B. Sc I June 2008: New syllabus: UNIT 5 Carboxylic acids and their derivatives [7]

Transcription

1 B. Sc I June 2008: New syllabus: UNIT 5 arboxylic acids and their derivatives [7] 5.1 Monocarboxylic acids: Introduction, Method of formation of halo acids, mono-, di- and trichloroacetic acids. Substitution reactions of monochloroacetic acids by nucleophiles N-, -, I- and N3 5.2 ydroxy acids: Malic acid and citric acid. Methods of formation of maleic acid from maleic acid, from bromo succinic acid and moist Ag2. Reactions of malic acid- action of heat, oxidation and reduction with I. Uses of Malic acid. Method of formation of citric acid from glycerol. Reactions of citric acid- acetylation by acetic anhydride, reduction by I and action of heat at 422K. Uses of citric acid. 5.3 Unsaturated acids: Acrylic acid and innamic acid. Methods of formation of acrylic acid from acrolin and by dehydration of P hydroxy Propionic acid. Reactions of acrylic acid addition of 2, reduction by Na/25. Uses of acrylic acid. Methods of formation of cinnamic acid from benzaldehyde using diethyl malonate and by using acetic anhydride and sodium acetate. Reactions of cinnamic acid - Bromination and oxidation. Uses of cinnamic acid. 5.4 Dicarboxylic acids: Succinic acid and Phthalic acid. Methods of formation of succinic acid from ethylene bromide, maleic acid Reactions of succinic acid:- action of heat, action of Na3, 25 in presence of acid. Uses of succinic acid. Method s of formation of Phthalic acid from o-xylene, naphthalene. Reaction of phthalic acid- action of heat, reaction with sodalime, N3. Uses of phthalic acid. 5.5 arboxylic acid derivatives:- Acetyl chloride and Acetic anhydride. Acid halide derivative:- acetyl chloride: methods of formation from acid by action with Pl5 and Sl2. Reactions with 2, alcohol and N3. Uses of acetyl chloride. Acid unhydride derivative:- Acetic anhydride: Method of formation by dehydration of acetic acid. Reactions with 2,alcohol and N3. Uses of acetic anyhydride. nline notes on

2 1. Introduction: lassification of acids carboxylic acids Aromatic acids Phthalic acid innamic acid Monocarboxylic acids Saturated acids Dicarbo. acids Aliphatic acids Unsaturated acids Acrylic acid succinic acid Tricarbo. acids Polycarbo. acids Substituted acids Unsubstituted acids At alkyl group alo- ydroxyaminoetc. eg. mono/di/tri- hloroacetic acid malic acid citric acid At carboxylic part Derivatives of acids Amides Acid halides Acid esters Unhydrides Acetyl chloride Acetic unhydride lassification of AIDS 2. hemistry of : mono, di and tri chloroacetic acid ydroxy acids: Malic acid and citric acid. Unsaturated acids: Acrylic acid and innamic acid Dicarboxylic acids: Succinic acid and Phthalic acid arboxylic acid derivatives:- Acetyl chloride and Acetic anhydride Mono carboxylic acids These are having only one - group. aloacids are halogenated derivatives of monocarboxylic acids where one is replaced by halogen.eg. chloroacetic acid. nline notes on

3 The haloacids are further divided into alpha, beta, gamma halo-acids, depending on the position of the halogen. l- alphachloroacetic acid Br Beta bromo propionic acid Br gamma bromo butanoic acid Also the halo-acids are classified as mono- di- tri- halo acids depending on the number of halogen atoms. hemistry of monochloroacetic acid l 3 acetic acid l 2 ethylene chlorohydrin l l trichloroethylene l 2, hv red P VZ () N 3 hemistry of chloroacetic acid 2 90 % S 4 l chloroacetic acid KN Na KI 2 N 3 Dichloroacetic acid: N cyanoacetic acid I N Kl hydroxy acetic acid iodo-acetic acid amino acetic acid N 4 l Nal Kl 3 2 l 2 VZ K, hv, red P 373 l 2 dichloro acetic acid l l a [l 3 2 ] 2 a al l S 4 -as 4 chloral hydrate Trichloro acetic acid l 3 3 l 2 VZ K, hv, red P 373 l 3 trichloro acetic acid () l l chloral nline notes on

4 ydroxy Acids : 1.Malic Acid Maleic acid Fumaric acid Maleic acid Dehydration heat ydroxy acids: Malic Acid dil. S 4 Maleic unhydride Malic acid reduction I Succinic acid Br Ag a-bromo succinic acid oxidation oxal acetic acid ydroxy Acid : 2. itric Acid itric acid: 3-carboxy,3-hydroxy,pentan-1,5-dioic acid 1. Preparation from Glycerol: l 2 l l [] N 3 l 2 l dichloroacetone glycerol 3-hydroxy, 1,3 dichloro propane N citric acid N N N 1,2,3 tricyano 2-hydroxy propane KN l l N 1,2 dichloroacetone cyanohydrin nline notes on

5 2. By Reformatsky reaction: Et Et Br Et Zn ether BrZn Et Et xaloacetic acid ethyl bromo acetate Et dil l ydrolysis citric acid B] Reactions of itric acid: Ac Ac 2 Acetylation acetyl citric acid citric acid I reduction dehydration heat 423K - tricarballylic acid aconitic acid nline notes on

6 Unsaturated acid: 1.Acrylic Acid Unsaturated acids: Acrylic acid methods of preparation 2 2 () AgN Acrolein 3 /N 4 Znl 2 /- 3-hydroxy propionic acid 2 propionic acid Acrylic Acid gs 4 / S 4 Na/Et reactions Unsaturated acids: innamic acid hydroxy propionic acid Unsaturated acid: 2.innamic Acid (Et) 2 diethyl malonate Pyperidine/- 3 3 Acetic unhydride 373K, 3 Na Knoevenagel condensation Perkin's Reaction 3 innamic Acid Reactions Br 2 () KMn 4 Br Br benzaldehyde Benzoic acid dibromocinnamic acid nline notes on

7 Dicarboxylic Acid: 1.Succinic Acid Br Br dibromoethane dicarboxylic acids: Succinic Acid 1. KN 2. Ni maleic acid eat succinic unhydride 3 Succinic Acid Na Na Na Na 3 disodium succinate 2Et 2 Na 3 2 Dicarboxylic Acid: 2.Phthalic Acid dicarboxylic acids: Phthalic Acid Et Et diethyl succinate V 2 5 o-xylene K () Naphthalene eat phthalic unhydride Phthalic acid benzene 4Na 2Na N 3 N phthalimide nline notes on

8 Acid Derivatives: arboxylic acid derivatives R RR' RR Rl RN Esters unhydrides acid chlorides Amides 3 1/3 Pl 3 Acetyl chloride 3 Sl 2-3 P 3 -S 2, -l 3 l Acetyl chloride N 3 -l Et -l -l 3 3 N 3 Et acetic acid ethyl acetate acetamide Acetic unhydride 3 Acetic acid Acetic unhydride Et N 3 3 Acetic acid 3 Acetic acid 3 Et Ethyl acetate 3 N acetamide 3 3 Acetic acid Acetic acid nline notes on