Derivative of carboxylic acidsDerivative of carboxylic acids( ( 11 ) )Acid halideAcid halide

NomenclatureNomenclature بـ alkanealkane من اسم من اسمeeباستبدال حرف باستبدال حرف -

oyl halideoyl halide alkanoyl halidealkanoyl halide AlkaneAlkane

باستبدال - الحمض اسم من باستبدال أو الحمض اسم من yl chlorideyl chlorideبـ ic أو

PreparationsPreparations

Chemical reactionsChemical reactions

Reaction of acid chloride with RReaction of acid chloride with R--MgXMgX

Hell volhard zelinskiHell volhard zelinski

H3CH2C C

O

Cl

propionyl chloride

Cl2

PH3C

HC C

O

Cl

Cl

Acid anhydride Acid anhydride )2()2(

التسمية تتم بذكر اسم الحمض متبوعا� التسمية تتم بذكر اسم الحمض متبوعا� - anhydrideanhydrideة ة ــــبكلمبكلم

PreparationPreparation ( (11 ) ) From acid chlorideFrom acid chloride

From acetyleneFrom acetylene )2( )2(

From From keteneketene )3()3(

Chemical reactionsChemical reactions

AmideAmide )3( )3(

e محذوفا� منه حرف alkane التسمية تتم بذكر اسم - oicأو اسم الحمض محذوفا� منه amideواستبداله بـ amide واستبدالها بـ

Preparation of amidesPreparation of amidesFrom acid chloride, anhydride, esterFrom acid chloride, anhydride, ester )1( )1(

From nitrilesFrom nitriles )2( )2(

From ammonium saltFrom ammonium salt ) 3 ( ) 3 (

Chemical reactionsChemical reactions

HydrolysisHydrolysis ) 1 ( ) 1 (

Hofmann degradation of amideHofmann degradation of amide ( 2 )( 2 )

Q. Convert acetic acid to methyl amine

اإلجابـةاإلجابـة

DehydrationDehydration ) 3 ( ) 3 (

( ( 44 ) ) Action of nitrous acidAction of nitrous acid

EstersEsters )4( )4(

:-:-التسمية تتم كاآلتيالتسمية تتم كاآلتي- - ̀`RR ذكر اسمذكر اسم- - 11 ateate ومضافا� اليهومضافا� اليه icic-- ذكر اسم الحمض محذوفا� منهذكر اسم الحمض محذوفا� منه- - 22

Ortho esterOrtho ester

Fats esterse.g .

PreparationPreparation

4) CH3COOAg + C2H5Br CH3COOC2H5 + AgBr

5) RCOOH + CH2N2 RCOOCH3 + N2

6)H2C C O + C2H5OH CH3COOC2H5

7) CHCl3 + C2H5ONa CH(OC2H5)3

Reactions of estersReactions of esters

Reaction with Grignard to form t-alcReaction with Grignard to form t-alc

MechanismMechanism

Claisen condensation of esterClaisen condensation of ester

MechanismMechanism

Substituted products of monocyclic acidsSubstituted products of monocyclic acids11 . .Halogenated acidsHalogenated acids

على حسب موقع الهالوجين. على حسب موقع الهالوجين.αα ، ، ββ ، ، γγ ،، δδتقسم الى تقسم الى

Preparation of α-halo acidPreparation of α-halo acid

1.1. Hell-Volhard-Zelinski reactionHell-Volhard-Zelinski reaction

Iodo derivative can be prepared as follow

2. From 2. From α-hydroxy acidα-hydroxy acid

preparation of preparation of β-halogenatedβ-halogenated acid acid

alkenealkene سلسله سلسله اتصالاتصالالحظ اإلضافة تتم عكس قاعدة ماركنكوف في حاله الحظ اإلضافة تتم عكس قاعدة ماركنكوف في حاله - COOHCOOH--أو أو الدهيد أو كيتونالدهيد أو كيتون بمجموعهبمجموعه

2. From hydroxy acid2. From hydroxy acid

Preparation of γ-HalogenatedPreparation of γ-Halogenated acid acid

CH2=CH-CH2COOH + HBr BrCH2CH2CH2COOH

Reactions of Halogenated acidReactions of Halogenated acid

Effect of NaOH on Halogenated acids1 .Effect of NaOH on α-Halo acid

ClCH2COOH +NaOH HOCH2COONa

2 .Effect of NaOH on β -Halo acid

ClCH2CH2COOH +NaOH CH2=CHCOOHAcrylic acid

3. Effect of NaOH on γ – and δ-Halo acid

)B( Hydroxy acids)B( Hydroxy acids OH على حسب موقع α ، β ، γ ، δتقسم الى -

أسماء يجب أسماء يجب - -حفظهاحفظها

Preparation of HydroxyacidsPreparation of Hydroxyacids

11 ) )Preparation ofPreparation ofαα-hydroxy acid-hydroxy acid 1.1. From halogenated acidFrom halogenated acid

2. From aldehyde or ketones2. From aldehyde or ketones

OOH OH

CH3CH +HCN CH3CH-CNH3O

+

CH3CH-COOH

Lactic acid

2( Preparation of 2( Preparation of β-hydroxy acidβ-hydroxy acid Reformatsky reaction

33)) Preparation of Preparation of γγ & & δδ-hydroxy acids-hydroxy acids

Chemical reactionsChemical reactions

1(1( Action of heatAction of heat1- 1- α-hydroxy acidα-hydroxy acid

2- 2- β-hydroxy acidβ-hydroxy acid

3- 3- γ-hydroxy acid or δ-hydroxy acidγ-hydroxy acid or δ-hydroxy acid

2( 2( Action of PCl3Action of PCl3

3( Reduction with HI3( Reduction with HI

)C( Amino acids)C( Amino acids

Preparation of amino acidsPreparation of amino acids

)2( Streacker’s synthesis)2( Streacker’s synthesis

)3( Gaberial synthesis)3( Gaberial synthesis

Gaberial synthesis can be used for synthesis amino acids & aminesa( For synthesis of amino acids e.g. Glycine

Question: Convert Phthalimide to Glycine?

Reaction of amino acidsReaction of amino acids11 ) )Amphoteric character of amino acidAmphoteric 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)

22 ) )Reactions of amino groupReactions of amino group

a( Conversion to hydroxy acid

b( b( AcetylationAcetylation

33 ) )Effect of heatEffect of heat

1- 1- α-amino acidα-amino acid

2- 2- β-Amino acidβ-Amino acid

3- 3- γ- Amino acid or δ- Amino acidγ- Amino acid or δ- Amino acid

Dicarboxlic acidsDicarboxlic acids

ExamplesExamples

General methods of preparation of dicarboxylic acids:-General methods of preparation of dicarboxylic acids:-

1.1.oxidation of glycols:oxidation of glycols:

2. hydrolysis of dinitriles:2. hydrolysis of dinitriles:

Special methods:Special methods:Oxalic acid:Oxalic acid:

1.1.Heating sodium formate:Heating sodium formate:

2. By passing dry CO2 over sodium metal heated to 360°2. By passing dry CO2 over sodium metal heated to 360°

3. By the oxidation of sucrose with conc. HNO3 in3. By the oxidation of sucrose with conc. HNO3 in the presence of V2O5.the presence of V2O5.

Malonic acid:Malonic acid:

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

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

Glutaric acid:Glutaric acid:1.1. By the action of methylene iodide on ethylmalonate.By the action of methylene iodide on ethylmalonate.

2. Oxidative fission of cyclopentanone with nitric acid in 2. Oxidative fission of cyclopentanone with nitric acid in the presence of V2O5.the presence of V2O5.

Adipic acid:Adipic acid:1.1.Catalytic air oxidation of cyclohexane obtained from petroleum.Catalytic air oxidation of cyclohexane obtained from petroleum.

2. Oxidative fission of cyclohexanol or cyclohexanone 2. Oxidative fission of cyclohexanol or cyclohexanone by nitric acid at 30-40°.by nitric acid at 30-40°.

Phthalic acid:-Phthalic acid:-Is prepared by the catalytic oxidation of naphthalene or o-xyleneIs prepared by the catalytic oxidation of naphthalene or o-xylene

Reactions:Reactions:1.1.Dicarboxylic acids show the same characteristic reactionsDicarboxylic acids show the same characteristic reactions

as monocarboxylic acids.as monocarboxylic acids.

2. Effect of heat2. Effect of heat

::b( Malonic acidb( Malonic acid acids of the typeacids of the type

where X is strongly electron attractingwhere X is strongly electron attracting )e.g. –COOH, -CONH)e.g. –COOH, -CONH

22, -COOR, -COR, -CHO, -CN, -NO, -COOR, -COR, -CHO, -CN, -NO22( (

lose COlose CO22 even on mild heating. even on mild heating.

)C( Succinic and glutaric acids yield the corresponding )C( Succinic and glutaric acids yield the corresponding cyclic anhydrides.cyclic anhydrides.

Heating adipic acid with Ba)OH(2, MnCO3 or the O2 give Heating adipic acid with Ba)OH(2, MnCO3 or the O2 give cyclopentanone.cyclopentanone.

)e( Phthalic acid form phthalic anhydride on heating at 200°.)e( Phthalic acid form phthalic anhydride on heating at 200°.

Unsaturated and substituted acidsUnsaturated and substituted acids

Nomenclature:Nomenclature:

Ordinary methods of nomenclature can be applied to substituted acids,Ordinary methods of nomenclature can be applied to substituted acids, but many acids have trival names.but many acids have trival names.

Preparation:Preparation:1.1.Maleic acid:Maleic acid:

)a( Rapid heating of malic acid to about 250°.)a( Rapid heating of malic acid to about 250°.

)b( Catalytic air oxidation of benzene at 400°.)b( Catalytic air oxidation of benzene at 400°.

)c( Air oxidation of crotonaldehyde.)c( Air oxidation of crotonaldehyde.

2. Fumaric acid and malic acid:2. Fumaric acid and malic acid:

3. Tartaric acid3. Tartaric acid:: : :Cyanohydrin synthesis from glyoxalCyanohydrin synthesis from glyoxal )1( )1(

)2( from dibromosuccinic acid)2( from dibromosuccinic acid

)3( Oxidation of maleic acid with neutral KMnO4)3( Oxidation of maleic acid with neutral KMnO4

4. Citric acid:4. Citric acid: 1- From 1,3-dichloroacetone:1- From 1,3-dichloroacetone:

1,3-Dichloroacetone can be prepared by treating glycerol1,3-Dichloroacetone can be prepared by treating glycerol with HCl followed by oxidation.with HCl followed by oxidation.

Reactions:Reactions:1- Addition of HX to α,β-unsaturated acids give β-haloacids.1- Addition of HX to α,β-unsaturated acids give β-haloacids.

2- Diels-Alder Reaction.2- Diels-Alder Reaction.

3- Heating tartaric acid gives pyruvic acid.3- Heating tartaric acid gives pyruvic acid.

4- Heating citric acid to 175oC gives aconitic acid.4- Heating citric acid to 175oC gives aconitic acid.

5. Reduction of tartaric acid with HI. 5. Reduction of tartaric acid with HI.

6- Citric acid loses water and CO on treatment with H2SO4 6- Citric acid loses water and CO on treatment with H2SO4 giving acetone dicarboxylic acid which on strong heating giving acetone dicarboxylic acid which on strong heating

decomposes into acetone and CO2.decomposes into acetone and CO2.

Preparation of urea:Preparation of urea:11 . .Urea may be obtained by the action of ammonia on ethyl carbonateUrea may be obtained by the action of ammonia on ethyl carbonate

of phosgeneof phosgene

2- Partial hydrolysis of cyanamide with dilute H2SO4 at 70.2- Partial hydrolysis of cyanamide with dilute H2SO4 at 70.

3- 3-

Reactions of urea:Reactions of urea:

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

2- Hydrolysis: urea undergo hydrolysis in acid 2- Hydrolysis: urea undergo hydrolysis in acid or alkaline solutions or in water in the presence or alkaline solutions or in water in the presence

of the enzyme urease present in soya beans.of the enzyme urease present in soya beans.

33 . .Reaction with nitrous acidReaction with nitrous acid

44 . .reaction with acid chloridesreaction with acid chlorides

5- Reaction with hypobromite.5- Reaction with hypobromite.

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

Barbital, 5, 5-diethylbarbituric acid, is hypnotic. For theirBarbital, 5, 5-diethylbarbituric acid, is hypnotic. For their

synthesis a disubstituted malonic ester is condensedsynthesis a disubstituted malonic ester is condensed

with urea.with urea.