a)From Nlries: Hydrolysis of nitriles with acid or base to form carboxvlic acids.
Propanoic acid
ЫВу Hydrolvsisofestert Esters.on bolling with alkali give the correspondinq salt of the aciд Whch on treatment with acid gives carЬохуlс acia. Carbonation of arignard reagents:Grignard reagents react w CO₂followed by hydrolysis gives carboxylic acids.
If R=C₂Hs,X=Cl
d)By the hydrolysis of Amides:Hydrolysis of Amides gives carboxylic acids.
Aromatic acids: .By oxidation of Alkyl benzenes:Oxidation of an alkyl group attached to benzene nucleus hich will be oxidised to-COOH group in the presence of alkaline KMnO4(or)acidified K₂Cr₂O₇ respective of the size of the alkyl group.
R=Any Alkyl group
2iv s carbo y ecileacids alosen derhvatvs:Hwaro yi eftt hsegen daaan A
3.Kolbe's reaction:Phenol reacts with CO₂and NaOH at 125°C and 6-7 atm pressure gives salicylic acid,is called kolbe's reaction.
Physical properties: 1.Carboxylic acids upto 3.Carbons are colourless,pungent smelling liquids. 2.Acids upto 4 carbons are freely soluble in water.due to Hydrogen bonding with water mol-
ecules.
"
"-- · Inter molecular
-- -H-bond
3.Lower members shows higher B.P S,than Higher members,due to the fact that hydrogen
bonding and they exist as dimers
f c r lic s 4.Acidity a : atCtyaa oidxsy are w ak acids as compared to inorganic acids.The acidic carboxvlicaridc ic due to resonance in the acidic group which imparts electron deficiency character of охудеп аtот ofthоNублохиогоно.dueгоIhб Нуагодеп аЕот оГтпе О-Н дгоир Лб еПп Proton and carbоxylate onls formea Which is staЫШsеа Ьу гебопапсє»
з.Itis important to note that carboxylc acids are stronger than alcohol because alkoxide t. fогmed bythe removal proton in alcoholls not stabiised by resonance.
-H Ф Р ——СОО Carboxylate ion —- Resonance is there R —СООН
R—OH— - р —сЭ Alkoxide ion No Resonance Strength ofthe acids- affecting factors: 1. Electron wlthdrawing groups (-1.E) increases the acidlty of carboxyllc acids, electron relez. ing groups decreases the acidity.
2. As the +l.E groups increases on carboxylic acid group decreases aciditv. This is due to
electron density on охуgen increases.
З. As the -1.E groups lncreases acldlty lncreasess. due to decrease the electron denslty 0
охудеп а(от. acefie aeid Due to resonance (-M.E)Aromatic carboxylic acids are stronger than aliphatic carboxylic acids,
uike Aliphatic,Aromatic acids acidity also increased by electron with drawing groups
(-NO₂,—Cl,—SO₃H … … hemical properties; Reactions involving H-atom of-COOH group:Carboxylic acids reacts with metals and bases form metal carboxylates
2)
3)
Benzoic acid
Reactions involving-OH part of the-COOH groupi
Esterification:Carboxylic acids react with Alcohols In the presence of Anhydrous ZnCl₂(or onc.H₂SO₄(or)dry HCl gas to form esters.This reactlon Is known as esterificatlon Mechanism:
2.Reaction with PCls,SOCl₂ :Carboxylic acids react with PCls,SOCl₂to form acid chlorides
1) 3,Reaction with Ammonia:Carboxylic acids react with Ammonia to form Amides.
Note:Acetamide which on heating with F2Os to give methyl cyanide
4,Formation of Anhydrides;Heating of two moles of carboxylic acids in the presence of
BO t Reclueton Rre i of -ccaor-hgor yulipc aciwidoslvwinit Li elaHc₄ nie :yl either gives primary alcohole (
Bouveault -Blanc reduction:Reduction of esters with Na in alcohol gives Alcohols.
Hunsdiecker reaction:A heavy metal (Ag.Hg.Pb)salt of a carboxylic acids heated with
bron or iodine gives an alkyl halide with one carbon less than the starting carboxylic acid.The read is called Huns diecker's reaction.
Schmidt reaction:Carboxylic acids reacts with hydrazoic acid in the presence of
Conc.H,SO give 1⁰-Amines.is known as schmidt reaction.
Mechanism: rndt-Eistert Аса сМопае гёасЕ иШ аатотеШапе дуеб Дахокаюпе уМсолклсНопмМкуа оtхnдoе з sп Еr-nЄdЫt-е зisуt tадsуyеnзthe аlsгЬохуlс aсd опе сагЬоп Nghertnan saruпд опеi wIh
Mechanism!
Наloaenatiom: нa- vоlhaгa - 2elenskу reaction (НУ2): Мопо сагЬохуIс aсds гeaсts иtп СЪ(ог)Врп гпе ргезепсе оГВед- рПобрПогоиб lo form a—Halo substtuted product. Ths reacton ls kпоvп аз НУ2-геасНоп
Trichloro acetic acid
a, c—dichloro propanoic acid
Reactons of Acid Haldes ,кацу оя,даТ 1.Acylation;Acid chlorides are important acylating agents for compounds naving -UH,、 -NH₂&-NHR groups.During acylation hydrogen atom of these groups is replaced by group.
Acetyl salicylic acid (Aspirin)
2.Reduction:Acetyl chloride reduced to Acetaldehyde in the presence of Pd /BaSO4
and alcohol in the presence of LiAlH4.
3.Frie el - Craft's e act o n:
r i Benzene reacts with Acetyl chloride in the presence of Anhyd A IC l ₃ t give A cet o p hen o ne
Acetophenone Reactions of Acetic anhydride CHg C— CH₃ 1.Acylation:When acetic anhydride reacts h these groups is substituted by acyl 2.Benzene reacts with Acetic anhydride in.the presence of AlCl₃gives Acetophenone.
3.Reaction with PCls:
Acetic anhydride reacts with PCls to form Acetyl chloride.
peelons of Aetamide 1.Hvdrolvsis:Hydrolysis of Acetamide in the presence of Acid /Base to form Acetic acid and Ammonia,
2.Dehydration:Dehydration of Acetamide with.R2Os gives methyl cyanide
Acetam ide r eacts wi
th Brz and KOH to form methy/amiht which contain one carbon atom less t han theparen t amide Reactions of ester(Ethyl acetate -CHʒ-COOC₂ H₅) 1.Claisen condensation reaction:Two moles of ethyi acetate react with sodium ethoxidey orm Acetoacetic ester is called claisen condensation reaction
ec hanis
C₂H₅OH+Na C,H₂ ONa C₂ H₅δN³
Aceto acetic est
Hydrolysis of ester: 1.Ester hydrolvsis by an acid /Acidic hydrolysis:Hydrolysis of ethyl acetate in the presem of an acid gives acetic acid and ethyl alcohol.
Mechanism: alcohol. yi acetate reacts with NaOH to form sodium acetate and Ethyl
Mechanism:
Gr 3.Re a ign rea gre act wi t h g rigna rd reagent to form ketone w hen excess reagent is used followed by hydrolysisgive3 0 -Alc o hol
Reformatsky reaction := Carbonyl compounds reacts with a-haloesters in the presence of zinc metal to form β- hydroxy esters. Organo zinc intermediate
Curtius rearrangement :- Acid chloride reacts with sod-azide to form acyl azide which on rearrangement to isocyanates,on furture reaction gives amines.
