1.

(a)

(i) (ii)

C6H6 + HNO3 C6H5NO2 + H2O (1) (concentrated) sulphuric acid (1) (accept H2SO4 but gi e ! "ar#s $or dilute % (a&))

1 1

(iii) (b) (i) (ii)

NO2+ (1) Cl2 2Cl % ' Cl2 Cl (1) Cl+ C6H5CH3 C6H5CH2 + HCl (1) C6H5CH2 + Cl2 Cl + C6H5CH2Cl (1)

1 1

(iii) (c) (i)

C6H5CHCl2 % C6H5CCl3 % C6H5 CHCHC6 H5 % other correct possible ans(er (1)

)

CN adding to ethanal correctl* sho(ing curl* arro( and curl* arro( $ro" double bond in C + O CH3CH(CN) ) O) H+ adding to abo e ion to $or" product ) ignore curl* arro(s (1) 3 2

(ii)

reaction 1 is nucleophilic (1) reaction 2 is electrophilic (1) or accurate idea o$ (h* nucleophile % electrophile attac#s aldeh*de % al#ene including polarit*

(d)

(i) (ii) (iii)

to satis$* "ar#et de"and $or s"aller % unsaturated "olecules % al#enes (1) 1 eg C14H3! C2H4 + C12H26 (1) o,ide(s) o$ S and their e$$ect eg acid rain not -ust pollutant or to,ic (1) 1
[15]

2.

(a)

Step 1. Type of reaction Reagent(s) Step 3. Type of reaction Reagent(s)

nitration or electrophilic substitution (1) CHNO3 + CH2SO4 (1) reduction or a"ination or h*drogenation (1) HCl%/e or Sn or 0n or SnCl2
+ )

H2%Ni or Cu or 1t or 1d (1) 4

(b)

HNO3 + 2H2SO4 NO 2 (1) + H3O+ + 2HSO 4 (1)

2
[6]

3.

(a)

Reagents

2lCl3 (1) C6H5CH2COCl or (C6H5CH2CO)2O (1)

Equation for formation of reactive intermediate C6H5CH2COCl + 2lCl3 C6H5CH2CO+ (1) 2lCl 4 (1) Name of mechanism Mechanism electrophilic substitution (1)
)

(1 )

+ CO CH 2C 6H

(1 )
5

+ (1 )

H CO CH 2C 6H

(b)

Type of reaction Reagent(s)

reduction or Na%6tOH

or

h*drogenation (1) H2%Ni or 1t or 1d (1) 2

Na4H4 or 5i2lH4 H2SO4 or H31O4 or 2l2O3 (1) eli"ination (1)

(c)

Reagents

Name of mechanism (d) (e) optical Type of isomerism Explanation

2 1 geo"etrical or cis7trans (1) restricted rotation or double bond rigid (1) 2

[15]

4.

(a)

(i) (ii) (iii)

2)"eth*lpropanenitrile (1) 8eagent 9CN (1) Conditions alcoholic%a& (1) Name of mechanism nucleophilic C H CH
) 3 3

substitution (1) :1 ; 4r :1 ; CH
3

C H C H

C H

CN + < .4 r
)

Mechanism (b) Reagents Name of mechanism Equation or

N C . :1 ;

conc HNO3 (1) conc H2SO4 (1) electrophilic substitution (1) C6H6 + HNO3 C6H5NO2 + H2O
+ C6H6 + NO 2 C6H5NO2 + H+ (1)

(c)

+ C in C H 4r (1) a electron de$icient C or 3 <

attracts%attac#ed b* nucleophiles (1) electron rich%delocali=ed electrons in C6H6 (1) repels%not attac#ed b* nucleophiles (1) "a, 3
[14]

5.

(a)

(i) (ii)

nucleophilic addition (1) 27h*dro,*butanenitrile condone "issing h*phen (1)

H H C H

H C H

H C H C N
(1) 2 1

(b)

(i)

CH3CH2CH24r + 9CN CH3CH2CH2CN + 94r (1) allo( C3H<4r allo( C4H<N

(ii) (c) (d)

nucleophilic substitution % SN2 (1)

CN) or NC) (1) lone pair o$ electrons on C ato" (1) chloro"ethane or CH3Cl (or 4r or >) (1) 2lCl3 % /eCl3 % 2l4r3 (as reagent or condition) (1) anh*drous (ignore re$erence to te"perature) (1) electrophilic substitution (1) 4
[11]

6.

(a)

CH3CH2CH + CH2 + 2lCl3 + HCl CH3CH2 C HCH3 (1) + 2lCl4) (1) 2 1 electrophilic substitution (1) alternati e CH3CH2CH2CH2+ or pri"ar* (1) less stable or 1 2 inducti e e$$ects (1) than CH3CH2C HCH3 or secondar* (1)
+

(b) (c)

(d)

protonation gi es CH3CH2C HCH3 onl* (1) or but)2)ene s*""etrical 1

CH
(e) CH3CH2 C l CH3 (1) or 4r 1
[8]

7.

(a)

(i)

CH3COCl or (CH3CO)2O (1) 2lCl3 (1)

(ii) (iii)

reduction or h*drogenation (1) Na4H4 or 5i2lH4 or Na%C2H5OH (or H2%Ni) eli"ination or deh*dration (1) or hot 2l2O3 (1) 6 or H2%Ni (1)

(i )

H2SO4 or H31O4 (b) (i) (ii)

pol*(phen*lethene) or pol*st*rene (1) CH3CH2+ or C2H5+ (1) 4

[10]

CH2 + CH2 + HCl + 2lCl3 CH3CH2+2lCl4) (1) (iii) eli"ination or deh*drogenation (1)

8.

(a)

Mechanism (1 ) ? 2 O (C H 3 C H 2 C H 2) ) N C. C (1 ) (H ) C H 3C H 2C H
2

) O . C

H + ? 4 (1 ) H

O H C H 3C H 2C H
2

C CN

(1 ) C N

? 3 ? 1 Allow !"# if structure shown elsewhere penalise " N splitting if wrong Name of product. 27h*dro,*penta(ne%o)nitrile (1) or 17c*anobutan717ol (b) Mechanism ? 2 (1 ) O (C H 3 C H 2) Cl ( 1 ) @@ O ? 1 H ( C H 3) C C H 3C H
2

) O . C O + C H
3

O Cl H CH 3CH
2

O CH

( C@ @l ) )

s tru c tu re (1 ) ? 3 3 a rro ( s (1 ) ? 4

Name of organic product. "eth*lpropanoate (1)

(c)

(i) (ii)

(:) CH3CO (;)+ (1) 4 + (1 ) ? 1 CH

3

(1 ) ? 2 CO CH ? 3 H

C +

(1 )

Notes (abc) e,tra curl* arro(s are penalised (a) be lenient on position o$ negati e sign on . CN) but arro( "ust co"e $ro" 1p

(a%b) C (a) (b) (c)

O alone loses ?2 but can score ?1 $or attac# on C+A si"ilarl* C

Cl

allo( 27h*dro,*pentanonitrile or 27h*dro,*penta(ne)nitrile @@@ pent*lnitrile in ?4A allo( e,tra. Cl) attac# on HA sho(ing loss o$ H+ (i) (ii) allo( $or"ula in an Be&uationC(balanced or not) be lenient on the position o$ the + on the $or"ula $or ?1 the arro( "ust go to the C or the + on the C donDt be too harsh about the horseshoeA but + "ust not be close to the saturated C ?3 "ust be $inal step not earlierE allo( ?3 e en i$ structure (?2) is (rong
[14]

Organic points (1) Curl* arro(s. "ust sho( "o e"ent o$ a pair o$ electronsA i@e@ $ro" bond to ato" or $ro" lp to ato" % space e@g@ 8 H 3N . C H (2) Structures penalise stic#s (i@e@ H H O C H H O H C H 1enalise once per paper 8 or 8 8 or 8 H 4r O 8 H 3N . 8 C H H 4 r

) once per paper H C H H C H H O H 2N ) e tc O H or )N H

3

CH
allo( CH3) or )CH3 or or H3C)

or CH3

9.

(a)

$tep % ac*lation or electrophilic substitution (1) 21C13 (1) CH3CH2COCl or (CH3CH2CO)2O (1) $tep & reduction or h*drogenation (1) Na4H4 or hi21H4 or Na%C2H5OH $tep ! deh*dration or eli"ination (1) H2SO4 or H31O4 or 212O3 (1) < H2%N1or 1t or 1d (1)

(b) (c)

optical (1) geo"etrical or cis7trans iso"ers (1) due to restricted rotation (1)

1 2

(d) (i)

C H 4 rC H 2 C H

C H 2 C H 4 rC H

(1 )
(ii) (iii)
+

(1 )
electrophilic addition (1) C6H5 C H CH2CH3 (1) both secondar* but one is "ore stable (1) C6H5CH2 C H CH3 (1) 6
[16]
+

10.

(a) (b)

di"eth*la"ine nucleophilic substitution ?

1

1 1 H H 3C ?
2

H 3C

N H

4r

H 3C

N H

CH ?
4

CH (c) &uaternar* a""oniu" salt

N H

4 1 1 (cationic) sur$actant % bactericide % detergent % $abric so$tener or conditioner% hair conditioner

(d) O H 3C C N CH ) CH 3CO O
3 3

+ C H 3N H

(allow "! ''" or "! ''( N")*)

2
[10]

11.

(a)

Nucleophilic substitution ? 2 CH 3C H 2CH

2

1 ? 3 CH 3CH 2CH 2C H
2

H N H
+

C H

4r

H 3N

:
? 1

? 4

:N

)
4

?1A ?2 and ?4 $or arro(sA ?3 $or structure o$ cation (Allow M& alone first+ i,e, $N% formation of car-ocation) (.enalise M) if /r( used to remove "*) (b) Step 1 CH3CH2CH2CN 1 CH3CH2CH24r + 9CN CH3CH2CH2CN + 94r balanced (or CN)) (or 4r)) (not " N) Step 2 CH3CH2CH2CN + 2H2 (or 4:H;) (c) (i) 5one pair (on N) (in correct conte,t) 8 group increases electron densit* % donates electrons %pushes electrons % has positi e inducti e e$$ect 2n* strong acid (but not concentrated) or an* a"ine salt or a""oniu" salt o$ a strong acid 1 1 1 1
[12]

1 1 1

CH3CH2CH2CH2NH2

(ii) (d)

CH3CH2N(CH3)2

12.

(a)

(i)

chloro"ethaneA an* halogeno"ethane (correct $or"ula accepted) (1) alu"iniu" chloride % /e % /eCl3 %4/3 (1) anh*drous (1) 3 2

(ii)

electrophilic (1) substitution (1)

C H 2C l

C H C l2

CC l

(b)

(1 )

(1 )

(1 ) 3

and other correct products penalise C6H5 once onl* (c) (i) reduction % redo, (1) N H
+ 3

C l

(ii) cation onl*A gi e 2 onl* phen*la"ineA gi e salt correct (ith charges o"ittedA gi e 2

H H
(d) (i) (1)

H C H

H C H
2

C H

O H

reduction % redo, % h*drogenation % addition not electrophilic addition (1)

H H
(ii)

H C H H C H O H C H C

C H H

O H
2

o,idation %redo, (1)

H
(iii)

C H

C N

(1) addition not electrophilic addition (1) 2

[17]

13.

(a)

CHNO3 + CH2SO4 (1) HNO3 + 2H2SO4 NO 2 (1) + H3O+ + 2HSO 4 (1) electrophilic substitution (1) (1 ) + N O +
2

(1 )

H N O
2

(1 ) (b) reduction HC1%/e or Sn or 0n or Sn Cl2 (c) or h*drogenation (1) H2%Ni or 1t or 1d or Cu (1)

< 2

C6H5NH2 + CH3 COCl (1) C6H5NHCOCH3 + HCl (1) or C6H5NH2 + (CH3CO)2O C6H5NH COCH3 + CH3 COOH nucleophilic addition7ele"ination (1) (1 ) C 6H 5N H
2

Cl C C H
3

(1 ) O C 6H 5N H
+ 2

Cl C CH
3

(1 ) O
)

O C 6H 5N H (1 ) H
+

C C H
3

<
[16]

14.

(a)

lone pair on N (1) donated to H+ or proton acceptor (1) 2 2

(b) (c)

lone pair on N less a ailable (1) due to delocatisation (1) (i) (ii) nucleophilic substitution (1) (CH3)2 NH (1) (CH3)3 N (1) (CH3)4 N+ 4r) (1) (iii) &uaternar* a""oniu" salt (1) 5
[9]

10

15.

(a)

(i) (ii)

CH3CN + 4:H; (or 2H2) CH3CH2NH2 (1) 5i2lH4 or Na%C2H5OH (or H2%Ni) (1) .roduct & (C2H5)3N (1) (1 ) H
2

(b)

(nucleophilic) substitution or al#*lation (1) .roduct % (C2H5)2NH (1) .roduct ! (C2H5)4N+4r) (1) 4

(1 ) @@ C H 3C H 2 N H (c) (d)

4r

C H 3C H 2N H 34 r (1 )

lone pair on N less a ailable or electron densit* on N decreased (1) due to delocalisation (1) electron (ithdra(al b* O or CO or delocalisation b* CO (1) reduces electron densit* on N or "a#es N lone pair less a ailable (1) 2C2H5NH2 + CH3COCl (1) CH3CONHC2H5 + C2H5NH3+Cl) (1) (nucleopholic) addition ) eli"ination (1)

(e)

($)

(1 ) @@ C 2H 5N H
2

C l C C H
3

(1 ) O C 2H 5N H
+ 2

C l C C H
3

(1 ) @@ O
)

C 2H 5N H C O C H (1 ) H

<
[20]

16.

(a)

(i) (ii)

H+ or proton acceptor (1) CH3NH2 + H2O ( ) CH3+NH3 (+) OH) (1) CH3NH3Cl or HCl (1)
Or any ammonium compound or strong acid name or formula
+

(iii)

e,tra OH) reacts (ith C H 3 N H 3 or reaction % e&uilibriu" "o es to le$t or ratio salt % base re"ains al"ost constant (1)
Any 2

5
11

(b)

lone pair (on N accepts H+) (1) CH3 increases electron densit* (on N) donates % pushes electrons has positi e inducti e e$$ect (1) 2

(c)

nucleophilic substitution (1) C 2H 5

C H

C 2H
5

C 2H

(1)

2
[9]

17.

(a)

(i)

Equation Type of reaction Explanation

C6H5CH24r + 2NH3 C6H5CH2NH2 + NH44r (1) (1) nucleophilic subsn or al#*lation (1) $urther substitution occurs (1) o gi e a "i,ture o$ products (1)

(ii)

reduction or h*drogenation (1) C6H5CN + 4:H; C6H5CH2NH2 (1) or 2H2 Na%C2H5OH or 5i2lH4 or H2%Ni (1) onl* one product $or"ed (1) or a oids $urther substitution F

(b)

0ea1er Explanation

base phen*la"ine (1) lone pair on N less a ailable or electron densit* on N lo(ered (1) due to delocalisation or o erlap (1)

3
[12]

18.

(a)

(i)

cHNO3 + cH2SO4 (1) HNO3 + 2H2SO4 NO2+ (1) + H3O+ + 2HSO4) (1) electrophilic substitution (1) C O CH
3

(ii)

C O C H +

:1 ;

:1 ; :1 ; N O
2

N O (b) Type of reaction Reagent(s)

:1 ; H

<

reduction (1) not h*drogenation not H2%Ni 2

Na4H4 or Na%C2H5OH (1) not 5i2lH4 CH3COCl or (CH3CO)2O (1) (nucleophilic addition)eli"ination (1)

(c)

Reagent

Name of mechanism Mechanism

12

:1 ; @@ 8 O H

Cl C CH
3

:1 ; O 8 O
+

Cl C CH
3

@@ O

:1 ;

8 :1 ; (d)

O H

O C CH
3

Type of reaction reduction or h*drogenation (1) Reagent(s) HCl%/e or Sn or 0n H2%Ni or 1t or 1d (1) or SnCl2 or Ni%H2 not 2iAl") 2

(e)

optical (1)

1
[18]

19.

(a)

(i) (ii)

lone pair on N (1) inducti e e$$ect o$ CH3 or electron donation (1) increases electron densit* on N or lone pair "ore a ailable (1)

(iii)

electron densit* on N decreased or lone pair less a ailable (1) due to delocalisation (1) Equation atalyst CH3CH2CN + 2H2 CH3CH2CH2NH2 (1) Ni (1)

(b)

(i) (ii) (iii)

nucleophilic substitution (1) $urther reaction can occur (1) bet(een prop*la"ine and 17bro"opropane (1) 5 1

(c) (d)

CH3CH2CH2NHCOCH3 (1) Type of product &uaternar* a""oniu" salt or chloride (1) $tructural formula CH3(CH2)11N+(CH3)3 (1) Cl) (1)

3
[14]

20.

(a)

5one pair on nitrogen (1) less a ailable or electron densit* lo(ered (1) due to delocalisation or resonance or "eso"eris" or part o$ , bond (1) Equation Name of mechanism Mechanism C6H114r + 2NH3 C6H11NH2 + NH44r (1) nucleophilic substitution (1)

(b)

13

(1 ) 4 r (1 ) (1 ) (c) (i) (ii) .N H

3

+ N H H (1 )

.N H

NaCN or 9CN (1) Reagent(s) Type of reaction Equation Na%C2H5OH or 5i2lH4 or H2%Ni (1) reduction or h*drogenation (1) C6H11CN + 4:H; C6H11CH2NH2 (1) or 2H2 i$ h*drogenation 4

(d)

Equation Name of mechanism Mechanism (1 ) 8N H .

2

28NH2 + CH3COCl 8NHCOCH3 (1) + 8NH3Cl (1) (nucleophilic) addition7eli"ination (1) (1 ) O

3

C l C C H

C l 8N H +
2

(1 ) O .
3

C C H

O + 8N H (1 ) H
2

C C H
3

<
[20]

21.

(a)

(i) (ii)

suitable graphical $or"ula $or ethanoic anh*dride (1) (acid) anh*dride (1) F = eth*la"ine % a"inoethane (1) reduction or h*drogenation or addition (ignore re$erence to "echanis") (1)

1 1 1

(b)

(i) (ii)

1 (c) CH3COCl + CH3CH2NH2 CH3CONHCH2CH3 + HCl CH3CONHCH2CH3 (1) balanced (1) 2

14

[6]

22.

(a)

5one pair on N or electron densit* on N (1) "ore a ailable or electron densit* increased (1) electron donation or inducti e e$$ect (1) Reagent(s) Type of reaction Equation 5i2lH4 or Na%6tOH or H2%Ni (1) reduction or h*drogenation (1) CH3CN + 4:H; or 2H2 CH3CH2NH2 (1)

(b)

(c)

(C2H5)4N+4r) (1) &uaternar* a""oniu" salt (1) cationic sur$actant (1) or $abric so$tener 3

(d)

Name of mechanism addition7eli"ination (1) Mechanism

(1 ) C 2H 5N H .
2

C l C C H
3

(1 ) O + C 2H 5N H

(1 )
2

Cl C CH
3

+ C 2H 5N H (1 ) H

O C CH
3

(e)

C2H5NH2 + (CH3CO)2O C2H5NHCOCH3 + CH3COOH (1) or 2C2H5NH2 + (CH3CO)2O C2H5NHCOCH3 + CH3COO) N H3C2H5
+

1
[15]

15

23.

(a)

(nucleophilic) addition7eli"inationE ? 2

1 a llo ( C 2 H C H 3C H
2 5

C H 3C H

)
? 1
3

O Cl

) O C N + Cl H

H C

(C H )

H N H 2 (M! for structure) (M) for ! arrows and lone pair) (M& not allowed independent of M%+ -ut allow M% for correct attac1 on * if M& show as independent first,) (*on of 3' loses M& -ut ignore * if correct) ( l( removing 4t loses M))
O C N H C H 3 (5f M$ lost a-ove for wrong error again here)

C H 3C H

5 chain+ do not penalise same 1

(b)

CH3CH2COCl + 2lCl3 :CH3CH2CO;+ + 2lCl4)E (penalise wrong al1yl group once at first error) (position of * on electrophile can -e on ' or or outside 6 7) (penalise wrong curly arrow in the equation or lone pair on Al l!)
+ ? 2 s tr u c tu re
3

? 1 + C O C H 2C H
3

C O C H 2C H H ? 3 a rro (

(horseshoe must not extend -eyond & to 9 -ut can -e smaller) (* not too close to %) (penalise M& if "3 chain wrong again -ut allow M% and M!) (M! arrow into hexagon unless :e1ule) (allow M! arrow independent of M& structure) 3

(M% arrow from within hexagon to or to * on ) (don8t penalise position of * on of R '*)

) 2lCl 4 + H + 2lCl 3 + HClE

(or can -e gained in mechanism);

16

(c)

?1 CH3CH2COCl + H2O G CH3CH2COOH + HCl 1 (penalise wrong al1yl group once at first error) ?2 ?r o$ CH3CH2COCl + F2@5 1 (if Mr wrong+ penalise M& only) ?3 "oles o$ CH3CH2COCl + 1@43%F2@5 + !@!16 1 ?4 "oles NaOH + 2 H !@!16 + !@!32 1 (allow for H & conseq to wrong no of moles) ?5 olu"e o$ NaOH + !@!32%!@42 + !@!<62 d"3 or <6@2 c"3 1 (with correct units) (if H& missed in M) lose M< also)

1 1 1 1

1
[16]

24.

(a)

CH3COCl + 2lCl3 CH3 C O + 2lCl 4 e&uation

1 1

penalise (rong al#*l group once at $irst error position o$ + on electrophile can be on O or C or outside : ; penalise (rong curl* arro( in the e&uation or lone pair on 2lCl 3 else ignore 6lectrophilicIsubstitution N'T 4= acylation ? 1
+

1 ? 3

C O

CH

H
3

C O CH

? 2 horseshoe must not extend -eyond & to 9 -ut can -e smaller * not too close to % M! arrow into hexagon unless :e1ule allow M! arrow independent of M& structure ?1 arro( $ro" (ithin he,agon to C or to + on C + "ust be on C o$ 8CO 3

17

(b)

NucleophilicIaddition ? 1
)

NOJ reduction CH C
3

1 CH
3

? 4 O
)

O ? 2

? 3 4 M& not allowed independent+ -ut can allow M% for attac1 of "( on * formed 1)phen*lethan()1))ol or (1)h*dro,*eth*l)ben=ene (c) deh*dration or eli"ination (conc) H2SO4 or (conc) H31O4 allow dilute and Al&'! >o not allow iron oxides
[14]

1 1 1

25.

(a)

eth*l ben=ene chloroethane or bro"oethane (or ethene and hydrogen chloride=-romide) alu"iniu" chloride%bro"ide or iron(>>>) chloride %bro"ide or iron + chorine%bro"ine CH3CH2Cl + 2lCl3 G CH3CH2+ + 2lCl4) electrophilic substitution
+

1 1 1 1 1
? 2 s tru c tu re C H 2C H a rro (
3

? 1
+

C H 2C H

H ? 3

3 (b) 1

C O

C H 2C H

CH3CH2COCl % propano*l chloride or (CH3CH2CO)2O % propanoic anh*dride Na4H4 or 5i2lH4 or H2%Ni (not $n=4e with " l)

1 1
[11]

18

26.

X is CH3CN or ethanenitrile or ethanonitrile or "eth*l c*anide or c*ano"ethane or eth*l nitrile or "ethanecarbonitrile Not ethanitrile -ut contradiciton of name and structure lose mar1s Y is CH3CH2NH2 or eth*la"ine or a"inoethane or ethana"ine Step 1. reagent 9CN not HCN%HCl condition (a&)%alcohol 7 onl* allo( condition i$ reagent correct or inco"plete Step 2. reagent condition H2 Ni%1t%1d 5i2lH4 ether Na ethanol 0n%/e%Sn HCl Not Na4H4

1 1 1 1 1 1

Z is an a"ine or a"inoal#ane or na"ed a"ine e en i$ incorrect na"e $or Z secondar* (onl* a(ard i$ a"ine correct) C H C H 3CH
2 3

+ C H
3

N C H
3

(4r)) + can be on N or outside brac#ets as sho(n

1 1
[9]

nucleophilic substitution 27. (a) C*clohe,ane e ol es 12! #K "ol)1 (e,pect triene to e ole) 36! #K "ol)1 (1) or 3 H 12! 36! ) 2!3 + 152 #K (1) NOJ 15! %<& can score first & ?of2@ -enAene lower in energy = more (stated) sta-le (1) Not award if mentions energy required for -ond -rea1ing due to delocalisation (1) or explained

19

(b)

(i)

phen*la"ine (ea#er (1) if wrong no mar1s lone pair on N (less a ailable) (1) delocalised into ring (1) or Be,plainedC 3 H C 6H C H Cl structure (1) M! ! arrows (1) M) N7phen*l ethana"ide (1)
+ 5 3

(ii)

addition ) eli"ination (1) ( C 6 H 5 ) N@ @ H (1 ) ? 1 (C H 3 )

2

O C

? 2 (1 )

N C Cl

H @@ O

(iii)

conc HNO3 (1) conc H2SO4 (1) HNO3 + 2H2SO4 N O2 + H3O+ + 2HSO4) (1) N O (1 ) ? 1 (1 ) ? 2 6 2
+ 2 + +

(1 ) ? 3 H N O
2

(i )

peptide % a"ide (1) NaOH (a&) (1) " l conc or dil or neither "&$') dil N'T conc N'T Bust "&'

20

Notes (a) 36! or 3 H 12! or in (ords (1)E 152 NOJ 15! (1)E (152 can get $irst t(o "ar#s) Q of ben=ene "ore stable but not a(ard i$ H alues used to sa* that "ore energ* is re&uired b* ben=ene $or h*drogenation co"pared (ith the triene or i$ ben=ene is onl* co"pared (ith c*clohe,ene (1)E delocalisation or e,plained (1) (ii) or N7phen*laceta"ide or acetanilide "echanis". i$ sho(n as substitution can onl* gain ?1 i$ CH3CO+ $or"ed can onl* gain ?1 lose ?4 i$ Cl) re"o es H+ be lenient (ith structures $or ?1 and ?2 but "ust be correct $or ?3
C O alone loses ?2

(b)

(iii)

No !ar"s for na!e of !e#$an%s! %n t$%s &art i$ conc "issing can score one $or both acids (or in e&uation) allo( t(o e&uations allo( HNO3 + H2SO4 NO2+ + HSO4) + H2O ignore side chain in "echanis" e en i$ (rong arro( $or ?1 "ust co"e $ro" niside he,agon arro( to NO2+ "ust go to N but be lenient o er position o$ + + "ust not be too near BtetrahedralC Carbon horseshoe $ro" carbons 276 but donDt be too harsh

(i )

reagent allo( NaOH HCl conc or dil or neither H2SO4 dil or neither but not conc not -ust H2O
[21]

21