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The Carbonyl Compounds Aldehydes and Ketones

Aldehydes and Ketones both have the general formula, CnH2nO and both contain the carbonyl group,

Aldehydes have an alkyl (or aryl) group and a hydrogen atom attached to the carbonyl carbon, whereas ketones have two alkyl (or aryl) groups attached to the carbonyl carbon atom.

Methanal, the first aldehyde, has all of its atoms lying in the same plane. All other aldehydes and ketones have the three atoms around the carbonyl carbon lying in one plane.

ALDE !DE" # at least one hydrogen atom attached to the carbonyl carbon atom $E%&'E" # ( carbon atoms attached

"ome e)amples of aldehydes and ketones are shown below * #

Nomenclature
Aldehydes + look for the longest chain of , atoms containing the carbonyl group e-uivalent alkane name and add A!
+ substituents are numbered based on the , with the & being number .. + remove E from the

$etones + look for the longest chain of , atoms containing the carbonyl group + remove E from the e-uivalent alkane name and add ONE "
+ if necessary, the position of the ,/& is given (lower number counting from one end) + substituents are numbered based on the number allocated to the , in the ,/&

#$st$ngu$sh$ng bet%een Aldehydes and Ketones


1

0ost of the reactions of Aldehydes and Ketones are similar and are due to the carbonyl functional group. %hey differ in their ability to be o&$d$sed and this is the reaction that is used to distinguish them. Aldehydes are easily o)idised to carbo)ylic acids but ketones are difficult to o)idise. %his is because aldehydes have a hydrogen atom attached to the carbonyl carbon atom but ketones do not. %he o)idising agent used to distinguish them must be mild because powerful o)idising agents can o)idise ketones by rupturing the carbon 1 carbon bond. 0ild o)idising agents will not affect ketones but will affect aldehydes.

Tollens reagent is a solution of the comple& ion 2Ag(' 3)(4 5 , and is made by adding a-ueous ammonia to a solution of s$lver n$trate. A brown precipitate of s$lver o&$de appears which redissolves in e)cess ammonia. (,omple) ions are often -uite soluble)

( Ag

5 5

(' 6'

& &

Ag( & ( 2Ag('

5 )45

&

('

Ag( &

3 (

5 (&

&

%he Ag5 in the 2Ag(' 3)(4 5 comple) ion is very easily reduced to silver metal and so when a few drops of an aldehyde are added to a few cm 3 of tollens reagent in a perfectly clean test tube and carefully warmed, metall$c s$lver is deposited on the walls of the test tube as a m$rror. $etones have no effect.

Ag'

'

Ag

A safety aspect of this particular reaction is that the product mi)ture must be disposed of as soon after the reaction as possible because %ollens 7eagent deteriorates rapidly forming an e)plosive comple).

(ehl$ng s )olut$on or *ened$ct s )olut$on is a solution containing a deep blue comple) copper (88) ion. 8n this comple) state, it is very easy to reduce the ,u(5 ion to ,u5 that is produced in the form of red insoluble copper +,- o&$de (Cu2O).

, &

( ,u(5 5 6 &

,&&

,u(& 5 (

&

9arming a mi)ture of a few cm 3 of :ehling;s solution or <enedict;s solution, to which has been added a few drops of an aldehyde, will result in the formation of a red or a green precipitate of copper (8) o)ide. $etones fail to react.

.CHO CH1CHO+l- '

'

/O0 /O0

.COOH CH1COOH+l-

#$st$ngu$sh$ng bet%een 2r$mary3 )econdary and Tert$ary alcohols


"eparate samples are warmed with a few drops of acidified potassium dichromate (=8). %he primary and secondary alcohols react showing a colour change from orange to green. %he tertiary alcohol remains uno)idised and there is no colour change. %herefore the tertiary alcohol can now be identified. %he primary alcohol is o)idised to an ALDE !DE, whilst the secondary alcohol is o)idised to a $E%&'E. %he products of these two reactions should now be separated from their mi)tures by distillation. A few 2

drops of tollen;s reagent or benedict;s solution added to the distillates and warmed should distinguish between the primary and the secondary alcohols. %he distillate from the primary alcohol will show a positive result (either a silver mirror or a red ppt) when warmed with tollen;s or benedict;s showing that an ALDE !DE had been formed as the alcohol o)idation product, whereas the secondary alcohol distillate will show no result, showing that a $E%&'E was formed as the alcohol o)idation product.

The Nature o4 the C5O bond


%he double bond between the carbon and the o)ygen atoms consists of a s$gma bond and a bond. %he difference between the bond in the alkene and in carbonyl compounds like aldehydes and ketones is that the differences in electronegativities between the carbon and o)ygen atoms makes the carbonyl double bond polar. %he o)ygen atom attracts electrons in the bond towards itself as shown in the diagram below.

Addition reactions across the double bond are a feature of the chemistry of aldehydes and ketones, but, unlike the case with alkenes where the addition is characterised by electroph$l$c add$t$on, carbonyl compounds react by nucleoph$l$c attack.

6" .educt$on o4 Carbonyl Compounds a- Hydrogenat$on


%his is e)actly the same reaction as hydrogenation of alkenes. <oth the carbon 1 carbon and the carbon 1 o)ygen double bonds are saturated in the same way by this process. %he aldehyde or ketone is vaporised and mi)ed with the correct amount of hydrogen and passed over a nickel catalyst at (>> o ,. (or platinum at 7.%.)

CH1 CO CH2 CH1


<utanone

'

H2

CH1 CH+OH- CH2 CH1


butan 1 ( 1 ol ( a "E,&'DA7! alcohol)

CH1 CH2 CH2 CHO


<utanal

'

H2

CH1 CH2 CH2 CH2 OH


butan 1 . 1 ol (a ?780A7! alcohol)

CH2 5 CH CH2 CHO '


<ut 1 3 1 enal

2 H2

CH1 CH2 CH2 CH2 OH

ALDE !DE"
whereas

are reduced to

?780A7! alcohols

$E%&'E"

are reduced to

"E,&'DA7! alcohols.

b- by react$on %$th sod$um tetrahydr$doborate +,,,- $n methanol Nucleoph$l$c Add$t$on


Na*H7 is a reagent that adds hydrogen across the double bond of a carbonyl group by nucleoph$l$c attack on the carbonyl carbon atom. %he mi)ture is then acidified and the intermediate formed is then converted to the alcohol. %his is the reverse of the o)idation reaction where the alcohol is o)idised by acidified potassium dichromate to the aldehyde or the ketone.

"ince the electron rich cloud around the double bond of an alkene would repel nucleophiles, this reagent is specific to the double bond of the carbonyl group and leaves the alkene double bond untouched.

%he mechanism involves the initial attack on the carbonyl carbon by the nucleophile,

, from the 'a<

"odium tetrahydrido borate (888) is in a-ueous or alcoholic solution. %he water provides the proton to attach onto the carbonyl o)ygen. &verall, the reaction is

'@,LE&? 8L8, ADD8%8&'.

Aldehydes form primary alcohols, whilst ketones form secondary alcohols. A similar result can be obtained if the aldehyde or ketone is first vaporised and then mi)ed with the correct volume of hydrogen and passed over a heated nickel catalyst at (>>>,. 4

'a<

will '&% attack the carboncarbon double bond in an alkene because this bond is not polar.

2" Another Nucleoph$l$c Add$t$on to Carbonyl compounds


%he carbon 1 o)ygen double bond is unsaturated and so is able to undergo add$t$on reactions. %he # electron cloud is unevenly distributed over the bond and is more concentrated over the o&ygen atom because of its electronegat$v$ty whereas it is evenly distributed over the carbon 1 carbon double bond in alkenes. A feature of the reactivity of the alkene double bond is, therefore, electroph$l$c add$t$on.

%he nature of the carbon 1 o)ygen double bond means that the initial attack on the carbonyl carbon atom is nucleoph$l$c attack on the 5 carbon atom. HCN, which is usually generated by adding dilute H2)O7 to KCN at 7.%., will produce an hydro&yn$tr$le.

( 1 hydro)ypropanenitrile ( 1 hydro)ypropanenitrile has a ch$ral or asymmetr$c carbon atom and therefore has optically active isomers. 8n fact, all aldehydes (e)cept methanal) and all ketones produce hydro)ynitriles that have optical activity. %he product formed in these reactions is not optically active, but is a racemate or a racem$c mi)ture because attack by the cyanide ion occurs on either side of the carbonyl carbon with e-ual probability (since the carbonyl group is planar).

:rom above

:rom below 5

%he hydro)ynitrile compounds can then be converted into hydro)ycarbo)ylic acids by reflu)ing them with concentrated hydrochlor$c ac$d. (see haloalkanes) H+

CH1 CH+OH-CN

CH1 CH+OH-COOH
2 8 hydro&ypropano$c ac$d or lact$c ac$d

Lactic acid found as an energy store in muscle tissue is the d 1 enantiomer and is optically active. Lactic acid made in the laboratory from ethanal is optically inactive.

,dent$4y$ng a Carbonyl compound 8 a Nucleoph$l$c Add$t$on 8 El$m$nat$on .eact$on


+ reacts with carbonyl compounds (aldehydes and ketones) + used as a s$mple test 4or aldehydes and ketones + makes orange crystalline derivatives # (,6# dinitrophenylhydraAones + derivatives have sharp3 %ell9de4$ned melt$ng po$nts + also used to character$se +$dent$4y- carbonyl compounds.

A carbonyl compound will form yellow or orange crystals with *.A#: ) (,6#dinitrophenylhydraAine and is, itself, an orange solution in ethanol.

.EA;ENT

which is

%he first initial reaction is an addition reaction of the (,6#dinitrophenylhydraAine to the carbonyl group. %his is then followed by an elimination reaction where a molecule of water splits off from the adBacent C,; and C'; atoms leaving a ,/' double bond. %he product is a dinitrophenylhydraAone.

H CH3C O :NH2 NH2

NO2 NO2

addition

H CH3C NH NH2 OH

NO2 NO2

elimination H2O

H CH3C N NH2

NO2 NO2 + H2O

ethanal 2,4 dinitrophenylhydrazone 6

%his reaction is used to tell if the compound is an aldehyde or a ketone, but it cannot be used to distinguish between the two. :or this, a further test such as *ened$ct s Test3 or Tollen s .eagent, or ac$d$4$ed 2otass$um #$chromate +<,- is re-uired. (see p (). %he production of orange or yellow crystals with (, 6 1 dinitrophenylhydraAine shows that the compound being test is E,THE. and aldehyde or a ketone. %he aldehyde or ketone (, 6 1 dinitrophenylhydraA one product can then be used to actually identify the e)act aldehyde or ketone it has been derived from. Every aldehyde or ketone (, 6 1 dinitrophenylhydraA one product has its own specific melting point and, because these compounds can be very easily recrystallised from ethanol and obtained in a high state of purity, their melting points can be determined very accurately and can be used to identify the original carbonyl compound with a high degree of certainty. %he products can also be used to determine which isomer is obtained. :or E)ample, the three isomeric chlorophenylmethanals below have very similar van der 9aal;s forces between their molecules and therefore very similar boiling points. %he (, 6, dinitrophenylhydraAone products have -uite widely differing melting points and so the three compounds can be readily recognised.