Aldehydes and Ketones

OMIT 11.3, 11.4, 11.5E, 11.5F, 11.5H

STRUCTURE
O C H c
3

C H

O H
3

C H

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O C H a ethrsidanyog sn
3

C H

O C H :cek nt onbthsider
3

C H

C H

C H

NOMENC ATURE Functional Group Priorities aldehyde ketone alcohol amine alkene/alkyne hydrocarbon skeleton substituents

Simple Examples

O C H mo-2penta4br o
3

C H B

C H

C H

O O H

O antriohyc2x odh c5

O H C

C H C B

O C H
2

O H C C H
2

O C H
2

C H

C H

l-4mo62 ytob 1,8-octandil

Aldehydes & Ketones With Alkenes & Alkynes 1. Name and number longest chain with highest priority pathway. 2. n-alk(adi, atri, ...)en-n-(di, tri, ...) yn-n(di, tri, ...)al/one becomes root name. 3. Number and alphabetize everything else as substituents.

Examples

OH CH CH2 C O C C CH C CH2 CH2 CH2 CH CH2 CH C O CH3

1. dec, numbered right to left 2. 3,9-decadien-6-yn-2,8-dione 3. 5-hydroxy-4-(4-pentenyl)-3,9-decadien-6yn-2,8-dione

Problem 11.3c:
OH O CH3 O CH2 CH CH

CH3 CH CH CH C

1. oct, numbered right to left 2. 5-octenal 3. 7-hydroxy-2-methyl-4-oxo-5-octenal Common Nomenclature See page 329.
O a lk y l1 alky 1 lky C 2 net a lk y l2

REACTIONS

O CH3 CH2

oxidizing CH CH3 CH2 C OH agent

Oxidizing agents: Cr6+(Na2Cr2O7), Mn7+ (KMnO4), O2(gas), any transition metal in highest oxidation state.

O C H
3

C H

C H

H 2 stlca

O H C H
3

C H

C H

O C H
3

O H C H HCN C H ydrinoca
3

C H

C H

C H C N

O C H a ldehy
3

O C H C H CH H 3 O C H mh
3

C H O H a ltc

C H

3 O

O C H C H
3

C H O C H
3

a ltc

O C H
3

C H

C
3

3 O H

O C H C H hem
3

C O H k ae

C H

k eo O C H C H
3

C H

3 O

C O C H k ae

C H
3

O C H
3

C H

H 2 O H

O H C H
3

C O H nk t teh ad

C H

Aldehydes also form hydrates.

C H C H O C H
3 2

C H O H

C H O

O H C C H
3

O C H -akeycli alcohsb t insame molecu O

3

C H

HX

O C H
3

C H

C H

C O

C H

base
3

C H C H
3

C C H
3

C H

Base-catalyzed coupling (aldehydes or ketones) known as aldol condensation. Table 1.11 (pg. 334) has aldehyde/ketone reactions.

Mechanism of Carbonyl Addition Reactions BASE CATALYZED: H-Nu

+

Base O

Base-H

Nu-

Nu- + CH3 C

CH3

O CH3 C CH3 Nu

Hi! I'm tetrahedral intermediate. I'm just gonna grab this proton and settle down for a nice nap!!

OH CH3 C Nu CH3

ACID CATALYZED:
! O! CH3 C CH3+ H-X

OH CH3 C CH3
+

+
Here's acid in yer eye buddy!!!

X-

OH CH3 C CH3 Nu

The aldol condensation is a base-catalyzed carbonyl-addition reaction. The nucleophile in this reaction is a carbanion living next door to a carbonyl group.

Remember the antisocial carbanion with the negative attitude? He doesn't like to live next door to ordinary carbon neighbors the way carbocations, radicals (cyclops), & alkenes do. Hes a snob. If he lives next door to a carbon it must be a special carbon like alkene or Billionaire Benzene. Carbanion also likes to live next door to atoms which have multiple bonds to electronegative neighbors (C=O, CN, and NO2, for example). Why does carbanion like living next to this kind of neighbors? Aside from the fact that these neighbors suck electrons and help alleviate some of carbanion's negative charge, there is another reason.

Electronegative atoms double- or triplebonded to one of carbanion's neighbors can delocalize carbanion's eyeballs into the neighbor's house.
. C H
3

. C N ! C H
3

C H

C H

N .

Being antisocial, carbanion loves to snoop on the neighbors.

. C H
3

C H

. O . C H
3

C H

!O ! . steadhol'K ie sidethmyoab t ghbor?etna '

!O ! .

O ! .

O C H
3

O C C H Base
3

C H

C HsB +

C H

+
O C H
3

H C C H

C H

C C H
3

O C H
3

H C C H O H C C H

C H C C H C H C C H

-sB O

C H

O H
3

seB

O C H
3

H C C

C H C C H

e'rWcabonyl. e' opulagnextiv n lyie.Wrak n lkengxtoiv n

The fact that carbanion likes to live next door to atoms which have multiple bonds to electronegative neighbors explains why the aldol condensation works. The lot next door to carbonyl is known as the alpha position. We can speak of alpha carbon living here or alpha hydrogen being attached to alpha carbon.

Base can easily pull off an alpha hydrogen (from aldehyde or ketone) because this leaves an alpha carbanion behind. The eyeballs on this alpha carbanion can be eaten by (bond to) the carbonyl carbon of another aldehyde or ketone molecule because carbonyl carbon has an acidic temperament. When this happens carbonyl oxygen gets to swipe all of the electrons in the carbonyl pi bond. It gets three pairs of eyeballs and a negative charge. All those luscious eyeballs on carbonyl oxygen anion are just too tempting a target for any acidic hydrogens which happen to be in the area. Carbonyl oxygen anion soon gets a proton in the face and becomes alcohol.

We now have alcohol living two doors down from carbonyl. Carbonyl likes to live next door to alkene (doesn't everybody?), so carbonyl enlists the help of some base in the area to help it make alkene neighbor. Base pulls off an alpha hydrogen which was previously living on carbon right between carbonyl and alcohol. Eyeballs of the resulting carbanion will bump into carbon bearing alcohol hydroxide group while attempting to snoop on this neighbor on opposite side of itself from carbonyl. This bump jars hydroxide loose (antisocial carbanion can be pushy) and forms the double bond.

Products of Aldol Condensations Problem 11.36. 1. Erase the carbonyl oxygen on one aldehyde/ketone molecule. 2. Remove two hydrogens from the alpha carbon of another molecule. 3. Attach this alpha carbon to the free end of the carbonyl double bond where the oxygen used to be.

Retro-aldol Analysis

Problem 11.38 1. Erase the alkene double bond which lives next door to carbonyl. 2. Place two hydrogens on the alpha carbon which was originally an alkene carbon. 3. Turn the other carbon into carbonyl.

Keto-enol tautomerism Problem 11.44(a)

O CH3 CH2 C CH2 CH3 keto form OH CH3 CH2 C CH CH3 enol form

Aldol-type Condensations Problem 11.48(a) Replace carbonyl oxygen with nitromethane carbon. Lose 2 H's from C of nitromethane CH3 NO2

H C O base

H NO2 C CH