16 bg hhc ptsnam

Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu C Khoa K Thut Ha Hc Trng i Hc Bch Khoa TP. HCM in thoi: 8647256 ext. 5681 Email: [email protected]://hhud.tvu.edu.vn

1

Ti liu tham kho[1] Paula Y. Bruice, Organic chemistry, fifth edition, Pearson Prentice Hall, 2007 [2] Graham T.W. Solomons, Craig B. Fryhle, Organic chemistry, eighth edition, John Wiley & Sons, 2004 [3] Francis A. Carey, Organic chemistry, fifth edition, McGrawHill, 2003 [4] Robert T. Morrison, Robert N. Boyd, Oragnic chemistry, sixth edition, Prentice Hall, 1992 [5] Trn Th Vit Hoa, Phan Thanh Sn Nam, Ha hu c, NXB i Hc Quc Gia HCM, 2007 [6] Trn Th Vit Hoa, Trn Vn Thnh, Bi tp ho hu c, NXB i Hc Quc Gia HCM, 2004 [8] Thi Don Tnh, C s l thuyt ho hu c, NXB Khoa Hc K Thut, 2000 [9] Trn Quc Sn, C s l thuyt ha hu c, NXB Gio Dc, 19792

http://hhud.tvu.edu.vn

NI DUNG CHNH ng phn ca hp cht hu c Hiu ng trong hp cht hu c C ch cc phn ng ca hp cht hu c Alkane Alkene Alkyne Alkadiene Hp cht hydrocarbon thm Dn xut halogen Alcohol Phenol Aldehyde Ketone Carboxylic acid Amine Hp ch thttp://hhud.tvu.edu.vn

Chng 1:

NG PHN

ng phn: nhng hp cht hu c c cng thc phn t ging nhau, cng thc cu to khc nhau tnh cht ha hc, vt l, sinh hc khc nhau

Phn loi:

+ ng phn cu to (phng) + ng phn lp th: ng phn hnh hc (cis, trans), ng phn quay (cu dng), ng phn quang hchttp://hhud.tvu.edu.vn

4

I. ng phn cu toDo c s sp xp khc nhau ca cc nguyn t trong mch C I.1. ng phn mch Cn-butane

iso-butane

C6H12

m ethyl cyclopentane

cyclohexanehttp://hhud.tvu.edu.vn

5

I.2. ng phn do v tr cc lin kt bi, nhm chcbutene-1 butene-2

C4H8

OH OH

OH

OH

OH 1,21,3dihydroxy benzene OH 1,4-


6

I.3. ng phn c nhm nh chc khc nhaudim ethyl ketone C3H6O O propan-2-one acetone

CHO

propionaldehyde propanal propionic aldehyde

C3H6O2

COOH

Propionic acid

O Ohttp://hhud.tvu.edu.vn

m ethyl acetate7

I.4. ng phn c nhm th khc nhau lin kt vi nhm nh chc

C4H10O

O

diethyl ether

O m ethyl propyl ether


8

II. ng phn lp thII.1. ng phn hnh hc II.1.1. iu kin xut hin ng phn hnh hc

Xut hin khi phn t c 1 b phn cng nhc cn tr s quay t do ca cc nguyn t 2 nguyn t lin kt vi cng 1 nguyn t ca b phn cng nhc phi khc nhauhttp://hhud.tvu.edu.vn

9

Thng xut hin cc hp cht c cha: C=C, C=N, N=N, h lin hp, vng phng 3 hay 4 cnh abC=Ccd: a b, c d

Cl H

Cl H


10

II.1.2. Danh php ca ng phn hnh hc a. H cis-trans: abC=Cab Nhm th tng ng nm cng pha mt phng lin kt cis Khc pha trans

H3C H

CH3 Hhttp://hhud.tvu.edu.vn

H3C H

H CH311

cis-butene-2

trans-butene-2

b. H Z-E: abC=Ccd

a>b c>d

Quy tc Kahn-Ingold-Prelog: da theo th t u tin trong bng HTTH ca nhm th a, c cng pha so vi mt phng ni i: Z (zusammen) a, c khc pha so vi mt phng ni i: E (entgegen)12


35 Br I 53 Br I

17 Cl (E)-1-Bromo-2-chloro-2-fluoro-1-iodoethene F 9 F (Z)-1-Bromo-2-chloro-2-fluoro-1-iodoethene Cl

Lu : Khi dng Z-E, ch Z, E khng phi lun trng vi cis, trans

Cl F

Cl H

Cl H

Cl Br

Z-, cis-

E-, cishttp://hhud.tvu.edu.vn

13

II.1.3. ng phn hnh hc ca abC=Nd v aN=Nb a. abC=Nd Trc y, dng h syn-, anti-, nhng khng chnh xc nn hin nay dng h Z-E

a>b: a, d khc pha so vi mt phng ni i E, cng pha Z i vi aldoximeH3C OH C N H anti-acetaldoxime (Z)-acetaldoxime H3C C N OH Hhttp://hhud.tvu.edu.vn

syn-acetaldoxime (E)-acetaldoxim e

14

i vi ketoxime: Cng 1 cht, c th gi l syn- hay anti- !!!H3C H3C

OH C N

C N OH

anti-phenyl-p-tolylketoxime syn-p-tolyl-phenylketoxime

syn-phenyl-p-tolylketoxime anti-p-tolyl-phenylketoxime

h syn-anti khng chnh xc chuyn sang h Z-Ehttp://hhud.tvu.edu.vn

15

b. aN=Nb

C6H5 N N C6H5 anti-azobenzene

N N C6H5 C6H5

syn-azobenzene


16

II.1.4. ng phn hnh hc ca hp cht cha C=C lin hp a(HC=CH)nb C H H6 5

H H H C6H5

trans,trans-1,4-diphenyl-1,3-butadiene

H C6H5

H C6H5 cis,cis-1,4-diphenyl-1,3-butadiene

H

H

H C6H5

C6H5 H cis,trans-1,4-diphenyl-1,3-butadiene

H

H

* S p hnh hc ca h lin hp C=C N = 2n-1 + 2p-1 n: s ni i lin hp p = n/2 nu n chn http://hhud.tvu.edu.vn p = (n + 1)/2 nu n l

17

II.1.5. ng phn hnh hc ca vng no 3, 4 cnh c b tr trn 1 mt phng cc nhm th khng th quay t do xut hin ng phn hnh hc * Cc nhm th tng ng cng pha mt phng cis, khc pha transHOOC H COOH H HOOC H H COOH

cis-cyclopropane-1,2-dicarboxylic acid

trans-cyclopropane-1,2-dicarboxylic acid


18

II.1.6. Cch xc nh v so snh cc ng phn hnh hc a. xc nh khong cch gia cc nhm th Khong cch gia 2 nhm th tng ng trong ng phn cis < transH Cl H Cl 3.7 H Cl Cl H 4.7


19

b. Moment lng cc 2 nhm th ging nhau aHC=CHaH Cl H Cl H Cl Cl H

cis (1.89D) > trans (0D) 2 nhm th khc nhau aHC=CHb (a b) 2 nhm th cng ht hay cng y in t: cis > trans 2 nhm th c tnh cht in t ngc nhau: cis < transhttp://hhud.tvu.edu.vn

20

c. Nhit nng chy ng phn trans-: i xng mng li tinh th cht ch tonc cis < tonc trans

Lu : mi lin h gia to si v ng phn hnh hc khng cht ch V d:

CHCl=CHCl tosi ca cis-: 60.3 oC, tosi ca trans-: 48.4 oC CH3CH=CHCl tosi ca cis-: 32.8 oC, tosi ca trans-: 37.4 oChttp://hhud.tvu.edu.vn

21

II.2. ng phn cu dng (ng phn quay)

L nhng cu trc khng gian sinh ra do 1 nhm th quay xung quanh trc C-C (khng lm t C-C) so vi 1 nhm nguyn t khc Thng cn nng lng 3-4 Kcal/mol Ch tn ti nhng cu dng tng i bn

Khng th tch thnh nhng ng phn ring r!!! ng phn cu dng l cc dng khc nhau trong khng gian ca cng 1 cu hnh!!!http://hhud.tvu.edu.vn

22

II.2.1. Cch biu din a. Cng thc phi cnh (khng gian 3 chiu)a b a b c a c c b b c b c a a

che khut

xen k

Lin kt C-C: ng cho tri qua phi, xa dn ngi quan sthttp://hhud.tvu.edu.vn

23

b. Cng thc Newman Quan st dc theo C-C 2 nguyn t C dng che khut, biu din bng vng trn chiu cc nhm th ln mt phng vung gc vi C-C

aa b c c b b c

a c a b

che khuthttp://hhud.tvu.edu.vn

xen k

24

II.2.2. Cu dng ca cc hp cht mch h a. Ethane Quay 1 nhm CH3 & c nh nhm cn li 2 ng phn cu dng ti hn Che khut: khong cch gia cc H gn nhau nng lng cao nht km bn nht


25

Xen k: khong cch gia cc H xa nhau nng lng thp nht bn nht


26

b. n-Butane Quay cc nhm th quanh trc C2-C3 2 dng c nng lng cao: che khut ton phn & che 1 phnCH3 CH3 H H H H H H CH3 H H CH3

2 dng c nng lng thp: anti (i) & syn (lch)CH3 H H H H CH3 H CH3 H H27

CH3 http://hhud.tvu.edu.vnH

HHgauche

E

Hgmzchc

DIhedrsI angle


240*

28

II.2.3. Cu dng ca hp cht vng no Vng no 3,4 cnh khng c ng phn cu dng

Sc cng bayer: do s khc bit ca gc lin kt so vi gc ha tr bnh thng (109o28) = (109o28 gc lin kt ca vng)


29

a. Cyclohexane Cc C khng cng nm trong 1 mt phng bo m gc lin kt ~ 109o28 Cc nhm th c th quay quanh C-C ng phn cu dng C 2 dng c trng: gh (bn) & thuyn * Gh:

Xem nh 1 t hp ca 6 h thng n-butane Tt c 6 h thng u dng xen k (syn butane)5 4 6 3 2.5 2 1 2.49 http://hhud.tvu.edu.vn

3 4 6 230

1.84

* Thuyn:1

4 5 6 3 22.27

42.49

1 3

5

4 h thng dng xen k: C1-C2, C3-C4, C4C5, C6-C1 2 h thng dng che khut hon ton: C2C3, C5-C6 Khong cch H C1 & C4 rt nh lc y km bn hn dng gh *** Ngoi dng gh & thuyn, cyclohexane cn c dngxon, dng na gh km b n (htu ht tp://h d.tvu .ed u.c vn)31


32

b. S b tr cc lin kt C-H

6 C phn b trn 2 mt phng song song (1-3-5 & 2-4-6), cch nhau 0.5 Lin kt C-H gm 2 nhm: lin kt trc a (axial) & lin kt bin e (equatorial)

a e e

a e a a e a

109o28'

e ae


33

Cn bng (khng th tch):a e

CH3 CH3

Dn xut 1 ln th: e-methyl cyclohexane bn hn a-methyl cyclohexane http://hhud.tvu.edu.vn

Khi c 2 nhm th khc nhau: nhm ln

II.3. ng phn quang hc II.3.1. nh sng phn cc

nh sng t nhin: sng in t, dao ng mi hng vung gc vi phng truyn nh sng phn cc: ch dao ng trong 1 mt phng nht nh mt phng phn cc ASTN qua lng knh Nicol s tr thnh ASPC35


II.3.2. cht hot ng quang hc ASPC i qua 1 s hp cht hu c lm mt phng phn cc quay 1 gc cht hot ng quang hc

Gc quay c xc nh bng phn cc khttp://hhud.tvu.edu.vn

36

quay cc ring: []t0 = /(l.d) : gc quay cc quan st c () l (dm): b dy dung dch cht quang hc d (g/ml): nng dung dch cht quang hc to: nhit o : bc sng nh snghttp://hhud.tvu.edu.vn

37

II.3.3. iu kin xut hin ng phn quang hc Vt & nh trong gng khng chng kht c 2 ng phn khng chng kht nhng i xng nhau 2 ng phn ny quay mt phng phn cc nhng gc nh nhau nhng ngc chiu 1 i i quang ng phn quang hc thng xut hin khi c C bt i xng (C*) * C bt i xng: a b c d khng c tnh i xng trong khng gian 38http://hhud.tvu.edu.vn

Cabcd

V d phn t lactic acid 2 ng phn quang hc

COOH C* OH CH3 (+)http://hhud.tvu.edu.vn

COOH C* CH3 (-)39

H

HO

H


40

Cc nhm th khc nhau v ng phn cu to ng phn quang hcH n-C3H7 C* COOH iso-C3H7

Cc nhm th khc v ng v ng phn quang hcCH3 D C* H C6H5http://hhud.tvu.edu.vn

41

ng phn quang hc khng cha C* Phn t b tr cht ch trong khng gian, c cu to bt i xng trn ton phn t

ng phn allene

C10H7 C C C C6H5HO OC

C10H7 C6H5COOH

ng phn cn quayhttp://hhud.tvu.edu.vn

Cl Cl

42

II.3.4. Cng thc biu din ng phn quang hc a. Cng thc t din (3 chiu)

COOH

H

CH3

OH

khng thun li cho phn t phc tphttp://hhud.tvu.edu.vn

43

b. Cng thc chiu Fisher (2 chiu) Chiu cng thc t din ln mt phng Cnh nm ngang gn ngi quan st, nm dc xa ngi quan st

COOH

H

OH CH3

C th c nhiu cng thc Fisher khc nhau c. Cng thc phi cnh & Newmanhttp://hhud.tvu.edu.vn

44

II.3.5. Danh php v cch xc nh cu

hnh ca ng phn quang hc Cu hnh: s phn b trong khng gian ca cc nhm th xung quanh C* (khi nim m t ng phn quang hc) Cu dng: cc dng khc nhau trong khng gian ca cng 1 cu hnh!!!http://hhud.tvu.edu.vn

45

a. H danh php D-L: cu hnh tng i Phi so snh vi 1 cht chunCHO H OH CH2OH D-glyceraldehyde HO CHO H

CH2OH L-glyceraldehyde

Quy c: cc ng phn cha d t (O, N, S) lin kt trc tip vi C*, nm bn phi ca cng thc Fisher D, bn tri L V d lactic acid c 2 ng phn khi so vi glyceraldehydeCOOH H OH CH3 D-lactic acid HO COOH H CH3 L-lactic acidhttp://hhud.tvu.edu.vn

46

Rt kh xc nh khi phn t c nhiu C*!

b. H danh php R-S: Cu hnh tuyt i: L cu hnh thc s, ni ln s phn b cc nhm th trong khng gian xung quanh C* Dng quy tc Kahn-Ingold-Prelog xc nh ln ca nhm th: da theo th t u tin trong bng HTTH


47

C H C* O H H C O H H

H

O

Vng 1: C1 6, C3 6, O 8, H 1 Vng 2 (khi vng 1 khng xc nh c th t): O-C-O > -C-O -OH > -CHO > -CH2OH > H Lu :C A C A A C C A A C C A A C HC CH C C48

C

-CCH > -C(CH3)3 p://hhud.tvu.edu.vn -CH=CH htt> -CH(CH )2

3 2

Lu : cch cng s th t ch p dng so snh cc nhm th c cha cc nguyn t ging nhau. V d -CH(CH3)2 & -CH=CH2 Hoc CHO & -CH2OH

-CH2OH > -CH=CH2http://hhud.tvu.edu.vn

49

Cch xc nh cu hnh: C*abcd, gi s a>b>c>d +Theo cng thc t din / phi cnh (khng gian): t d xa ngi quan st: i t a b c: cng chiu kim ng h: ng phn R i t a b c: ngc chiu kim ng h: ng phn Shttp://hhud.tvu.edu.vn

50


51

+Theo cng thc Fisher: t d nm di hay trn trong cng thc Fisher, sau xt th t cc nhm cn li: i t a b c: cng chiu kim ng h: R i t a b c: ngc chiu kim ng h: S Quy c: i v tr 2 cp nhm th cu hnh khng thay i Thay i v tr 1 cp nhm th cu hnh s thay i Hay l Quay cng thc Fisher 180o cu hnh khng i, quay 90o hay 270o cu hnh thay ihttp://hhud.tvu.edu.vn

52

V d lactic acid:H

COOH OH CH3

a OH c CH3 H d (R) CO OH b

i H & CH3 (1 cp), OH & COOH (1 cp)

b COOH

Nu ch i 1 cp H & CH3

c CH3 H d (S)

OH a

Lu : R & S ch l i lng l thuyt!!! thc t ch o c d(+) & l(-)!!! R & S khng lin h vi (+) & (-)!!!http://hhud.tvu.edu.vn

53

II.3.6. Cc hp cht cha nhiu C* a. Hp cht cha cc C* khng tng ngCHO H C* OH H C* OH CH2OH

2 C* khng tng ng v CHO CH OH 2 4 ng phn (2 i i quang):

CHO H C* OH H C* OH CH2OH

HO HO

CHO C* H C* H CH2OH

CHO H C* OH HO C* H CH2OH

HO H

CHO C* H C* OH CH2OH

(2R,3R)(2S,3S)erythro-aldotetrose

(2S,3R)(2R,3S)threo-aldotetrose54

http://hhud.tvu.edu.vn n S p quang h c: N = 2

n: s C*

b. Hp cht c cha C* tng ng Tactric acid:H H HO OC C* C* COOH OH OH 2 C* tng ng 3 ng phn

COOH H C* OH HO C* H COOH

HO H

COOH C* H C* OH COOH

COOH HO C* H HO C* H COOH meso-tactric acid

(2R, 3R)-tactric acid (2S, 3S)-tactric acid


55

Trong ng phn meso: quay cc ca 2 C* trit tiu nhau khng cn hot tnh quang hc S ng phn quang hc ca hp cht cha C* tng ng (tnh c ng phn meso): N = 2n-1 (n: l) N = 2n/2-1(2n/2 +1) (n: chn)


56

II.3.7. Hn hp racemic

L hn hp 50% p quay tri + 50% p quay phi hn hp khng c tnh cht quang hc v quay cc t b tr nhau Hn hp racemic: khng ch cc phn t ring r m l 1 tp hp cc phn t


57

V d: Xc nh cu hnh tuyt i ca 1 s cht

CH2OH H OH CH3 (R)-

CHO OH CH3 CH2OH (S)-

COOH H2N H CH3 (S)-

COOH H2N H CH2OH (S)CH2OH H OH H OH CH 2OH (2S, 3R)-

H

CH3 C6H5 (R)-

CH2OH H OH OH H CH 2 OH (2S, 3S)-


58


1

Chng 2: CC LOI HiU NG * Hiu ng s dch chuyn in t trong phn t nh hng n c ch phn ng, kh nng phn ng, tnh acid-base Chia lm 2 loi: a. Hiu ng in t: HU cm ng I (inductive effect) HU lin hp C (conjugation effect) HU siu lin hp H (hyperconjugation effect) b. Hiu ng khng gian: HU khng gian loi 1 HU khng gian loi 2 HU ortho


2

I. Hiu ng cm ngI.1. nh ngha HU cm ng s dch chuyn in t ca cc lin kt do cc nguyn t trong phn t c m in khc nhau phn t phn cc V d:H H C3 H H C2 H H C1 H Cl

m in Cl > C s dch chuyn t C1-Cl, 3 C2-C1, C3-C2http://hhud.tvu.edu.vn

I.2. Phn loi a. HU cm ng dng (+I) Gy ra bi cc nguyn t hay nhm nguyn t c khuynh hng nhng in t b. HU cm ng m (-I) Gy ra bi cc nguyn t hay nhm nguyn t c khuynh hng ht in t * Quy c: C-H c I = 0 Chiu chuyn dch t : Nhm nguyn t c khuynh hng nhng 4 in t > H cho +I (v ngc li)http://hhud.tvu.edu.vn

I.3. c im ca HU cm ng Cc nguyn t hay nhm nguyn t mang in tch + Cho I

Cc nguyn t hay nhm nguyn t mang in tch - cho +I in tch cng mnh I cng mnh, nhm nguyn t mang in tch c I mnh hn trung ha -N(+)R3 -O-O(+)R2 -I -N(-)H +I5

p://hhud.tvu.edu.vn 2 > -OR -O(+h)ttR

Trong cng 1 chu k trong bng HTTH: -I tng t tri qua phi -I: -NR2 < -OR < -F Trong cng 1 phn nhm chnh : -I gim t trn xung di -I: -F > -Cl > -Br > -I -I: -OR > -SR > -SeR

Cc nhm alkyl lun y in t (+I), tng dn t bc 1 n C bc 3 +I : -CH3 < -CH2CH3 < -CH(CH3)2 < -C(CH3)3http://hhud.tvu.edu.vn

6

Cc nhm khng no u mang I, tng dn theo khng no -I:R2C=CR< < RCC

HU cm ng gim dn theo mch C nh hng n tnh cht ca phn t V d Ka.105 ca cc acid: 1.5 CH3CH2CH2COOH CH3CH2CH(Cl)COOH 139 CH3CH(Cl)CH2COOH 8.9 ClCH2CH2CH2COOH 3.0


7

II. Hiu ng lin hpII.1. nh ngha H lin hp: l nhng phn t c lin kt & v tr lun phin nhau V d: CH2=CH-CH=CH2 hay CH2=CH-CH=CH-CH=CH2


8

HU lin hp s dch chuyn t trong 1 h lin hp, lm cho h lin hp tr nn phn cc V d: CH2=CH-CH=CH2 mt in t phn b u trn cc C Tuy nhin: CH2=CH-CH=CH-CHO m in ca O > C nhm C=O s ht in t ca h phn t tr nn phn cc ( LH - )


9

CH2=CH-CH=CH-N(CH3)2 N c i in t t do (p) c xu hng nhng in t cho h lin hp phn t phn cc (LH -p)

Cl

NH2

Lin hp -p (-Cl, -NH2 ng thi c I!)http://hhud.tvu.edu.vn

10

II.2. Phn loi II.2.1. HU lin hp dng (+C) Cc nt hay nhm nguyn t c kh nng y in t t bn thn n ra h lin hp +C c im ca +C: a. Cc nguyn t hay nhm nguyn t c cp in t cha s dng hoc nhng ion mang tch (-) u mang +C -O- -S-H -R SH SRNH2 NR2 H N C CH3http://hhud.tvu.edu.vn

-F

-Cl

-Br

-I11

O

b. Cc ion mang in tch m c +C mnh hn cc nguyn t trung ha +C: -O- > -OR -S- > -SR c. Trong cng 1 chu k ca bng HTTH: +C gim t tri qua phi +C: -N(R)2 > -OR > -F d. Trong cng 1 phn nhm chnh: +C gim t trn xung di +C: -F > -Cl > -Br > -I +C: -OR > -SR > -SeRhttp://hhud.tvu.edu.vn

12

II.2.2. HU lin hp m (-C) Cc nguyn t hay nhm nguyn t c kh nng ht in t ca h lin hp v pha n -C c im ca C: a. a s cc nhm nguyn t mang C l nhng nhm khng no -NO2 -CN -CHO -CORhttp://hhud.tvu.edu.vn

-COOH -CONH213

b. Trong cc nhm C=Z: -C ph thuc Z Z c m in cng ln, -C cng mnh -C: C=O > C=NR > C=CR2

c. i vi cc nhm nguyn t tng t: in tch cng ln th C cng mnh -C: C=N+R2 > C=NR


14

II.3. c tnh chung ca HU lin hp a. HU lin hp thay i rt t khi ko di mch lin hp *** HU cm ng: gim nhanh theo mch C !!!O H CH2 CH CH C H O H CH2 CH CH CH CH C H

linh ng ca H 2 cht ging nhauhttp://hhud.tvu.edu.vn

15

Tc phn ng ging nhau:OH

O

RCHO + H

CH2

CH

CH

C H

OH

-

O R C H O CH2 CH CH C H

RCHO + H

CH2

CH

CH CH

CH

C H OH

OH-

O R C H CH2 CH CH CH CH C H


16

b. Mt s nhm th cha no, du ca HU lin hp s thay i ty thuc vo nhm nt lin kt vi n-

O N+

O NH2

-C6H5: +C

-C6H5: -C

c. HULH ch c hiu lc trn h lin hp phng

H

C6H5NH2

R

N H

C6H5NR2

N R

+C ca NR2 gim so vi NH2http://hhud.tvu.edu.vn

17

III. Hiu ng siu lin hp III.1. HU siu lin hp dng (+H)L s tng tc ca cc in t ca lin kt C-H vi h t (C=C, -C6H5 ), hoc trong carbocation (vd: (CH3)3C+) hay gc t do (vd: (CH3)3C.)


18

Xt phn ng: CH3-CH=CH-CH2-CH3 + HCl Nu xt theo +I: sn phm chnh l: CH3-CH2-CHCl-CH2-CH3 Tuy nhin, thc t, do tc dng ca +H, sn phm chnh l:H H C Hhttp://hhud.tvu.edu.vn

+

CH

CH

CH2

CH3

HCl

CH3 CHCl

CH2

CH2

CH3

19

+H cng mnh khi s nguyn t H C cng nhiu:

H

H

H C

+H:

H

C H

>

H3C


20

III.2. HU siu lin hp m (-H)L s tng tc ca cc t ca lkt C-F vi h t (C=C, -C6H5)

F C F F


21

IV. Hiu ng khng gianL nhng loi hiu ng do kch thc ca cc nhm th trong phn t gy nn IV. 1. HU khng gian loi 1 (S1) Do cc nhm th c kch thc ln, chim 1 khong khng gian ng k cn tr khng cho 1 nhm chc no trong phn t tc dng vi phn t hay ion khcCH3 O O + H2N OH CH3 HOhttp://hhud.tvu.edu.vn

CH3 N O + H2O CH322

IV. 2. HU khng gian loi 2 (S2) Do cc nhm th c kch thc ln h lin hp b mt tnh phng khng cho 1 s phn ng Xy raR H3C N H3C R + Cl-N N+ H3C N H3C R R N N

R = H: phn ng xy ra R=-CH3: h lin hp mt tnh phng +C ca N(CH3)2 gim mnh phn ng khng x y rahttp://hhud.tvu.edu.vn

23

IV. 3. Hiu ng OrthoGy ra bi cc nhm th v tr ortho trong vng benzene gy nh hng c bit so vi cc nhm th v tr khc HU ortho: hn hp ca nhiu yu t (S1, S2, I, lin kt H)http://hhud.tvu.edu.vn

24

Xt hng s phn ly (Ka.105) ca dn xut ca benzoic acid C6H4(R)COOHV tr / R ompOH 10.5 8.3 2.9 F 54.4 13.7 7.2 NO2 67.1 32.1 37.6

Lu : -I ca NO2 > -I ca Fhttp://hhud.tvu.edu.vn

25

Tnh acid:H O C O H O > OH OH H O C > O H O C O

o-: OH c I ht t & lin kt H O-H trong COOH phn cc mnh nht p-, m-: OH c I ht in t nhng -I gim dn theo chiu di mch C O-H trong COOH p- t b phn cc nht lu : OH trong o- & p- c +C y in t ln h lin hp p--o C=O trong m-: h lin hp ny b t on do - lin tc !!! cng 26http://hhud.tvu.edu.vn lm cho tnh acid ca m- > p-

Tnh acid ca C6H4(F)COOH: o- > m- > pdo I gim theo chiu di mch C Kh nng ht (-I) hay y (+C) in t ca F, Cl, Br, I: -I > +C

Tnh acid ca C6H4(NO2)COOH: o- > p- > m27


-

O

N+

O H O

-

O

N+

O

OH

o-nitrophenol: lin kt H ni phn t tosi thp, khng tan trong nc c th chng li cun hi nc p-nitrophenol: ch c lin kt H ngoi phn t trong nc tan tt trong nc, tosi caohttp://hhud.tvu.edu.vn

28

V. nh hng ca cc hiu ng ln tnh acid base v bn ca carbocationV.1. nh hng ca HU cm ng ln tnh acid Cc R-OH, R-COOH c cha nhm th c +I tnh acid gim

Cha nhm th c I: tnh acid tng do O-H cng phn cchttp://hhud.tvu.edu.vn

29

Tnh acid ca cc acid: F3C-COOH (pKa 0.23) > Cl2CH-COOH (1.25) > Cl3C-COOH (0.66) >

NO2-CH2-COOH (1.68) >

NC-CH2-COOH (2.47) > F-CH2-COOH (2.57) > Cl-CH2-COOH (2.87) > Br-CH2-COOH (2.90) > HCOOH CH3COOH (3.75) (4.76) > > HO-CH2-COOH CH3CH2COOH (3.83) (4.87)30

> >

(CH3)3C-COOH (5.03)http://hhud.tvu.edu.vn

Nhm th cng xa C nh hng cng yu do I gim mnh: Tnh acid: F3C-COOH > F3C-CH2-COOH > F3C-CH2-CH2-COOH


31

V.2. nh hng ca HU lin hp, HU siu lin hp ln tnh acid Tnh acid ca alcohol < phenol Nhm th c C s lm tng tnh acid & ngc li-

O N+

O -I, -C > O H >

Tnh acid:+I H H C H >

H H C H +H, +I > O H O H

+C, -I NH2

O H

O H

Thng thng (khng lun lun!) : C > H > Ihttp://hhud.tvu.edu.vn

32

a. Acid bo khng no:

Tnh acid mnh hn acid no cng mch C (do C=C c I) Ni i C=C cng gn COOH th tnh acid cng mnh Tuy nhin: nu C=C lin hp vi C=O trong COOH th tnh acid gim do +C ca C=C!!! Tnh acid: CH3-CH=CH-CH2-COOH (pKa 4.48) > CH2=CH-CH2-CH2-COOH (4.68) > CH3-CH2-CH=CH-COOH (4.83)http://hhud.tvu.edu.vn

33

Ni ba CC cho d v tr lin hp vi C=O th vn lm tng mnh tnh acid (khc C=C): do I

ca CC mnh & ch c 1 lkt ca CC cho +C lin hp vi C=O, lkt cn li cho I nhng khng c +C!!!

Tnh acid: CHC-COOH (pKa 1.84) > 34 CH3-CC-COOH (2.60) > CH2=CH-COOH (4.25)http://hhud.tvu.edu.vn

b. Acid c vng thm: Tnh acid H-COOH (pKa 3.75) > C6H5-COOH (4.18) do +C ca C6H5- mnh hn I Tnh acid ty thuc bn cht & v tr nhm th: o- NO2-C6H5-COOH > p- > mHalogen cho I > +C o-Cl-C6H5-COOH > m- > phttp://hhud.tvu.edu.vn

35

V.3. nh hng ln tnh base

Mt in t trn N cng ln tnh base ca amine cng mnh

Nhm th y in t (+I) s lm tng tnh base ca amine & ngc li (-I, -C)

Tnh base: (CH3)2NH > CH3NH2 > NH3 > C6H5NH2 > p-NO2-C6H4-NH2http://hhud.tvu.edu.vn

36

Tnh base: p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2 < p-Cl-C6H4-NH2 < C6H5-NH2 < p-CH3O-C6H4-NH2

pO2: -I, -C mnh nht, m-NO2: -I mnh, -C khng nh hng nhiu do h lin hp b t on -Cl: -I mnh hn +C, -I yu hn -NO2 p- CH3O: +C mnh hn I mt in t trn N cao nht base mnh nht Acid lin hp cng yu th tnh base cng mnh Tnh base: HCC- > (CH3)3CO- > CH3O- > OH- >

C6H5O- > CH3COOhttp://hhud.tvu.edu.vn

37

V.4. nh hng ln bn ca cc

carbocation

in tch dng trn cc cation cng c gii ta (cng nh) th cation cng bn bn do hiu ng y in t ca +H, +I:

H H C CH2 H

+H & I ca CH3 -NH- & -O- ng thi c I nhng +C nh hng mnh hn -NH- gii ta tch dng mnh nht bn nht Gc allyl CH2=CH-CH2+ hay C6H5-CH2+ rt bn do +C ca vinyl hay phenylhttp://hhud.tvu.edu.vn

40


1

Chng 3: C CH PHN NG CA HP

CHT HU CI. Phn ng th i nhn nguyn t carbon no I.1. Khi nim chung

Phn ng th: 1 nguyn t hay nhm nguyn t ca cht ban u b thay th bi 1 nguyn t hay nhm nguyn t khc CH3-CH2-Cl + OH- CH3-CH2-OH + Cl-

Tc nhn i nhn: cc tc nhn mang in tch m (hay phn t trung ha cha cp in t t 2 do) tn cng vo trung tm tch in +http://hhud.tvu.edu.vn

Phn ng th i nhn (SN) y- + R-X R-y + Xy-: RO-, OH-, RCOO-, NH3, NH2R, H2O, ROH R: gc hydrocarbon X: Cl, Br, OH, OR, OSO2R V d: CH3-CH2-Cl + OH- CH3-CH2-OH + ClCH3-CH2-Br + CH3O- CH3-CH2-O-CH3 + BrCH3-CH2-Br + NH3 CH3-CH2-NH2 + HBrhttp://hhud.tvu.edu.vn

3

I.2. Phn ng th i nhn lng phn t (SN2) Lng phn t: giai on chm, c s tham gia ca 2 tiu phn

cham y + R-X-

a.C ch:

[y-... R ... X-]

nhanh

R-y + X-

trang thai chuyen tiep Lin kt gia C & y hnh thnh ng thi vi s yu i & t ca C & X 2 tiu phn tham gia vo giai on chm Nu y- khng d nhiu: r = k[y-].[R-X] phn ng 4 bc 2http://hhud.tvu.edu.vn

Gin nng lng:


5

R-OH: phn ng th ch xy ra trong mi trng acid v C-O bn Dn xut ca carbon bc 1 ch cho SN2 SN2: carbon bc 1 (ch cho SN2) > carbon bc 2 > carbon bc 3 (ch cho SN1) SN2: CH3-CH2-Cl + OH- CH3-CH2-OH + Cl6


b. Tnh lp th ca SN2 Phn t c cha C*: s c s thay i cu hnh (R S & ngc li) (nghch o Walden)R1 R1 C* R2 X R1 X R2

y- +

H

chamy H

C*

nhanh

y

C*

H R2

(R)-

(S)-

y- tn cng ngc hng so vi X sn phm c 7 cu hnh ngc vi tc chthttp://hhud.tvu.edu.vn

I.3. Phn ng th i nhn n phn t (SN1) n phn t: giai on chm ch c s tham gia ca 1 tiu phn a. C ch

R-X R+

cham

R+ +

X-

+ y-

nhanh

R-y

giai on chm: y- khng tham gia SN1 thng c bc 1 r = k[R-X]http://hhud.tvu.edu.vn

8

Gin nng lng:


9

Dn xut ca carbon bc 3 ch cho SN1 SN1: carbon bc 3 (ch cho SN1) > carbon bc 2 > carbon bc 1 (ch cho SN2) V d SN1:

CH3 H3C C CH3http://hhud.tvu.edu.vn

CH3 Br

+ OH-

H3C

C CH3

OH

+ Br-

10

Tnh lp th ca SN1R1 y R1 R1 C* R2 R3

chamR2 R3 C* X

-X

-

C* R2 R3 R2 R1 C* R3 y

(R1 R2 R3)

Sn phm c th l hn hp racemic Carbocation c cu trc phng kh nng tn cng ca y- 2 pha l nh nhau 50% S + 50% 11 Rhttp://hhud.tvu.edu.vn


12

I.4. Cc yu t nh hng ln phn ng th

i nhna. nh hng ca gc R Gc R bc cng cao: kh nng SN1 tng & SN2 gim SN1: carbon bc 3 (ch cho SN1) > carbon bc 2 > carbon bc 1 (ch cho SN2) Do SN1 ph thuc vo bn ca carbocation to thnh:CH3+ H H C CH2 H < H H < H C C+ H C C+ HH C H HH C H H 13 H H HH C H

carbon bc 2 > carbon bc 3 (ch cho SN1)


14

b. nh hng ca tc nhn i nhn y SN1: khng ph thuc y

SN2: ph thuc nhiu vo y- do giai on chm c y- tham gia

Tc nhn c tnh i nhn cng cao th cng d cho SN2 Thng thng, tnh i nhn ng bin vi tnh base NH2- > (CH3)3CO- > (CH3)2CHO- > C2H5O- > CH3O> OH- > C6H5O- > HCO 3- > CH3COO15http://hhud.tvu.edu.vn

Trong cng 1 phn nhm chnh ca bng HTTH: tnh i nhn nghch bin vi tnh base (phn ng thc hin trong H2O, ROH): Tnh base: F- > Cl- > Br- > ITnh i nhn: F- < Cl- < Br- < ITnh i nhn: HS- > OHTnh i nhn: C2H5S- > C2H5OTuy nhin trong pha kh, tnh i nhn: F- > Cl- > Br- > I

Phn bit tnh base & tnh i nhn: Tnh base v 16 tr cn bng, tnh i nhn tc !!!http://hhud.tvu.edu.vn

c. nh hng ca nhm b th -X Cc nhm th c tnh base cao rt kh b tch ra, v d: -OH, -OR, -NH2, -F V d: R-OH + HBr R-Br + H2O cn xc tc H2SO4 R-OH khng phn ng vi KBr

Halogen, kh nng tch nhm: F- < Cl- < Br- < I(Do I c bn knh ln C-I d phn cc hn Nng lng t lin kt: C-I < C-Br < C-Cl < C-F)http://hhud.tvu.edu.vn

17

d. nh hng ca dung mi Dung mi phn cc c proton nh H2O, ROH, HCOOH c kh nng solvate ha cao c anion & cation thun li cho SN1

R1 R2 C X R3

cham

R1 H - C+ O + -X R2 R3 H

-

X

H O H

Dung mi phn cc khng c proton nh (CH3)2SO, (CH3)2NCHO khng c kh nng solvate ha anion thun li cho SN2 18http://hhud.tvu.edu.vn

II. Phn ng tch loi L phn ng trong c s tch 1nguyn t hay nhm nguyn t ra khi cht ban uR CH2 CH2 Br

ROto H+ to HOto

R

CH

CH2 +

HBr

R

CH2

CH2

OH

R

CH

CH2 +

HOH HOH + NR3

R

CH2

CH2 N+R3

R

CH

CH2 +

Nhm b tch cng H: -OH, -OR, -X, -O+(R)2, -N+(R)3, -OSO2R 19 Base s dng: cc base mnh nh OH-, RO-, NH 2http://hhud.tvu.edu.vn

II. 1. Phn ng tch loi lng phn t (E2) a. C chR y + R CH2 CH2 X-

cham

y

H

C CH2

X

nhanh

H trang thai chuyen tiep H-y + R CH CH2 + X-

giai on chm, c s tham gia ca 2 tiu phn lng phn t Tc phn ng r = k[R-X].[y-] R-CH2-CH2-OH: ch tch loi trong mi trng acid 20 to cao (thng l sulfuric acid, acid rn)http://hhud.tvu.edu.vn

b.Tnh lp th ca E2 Cc hydrocarbon khng no tch loi d khi cc nhm b tch v tr trans vi nhau(1)HOOC Cl COOH

(2) OH-HCl

HOOC

Cl

OH-HClH COOH COOH

HOOC

H

chlorofumaric acid

chloromaleic acid

Tc (1) ln hn (2) 30 lnhttp://hhud.tvu.edu.vn

21

Cc hydrocarbon no hay vng no tch loi d khi cc nhm b tch v tr trans, anti vi nhau Lu : dn xut ca cyclohexane ch tch c khi nhm b tch v tr trans & phi kiu lin kt axial (trc)!!!Br CH3 H H CH3 CH3

+

san pham chnhBr

khoH H CH3http://hhud.tvu.edu.vn

22CH3

II.2. Phn ng tch loi n phn t (E1) C ch:

H C C X

cham

H C C+

+

X-

H C C

+

nhanh

H+

+

Thng cc dn xut ca hydrocarbon carbon bc 3 bao gi cng cho E1 Carbocation cng bn, cng d cho E1 Tc r = k [R-X] Nhng yu t lm thun li SN1 cng lm thun li 23 cho E1http://hhud.tvu.edu.vn

V d:

CH3 H3C C Br CH3 H HH C H H C C+ HH C H H cham

H HH C H H C C+ HH C H Hnhanh

+ Br-

+ C2H5O-

CH3 H2C C + CH3

C2H5OH


24

II.3. Hng ca phn ng tch loi a. Quy tc Zaitsev Dn xut bc 1 thng ch cho 1 sn phm duy nht khi tch loi CH3-CH2-CH2-Br ch cho CH3-CH=CH2 Dn xut bc 2, bc 3: cho nhiu hn 1 sn phmH H H H3C C C C H H Br H OH H3C CH2 CH CH2 (Hofmann)-

H3C CH CH CH3

(Zaitsev)

Sn phm Zaitsev : bn hn (do +H) thng thng, phn ng tch loi cho sn phm Zaitsev Quy tc: phn ng tch loi s cho sn phm m 25 carbon ca ni i lkt vi nhiu nhm alkyl nhthttp://hhud.tvu.edu.vn

b. Quy tc Hofmann Khi gc R (bc 1 & 2) ca R-X cha nhiu nhm th kch thc ln, tc nhn base c kch thc ln (vd (CH3)3CO-) hoc X l nhm th mang in tch dng c kch thc ln (vd N+R3, S+R2, SO2R) sn phm Hofmann chim ch yu (E2)CH3 H2C C CH2 CH3 (CH3)3COCH3 H3C C CH CH3http://hhud.tvu.edu.vn

72%

CH3 H3C C CH2 CH3 Br

28%

Nu base l C2H5O- th sn phm chnh l Zaitsev2 !6!!

H H3C C CH2 CH3 N+(CH3)3

OH(E2)

CH2=CH-CH2-CH3

CH3CHCH2CH2CH3 SO2CH3

OH(E2)

CH2=CH-CH2-CH2-CH3

Lu : Nu trong phn t c sn 1 ni i (C=C, C=O), sn phm lin hp thng l sn phm chnh (bn hn) 27http://hhud.tvu.edu.vn

II. 4. Quan h gia phn ng th i nhn & tch loi Nhit phn ng cng cao phn ng tch loi cng chim u th

170oChttp://hhud.tvu.edu.vn

C2H5-O-C2H5

CH2=CH2 + H2O28

Gc R c bc cng cao, hay base cng mnh th tch loi cng chim u th

to thng CH3-CH2-CH2-Br + C2H5OCH3-CH2-CH2-O-C2H5

CH3 H3C C Br CH3

C 2H5Ot caoo

CH3 H2C C CH3


29

III. Phn ng cng hpIII. 1. Phn ng cng hp i in t (AE) Phn ng cng hp vo ni i ca hydrocarbon khng no nh alkene, alkyne vi cc hp cht nh X2 (halogen), HX, H2O, HOX, H2SO4

C C

+ X-Yhttp://hhud.tvu.edu.vn

X C C Y30

a. C ch: Giai on 1:C C + X+-Y dung moi xuc tac nhanh C C X Y phc khong ben+

cham

C+ C X

ben hoa C C X+

Giai on chm: X+ tn cng vo C=C i in t

Giai on 2:

Y YC C X+ nhanh C C X31

Y-

tn cng vo pha i lp vi Xhttp://hhud.tvu.edu.vn

Chng minh AE c 2 giai on: Phn ng cng hp ca CH2=CH2 vi Br2 vi s c mt ca NaCl, NaNO3, sn phm thu c l 1 hn hp: Br-CH2-CH2-Br + Br-CH2-CH2-Cl + Br-CH2-CH2-ONO2 Nu phn ng thc hin trong dung mi l CH3OH, sn phm chnh l Br-CH2-CH2-OCH3 !!!32


H2C CH2 + Br2

CCl4

H2C CH2 Br Br

H2C CH2 + Br2

CH3OH

H2C CH2 Br OCH3

H2C CH2 + Br2

H2Ohttp://hhud.tvu.edu.vn

H2C CH2 Br OH33

b. Quy lut cng hp Quy tc Markonikov (dnh cho C=C khng i xng): H+ s tn cng vo C cha nhiu H CH3-CH=CH2 + H+ CH3-C+H-CH3 (bn hn) + CH3-CH2-C+H2 Quy tc Zaitsev-Wagner: H+ s tn cng vo pha to thnh carbocation trung gian bn nhtHBrhttp://hhud.tvu.edu.vn

CH3-CH=CH-CH2-CH3

CH3-CH-CH-CH2-CH3 34 Br

c. Ha lp th ca phn ng AE Phn ng cng hp AE xy ra theo kiu trans ph thuc vo tc cht ban u m c cc ng phn lp th khc nhau ng phn cis sn phm threo (nhm th tng ng khc pha)C2H5 Br C2H5 H CH3 H Br2 C2H5 Br+ CH3 H Brhttp://hhud.tvu.edu.vn

H

Br H

CH3

CH3 Br H H Br C2H5 CH3 H Br Br H C2H535

H

CH3 Br C2H5 Br

H

H

threo-

ng phn trans sn phm erythro (nhm th tng ng cng pha)

C2H5 H

H CH3

Br2

CH3 Br H Br H C2H5

CH3 H Br H Br C2H5 erythro


36

d. nh hng ca nhm th lin kt vi ni i

Nhm th y in t tng mt in t ca C=C tng kh nng phn ng AE Nhm th ht in t gim kh nng AE Cc nhm th nh phenyl nu c kh nng cho +C vi carbocation bn ha cation thun li cho AEhttp://hhud.tvu.edu.vn

37

Kh nng AE:O2N H H HOOC < H H H < H H H Cl H < H H3C H H3C < H H CH3 < H H H3C CH3 H3C < CH3 H3C CH3 CH3

Phenyl gy nh hng mnh hn 1 nhm methyl nhng yu hn 2 nhm methyl CH3CH=CH2 < C6H5CH=CH2http://hhud.tvu.edu.vn

< (CH3)2 C=CH238

III.2. Phn ng cng hp i nhn vo C=O (AN)

C O + X+-Y

OX C Y

X-Y c th l H-OH, H-OR, H-CN, H-SO3Na, Li-R, BrMg-R


39

a. C ch: 2 giai on, lng phn t Giai on 1:

C +

O

+ Y

-

cham

C OY carbanion

Giai on chm: Y- tn cng vo C+ i nhnhttp://hhud.tvu.edu.vn

40

Giai on 2:

C O Y

-

+ X+

nhanh

C OX Y

Phn ng AN c th khng cn xc tc. Tuy nhin, pH c nh hng V d: Trong acid yu (pH 4)

C O

+

H+

C+ OH

in tch (+) ca carbon c tng cng AN cng thun li Tuy nhin, acid qu mnh: R-NH2 + H+ R-N+ H3 41 Kh nng phn ng vi C=O gimhttp://hhud.tvu.edu.vn

b. nh hng ca nhm th lin kt vi C=O Nguyn t C trong C=O c in tch dng cng ln AN cng thun li Nhm th y in t (+C, +I, +H) lm gim kh nng phn ng Nhm th ht in t (-C, -I) lm tng kh nng phn ngNO2 CH2 C O H > H3C C NH2 o > Cl CH2 C O H > CH3 C O H > H3C C CH3 o

> H3C C OR o

> H3C C Oo

42


IV. Phn ng th i in t vo nhn thm (SE)

X + X+ acid + H+

Xc tc: cc acid v c: H2SO4, H3PO4, HF hay Lewis acid: FeCl3, AlCl3, ZnCl2 V d: C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBrhttp://hhud.tvu.edu.vn

43

C ch phn ng: 2 giai on, lng phn t Giai on 1: to phc ( benzonium cation)xt nhanh

+ X -Y

+

X+-Y

phc

X cham

H +

X

H +

X

H

X +

H

phc

+

Trong phc : X khng lin kt trc tip vi C no c Phc : X c lin kt trc tip vi 1 C ca benzenehttp://hhud.tvu.edu.vn

44

Giai on 2: tch proton

X +

H nhanh

X + HY


45

+++ Nhm th y in t (+C, +H, +I) SE tng V d: * alkyl +I, +H *-NR2 (R: H hay gc alkyl), -OH, -OCH3, -NH-CO-CH3 (+C > -I) Anion: -O- : +C, +I mnh +++ Nhm th ht in t (-C, -I) SE gim V d: -N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH, -CO-NH2 (-I, -C) Cation: -N+R3 (-I mnh) * halogen (-I > +C)http://hhud.tvu.edu.vn

46


1

Chng 4: Alkane I. Gii thiu chung Alkane hydrocarbon no mch h, nguyn t carbon lai ha sp3 Cng thc tng qut: CnH2n+2

methane Gc ha tr 109o5, lin kt C-H: 1.09, C-C: 1.53 2 ng phn: cu to, cu dng (quay)http://hhud.tvu.edu.vn

II. Danh php IUPAC II.1. Alkane khng phn nhnh: 4 alkane u: gi theo tn thng thng methane, ethane, n-propane, n-butane Cc alkane t C5: da theo cch m s ca Hy Lp hoc Latin. V d: pentane, hexane, heptane, octane(t c)http://hhud.tvu.edu.vn

3

II. 2. Alkane phn nhnh Chn mch di nht lm mch chnh nh s sao cho mch nhnh c ch s nh nht Dng ch s & gch (-) ch v tr nhnh, nhm cui cng phi vit lin vi tn mch chnh Nu c nhiu nhnh tng ng: dng tip u ng di-, tri-, tetra- ch s lng nhm tng nghttp://hhud.tvu.edu.vn

4

Nu c nhiu nhm th khc nhau: sp xp theo th t alphabetical. Lu : b qua cc tip u ng di-, tri-, tetra- khi xt th t alphabetical. Tuy nhin khng b qua iso!!! sec- & tert- c b qua khi xt th t vi cc nhm khc, nhng vn dng so snh gia chng vi nhau. V d: dimethyl hoc methyl s i sau ethyl hay diethyl isopropyl i trc methyl tert-butyl i trc isobutyl sec-butyl i trc tert-butylhttp://hhud.tvu.edu.vn

5

V d (H vit tt):C C C C C C C C C C 4-Ethyl-2,2-dimethylhexane

C C C C C C C C C C C C C C C C 3,3-Diethyl-5-isopropyl-4-methyloctane

C C C C C C C C C C C C 5-Ethyl-2,3,5-trimethylheptane

C C C C C C C C C C C C C C C 2-methyl-5-(1,2-dimethylpropyl)nonane6


II.3. Tn gc alkyl c ly 1 H t alkane, gi theo tn alkane nhng i ane yl CH3-: methyl CH3-CH2-: ethyl CH3-CH2-CH2-: n-propyl

CH3CHCH3

: isopropyl

CH3CH2CHCH3

: sec-butyl (CH3)2CHCH2-: isobutyl (CH3)3C-: tert-butyl 7


III. Cc phng php iu ch alkane III.1. Kh cc dn xut ca halogen, alcohol, carbonyl: a. Kh bng HI 80%, 180oC:P o CH3-CH2-OH + HI CH3-CH3 + I2 + H2 O

CH3I + HI

P o

CH4 + I2

b. Kh bng Zn/HClR C R' O

(Kh Clemmensen)

Zn(Hg)/HCl

R-CH2

-R'8


III.2. Hydro ha alkeneR-CH=CH2 + H2 Ni, Pd, Pt R-CH2-CH3

alkene c th iu ch t alcohol (H2SO4/toC) III.3. Thy phn hp cht c kim (CH3)2Zn + H2O CH4 + Zn(OH)2 C2H5-MgBr + H2O C2H6 + Mg(OH)Br iu ch hp cht c magnesium (Grignard): C2H5-Br + Mg/ether khan C2H5-MgBrhttp://hhud.tvu.edu.vn

9

III.4. Phn ng Wurtz CH3CH2Br + Na CH3CH2CH2CH3 + NaBr

Ch c hiu qu khi iu ch alkane i xng: CH3CH2Br + CH3Br CH3CH2CH3 + CH3CH3 + CH3CH2CH2CH3 khng c tnh chn lc t s dng Ch hiu qu cho R-Br & R-I Hiu sut: bc 1 (60%) > bc 2 (40%) > bc 3 (10%)http://hhud.tvu.edu.vn

10

III.5. in phn mui ca carboxylic acid CH3COONa CH3COO. CH3. CH3-CH3

III.6. Nhit phn mun natri ca carboxylic acid CH3COONa + NaOH CH4 + Na2CO3 IV. Tnh cht vt l (t c) Alkane khng phn cc ch tan trong dung mi khng phn cc to si ca alkane nhnh < thnghttp://hhud.tvu.edu.vn

11

V. Tnh cht ha hc Alkane tr khng c phn ng cng, c trng l phn ng th H V.1. Phn ng th H bng halogen Ch xy ra nhit cao hoc khi c nh sng

R-H

+ X2

to h http://hhud.tvu.edu.vn

R-X

+

HX12

a. C ch phn ng (gc t do SR ) Khi mo:X-X to

2X

h

Truyn mch:

R-H R +

+ X X2

R RX

+

HX

+ X

Phn ng c th tip tc to sn phm di-, tri-, tetra V d chlor ha CH4 c th thu c CH3Cl, CH2Cl2, CHCl3, CCl4 CH4 + Cl2 CH3Cl + HCl H = -25Kcal/mol13


Ngt mch:

X R R

+ X + R + Xhttp://hhud.tvu.edu.vn

X-X R-R R-X14

. Giai on to CH 3 . kh hn giai on to CH3Cl . (hay R ni chung) s quyt nh giai on to CH3 tc phn ng chung


15

b. So snh kh nng thay th H H bc 1 & bc 2:25 oC CH3-CH2-CH3 + Cl2 h CH3-CH2-CH2-Cl 45% + CH3-CHCl-CH3 55%

Vn tc tng i khi thay th H bc 1: 45 / 6 = 7.5 Thay th H bc 2: 55 / 2 =27.5 t l vn tc tng i H bc 1/ H bc 2 = 7.5/27.5 ~ http://hhud.tvu.edu.vn

16

H bc 1 & bc 3:CH3 H3C C CH3 + Cl2 H 25 oC h CH3 H3C C CH2Cl H 64% CH3 + H3C C CH3 Cl 36%

Vn tc tng i khi thay th H bc 1: 64 / 9 ~7 Thay th H bc 2: 36 / 1 ~ 36 t l vn tc tng i H bc 1/ H bc 3 = 7/36 ~ 1/5

T l vn tc tng i bc 1/bc 2/bc 3 = 1/4/5 nhit thng, kh nng thay th H C bc 3 cao nht Lu : 600oC: t l ny l 1/1/1http://hhud.tvu.edu.vn

17

c. Kh nng phn ng ca dy halogen F2 > Cl2 > Br2 > I2 F ha: mnh lit, t lin kt t dng I ha: rt kh xy ra (H = + 13 Kcal/mol), ch xy ra khi loi HI trong qu trnh


18

d. Tnh chn lc ca phn ng Phn ng Br ha c tc chm hn Cl ha nhng c chn lc cao T l vn tc tng i 127 oC ca Br ha: bc 1/bc 2/bc 3 = 1/82/1000CH3 H3C C CH3 + Cl2 H 25 oC h CH3 H3C C CH2Cl H 64%CH3 H3C C CH3 + Br2 H 127 oC h CH3 H3C C CH2Br H 1%

CH3 + H3C C CH3 Cl 36%CH3 + H3C C CH3 Br 99%

127 oC CH3-CH2-CH3 + Br2 h CH3-CH2-CH2-Brhttp://hhud.tvu.edu.vn

+

CH3-CHBr-CH3 97%19

3%

V.2. Phn ng nitro ha alkane R-H + HNO3 R-NO2 + H2O

Phn ng xy ra nhit cao,c ch gc t do Thng xy ra phn ng t mch carbon CH3-CH2-CH3 + HNO3 CH3-CH2-CH2-NO2 (25%) + CH3-CHNO2-CH3 (40%) + CH3-CH2-NO2 (25%) + CH3NO2 (10%)http://hhud.tvu.edu.vn

20

V.3. Phn ng ng phn ha Chuyn cc alkane mch thng thnh alkane mch nhnh di tc dng ca xc tc nhit cao Xc tc thng dng: acid Lewis nh AlCl3, xc tc acid trn c s zeolite V d:CH3 H3C C CH3 H21

CH3-CH2-CH2-CH3

AlCl3 tohttp://hhud.tvu.edu.vn

C ch:H HH C H H C C+ HH C H H

CH3-CH-CH2-CH3 H AlCl3

+ CH3-C-CH2-CH3 H -HAlCl3 to

HAlCl3

CH3 H3C C CH3 H

+ AlCl3

Xu hng: to carbocation bn hn chuyn vhttp://hhud.tvu.edu.vn

22

V.4. Phn ng cracking To alkane c mch carbon ngn hn di tc dng ca xc tc & nhit Km theo phn ng tch loi hydrogen & phn ng ng vng Cracking nhit: 800oC 1000oC, cracking xc tc (thng l zeolite): 500oC -600oC S dng trong sn xut nhin liu (khng dng iu ch alkane hay alkene v khng chn lc)http://hhud.tvu.edu.vn

23

V.5. Phn ng oxy ha alkane Alkane bn vi tc nhn oxy ha nhit thng nhit cao hoc c mt xc tc c th phn ng vi oxygen, KMnO4, K2Cr2O7 phn ng t mch to alcohol (ROH), aldehyde (RCHO), ketone (RCOR), carboxylic acid (RCOOH) Phn ng quan trng: 2CnH2n+2 + (3n + 1)O2 2nCO2 + (2n+2) H2O ta nhit mnh, -341 kcal/mol alkane c dng 24 lm nhin liuhttp://hhud.tvu.edu.vn


1

Chng 5: ALKENE I. Gii thiu chung Alkene: hydrocarbon mch h, cha 1 lin kt i C=C (CnH2n, n2) Trong C=C: 1 & 1, hnh thnh do lin kt ca orbital sp2


2

Lin kt vung gc vi mt phng phn t Alkene n gin nht l ethylene CH2=CH2

121.7o 116.6o 1.8 1.33 http://hhud.tvu.edu.vn

3

II. H danh php II.1. Tn thng thng Tn alkane tng ng, i ane ylene t dng, tr 3 alkene thng dng: CH2=CH2 ethylene CH2=CH-CH2 propylene (CH3)2C=CH2 isobutylenehttp://hhud.tvu.edu.vn

4

II.2. Danh php IUPAC Tn alkane tng ng, i ane ene Chn mch carbon di nht & cha C=C lm mch chnh nh s sao cho C=C c ch s nh nht Ch s ca C=C chn theo v tr C gn C1 nht, vit cch tn mch chnh 1 gch nganghttp://hhud.tvu.edu.vn

5

CH3-CH-CH=CH2 CH3CH3 CH3-C-CH=CH-CH3 H

3-methyl-1-butene

4-methyl-2-pentene (c cis & trans)

II.3. Tn gc ca alkene Alkenyl CH2=CH- 1-ethenyl (vinyl) CH2=CH-CH2- 2-propenyl (allyl) CH3-CH=CH- 1-propenylhttp://hhud.tvu.edu.vn

6

III. Cc phng php iu ch III.1. Tch nc t alcohol Phn ng c th pha lng (xc tc acid H2SO4, H3PO4, 100-170oC) hay pha kh (xc tc Al2O3, zeolite, 350-400oC)

C C H OH

to xt

C C

+ H2O


7

Kh nng tch nc: alcohol bc 3 > bc 2 > bc 1

CH3CH2CH2CH2-OH

H2SO4 75% 140 Co

CH3CH=CHCH3

CH3-CH-CH2-CH3 H2SO4 50-60% CH -CH=CH-CH 3 3 o 100 C OH (CH3)3C-OH H2SO4 20% 80 Co

CH2=C(CH3)2


8

III.2. Tch HX t dn xut ca halogenC C H X to KOH/ethanol C C + H2O + KX

Kh nng tch HX: RX bc 3 > bc 2 > bc 1CH3CH2CH2CH2Cl to KOH/ethanol CH3CH2CHCH3 Cl to KOH/ethanol CH3CH2CH=CH2

CH3CH2CH=CH2 20%

+

CH3CH=CHCH3 80%

Lu : tch R-X bc 1 khng c chuyn v R-OH bc 1 H2SO4 75%http://hhud.tvu.edu.vn

CH3CH2CH2CH2-OH

140 C

o

CH3CH=CHCH3

9

III.3. Kh dn xut 2 ln th ca halogenZn C C X XH H H3C C C CH3 Br Br

t

o

C C

+ ZnX2

Zn to

CH3CH=CHCH3 + ZnX2

III.4. Hydro ha alkyneR H R C C R' R' H

Rhttp://hhud.tvu.edu.vn

H R'10

H

III.5. Nhit phn ester CnH2n+1-O-COR CnH2n + RCOOH

Nhit phn ester ca ru bc 1 < bc 2 < bc 3 Ester bc 1 1 sn phm, bc 2 & bc 3 nhiu sn phm IV. Tnh cht vt l (t c)Ch tan trong dung mi khng phn cc hay t phn cc

V. Tnh cht ha hc Lin kt (E phn ly = 60 kcal/mol) yu hn lin kt o (E = 80 kcal/mol) 11 Xc tc, to... lin kt d b thttp://hhud.tvu.edu.vn

V.1. Phn ng cng hp i in t V.1.1. C ch: Giai on 1:

C C

+ X+-Y

dung moi xuc tac nhanh

C C X Y phc khong ben+

cham

C+ C X

ben hoa C C X+

Giai on chm: X+ tn cng vo C=C i in thttp://hhud.tvu.edu.vn

12

Giai on 2:

Y YC C X+ nhanh C C X

Y- tn cng vo pha i lp vi X Nhm th y in t (+C, +I, +H) tng mt in t ca C=C tng kh nng phn ng AEhttp://hhud.tvu.edu.vn

13

V.1.2. Phn ng cng hp halogen

Phn ng cng hp ca CH2=CH2 vi Br2 vi s c mt ca NaCl, NaNO3, sn phm thu c l 1 hn hp: Br-CH2-CH2-Br + Br-CH2-CH2-Cl + Br-CH2-CH2-ONO2 Nu phn ng thc hin trong dung mi l CH3OH, sn phm chnh l Br-CH2-CH2-OCH3 !!!


14

H2C CH2 + Br2

CCl4

H2C CH2 Br Br

H2C CH2 + Br2

CH3OH

H2C CH2 Br OCH3

H2C CH2 + Br2

H2O

H2C CH2 Br OH15


***Lp th ca phn ng cng X2: Cng hp trans (anti) cis sn phm l hn hp racemic (1 i i quang) trans sn phm c th l meso (1 sn phm)H H C C CH3 Br2 CH3 CH3 H C Br Br C H CH3 racH3C H C C H CH3 Br2 CH3 H C Br H C Br CH3 http://hhud.tvu.edu.vn meso CH3 Br C H H C Br CH3

V.1.3. Phn ng cng HX a. Quy tc Markonikov (dnh cho C=C khng i xng): H+ s tn cng vo carbon cha nhiu HCH3-CH=CH2 + HBr CH3-CH-CH3 Br Br CH3-C-CH3 CH3

CH3-C=CH2 + HBr CH3

b. Quy tc Zaitsev-Wagner: H+ s tn cng vo pha to thnh carbocation trung gian bn nhtCH3-CH=CH-CH2-CH3 HBr CH3-CH-CH-CH2-CH3 Br17


c. Quy tc Kharasch: khi c mt peroxide, phn ng s i theo hng ngc vi Markonikov & theo c ch cng hp gc t do CH3-CH=CH2 + HBr CH3-CH2-CH2-Br Cc peroxide: H2O2, acetyl peroxide CH3CO-O-OCO-CH3, benzoylperoxide C6H5CO-O-O-COC6H5


18

C ch: Theo hng to gc t do bnto CH3-C-O-O-C-CH3 O O CH3-CO-O + HBr Br CH3 + CH3-CO-O + CO2

Br

+ CH3COOH + CH3-CH-CH2Br

CH3-CH=CH2

CH3-CH-CH2 Br

CH -CH-CH Br3 2

HBr

CH -CH -CH Br3 2 2

+ Br

Lu : HI & HCl khng tham gia phn ng cng 19 gc t do nh HBr!!!http://hhud.tvu.edu.vn

V.1.4. Phn ng cng hp nc Cn xc tc acid: H2SO4, H3PO4 (khng dng HX)H2SO4 CH3-CH=CH2 + H O 2 CH3-CH-CH3 OH

Tun theo quy tc Markonikov C ch:CH3-CH=CH2 +H -H+ +

+ CH3-CH-CH3

+ H 2O -H2O

H H3 C C O CH3

H H

-H+ + H+

CH3-CH-CH3 OH

Nu dng nhiu H2SO4: CH3-CH=CH2 + H2SO4 (CH3)2CH-OSO3H (CH3)2CH-OSO3H + H2O (CH3)2CH-OH + H2SO4http://hhud.tvu.edu.vn

20

V.1.5. Phn ng cng hp B2H6 Phn ng quan trng iu ch alcohol bc 1 & 2 t alkene, ngc vi sn phm MarkonikovCH3-CH=CH2 1. B2H6 2. H2O2 / NaOH CH3-CH2-CH2-OH

C ch: B2H6 BH3BH3 CH3-CH=CH2 (Lewis acid) H + CH3-CH-CH2-B H H CH3-CH2-CH2-BH2

HOH[CH3-CH2-CH2-O]3B21

[CH3-CH2-CH2]3B

H2O2


CH3-CH2-CH2-OH

V.2. Phn ng hydro ha V.2.1. C ch:Ni C C + H2 C C H H

Xc tc thng dng: Ni, Pd, Pt C ch: gc t do (AR), 2 H gn vo cng pha ni i (khc phn ng +X2) cng hp cisC C C C H H22

H H + H2http://hhud.tvu.edu.vn

H H

V.2.2. Tnh lp th Phn ng cng hp cis (syn) ng phn cis c th thu sn phm meso (1 sn phm) ng phn trans sn phm l hn hp racemic (1 i i quang)H H C C COOH COOH D2 Ni COOH H C D H C D COOH meso COOH H C D D C H COOH COOH D C H H C D COOH rac-

maleic acid H HOOC C C COOH H D2 Ni

fumaric acid


23

V.3. Phn ng oxy ha V.3.1. Tc nhn oxy ha peracid

+

C C

+

R-C-O-O-H O

O C C

+ RCOOH

O C C

OH H2O C C (H+, OH-) OH

Cng hp trans, to -diol Phn ng khng gy ct mch C=Chttp://hhud.tvu.edu.vn

24

V.3.2. Oxy ha bng ddch KMnO4 long (pH 7, 0oC ) Cng hp cis, to diolOHC C O O Mn O OH2O H+

C C

+

MnO4

-

0 oC pH 7

C C OH OH

+ MnO3-

Phn ng khng ct mch C=Chttp://hhud.tvu.edu.vn

25

V.3.3. Oxy ha bng ddch KMnO4 m c, to cao Phn ng gy ct mch C=C Sn phm l carboxylic acid CH3-CH=CH-CH3 + KMnO4 / to 2 CH3COOH (CH3)2CH=CH-CH3 + K2Cr2O7 /H2SO4/to (CH3)2C=O + CH3COOHhttp://hhud.tvu.edu.vn

26

V.3.4. Oxy ha bng ozone Phn ng gy ct mch C=C Sn phm l carbonyl (khc KMnO4 )C O + H2O C C O3 C O C O O C C O O ozonide H /Pt2

C O + H2O

O molozonide

C O + H2O2

CH3-C=CH-CH2-CH3 CH3

1. O3 2. H2O

CH2-C-CH3 + O

CH3-CH2-CHO

+ H 2O 2

Lu : H2O2 d dng oxy ha carbonyl thnh27 carboxylic acid sn phm cui l acid!!!http://hhud.tvu.edu.vn

V.4. Phn ng polymer ha Phn ng to polymer di tc dng ca nh sng, to cao, xc tc C th xy ra theo c ch gc t do (xc tc peroxide), c ch cation (xc tc H2SO4, AlCl3, BF3) hay anion (xc tc LiNH2)CH3 H2C C CH3nCH2=CH Cl

H+

CH3 H3C C CH2 CH3

CH3 C CH2 CH3

CH3 C CH3

peroxide

--CH2-CH- CH2-CH- CH2-CH-Clhttp://hhud.tvu.edu.vn

Cl Cl polyvinyl chloride

28


1

Chng 6: ALKADIENE I. Phn loi I.1. Hai ni i ng lin nhau (allene) CH2=C=CH2 propadiene CH3-CH2=C=CH2 1,2-butadiene


2

I.2. Hai ni i lin hp C cu to c bit c tnh cht ha hc quan trng ch trng cc hp cht ny CH2=CH-CH=CH2 1,3-butadiene CH2=C(CH3)-CH=CH2 2-methyl-1,3-butadiene (isoprene)


3

I.3. Hai ni i xa nhau Tnh cht ging nh alkene CH2=CH-CH2-CH=CH2 1,4-pentadiene


4

II. Cc phng php iu ch II.1. Tch nc t 1,3-butadiol i t acetyleneHgSO4 HC CH + H2O H2SO4-

CH3-CHO

O H3C C + + H

O H2C C H H

OH

OH O H3C C CH2 C H H

H /Ni2

OH H3C C CH2 CH2OH H

Al2O3 350 C http://hhud.tvu.edu.vno

CH2=CH-CH=CH2

+ 2H2O5

II.2. ethanol2 CH -CH -OH3 2

ZnO/Al2O3 450-500 Co

CH =CH-CH=CH2

2

II.3. 1,4-butadiol

HC CH + HCHO HO-CH2-CH2 CH2-CH-OH

HO-CH2-C Al2O3 350 Chttp://hhud.tvu.edu.vn

C-CH2-OH

H2/Ni

o

CH2=CH-CH=CH2

6

III. Tnh cht ha hc Cc in t c gii ta u trn ton b phn t linh ng

C1-C2: 1.38 (C=C bnh thng: 1.34) C2-C3: 1.46 (C-C bnh thng: 1.54) Khi c mt tc nhn khc, h lin hp s phn cc:CH2=CH-CH=CH2 + CH2-CH=CH-CH2 + CH2-CH-CH=CH2


khc alkene bnh thng7

III.1. Phn ng cng halogen Thu c 2 sn phm cng 1,2 & 1,4CH2=CH-CH-CH2 CH2=CH-CH=CH2 + Br-Br Br Br CH2-CH=CH-CH2

C ch:+ + Br-Br

Br+ CH2=CH-CH-CH2 Br BrCH2=CH-CH-CH2http://hhud.tvu.edu.vn

Br

CH2=CH-CH=CH2

+ CH2-CH=CH-CH2 Br BrCH2-CH=CH-CH2 Br Br 8

Br Br

III.2. Phn ng cng HX Ty theo nhit m thu c hn hp sn phm khc nhauCH2=CH-CH=CH2 + HBr -80 oC CH2=CH-CH-CH2 Br H CH2-CH=CH-CH2 Br Hhttp://hhud.tvu.edu.vn

40 oC CH2=CH-CH-CH2 80% 40 oC Br H CH2-CH=CH-CH2 Br H9

20%

20%

80%

III.3. Phn ng Diels-Alder Phn ng cng hp & ng vng ca1,3butadiene hay dn xut ca n vi cc hydrocarbon khng no khc (i diene)

H

C C

H C

H H

H + H C C

O C CH3 Hhttp://hhud.tvu.edu.vn

O to CH3

H

C H

10

Cc hp cht i diene phi mang nhm th ht in t, ethylene phn ng rt chm CH2=CH-CHO acrolein CH2=CHCN acrylonitrile (CN2)C=C(CN)2 tetracyan ethylene C6H5-CH=CH-COOH cinnamic acidO O O

maleic anhydrideO

benzoquinonehttp://hhud.tvu.edu.vn

O

11

III.4. Phn ng trng hp

n CH2=CH-CH=CH2

--CH2-CH=CH-CH2--

n

Trng hp isoprene cha 94% cis ~ cao su thin nhin

n CH2=C-CH=CH2 CH3http://hhud.tvu.edu.vn

--CH2-C=CH-CH2-n CH3

12


1

Chng 7: ALKYNE I. Gii thiu chung Hp cht hydrocarbon khng no, mch h, cha lin kt ba CC Cng thc chung: CnH2n-2


2

180o

1.06


1. 2

3

II. Danh php II.1. Tn thng thng Alkyne n gin nht l HCCH acetylene Cc alkyne n gin khc c xem l dn xut ca acetylene HCC-CH2-CH3 ethylacetylene CH3-CC-CH(CH3)2 isopropylmethylacetylenehttp://hhud.tvu.edu.vn

4

II. 2. Tn IUPAC Cch gi tn ging nh alkene, ch i ene thnh yne Mch chnh phi cha CC Nhng hp cht cha nhiu hn 1 ni ba diyne, triyne Hp cht va c ni i va c ni ba enyne6-methyl-3-octyne


5

4-methyl-7-nonene1-yne

1-heptene-6-yne

III. Cc phng php iu ch III.1. Thy phn calcium carbide CaC2CaO + 3C 2000 oC CaC2 + CO HC CH + Ca(OH)2

CaC2 + 2H2O

III.2. Oxy ha methane1500 oC 2 HC CH + 2CO + 10H2http://hhud.tvu.edu.vn

6CH4 + O2

6

III.3. i t dn xut dihalogenH2C CH2 KOH/EtOH to Br Br CH3-CH2-CHCl2 HC CH

KOH/EtOH to

CH3-CH

CH

CH3-C Cl CH3-CH2-C-CH3 Cl

C CH3

CH3-CH2-Chttp://hhud.tvu.edu.vn

CH7

III.4. Alkyl ha dn xut natri hay c magnesium ca acetylene HCCNa HCC-MgX + R-X HCC-R + NaX

+ R-X HCC-R + MgX2

iu ch dn xut ca acetylene HCCH HCCH + NaNH2 HCCNa + CH3MgX HCC-MgX IV. Tnh cht vt l (t c)http://hhud.tvu.edu.vn

+ NH3 + CH4

8

V. Tnh cht ha hc V.1. Phn ng th H u mch H u mch th hin tnh acid HCC-H + NaNH2 HCCNa + NH3 + HCC-H + [Ag(NH3)2] NO3 Ag-CC-Ag + NH4NO3 + NH3 C trong CC-H trng thi sp, m in ln hn sp2 hay sp3 ht in t ca lin kt C-H H+ d tch ra Alkene & alkane khng c tnh cht nyhttp://hhud.tvu.edu.vn

9

V.2. Phn ng cng hydrogenR C C R' + H2 Ni hay Pt R-CH2-CH2-R'R-CH2-CH2-R'

R C C R'

+ H2 H H C C R R'

R C C R' + Na/NH3http://hhud.tvu.edu.vn

H R' C C R H

10

V.3. Phn ng cng halogen

H3C C CH

+ Br-Br

Br H3C C CH Br

Br2

Br H3 C C CHBr2 Br

Sn phm trans trong ln cng th nht Lu : nu ni i & ni ba khng lin hp, X2 s cng vo ni i!!! CH2=CH-CH2-CCH + Br2 BrCH2-CHBr-CH2-CCHhttp://hhud.tvu.edu.vn

11

V.4. Phn ng cng HX

H H C C CH H

H-Br

H H C C CH2 H Br

H-Br

H Br H C C CH3 H Br

Tun theo quy tc Markonikovhttp://hhud.tvu.edu.vn

12

V.5. Phn ng cng ncHC CH + H O2

HgSO4 H2SO4

HC CH2 OH enol

CH CHO3

R C CH + H2O

HgSO4 R C CH2 H2SO4 OH enol

R C CH3 O

Ch c acetylene mi to thnh aldehydehttp://hhud.tvu.edu.vn

13

V.6. Phn ng cng hp alkylborane

H + H H C C C C CH3 H H BHR2

H3C H3C C C CH2 CH3 CH3COOH H BR2 H2O2/OHH3C C C CH2 CH3 H OH H

C2H5 H

C C

H3C CH2 C CH2 CH3 O

To alken: cng cishttp://hhud.tvu.edu.vn

14

V.7. Phn ng cng hp cht carbonyl Cng hp i nhn

+ H C C H

H

C O + H

H C C CH2-OH HCHO

HO-H2C C C CH2-OH

H C C H

R + 2 C O Rhttp://hhud.tvu.edu.vn

R R HO-C C C C-OH R R15

V.8. Phn ng cng hp i nhnR-OH, R-SH, R-COOH, H-CN, amine monomer quan trngROHC CH 150 oC ROCH CHR2NH C6H5CO C CH ROH ROCH CH2 C6H5CO NR2 C C H H + RO-

C2H5ONa C6H5C CH

C6H5 OC2H5 C C H H

CH2 CH C CH

ROH RO150 oC

CH2 CH CH CHOR16


V.9. Phn ng oxy ha Oxy ha alkyne bng KMnO4 hay ozone to carboxylic acid R-CC-R + KMnO4 hay ozone RCOOH + RCOOH R-CC-H + KMnO4 hay ozone RCOOH +CO2 V. 10. Phn ng trng hp2H C C H CuCl to CH2=CH-C CH HCl CH2=CH-C CH2

Cl chloroprene cao su neoprene17http://hhud.tvu.edu.vn

CH2-CH=C CH2 Cl n


1

Chng 6:

HYDROCARBON THMI. Cu to ca benzene

Kkul a ra cng thc cu to ca benzene nm 1865 6C, 6H vng 6 cnh c 3 ni i nhng khng th l cyclotriene H H C H C C C C H C H2http://hhud.tvu.edu.vn

Kkul chng minh rng v tr 3 Lin kt i khng c nh m c th thay i

Phn ng th 2 ln Br ch cho 1 sn phmBr Br + Br2 Br Brhttp://hhud.tvu.edu.vn

3

Cu to thc t: h in t phn b u cho 6C (khng phi ca ring 3 cp C=C)

6C nm trong cng 1 mt phng, trng thi lai ha sp2http://hhud.tvu.edu.vn

4

120

o

120

o

1201.9

o

1.39

121.7o 116.6o 1.08 1.33 http://hhud.tvu.edu.vn

5

II. Tnh thm Hydrocarbon thm (arene) nhng hp cht vng lin hp c cu to phng, c cu to in t ging benzene, kh cho phn ng cng, d cho phn ng thH Br2 CCl4 Br Br2 CCl4 Br HH KMnO4 L H2O H KMnO4 L H2Ohttp://hhud.tvu.edu.vn

OH OH

6

Arene thng l vng phng 5, 6, 7 cnh, c h in t lin hp, s t tun theo quy tc Hkel 4n + 2, n = 0,1,2,3,4 V d cc hp cht arene thng dng

n=1

n=2http://hhud.tvu.edu.vn

n=37

Mt s trng hp c bitcyclopentadienyl 6 in t (i t ca anion tham gia h lin hp) n=1 c tnh thm cycloheptatrienyl 6 in t (C+ tham gia orbital trng p vo h lin hp) c tnh thm

(-)

(+)

4 in t khng c tnh thm (+) 2 in t c tnh thm(+)http://hhud.tvu.edu.vn

8

5 in t khng c tnh thm(.)

(.)

7 in t khng c tnh thm

(-)

8 in t khng c tnh thm 6 in t (i in t p tham gia h lin hp) c tnh thm9

N H Pyrrole

O Furan

S

http://hhud.tvu.edu.vn Thioph ene

III. Danh php

Hu ht cc arene u c tn thng thng, 1 s tn thng thng c chp nhn lm tn IUPAC Tn IUPAC: benzene c chn lm tn gc, tn cc nhm th t trc, nhm th c nh s theo nguyn tc tng ch s nh nht, xp theo alphabetical


10

III.1. Dn xut ca benzene


11

anisole

methoxybenzene

phenol

benzenol benzenamine

aniline

benzenecarboxylic acid

benzoic acid benzenecarbal dehyde

benzal dehyde

I NO2 CH3 NO2 Br Cl

p-bromoiodobenzene m-chloronitrobenzene

o-nitrotoluene

OH COOH NH2 I Br NO2

4-bromophenol

m-nitrobenzoic acid

o-iodoaniline

HC CH2

HC CH2

1,4-divinylbenzene hay p-divinylbenzene ttp://hhud.tvu.edu.vn khohn g goi la p-vinylstyrene

13

NO2

NH2 Br Br Cl

OH Cl

Cl

Br

Br

Cl

3-bromo-5-chloronitrobenzene

2,4,6-tribromoaniline

2,4,6-trichlorophenol

Br Br

OH Cl O 2N

CH3 NO2

Br

NO 2

1,2,4-tribromobenzene

2-chloro-4-nitrophenol

2,6-dinitrotoluene


14

III.2. Vng a ngng t

8 7 6 9

1 2 3 7 6

8

9

1 2 3

10 5 4 Naphthalene

10 4 Anthracene

5


15

III.3. Cc arene c d t trong vng

N Pyridine

N

CH3

2-methylpyridine

N H Pyrrole

O Furan

S Thiophene


16

IV. Cc phng php iu ch X.1. Chng ct mui ca benzoic acidCOONa + NaOH to + Na2CO3

X.2. i t acetylene

3HC CH Cu hay phc Ni tohttp://hhud.tvu.edu.vn

17

X.3. Alkyl ha benzeneR + R-Cl AlCl3 + HCl

X.4. ng vng & dehydro ha phn on du m C6-C8

CH3(CH2)4CH3

Cr2O3 / Al2O3

V. Tnh cht vt l (t c)http://hhud.tvu.edu.vn

18

V. Tnh cht ha hcV.1. Phn ng th i in t V.1.1. C ch phn ng X+ X+ acid + H+

Xc tc: H2SO4, H3PO4, HF hay Lewis acid: FeCl3, AlCl3, ZnCl2 C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBrhttp://hhud.tvu.edu.vn

19

C ch phn ng: 2 giai on, lng phn t Giai on 1: to phc ( benzonium cation)xt nhanh

+ X -Y

+

X+-Y

phc

X cham

H +

X

H +

X

H

X +

H

phc

+

Trong phc : X khng lin kt trc tip vi C no c Phc : X c lin kt trc tip vi 1 C ca benzenehttp://hhud.tvu.edu.vn

20

Giai on 2: tch proton

X +

H nhanh

X + HY


21

V.1.2. Kh nng phn ng v quy lut th a. Kh nng phn ng: Nhm th y in t (+I, +C, +H) mt in t trong nhn thm tng tc nhn i in t cng d tn cng tc phn ng tng Cc nhm th y in t (tng hot) thng gp: * alkyl ( +I, +H) *-NR2 (R: H hay gc alkyl), -OH, -OCH3 -NH-CO-CH3 (+C > -I)

* anion: -O- (+C, +I mnh)http://hhud.tvu.edu.vn

22

Nhm th ht in t (-C, -I) mt in t ca nhm thm gim khng thun li cho tc nhn i in t gim tc phn ng Cc nhm th ht in t (gim hot) thng gp: * -N+N, -NO2, -CN, -CHO, -COR, -COCl, -COOH, -CO-NH2 (-I, -C) * cation: -N+R3 (-I mnh) * halogen (-I > +C)OH Cl > > >23

NO2

V d: kh nng th i in t:http://hhud.tvu.edu.vn

b. Tnh chn la quy lut th Nhm th y in t nh hng nhm th th 2 vo v tr o- hay p Nhm th ht in t nh hng nhm th th 2 vo m Ring dy halogen gim hot, nhng vn nh hng nhm th 2 vo o-, p-


24

Nhn thm c nhm th y in t:Y Y Y Y

mt t o-, p- cao nht nhm th th 2 (i in t) s vo o-, p Nhn thm cha nhm th ht in t:Y Y Y Y

mt t o-, p- thp nht nhm th th 225 s vo mhttp://hhud.tvu.edu.vn

C th gii thch da vo bn ca phc Y + X+

Th o-:Y X H Y X H Y X H

Y

Y

Y

Th p-:X H http://hhud.tvu.edu.vn X H X26

H

Th m-:Y H X X Y H X Y H

khi Y y in t: trong th o-& p-: c 2 trng thi cation bn (+ gn Y nht) d to thnh nhm th th 2 s vo o-, p khi Y ht in t: trong th o-, p-: c 2 trng thi rt km bn (+ gn Y) nhm th 2 s khng vo o27 , p- m vo mhttp://hhud.tvu.edu.vn

c. Nhn thm c 2 nhm th: Nhm th th 3 s nh hng da theo nh hng ca nhm th tng hat nht V d:-I>+C Cl +C>-I OH

+C>-I OH

+C>-I NH2

NH2 +C>-I

CH3 +I, +H

HN C CH3 O +C>-Ihttp://hhud.tvu.edu.vn

NO2 -C, -I28

d. T l 2 ng phn o-/p-: D on: o-/p- = 2/1 Thc t o-/p- 170 oC 170-180 oC

SO3H


37

V.2.3. Phn ng halogen ha

X + X2 xt + HX

Xc tc: AlCl3, FeBr3, ZnCl2 Flor ha: mnh lit, t mch t s dng Iodo ha: thun nghchhttp://hhud.tvu.edu.vn

38

C ch phn ng:

+ Cl

+

- Cl

FeCl3 nhanh Cl + FeCl3 + HCl Cl+-Cl FeCl3

cham

Cl +

H

FeCl4-


39

iu ch C6H5I:I + I2 + HNO3 H+ + I2 + HNO3 I+ + NO2 + H2O + NO2 + H2O

Tc nhn i in t I+ tn cng nhn thm theo c ch nh trnhttp://hhud.tvu.edu.vn

40

Halogen ha mch nhnh ca arene: Nu c xc tc & nhit thp phn ng th i in t (SE) Nhit cao, nh sng hay peroxide: th vo mch nhnh (SR)CH3 Cl2 130 oC CH2Cl Cl2 140-160 oC CHCl2 Cl2 >180 oC CCl3

Kh nng chlor ha SR: C bc 3 > C bc 2 > bc 1http://hhud.tvu.edu.vn

41

V.2.4. Phn ng alkyl ha Friedel-Crafts a. Alkyl ha vi R-X, xc tc Lewis acid (AlCl3, FeBr3)R AlCl3 + R-Cl + HCl

C ch:+ R - Cl+

AlCl3 nhanh

R+-Cl AlCl3

cham

R +

H

AlCl4

-

R + AlCl3 + HClhttp://hhud.tvu.edu.vn

42

b. Alkyl ha vi alkene, xc tc Lewis acid hay Bronsted acid (HF, H3PO4)R-CH=CH2 H+ + R-CH-CH3

Carbocation tn cng nhn thm theo c ch th i in t nh trn, to thnhH R C CH3


43

c. Alkyl ha vi alcohol, xc tc Lewis acid hay Bronsted acid (HF, H3PO4)

R-OH

H

+

+ H R-O H

R+ + H2O

Carbocation tn cng nhn thm theo c ch th i in t nh trn, to C6H5-Rhttp://hhud.tvu.edu.vn

44

d. Cc im cn lu ca phn ng alkyl ha Friedel-Crafts C6H5-X khng th to tc nhn i in t Tc phn ng alkyl ha ca R-X: bc 1 < bc 2 < bc 3 < dn xut benzyl hay allyl carbocation cng bn, phn ng cng d Alkyl ha khng dng li sn phm monohttp://hhud.tvu.edu.vn

45

Carbocation lun c chuyn v to cao:CH3-CH2-CH2-Cl AlCl3 + CH3-CH2-CH2 H H3C C CH3 CH3-CH2-CH2-Cl AlCl3 70% + 30% + CH3-CH-CH3 CH2-CH2-CH3

Alkyl ha phenol, khng dng AlCl3 (to phc phi tr vi OH), phi dng H2SO4, H3PO4 lm xc tc Vng thm c nhm th ht in t mnh hn 46 halogen khng tham gia phn ng akyl hahttp://hhud.tvu.edu.vn

Sn phm c th b ng phn ha hay d ha khi xc tc d:CH3 Lewis acid to CH3 CH2CH3 2 Lewis acid tohttp://hhud.tvu.edu.vn

CH3

CH3

CH2CH3 + CH2CH347

V.2.5. Phn ng acyl ha Friedel-CraftsR-CO-Cl (R-CO)2O Lewis acid R C O

a.C ch:R C Cl O O R C O R C O + AlCl3 R-C+ O_

+ AlCl3

+ R-C O

+ AlCl4-

+ [RCOOAlCl3]

Tc nhn i in t RC+=O tn cng nhn thm 48 theo c ch th i in t nh trnhttp://hhud.tvu.edu.vn

b. c im quan trng Lng xc tc AlCl3 rt nhiu, do:O C AlCl3 O C+ R

R

AlCl3

HCl O Chttp://hhud.tvu.edu.vn

R49

iu ch alkyl benzene bc 1 hoc mono-

CH2CH2CH3 C O CH3CH2CH2COCl AlCl3 Zn(Hg)/HCl

CH2CH2CH2CH3

Kh nng phn ng: RCOI > RCOBr > RCOCl > RCOF HCOCl khng bn phi dng CO/HCl/AlCl3 lm tc nhn acyl hahttp://hhud.tvu.edu.vn

50

Nhm th phn hat ha khng thun li cho phn ng:

O2N C O AlCl3 O2N + ClOC + AlCl3 O2N COCl


51

V.3. Phn ng th i nhn ca vng thm (SN) Vng thm giu in t SN ca benzene hay dn xut rt kh xy raX + Y-

Y + X-

Cl + KOH 300 oC 280 atm

OH + KCl

Khng xy ra iu kin thnghttp://hhud.tvu.edu.vn

52

Trng hp c bit: nhm th th 2 ht in t mnh & v tr o-, p- th i nhn ca nhm th 1 c th xy ra Cc nhm th ht in t mnh: -N+N, -NO2, -CN, CHO, -COR V d:

Cl + Na2CO3 L NO2

OH


NO2

53

NO2 Cl NaOH to NaNH2 N to

NO2 OH

NO2 NaOH to CH3ONa

NO2 OH

N

NH2

N

Cl

N

OCH3

C ch: th i nhn lng phn tO N cham HOO-

O + ON nhanh -Cl-

O

N

O-

Cl

Cl

OH


OH

54

Cc mui diazonium ca arene c kh nng cho phn ng th i nhn n phn tN+ NCl+ to cham nhanh YY Y- : H2O, HOCH3, I-, CNhttp://hhud.tvu.edu.vn

+ N2 + Cl-

55

V.4. Phn ng oxy ha Nhn thm thng tr vi tc nhn oxy ha k c KMnO4, K2Cr2-O7 Trong iu kin nghim ngt:

O O2/ V2O5 450-500 oC Ohttp://hhud.tvu.edu.vn

O2/ V2O5

HC COOH 450-500 oC HC COOH

56

Nhnh alkyl ca vng thm rt d b oxy ha bi CrO3, K2Cr2O7/H2SO4, KMnO4/H2O, KMnO4/KOH -COOH

CH3 KMnO4 H2O, to NO2

COOH

NO2http://hhud.tvu.edu.vn

57

Gc alkyl mch di ct mch, vn to COOH

CH2CH2CH2CH3 KMnO4 H2O

COOH

Nu khng c H benzyl, khng phn ng:H3C C CH3 CH3

KMnO4 H2Ohttp://hhud.tvu.edu.vn

58


1

Chng 9:

CC DN XUT HALOGENI.Phn loi

Cc hydrocarbon trong 1 hay nhiu H c thay bng nguyn t halogen Halogenoalkane: v d CH3-CH2-CH2-Cl Halogenoalkene: v d CH2=CH-CH2-CH2-Cl Halogenoalkyne: v d CHC-Cl Halogenoarene: v d C6H5-Cl Halogenocycloalkane: v dhttp://hhud.tvu.edu.vn

Cl2

II. Danh php II.1. Tn thng thng (dnh cho dn xut n gin) Gc alkyl + halide (halogenua) V d: n-butyl bromide (bromua)

CH3-CH2-CH2-CH2-Br

(CH3)2CH-Cl isopropyl chloride (CH3)2CH-CH2-Cl isobutyl chloride C H -CH -Cl benzyl chloride6 5 2http://hhud.tvu.edu.vn

3

II.2. Tn IUPAC

Halogen c xem l nhm th halo: chloro-, bromo-, iodo-, fluoro Chn mch di nht cha halogen lm mch chnh nh s sao cho nhm th c ch s nh nht, bt k l halo- hay alkyl Khi c nhiu nhm th ging nhau, dng cc tip u ng di-, tri-, tetrahttp://hhud.tvu.edu.vn

4

Nu c nhiu nhm th halo khc nhau, sp xp theo th t alphabetical Nu mch chnh c th nh s t 2 u, u tin nhm ng trc theo th t alphabetical

CH3 CH3 CH3-CH2-C-CH2-CH-CH3 Br 4-bromo-2,4-dimethylhexane

H3C CH3 CH3-C-C-CH3 ClBr

2-bromo-3-chloro-2,3-dimethylbutane5


III. Cc phng php iu ch III.1. Halogen ha alkaneCH3 H3C C CH3 + Cl2 H 25 oC h CH3 H3C C CH2Cl H 64% CH3 + H3C C CH3 Cl 36%

CH3 H3C C CH3 + Br2 H

127 oC h

CH3 H3C C CH2Br H 1%

CH3 + H3C C CH3 Br 99%

127 oC CH3-CH2-CH3 + Br2 h CH3-CH2-CH2-Br http://hhud.tvu.e d% u.vn 3 + CH3-CHBr-CH3 6 97%

III.2. Cng hp halogen hay HX vo alkene, alkyneCCl4 H2C CH2 + Br2 H2C CH2 Br Br

H2C CH2

+ Br2

CH3OH

H2C CH2 Br OCH3

H2C CH2 + Br2

H2O

H2C CH2 Br OHCH3-CH-CH-CH2-CH3 Br

CH3-CH=CH-CH2-CH3

HBr

C mt peroxide: CH3-CH=CH2 + HBr CH3-CH2-CH2-Brhttp://hhud.tvu.edu.vn

7

III.3. Halogen ha areneX + X2 xt + HX

Xc tc: AlCl3, FeBr3, ZnCl2CH3 Cl2 130 oC CH2Cl Cl2 140-160 oChttp://hhud.tvu.edu.vn

CHCl2 Cl2 >180 oC

CCl3

8

III.4. i t alcohol a.Tc nhn HXCH3-CH2-OH CH3-CH2-OH + HBr + HCl H2SO4 CH3-CH2-Br + H2O ZnCl2 CH 3-CH2 -Cl + H2O

b. Tc nhn PX3, PX5, SOCl2R-OH R-OH R-OH + + + PCl3 PCl5 SOCl2 pyridine pyridine pyridine R-Cl R-Cl R-Cl + H3PO3 + POCl3 + SO2 + HCl + HCl9


IV. Tnh cht vt l (t c) To s ca R-X bc 1 > bc 2 > bc 3 Ch tan tt trong dung mi hu c & khng tan trong nc V. Tnh cht ha hc V.1. c im chung+ R-CH2-CH2 Cl

m in ca Cl >> C C-Cl phn cc mnh R-Cl c hot tnh cao Trong dy halogen, kh nng tch X: -I > -Br > -Cl > -F Nng lng phn ly lin kt C-I nh nht, bn knh 10 nguyn t I ln nhthttp://hhud.tvu.edu.vn

Dn xut R-X c chia thnh 3 nhm : a. R-X hot ng mnh nht Dn xut bc 3, dn xut m C-X lin kt vi nhm vinyl hay aryl carbocation bn nhtCH3 H3C C Br CH3-

CH3 H3 C C+ CH3 +I, +H

-Br

C Br

-Br

-

C+

+C > -I CH2=CH-CH-Br -Br-


+ CH2=CH-CH +C > -I

11

a.Nhm hot ng yu hn nhm a R-X bc 1: CH3-CH2-CH2-CH2-Br Nhm khng no nm xa nt halogen: CH3-CH=CH-CH2-CH2-Br a.Nhm hot ng yu Nguyn t halogen lin kt trc tip vi lin kt i, lin kt ba, vng thmH3C CH CH Cl +C>-I Cl +C>-I

+C ca X lm cho C-X bn kh phn cc, kh tchhttp://hhud.tvu.edu.vn

12

V.2. Phn ng th i nhn R-X + Y- R-Y + X-

Dn xut bc 1 SN2 Dn xut bc 3 SN1 Phn ng thy phn R-X R-X + OH- R-OH + X-

CH3-CH2-Br + OH- CH3-CH2-OH + Brhttp://hhud.tvu.edu.vn

13

Phn ng to ether (Williamson) R-X + R-O- R-O-R + XCH3-CH2-Br + CH3-O- CH3-CH2-O-CH3 Phn ng to amine R-X + NH3 R-NH2 + HX CH3-CH2-Br + NH3 CH3-CH2-NH2 + HBr CH3-CH2-CH2-CH2-NH2 + CH3-CH2-Br CH3-(CH2)3-NH-C2H5 + HBrhttp://hhud.tvu.edu.vn

14

Phn ng to nitrile R-X + KCN R-CN + KX CH3-CH2-Br + CN- CH3-CH2-CN + BrLu : R-CN d b thy phn trong nc to R-COOH


15

V.3. Phn ng tch loiCH3-CH-CH-CH3 KOH/ethanol CH3-CH=CH-CH3 o t H Br

Gc R c bc cng cao, hay base cng mnh th tch loi cng chim u thto thng CH3-CH2-CH2-Br + C2H5OCH3-CH2-CH2-O-C2H5

CH3 H3C C Br CH3

C2H5Oto caohttp://hhud.tvu.edu.vn

H2C C

CH3 CH316

V.4. Phn ng vi kim loi-Hp cht Grignard CH3-CH2-Br + Na CH3-CH2-CH2-CH3 + NaBr Quan trng: phn ng vi magnesium

R-X

+ Mg

ether khan

R-Mg-X

+ C Mg Br

C-MgX phn cc rt mnh, rt d to R- base rt mnh & tc nhn i nhn rt mnhhttp://hhud.tvu.edu.vn

17

V.4.1. Phn ng vi H linh ng CH3-CH2-MgBr + HOH CH3-CH3 + HO-MgBr CH3-CH2-MgBr + ROH CH3-CH3 + RO-MgBr CH3-CH2-MgBr + RNH2 CH3-CH3 + RNH-MgBr CH3-CH2-MgBr + RCOOH CH3-CH3 + RCOO-MgBr CH3-CH2-MgBr + RCCH CH3-CH3 + R-CC-MgBrhttp://hhud.tvu.edu.vn

18

V.4.2. Phn ng vi carbonyl + O CH3-CH2-MgBr + H3C C + H O-MgBr H3C C H C2H5 H O /H+2

OH H3C C H C2H5 + HO-MgBr

Phn ng vi HCHO alcohol bc 1 Vi aldehyde alcohol bc 2 Vi ketone alcohol bc 3http://hhud.tvu.edu.vn

19

V.4.3. Phn ng vi CO2 + + CH3-CH2-MgBr O C O H2O /H+ C2H5-C-O-MgBr O C2H5-COOH + HO-MgBr

V.4.4. Phn ng vi nitrile + CH3-CH2-MgBr + + R-C N R C N MgBr C2H5 H2O /H+

R C NH C2H5

H2O /H+ R C O C2H5

Kh nng phn ng: nitrile > ketone ch khi d Grignard phn ng tip vi ketone to alcohol 20 bc 3http://hhud.tvu.edu.vn

V.4.5. Phn ng vi dn xut ca carboxylic acid + O CH3-CH2-MgBr + H3C C + Cl OH O-MgBr H O /H+ 2 H3C C Cl H3C C Cl C2H5 C2H5

-HCl

H3C C O C2H5

Kh nng phn ng: dn xut acid > ketone ch khi d Grignard phn ng tip vi ketone to alcohol bc 3 Tng t cho phn ng vi anhydridehttp://hhud.tvu.edu.vn

21

Phn ng vi ester:

+ O CH3-CH2-MgBr + H3C C + OCH3

OH O-MgBr H2O /H+ H3C C OCH3 H3C C OCH3 C2H5 C2H5 C2H5 H3C C OH C2H5

-CH3OH

H3C C O C2H5

1. C2H5-MgBr 2.H2O /H+

Kh nng phn ng: ester < ketone khng th 22 tch ketone trung gianhttp://hhud.tvu.edu.vn

V.4.5. Phn ng vi oxide

CH3-CH2-MgBr +

CH2 O

CH2

ether khan

CH3-CH2-CH2-CH2-OMgBr

H2O /H+ CH3-CH2-CH2-CH2-OH

MgBr + CH2 O CHCH3 1. ether khan 2. H2O / H+http://hhud.tvu.edu.vn

OH CH2CHCH3 60%23

V.4.6. Phn ng ghp i Kumada KharashRMgX + R'X CoCl2 R R' + MgX2

Kumada: t sn phm ph hn KharashL2NiX2 RMgX' + R'X'' or L2PdX2 R-R' + MgX'X''


24


1

Chng 10: ALCOHOL-PHENOL Chng 10A: AlcoholR-OH trong : R: no hay khng no CH3-CH2-OH CH2=CH-CH2-OH R: nhnh ca arene C6H5 -CH2 -OHhttp://hhud.tvu.edu.vn

2

I. Danh phpI.1. Tn thng thng (dng cho alcohol n gin) Gc alkyl + alcohol CH3-CH -OH (CH3)2CH-OH (CH3)2CH-CH2-OH (CH3)3C-OH C6H5-CH2-OH CH2=CH-CH2-OH ethyl alcohol isopropyl alcohol isobutyl alcohol tert-butyl alcohol benzyl alcohol allyl alcohol

C th gi CH3-OH l carbinol, cc alcohol khc l dn xut ca carbinol, v d: methyl carbinol 3 (ethyl alcohol)http://hhud.tvu.edu.vn

I.2. Tn IUPAC Chn mch di nht c cha nhm OH lm mch chnh Ly tn alkane, i ane anol nh s mch chnh t u gn nhm OH nht Khi c nhiu nhm th, sp xp theo th t alphabetical CH3-OH CH3-CH2-OHhttp://hhud.tvu.edu.vn

methanol ethanol4

CH3 H3C C CH2-OH CH3

2,2-dimethyl-1-propanol

CH3 CH3-CH-CH-CH3 OH

3-methyl-2-butanol

OH

7-ethyl-8,9-dimethyl-5-dodecanol

C6H5-CH2-OH

phenylmethanolhttp://hhud.tvu.edu.vn

5

II. Cc phng php iu chII.1. ng hp nc vo alkene Phn ng cn xc tc acid: H2SO4, H3PO4 (khng dng HX)

CH3-CH=CH2 + H2O

H2SO4

CH3-CH-CH3 OH

Tun theo quy tc Markonikovhttp://hhud.tvu.edu.vn

6

Phn ng quan trng iu ch alcohol bc 1 & 2 t alkene, ngc vi sn phm Markonikov:

CH3-CH=CH2

1. B2H6 2. H2O2 / NaOH

CH3-CH2-CH2-OH


7

II.2. Kh ha carbonyl, carboxylic acid v dn xut Kh bng H2

Ni R C R' O + H2

H R C R' OH

aldehyde alcohol bc 1 ketone alcohol bc 2http://hhud.tvu.edu.vn

8

Kh bng LiAlH4, NaBH4 R-CHO + LiAlH4 R-COOH + LiAlH4 R-CH2-OH + R-CH2-OH

Kh bng [(CH3)2CH-O]3Al trong (CH3)2CH-OH R-CHO + [(CH3)2CH-O]3Al/(CH3)2CH-OH R-CH2-OH + (CH3)2COhttp://hhud.tvu.edu.vn

9

II.3. i t hp cht Grignar + O CH3-CH2-MgBr + H3C C + H O-MgBr H3C C H C2H5 H O /H+2

OH H3C C H C2H5 + HO-MgBr

II.4. Thy phn R-X, dn xut ca esterO R C OR' + H2 O OHR-COO+ R'-OH

R-X + OH- R-OH + Xhttp://hhud.tvu.edu.vn

10

III. Tnh cht vt lR-OH to lin kt H to si cao hn cc dn xut ca hydrocarbon c khi lng phn t tng ng C1-C3: tan tt trong nc C4-C7: tan 1 phn trong nc >C7: khng tan trong nchttp://hhud.tvu.edu.vn

11

IV. Tnh cht ha hcIV.1. Gii thiu chung a. Kh nng t lin kt C-O Ch xy ra trong mi trng acid+ H R O H

R OH

+ H

+

R+

+ H2O

Kh nng phn ng: bc 1 < bc 2 < bc 312 C-OH cha nhiu nhm th y in t thun lihttp://hhud.tvu.edu.vn

b. Kh nng t lin kt O-H Ch xy ra trong mi trng base mnh

R OH

R-O-

+ H+

Kh nng phn ng: bc 1> bc 2> bc 3 R cha nhiu nhm y in t khng thun lihttp://hhud.tvu.edu.vn

13

IV.2. Tnh acid-base Tnh acid ca alcohol rt yu Tnh acid: C2H5-OH (Ka 1.3x10-18) < H2O (1.3x10-14) < C6H5-OH (1.3x10-10) < CH3COOH (1.8x10-5) Alcohol hu nh khng phn ng vi NaOH

R OH

+ NaOHhttp://hhud.tvu.edu.vn

R-ONa + H2O14

Alcohol ch tc dng vi Na hay NaNH2R OH R OH + Na + NaNH2 R-ONa + H2 R-ONa + NH3

Mui alkoxide l base rt mnh Tnh base: (CH3)3C-O- > (CH3)2CH-O- > CH3-CH2-O> CH3-O- > OHhttp://hhud.tvu.edu.vn

15

IV.3. Phn ng to ether2 CH3-CH2-OH H2SO4 CH3-CH2-O-CH2-CH3 + H2O

2 CH3-CH2-OH

Al2O3 350-400 Co

CH3-CH2-O-CH2-CH3 + H2O

Alcohol bc 1: SN2 Alcohol bc 3: SN1 ***Danh php ca ether: tn gc alkyl + ether C2H5-O-C2H5 diethyl ether16

CH3-O-C(CH3)3 tert-butyl methyl etherhttp://hhud.tvu.edu.vn

Nu gc alkyl phc tp, c th xem l nhm th alkoxyCH3-CH2-CH2-CH-CH2-CH3 OCH3

3-methoxyhexane

CH2 OHH3C CH3

CH2 OC2H5

2-ethoxyethanol

CH3-CH-CH CH3 OC2H5

2-ethoxy-2,3-dimethylbutanehttp://hhud.tvu.edu.vn

17

IV.4. Phn ng ester haR C OH O R C Cl O O R C O R C O + R'-OH H2SO4 R C O-R' O R C O-R' O + H2O

+ R'-OH

+ HCl

+ R'-OH

R C O-R' O

+ RCOOH

Kh nng phn ng: RCO-Cl (khng cn xc tc) > (RCO)2O (khng cn xc tc) > RCOOH 18http://hhud.tvu.edu.vn

R'-OH + R C OH O + H O R' R C OH OH O R' R C OH + HSO4-H+

C ch phn ng:

+ H

+

+ R C OH OH

O R' R C OH OH2 + O R' R C O

-H2O

Kh nng phn ng: alcohol bc 1> bc 2> bc 3 HCOOH > CH3COOH > RCH2COOH > R2CHCOOH >19http://hhud.tvu.edu.vn

3

IV.5. Phn ng th -OH bi halogen a.Tc nhn HXH2SO4 ZnCl2

CH3-CH2-OH CH3-CH2-OH

+ HBr + HCl

CH3-CH2-Br + H2O CH3-CH2-Cl + H2 O

Kh nng phn ng: HI > HBr > HCl > HF HCl kh phn ng, cn xc tc ZnCl2 Lewis acid tn cng vo O lin kt C-O d t Kh nng thay th: bc 3 > bc 2 > bc 1http://hhud.tvu.edu.vn

20

b. Tc nhn PX3, PX5, SOCl2

R-OH R-OH R-OH

+ + +

PCl3 PCl5 SOCl2

pyridine pyridine pyridine

R-Cl R-Cl R-Cl

+ H3PO3 + POCl3 + SO2 + HCl

+ HCl


21

IV.6. Phn ng dehydro ha v oxy ha a. Phn ng dehydro haR-CH2OH Cu 200-300 oC R-CHO + H2

R R C H OH

Cu 200-300 Co

R C R O

+ H2

CH3 CH3-C-CH2-CH3 OH

Cu 200-300 oChttp://hhud.tvu.edu.vn

CH3 CH3-C=CH-CH3

+ H2O22

b. Phn ng oxy ha Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3 Alcohol bc 1 aldehyde carboxylic acid Rt kh dng li giai on aldehyde thng i thng n RCOOHR-CH2OH + MnO2 + KOH

+ KMnO4

R-COOK H+http://hhud.tvu.edu.vn

RCOOH

23

Mun dng li giai on aldehyde: phi dng pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):C5H5NH+CrO3ClR-CH2OH CH2Cl2 RCHO + Cr3+

Alcohol bc 2 ketone(H3C)3C OH Na2Cr2O7 CH3COOH, H2O to (H3C)3C O

Alcohol bc 3 ch b oxy ha trong acid (tch nc thnh alkene oxy ha ct mch alkene)CH3 CH3-C-CH2-CH3 OH KMnO4 H3C C CH3 O + CH3-COOH24

H2SO4, to http://hhud.tvu.edu.vn

Chng 10B:

Phenol

-OH lin kt trc tip vi nhn thmo

1,36 A

109 o


25

I. Danh phpOH OH CH3 CH3 OH OH

phenol

o-cresol

m-cresol

CH3

p-cresolOH OH OH OH O2N OH OH NO2 OH NO2

Tn thng thng

catechol

resorcinol

hydroquinoneOH CH(CH3)2

picric acidOH

OH OCH3 H3C CH2CH CH2

OH


26

eugenol

Thymol

-naphthol

-naphthol

Tn IUPACOH OH OH CH3 Br OCH3 Cl Cl

4-methoxyphenol

3-bromo-4-chlorophenol 5-chloro-2-methylphenol

OH OH

OH

OH

OH OHttp://hhud.tvu.edu.vn 1,3-benhz enediol

1,2-benzenediol

1,4-benzenediol

27

II. Cc phng php iu ch II.1. Chng ct nha than Ly phn on 170-240 oC Tch phenol bng cch chuyn thnh phenolate ha tan Hon nguyn phenol C6H5ONa + CO2 + H2O C6H5OH + NaHCO3http://hhud.tvu.edu.vn

28

II.2. Thy phn chlorobenzeneCl + KOH 300 oC 280 atm OH + KCl

Khng xy ra iu kin thng II.3. Phng php kim chySO3H + NaOH R 300 oC ONa + Na2SO3 H+ OHhttp://hhud.tvu.edu.vn

29

II.4. Oxy ha cumene (dng trong cng nghip)

CH(CH3)2 O2

OH O H3C C CH3 H2O, H+ cumene hydroperoxide

OH + H3C C CH3 O


30

II.5. Thy phn mui diazonium (phng TN)N+ N Cl40-50 oC + H2O OH + N2 + HCl

iu ch mui diazonium:NH2 + NaNO2 + HCl N+ N Cl+ NaCl + H2O


31

III. Tnh cht vt l +C ca OH vi nhn thm O-H phn cc mnh kh nng to lin kt H ca phenol > alcohol to si , to nng chy, ha tan trong nc > alcohol tng ng

phenol tosi (oC) 180 tonc 41 ha tan (g/100g H2O)9.3http://hhud.tvu.edu.vn

cyclohexanol 161 25.5 3.632

IV. Tnh cht ha hc

O H

IV.1. Tnh acid O-H phn cc tnh acid > HOH > alcoholOH NaOH OH Na ONa + H2 ONa + H2O

Tnh acid: phenol < H2CO3 : OH + NaHCO C H ONa + CO + htH tp://hhud.tvu.edu.vn O C H 6 5 2 2 6 5 333

So snh tnh acid ca 1 s phenol:OH > pKa NO2 7.15 OH > 10.08 CH3 CH3 OH NO2 > NO2 7.23 OH > 10.14 OH 10.28 > OCH3 9.65 OH Cl > Clhttp://hhud.tvu.edu.vn

OH

8.4 OH CH3 OH OH OCH3 > 9.98 OH > C 3 4l 9.38 OCH3 10.21 OH

8.48

9.02

IV.2. Phn ng to ether Khc vi alcohol

OH + C2H5OH H+

OH +

OH H+


35

Gii thch:H+ CH3-CH2-OH + + H CH2-CH2-O H

O H

+C ca OH lm gim mt in t ca O khng c kh nng tn cng vo oxonium cation khng c SN2http://hhud.tvu.edu.vn

36

Ngoi l:OH + CH3OH

H2SO4

O-CH3 + H2 O methyl ethyl ether /nerolin

Mt in t O trn naphthol > trn phenol iu ch ether ca phenol bng phng php Williamson:ONa + C2H5-Brhttp://hhud.tvu.edu.vn

O C2H5 + NaBr37

ONa + CH2=CH-CH2-I

O CH2

CH

CH2 + NaBr

ONa + H3C O O S H3C O O

O CH3 + Na O O S H3C O O

ONa +

I O + NaIhttp://hhud.tvu.edu.vn

38

Lu : iu ch C6H5-O-C2H5 , cn i t C6H5ONa+ C2H5-Br nhng khng i t C6H5-Br + C2H5ONa Ether ca phenol c th b ct mch:OCH3 57% HI 120-130 Chttp://hhud.tvu.edu.vn

OH + CH3I39

o

IV.3. Phn ng ester ha Khc vi alcoholOH + CH3COOH H+

Phi dng dn xut chloride hay anhydride ca carboxylic acidOH + H3C C Cl Otp:e //hhud.tvu.edu.vn acetyl chlorh itd

O C CH3 O + HCl40

OH + C6H5 C Cl O benzoyl chloride OH +

O C C6H5 O + HCl

O H3C C O H3C C O

O C CH3 O + CH3COOH

Lu :O C C2H5 O AlCl3 tohttp://hhud.tvu.edu.vn

OH

O C

OH C2H5 + O C41

C2H5

IV.4. Phn ng th nhm OH Khc vi alcoholOH + X-

Ngoi l:OH O2N NO2 + PCl5 NO2 NO2 O2N Cl NO2 + POCl 3 + HCl

OH Znttp://hhud.tvu.edu.vn 400 h o C

+ ZnO

42

IV.5. Phn ng th i in t -OH (+C>-I) vng thm tham gia SE d dng, sn phm o-, p Halogen haOH + Br2 H2O -HBr Br OH CS2 + Br2 -HBrhttp://hhud.tvu.edu.vn

OH Br Br

OH Br +

OH

Br

43

Nitro ha phenol: Khng cn H2SO4, xy ra to thng, ng phn od tch bng chng ct li cun hi ncOH HNO3

OH NO2 +

OH

NO2 35%http://hhud.tvu.edu.vn

65%44

Sulfo haOH SO3H 15-20 oC H2SO4 H2SO4 100 oC

OH

100 oC

OH

SO3H

Friedel-Crafts: thng cho hiu sut thp (cn dng xc tc HF, H3PO4)http://hhud.tvu.edu.vn

45

IV.6. Phn ng Kolbe (trong cng nghip)O-Na+ + 125 oC + O C O 4-7 atm O O HC ONa

OH O C

ONa H+

OH O C

OH

Sn phm ph l p-hydroxybenzoic acid, c th tch khi salicylic acid bng chng ct li cun hi nc 46http://hhud.tvu.edu.vn

IV.7. Phn ng vi formaldehyde Trong mi trng base:OH + + C O H SE HOCH2OH OH H+ + CH2OH OH CH2OH + OOCH2OH

Trong mi trng acid:

OH OH H + C O H H+

OH CH2OH +

H+ C OH H

SEhttp://hhud.tvu.edu.vn

CH2OH

47


1

Chng 9: ALDEHYDE-KETONE

I. Gii thiu chung

C O

R-CHO aldehyde RCOR ketonehttp://hhud.tvu.edu.vn

2

Ty theo cu to ca R, s c hp cht carbonyl mch h (no + khng no) & carbonyl thm CH3-CH2-CH2-CHO CH2=CH-CH2-CHOCH3-CH2-C-CH3

O C H

O O C CH3http://hhud.tvu.edu.vn

3

II. Danh phpII.1. Aldehyde *Tn thng thng Da theo tn carboxylic acid tng ng, thay ic acid bng aldehyde Aldehyde mch nhnh xem nh l dn xut ca mch thng, dng , , ... ch v tr nhnh Mt s tn thng thng c chp nhn lm tn IUPAChttp://hhud.tvu.edu.vn

4

* Tn IUPAC Mch chnh di nht & cha CHO Gi theo tn hydrocarbon tng ng thay ne nal HCHO formaldehyde / methanal CH3CHO acetaldehyde / ethanal C6H5CHO benzaldehyde /phenylmethanal C6H5CH2CHO phenylacetaldehyde / phenylethanal

CH3-CH2-CH-CH2-CHO CH3

-methylvaleraldehyde / 3-methylpentanalhttp://hhud.tvu.edu.vn

5

II.2. Ketone Tn thng thng Tn 2 gc alkyl + ketone Nu nhm carbonyl gn trc tip vng thm phenone Tn IUPAC Mch chnh di nht cha nhm carbonyl nh s nhm carbonyl c ch s nh nht Gi theo tn hydrocarbon, thay ne nonehttp://hhud.tvu.edu.vn

6

H3C C CH3 acetone / propanone O

CH3-CH2-CH2-C-CH3 O

methyl n-propyl ketone / 2-pentanoneCH2 C CH3 O

benzyl methyl ketone / 1-phenyl-2-propanone C CH3 O acetophenone / 1-phenylethanone / methyl phenyl ketone

H3C C CH CH2

methyl vinylO ketone / 3-butane-2-onehttp://hhud.tvu.edu.vn

7

III. Cc phng php iu chIII.1. Oxy ha hydrocarbonNO 600-700 oC CuCl2 H2C CH2 + O2 50 Co

CH4

+ O2

HCHO

+ H2 O

CH3-CHO

CH3 + O2 Co2+

CHO


8

III.2. i t alkyneHC CH + H O2

HgSO4 H2SO4

HC CH2 OH enol

CH CHO3

R C CH + H2O

HgSO4 R C CH2 H2SO4 OH enol

R C CH3 O

H + H C C C C CH3 H H BHR2

H

H3C H3C C C CH2 CH3 CH3COOH H BR2 H2O2/OHH3C C C CH2 CH3http://hhud.tvu.edu.vn

C2H5

C C H H

H3C CH2 C CH2 CH3 O9

H OH

III.3. Ozone ha alkene

C O + H2O O3 C O C O O C C O O ozonide H /Pt2

C

C

C O

+ H2O

O molozonide

C O + H2O2

CH3-C=CH-CH2-CH3 CH3

1. O3 2. H2O

CH2-C-CH3 + O

CH3-CH2-CHO

+ H2O2

Lu : H2O2 d dng oxy ha aldehyde thnh carboxylic acid sn phm cui l acid!!! 10http://hhud.tvu.edu.vn

III.4. i t alcohol Dehydro ha alcohol bc 1, bc 2R-CH2OH Cu 200-300 oC R-CHO + H2

R R C H OH

Cu 200-300 oC

R C R O

+ H2

CH3 CH3-C-CH2-CH3 OH

Cu 200-300 oChttp://hhud.tvu.edu.vn

CH3 CH3-C=CH-CH3

+ H2O11

Oxy ha alcohol: Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3 Alcohol bc 1 aldehyde carboxylic acid Rt kh dng li giai on aldehyde thng i thng n RCOOH Mun dng li giai on aldehyde, phi dng pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):

R-CH2OH

C5H5NH+CrO3ClCH2Cl2http://hhud.tvu.edu.vn

RCHO + Cr3+12

Alcohol bc 2 ketone

(H3C)3C

OH

Na2Cr2O7 CH3COOH, H2O to

(H3C)3C

O

OH

Na2Cr2O7 H2SO4 / H2O

O 85%

OH H2C CHCHCH2CH2CH2CH2CH3

PCC CH2Cl2http://hhud.tvu.edu.vn

O H2C CHCCH2CH2CH2CH2CH3 80%13

III.5. i t dn xut ca carboxylic acidO R C Cl + H2

Pd/BaSO4

R-CHO

+ HCl

COCl LiAlH(O-tBu)3

CHO

NO2

NO2

(RCOO)2Ca

to

R C

16 bg hhc ptsnam

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