Derivative of carboxylic acids (1) Acid halide Nomenclature باستبدال حرف e من اسم alkane بـ oyl halide alkanoyl halide Alkane - أو من اسم الحمض باستبدال ic بـ yl chloride

Preparations Chemical reactions

Acid anhydride (2) Reaction of acid chloride with R-MgX Hell volhard zelinski Acid anhydride (2)

Preparation التسمية تتم بذكر اسم الحمض متبوعاً بكلمــة anhydride ( 1 ) From acid chloride

From acetylene (2) From ketene (3)

Chemical reactions Amide (3) التسمية تتم بذكر اسم alkane محذوفاً منه حرف e واستبداله بـ amide أو اسم الحمض محذوفاً منه oic واستبدالها بـ amide

Preparation of amides From acid chloride, anhydride, ester (1) From nitriles (2)

Chemical reactions From ammonium salt ( 3 ) Hydrolysis ( 1 ) Hofmann degradation of amide ( 2 )

الإجابـة Q. Convert acetic acid to methyl amine Dehydration ( 3 ) ( 4 ) Action of nitrous acid

Esters (4) - التسمية تتم كالآتي:- 1- ذكر اسم R` 2- ذكر اسم الحمض محذوفاً منه -ic ومضافاً اليه ate

Ortho ester Fats esters e.g.

Preparation

Reactions of esters Reaction with Grignard to form t-alc

Mechanism Claisen condensation of ester

Mechanism

Substituted products of monocyclic acids 1. Halogenated acids تقسم الى α ، β ، γ ، δ على حسب موقع الهالوجين. Preparation of α-halo acid Hell-Volhard-Zelinski reaction

preparation of β-halogenated acid Iodo derivative can be prepared as follow 2. From α-hydroxy acid preparation of β-halogenated acid لاحظ الإضافة تتم عكس قاعدة ماركنكوف في حاله اتصال سلسله alkene بمجموعه الدهيد أو كيتون أو -COOH

Effect of NaOH on Halogenated acids 1. Effect of NaOH on α-Halo acid 2. From hydroxy acid Preparation of γ-Halogenated acid Reactions of Halogenated acid Effect of NaOH on Halogenated acids 1. Effect of NaOH on α-Halo acid 2. Effect of NaOH on β -Halo acid

(B) Hydroxy acids - تقسم الى α ، β ، γ ، δ على حسب موقع OH 3. Effect of NaOH on γ – and δ-Halo acid (B) Hydroxy acids - تقسم الى α ، β ، γ ، δ على حسب موقع OH - أسماء يجب حفظها

Preparation of Hydroxyacids From halogenated acid 2. From aldehyde or ketones

2) Preparation of β-hydroxy acid Reformatsky reaction 3) Preparation of γ & δ-hydroxy acids

Chemical reactions Action of heat 1- α-hydroxy acid 2- β-hydroxy acid

3- γ-hydroxy acid or δ-hydroxy acid 2) Action of PCl3 3) Reduction with HI

(C) Amino acids Preparation of amino acids

(2) Streacker’s synthesis (3) Gaberial synthesis Gaberial synthesis can be used for synthesis amino acids & amines a) For synthesis of amino acids e.g. Glycine

Reaction of amino acids Question: Convert Phthalimide to Glycine ? Reaction of amino acids 1) Amphoteric character of amino acid Amino acids are amphoteric because it contains both acidic –COOH group and basic group –NH2 , thus it is present in an inner salt (B) which is called Zeitter ion In acidic medium it exist in (C) In basic medium it exist in (A) Isoelectric point of amino acid It is the pH at which the amino acid exists as the inner salt (B)

2) Reactions of amino group a) Conversion to hydroxy acid b) Acetylation

3) Effect of heat 1- α-amino acid 2- β-Amino acid

3- γ- Amino acid or δ- Amino acid Dicarboxlic acids Examples

General methods of preparation of dicarboxylic acids:- oxidation of glycols: 2. hydrolysis of dinitriles:

Special methods: Oxalic acid: Heating sodium formate: 2. By passing dry CO2 over sodium metal heated to 360°

3. By the oxidation of sucrose with conc. HNO3 in the presence of V2O5. Malonic acid:

Preparation of diethylmalonate: Diethylamalonate is much more important than the acid.

Succinic acid can also be prepared by reduction of malic and tartaric acids with HI and red P.

Glutaric acid: By the action of methylene iodide on ethylmalonate.

2. Oxidative fission of cyclopentanone with nitric acid in the presence of V2O5. Adipic acid: Catalytic air oxidation of cyclohexane obtained from petroleum.

Phthalic acid:- 2. Oxidative fission of cyclohexanol or cyclohexanone by nitric acid at 30-40°. Phthalic acid:- Is prepared by the catalytic oxidation of naphthalene or o-xylene

Reactions: Dicarboxylic acids show the same characteristic reactions as monocarboxylic acids. 2. Effect of heat :b) Malonic acid acids of the type where X is strongly electron attracting (e.g. –COOH, -CONH2, -COOR, -COR, -CHO, -CN, -NO2) lose CO2 even on mild heating.

(C) Succinic and glutaric acids yield the corresponding cyclic anhydrides. Heating adipic acid with Ba(OH)2, MnCO3 or the O2 give cyclopentanone.

Unsaturated and substituted acids (e) Phthalic acid form phthalic anhydride on heating at 200°. Unsaturated and substituted acids Nomenclature: Ordinary methods of nomenclature can be applied to substituted acids, but many acids have trival names.

Preparation: Maleic acid: (a) Rapid heating of malic acid to about 250°. (b) Catalytic air oxidation of benzene at 400°.

2. Fumaric acid and malic acid: (c) Air oxidation of crotonaldehyde. 2. Fumaric acid and malic acid:

3. Tartaric acid: (2) from dibromosuccinic acid : Cyanohydrin synthesis from glyoxal (1) (2) from dibromosuccinic acid

4. Citric acid: (3) Oxidation of maleic acid with neutral KMnO4 1- From 1,3-dichloroacetone:

Reactions: 1,3-Dichloroacetone can be prepared by treating glycerol with HCl followed by oxidation. Reactions: 1- Addition of HX to α,β-unsaturated acids give β-haloacids.

2- Diels-Alder Reaction.

3- Heating tartaric acid gives pyruvic acid. 4- Heating citric acid to 175oC gives aconitic acid.

5. Reduction of tartaric acid with HI. 6- Citric acid loses water and CO on treatment with H2SO4 giving acetone dicarboxylic acid which on strong heating decomposes into acetone and CO2.

Preparation of urea: 1. Urea may be obtained by the action of ammonia on ethyl carbonate of phosgene 2- Partial hydrolysis of cyanamide with dilute H2SO4 at 70.

3- Reactions of urea: 1- Urea is a very weak base. By accepting a proton on the oxygen atom, urea forms a positive ion which is stabilized by resonance.

2- Hydrolysis: urea undergo hydrolysis in acid or alkaline solutions or in water in the presence of the enzyme urease present in soya beans. 3. Reaction with nitrous acid 4. reaction with acid chlorides

5- Reaction with hypobromite. 6- Reaction with malonic ester (Synthesis of barbituric acid).

Barbital, 5, 5-diethylbarbituric acid, is hypnotic. For their synthesis a disubstituted malonic ester is condensed with urea.