4.4, 4.5 HW MS 1.

(a) nucleophilic addition M 2 CH 3CH

2

1 C H 3C H O C H CN C N M 4 H
+

C H M 1

M 3 4

(b)

(i) (ii)

2-hydroxybutanenitrile H 3C C H C C N H
2

1 2 H O

(allow 1 for amide even if not C4H7NO, i.e. RCONH2) (if not amide, allow one for any isomer of C4H7NO which shows eometric isomerism) (c) (i) H CH 3C H
2

O H
3

CO O CH (ii)

O CH 3C H
(iii) CH3CH CHCOOH
2

CO O H
1
[11]

Mill Hill High School

2.

(a)

(i) (ii) (1 )

2! 3 di"ethylbutan 2 ol (1) eli"ination (1) !echanism H

+

O H

(1 )
2

O H

(C H 3 )2 C

C H (C H 3 )

(C H 3 )2 C

C H (C H 3 )

(1 ) H (C H 3 )2 C (1 ) (iii) "tr#ct#re C (C H 3 )
2

(C H 3 )2 C

C (C H 3 )

C H (C H 3 ) H 2C C C H
3

(1 )

Name of isomer $%&lanation

2! 3 di"ethylbut 1 ene (1) lo## o$ H+ or H (1) $ro" end C al#o po##ible (1)

1%

(b)

(i)

$'#ation
(C H 3 )2 C

O H C H (C H 3 )
2

O C O CH + C H 3C O C l (C H 3 ) 2 C

3 2

C H (C H 3 )

+ H C l

(1 )

Name of mechanism !echanism (1 ) ' O & H C l C C H O C C H

3 3

addition eli"ination (1) Cl ' + O H C CH

3

(1 ) O

(1 ) O a llo ( lo # # o $ H + h e re

' (ii)

+ O (1 ) H

(y&e of reaction Rea ent(s) Conditions

e#teri$ication (1) CH3COOH or ethanoic acid (1) #tron) acid cataly#t (1) or H2*O4 or HC+ ,
[19]

Mill Hill High School

3.

(a)

(i)

propyl "ethanoate (1) not &ro&anyl ) wron rea ent or no rea ent scores *ero

)n incom&lete rea ent s#ch as silver nitrate for (ollens, or &otassi#m dichromate loses the rea ent mar+, ,#t can et ,oth o,servation mar+s &enalise o,servations which -#st say colo#r chan e occ#rs or only state startin colo#r
(ii) Rea ent& NaHCO3 (1) O,servation with C& no reaction (1) O,servation with D& e$$er-e#cence (1) for C and D NO( (ollens .e#t an identi$ied (hydro)en) carbonate no reaction bubble# or CO2 acidi$ied /2Cr2O0 )oe# )reen no chan)e acidi$ied /MnO4 )oe# colourle## no chan)e correct "etal no reaction bubble# or H2 12 or #tated indicator no chan)e red or correct colour pH 3 56, 4 3Cl4

Ob#er-ation (ith C ob#er-ation (ith D

no reaction ("i#ty) $u"e#

(b)

(i)

Rea ent& pentan-2-one (1) or 2.&entanone ,#t not &ent.2.one or &entyl Rea ent& .ollen7# or 8ehlin)7# (1) O,servation with E& no reaction (1) O,servation with F& #il-er "irror or red ppt (1) 4 acidi$ied /2Cr2O0 no chan)e )oe# )reen *chi$$7# no reaction )oe# pin; $or E and F .ollen# no reaction #il-er or "irror or )rey or ppt H

(ii)

.e#t ob#er-ation (ith E ob#er-ation (ith F

8ehlin)# or 9enedict# no reaction red or ppt not red #olution

iodo$or" or 22:NaOH yello( (ppt) no reaction

C H 3C H (c)

CH O 1

CH 3 (1) m#st ,e aldehyde. )llow C2H/ for CH0CH2 otherwise this is the only answer

[9]

Mill Hill High School

Mill Hill High School

4.

(a)

(i)

B& propanoyl chloride (or con#e<uentially on part (a) (ii)) (1) C& propanoic anhydride (or con#e<uentially on part (a) (ii)) (1) do not allo( $or"ulae 2

(ii) (iii)

e$$er-e#cence : "i#ty $u"e# : #tea"y $u"e# : $u"e# : #olution beco"e# (ar" : $i==in) not >u#t )a# (1)

(1) (the "ini"u" nece##ary $or the "ar; i# C O and CN #ho(n) (i-)

(CH3CH2CO)2O + H2O
allo( C2H4?66

2CH3CH2COOH

(1)

(b)

(i)

"ethanol (1) "ethyl propanoate (or con#e<uentially on part (a) (ii)) (1) do not allo( $or"ulae 2

(ii)

A& in pre#ence o$ (concentrated) #ulphuric acid : H2*O4 : #tron) acid : )a#eou# hydro)en chloride or HCl allo( dilute H2*O4 (1) heat : re$lux (but only i$ $ir#t "ar; a(arded) (1) allo( 1 "ar; $or acidic condition# : H+ and heat B& roo" te"perature : in the cold : not heated : coolin) not acid (1) C& heat : re$lux not acid (1) 4
[11]

5.

(a) CH

(i) O CH O H C H 2C H + C H 3C O O H CH C O C H C H 2C H (1 ) (ii) (iii) e#ter (1) #ol-ent! $la-ourin)# (1) conc H2*O4 (1) 5 1
3

CH

+ H 2O e<
n

(1 )

in #a"e phy#ical #tate (1) (b) C4H1%O + 5O2 4CO2 + 4H2O (1)

Mill Hill High School

(c) C H

(i) C H O H C H 2C H CH CH O H (1 ) C H (ii) t(o H on carbon in double bond (1) C H 3 CH 3 C H 3

2 2

C H 2C H

C H

+ C H (1 )

C H 2C H

+ H
+

H (1 )

(1 )

C H C H 2C H

H C C C H
3

C
(iii)

C H

(1 ) o r H

ci# but-2-ene (1) tran# but-2-ene

0
[14]

6.

(a)

Rea ents (y&e of reaction

Na9H4 (1) reduction (1) /2Cr2O0 (1) H2*O4 (1) re$lux (1) 4 2

(b)

(i)

Rea ents(s) Conditions

(ii) (c) (d)

CH3CH2CH2OH + 2@OA CH3CH2COOH + H2O (1) HCN or NaCN:H+ (1) nucleophilic addition (1)

Rea ents Name of mechanism (i) (ii) "irror i"a)e# (1)

plane polari=ed li)ht (1) rotated in oppo#ite direction# (1) 3

O C H 3C H 2C
(e) (i) *tructure Na"e

O C H 2C H 2C H
propyl propanoate (1)

(1 )

O H
(ii)

C O C H 2C H
3

(1 )

($)

CH3CH2CO or C3H5O + 4 O2

(1)

3 CO2 + 3H2O (1)

2
[16]

Mill Hill High School

7.

(a)

(i)

correct )raphical $or"ula $or tertiary alcohol allo( CH3 not C2H4 (1) 2-"ethylbutan-2-ol : 2-hydroxy-2-"ethylbutane : 2-"ethyl2-hydroxybutane a(ard na"e "ar; e-en i$ it $ollo(# incorrect $or"ula (1)

2 2 1 1 1 1

(ii)

)raphical $or"ula o$ pent-1-ene (1) )raphical $or"ula o$ pent-2-ene (1) accept )eo"etrical i#o"er# o$ pent-2-ene i$ clearly #ho(n to be di$$erent

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

dehydration : eli"ination (1) no H ato"# on C ato" next to COH : three "ethyl )roup# on C (1) ethanenitrile : ethanonitrile : "ethyl cyanide : cyano"ethane : acetonitrile (1) any hydroly#i# (1) CH3COCl + CH3NH2 B CH3CONHCH3 + HCl $or correct $or"ula o$ "ethyla"ine : HCl product (1) o-erall correct (1)

2
[10]

8.

(a) (b)

Na9H4 (1) nucleophilic addition (1)

(1 )

O (1 ) &C N (1 )

(1 ) H O & CN

(1)

(c)

(i) (ii)

hexanedioic acid (1) C5H1%O Mr ,C (1) C5H1%O4 Mr 145 (1) 264% ,C D 145 364C ) (1)

264% )

4
[10]

9.

(a)

(i)

ethyl ethanoate H H C H C O O H C H (1) H C H 2 1

7

(ii)
Mill Hill High School

e#teri$ication : conden#ation : addition - eli"ination (1)

(b)

(i)

a<ueou# : dilute #ulphuric : hydrochloric acid (allo( HCl(a<)E H2*O4(a<) not (ater) (1) te"p6 F 1%%G : (ar" : heat : re$lux (thi# "ar; dependent on #en#ible rea)ent) (1) 2

(ii)

CH3COOC2H4 + H2O CH3COOH + C2H4OH (allo( C4HCO2! C2H4O2 but "u#t ha-e C2H4OH) (1) 1

(c)

(i)

#odiu" hydroxide : #odiu" carbonate : #odiu" hydro)en carbonate (allo( $or"ula) (1) roo" te"perature : a<ueou# (2nd "ar; dependent on correct rea)ent) (1) 2

(ii)

ethanoic anhydride H H C C O (1) ("ethyl )roup# can be #ho(n a# CH3 but the CC bond "u#t be dra(n) O H H H C C O 2 H

(iii)

addition o$ (ater : hydroly#i# (1) (CH3CO)2O + H2O 2CH3COOH (1) 2

(d)

(i)

ethana"ide not ethyla"ide6

H H C H H
(1) (ii)

O C N H

a""onia (not i$ dilute i"plied) : a""oniu" carbonate :3Cl 4 $ollo(ed by NH3 (allo( $or"ulae) (1) heat or te"perature F 1%%G (1) 2 1
[17]

(iii)

CH3CONH2 + HCl + H2O CH3COOH + NH4Cl (1)

Mill Hill High School

10.

(a)

(i)

Hn appropriate al;eneE CH3CH2CHCH2 or (CH3)2CCH2 2#o"er 1 2#o"er 2 3o#ition i#o"eri#" Mechani#" electrophilic attac; and electron #hi$t to 9r (1nle## H + u#ed) carbocation reaction (ith carbocation 1)llow mechanism mar+s for the al+ene CH0CHCHCH02 1)llow one mar+ if mechanism for minor &rod#ct iven2

1 1 1 1 1 1 1

(ii)

Hn appropriate carbonylE CH3CH2CHO Mechani#" nucleophilic attac; and electron #hi$t to O anion inter"ediate reaction (ith anion 1)llow mechanism mar+s for the car,onyl (CH3)2CO2

1 1 1 1 1 1 1

2#o"er 1 2#o"er 2 Optical i#o"eri#" N3 N3 (b) 4somer str#ct#res m#st ,e tetrahedral 5enalise 6stic+7 str#ct#res once in &art (a)

Io+ +ar)e char)e on carbonyl carbon ato" due to bondin) to O and Cl Nucleophile# ha-e electron pair# (hich can be donated J<uation *pecie# 9alanced

1 1 1 1
[18]

Mill Hill High School