الالديهايدات والكيتونات aldehydes and ketones

يؤذ احذ ردؼا . داالنذهاذاث وانكخىاث : انفصم انثانث

Aldehydes and Ketones قسى انكاء /انرازي / كهت انخربت

1

: Aldehydes and Ketones االنذهاذاث وانكخىاث

رزض ػ غشب اىشمجبد اىؼضخ ثبؽزاء ثزب ( CnH2nO )اىشمجبد ثبىصغخ اىؼبخ زرشزشك

. , C=O( Carbonyl group)ػي غػخ اىنبسثو

رن أن R أ(. )ا ( R-CHO )ػب ثبىصغخ ( Aldehy des)رضو االىذبذاد

( Aliphatic aldehyde )ػذب زظ اىذبذ اىفبر ( Alkyl group )غػخ اىنو أرسح ذسع

( . Aromatic aldehyde) ػذب زظ اىذبذ اسبر ( Aryl group ) أسوغػخ أ

R=R رن أقذ ن ( -

زبصيز RCOR))رضو اىنزبد ػب ثبىصغخ -

) أ

R≠Rغش زبصيز أ( Symmetrical)ػذئز ن ىذب مز زبظش -

ػذب ن ىذب مز غش

أرن ميزب اىغػز اىفبرز زظ ىذب مز اىفبر أن ( . Unsymmetrical) زبظش

اسبرخ فزظ ىذب مز خزيظ األخشاؽذح اىفبرخ رن أ أ. ارز زظ ىذب مز اسبر اس

(Mixed Ketone )

This difference in structure affects their properties in two ways :

A: aldehydes are usually more reactive than ketones toward nucleophilic addition , the

characteristic reaction of carbonyl compounds.

B: aldehyde are quite easily oxidized , whereas ketone are oxidized only with

difficulty

R C

O

H

R C

O

R

C O

H

H

C O

R

H

Aldehyde

C O

R

R120

Ketone



2

Nomenclature :انخست اىظب اىشبئغ ثأرجبعرغ أن إربك طشقز ىزغخ شمجبد اىنبسثو

(Common Trivial System )ثبعزخذا اىطشقخ اىظبخ أاىشمجبد زن رغخ ثؼض إر

(Systemauc,IUPAC System )اىنبسثو ش ن خالىب رغخ عغ شمجبد ػ .

: حست االنذهاذاث

: انظاو انشائغ: أوال

اىز رنب االىذبذاد اىؼخ ( Carboxylic acid)اىؾاض اىنبسثمغيخ أعبءرشزق اىزغبد ب

. ثذال ػخ ( aldehyde)ضغ ميخ االىذبذ ( ic-)شفغ اىقطغ اىبئ أمغذربػذ

Carboxylic acid - ic - acid + aldehyde → carboxaldehyde

ىزؼ ( . α ,β ,γ ,δ) ػذئز اإلغشقخف ؽبىخ عد غػخ ؼضخ ف ثخ االىذبذ رغزخذ اىؾشف

CHO–غػخ اىفسو سح ربب هىزسح اىنبسث اىغب -αاقؼب جزذئ ثبىؾشف

ؽبض مبسثمغي اىذبذ

ؾزف ضبف Aldehyde

H3C CH2 CH2 CH2 C H

O

CH3 C H

O

CH3 C OH

O

Acetic acid Acetaldehyde

H2C CH2 CH2 CH2 C H

O

Br

-Bromobutyraldehyde

H2C CH2 CH2 CH2 C OH

O

Br

- Bromobutyric acid

H3C C CH2 CH2 C H

OO

H3C C CH2 CH2 C OH

OO

- Acetylpropionic acid- Acetylpropionaldehyde



3

C

O

H

Benzaldehyde

C

O

OH

Benzoic acid

C

O

H

OCH3

P-Anisaldehyde

C

O

OH

OCH3

P-Anisic acid



4

: نطرقت انظايت ا

رض غػخ اىفسو ( continuous open chain)عيغيخ مبسثخ غزشح أطهخزبس

(-CHO ) مب رشق ثقخ اىغيغيخ ىزؼ اقغ اىغبغ ( . 1)رشق ثؾش رؼط غػخ اىفسو اىشق

اػزبدا ػي ػذد رساد اىنبسث اىشقخ اع االىنب ثبألخششزق اع اىشمت ( . عذد أ) اىؼضخ

(Alkane )ثشفغ اىؾشف األ ( -e ) ضغ اىبخ (al- ) ثذال ػخ :

Alkane - e + al → alkanal

صالص ىزؾذذ ( -tri)صبئ ( -di)رغزخذ اىجذابد األ غػخ اؽذح ف اىشمت أمضشف ؽبىخ عد

: أػذادب

H3C CH2 CHO

Propanal

H3C CH

CH3

CH2 CH2 CH2 CHO

5-Methylhexanal

C CH2 CH2 CH CH CH2 CHO

CH3CH3

HC

3,4-Dimethyl-7-octynal

12345678

CH3 CH2 CH2 CH CHO

CH3

2-Mehtylpentanal

CH2 CH2 CHOOHC

Butandial

CH2 CHO

Phenylethanal



5

: حست انكخىاث

: انظاو انشائغ

ؽغت )أالاىشرجطخ ثغػخ اىنبسثو Rزن االع ب صالصخ قبطغ فصيخ ؽش غ اىغبغ

زجغ االع ثنيخ ( Mقجو Eال Ethyl before Methylاىزشرت اىغبئ ىيؾشف أ قجو اىضو ضال

: مب ف ؽبىخ االىذبذاد اإلغشقخف ؽبىخ عد غبغ فشػخ ؼضخ فغزخذ ؽئز اىؾشف . مز

H3C CH2 C CH3

O

EthylMethylKetone

CH3 C CH2

O

CH CH3

Br

-BromopropylMethyl Ketone

H3C CH C

CH3 O

CH2 CH3

EthylIsopropyl Ketone

CH2 C

O

CH3

BenzylMethyl Ketone

C

O

CH3

MethylPhenyl Ketone

H3C CH2 C

O

CH2 CH3

DiethylKetone

C

O

CyclohexylPhenylKetone

C

O

DicyclohexylKetone



6

: انخست انظايت

ط اقو سق ن ىيغػخ عيغيخ مبسثخ غزشح رؾ غػخ اىنبسثو رشق ثؾش رغ أطهخزبس

ثؾزف األػذد اىزساد اىشقخ اع االىنب إىص شزق االع ثبالعزبد ( ketonic group)اىنزخ

. ثذال ػخ one–ضغ اىبخ e- اىؾشف

Alkane -e + one → alkanone

صبئ اىنز dione- غػخ مزخ ف اىشمت رغزؼو اىقبطغ اىبئخ أمضشف ؽبىخ عد

, ( trione ) صالص اىنز اػزبدا ػي ػذد اىغبغ اىنزخ .

H3C CH C

CH3 O

CH3

3-Methyl-2-butanone

1234

H3C CH2 CH2 C

O

CH3

2-Pentanone

C

O

CH3

Acetophenone

C

O

Benzophenone

C CH2 CH2 C

O

CH3

O

H3C

2,5-Hexadione

C

O

CH2 CH3

1 2 3

1-Cyclohexyl-1-propanone

C

O

CH3H3C CH

1234

3-phenyl- 2-butanone

C

O

CH3H3C

1

23

4

5 6

4-Methylacetophenone

O

Cyclopentanone

C

O

NO2

H3C1

2 3

4

56

1-

2-

3-

4-

5-

6-

4--Methyl-3-nitrobenzophenone



7

Physical properties:انخىاص انفسائت

The polar carbonyl group makes aldehydes and ketones polar compounds, and hence

they have higher boiling point than non-polar compounds of comparable molecular

weight .

األاصشاىغضئخ اىاطئخ زقؼخ مزغخ ىزن األصاقبثيخ اىزثب ىؼظ شمجبد اىنبسثو راد أ

راد اىغبىجخ اىنشثبئخ ف األمغغث عضئبد اىبء رساد ( Hydrogen bonds)اىذسعخ

غػخ اىنبسثو

اىذسعخ صشاألازثخ شمجبد اىنبسثو ػجش

C O

H O

H

Hydrogen bonding

H.b



8

Preparation of aldehyde:ححضر االنذهاذاث Oxidation of primary alcohols: األونتانكحىالث أكسذة -1

Oxidation of methyl benzene :اكسذة انثم بس -2

R CH2 OH

1 Alcohol

R C

O

H

Aldehyde

H3C CH2 CH2 CH2 OH

n-Butylalcohol

1-Butanol

H3C CH2 CH2 C H

O

n-Butyraldehyde

Butanal

Ar CH 3

Ar CHCl 2

Ar CHCH(OOCH 3) 2

Cl 2 . heat

CrO 3

Acetic acid

CHOAr

aromatic aldehyde

H2O

H2O

CH3

Br

P-Bromotoluene

Cl2 . heat

light

CHCl 2

Br

H2O

CaCO3

CHO

Br

P-Bromobenzaldehyde

CH3

NO2

P-Nitrotoluene

CH(OAC ) 2

NO2

CrO3

AC2O

CHO

NO2

P-Nitrobenzaldehyde

H2O

H2SO4



9

: حسال كهىرذاث انحىايض اخ -3

Reimer – Tiemann reaction . Phenolic.االىذبذاد اىفىخ . رب –رفبػو ساش -4

aldehyde

ساعغ فصو اىفالد

R C

O

Cl

or

Ar C

O

Cl

acid chloride

LiAlH(OBu-t) 3

Red.

R C

O

H

Ar C

O

H

or

Aldehyde

C

NO2

O

Cl

P-Nitrobenzoylchloride

LiAlH(OBu-t) 3

Red.

C

NO2

O

H

P-Nitrobenzaldehyde



10

Preparation of ketones: انكخىاث ححضر

Oxidation of secondary alcohol: انكحىالث انثاىت أكسذة -1

Examples:

Friedel- Ceafts acylation: كرأفج –أسهت فرذل -2

R CH R-

OH

2 Alcohol

CrO3 or K2Cr2O7

R C

O

R-

Ketone

H3C C

O

CH3H3C CH

OH

CH3

Propanol Acetone

CrO3 or K2Cr2O7

CH3

CH

OH

CH3

(-)- Menthol

H3C

CH3

CH

CH3

(-)- Menthone

H3C

O

CrO3 or K2Cr2O7

R C

O

Cl

Acid chloride

+ Ar HLewis acid

AlCl3R C

O

Ar + HCl

ketone



11

C

O

Cl

Benzoylchloride

+

C

O

Benzene Benzophenone

or Diphenyl Ketone

C

O

Cl

Benzoylchloride

+

NO2

Nitrobenzene

N.RAlCl3

Acetic anhydride

+

AlCl3

C

O

CH3

Acetophenone

or Methyl phenyl Ketone

+ CH3COOH

Acetic acid

(CH3-CO )2O



12

Reaction of acid chloride with:حفاػم كهىرذاث انحىايض يغ يركباث انحاش انؼضىت -3

organocopper compounds

-R LiCuX

-R CuLi

-R

R C

O

Cl

or

Ar C

O

Cl

R C

O

R- or Ar C

O

R-

Br

H3C

m- Bromotoluene

Li

Li

H3C

CuI

H3C

2

CuLi

H3C CH2 CH2 C

O

Cl2 moles of

Butyrylchloride

C

O

CH2 CH2 CH3

H3C

n-Propyl-m-tolylketone



13

Reaction: Nucleophilic additionانىكهىفهت اإلضافت:نخفاػالث ا

The typical reaction of aldehyde and ketone is nucleophilic addition

اىميفيخ اإلضبفخ

Nucleophilic addition

اىميفيخ ثعد اىؾبض مؼبو غبػذ اإلضبفخ

Acid – Catalyzed nucleophilic addition

R-

C

R

O

Reactant trigonal

Z

R- C

R

O

Transition state

R- C

R

O-

ZZ

product tetrahedral

H2O

R- C

R

OH

Z

R-

C

R

O

H+ R-

C

R

OH

Z

R- C

R

OH

Transition state

Z

R- C

R

OH

Z



14

Reaction of aldehydes and ketones:حفاػالث االنذهاذاث وانكخىاث Oxidation: األكسذة -1

a- االنذهاذ :aldehyde

b- كخىاث انثم :Methyl Ketones

R CHO

or

Ar CHO

Ag(NH3) +

2

KMnO4

K2Cr2O7

R COOH

or

Ar COOH

aldehyde carboxylic acid

H3C CHO + 2 Ag(NH3) +

2 + 3 OH- 2 Ag + CH3COO

- + 4 NH3 + 2H2O

Tollen test

Silver

mirror

H3C CH2 C

O

H

Propanal

H3C CH2 C

O

OH

Propanoic acid

KMnO4

C CH3

O

R

or

C CH3

O

Ar

OX-

KOCl

or

ONaI

R COO-

or

Ar COO-

+ CHX3

Haloform reaction

Haloform

60 C

C CH3

O

C2H5

Butanone

or Ethyl methyl ketone

3 KOCl+60 C

C2H5 COOK

H2SO4

+ CHCl3

C2H5 COOH

Chloroform

Propanoic acid



15

Reduction:االخخسال -2

a- االخخسال انى انكحىالث: Reduction to alcohols

b- انهذروكاربىاث إنىاالخخسال :Reduction to hydrocarbons

Clemmensen reduction:اخخسال كهس -1

اخزضاه إىز االخزضاه ف ؾظ ؽبض ثبعزخذا اىخبسص اىيغ ؽبض اىذسميسل اىز ؤد

.غػخ ضي إىغػخ اىنبسثو ف اىنزبد

C O

H2 , Ni

LiAlH4

or NaBH4 then H+

C

H

OH

Aldehyde

or

Ketone

alcohol

or Pt

O

Cyclopentanone

H2 , Ni

H OH

Cyclopentanol

C

O

CH3

Acetophenone

LiAlH4 H+

CH CH3

OH

--Phenyl ethyl alcohol

C O +

Zn(Hg)2 / HClCH2

C

O

(CH2)4 CH3

n-Pentylphenylketone

+

Zn(Hg)2 / HCl

(CH2)4 CH3CH2

n-Hexylbenzene



16

Wolff- Kishner:كشر –اخخسال وونف -2

C O + CH2

NH2 - NH2 / OH--

200 C

+C

O

(CH2)2 CH3

H3C

n-Propyl-m-tolylketone

NH2 - NH2 / OH--

200 C(CH2)2 CH3

H3C

CH2

m-(n-Butyl)toluene

C

O

CH2 CH3

CH3 CH2 C

O

Cl +

AlCl3

Zn(Hg)2 / HClCH2 CH3CH2

n-Propylbenzene

Feidel-Crafts acylation

PropanoylchlorideBenzene

Ethylphenylketone

O

Cyclopentanone

NH2 - NH2 / OH--

200 C

HH

Cyclopentane



17

c- االخخسانت األيت :Reductive amination

C O

H

RC NH

H

R

imine

H2 , NiC NH2

H

H

R

1 Amine

aldehyde

NH3

ammonia

+

+C O

R--

R

C

R--

R

NH

imine

H2 , Ni

C NH2

R--

H

R

1 Amine

ketone

NH3

ammonia

NH3

ammonia

H3C (CH2)5 C

O

H

Heptaldehyde

or Heptanal

+

H2 , Ni

H3C (CH2)5 CH2 NH2

n-Heptylamine

or 1-Aminoheptane

C O

Benzaldehyde

NH3

ammonia

+

H2 , Ni

CH2 NH2

Benzylamine

H

H3C (CH2)2 C

O

CH3

2- Pentanone

or Methyl-n-propylketone

NH3

ammonia

+

H2 , Ni

H3C (CH2)2 CH CH3

NH2

2- Aminopentane

125 4 ,3

C

O

CH3

Acetophenone

NH3

ammonia

+

H2 , Ni

CH CH3

NH2

- Phenylethylamine



18

Preparation of secondary amine: ححضر األي انثاىي

غ شمت اىنبسثو أى أ فبػيز رىل ػ طشق

Addition of cyanide .Cyanohydrin formation: حكى انساىهاذر .انساذ إضافت -3

OH

Cyclohexanol

O

K2Cr2O7

H2SO4

PBr3

Br

Cyclohexanone

Bromocyclohexane

NH3

ammonia

+

H2 , NiNH2

Cyclohexylamine

NH3

Cyclohexene

R C

H

O +

Aldehyde

H2N CH2 R

1 amine

R C

H

N CH2 R

imine

H2 , Ni

reductionR CH2 N

H

CH2 R

2 Amine

H3C C

H

O +

Acetaldehyde

H2N CH2 CH3

1 amine

H3C C

H

N CH2 CH3

imine

H2 , Ni

reductionH3C CH2 N

H

CH2 CH3

2 Amine

Ethylamine Diethylamine

C

O

+ CN--

H+

C CN

OH

Cyanohydrin



19

C O

H

NaCN

NaHSO3

Benzaldehyde

C

H

CN

OH

Mandelonitrile

H2O , HClC

H

COOH

OH

Mandelic acid

H3C C

O

CH3

Acetone

NaCN

H2SO4

H3C C

CH3

CN

OH

Acetone cyanohydrin

H3C C

CH3

COOH

OH

H2O , HCl

-- H2O

C

CH3

COOHH3C

Methacrylic acid

or 2-Methylpropenoic acid

123

H3C CH2 C

O

CH3

Ethylmethylketone

or 2-Butanone

NaCN

H2SO4

C

CH3

CN

OH

H3C CH2

H2O , HCl

C

CH3

COOH

OH

H3C CH2

-- H2O

C

CH3

COOHH3C CH3 2 14

2-Methyl-2-butenoic acid



20

Addition of derivatives of ammonia :يشخقاث االيىا إضافت -4

C

O

+ H2N G C

OH

NH GC N G + H2O

H2N G

H2N OH

H2N NH2

H2N NH

H2N NH C

O

NH2

Hydroxylamine

Hydrazine

Phenylhydrazine

Semicarbazide

C N G

C N OH

C N NH2

C N HH

C N NH C

O

NH2

Hydrazone

Oxime

Phenylhydrazine

Semicarbazone

namename

H3C C

H

O

Acetaldehyde

H2N OH+

H+

H3C C

H

N OH

Acetaldoxime

+ H2O

Hydroxylamine

H3C C

O

CH3

Acetone

H2N OH+

H+

C

H3C

H3C

N OH

Acetoxime Hydroxylamine

C

H

O H2N NH+H

+

C

H

N NH

BenzadehydephenylhydrazonePhenylhydrazineBenzaldehyde



21

Addition of alcohols . Acetal formation: حكى االسخال .انكحىالث إضافت -5

ىزظ االعزبه إلبئغػخ اىنبسثو ىالىذبذ ثعد ؽبض إىاىنؾه ضبف ى

O

Cyclohexanone

N NH C

O

NH2

Cyclohexanone semicarbazone

H2N NH C

O

NH2+

H+

Semicarbazide

C

H3C

O H2N NH

Phenylhydrazine

+H

+ C

H3C

N NH

Acetophenonephenylhydrazone

Acetophenone

--R C

H

O + first mole of ROH --R C

H

OR

OH

hemiacetal

--R C

H

OR

OH

hemiacetal

+ H+ --R C

H

OR

O

HH

-H2O--R C

H

OR

--R C

H

OR

( more stable)

+ H2O

--R C

H

OR + second mole of ROH

--R C

H

OR

O--

H

--R C

H

OR

OR

H

-H+

--R C

H

OR

OR

+ H+

Acetal



22

: األحيكاكت انخفاػم أػظ

:انحم

Cannizzaro Reaction: حفاػم كاسارو -6

رؾز ػي رسح اىذبذ ال عضئزا اىزفبػو ز ثعد قبػذح قخ شو ازقبه ذسذ إ

اىذبذ عضئ إى( enol أهنب رن ثزىل ال) , R3CHO , Ph- CHOضو -α أىفبذسع

اىذبذ خزيفخ عضئ أ فظ اىع أب أخش

. رن ؽبض مؾه إىؤدب ( Crossed- Cannizzaro reaction رفبػو مبضاس خزيظ)

: انكاكت

H3C C

H

O

Acetaldehyde

+ tow mole s of CH3CH2OH

Ethylalcohol

dry HCl

2 moles of HCHO

Formaldehyde

50% NaOH

R.THCOO

-- CH3OH

Acid salt Methanol

H C

O

H

OH

H C

O--

H

OH

H C

O--

H

OH

+H C

O

H

first mole of

second mole of H C

O

OH H C

H

O--

H

+

- H+

H C

O

O-- CH3OH

1-

2-

Acid salt Methanol

H3C C

H

O + first mole of CH3CH2OH H3C C

H

OCH2CH3

OH

hemiacetal

+ H+

H3C C

H

OCH2CH3

O

HH

-H2OH3C C

H

OCH2CH3

H3C C

H

OCH2CH3

( more stable)

+ H2O

+ second mole of

H3C C

H

OCH2CH3

O--

H

H3C C

H

OCH2CH3

OCH2CH3

H

-H+

+ H+

H3C C

H

OCH2CH3

OH

hemiacetal

H3C C

H

OCH2CH3 CH3CH2OH H3C C

H

OCH2CH3

OCH2CH3

Acetal

Acetaldehyde

Ethylalcohol



23

Addition of Grignard reagents:اضافت كىاشف كرارد -7

CHO

Cl

m-Chlorobenzaldehyde

50% NaOH

R.T2 moles of

COO--

Cl

CH2OH

Cl

m-Chlorobenzoate ion m-Chlorobenzylalcohol

+

CHO

OCH3

OCH3

1

2

3

4

5

6

Veratraldehyde

or 3,4-Dimethylbenzaldehyde

+ HCHO50% NaOH

65 C

CH2OH

OCH3

OCH3

1

2

3

4

5

6

+ HCOO--

3,4-Dimethylbenzylalcohol

Crossed Cannizzaro reaction:

C O + R MgX C

R

OMgX

H2O

C

R

OH + Mg2+

+ X--

Grignard reagent



24

C

H

R--

O

C

H

H

O

R MgX

R MgX

R MgX

+ H C

H

R

OMgX

H2OH C

H

R

OH + Mg2+

+ X--

C

R=

R--

O

--R C

H

R

OMgX--R C

H

R

OH

H2O

+ Mg2+

+ X--

+

+--R C

R=

R

OMgX --R C

R=

R

OH

H2O

+ Mg2+

+ X--

Formaldehyde

Higher aldehyde

Ketone

1 alcohol

2 alcohol

3 alcohol

Grignard reagent

Grignard reagent

Grignard reagent

H3C (CH2)3 OH

n-Propylalcohol

HBr

H3C (CH2)3 Br

Mgdry ether

H3C (CH2)3 MgBr + H3C C

O

CH3

Acetone

H3C CH

OH

CH3

Isopropylalcohol

K2Cr2O7

H3C (CH2)3 C

OH

CH3

CH3

126

2-Methyl-2-hexanol

H3C (CH2)3 C

O

CH3

2-Hexanone

126CH3 MgBr

Methylmagnesiumbromide

+ H3C (CH2)3 C

OH

CH3

CH3

126

2-Methyl-2-hexanol

alcohol

alkylhalide

aldehyde

Grignared

reagent

oxidation

more complicated

alcohol

or ketone



25

H3C CH2 CH

OH

CH3

Sec- butylalcohol

PBr3

CrO3

H3C CH2 C

O

CH3

H3C CH2 CH

Br

CH3

C2H5MgBr

Mg

dry etherH3C CH2 CH

MgBr

CH3

H3C CH2 C

OH

CH2

CH3

CH3

CH3CHO

3-Methyl-3-pentanol

H3C CH2 CH CH CH3

CH3 OH

3-Methyl-2-pentanol

then H2O , H+

then H2O , H+

CH3 CH2 Cl CH2 MgClMg

H3C CH CH3

OH

H3C C CH3

O

CH2 C

OH

CH3

CH3

2-Methyl-1-phenyl-2-propanol

1 2 3

Cl2 , heat

dry ether

Isopropylalcohol

Toluene

K2Cr2O7



26

Br2 , Fe

BrMg

dry etherMgBr

H3C CH2

CrO3OH H3C C H

O

C

H

CH3

OH

1-Phenylethanol

phenylmagnesium

bromide

CH3 CH2 Cl CH2 MgClMgCl2 , heat

dry ether

Toluene

H3C CH CH2

CH3

OH

Isobutylalcohol

or 2-Methyl-1-propanol

H3C CH C

CH3

O

H

2-Methylpropanal

K2Cr2O7

CH2 CH

OH

CH

CH3

CH3

1-Phenyl-3-methyl-2-butanol

1 2 3 4

HC C Li

Ethynylithium

H3C C

O

CH3

Acetone

+ HC C C

OLi

CH3

CH3

H+

HC C C

OH

CH3

CH3

2-Methyl-3-butyn-2- ol

C C MgBrH3C

Propyn-1-ylmagnesium

bromide

H3C C

O

H+ C C CHH3C CH3

OMgBr

C C CHH3C CH3

OH

3-Pentyn-2-ol

12345

H+



27

Aldol condensation:حكاثف االنذول

إال.ؽبض خفف أقبػذح ثزأصشذسع رنبصف رار – أىفبرؼب االىذبذاد اىنزبد اىؾبخ ػي

ذػ .ذسمغ مز -ثزب أذسمغ اىذبذ -غيت اىؾبالد قاػذ خففخ ىزؼط ثزبرغزخذ ف ا أخ

. ىزا اىع اىزنبصفبد األضيخفب ي ثؼض .زا اىع اىزنبصف ثزنبصف االىذه

-أىفبرؾز ػي إمبصفب خاله رنبصف االىذه غت االىذبذاد اىنزبد اىز شغت ثذ :يالحظت

نب اىزنبصف رارب رؾذ ذسع ششطب ىؾذس اىزنبصف فب ي ثؼض اىشمجبد اىنبسثيخ اىز ال

. ذسع – أىفبششط رنبصف االىذه ىؼذ اؽزائب ػي رسح

اىذبذاد

H3C C

O

H H3C C

O

H+

2 mole from acetaldehyde

dil. --OH

H3C C

H

OH

C

H

H

C

2-Hydroxybutanal

O

H

H3C CH2 C

O

H

2 mole from propanal

H3C CH2 C

O

H+dil.

--OH

H3C CH2 C

OH

C

H

CH3

H

C

O

H

3-Hydroxy-2-methylpentanal

12345

H3C C

O

CH3 H3C C

O

CH3+

2 mole from acetone

dil. --OH

H3C C

OH

CH2

CH3

C

O

CH3

4-Hydroxy-4-methyl-2-pentanol

12345

C

O

H

Benzaldehyde

H C

O

H

Formaldehyde

H3C C

CH3

CH3

C

O

H

2,2-Dimethylpropanal

C

O

Benzophenone

C

O

CR3



28

مزبد

: يكاكت انخفاػم

اىقبػذح ىزىذ اال اىنبسث ثزأصشرىل أىفب–عؾت اىجشر اىزصو ثزسح مبسث األىرزض اىخطح

I) ) ( اىز ؼو مؼبو ميفي.) زأصشحغش أخش ىغضئ) رسح مبسث غػخ اىنبسثو اىز بع

II أاالىذه زا ؼ أمغغػي رسح أالالؽع اىشؾخ اىغبىجخ ؾىخ IIىؼط اال ( ثبىقبػذح

اىبء اىزنخ ف عضئػي عؾت ثشر II ؼو ا االىنمغذ األخشحف اىخطح . اىنمغذ

ذسمغ اىذبذ –ىؼط اىبرظ اىبئ ثزب األىاىخطح

ف وسظ قاػذي -1

Ar-CHO

HCHO

(CH3)3-C-CHO

Ar-CO-Ar

Ar-CO-CR3

NO - hydrogen atoms

N.Rdilute

OH

H C

H

H

C

O

H H2C C

O

H+ OH + H2O

H3C C

O

H H2C C

O

H+

first mole

second mole

1-

2-H3C C

O

CH2 C

O

H

H

H3C C

O

CH2 C

O

H

H

3- + H2O H3C C

OH

CH2 C

O

H

H

+ OH

first stage

second stage

third stage

( I )

( II )

( III )



29

: ف وسظ حايض -2

Dehydration of aldol products: اخساع اناء ي ىاحج االنذول

H3C C

OH

H

C

H

H

C

O

H

Aldol

dilute HCl

warm

H3C C

H

C

H

C

O

H

2-Butenal

or crotonaldehyde

1234+ H2O

H3C C

OH

CH3

C

H

H

C

O

CH3

4-Hydroxy-4-methyl-2-pentanone

dilute HCl

warm

H3C C

CH3

C

H

C

O

CH3 + H2O

4-Methyl-3-penten-2-one

12

345

C

O

CH3 + C

O

CH3

Acetophenone

2 moles

C

OH

CH2

CH3

C

O

C CH

CH3

C

O

-H2O

1,3-Dimethyl-2-buten-1-one

12

3

4



30

Use of aldol condensation in organic synthesis:فائذة حكاثف االنذول ف االصطاع انؼضىي

اىؼذذ اىشمجبد اىؼضخ رىل ثبعزخذا اىؼذذ إىاله ارظ االىذه رؾيب اىن اعزغ

. اىشمجبد زرؼبب ضو أاىزفبػالد اىؼبخ اىز ن

H3C C

O

H

2 mole from

Acetaldehyde

OH

CH2 C

O

HHCH3C

OH

Aldol

H2O

CH C

O

HCHH3C

2-Butenol

H2 , Ni

CH2 CH2CH2H3C

n-Butylalcohol

OH

H3C C

O

H

2 mole from

Acetaldehyde

OH

CH2 C

O

HHCH3C

OH

Aldol

H2O

CH C

O

HCHH3C

2-Butenol

H2 , Ni

CH2 CH2CH2H3C

n-Butylalcohol

OH

or 1-Butanol

NaBH4 / H+

CH CH2-OHCHH3C

Crotonylalcohol

CH2 CH2CH2H3C

n-Butylalcohol

OH

or 1-Butanol

CH2 CCH2H3C

Butanal

H

or n-Butyraldehyde

K2CrO7

O

OH

2 mole from

(aldol condensation)

CH2 CHCH2H3C CH

C2H5

C

O

H

HO

- H2O

CH2 CHCH2H3C C

C2H5

C

O

H

H2 ,NiCH2 CH2CH2H3C CH

C2H5

2-Ethyl-1-hexanol

CH2 OH

123456



31

Crossed aldol condensation :حكاثف االنذول انخقاطغ

-أىفبػي رسح األقوؾز اؽذب ػي إششط )ف ث شمج شمجبد اىنبسثو اىخزيف ذػ اىزنبس

خيظ إىزا اىزفبػو ؤد ػيب أى . ثعد قبػذح خففخ ثزنبصف اىذه زقبطغ ( ذسع اؽذح

ن اىؾصه ثأخرؾذ ظشف ؼخ عذ أخ إال. اىارظ اىز ؼزذ ػذدب ػي ع اىشمج اىزفبػي

: اىظشف ز . ػي زط ػبه برظ اؽذ

عف ال ؾذس رنبصف ث فأخذسع – أىفبمب اؽذ شمج اىنبسثو ال ؾز ػي رسح إرا -1

. عشئز زا اىشمت مضبه ػي رىل االىذبذاد االسبرخ ا اىفسبىذبذ

ح اعزخذا ؽبفض ف ؽبه -2

ذسع ثصسح ثطئخ ػي خيظ اىاد – أىفبشمت اىنبسثو اىؾب ػي إضبفخر أرا -3

.اىزفبػيخ اىؾبفض

C

O

H

Benzaldehyde

OH

CH3-CHO

CH3-C-CH3

O

H3C C

O

Acetaldehyde

Acetone

Acetophenone

CH CH C

O

H

3-Phenyl-2-propanal

CH CH C

O

CH3

4-Phenyl-3-buten-2-one

1234

CH CH C

O

1,3-Diphenyl propenone

123



32

The Witting reaction:حفاػم فخك

ص ثعد قبػذح فعف اىنبيذ اىضالص ا يذاالىو غ اىفعف اىضال أؼط رفبػو بىذ االىنو

(Ylid ) أاعقذ اعزؼيذ .رزفبػو اىيذاد غ اىنزبد االىفبرخ االسبرخ ىزؼط شمجب اىفب أن

. خزيفخ اىقاػذ

: انكاكت

,( اىفعف اىضالص اىبىذ )ف رؾضش يؼ اىفط األى:بك صالس خطاد زضح ف زا اىزفبػو

زفبػو زا اىيذ غ شمت أخشا,ثبىؼبيخ غ قبػذح قخ رىل ( يذ ) ا ( اىفعفسا)ص ؾصو ػي

. اىنبسثو ىؼط اىفب

R3P

tri phosphine

R-CH2-Br

alkyl halide

allyl halide

+ R3P CH -R

Br

R3P CH -R

R3P CH -R

NaNH2

alkydene tri phosphine

(Ylid )

H

ph3P

tri phenyl phosphine

R-CH2-Br

alkyl halide

allyl halide

+ ph3P CH -R

Br

ph3P CH -R

ph3P CH -R

NaNH2

phenylene tri phosphine

(Ylid )

H

C O

R

R

+ CHph3P R=

C C

R

R

CHR=



33

ph 3P CH -R + R-C-R

O

Ketone(Ylide)

CH R

C

ph3P

O

ph3P CHR

CR2O

Oph3P +

CHR

CR2

Alkene

R

R

tri phenylphosphine

oxide

ph3P

tri phenyl phosphine

CH3-Br

Methyl

bromide

+ ph3P CH 2

Br

ph3P CH2

ph3P CH 2

NaNH2

phenylene tri phosphine

(Ylid )

H

ph 3P CH 2 CH 3-C-CH 3

O

+

CH2

C

ph3P

O

CH3

CH3

ph3P CH 2

C(CH 3) 2O

Oph3P +

tri phenylphosphine

oxide

CH2

C( CH 3) 2

2-Methyl-1-prpene



34

غشع اىزفبػو ثعد غبغ عبؽجخ ىالىنزشبد ػي غػخ اىنبسثو غبغ دافؼخ ىالىنزشبد ػي

. اىفعف

اىزشو اىز أػي غػخ عبؽجخ ىالىنزشبد ضو االعزش األىاؽز اىبىذ أرا( ylid)غشع رن

.زفبػو ثغشػخ غ االىذبذاد ( ylid) ثزىل ضو زا رضجذ اىشؾخ اىغبىجخ ػي اىنبسة

H2C CH CH2 Cl ph3P+ H2C CH CH2ph3P

Cl

NaOEt

HC CH CH2ph3P

HC CH CH2

ph3P

ylid

Allylchloride

CH2ph3P

Methylenetriphenylphosphine

H3C Cl + ph3P

Methylcloride

NaOEt

+ C CH2C

O

Benzophenone

O Pph3

C CH2

1,1-Diphenylethene

C

O

H

Benzaldehyde

HC CH CHph3P+ HC CH CH

ph3P

CH

O

HC CH CHCH

1,4-Diphenyl-1,3-butandiene

1234

H2C CH CH

Cl

+ph3P

NaOEt



35

Problem:Give structure of an (yild) and a (carbonyl compound ) which each of

following could be made:

1-

2-

3-

4-

5-

6-

H3C CH2 CH2 CH C

CH3

CH2 CH3

12345673-Methyl-3-heptene

CHC CH2

123

CH34

1,3-Diphenyl-2-butene

HC CH 1,2-Diphenylethene12

CH CH3

HC CH CH CH

1234

1,4-Diphenyl-1,3-butadiene

H2C CH CH C

CH3

C

2345

O

O CH3 Methyl 2-methyl-2,4-pentandienoate

1

Ethylidenecyclopentane

CH CH3Ethylidenecyclohexane

CH2

CH2

MethylenecyclohexaneMethylenecyclopentane

,

7-

8-



36

Reformatsky Reaction :حفاػم رفىرياحسك

بىع اعزش غ اىخبسص اىؼذ ف زت خبو شمت اىخبسص اىؼض اىز – أىفبؼط رفبػو

–ثزب أعزشاداالسبرخ اىشجؼخ غش اىشجؼخ ىزؼط االىذبذاد اىنزبد االىفبرخ إىضبف أن

ذسمغو

XCH2CO2Et + C O

R

R

Zn / BenzeneC

R

R

OH

CH2CO2Et

HC CO2EtR

Br

Zn

RCH

+

ZnBr

C

O

OEt RCH C

O ZnBr

OEt

RCH C

O ZnBr

OEt + R C

O

H R CH

O

CH C

R

O

OEt R CH

OH

CH C

R

O

OEt

+

ZnBr(OH)

CH3(CH2) 3CH CHO

CH3

+ CH3CH2 CO2Et

Br

CH3(CH2) 3CH CH2

CH3

CH2CO2Et

CH3OH

Zn / Benzene

2-Methylhexanal Ethyl 2-bromopropanoate

123 123

48

Ethyl 3-hydroxy-2,4-dimethyloctanoate

126

الالديهايدات والكيتونات aldehydes and ketones

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