F324: Rings, Polymers and Analysis

Reactions to learn
alessandro genova Leonardo Greco e Diletta Pagliano

Arenes c.+ 0, 1. Ben ene ! c. "itric Acid "itro#en ene $%&'%%o()

2

eg (*+* ! +",3
Fe(l 2. Ben ene ! +alogen +ydrogen +alide
3

(*+%",2 ! +2, +alo#en ene !

Fe(l3 -

eg (*+* ! (l2
/alide

(*+%(l ! +(l -

can .se Fe, or any iron /alide and al.mini.m

3. P/enol ! Base eg. (*+%,+ ! "a,+

0alt ! 1ater (*+%,'"a! ! +2, sodi.m 2/eno3ide 0odi.m P/eno3ide !

4. P/enol ! 0odi.m +ydrogen eg 2(*+%,+ ! 2"a

2(*+%,'"a! ! +2

%. P/enol ! Bromine /ydrogen #romide $R4)

OH Br

2,4,*'tri#romo2/enol !

OH Br

+ 3Br2

3HBr

Br

Carbonyl Compounds 1. Red.ction red.cing agents "aB+4 or AlLi+4 .se 5+6 in e7.ations Alde/yde ! 25+6 Primary Alco/ol 8g (+3(+, ! 25+6 et/anol 9etone ! 25+6 (+3(+2,+ et/anal 0econdary Alco/ol (+3(+$,+)(+3 2ro2an'2'ol

8g (+3(,(+3 ! 25+6 2ro2anone

2.,3idation .sed to disting.is/ #et:een alde/ydes ; <etones= alde/ydes o3idised to car#o3ylic acids :/ilst <etones :ill not react. a) 4ollens Reagent > $ammoniacal silver nitrate)

O C H

[Ag(NH3)]2+
O C OH

+ Ag

+ 2NH3

Ben alde/yde silver mirror

#en oic acid

#) Fe/lings 0ol.tion > $com2le3 ion o? (.2! )

H

Cu2+ complex ion

C H O

H C HO O

Cu2O

(blue); warm

met/anol red@#ro:n 22t

met/anoic acid

3.(ondensation $not e32ected to memorise #.t to #e ?amiliar :it/) .sed to identi?y t/e 2resence o? a car#onyl com2o.nd .sing 2,4'dinitro2/enyl/ydra ine.
H H2N N NO2 H3C H3C C H3C O2N O H3C O2N C H N NO2

+2,

2,4'dinitro2/enyl/ydra ine

yello:@orange 22t

Carboxylic Acids 1. (ar#o3ylic Acid ! Al<ali 1ater eg (2+%(,,+ ! 9,+ +2, 0alt ! (2+%(,,9 !

2ro2anoic acid 2ro2anoate 2. (ar#o3ylic Acid ! Aetal +ydrogen eg (3+B(,,+ ! Ag ! +2 #.tanoic acid #.tanoate

2otassi.m 0alt ! $(3+B(,,)2Ag magnesi.m

3. 8steri?ication mineral (ar#o3ylic Acid ! Alco/ol acid ! 1ater

O CH2CH3C OH

8ster
O

c H2!O" C2H5OH
CH2CH3C

+
OC2H5

H2O

2ro2anoic acid

et/yl 2ro2anoate

Esters 1. +ydrolysis $acid catalyst) mineral 8ster ! 1ater acid Alco/ol c.+ 0,
2

(ar#o3ylic Acid !
4

+
O

H2O
OH

OH

et/yl et/anoate et/anol

et/anoic acid

2. +ydrolysis $al<ali catalyst) al<ali 8ster ! 1ater Alco/ol

(ar#o3ylic Acid 0alt !

O C OC2H5

NaOH + H2O
C

+
ONa

C2H5OH

et/yl #en oate

sodi.m #en oate

Amines 1. Pre2aration a) +alogenoal<ane ! Ammonia +ydrogen /alide

$et/anolic soln)

Amine !

eg (+3(+2(+2(l ! "+3 ! +(l 1'c/loro2ro2ane #) "itro#en ene ! 4in ! c.+(l P/enylamine ! 1ater
!n$c HCl
NO2

(+3(+2(+2"+2 2ro2ylamine

#[H]

NH2

2H2O

2. 0alt Formation Primary Amine ! Acid eg (2+%"+2$a7) ! +(l$a7)

et/ylamine c/loride

0alt (2+%"+3!$a7) ! (l'$a7)

et/ylammoni.m

3. Dia otisation P/enylamine reacts :it/ nitro.s acid $?ormed in situ , C 1&o() eg. "itro.s acid ?ormation a) "a",2 ! +(l +",2 ! "a(l
nitro.s acid

NH2

HNO2

+ HCl

N.Cl-

2H2O

2/enylamine c/loride

#en enedia oni.m

#) (o.2ling Reaction t/e dia oni.m salt can ta<e 2art in a co.2ling reaction :it/ 2/enols $al<ali conditions) to ?orm a o dyes. eg
+

N.Cl-

OH

N N

F324: Rings, Polymers and Analysis

OH

+ HCl

Mechanisms to learn

1. Electrophilic Substitution Ben ene +20,4 ! +",3 +2",3!

%NO2+ +
NO2

+0,4' ! +2",3! +2, ! ",2!

H NO2

+ H+

+!

+0,4'

+20,4

2. Nucleophilic Addition Alde/ydes or 9etones

H3C C H H3C H H C OH H O H CH3 C H OH

+ OH&

H&

(AS Mechanisms you will be expected to these as well!

now

". Nucleophilic Substitution +alogenoal<anes

&
H H H C H Cl H H HO H H C C Cl H H H HO H C C H H H

+ Cl&

OH&

#. Electrophilic Addition Al<enes

H H C H H C H H H C H C H H H H C H H C Br H

Br&

Br -

$. %ree Radical Substitution Al<anes i) Dnitiation

Cl2 '( )ig*+ Cl + Cl

ii) Pro2egation
CH" CH3 + + Cl Cl2 CH3 CH3Cl + + HCl Cl

iii) 4ermination
CH3 CH3 + + Cl CH3 CH3Cl CH3CH3