HIDROCACBON THM 1.

Cho bit E+ (electrofin) ca cc phn ng ng sau: (i) Cl2 + AlCl3, (ii) HNO3 + H2SO4, (iii) Br2 + FeBr3, (iv) H2SO4 v (v)H2S2O7 (axit pyrosunfuric). (b) Xc nh baz cho mi trng hp. (i) Cl2 + AlCl3 [ +ClCl -AlCl3] + (ii) HONO2 + H:OSO3H [H2ONO2]+ H2O + NO 2 (iii) Br2 + Fe FeBr3 Br2 + FeBr3 [ +BrBr -FeBr3] (iv) 2H2SO4 H3O+ + HSO 4 + SO3 (v) HOSO2OSO2OH H+ + HSO 4 + SO3 (b) Phn baz (i) AlCl 4 (ii) HOSO2O , (iii) FeCl 4 (iv) v (v) HOSO2O . 2. Vit phng trnh phn ng v xc nh electrophin (E) v baz (B) cho mi trng hp. (a) HOCl + H+, (b) HNO3, (c) ICl + ZnCl2, (d) HONO + H+ (a) HOCl + H+ H2OCl+ Cl+ (E) + H2O (B) + + (b) 2HONO2 NO 3 + H 2 ONO 2 NO 2 (E) + H2O (B) 2 (c) 2I-Cl + ZnCl2 2I+ (E) + ZnCl 4 (B) (I+ bn hn hn Cl+) (d) HONO + H+ H2ONO NO+ (E) + H2O (B) 3. (a) Xc nh electrophin t phn ng CH3CH2Cl + AlCl3. (b) Trnh by cch iu ch elctronphin t (i) CH2=CH2 v CH3CH2OH. (c) Trnh by phan ng gia benzen v cc electronphin trong (a). (d) Cho bit sn phm ca phn ng gia benzen v cc electrophin trong (b). + + (a) CH 3 CH 2 to ra t CH 3CH 2 ...Cl ... AlCl 3 .

+ (b) (i) Cng vi H2SO4 c: CH 3 CH 2 ... OSO 3 H (ii) Cng vi BH3 hoc H2SO4, H3PO4 c.
C H
3

C H

+ 2

. . . O. . . | H

B H

(c) Phn ng Friedel Crafts.

Et EtCl AlCl3 H

C2 H5

AlCl 4

HAlCl4

(d) PhEt. 4. (a) Cho bit sn phm ca phn ng gia benzen vi i-PrCl v n-PrCl trong AlCl3. Vi i-PrCl to ra Ph-CHMe2. (b) Gii thch Vi n-PrCl to ra c hai Ph-CH(Me)2 v Ph-CH2CH2CH3. (a) Halogen bc 1 hot ng yu hn bc 2 v 3. nhit cao:
PhH H 3C CH CH 2

Cl

AlCl3

Ph

CHMe2

HAlCl4

H v RCOCl. (b) Trnh by c ch phn ng. 5. (a) Vit phn ng gia benzen Cht xc tc cho phn ng ny l axit Lewis, thng thng l AlCl3, c th BF3, FeCl3, ZnCl2. RCOCl + AlCl3 RCO+ + AlCl 4

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HIDROCACBON THM
O R RCO+ C H

AlCl4

C 2H 5

HAlCl4

6. Cho bit cng thc cu to ca sn phm phn ng gia benzen vi (a) CH 2=CH-CH3 (HF, 00C), (b) Xiclohexanol (BF3, 600C), (c) [Me2CHCO]2O (AlCl3) v (d) CH2=CH-CH2Cl (ZnCl2). (a) PhCH(CH3)2 (b) Xiclohexylbenzen (c) Ph-CO-CHMe2 (d) PhCH2CH=CH2 7. Cho bit sn phm ca phn ng gia benzen v etilen oxit trong AlCl3.
O O

AlCl3

PhCH CH2 OH AlCl 8. PhnAlCl ng PhHgOCOCH by c 3 gia benzen v thy ngn (II) axetat trong HClO 4 to 2 3. Trnh 3 ch phn ng.
O H 3C C O C O H 3C C O Hg H O Hg O O C OH C CH 3 H+ H3 C O C O C O Hg O OH C O C CH 3

PhH

H+ H 3C O Hg O CH3 H3C O Hg HO

(E)
HgOCOCH3

CH 3

HgOCOCH 3 H+

9. (a) V sao benzen khng th iot ha trc tip t I2? (b) Trnh by s iot ha benzen. (a) S iot ha bng I2 rt chm (F2 > Cl2 > Br2 > I2) v phn ng thun nghch H = 12 kcal/mol. (b) HNO3 phn ng vi I2 to ra electron mnh hn: I+
1 I 2 + 2H + + NO 3 + I+ OH 2 + NO 2 2 H 2O 2O PhH + + I+ OH 2 H Ph + I H PhI + H 3O +

Tc nhn HO I tao ra khi tc nhn oxi ha l H 2O2. Iot ha trc tip, I to ra s phn ng vi cc cht oxi ha ti to I2. 10. (a) V sao khng th to ra flobenzen bng phn ng trc tip vi F2. (b) Flobenzen c iu ch bng cch cho benzen phn ng vi Tl(OCOCF3)3 sau cng vi KF v BF3. Vit phng trnh phn ng. (a) F2 hot ng qu mnh, nn n c th tham gia c hai phn ng cng v a th. + Tl (OCOCF 3 ) 2 + CFCOO (b) Tl (OCOCF 3 ) 3
+ / BF3 H Tl (OCOCF 3 ) 2 + PhH PhTl (OCOCF 3 ) 2 KF PhF
+

11. (a) Nu qui lut th electrophin vo nhn thm c mt nhm th. (b) Nhm no trong cc nhm cho di y nh hng ortho, para ; nhm no nh hng meta. ng Cng Anh Tun http://dangtuanlqd.violet.vn 2

HIDROCACBON THM -OH, -NH2, -NHR, -NR2, -NHCOR, -OCOR, -OR, -R, -Ar, >C=C<, -I, -Br, -Cl, -F, -CH2X, -NO, O=S<, -SO3H, -CN, -CHO, -COOH, -COOR, -COCl, -NO2, -CF3, N R 3 Xem bng ortho, para meta VSA SA A D SD VSD -OH, -NH2, -NHCOR, -R, -Ar, -I, -Br, -Cl, -SO3H, -CN, -NO2, -CF3, -NHR, -NR2 -OCOR, >C=C< -F, -CH2X, -CHO, -COOH, N R3 -OR -NO, O=S< -COOR, -COCl 12. So snh kh nng phn ng vi tc nhn electrophin. (a) p-nitroclobenzen, clobenzen, 2,4-initroclobenzen. (b) axetamit (PhNHCOCH3), anilin, axetophenol (PhCOCH3). (c) 1,3-imetylbenzen, 1,4-imetylbenzen, toluen, benzen, 1,3,5-trimetylbenzen. (d) p-CH3C6H4COOH, p-HOOCC6H4COOH, p-CH3C6H4CH3, C6H5CH3. (a) clobenzen > p-nitroclobenzen > 2,4-initroclobenzen. (b) anilin > axetamit > axetophenol (c) 1,3,5-trimetylbenzen > 1,3-imetylbenzen (ng thun) > 1,4-imetylbenzen (khng ng thun) > toluen > benzen. (d) p-CH3C6H4CH3 (2A) > C6H5CH3 (1A) > p-CH3C6H4COOH (1A+1D) > pHOOCC6H4COOH (2D). 13. Cc gi tr f ca s nitro ha t-butylbenzen l: fo = 4,5 ; fm = 3,0, v fp = 75. (a) Kh nng th ca t-butylbenzen gp bao nhiu ln benzen? (b) Tnh % ca mi loi sn phm. (a) Kh nng phn ng ca t-butylbenzen gp 15 ln benzen. (b) ortho :
2 4,5 100% = 10% 90 meta :

t BuPh 2 4,5 + 2 3,0 + 75 90 = = = 15 PhH 6 1 15

2 3,0 1 75 = 6,7% para : = 83% 90 90

14. 450C kh nng phn ng nitro ha trong dung dch CH3COOH gp 25 ln benzen, t l sn phm: ortho: 56,5; meta: 3,5 v para: 40,0.(a) Tnh f. (b) Gii thch. (a) Tnh f.
fo = 6 25 0,565 = 42,2 2 fm = 6 25 0,035 = 2,6 2 fp = 6 25 0,400 = 60 1

(b) Nu f > 1, G l nhm hot hot, nu f < 1, G l nhm phn ha. nhm CH3 hot hot cho tt c cc H vng benzen, tuy nhin sn phm v tr v tr meta thp hn. 15. Dng mi tn ch E+ thay th H v tr no nhiu nht trong vng benzen trong cc trng hp sau: (a) Ba ng phn nitrotoluen. (b) Ba ng phn metoxitoluen (c) Ba ng phn metoxiacetanilit. (d) p-CH3C6H4NH3Cl, o-HOC6H4COOH, m-C6H4(NO2)2.
CH3 NO 2 CH 3 CH 3

(a)
NO2 NO 2

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HIDROCACBON THM
OCH3 CH 3 OCH 3 OCH 3

(b)
CH3 CH 3 NHCOCH 3 OCH 3 NHCOCH3 NHCOCH 3

(c)
OCH 3 OCH 3 NH 3Cl OH COOH NO 2

(d)
CH NO

NR

2 3 16. (a) Cho bit c ch phn ng bromdeankyl ha sau: ArC(CH3)3 + Br2 ArBr + (CH3)2C=CH2 (b) V sao ArCH2CH2CH2CH3 khng xy ra phn ng. (a) Me3C+b thay th bi Br+, n tch H+ to thnh isobutylen. ArC(CH3)3 Br [Br-Ar-C(CH3)3]+ ArBr + (CH3)3C+ CH2=C(CH3)2 + H+ (b) V to ra n-Bu+ km bn i hi nng lng qu ln. 17. iu ch (a) meta-, (b) para- v (c) o-clonitrobenzen.
+

3 C6 H 5 N O2 2 m C lC6 H 4 N O2 (a) C 6 H 6 H SO F eC l
HNO
2

Cl

C 6 H 5C l p C lC6 H 4 N O2 (b) C 6 H 6 FeC l H SO

C l2 HNO 3
2 3 4

Cl H 2SO 4 SO 3

Cl HNO 3 H 2SO 4 SO 3H

Cl NO2 H 2 SO 4 SO3H
K M nO

Cl NO2

(c)

18. T benzen v cc cht v c cn thit, vit cc phn ng iu ch cc cht sau vi hiu sut cao: (a) axit p-brombenzoic, (b) axit p-brombenzoic, v (c) axit m-brombenzoic.
3 2 C 6 H 5C H3 p C H3C 6 H 4 B r 4 p H O O C C (a) C 6 H 6 6H 4B r A lC l Fe nng

CH Cl
3

Br

CH 3 H 2 SO 4 SO 3

CH3 Br2 Fe SO 3H

CH 3 Br

CH 3 Br KMnO4

COOH Br

(b)

H 2SO 4 SO3 H

C H3C l M nO B r2 C 6 H 5C H3 K 4 C 6 H 5C O O H m HOOCC (c) C 6 H 6 6H4B r A lC l n n g Fe

3

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HIDROCACBON THM 19. iu ch (a) ortho-, (b) para- v meta-bromtoluen t toluen.

CH 3 H 2 SO 4 SO 3 SO 3H CH3 Br2 Fe Br CCl3 Cl2 as Br2 Fe CH3 Br2 Fe SO3H CH 3 Br CH 3 Br

(a)

H 2 SO 4

CH 3

(b)

CH 3

CCl3

CH 3

(c)

Zn/HCl Br Br

20. T toluen, benzen v cc cht v c cn thit, vit cc phn ng iu ch: (a) axit 3-nitro-4-brombenzoic (A) (b) axit 2-nitro-4-brombenzoic (B) (c) axit 4-nitro-2-brombenzoic (C) (d) axit 3,5-initrobenzoic (D)
3 (a) p-BrC6H4COOH HSO A

HNO
2 4

CH 3 H2 SO4 SO3

CH3 HNO3 H2 SO4 SO 3H

CH 3 NO2 H 2SO4

CH 3 NO2

(b)

SO3H COOH NO2 KMnO4 nng NO2

CH 3 NO 2 Br 2 Fe CH 3 HNO3 H2 SO4

CH 3

CH3 Br Br 2 Fe NO2

CH 3

Br Br KMnO4 nng

COOH Br

(c)

NO 2

NO 2

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HIDROCACBON THM
CH 3 KMnO4 nng COOH COOH HNO3 H2 SO4 HNO 3 H 2SO 4, t0 NO2 COOH Br

(d)

21. (a) So snh kh nng th gc ca cc ca nguyn t H: benzyl, allyl, 30, 20, 10, MeNO v 2 vinyl. (b) Vit phn ng khi cho PhCH2CH2CH3 tc dng vi Br2 (nh sng). Trnh by c ch phn ng. (a) benzyl > allyl > 30 >20 >10 > Me v vinyl. 22. Cho bit cng thc cu to ca cc cht c tn sau: (a) -nitronaphtalen, (b) -naphtol, (c) 1,5-iclonapthalen, (d) axit 1-naphthalensunfonic v (e) axit 2-naphthoic. Cch nh s:
8 1 2 3

7 6

OH NO2

Cl

(a)
SO3 H

(b)

(c)

Cl COOH

(d)

(e)

23. Cho bit cng thc cu to ca cc cht c tn sau: (10.49) (a) axit anthran-1-oic. (b) 9,10-ibromanthracen, (c) 1,2,6,7-tetrametylanthracen, (d) 1,2-benzanthracen (e) 9-anthrol.
7 6 8

1 2 3

10

COOH

Br

(a)

(b)
Br

(d) Anh Tun ng Cng

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HIDROCACBON THM 24. Cho bit cng thc ca cc cht sau: (a) -bromphenanthren, (b) 2,6,9-trimetylphenanthren. Cch nh s:
9 8 7 6 5 4 3 10 1 2

Br

Me

(a)

(b)

Me

25. (a) Cho bit sn phm khi oxi ha naphtalen trong Me cc trng hp sau (i) CrO 3/CH3COOH, (ii) O2/V2O5. (b) Gii thch v sao napthalen (255 kJ/mol) d oxi ha hn benzen (151 kJ/mol). (a)
O O C COOH O C O O

(i)

(ii)

hay
COOH

(b) Oxi ha mt vng ca naphtalen c nng lng thp hn benzen. Oxi ha vng th nht ch mt 104 kJ/mol, cn oxi ha vng th hai phi mt 151 kJ/mol. 26. Khi oxi ha 1-nitronaphtalen th thu c axit 3-nitrophthalic trong khi oxi ha 1aminonaphtalen th thu c axit phthalic. Gii thch.
NO 2 NH 2

A [O]
NO2

Sn/HCl

A [O]
COOH

HOOC

B
COOH

HOOC Nhm NO2 l nhm ht electron lm bn ha vng A, nn vng B b oxi ha. Trong khi nhm NH2 lm cho vng A km bn nn vng A b oxi ha. 27. (a) Cho bit sn phm kh naphthalen bi (i) Na trong C 2H5OH un si (nhit si ca C2H5OH l 780C), (ii) Na trong C5H11OH un si (nhit si ca C5H11OH l 1320C). (b) Gii thch s khc nhau ca hai sn phm kh. (c) iu ch teralin bng tng hp DielsAlder. (a) (i) 1,4-ihidronaphthalen, (ii) 1,2,3,4-tetrahidronaphthalen (tetralin)

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HIDROCACBON THM

(b) Nhit si l nhit ca phn ng, nhit si ca C 5H11OH cao hn nn sn phm kh lag tetralin. (c) Tng hp tetralin
Br

2NBS

EtOK

28. (a) Cho bit sn phm (i) oxi ha anthracen bng K2Cr2O7/H2SO4 v (ii) kh n bng Br Na/C2H5OH. (b) Cho bit sn phm (i) oxi ha phenanthren bng K2Cr2O7/H2SO4 v (ii) kh n bng Na/C2H5OH. (a)
O H H

(i)
O

(ii)
H H

H H

H H

(i)

(ii)

29. Vit sn phm ca phn ng Diels-Alder gia phenanthren vi (a) etielen v (b) anhdrit maleic.
H2 C H2C HC HC CO CO O

(a)

(b)

30. (a) Vit cng thc cu to ca sn phm ca phn ng nhit thp gia anthracen vi Br2/CCl4 v trnh by c ch phn ng (b) Cho bit kiu phn ng cng. (c) Xc nh phn phm nu thc hin phn ng nhit cao? (a)
Br Br H

Br +

Br-

9,10-ibrom-9,10ihidroanthracen (cis/trans) (b) Phn ng cng 1,4. ng Cng Anh Tun http://dangtuanlqd.violet.vn 8

Br

HIDROCACBON THM (c) Nu nhit cao, s tch H+ trn C9 to thnh 9-bromanthracen.

Br

31. Phenanthren phn ng vi Br2 (1:1) nhit thp cho sn phm cng l 9,10-ibrom-9,10ihidrophenanthren (G) l hn hp hai ng phn cis v trans. (a) Vit cng thc phn t ca G v c ch phn ng to ra n. (b) Gii thch v sao phn ng to ra G m khng to ra sn phm khc. (c) V sao c ng thi hai kiu cng syn v anti. (d) Cho biu kiu ca phn ng cng? (e) Nu thc hin phn ng nhit cao, cho bit sn phm to thnh. (a)
H H H Br Br H Br

Br+

Br cis/trans G

(b) Lin kt i C9-C10 l mt lin kt i c bit, khi cng vo ni i ny s cho hp cht iphenyl vi hai vng benzen mi vng c nng lng l 151 kJ/mol. (c) Cacbocation to ra c bn ha bi vng phenyl. (d) Kiu phn ng cng 1,2. (e) nhit cao, s tch proton t cacbocation F to ra 9-bromphenanthren.
H H Br Br

-H +

32. 1-etenylnaphthalen phn ng vi etylen to thnh cht A, un nng A c Pd hoc S s cho cht B c cng thc phn t C14H10. Cho vit cng thc cu to ca A v B.

S t0 A
33. (a) Trnh by c ch ca phn ng Birch Reduction.
Na/NH 3 ROH Na/NH 3

B: phenanthren

(b) Vit cc phn ng ca cc cht sau vi Na/NH3(ROH) (i) ArOCH3, (ii) o-xilen, (ii) ArCOOH, v Ar-C(CH3)=CH2 ng Cng Anh Tun http://dangtuanlqd.violet.vn 9

ROH

HIDROCACBON THM (a)

(b)

34. Trnh by c ch phn ng Blanc:

Lu :

35. (a) Trnh by c ch ca phn ng Friedel-Crafts Acylation

(b) Hon thnh cc phn ng sau: (i)Ar-H + PhCOCl, (ii) Ar-H + Ac2O, (iii) ArH + ClCOCOOEt. (a) C ch:

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HIDROCACBON THM

(b) Cc phn ng (i) Ar-H + PhCOCl x t ArCOPh + HCl (ii) Ar-H + Ac2O x t Ar-COCH3 + CH3COOH (iii) Ar-H + ClCOCOOEt ArCOCOOEt + HCl

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