Carboxylic Acid Questions

1.-Arrange the following in order of (i) increasing acidity, (ii) increasing pKa (a) C!"C#$! (c) C!"C!$#! (b) CCl"C#$! (d) C!"C!$%!

$.-&hat would be the 'a(or products of the reactions of (i) butanoic acid and (ii) ben)oic acid with each of the following (a) %#Cl$, *t"+ (b) ,iAl!- . /!0 then acidic wor1-up (d) +a#! (c) (C!")$C!#! . !2 . heat ".-!ow could you use 1-bro'obutane to prepare each of the following carboxylic acids 3 (a) propanoic acid (b) butanoic acid (c) pentanoic acid (d) hexanoic acid

Carboxylic Acid Answers

1 (i) increasing acidity C!"C!$#! 4 C!"C!$%! 4 C!"C#$! 4 CCl"C#$! 5esonance stabili)ation in carboxylates 'a1es carboxylic acids 'ore acidic than alcohols or thiols. *lectron withdrawing groups, here -Cl, increase the acidity due to further stabili)ation of the carboxylate. /hiols are 'ore acidic than alcohols due to wea1er 6-! bond and the ability of % to acco''odate extra electrons (si)e). (ii) increasing pKa CCl"C#$! 4 C!"C#$! 4 C!"C!$%! 4 C!"C!$#! 5e'e'ber the lower the pKa the stronger the acid, so once you ha7e part (i), this is (ust the opposite. Tip &hen as1ed about pKa trends, it 'ay be easier to thin1 in ter's of acidity then re'e'ber to flip the order. +ote the identical nature of the reactions that the aliphatic and aro'atic acid undergo

(a) /hionyl chloride, %#Cl$, is used to prepare acyl chlorides, the base re'o7es the !Cl by-product. (b) ,iAl!- is a hydride reducing agent, acids to pri'ary alcohols. (c) An alcohol and a carboxylic acid gi7e an ester. (d) Carboxylic acids react with bases to gi7e carboxylates. " 0irst, note that we ha7e an ho'ologous series of C" to C8 acids we are trying to 'a1e. !ere is a sche'e collecting possible syntheses together (based on the 'ore i'portant reactions)

(a) Propanoic acid need to lose a C fro' C-. &e can do this 7ia o)onolysis of an al1ene, which we can obtain by eli'inating the al1yl halide. (b) Butanoic acid oxidation of the corresponding alcohol will gi7e the carboxylic acid, so prepare the alcohol by substitution.

(c) Pentanoic acid need to gain a C to get C9. #ne way to do this is 7ia the reaction of the :rignard reagent with carbon dioxide. Alternati7ely, substitution with +aC+ then hydrolysis would also wor1. (d) Hexanoic acid need to gain $C to get C8. 5eaction of the :rignard reagent with ethylene oxide gets the right nu'ber of C and a pri'ary alcohol ready for oxidation to the acid.

More questios..

4:

Arrange the following in order of decreasing reactivity towards hydrolysis

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using aqueous NaOH. (a) CH3CO CH3 (!) CH3COCl (c) CH3CON(CH3) (d) CH3CO COCH3 #hat are the $roducts of the hydrolysis reactions considered in %u & after a dilute acid wor'(u$ ) (a) Arrange the following in order of decreasing reactivity towards +iAlH 4 , -H. followed !y dilute acid wor'(u$.

*:

(!) #hat are the $roducts of each of the reactions in $art (a) ) /: #hat is the $roduct of each of the following reactions )

Answers:

4:

Hydrolysis is a nucleo$hilic acyl su!stitution reaction0 ty$ical of car!o1ylic acid derivatives.

.irst tas' should !e to identify the functional grou$s in each 2olecule then use the reactivity order. 3t can !e rationalised !ased on (i) the interaction of the substituent and the car!onyl grou$0 and0 (ii) the a!ility of the substituent to function as a leaving grou$. CH3COCl CH3COOCOCH3 CH3COOCH3 CH3CON(CH3) 4 4 4 acid anhydride ester a2ide chloride ": All the car!o1ylic acids in %u & are derivatives of ethanoic acid0 so they all give the sa2e car!o1ylic acid... (a) CH3CO H (c) CH3CO H and CH3OH (!) 2oles CH3CO H (d) CH3CO H and HN(CH3)

*: +iAlH4 is a source of H( (a nucleo$hile) which functions as a reducing agent. .irst tas' should !e to identify the functional grou$s: car!o1ylic acid0 'etone0 aldehyde0 ester. -he aldehyde and 'etone will undergo nucleo$hilic addition0 the acid and the ester nucleo$hilic acyl su!stitution. Consider the electro$hilicity of the car!onyl grou$ in each co2$ound in each $air. Aldehydes are 2ore reactive than 'etones 555 as they are less hindered and the al'yl grou$ in the 'etone is a wea' electron donor. 6nder the reaction condition s the car!o1ylic acid will de$rotonate to give the car!o1ylate which is a very $oor electro$hile (after all0 it has a negative charge 5) so the ester is 2ore reactive than the acid. Now co2!ine the two $airs. 7ince the (O8 grou$ is a stronger electron donor (resonance) than the al'yl grou$ of the 'etone0 the ester is less reactive than the 'etone... so we get :

(!) -he aldehyde0 car!o1ylic acid and ester will !e reduced to the sa2e

$roduct0 !en9yl alcohol. -he 'etone will !e reduced to &($henylethanol0 C*H"CH(OH)CH3

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-he answers the these questions involve 2aterials fro2 this cha$ter and review fro2 cha$ters &: and &;