nomenclature

program.
 EXAMPLES
aldehyde group is
CH2 CH2 O always carbon 1
H3 C CH2 C
H
pentanal
Cl
CH3 3 CH 1
O
4 CH 2 C
CH3 H

2-chloro-3-methylbutanal
Common Names of the Aldehydes
O O O

C C C
H H CH3 H H3C CH2 H
Formaldehyde Acetaldehyde Propionaldehyde
1 2 3
O O

C C
H3C CH2 C H H3C CH2 CH2 C H
Butyraldehyde Valeraldehyde
4 5
O

C
H3C CH2 CH2 CH2 CH2 H RECOGNIZE
Caproaldehyde THESE
6
 SPECIAL CASES
O

C
H H
O
formaldehyde C H

O
benzaldehyde
C
H CH3
KNOW
THESE
acetaldehyde
 Forming Common Names of Aldehydes
USE OF GREEK LETTERS O

C C C C C C C H

…….

 is always the end of the chain, no matter how long

CHO CHO

Cl Cl

-chlorocaproaldehyde -chlorocaproaldehyde
( -chlorohexanal ) ( -chlorohexanal )
REACTIVITY OF THE C=O GROUP

NUCLEOPHILIC ADDITION
 GENERALIZED CHEMISTRY

THE CARBONYL GROUP

nucleophilic
at oxygen
electrophiles H+ or E+
add here
.. - .. -
O: :O :
+
C C
+
nucleophiles
attack here
Nu:
electrophilic
at carbon
STEREOCHEMISTRY
THE CARBONYL GROUP IS PLANAR
(SP2 HYBRIDIZED)
Nu:
. .
..
C O ..

Nu:
nucleophiles can attack from either top or bottom
 LUMO OF FORMALDEHYDE
CH
CO
* (LUMO)
nO H H

CO
CH

H ..
C O: Nu: nucleophiles add
to the larger lobe
H (on carbon)
– Relative Reactivity: Aldehydes versus Ketones
• Aldehydes are generally more reactive than ketones
– The tetrahedral carbon resulting from addition to an aldehyde
is less sterically hindered than the tetrahedral carbon resulting
from addition to a ketone
– Aldehyde carbonyl groups are more electron deficient because
they have only one electron-donating group attached to the
carbonyl carbon
NUCLEOPHILIC ADDITION TO C=O
MECHANISMS
IN ACID AND IN BASE
Nucleophilic Addition to Carbonyl
Basic or Neutral Solution
.. _
.. :O:
O: an
+
-:Nu slow
C alkoxide
C ion
Nu
.. _ ..
:O: :O H
fast
C + H 2O C

Nu or on adding acid Nu

Good nucleophiles
and strong bases BASIC SOLUTION
(usually charged)
Nucleophilic Addition to Carbonyl
Acid Catalyzed
+
.. :O more reactive to
H
O: fast addition than the un-
+
+ H C protonated precursor
C

..
.. + :O H
O H slow
+ C
C :Nu

Nu
(+)

Acid catalysis speeds the rate of

addition of ACIDIC SOLUTION
weak nucleophiles and stronger acid
weak bases (usually uncharged). pH 5-6 protonates the
nucleophile
CYANOHYDRINS
 Addition of Cyanide :C N:
Buffered to pH 6-8 .. _
:O : :O :
_
R C R + CN R C R

CN
.. _ ..
:O : :O H

R C R + H2O R C R

CN CN
a cyanohydrin

A -cyanohydrin
In acid solution there would be little CN ,
and HCN (g) would be a problem (poison).
 CYANIDE ION BONDS TO HEMOGLOBIN
..
CYANIDE IS
N Cyanide bonds
IS A POISON C (irreversibly) to the
.. site (Fe II) where
CH3 oxygen usually bonds.

H3C
N N You die of
Fe suffocation -
N N lack of oxygen.
H3C CH3

CH2CH2COOH
CH2CH2COOH

HCN is a gas that you can easily breathe into your lungs.
 SYNTHESIS OF
-HYDROXYACIDS
 SYNTHESIS OF AN -HYDROXYACID
OH
O NaCN
C CH3 a cyanohydrin
pH 8
CH3 C N

acetophenone 1) NaOH/H2O/
2) H3O+
OH
C CH3
C O
HO
Aldehydes also work unless
they are benzaldehydes,
which give a different reaction
(benzoin condensation).
HYDROLYSIS OF THE
NITRILE GROUP
SYNTHESIS OF NITRILES (AND CYANOHYDRINS)
REVIEW

C=O + NaCN C-OH

CN
cyanohydrin

acetone
R-X + NaCN R-CN + NaX
SN2
nitrile

….. both can be hydrolyzed

HYDROLYSIS OF THE CYANO GROUP (NITRILES)
METHOD ONE : strong base + H2O + heat

.. gas
NaOH O:
R C N R C .. + :NH3
H2O/ -
O : Na+
..
H3 O+ neutralize
OVER ALL
..
O:
R-CN
synthesis of R C ..
carboxylic acids O H
..
R-COOH

Nitriles are hydrolyzed to carboxylic acids.

HYDROLYSIS OF THE CYANO GROUP (NITRILES)

METHOD TWO : strong acid + H2O + heat

..
H2SO4 O:
R C N R C .. + (NH4)2SO4
H2O/ O H
..
OVER ALL no mechanism
at this time
R-CN synthesis of
carboxylic acids

R-COOH

Nitriles are hydrolyzed to carboxylic acids.

HYDRATES
 Addition of Water
O O H
+
H
C + H2O R C R'
R R'
O H
aldehyde or ketone
favored a hydrate

hydrates are unstable

most hydrates revert to an aldehyde and cannot be isolated
or ketone as soon as they form in most cases
O H
O
R C R' + H2O
C
R R'
O H
• Dissolving aldehydes (or ketones) in water causes
formation of an equilibrium between the
carbonyl compound and its hydrate
– The hydrate is also called a gem-diol (gem i.e. geminal,
indicates the presence of two identical substituents on the
same carbon)
– The equilibrum favors a ketone over its hydrate because
the tetrahedral ketone hydrate is sterically crowded
WATER ADDS TO THE CARBONYL GROUP OF
ALDEHYDES AND KETONES TO FORM HYDRATES
H catalyzed by a
+ trace of acid
O H
.. H .. .. ..
+ H H
:O :O :O H :O
C C

.. O+
.. :O
..
a hydrate
H H H
O H
H
.. .. H
O H
H
.. +
O H
H ..

for most compounds the equilibrium MICROREVERSIBILITY:

favors the starting materials In a reaction where all steps are
and you cannot isolate the hydrate reversible, the steps in the reverse
reaction are the same as those in
the forward reaction, reversed!
 ACID CATALYSIS
RECALL
H
+
O H
H ..
.. + H ..
:O :O :O H

Acid catalysis enhances the reactivity :Nu

of the carbonyl group - nucleophilic
weak nucleophiles
addition proceeds more easily. can react
ISOTOPE EXCHANGE REVEALS THE PRESENCE
OF THE HYDRATE

O O18 an excess of H2O18

18 H+
+ H2O shifts the
R R R R equilibrium
to the right

O H
+H2O18 -H2O
R C R
18 O
H exchange shows the
presence of a symmetric
intermediate
 SOME STABLE HYDRATES
these also indicate that hydrates are possible


Cl O Cl OH
Cl C Cl C OH
 +Cl H
Cl H
chloral chloral hydrate


120o expected
60o required OH
109o expected
O 60o required
sp2 sp3 OH
cyclopropanone cyclopropanone
hydrate
SOME ADDITIONAL STABLE HYDRATES

O O O OH
H C C H C C OH
glyoxal H
H

O O O OH
Ph C C Ph C C OH
H
H
phenylglyoxal
ACETALS AND
HEMIACETALS
 Addition of Alcohols
TWO MOLES OF ALCOHOL WILL ADD

addition of one mole

O O H
H+
R C R' + ROH R C R' hemiacetal

O R
addition of second mole
O H O R
H+
R C R' + ROH R C R' + H O
O R O R H
an acetal
ACETALS AND HEMIACETALS
R R OH ROH R OR
ROH
C O C C
OR OR
H aldehyde H H

hemiacetal acetal

R R OH ROH R OR
ROH
C O C C
OR OR
R ketone R R
(hemiketal)* (ketal)*
*older term *older term
 ..
ROH + H 2 SO4 R O H Like a
+ hydronium
H ion
R
H O
+
.. .. H + ..
:O :O H :O H

R C R R C R R C R
.. O+
O H .. R
H .. R ..
ACID CATALYZED :
first R O
FORMATION OF A addition H
HEMIACETAL
.. H
Normally the starting :O H
material is favored -
but a second molecule R C R + R O+
of alcohol can react .. H
if in excess (next slide) : ..
O
hemiacetal R
FORMATION OF THE ACETAL ( from the hemiacetal )
remove
R
H O
+ H ..
.. H O H
H
.. second
.. H .. : ..
O
addition
:O H + O H R
R C R R C R R C R
R C R +
:O
.. R
:O
..
SN1 :O+
R
:O :
R R
hemiacetal
Resonance
stabilized
.. .. .. carbocation
: H
:O R R O O R
+ H H +
R O
: R C R R C R
H
:O
.. R
:O
.. R
acetal
 WATER SEPARATOR
AZEOTROPE
Two miscible liquids that distill
as a single substance with a
boiling point that is lower than
either of the original liquids.
when cooled,
benzene 80o C the azeotrope
water 100o C separates
benzene-water
azeotrope benzene
69.4o C
water
benzene and water do not mix,
but in the azeotrope the vapors
(gases) mix and distill together
Az
benzene
+ water
REMOVAL OF WATER SHIFTS THE EQUILIBRIUM
( Le Chatelier Principle )

O O H O R
C + H
R R R C R R C R O H
+ O O
O R R
2 R
H

starting materials Removal of water

are favored shifts equilibrium
STABILITY OF ACETALS AND HEMIACETALS

Most hemiacetals are not stable, except for those of sugars

(see later).

Acetals are not stable in aqueous acid, but they are stable to
aqueous base.

OR H2SO4 ROH
AQUEOUS
ACID
C C O +
H2O
OR
ROH

AQUEOUS OR NaOH
BASE C no reaction
OR H2O
CYCLIC ACETALS
Formation of 2,2-Dimethoxypropane
THIS IS A NON-CYCLIC ACETAL

H3C C CH3 O CH3

dry acid
+ H3C C CH3
remove
2 CH3OH H2 O O CH3

dry acidDry
= acid = HCl
HCl gas or gas
p-toluenesulfonic acid
HCl in methanol
O mp 106oC
HCl (g)
HOTs
CH S OH
3
O (TsOH)
 CYCLIC ACETALS
Cyclic acetals can be formed if a bifunctional alcohol is used.

1,2-ethanediol
H2C CH2
HO OH H2C CH2
O H+ / benzene O O
C C
CH3 CH3
H2 O
acetophenone

1,3-propanedithiol

O
HS SH S S
H+ / benzene

H2 O
 PROTECTING GROUP STRATEGY
Functional Group 1 Functional Group 2

TARGET NON-TARGET
Add
Protecting
Group

TARGET NON-TARGET
React
Unprotected
Group
NEW
GROUP NON-TARGET

Remove
Protecting
NEW Group
GROUP NON-TARGET

Unchanged
Changed
USE OF A CYCLIC ACETAL AS A PROTECTING GROUP

O
O O O O

The Grignard
Br Br MgBr Reaction Takes
Place in Basic
Solution - The
Acetal is Stable
O
O O
H3O+

Acetals Hydrolyze
COOH in Acidic Solution COOMgBr
SUMMARY
ADDITION OF WATER AND ALCOHOLS
WATER O
H2O HO OH
C hydrate

ALCOHOLS
O R-O-H R-O-H
HO OR RO OR
C
H 2O
hemiacetal acetal

RO OR O acetals are
+
H +2 ROH stable to base
H2 O
but not to
H2O aqueous acid
no reaction
NaOH
 CYCLIZATIONS
H2C CH2
O OFTEN USED
HO OH O O cyclic AS A PROTECTIVE
C acetal GROUP
H2O

O
OH OR
C
O R-O-H O
OH
H2O
cyclic hemiacetal cyclic acetal

STABLE IF A STARCH OR
FORMED FROM A “POLYSACCHARIDE”
CARBOHYDRATE IF FORMED FROM
CARBOHYDRATES
Tuliskan mekanisme dan produk dari reaksi berikut:

O
H+
1. HO
H
O

H+
2.
HOCH2CH2OH
ADDITIONS OF AMINES
TO CARBONYL GROUPS

Aldehydes and Ketones

 MANTRA (Memorization Jingle)

Reactions with C=O :

Primary amines yield imines

Secondary amines yield enamines
Tertiary amines do not react

we will come back to this again and again

H R R
AMINES: R N H R N H R N R
.. .. ..
primary secondary tertiary
PRIMARY AMINES

IMINES
 Addition-Elimination:
The Formation of Imines
R O H OH
ketone or .. a “carbinolamine”
C N G C
aldehyde intermediate
H N
R
R R
.. .. HA
G NH2 + C O+ C N G + H2O
H
R R
primary an imine
amine

G is a primary Addition of the amine Imines are compounds

alkyl group is followed by a loss with a C=N bond
of water (elimination).
 Mechanism of Imine Formation
H weak base addition - acid catalyzed
H-O
2 R H R R
.. .. slow + .. ..
G NH2 + C O G N C O H G N C OH
.. 1 ..
R H R H R
H
H-O-H H
acid-catalyzed proton exchanges
+ H-O-H
addition +

R
an imine
R R
.. .. fast + ..
G N C O H G N C G N C
+
H R H H R R
+
loss of water H-O deprotonation
+ H-O-H
(elimination) H H
Formation of Simple Imines
overall result remove

R R
..
C O + H2N R C N R + H2O
R R
an imine

Reactions occur fastest at pH 4-5

Mild acid facilitates departure of the hydroxyl group
from the aminoalcohol intermediate without also
protonating the nitrogen of the amine starting compound
These reactions do not favor the formation of the
imine unless:
- the product is insoluble
(crystallizes or precipitates) or
- water is removed to drive the equilibrium
 Hydrolysis of Simple Imines
REVERSAL

In an excess of aqueous acid, simple imines hydrolyze

back to the aldehyde or ketone and the amine from
which they were orginally formed …..

R R
H3O + ..
C N R + H2O C O + H2N R
R R
an imine

Imines that are not soluble, however, are difficult to

hydrolyze.
CRYSTALLINE IMINES

HYDRAZONE AND OXIME DERIVATIVES

 shown
CRYSTALLINE IMINES below

There are some special amines that

yield insoluble products (imines)
that are easy to crystallize …..

O
..
:NH2OH hydroxylamine H2N C NHNH2 semicarbazine

.. ..
R-NH-NH2 various O2N NHNH2
hydrazine 2,4-dinitrophenyl-
compounds NO2 hydrazine
 Formation of Oximes

R R
..
C O + H2N OH C N OH + H2O
R R
hydroxylamine
an oxime
aldehyde
(usually crystallizes)
or ketone
 Formation of Hydrazones

R R
..
C O + H2N NH R C N NH R + H 2O
R R
a hydrazine
a hydrazone
aldehyde
or ketone
 2,4-Dinitrophenylhydrazones
2,4-dinitrophenylhydrazine
NO2
R
..
C O + H2N NH NO2
R
2,4-dinitrophenylhydrazine
NO2
aldehyde
or ketone R
C N NH NO2 + H2O
R
insoluble
2,4-dinitrophenylhydrazone
red,
red orange or yellow
precipitate forms a 2,4-DNP (precipitates)
 Formation of Semicarbazones
semicarbazine

R O
..
C O + H2N NH C NH2
R semicarbazide

aldehyde R O
or ketone
C N NH C NH2 + H2O
R
a semicarbazone

(usually crystallizes)
 DERIVATIVES
CRYSTALLINE IMINES CAN BE USED AS DERIVATIVES

A derivative is a solid compound (formed from the

original compound) whose melting point can help
to identify the original compound.

What you will see in the tables of unknowns:

semicarbazone
2,4-dinitrophenyl-
ketones bp mp hydrazone
2-undecanone 231 12 122 63
4-chloroacetophenone 232 12 204 236
4-phenyl-2-butanone 235 - 142 127
BIOLOGICAL REACTIONS
 Pyridoxyl-5’-phosphate (P-5’-P)
Converts amino acids to -ketoacids, and vice versa.
Biologically important in transamination reactions.

O
O C H H O
..
HO P O CH2 OH H2N C
R OH
O
an amino acid
N CH3
+ H O
H N C
- H2O
pyridoxyl-5’-phosphate H OH
C R
( P-5’-P ) R OH

continued
formation of N CH3
the imine +
H
first imine
 :Enz O O O
Enz-H R CH C
H O R C C
NH2 OH OH
N C converts
H OH
C R
R OH tautomerism
H-Enz

N CH3 O
+
H H N C
Enz: OH
H C R
-ketoacid
first imine
R OH
O O
H2 O
NH2 R C C
N CH3
+ CH2 OH
new imine H
R OH

Removing the
N CH3
amino group hydrolysis of +
H pyridoxamine
the new imine
TRANSFERRING THE AMINO GROUP
a different-ketoacid
O O O
NH2 R C C H N C
OH OH
CH2 H C R
R OH R OH

N CH3 N CH3

H H
pyridoxamine
tautomerism

hydrolysis of the imine

These steps are the H O

reverse of those on a different
the previous slides. H2N C
amino acid
R OH
 SUMMARY

Amino Acid-1 + pyridoxyl-5’-phosphate -Ketoacid-1 +

( takes NH2 group )
pyridoxamine
( has NH2 )

-Ketoacid-2 + pyridoxamine Amino Acid-2 +

( gives NH2 back )
pyridoxyl- 5’-phosphate

a different
one reacts
here
SECONDARY AMINES

ENAMINES
 Formation of Enamines
-hydrogen
secondary is required
amine
H O H OH
+
.. H
R C C R + R2NH R C C R
benzene
R R NR2

“carbinolamine”
+ R NR2
H
C C + H2O

R R
generally removed
an enamine by azeotropic
distillation
 COMPARISON
carbinolamine intermediates
PRIMARY AMINES SECONDARY AMINES
hydrogen on the
adjacent carbon

R O H H OH
..
C N G R C C R
R H R NR2
..

-H2O -H2O no hydrogen

hydrogen
on nitrogen
on the
nitrogen imine enamine

When there is no hydrogen on

nitrogen, one is lost from carbon.
 piperidine
N
H

SOME SECONDARY
pyrrolidine
AMINES FREQUENTLY
N
USED TO FORM
H
ENAMINES
O
Water must be removed
morpholine
N
H
 Enamine Formation
MECHANISM
H
H-O-H .. ..
1) H :O : + H +O H H :O H
+
R C C R + H R C C R R C C R
+
R R R

H
H-O-H
2) + ..
.. ..
H +O H H :O H H +OH2
slow
R C C R R C C R R C C R

R .. R +N H R N:
N H
R R O-H R R
R R H

continued ….
 Enamine Formation (cont)
MECHANISM

3) ..
H +OH2 H H
+
R C C R R C C R R C C R

R N: R N: R N+
+
R R R R R R
+ H2O
4) H H2O
O-H
H
+ +
R C C R R C C R + H O+
H water must
3

: N:
be removed
R N+ R
to force the
R R R R
equilibrium
enamine
 Nucleophilic Character of Enamines

R R

R :N R R _ +N R
..
C C C C

R R R R

C
nucleophilic
at carbon
X
SN2
2)
 Reactions of Enamines as Nucleophiles

R R R R R

:N R +N R :N
R R

C C R C C R R C C R
+
R R SN2 R R
an iminium salt
R X _
+ X
hydrolysis

R O R O

R C C R R C C R

H R alkylation
ALKYLATION OF A KETONE
pyrrolidine
..
N
iminium
H
H+ .. + salt
O N CH3I N
CH3

H2O enamine
H3 O+
remove workup
water O
CH3
+ N
H

Az
 Hydrolysis of Iminium Salts
MECHANISM
1) H
R R R R H-O-H R R
+
R +N R N: R +N H
slow
R C C R R C C R R C C R

R R +O : R :O H
.. ..
O
.. H H
H H O-H
H
2)
R R

R +N H R R R

R C C R + N H
R C C R ..

:O R +O H
R .. H ..

continued ….
 Hydrolysis of Iminium Salts
MECHANISM

3)
R R

R C C R R C C R + H3O+

R +O H R :O :
..
O-H
H
 SUBSTRATES FOR ENAMINE ALKYLATION
(and acylation)
R X CH2CH3 alkylation
R N: R
X CH2 CH CH2
C C
O
R R
X = Cl, Br, I
X CH2 C CH3
R R X
O
R N+ _ R
.. X CH2 C O CH3
C C

R R primary
secondary O acylation
allylic Cl C CH3
enamine
acyl compounds O
may be used O O
Cl C O CH2CH3
R C Cl RO C Cl
CHLORIDES, BROMIDES AND IODIDES
In SN2 reactions you learned the rate sequence R-I > R-Br > R-Cl
and that iodides are better substrates than chlorides.
This is true.
Based on this knowledge …..
many students assume that if acid chlorides are good
the acid bromides and iodides must be better.

However …… acid bromides and iodides are difficult to

prepare, and the iodides are quite unstable
….. you should use the chlorides.

O O
They are easily prepared
R C Cl RO C Cl from the acid by:
R-COOH + SOCl2
Enamine Reactions -- Summary
secondary R R R R
amine
O N +N

R
R2NH R X
+
H

H2O
alkyl or
H+
acyl
halide
O

R
TERTIARY AMINES

DO NOT REACT
 PRIMARY AMINE COMPARISON
loses H from N You need to lose two H’s,
one to form the intermediate,
R O H one to eliminate water.
H N R ..
C N R
H H
R SECONDARY AMINE
H is lost to form intermediate loses H from C

H OH
H N R
R C C R
R
R
TERTIARY AMINE : N-R
H is lost
R
.. H
H :O
R N R R C C R unstable The tertiary amine can’t
R R reverses form the carbinolamine
N-R
+ intermediate because
R
no H to lose R it lacks an H on N.
FORMING RINGS

SOME GUIDELINES
 DILUTE SOLUTION AND EXACT STOICHIOMETRY
FAVOR RING FORMATION
NH2 H
+ O C
NH2 H
pH = 5 Excess formaldehyde (>2:1)
and a more concentrated
solution favor the diimime.
Also remember
that unstrained
5- and 6-rings
form easily,
NH N CH2
other sizes are CH2
difficult.
NH N CH2

1:1 molar ratio and

dilute solution favor In dilute solution the molecule is more
the ring formation likely to react internally with itself
because encounters with other molecules
will be less frequent.
 HINT ON THE MECHANISM …..
C=N can undergo additions just like C=O

protonation Both are polar multiple bonds

first and both can undergo acid-
H catalyzed nucleophilic addition.

CRUCIAL +
STEP N CH2
forms ring
.. pH 5
NH2 mildly
acidic

….. see if you can figure out the rest of the mechanism
for Problem 16-18 on your own.
WITTIG REACTION
 Ylide
A compound or intermediate - .. +
with both a positive and a
negative charge on adjacent
atoms.
X Y
BOND

Betaine or Zwitterion
A compound or intermediate +
with both a positive and a
negative charge, not on
MOLECULE
Y
adjacent atoms, but in different
-:
parts of the molecule.
X
 Preparation of a Phosphorous Ylide
( WITTIG REAGENT )
precipitates
R2 R1
benzene + _
R1 C X + (C6H5)3P : (C6H5)3P C R2 X
heat H
H
- ..
: O-CH
.. 3
..
Ph P Ph ether strong base
Ph
R1
+ - ..
Triphenylphosphine (C6H5)3P C
( Ph = C6H5 )
R2
an ylide
 Resonance in Ylides
_ R R
+ ..
(C6H5)3P C (C6H5)3P C
R R

d-p BACKBONDING
..
Remember that Phosphorous

P C is a Period III element (d orbitals).

Backbonding to phosphorous
3d 2p reduces the formal charges
and stabilizes the negative
charge on carbon.
 The Wittig Reaction
MECHANISM

R1 R3 R1 R3
+
-..
C O + (C6H5)3P C R2 C C R4
R2 R4
: O: P(C6H5)3
.. _ +
ylide betaine

R1 R3
R1 R3
C C + O P(C6H5)3 R2 C C R4
R2 R4 :O P(C6H5)3
INSOLUBLE ..
synthesis of very thermodynamically
an alkene stable molecule
oxaphosphetane
(UNSTABLE)
SYNTHESIS OF AN ALKENE - WITTIG REACTION

H 3C CH2CH3 H3C Br CH2CH3

O
H 3C H H3C H H

H3C
O :P(C6H5)3
H3C

+ + CH2CH3
(C6H5)3P CH2CH3 (C6H5)3P
ylide : CH3ONa
- H H H
ANOTHER WITTIG ALKENE SYNTHESIS

H
+
CH2Br C P(C6H5)3 Br-
H
:P(C6H5)3 PhLi

H
C C P(C6H5)3
O ..
H - +

+ ylide
..
:O
..
P(C6H5)3
- + Br
C O
triphenylphosphine H H
oxide (insoluble)
 Muscalure
Sex pheromone of the
common house fly.
H H Musca Domestica

CH3(CH2)6CH2 CH2(CH2)11CH3

(Z)-9-tricosene

Wittig The reaction can be made to give the

cis alkene (Z) by correct choice of
solvent and temperature, or by the
separation of a mixture of cis and trans.

O
CH3(CH2)6 C Cl CH2(CH2)12CH3
H
ORGANOMETALLICS
 Synthesis of Alcohols
Addition of Organometallic Reagents
.. _ +
:O : :O: M
ether
R M + R C R
C
(R-MgBr) R R
R
(R-Li)
:R - H2O workup
+ step
H
These reagents cannot ..
exist in acid solution :O H

R C R + M (OH)x

alcohol
R
 Summary of Reactions of
Organometallics with Carbonyl
Compounds
All review
• Organometallics with ketones yield to you
tertiary alcohols
• Organometallics with aldehydes yield
secondary alcohols
• Organometallics with formaldehyde yield
primary alcohols.
• Organometallics with carbon dioxide yield
carboxylic acids.
etc.