Trng THPT Chuyn H Long

Ho Hc Hu C

(Ti liu tp hun ti H Ni) Gio vin ging dy: Gio s Trn Quc Sn i tuyn Ho quc gia nm hc 2005-2006 knh tng cc Thy C t Ho trng THPT Chuyn H Long.

_ Qung Ninh _

Bi 1: a/ Vit cng thc cu to thu gn nht v gi tn cc ankan cha 11 C, 21C, 101C v 201C, bit rng tn ankan cha 100C l hectan, cha 200C l ictan. b/ n- ankan cha 101C c bao nhiu lin kt ? Khi Clo ho nh sng sinh ra bao nhiu dn xut mono Clo ? Trong s cc dn xut c bao nhiu cht c ng phn quang hc. c/ Gi tn cc hp cht sau.

Bi lm: a/ 11 C 21 C 101 C 201 C CH3[CH2]9CH3 CH3[CH2]19CH3 CH3[CH2]99CH3 CH3[CH2]199CH3 Undecan Hen icosan Hen hectan Hen ictan nH n C H m C (m-1) C C cu to i xng Tin t -OH hidroxi -NH2 amino Hu t ol amin

b/ C101H204 204 lk C-H 100 lk C-H 304 lk c/ 51 dn xut mono Clo trong 49 dn xut c ng phn quang hc. d/ A: 1-amino-2-hidroxi xiclohectanol 2-amino xiclohectanol B: Spiro [49.50] hectan-51-amin C: 54-Clobixiclo [35.33.30] hectan Chung cnh m t im chung1 cu ln im chung2 cu nh cu nh hn cu nh nht
C1 C7 C6 C2 C8 C3 C5 C4

Chung nh m t cu nh nh cu ln
C1 C2 C3 C4 C5 C6 C8 C7

spiro[3.4]octane
C1 C2 C3 C4 C5 C6 C8 C7

bicyclo[3.2.1]octane

Cl (6R)-6-chlorospiro[3.4]octane

Bi 2: So snh nhit si ca cc cht trong mi dy sau: a/ C6H6; C6H5OH; C6H5CH3; C6H5CH2CH3 b/ CH3SH; CH3CH2OH; CH3OH c/ Cc ng phn cu to ca C4H9Cl d/ penta-1,4-ien; penta-1,3-ien e/ cis_CH3-CH=CHCl; trans_CH3-CH=CHCl Bi lm: a/ C6H6 < C6H5CH3 ko lk H ko lk H ko phn cc phn cc yu M nh c M trbnh b/ < C6H5CH2CH3 < C6H5OH Rt mnh ko lkH lin pt c lkH lin pt + phn cc yu O m in mnh pht phn cc c M ln +

CH3SH < CH3OH < CH3CH2OH yu lkH rt yu (gn nh c lkH lin phn t c lkH lin phn t + + ko c, 0,1-0,3Kcal/mol) (5 Kcal/mol) S < O MCH3OH<MCH3CH2OH MCH3OH<MCH3CH2OH rt yu c/
CH3 H3C C CH3 Cl
C C C C Cl
C C Cl C C
C C C C Cl

_Cl: _OH: d/

51

69 C 108 C

68 C 100 C

78 C

phn cc tc thi ph thuc vo phn t khi i xng phn t Lc ht Van ph thuc vo M

Trong thc t: phn iso t s>sec

C > h lin hp pht phn cc

C C C

C C

C C

e/
H3C C H C Cl H H H C H3 C C Cl

>

Momen lng cc

Bi 3: So snh nhit nng chy cu cc cht: a/ C6H6; C6H5OH; C6H5CH2CH3 b/ 1,2,3,4-Tetrametylbenzen c/ 1,2,4,5-Tetrametylbenzen d/ Imidazol Inol
N N H
N H N

Purin
N N H

e/ (CH3)2CHCH2COOH; (CH3)2NCH2COOH; (CH3)2PCH2COOH Bi lm: a/ C6H5CH2CH3 b/

CH3 CH3 CH3

<

C6H6

< C6H5OH

t nc: cng ph thuc vo cc lc tng tc, khi cc lc gn # nhau ta xt tnh i xng phn t.

<
CH3 CH3 H3C CH3

CH3

i xng

c/
H C O N CH3 CH3

<

H3C

H N C O CH3

<

H3C

C CH2 NH2

Lin kt H
R-H N N N N H N N N N H R-H

ko c d/

lk H mng

R-H

Inol < Imiazol < Purin gn nh ko cn lkH 2trtm yu do lhp nhiu lkH e/
H3C CH3 O OH H3C

<

P CH3 O

OH H3C

<

N CH3 O

OH H C H 3 +
N CH3 O

M ln
COOH COOH

lng cc

lk H mnh

COOH

<
S

<

Bi 4: So snh bn ca lin kt H: a/ HF vi HF; HF vi F b/ Cc lin kt H trong hn hp CH3OH v CH3SH c/ i-C4H9SH vi CH3CN; CH3COCH3 v CH3SCH3 Bi lm: a/ F-H...F-H < F -...H-F (50 Kcal/mol) [F-H-F]- lk H bn nht
S H O CH3 H

HF kh
F H H F H F H F H F H

b/
S CH3 H S CH3 H

F
O H O CH3 H

<

CH3

< CH3

O CH3

S CH3

0,10,3 Kcal/mol c/
CH3 S H2 C H3C CH3 H S CH3

0,50,8 Kcal/mol

5 Kcal/mol

: O > S

<
S H CH2 H3C CH3 N C CH3

<
CH3 S H2 C H3C CH3 H O CH3

ghi thm: H/ Octo:_OH>_SH

Bi 5: Hy cho bit nhng ion hay phn t no c tnh thm: Bi lm: - Hp cht thm: Vng phng, lin hp khp kn v phi c e tho mn: e = k = 4n + 2 (vi nN)

N (-)

thcra

k = 4 (ko) k = 6 (thm) k = 6 (thm) k = 6 (thm)

+

+
k = 6 (thm) k = 2 (thm)
B

k=6 s e lin hp l 6 mc d c 8 e
N (-)

k = 6 (thm)
O

k = 2 (thm)
H O
+

thc ra l

k = 4 (thm)

k = 6 (thm)

k=6 nhng lhp h-> ko thm

k = 6 (thm)

+
Thm:

H H H H H H

H H H H

HH

k = 10 nhng ko phng v 2 nguyn t H y nhau lm h mt phng. Ngoi ra, cn mt s cu dng khc cng tho mn cng thc v khng phi l h phng cng do s y ca cc H: H H H H H
H H H H H H H
H H H H H H H H

k = 10

(cu dng)

Bi6: a/ So snh ca 2 hirocacbon sau:

(A) (B) b/ So snh nng lng lin hp: Buta-1,3-ien; Benzen; Alen; Hexa-1,3,5-trien Bi lm: a/ Do s bt i xng trong phn t nn trong t phn t b phn cc: A

+
+
thm B

thm

khng

+
khng

+ (khng bn)

+
+
thm => A > B b/

khng

khng

+ +
thm

H2C

CH2

<

H2C

CH2

<

ko lin hp

< lhp ko gim theo mch thm lin hp kn (36 Kcal/mol)

H2C

CH2

Bi 7: Hy phn tch ch ra hng tn cng ca Brm trong mi trng hp sau: a/ C6H5CONHC6H5 + Br2/FeBr3 ..... b/
CH3CH2S OCH2CH3

+ Br2/xt (1 ng lng) ..... c/ CH2=CHCOOCH=CH2 + Br2/H2O ..... (1 ng lng)

Bi lm: a/ SE 2
O C NH

Xc nh c ch, tc nhn, cu trc v cc hiu ng => s nh hng

+ 1

para
Br

Octo b n ng ko gian
b/ SE 2
Br
+

Hng chnh

Hng chnh
CH3CH2S OCH2CH3

O cng 1 hng (cng chu k) vi C nn h/ +C mnh hn S

+ C1

<

+ C2

+ C1

+ C2
Br
+

Hng chnh
c/ AE
Br O H2C CH2
+
O H2C O OH CH2 Br

+ 1

.........

Bi 8: So snh tc dung mi phn trong etanol c mt AgNO3: a/ CH3[CH2]3Br ; (CH3)3CBr ;

H3C CH2Br H3C Br

Br Cl

CH2Br

CH2Br

; ; ; b/ c/CH3CH2CH2CH2Cl ; CH3CH2OCH2Cl ; CH3CH2SCH2Cl ; CH3CH2SeCH2Cl Bi lm:

a/ SN 1 v xc tc AgNO3 (CH3)3CBr > CH3[CH2]3Br > b/

CH2Br CH2Br H3C Br Cl CH2Br Br

c ch SN 1 cacbocation c cu trc phng Csp2 gc lai ho 120 nn dng vng gc < 120 ko bn
C
+

< lk C-Br bn -I > +C

<

<

CH3

SN1 kh vi dn xut bc I d vi dn xut bc III v cacbocation sinh ra bn ...

c/ CH3CH2CH2CH2Cl< CH3CH2SeCH2Cl< CH3CH2SCH2Cl < CH3CH2OCH2Cl

CH3CH2ZCH2-Cl CH3CH2ZCH2(+) Z: CH2 < Se < S <O

Bi 9: pKa ca mt s loi hp cht hu c RCOOH; ROH; RSO2OH; RH; ArOH c gi tr ghi theo trnh t tng dn l : ~0; ~5; ~10; ~15; ~50. Hy vit CTCT ca cc loi h/c trn theo trnh t tng dn tnh axit c ghi pKa. Gii thch ngn gn nguyn nhn gy ra tnh axit v nguyn nhn ca s khc nhau v pKa. Bi lm: Tnh axit f thuc H linh ng, ngoi ra cn f thuc vo bn ca baz lin hp. Baz lin hp cng bn khi cng c nhiu nhm ht e lm gii to in tch m BH+ + A B + HA baz axit axit baz lhp lhp PKa ~50 ~15 ~10 ~5 ~0 O R-H R-OH Ar-OH R C O H lk C-H gn nh Ar c h/ -C lk OH R S O C O ko phn cc phn cc R in tch (-) ko c gii to

R-O in tch (-) ko c gii to nhng ca O ln gi e

Ar-O tch (-) c gii to nh h/ -C ca Ar

C O

O O

S O O

in (-) c gii to nh -C mnh ca C=O

O1/ 2R C O 1/ 2-

in (-) c gii to rt mnh nh -C mnh ca 2 nhmoS=O

Bi 10: Cho 5 hp cht hc cng vi cc gi tr pKa (ghi theo trnh t tng dn):
COOH OH COOH OH O 2N COOH OH NO 2 COOH SH

3,0 3,5 4,2 9,9 pK1 : 0,3 pK2 : 7 8 13 Hy qui kt cc gi tr pK cho tng nhm chc. Bi lm: Trong cc hp cht tp chc trn pK1 l ca nhm -COOH, pK2 ca -OH v -SH pK1:
HO O H O O
-

O H O

Bn
Hiu ng Octo Lin kt H ni phn t lm Cacbanion sinh ra bn, bn hn khi c nhm ht e vng thm lm gii to in tch m v ng thi cng lm lk O-H trong phn cc hn. Lk H vi O bn hn vi S v O m in hn. pK2:
COOH 3,5 OH 13

v lk H ni phn t ko lm H+ ca phenol phn li c

COOH SH

3,5 8
lk H vi S ko bn = vi O

COOH 3,0 OH

O 2N

NO 2

C nhiu nhm ht e lm lk O-H phenol phn cc mnh

Bi 11: Sp xp cc cht trong mi dy sau theo trnh t tng dn tnh axit: a/ CH3COOH ; CH3COO2H ; Cl3CCOOH ; (CH3)3CCOOH b/ CH3COCH2COOCH3 ; CH3COCH2COCF3 ; CH3COCH2COCH3 c/
CH3 CH3 NC NC H H H H H3C H H H CN CN

(A)

(B)

(C)

(D) Bi lm:

a/ CH3COO2H<(CH3)3CCOOH< CH3COOH< Cl3CCOOH

R O

R O

b/

CH3COCH2COOCH3< CH3COCH2COCH3 <CH3COCH2COCF3

H3C C

lin hp trc tip ko trc tip lm lk O-H ph cc mnh ring: CH3COCH2COCH3

H3C O O CH3

u c nhm
R O O

ta xt phn cn li:
CH3 R O O CF3

H3C O O H

CH3

R
CH3

c/ C < A < B < D thm

<

enolbn F tng k/n ht lk H ni phn t to h lhp e ca O Vng thm bn anion thmbn

NC CN CN NC

NC

CN

NC

CN

thm, nhiu nhm ht e

CH3

CH3

CH3

km bn

Bi 12: So snh tnh baz: CH3CH2NH2; Cl3CCH2NH2; Cl3CCH2CH2NH2; (CH3)3SiCH2NH2; (CH3)3CCH2NH2 Bi lm: Cl3CCH2NH2 < Cl3CCH2CH2NH2< CH3CH2NH2 < (CH3)3CCH2NH2 < (CH3)3SiCH2NH2 c nhm ht e< CH3CH2NH2<c nhm y e Tnh baz ph thuc vo mt e trn nguyn t N I gim theo mch C Si<C => +I Si>+I C

Bi 13: Sp xp cc cht sau theo trnh t tng dn tnh baz: a/

O H N H3C CH3

-IO > -IN v ca O > N

N
H
CH3 H3C

N H

N H

N H

NH

N H

+
H

ho bn
H3C

sonvat
+ N
H H CH3

(A) b/
CH3

(B)

(C)

(D)
H

+ N
H

N N H3C N CH3 N

Sonvat ho kh do s quay ca nhnh amin c nhm ht e <ko c amin b3 vng > amin b3 h

c/

(A)

(B)

(C)
N

(A)

(B) Bi lm:

(C)

gim e trn N tnh baz nh nht, cp e N lhp +C

-C, -I

a/ C < B < D < A b/ C < A < B c/ B < C < A

Cp e vung gc ko lin hp +C Csp2 c > Csp3 k/n ht e ln hn

Bi 14: Cho (R,S)-But-3-in-2-amin (B)v axit (2R,3S)-2,3-ihiroxi butanioic (A). a/ Vit CT phi cnh ca A v B b/ Trnh by pp tch ring 2 i quang ca B Bi lm: a/ (B) (A) HOOC-CHOH-CHOH-COOH
HC C CH NH2 CH3

B:
H H3C C C CH NH2 H2N C C H CH3

R
OH

CH

A:
HOOC H H

(R)
HO

(S)
COOH

Phng php tch ring 2 i quang: 2 ng phn i quang ging ht nhau v tnh cht ho hc cng nh vt l, ch c gc quay mt phng phn cc l khc nhau. Nhng ng phn i-a li c tnh cht vt l khc nhau, da vo t/c ny ta c phng php sau:

(+)-B (- )-B

+ (+)-A

(+)-B-(+)-A (- )-B-(+)-A

NaOH

(+)-B-(+)-A kt tinh li (- )-B-(+)-A trong nc

(+)-B (- )-B

NaOH

Hh 2amin quang

Hh 2 mui l phn i-a

Bi 15: C 3 dn xut Halogen ko no: CH3CBr=CHCH2CCl2CH2CH=CBrCH3 (A) CH3CCl=CHCH2CHClCH2CH=CBrCH3 (B) CH3CBr=CHCH2CHClCH2CH=CBrCH3 (C) a/ Gi tn A,B,C b/ Cho bit mi cht A,B,C c bao nhiu ng phn cu hnh c/ Vit cng thc lp th cc ng phn cu hnh ca C. Bi lm:

a/ A: 2,8-ibrom-5,5-iclonona-2,7-ien B: 2-brom-5,8-iclonona-2,7-ien C: 2,8-ibrom-5-clonona-2,7-ien b/ A: Z,Z E,E E,ZZ,E 3 phn B: 23 = 8 phn C:

Br H3C (E) H CH3 Br (E) H
Br H3C (E) H C* Cl

Br (Z) CH3 Cl CH3 (E) Br Cl

CH3 (E) Br CH3 Br (E) Cl C* H

nC* 2n p quang hc - 2 na xng < 2n mC=C 2m p hnh hc - 2 na xng < 2m

nC* mC=C

2(n+m) phn cu hnh

-2 na xng < 2(n+m)

Br (E) CH3

thng Z hn cp hn E khi xt C* Bi 16: Vit CT cc cu dng bn v ch r cu dng bn hn i vi mi cht sau: a/ cis-1,3-icloxiclohexan b/ cis-1-isopropyl-2-metylxiclohexan c/ (1S,3R)-Xiclohexan-1,3-iol. Bi lm: Xiclohexan bn khi dng gh: C1 v 1C, lun c s chuyn ho ln nhau:
C1 1C
Cl Cl cis-(a,a) b/ Cl Cl

a/

cis-(e,e) bn hn v cc 2 ngt Cl u v tr bin

CH3 CH3 CH3 H3C CH3 CH3

c/ dng C1 a,a bn hn v c lk H ni phn t:

OH H (R) O H a,a H (S) OH

HO e,e

Bi 17: Cng thc cu to ca mt s dc phm nh sau:

CH3 H COOH CH3O H3C CH3 CH3 COOH CH CH2N(CH3)2 OCOC2H5

H3C

C6 H 5 C

CH2C6H5

Naproxen Ibuprofen arvo (thuc gim au) (thuc chng vim) (thuc gim au) Novrat (thuc ho) a/ S-Naproxen c hot tnh cao hn R-Naproxen 28 ln nn trn th trng ch c S-Naproxen. Vit CT phi cnh, gi tn h thng. b/ S-Ibuprofen c hot tnh cao hn R-Ibuprofen nn ngi ta ch sn xut SIbuprofen. Vit CT phi cnh, gi tn h thng. c/ arvo c cu hnh 2S, 3R cn Novrat c c/h 2R, 3S Bi lm: a/
CH3 H H CH3

COOH HOOC CH3O axit (2R)-2-(6-metoxy-2-naphthyl)propanoic OCH3 axit (2S)-2-(6-metoxy-2-naphthyl)propanoic

b/
CH3 H H CH3

COOH HOOC i-Bu axit (2R)-2-(4-isobutylphenyl)propanoic i-Bu axit (2S)-2-(4-isobutylphenyl)propanoic

c/

2R, 3S
H (S) OCOC2H5 (R) C 6H 5 CH2C6H5 H 2C CH2N(CH3) 2 CH3 H 5C 2 O O H CH3

(R)

(S)
CH2N(CH3)2

2S,3R
H (R) OCOC 2 H5 (S) H5C6H2C C6H5 CH3 CH2 CH2N(CH3)2 H5C2 O O H CH2N(CH3)2

(S)

(R)
CH3

Bi cha: a/
H CH3 (S) COOH CH3O

axit 2-(6-metoxi-2-naphtyl)propanoic
H CH3 (S) COOH

b/

i-C 4H9

axit 2-(4-isopropylphenyl)propanoic
H
2S

c/
H3C (CH3)2N
3R

H CH3 O C O H3C O C C 6H 5

CH3 C6H5

N(CH3)2

C6 H5

C 6H 5

COOH CH CH3

phng php iu ch

i-C4H9

O CN COOH C CH3 OH i-C 4H9

CH3COCl
i-C 4H9 i-C 4H9

CH3 HCN

KCN
i-C 4H9

C CH3 OH

COOH CH CH3 OH i-C4H9 i-C4H9 C CH2

+ CO
H
CH CH3 Br i-C 4H9

i, t /N 2

KCN
i-C 4H9

CH CH3 CN i-C 4H9

COOH CH CH3

CH CH3 MgBr i-C 4H9

O2 1. C + O 3 2.H

Bi 18: Cho 2 h/c : CH3CH2OCH2CH2OH (A) ; CH3CH2SCH2CH2OH (B) a/ Vit Ct Niwmen dng bn nht ca mi cht. b/ Tng hp 2 cht xut pht t etilen v cc cht v c cn thit. c/ A v B c chuyn ho theo s :
A B
[O] [O]

axit A1 axit B1

HI HI

axit A2 cha 3 O axit B2 cha 1 S

Vit CTCT v so snh tnh axit gia A1 v B1; A2 v B2. Bi lm: a/

H O O H O O C2 H5 H O H S C2 H5

<
OC 2H5

>
SC2H5

lk H bn
H2O/H+ C2H5OH/H+
O

lk H yu
+ O ROH/H

H2C

CH2 (HCOOOH)

+ O2/Ag

C2H5-O-CH2CH2OH C2H5-S-CH2CH2OH

HO

OR

b/

C2H5Br

C2H5SH

c/ A1: CH3CH2OCH2COOH CH3CH2I + A2: HOCH2COOH B1: CH3CH2SCH2COOH CH3CH2I + B2: HSCH2COOH Tnh axit: A1 > B1 ; A2 > B2
O S CH3 C HO O HO H 2C C O CH3 H2 C

Do ca O > S

Bi 19: Cho s chuyn ho:

Br2 CH3SH NBS KOH/EtOH HBr D B C A E (dx i brom) 2-Metylpent-1-en (khng peoxit) (Metanthiol) CH3Cl

a/ CTCT sn phm A E b/ Trnh by c ch ca phn ng c/ Gi tn E v cho bit E c bao nhiu ng phn lp th d/ Khi cho Oto-1-en t/d vi NBS thu c 2 dx mono brom. Vit CTCT ca 2 sp v gii thch. e/ T d kin trn cu d em hy suy ngh g v cu to ca C. Bi lm: O a,b/
C C C C C C

HBr C AE qui tc Marcop NBS SR Br2/CCl3

C (C)

Br KOH/EtOH C C C C C (A) E1

NBr

qui tc Zai
C C C C C Br

C (B) C

C C

C C C

CH3SH SN2

C (D) C

C C C SCH3

SCH3 Br C C C C C Br (E)

AE trans

c/ 2,3-ibrom-2-metyl-4-metylsunfanylpentan d/
CH3[CH2]4CH2CH=CH2 NBS CH3[CH2]4CH-CH=CH2

NBS: N-Brom sucxinimit th Br theo c ch SR vo Alyl, benzyl theo t l 1:1 t CB : S tc nhn nu mnh, CH3SH lng nhiu p/ SN2 mc d Alyl, benzyl theo c ch SN1 cng c.
O

CH3O_ Metoxi CH3S_Metylsunfanyl

2 sn phm p cto

CH3[CH2]4CH=CH-CH2

e/ C cng c 2 phn:
C C C C C C C C C C C C

Bi 20: MTBE (Metyl tert butylete) l mt trong nhng cht ph gia cho xng khng ch. Khi c hi v cch iu ch MTBE xut pht t Metanol v cc hp cht khc, mt s hc sinh xut 4 phng php sau y.
(1) CH3OH (2) CH3OH (3) CH3OH (4) CH3OH CH3Cl CH3ONa
(CH3)CONa (CH3)CCl H+ H
+

MTBE MTBE

+ HOC(CH3)3 + (CH3)2C=CH2

MTBE MTBE

Hy phn tch cho bit nhng phng php no l kh thi, nhng phng php c th p dng trong CNghip. Trnh by c ch phn ng ca nhng phng php kh thi. Bi lm: PP (1) (2) (3) (4) Gii thch:
(1) CH3OH (2) (CH3)3CCl (3)(CH3)3COH (4)(CH3)2C=CH2
HCl(xt) PCl5(SOCl2)

Kh thi +

Khng kh thi + +

Cng nghip

CH3Cl

(CH3)CONa

SN2

MTBE

E
H+

(CH3)2C=CH2

E
H+

(CH3)2C=CH2 (CH3)3C +
CH3OH - H+

MTBE

Bi 21: Cho s phn ng:

Cl CH3C C Na H D CH2OCH3

H2/xt Lindlan

(A)

a/ Vit CTCT cu B v C, trnh by c ch p/ng b/ X/ cu hnh lp th ca A, B, C Bi lm: