16 bg hhc ptsnam.pdf

7/30/2019 16 BG HHC PTSNAM.pdf

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1

Ha

Hc Hu C

TS Phan Thanh Sn NamB

mn

K

Thut Hu C

Khoa K Thut Ha HcTrng i Hc

Bch

Khoa

TP. HCM

in thoi: 8647256 ext. 5681Email:[email protected]

http://hhud.tvu.edu.vn
mailto:[email protected]:[email protected]:[email protected]:[email protected]:[email protected]:[email protected]


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2

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, McGraw-Hill, 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,

1979



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3

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 cht diazonium



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Chng 1: NG PHNng phn: nhng hp cht hu c ccng thc phn t ging nhau, cng thccu to khc nhau tnh cht ha hc, vtl, 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


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5

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

I.1.ng phn mch C

C6H12

n-butane

iso-butane

methyl cyclopentane

cyclohexanehttp://hhud.tvu.edu.vn


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I.2.ng phn do v tr cc lin kt bi, nhm chc

OH

OH

OH

OH

OH

OH

C4H8butene-1 butene-2

1,2- 1,3- 1,4-

dihydroxy benzene



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I.3.ng phn c nhm nh chc khc nhau

O

CHO

C3H6O

dimethyl ketone

propan-2-one

acetone

propionaldehyde

propanal

propionic aldehyde

C3H6O2COOH

O

O

Propionic acid

methyl acetate



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

chc

O

O

C4H10O diethyl ether

methyl propyl ether



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9

II.ng

phn

lp th

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

Xut hin

khi

phn

t

c

1 b

phn cng

nhc

cn trsquay tdo ca cc nguyn t

2 nguyn t lin kt vi cng 1 nguyn t ca b

phn cng

nhc phi

khc

nhau



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H

Cl Cl

H

Thng

xut hin

cc

hp cht c c ha:

C=C, C=N, N=N, h lin hp, vng phng 3hay 4 cnhabC=Ccd: a b, c d



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II.1.2. Danh php ca ng phn hnh hca. H cis-trans: abC=Cab

Nhm

th

tng

ng

nm

cng

pha

mt phng lin kt cis Khc pha trans

H

H3C CH3

H H

H3C H

CH3

cis-butene-2 trans-butene-2http://hhud.tvu.edu.vn


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b. H Z-E: abC=Ccd a>b c>dQuy tc Kahn-Ingold-Prelog: da theo th t u tin trong bng HTTH ca nhm tha, c cng pha so vi mt phng ni i: Z(zusammen)a, c khc pha so vi mt phng ni i: E(entgegen)



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I

Br Cl

F

I

Br F

Cl

(E)-1-Bromo-2-chloro-2-fluoro-1-iodoethene

35

53

17

9

(Z)-1-Bromo-2-chloro-2-fluoro-1-iodoethene

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

H

Cl Cl

Br

E-, cis-

F

Cl Cl

H

Z-, cis-



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II.1.3.ng phn hnh hc ca abC=Nd v aN=Nba. 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 aldoxime

C N

H

H3C OH

C N

H

H3C

OH

anti-acetaldoxime(Z)-acetaldoxime

syn-acetaldoxime(E)-acetaldoximehttp://hhud.tvu.edu.vn


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i vi

ketoxime: Cng

1 cht, c

th

gi l

syn- hay anti- !!!

C N

OH

H3C

C NOH

anti-phenyl-p-tolylketoximesyn-p-tolyl-phenylketoxime

syn-phenyl-p-tolylketoximeanti-p-tolyl-phenylketoxime

H3C

h syn-antikhng chnh xcchuyn sang h Z-E



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b. aN=Nb

N NC6H5

C6H5

N NC6H5 C6H5

anti-azobenzene syn-azobenzene



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II.1.4.ng phn hnh hc ca hp cht cha C=Clin

hp

a(HC=CH)n

bHH

C6H5

C6H5

H

H

H

C6H5

H

H

C6H5

H

H

C6

H5

H

C6H5

H

H

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

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

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

* 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 chnp = (n + 1)/2 nu n l



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II.1.5.ng phn hnh hc ca vng no 3, 4cnh c b tr trn 1 mt phng cc nhm thkhng th quay tdo xut hin ng phn

hnh hc

* Cc

nhm

th

tng

ng

cng

pha

mt phng

cis, khc pha trans

HOOC

H

COOH

H

HOOC

H

H

COOH

cis-cyclopropane-1,2-dicarboxylic acid trans-cyclopropane-1,2-dicarboxylic acid



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II.1.6. Cch xc nh v so snh cc ng phn hnh

hc

a. xc nh khong cch gia cc nhm thKhong cch gia 2 nhm th tng ng trong ng phn cis < trans

Cl

H H

Cl Cl

H Cl

H

3.7 4.7



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b. Moment lng cc 2 nhm

th

ging

nhau

aHC=CHa

Cl

H H

Cl Cl

H 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


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c. Nhit nng chyng phn trans-: i xng mng litinh th cht ch tonc cis < tonc trans

Lu : mi lin h gia to

si v ng

phn hnh hc khng cht chV d:CHCl=CHCl t

o

si ca cis-: 60.3o

C, to

si ca trans-: 48.4oC

CH3

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


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II.2.ng phn cu dng (ng phn quay) L nhng cu trc khng gian sinh ra do 1 nhmth 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


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II.2.1. Cch

biu din

a. Cng thc phi cnh (khng gian 3 chiu)

c

b

c

a

b

a

a

b

c

a

b

c

c

b

a

che

khut

xen

k

Lin kt C-C: ng cho tri qua phi, xa dn ngi

quan

st



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b. Cng thc Newman Quan st dc theo C-C 2 nguyn tC dng che khut, biu din bng vng trn

chiu cc nhm th ln mt phng vung

gc viC-C

a

a

bc

aa

b

b

c

c

cb

che khut xen khttp://hhud.tvu.edu.vn


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II.2.2. Cu dng ca cc hp cht mch ha. Ethane Quay 1 nhm CH3

& c nh nhm cn li2 ng phn cu dng ti hn Che

khut: khong

cch

gia

cc

H gn

nhau nng lng cao nht km bnnht



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Xen

k: khong

cch

gia

cc

H xa

nhau nng

lng thp nht bn nht



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b. n-Butane

Quay cc

nhm

th

quanh

trc C2-C3 2 dng

c nng lng cao: che khut ton phn & che 1phn

CH3CH3

H

H

H

H

CH3

H

CH3H

H

H

2 dng

c

nng

lng

thp: anti

(i) & syn

(lch)

HH

HH

CH3

CH3

HH

H

CH3

H

CH3



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28http://hhud.tvu.edu.vn


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II.2.3. Cu dng ca hp cht vng noVng 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)



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a. Cyclohexane Cc C khng cng nm trong 1 mt phng bo m gc lin kt ~ 109

o28

Cc

nhm

th

c

th

quay quanh

C-C ng

phn cu dng C 2 dng c trng: gh (bn) & thuyn* Gh:

1

234

5 6

2.5 2.49

Xem nh 1 t hp ca 6 h thng n-butane Tt c

6 h

thng

u

dng

xen

k

(syn

butane)

24

3


* Th


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* Thuyn:

1

23

4

56

2.27

1.84

2.49

35

14

4 h thng dng xen k: C1-C2, C3-C4, C4- C5, C6-C1 2 h thng dng che khut hon ton: C2- C3, C5-C6 Khong cch H C1 & C4 rt nh lc ykm bn hn dng gh*** Ngoi dng gh & thuyn, cyclohexane cn c dng xon, dng na ghkm bn (t c)http://hhud.tvu.edu.vn


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b S b li k C H


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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 ktbin e (equatorial)

a e

a

e

a

a

e

e

a

e

a

e

109o28'



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Cn

bng

(khng

th

tch):

a

e

CH3

CH3

Dn xut 1 ln th: e-methyl cyclohexane bn hna-methyl cyclohexane Khi c 2 nhm th khc nhau: nhm ln v tr e



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II.3.ng

phn

quang

hc

II.3.1. nh

sng

phn

cc

nh sng t nhin: sng in t, dao ng mihng

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 ASPChttp://hhud.tvu.edu.vn


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II.3.2. cht hot

ng

quang

hc

ASPC i qua 1 s hp cht hu c lm mt phngphn

cc

quay 1 gc cht hot ng quang hc

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


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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 hcto: nhit

o

: bc sng nh snghttp://hhud.tvu.edu.vn


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II.3.3.iu kin xut hin ng phn quang hcVt & nh trong gng khng chng kht c 2ng phn khng chng kht nhng i xng nhau2 ng phn ny quay mt phng phn cc nhnggc

nh

nhau

nhng

ngc chiu 1 i i

quangng phn quang hc thng xut hin k h i c Cbt

i xng

(C*)

* C bt i xng:Cabcd

a

b

c

d khng c tnh i xng

trong khng gianhttp://hhud.tvu.edu.vn


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V

d

phn

t

lactic acid 2 ng phn quang hc

COOH

H OH

CH3

C*

COOH

H

CH3

C*HO

(+) (-)



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C h th kh h h t


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Cc nhm th khc nhau v ng phn cu tong phn quang hc

n-C3H7 C*H

COOH

iso-C3H7

Cc nhm th khc v ng vng phn quang hc

D C*CH3

H

C6H5http://hhud.tvu.edu.vn

ng phn quang hc khng cha C*


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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 C C CC10H7 C10H7

C6H5 C6H5

ng phn cn quayHOOC COOH

Cl Clhttp://hhud.tvu.edu.vn


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

COOH

H CH3 OH

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

b Cng thc chiu Fisher (2 chiu)


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

ngi

quan

st

H OHCOOH

CH3 C th c nhiu cng thc Fisher khc nhau

c. Cng thc phi cnh & Newmanhttp://hhud.tvu.edu.vn


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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!!!


H d h h D L h h t i


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a. H danh php D-L: cu hnh tng iPhi

so snh

vi 1 cht chun

H OH

CHO

CH2OH

HO H

CHO

CH2OH

D-glyceraldehyde 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 LV

d

lactic acid c

2 ng

phn

khi

so vi

glyceraldehyde

H OH

COOH

CH3

HO H

COOH

CH3

D-lactic acid L-lactic acid

Rt kh xcnh khi phn tc nhiu C*!



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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


OH


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H C* OC

C

OH

H

O HHH

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

C A C AA C

C A CA

AAC

C

CCHHC

CC

-CCH > -C(CH3)3-CH=CH2 > -CH(CH3)2



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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 & -CH2

OH

-CH2OH > -CH=CH2



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50

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 kimng h: ng phn R

i t a b c: ngc chiu kimng h: ng phn Shttp://hhud.tvu.edu.vn


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+Theo cng thc Fisher:


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+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: SQuy

c: i v

tr

2 cp

nhm

th cu hnh

khng thay iThay i v tr 1 cp nhm th cu hnh sthay i

Hay l Quay cng thc Fisher 180o cu hnh

khng i, quay 90o hay 270o cu hnh thay

ihttp://hhud.tvu.edu.vn

V d lactic acid: COOH


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d

act c ac d

H OH

CH3

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

OH

H

(R)d

a

bc

Nu ch

i 1 cp

H & CH3

CH3 OH

COOH

H

(S)d

b

ac

Lu : R & S ch l i lng l thuyt!!! thc t ch o c d(+)& l(-)!!! R & S khng lin

h

vi

(+) & (-)!!!


II.3.6. Cc hp cht cha nhiu C*


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II.3.6. Cc hp cht cha nhiu Ca. Hp cht cha

cc

C* khng

tng

ng

H C* OH

CHO

C*H OH

CH2OH

2 C* khng tng ng v CHO CH2OH

4 ng phn (2 i i quang):

H C* OH

CHO

C*HO H

CH2OH

OH

CHO

C*H OH

CH2OH

H C*

HO

HO C* H

CHO

C* H

CH2OH

HO

H

C* H

CHO

C* OH

CH2OH

threo-aldotetroseerythro-aldotetrose

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

S p quang hc: N = 2n n: s C*http://hhud.tvu.edu.vn

b. Hp cht c c ha C* tng ng


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b. Hp cht c c ha C tng ngTactric

acid:

HOOC C* C* COOHH

OH

H

OH2 C* tng ng 3 ng phn

H C* OH

COOH

C*HO HCOOH

HOH

C* H

COOH

C* OHCOOH

HOHO C* H

COOH

C* H

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



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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)



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II.3.7. Hn hp racemic L

hn hp

50% p

quay tri

+ 50% p

quay

phi hn hp khng c tnh cht quanghc 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


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


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V

d: Xc

nh

cu hnh tuyt

i ca 1 s

cht

(R)-

(R)-

H OHCH2OH

CH3

H CH3

COOH

C6H5

(S)-

OH CH3

CHO

CH2OH

H OHCH2OH

OH H

CH2OH

H2N HCOOH

CH3(S)-

H OHCH2OH

H OHCH

2OH

H2N HCOOH

CH2OH(S)-

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



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Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa K Thut Ha H cTrng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681

Email:[email protected]


Chng 2: CC LOI HiU NG


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Chng 2: CC LOI HiU NG* Hiu

ng s dch chuyn in t trong phn tnh 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 http://hhud.tvu.edu.vn

I. Hiu ng cm ng


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3

I. Hiu ng cm ngI.1.nh ngha HU cm ng sdch chuyn in tca cclin ktdo cc nguyn ttrong phn tc

m in khc nhau phn tphn cc V d:

H C3 C2 C1 Cl

H

H

H

H

H

H

m in Cl > C sdch chuyn tC1-Cl,C2-C1, C3-C2http://hhud.tvu.edu.vn

I.2. Phn loi


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4

I.2. Phn loia. 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 in t > H cho +I (v ngc li)http://hhud.tvu.edu.vn

I 3 c im ca HU cm ng


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5

I.3.c im ca HU cm ng Cc nguyn t hay nhm nguyn t mang intch + Cho I Cc nguyn t hay nhm nguyn t mang intch - cho +I

in tch cng mnh I cng mnh, nhmnguyn t mang in tch c I mnh hn trungha

-N(+)R3-O(+)R2 -I

-O- -N(-)H +I-O(+)R2 > -ORhttp://hhud.tvu.edu.vn


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6

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 trnxung di-I:

-F > -Cl > -Br > -I

-I: -OR > -SR > -SeR

Cc nhm alkyl lun y in t (+I), tng dn tbc 1 n C bc 3+I : -CH3 < -CH2 CH3 < -CH(CH3 )2 < -C(CH3 )3http://hhud.tvu.edu.vn

Cc nhm khng no u mang I, tng dn


65/457

7

Cc nhm khng no u mang I, tng dn theo

khng

no

-I: R2C=CR- CRC< C nhm C=O s ht in t

ca h phn t tr nn phn cc ( LH - )


CH2=CH-CH=CH-N(CH3)2


68/457

10

2

( 3

)2

N c i in t t do (p) c x u hng nhngin tcho h lin hp phn tphn cc (LH -p)

Cl NH2

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

II.2. Phn loi


69/457

11

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 SR

NH2 NR2

HN C

O

CH3 -F -Cl -Br -I



70/457

12

b. Cc ion mang in tch m c +C mnh hn ccnguyn t trung ha+C:

-O-

> -OR

-S-

> -SR

c. Trong cng 1 chu k ca bng HTTH: +C gimt

tri

qua phi

+C: -N(R)2 > -OR > -Fd. 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


71/457

13

II.2.2. HU lin hp m (-C)

Cc nguyn t hay nhm nguyn t c kh nnght 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 -COR -COOH -CONH2



72/457

14

b. Trong cc nhm C=Z: -C ph thuc ZZ 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


II.3. c tnh chung ca HU lin hp


73/457

15

II.3.c tnh chung ca HU lin hpa. HU lin hp thay i rt t khi ko di mch lin hp

*** HU cm

ng: gim nhanh theo mch

C !!!

H CH2 CH CH C

O

H

H CH2

CH CH CH CH C

O

H

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

T h i h


74/457

16

Tc phn ng ging nhau:

RCHO

RCHO H CH2

CH CH C

O

H

H CH2 CH CH CH CH C

O

H

OH-

OH

-

C CH2 CH CH CH CH C

O

H

R

OH

H

C CH2 CH CH C

O

HR

OH

H

+

+


b. Mt s nhm th cha no, du ca HU lin hp s


75/457

17

thay

i ty thuc

vo

nhm

nt

lin

kt vi n

N+

-O ONH2

-C6H5: +C -C6H5: -C

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

H

H

C6H5NH2 N

R

R

C6H5NR2

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

III. Hiu ng siu lin hp


76/457

18

III.1. HU siu lin hp dng (+H)

L s tng tc ca cc in t ca lin kt C-Hvi h t (C=C, -C6 H5), hoc trong carbocation(vd: (CH3

)3

C+) hay gc t

do (vd: (CH3

)3

C.)


Xt phn ng:


77/457

19

p gCH3

-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 phmchnh l:

C CH CH CH2 CH3H

H

H

HClCH3 CHCl CH2 CH2 CH3



78/457

20

CH

H

H

CH3C

H H

>+H:

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



79/457

21

III.2. HU siu

lin

hp

m

(-H)

L s tng tc ca cc t ca lkt C-F vi ht (C=C, -C6

H5

)

C F

F

F


IV. Hiu ng khng gian


80/457

22

L 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 trkhng cho 1 nhmchc no trong phn ttc dng vi phn t hay ion khc

OO

CH3

CH3

H2N OH+ ON

CH3

CH3

HO + H2O


IV. 2. HU khng gian loi 2 (S2)


81/457

23

Do cc nhm th c kch thc ln h lin hpbmt tnh phng khng cho 1 sphn ng

Xy ra

N

H3C

H3C

N+N

R

R

+ N

H3C

H3C

R

R

N NCl-

R = H: phn ng xy ra R=-CH3 : h lin hp mt tnh phng +Cca N(CH

3)2 gim m

nh

phn ng khngxy rahttp://hhud.tvu.edu.vn


82/457

24

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, linkt H)http://hhud.tvu.edu.vn

Xt hng s phn ly (Ka.105) ca dn xut ca


83/457

25

Xt hng s phn ly (Ka.10 ) ca dn xut ca benzoic acid C6

H4

(R)COOH

V

tr

/ R OH F NO2

o- 10.5 54.4 67.1

m- 8.3 13.7 32.1

p- 2.9 7.2 37.6

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

Tnh acid:


84/457

26

C

O OH

OH

>

C

O OH

OH

CO O

H

OH

>

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---

C=O

trong m-: h lin hp ny b t on do - lin tc !!! cnglm cho tnh acid ca m- > p-http://hhud.tvu.edu.vn


85/457

27

Tnh acid ca C6 H4 (F)COOH: o- > m- > p-do I gim theo chiu d i mch

C

Kh nng ht (-I) hay y (+C) in t caF, Cl, Br, I: -I > +C

Tnh acid ca C6 H4

(NO2

)COOH: o- > p- > m-



86/457

28

N+

-O O

OH

N+-O 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

V nh hng ca cc hiu ng ln tnh


87/457

29

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 +Itnh acid gim

Cha

nhm

th

c

I: tnh

acid tng

do O-H

cng phn cchttp://hhud.tvu.edu.vn


88/457

30

Tnh acid ca cc acid:F3

C-COOH (pKa 0.23) > Cl3

C-COOH (0.66) >

Cl2 CH-COOH (1.25) > 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 (3.75) >HO-CH2

-COOH (3.83) >

CH3

COOH (4.76) > CH3 CH2

COOH (4.87) >

(CH3 )3 C-COOH (5.03)



89/457

31

Nhm

th

cng

xa

C nh hng cng

yu do I gim mnh:

Tnh acid: F3 C-COOH > F3 C-CH2 -COOH >F

3 C-CH

2 -CH

2 -COOH


V.2. nh hng ca HU lin hp, HU siu lin hpln tnh acid


90/457

32

ln

tnh

acid

Tnh acid ca alcohol < phenol Nhm th c C s lm tng tnh acid & ngc li

Tnh

acid:

N+

-O O

O

C

OO

H

H H

H HH

-I, -C +H, +I

> >

NH2

O

H

>

+C, -I

O

H

>

CH

HH

+I

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

a.Acid bo khng no:


91/457

33

g Tnh acid mnh hn acid no cng mch C (doC=C c I) Ni i C=C cng gn COOH th tnh acid cngmnh 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

Ni b a CC cho d v tr lin hp vi C=O th


92/457

34

vn lmtng mnh tnh acid (khc C=C): do Ica CC mnh & ch c 1 lkt ca CC cho +Clin hp vi C=O, lkt cn li cho I nhng khng c +C!!!

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


93/457

35

b. Acid c vng thm:Tnh acid H-COOH (pKa 3.75) > C6

H5

-COOH (4.18)

do +C ca C6 H5

- mnh hn ITnh acid ty thuc bn cht & v tr nhm th:o-NO2

-C6

H5

-COOH >p-

> m-

Halogen cho I > +C o-Cl-C6H5-COOH > m- > p-


V.3. nh hng ln tnh base


94/457

36

V.3. nh hng ln tnh base

Mtin t trn N cng ln tnh baseca amine cng mnh Nhm thy in t (+I) s lm tng tnhbase ca amine & ngc li (-I, -C)

Tnh base:

(CH3

)2

NH > CH3

NH2

> NH3 > C6

H5

NH2

>

p-NO2

-C6

H4

-NH2http://hhud.tvu.edu.vn

Tnh base:p-NO2-C6H4-NH2 < m- NO2-C6H4-NH2


95/457

37

p 2 6 4 2 2 6 4 2

CH3

O-

> OH-

>

C6H5O- > CH3COO- http://hhud.tvu.edu.vn

V.4. nh hng ln bn ca cc


96/457

38

g 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 C CH2

H

H

C C+

H

C

H

H

H H

H

HC C

+

C

C

H

H

H H

H

H

H

HH

< +C ca O- > +H & I ca CH3-NH- & -O- ng thi c I nhng +C nh hngmnh hn -NH- gii ta tch dng mnhnht bn nht

Gc allyl CH2

=CH-CH2

+ hay

C6

H5

-CH2

+

rt bn

do +C ca vinyl hay phenylhttp://hhud.tvu.edu.vn


99/457

1

Ha Hc Hu CTS Phan Thanh Sn NamB mn K Thut Hu CKhoa

K

Thut Ha H c

Trng i Hc Bch Khoa TP. HCMin thoi: 8647256 ext. 5681Email:[email protected]


Chng 3: C CH PHN NG CA HPCHT HU C


100/457

2

CHT HU CI. Phn ng th i nhn nguyn t carbon noI.1. Khi

nim

chung

Phn ng th: 1 nguyn t hay nhm nguyn tca cht ban u b

thay

th

bi

1 nguyn

t

hay

nhm nguyn t khcCH

3 -CH

2 -Cl + OH- CH

3-CH

2-OH + Cl-

Tc

nhn

i

nhn:

cc

tc

nhn

mang

in tch

m (hay phn t trung ha cha cp in t t do) tn cng vo trung tm tch in +http://hhud.tvu.edu.vn

Phn ng th i nhn (SN)


101/457

3

y- + R-X R-y + X-y-: RO-, OH-, RCOO-, NH3, NH2R, H2O, ROHR: gc

hydrocarbon

X: Cl, Br, OH, OR, OSO2

R

V

d:

CH3

-CH2

-Cl + OH- CH3-CH2-OH + Cl

-

CH3

-CH2

-Br + CH3

O- CH3-CH2-O-CH3 + Br

-

CH3 -CH2

-Br + NH3 CH3-CH2-NH2 + HBrhttp://hhud.tvu.edu.vn

I.2. Phn ng th i nhn lng phn t(SN2)


102/457

4

Lng phn t: giai on chm, c s tham giaca 2 tiu phn

a.C ch:chamy- + R-X [y

-... R ... X -] nhanh R-y + X-

trang thai chuyen tiep

Lin kt gia C & y hnh thnh ng thi vi syu i & t ca C & X 2 tiu phn tham giavo giai on chm Nu y- khng d nhiu: r = k[y-].[R-X] phn ngbc 2 http://hhud.tvu.edu.vn

Gin nng lng:


103/457

5


R OH h th h t i t


104/457

6

R-OH: phn

ng

th

ch

xy ra trong mi trng

acid v C-O bn

Dn xut ca carbon bc 1 ch cho SN 2

SN

2: carbon bc 1 (ch cho SN

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

1)

SN

2: CH3

-CH2

-Cl + OH- CH3-CH2-OH + Cl

-



105/457

I.3. Phn ng th i nhn n phn t(SN1)


106/457

8

n phn t: giai on chm ch c s tham gia ca 1 ti u phna. C

ch

R+

R-X R+ X-

cham+

+ 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

Gin nng lng:


107/457

9


Dn xut ca carbon bc 3 ch cho SN1


108/457

10

SN

1: carbon bc 3 (ch cho SN 1) > carbon bc 2 >carbon bc 1 (ch cho SN

2)

V d SN 1:

H3C C

CH3

Br

CH3

+ OH- H3C C

CH3

OH

CH3

+ Br-


Tnh lp th ca SN1


109/457

11

C* X

R3

R2

R1

C*

R3R2

R1

cham

C*

R3

R2

R1

y

nhanh

-X- nhanh

C* y

R3

R2

R1

(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 nhnhau 50% S + 50% Rhttp://hhud.tvu.edu.vn


110/457


I.4. Cc yu t nh hng ln phn ng thi nhn


111/457

13

i

nhn

a. nh hng ca gc R

Gc R bc

cng

cao: kh nng SN1 tng & SN2

gim SN

1: carbon bc 3 (ch cho SN

1) > carbon bc 2 >

carbon bc 1 (ch

cho

S

N 2)

Do SN

1 ph thuc vo bn ca carbocation to thnh:

H C C H2

H

H

C C+H

C

H

H

H H

H

HC C+

C

C

HH

H H

H

H

H

HH< carbon bc 3 (ch cho SN1)


112/457

14

( N )

Bc ca

R cng

cao y- cng kh tn cng do in tch (+) C

gim & do hiu ng khng gian ca gc alkyl SN2 cng khxy ra


b. nh hng ca tc nhn i nhn y-


113/457

15

SN

1: khng ph thuc y-

SN

2: ph

thuc

nhiu

vo

y-

do giai

on chm c

y-

tham giaTc

nhn

c

tnh

i

nhn

cng

cao

th

cng

d

cho

SN

2

Thng

thng, tnh

i

nhn

ng

bin vi tnh

base

NH2-

> (CH3

)3

CO-

>

(CH3

)2

CHO-

> C2

H5

O-

>

CH3

O-

> OH-

> C6H5O

-

> HCO3

-

> CH3COO

-http://hhud.tvu.edu.vn


114/457

c nh hng ca nhm b th X


115/457

17

c. nh

hng

ca

nhm

b

th

-X

Cc nhm th c tnh base cao rt kh b tchra, v d: -OH, -OR, -NH2, -FV d: R-OH + HBr R-Br + H2O cn xc tcH

2

SO4R-OH khng phn ng vi KBr

Halogen, kh nng tch nhm: F- < Cl- < Br- < I-(Do I c bn knh ln C-I dphn cc hnNng

lng

t lin kt: C-I < C-Br < C-Cl

< C-F)


d. nh hng ca dung mi


116/457

18

Dung mi phn cc c proton nh H2 O, ROH,HCOOH c kh nng solvate ha cao c anion &cation thun li cho SN1

C XR3

R2

R1

C+R3R2

R1

-X-cham

O

H

H+ X

-

H OH

Dung mi phn cc khng c proton nh (CH3

)2

SO, (CH3

)2

NCHO

khng c kh

nng

solvate

ha anion thun li cho SN2http://hhud.tvu.edu.vn

II. Phn ng tch loiL phn ng trong c s tch 1nguyn t hay


117/457

19

L

phn

ng

trong

c s

tch

1nguyn t

hay

nhm nguyn t ra khi cht ban uR CH

2CH

2Br

RO-

R CH2 CH2 OHH+

R CH2 CH2 N+R3

HO-

R CH CH2

R CH CH2

R CH CH2

+ HBr

+ HOH

to

to

+ HOH + NR3

t

o

Nhm b tch cng H: -OH, -OR, -X, -O+(R)2

,

-N

+

(R)3 , -OSO2 R Base sdng: cc base mnh nh OH-, RO-, NH2-http://hhud.tvu.edu.vn

II. 1. Phn ng tch loi lng phn t(E2)a. C ch


118/457

20

y- + R CH2 CH2 X H C CH2

R

H

y Xcham nhanh

H-y + R CH CH2 + X-

trang thai chuyen tiep

giai on chm, c s tham gia ca 2 ti u phnlng phn t Tc

phn

ng

r = k[R-X].[y-]

R-CH2 -CH2 -OH: ch tch loi trong mi trng acid to cao (thng l sulfuric acid, acid rn)http://hhud.tvu.edu.vn

b.Tnh lp th ca E2


119/457

21

p

2

Cc hydrocarbon khng no tch loi d khicc nhm b tch v trtrans vi nhauHOOC Cl

COOHH

OH-

-HCl

COOH

COOH

OH-

-HCl

HOOC Cl

HHOOC

(1) (2)

chlorofumaric acid chloromaleic acid

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


120/457

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


121/457

23

H C C X H C C+ + X-

H C C+ H+ +

cham

nhanh

Thng cc dn xut ca hydrocarbon carbonbc 3 bao gi cng cho E1 Carbocation cng bn, cng d cho E1 Tc

r = k [R-X]

Nhng yu t lm thun li SN 1 cng lm thun licho E1 http://hhud.tvu.edu.vn

Vd:


122/457

24

H3C C B r

CH3

CH3

cham C C+C

C

H

H

H H

H

H

H

HH

+ Br-

C C+C

C

H

H

H HH

H

H

HH

+ C2H5O- nhanh H2C C

CH3

CH3

+ C2H5OH


II.3. Hng ca phn ng tch loia. Quy tc Zaitsev


123/457

25

Dn xut bc 1 thng ch cho 1 sn phm duynht khi tch loiCH3

-CH2

-CH2

-Br ch

cho

CH3

-CH=CH2

Dn xut bc 2, bc 3: cho nhiu hn 1 sn phm

H3C C C C H

H

BrH

H

H

OH-H3C CH CH CH3 (Zaitsev)

H3C CH2 CH CH2(Hofmann)

H

Sn phm Zaitsev : bn hn (do +H) thngthng, phn ng tch loi cho sn phmZaitsev

Quy tc: phn ng tch loi s cho sn phm mcarbon ca nii lkt vi nhiu nhm alkyl nhthttp://hhud.tvu.edu.vn

b. Quy tc Hofmann


124/457

26

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

)3

CO-)

hoc

X l

nhm

th

mang

in tch dng

c kch thc ln (vd N +

R3 , S+

R2 , SO2

R) snphm Hofmann chim ch yu (E2)

H3C C CH

2CH

3

CH3

Br

(CH3)3CO-

H3C C

CH3

CH CH3

H2C C CH2 CH3CH3 72%

28%

Nu base l C2H5O- th sn phm chnh l Zaitsev!!!http://hhud.tvu.edu.vn

H3CHC CH2 CH3

+

OH- CH2=CH-CH2-CH3(E2)


125/457

27

N

+

(CH3)3

(E2)

CH3CHCH2CH2CH3

SO2CH3

OH- 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)

(E2)


II. 4. Quan h gia phn ng th i nhn &tch loi


126/457

28

tch

loi

Nhit phn ng cng cao phn ng tch loicng chim u th

CH3-CH2-OH H2SO4

CH2=CH2

C2H5-O-C2H5170o

C + H2Ohttp://hhud.tvu.edu.vn

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


127/457

29

CH3-CH2-CH2-Br + C

2H

5O- CH3-CH2-CH2-O-C2H5

to thng

H3C C B r

CH3

CH3to cao

H2C C

CH3

CH3

C2H5O

-


III. Phn ng cng hp


128/457

30

III. 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, H2

O, HOX, H2

SO4

C C + X-Y X C C Y


a. C ch: Giai on 1


129/457

31

Giai on 2: C CX+

Y-nhanh C C

X

Y

Y- tn cng vo pha i lp vi X

Giai

on 1:

C C + X -Ydung moi

xuc tac C C

X

Yphc

khong ben

nhanh

C+ C

X

cham C Cben hoa

X+

Giai

on chm: X+ tn

cng

vo

C=C i in t


Chng minh AE c 2 giai on:


130/457

32

g

E

g

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 CH3 OH,

sn phm chnh l Br-CH2 -CH2

-OCH3

!!!


H2C CH2CCl4

H C CH+ Br2


131/457

33

H2C CH2

H2C CH2

H2C CH2H2O

CH3OH

H2C CH2

Br Br

H2C CH2

Br OH

H2C CH2

Br OCH3

+ Br2

+ Br2

+ Br2


b. Quy lut cng hp


132/457

34

Quy tc Markonikov (dnh cho C=C khng ixng): 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 phato

thnh

carbocation

trung

gian

bn nht

CH3-CH=CH-CH2-CH3HBr

CH3-CH-CH-CH2-CH3

Brhttp://hhud.tvu.edu.vn

c. Ha lp th ca phn ng AE


133/457

35

Phn ng cng hp AE xy ra theo kiu transph thuc vo tc cht ban u m c cc ngphn lp th khc nhau

ng phn cis sn phm threo (nhm th tngng khc pha)

H

CH3C2H5

H

Br2

H

CH3C2H5

H

Br+

Br-

C2H5

C2H5

H

Br

Br

CH3

H Br

BrCH3

H

H

Br H

CH3

H Br

C2H5

H Br

CH3

Br H

C2H5

threo-http://hhud.tvu.edu.vn

ng phn trans sn phm erythro (nhm thtng ng cng pha)


134/457

36

H

HC2H5

CH3

Br2 Br H

CH3

Br HC2H5

H Br

CH3

H Br

C2H5

erythro


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


135/457

37

Nhm th y in t tng mt in t caC=C tng kh nng phn ng A

E

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 licho AEhttp://hhud.tvu.edu.vn

Kh nng AE:


136/457

38

O2N H

HH

HOOC H

HH

Cl H

HH

H3C H

HH

H3C CH3

HH

H3C CH3

CH3H

H3C CH3

CH3H3C

< < < < < >

>

> > >


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


141/457

43

+ X+

acid + H+

X

Xc tc: cc acid v c: H2 SO4

, H3

PO4

, HF

hay Lewis acid: FeCl3

, AlCl3

, ZnCl2

V d: C6 H6

+ (CH3

)3

C-Br /AlBr3 C6H5-C(CH3)3 +

HBrhttp://hhud.tvu.edu.vn

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


142/457

44

p

(

)

+ X -Y

xt

nhanh X -Y phc

chamHX HXHX+ +

+

HX

+

Trong phc : X khng lin kt trc tip vi C no cPhc : X c lin kt trc tip vi 1 C ca benzene

phc



143/457

45

Giai on 2: tch proton

HX

+nhanh

X

+ HY


+++ Nhm th y in t (+C, +H, +I) SE tngVd:


144/457

46

* 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 gimV 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


145/457

1


K

Thut Ha H c



Chng 4: AlkaneI. Gii thiu chung


146/457

2

g

Alkane hydrocarbon no mch h, nguyn tcarbon lai ha sp3 Cng

thc tng

qut: C

n H

2n+2

Gc ha tr 109o5, lin kt C-H: 1.09, C-C: 1.53 ng phn: cu to, cu dng (quay)

methane


II. Danh php IUPAC


147/457

3

p p

II.1. Alkane khng phn nhnh:

4 alkane u: gi theo tn thng thngmethane, 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

II. 2. Alkane phn nhnh


148/457

4

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, nhmcui cng phi vit lin vi tn mch chnh Nu c nhiu nhnh tng ng: dng tip ung di-, tri-, tetra- ch s lng nhm tng ng


Nu c nhiu nhm th khc nhau: sp xp theoth t alphabetical. Lu : b qua cc tip u


149/457

5

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, nhngvn dng so snh gia chng vi nhau. V d: dimethyl hoc methyl s i sau ethyl haydiethyl

isopropyl i trc methyltert-butyl i trc isobutylsec-butyl i trc tert-butylhttp://hhud.tvu.edu.vn

V d (H vit tt):C C

C

C


150/457

6

C C C C C C

C

C

C

4-Ethyl-2,2-dimethylhexane

C C C C C C C C

C

CC

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)nonanehttp://hhud.tvu.edu.vn

II.3. Tn gc alkyl c ly 1 H t alkane, gi theo tn alkane nhng


151/457

7

c ly 1 H t alkane, gi theo tn alkane nhngi ane yl CH3

-: methyl

CH3 -CH2

-: ethyl CH3

-CH2

-CH2

-: n-propyl

CH3CHCH3 : isopropyl

CH3CH2CHCH3 : sec-butyl

(CH3 )2 CHCH

2 -: isobutyl

(CH3)3C-: tert-butylhttp://hhud.tvu.edu.vn

III. Cc phng php iu ch alkaneIII.1. Khcc dn xut ca halogen, alcohol,carbonyl:


152/457

8

carbonyl:a. Kh bng HI 80%, 180

oC:

CH3I + HIP o

CH4 + I2

CH3-CH2-OH + HIP o

CH3-CH3 + I2 + H2O

b. Kh bng Zn/HClR C R'

O

Zn(Hg)/HClR-CH2-R'

(Kh

Clemmensen)



153/457

III.4. Phn ng Wurtz


154/457

10

CH3 CH2

Br + Na CH3CH2CH2CH3 + NaBr

Ch

c

hiu qu

khi

iu ch

alkane

i xng:

CH3

CH2

Br + CH3

Br CH3CH2CH3 + CH3CH3 +CH3CH2CH2CH3

khng c tnh chn lc t s dng

Ch hiu qu cho R-Br & R-IHiu sut: bc 1 (60%) > bc 2 (40%) > bc 3 (10%)http://hhud.tvu.edu.vn

III.5.in phn mui ca carboxylic acid


155/457

11

CH3

COONa CH3COO. CH3. CH3-CH3

III.6. Nhit phn mun natri ca carboxylic acidCH3

COONa + NaOH CH4 + Na2CO3

IV. Tnh cht vt l (t c) Alkane khng phn cc ch tan trong dung mikhng phn cc

to si

ca

alkane

nhnh

< thng


V. Tnh cht ha hc


156/457

12

Alkane tr khng c phn ng cng, c trngl phn ng th HV.1. Phn ng th H bng halogen

Ch

xy ra

nhit

cao

hoc

khi

c

nh

sng

R-H R-X HX+ X2to

h

+


a. C ch phn ng (gc t do SR )

Khi mo:to


157/457

13

X-X 2Xt

h

Truyn mch:RX

R-H + X R + HX

R + X2 + X

Phn

ng

c

th

tip tc

to sn phm

di-, tri-,

tetra-

V d chlor ha CH4 c th thu c CH3

Cl,CH2

Cl2

, CHCl3

, CCl4

CH4

+ Cl2 CH3Cl + HCl H = -25Kcal/molhttp://hhud.tvu.edu.vn


158/457

14

X X

R R

R X

R-R

R-X

X-X+

+

+

Ngt mch:


Giai on to CH3. kh hn giai on to CH3

Clgiai on to CH3

. (hay R. ni chung) s quyt nh


159/457

15

tc phn ng chung


b. So snh kh nng thay th HH bc 1 & bc 2:


160/457

16

CH3-CH2-CH3 CH3-CH2-CH2-Cl + CH3-CHCl-CH3+ Cl2

25 oC

h 45% 55%

Vn tc tng i khi thay th H bc 1: 45 / 6 = 7.5Thay th H bc 2: 55 / 2 =27.5

t l vn tc tng i H bc 1/ H bc 2 = 7.5/27.5 ~


H bc 1 & bc 3:

CH3 CH3CH325 oC


161/457

17

H3C C CH3H

H3C CH CH2Cl H3C C CH3Cl+ Cl2

h+

64% 36%

Vn tc tng i khi thay th H bc 1: 64 / 9 ~7Thay th H bc 2: 36 / 1 ~ 36t l vn tc tng i H bc 1/ H bc 3 = 7/36 ~ 1/5T l vn tc tngi bc 1/bc 2/bc 3 = 1/4/5

nhit thng, kh nng thay th H C bc 3cao nht

Lu : 600oC: t l ny l 1/1/1http://hhud.tvu.edu.vn


162/457

18

c. Kh nng phn ng ca dy halogenF2

> Cl2

> Br2

> I2

F ha: mnh lit, t lin kt t dngI ha: rt kh xy r a (H = + 13 Kcal/mol), ch

xy

ra khi loi HI trong qu trnhhttp://hhud.tvu.edu.vn

d. Tnh chn lc ca phn ng Phn ng Br ha c tc chm hn Cl ha


163/457

19

nhng c chn lc caoT l vn tc tng i 127oC ca Br ha: bc1/bc 2/bc 3 = 1/82/1000

H3C C CH3

CH3

H

H3C CH

CH2Cl

CH3H3C C CH3

CH3

Cl

+ Cl2

25 oC

h

+

64% 36%

H3C C CH3

CH3

H

H3C C

H

CH2Br

CH3H3C C CH3

CH3

Br

+ Br2

127 oC

h

+

1% 99%

CH3-CH

2-CH

3 CH3-CH2-CH2-Br + CH3-CHBr-CH3+ Br

2

127 oC

h 3% 97%http://hhud.tvu.edu.vn

V.2. Phn ng nitro ha alkane


164/457

20

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%) +CH3-NO2 (10%)


V.3. Phn ng ng phn ha


165/457

21

Chuyn cc alkane mch thng thnh alkane mchnhnh di tc dng ca xc tc nhit cao Xc tc thng dng: acid Lewis nh AlCl3

, xctc acid trn c s zeolite

V d:

CH3-CH2-CH2-CH3AlCl3

H3C C CH3

CH3

Hto


C ch:


166/457

22

CH3-CH-CH2-CH3

H

AlCl3

HAlCl3 H3C C CH3

CH3

H

CH3-C-CH2-CH3

H

C C+C

C

H

H

H H

H

H

HHH

to +

+ AlCl3

-HAlCl3

Xu

hng: to

carbocation

bn hn chuyn v


V.4. Phn ng cracking


167/457

23

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)


V.5. Phn ng oxy ha alkane


168/457

24

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), carboxylicacid (RCOOH)

Phn ng quan trng:2Cn

H2n+2

+ (3n + 1)O2 2nCO2 + (2n+2) H2O

ta nhit mnh, -341 kcal/mol alkane c dnglm nhin liuhttp://hhud.tvu.edu.vn


169/457

1


K

Thut Ha H c



Chng 5: ALKENE


170/457

2

I. Gii thiu chung Alkene: hydrocarbon mch h, cha 1 lin kt iC=C (Cn

H2n

, n2)

Trong C=C: 1 & 1, hnh thnh do lin kt caorbital sp2



171/457

3

Lin kt vung gc vi mt phng phn tAlkene n gin nht l ethylene CH2

=CH2

121.7o

116.6o

1.33 1.08


II. H danh php


172/457

4

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 )2 C=CH

2 isobutylene


II.2. Danh php IUPAC


173/457

5

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

CH3-CH-CH=CH2

CH33-methyl-1-butene


174/457

6

II.3. Tn gc ca alkeneAlkenylCH2 =CH- 1-ethenyl (vinyl)CH2

=CH-CH2

- 2-propenyl (allyl)CH3

-CH=CH-

1-propenyl

CH3-C-CH=CH-CH3

CH3

H

4-methyl-2-pentene (c

cis

& trans)


III. Cc phng php iu ch


175/457

7

III.1. Tch nc t alcohol Phn

ng

c

th pha

lng

(xc

tc

acid H2

SO4

,

H3

PO4

, 100-170oC) hay pha kh (xc tc Al2 O3 ,zeolite, 350-400oC)

to

xtC C

H OH

C C + H2O


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


176/457

8

CH3CH2CH2CH2-OH

CH3-CH-CH

2-CH

3OH

H2SO4 50-60%

(CH3)3C-OHH2SO4 20%

H2SO4 75%

CH2=C(CH3)2

CH3-CH=CH-CH3

CH3CH=CHCH3

100 oC

80 oC

140 oC


III.2. Tch HX t dn xut ca halogento

KOH/ th l

C C

H X

C C + H2O + KX


177/457

9

KOH/ethanolH X

Kh nng tch HX: RX bc 3 > bc 2 > bc 1

CH3CH2CHCH3

Cl

CH3CH2CH2CH2Cl

CH3CH2CH=CH2

CH3CH2CH=CH2to

KOH/ethanol

to

KOH/ethanol20%

+

80%

CH3CH=CHCH3

Lu

: tch

R-X bc

1 khng

c

chuyn v R-OH bc 1

CH3CH2CH2CH2-OH

H2SO4 75%

CH3CH=CHCH3140 oChttp://hhud.tvu.edu.vn

III.3. Kh dn xut 2 ln th ca halogenC C

X X

C C + ZnX2Zn

to


178/457

10

X X to

H3C C C CH3

H

Br

H

Br

+ ZnX2Zn

to

CH3CH=CHCH3

III.4. Hydro ha

alkyne

C CR R'

H2,xt

Lindla

r

(Pd)

H

R R'

H

H

R H

R'

Na,NH3


III.5. Nhit phn ester

C H2 1

-O-COR C H2

+ RCOOH


179/457

11

n 2n+1 n 2n Nhit phn ester ca ru bc 1 < bc 2 < bc 3

Ester bc 1 1 sn phm, bc 2 & bc 3 nhiusn phm

IV. Tnh cht vt l (tc)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 (E = 80 kcal/mol)Xc tc, to... lin kt d bthttp://hhud.tvu.edu.vn

V.1. Phn ng cng hp i in t


180/457

12

V.1.1. C ch: Giai

on 1:

C C + X -Ydung moi

xuc tac C C

X

Yphc

khong ben

nhanh

C+ C

X

cham C Cben hoa

X+

Giai

on chm:

X+ tn

cng

vo

C=C i in t


Giai on 2:


181/457

13

C CX+

Y- nhanh

C CX

Y

Y-

tn cng vo pha i lp vi X Nhm th y in t (+C, +I, +H) tng mt in tca C=C tng kh nng phn ng AE


V.1.2. Phn ng cng hp halogen

Ph h CH CH i B i


182/457

14

Phn ng cng hp ca CH2 =CH2

vi Br2

vi s cmt ca NaCl, NaNO3

, sn phm thu c l 1 hnhp:Br-CH2

-CH2

-Br + Br-CH2

-CH2

-Cl

+

Br-CH2 -CH2

-ONO2

Nu phn

ng

thc hin

trong

dung mi

l

CH3

OH,

sn phm chnh l Br-CH2 -CH2 -OCH3 !!!http://hhud.tvu.edu.vn

H2C CH2 CCl4 H2C CH2+ Br2


183/457

15

H2C CH2

H2C CH2

H2C CH2

CCl4

H2O

CH3OH

H2C CH2

Br Br

H2C CH2Br OH

H2C CH2

Br OCH3

+ Br2

+ Br2

+ Br2



184/457

V.1.3. Phn ng cng HXa. Quy tc Markonikov (dnh cho C=C khng i

) H+ t b h hi H


185/457

17

xng): H+

s tn cng vo carbon cha nhiu H

CH3-CH=CH2

CH3-C=CH2

CH3

CH3-C-CH3

CH3

Br

CH3-CH-CH3

Br

+ HBr

+ HBr

b. Quy tc Zaitsev-Wagner: H+

s tn cng vo pha to thnh carbocation trung gian bn nhtCH

3-CH=CH-CH2-CH

3

HBr

CH3-CH-CH-CH2-CH3Br


Q t Kh h khi t id h


186/457

18

c. Quy tc Kharasch: khi c mt peroxide, phn ng

s i theo hng

ngc vi

Markonikov

&

theo c ch cng hp gc t doCH3

-CH=CH2

+ HBr CH3-CH2-CH2-Br

Cc peroxide:

H2

O2

,

acetyl peroxide CH3

CO-O-O-

CO-CH3

, benzoylperoxide C6

H5

CO-O-O-COC6

H5


Cch: Theo hng to gc t do bnCH3-C-O-O-C-CH3

CH3

to + CH3-CO-O + CO2


187/457

19

CH3-CH=CH2

CH3-C-O-O-C-CH3O O

Br

HBr

Br

3

CH3-CH-CH2

Br

CH3-CH2-CH2Br Br

2

+ HBr + CH3COOH

+ CH3-CH-CH2Br

+

CH3-CO-O

CH3-CH-CH2Br

L

u : HI & HCl khng tham gia phn ng cng gc tdo 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 CH CH CH


188/457

20

CH3-CH=CH2 H2SO4 CH3-CH-CH3OH

+ H2O

Tun theo quy tc Markonikov C

ch:

CH3-CH=CH2-H+

CH3-CH-CH3-H2O

H3C C

H

CH3

OH

H

-H+ CH3-CH-CH3

OH

+ H+ ++ H2O

+ H+

Nu dng nhiu H2 SO4

:

CH3

-CH=CH2

+ H2

SO4 (CH3)2CH-OSO3H

(CH3 )2

CH-OSO3

H + H2

O (CH3)2CH-OH + H2SO4http://hhud.tvu.edu.vn

V.1.5. Phn ng cng hp B2 H6 Phn ng quan trng iu ch alcohol bc 1 & 2

t lk i h M k ik


189/457

21

t alkene, ngc vi sn phm MarkonikovCH3-CH=CH2 CH3-CH2-CH2-OH

1. B2H6

2. H2O2 / NaOH

C ch: B2 H6 BH3

CH3-CH=CH

2

BH3

[CH3-CH2-CH2]3BH2O2

CH3-CH-CH2-B HH

H

H-

CH3-CH2-CH2-OH

[CH3-CH2-CH2-O]3B

CH3-CH

2-CH

2-BH

2

OH-

(Lewis acid)

+


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


190/457

22

C C + H2 Ni 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 cis

+ H2

H H H H

C C

C C

H H


V.2.2. Tnh lp thPhn ng cng hp cis (syn) ng phn cis c th thu sn phm meso (1 snphm)


191/457

23

phm) ng phn trans sn phm l hn hp racemic (1i i quang)

C

C

H COOH

COOHH

D2

C

C

H COOH

HHOOC

D2

Ni

Ni

H C D

COOH

CH D

COOH

H C DCOOH

CD H

COOH

D C HCOOH

CH D

COOH

mesomaleic acid

rac-fumaric acid http://hhud.tvu.edu.vn

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


192/457

24

C CR-C-O-O-H

O

C C

OH2O C C

OH

OH

C C

O

++ RCOOH

(H+, OH-)

Cng

hp

trans, to

-diol

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

V.3.2. Oxy ha bng ddch KMnO4 long (pH 7, 0

oC )

Cng hp cis to diol


193/457

25

Cng hp cis, to diol

Phn ng khng ct mch C=C

C C + MnO4- 0oC

pH 7

C C

O O

MnO O

-

OH-

H+

H2OC C

OH OH

+ MnO3-


V.3.3. Oxy ha bng ddch KMnO4 m c, to

cao


194/457

26

Phn ng gy ct mch C=C Sn phm l carboxylic acid

CH3

-CH=CH-CH3

+ KMnO4

/ to 2 CH3COOH

(CH3

)2

CH=CH-CH3

+ K2

Cr2

O7

/H2

SO4

/to

(CH3

)2

C=O + CH3

COOH


V.3.4. Oxy ha bng ozone Phn ng gy ct mch C=C

Sn phm l carbonyl (khc KMnO )


195/457

27

Sn phm l carbonyl (khc KMnO4 )

C CO3

C C

O O

O

C

O O

CO

C O

H

2O(H+) C O

C O

molozonide ozonide

Zn/CH3

COOH + H2O

H2/Pt + H2O

+ H2O2

CH3-C=CH-CH2-CH3

CH3

CH2-C-CH3

O

CH3-CH2-CHO1. O32. H2O

+ + H2O2

L

u : H2 O2 d dng oxy ha carbonyl thnh 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


196/457

28

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 H2

SO4

, AlCl3

,BF3

)

hay anion (xc

tc

LiNH2

)

ClCl

CH2-CH-

Cl

CH2-CH--

Cl

nCH2=CHperoxide

polyvinyl chloride

--CH2-CH-

H2C C

CH3

CH3

H+

H3C C

CH3

CH3

CH2 C

CH3

CH3

CH2 C

CH3

CH3


H H H C


197/457

1


K

Thut Ha Hc



Chng 6: ALKADIENEI Phn loi


198/457

2

I. Phn loi

I.1. Hai ni i ng lin nhau (allene)CH2

=C=CH2

propadieneCH3

-CH2

=C=CH2

1,2-butadiene


I.2. Hai ni i lin hpC cu to c bit c tnh cht ha hc quant h t h ht


199/457

3

C cu to c bit c tnh cht ha hc quantrng ch trng cc hp cht nyCH2 =CH-CH=CH

2

1,3-butadieneCH2

=C(CH3

)-CH=CH2

2-methyl-1,3-butadiene(isoprene)


I.3. Hai ni i xa nhauTnh cht ging nh alkene


200/457

4

Tnh cht ging nh alkeneCH2

=CH-CH2

-CH=CH2

1,4-pentadiene


II. Cc phng php iu chII.1. Tch nc t1,3-butadiol


201/457

5

i t acetylene

HC CH HgSO4

H2SO4CH3-CHO+ H2O

H3C CO

H

Al2O3

H2C CO

HH

CH2=CH-CH=CH2

OH- H3C C CH2 C

H

OOH

H

H3C C CH2 CH2OH

OH

H

+ H2/Ni

350o

C

+ 2H2O


II.2. T ethanol2 CH3-CH2-OH CH2=CH-CH=CH2

ZnO/Al2O

3

4 0 00 oC


202/457

6

450-500 oC

II.3. T 1,4-butadiol

HC CH

HO-CH2-CH2 CH2-CH-OHAl2O3

HO-CH2-C C-CH2-OH

CH2=CH-CH=CH2

+ HCHOH2/Ni

350oC



203/457

III.1. Phn ng cng halogenThu c 2 sn phm cng 1,2 & 1,4CH2=CH-CH-CH2


204/457

8

CH2=CH-CH=CH2

C C C C

Br

Br

Br

CH2-CH=CH-CH2

Br

+ Br-Br

C

ch:

CH2=CH-CH=CH2 CH2=CH-CH-CH2

CH2=CH-CH-CH2

Br-

Br Br

Br

Br

CH2-CH=CH-CH2

CH2-CH=CH-CH2

Br-

Br

Br+ Br-Br

+ +


III.2. Phn ng cng HXTy theo nhit m thu c hn hp sn phmkhc nhau


205/457

9

Ty theo nhit m thu c hn hp sn phmkhc nhauCH2=CH-CH=CH2

CH2=CH-CH-CH2

Br H

CH2-CH=CH-CH2

Br H

CH2=CH-CH-CH2

Br

Br

H

CH2-CH=CH-CH2

H

+ HBr

-80oC 40

oC

80%

20%

20%

80%

40oC


III.3. Phn ng Diels-AlderPhn ng cng hp & ng vng ca1,3butadiene

hay dn xut ca n vi cc hydrocarbon khng no


206/457

10

hay dn xut ca n vi cc hydrocarbon khng nokhc (i diene)

C

C C H

HC

H

H

H

H

C

CH

CH3CH

H

O

+to

CH3

O


Cc hp cht i diene phi mang nhm th htin t, ethylene phn ng rt chmCH2=CH-CHO acrolein

CH2=CH-CN acrylonitrile


207/457

11

CH2

CH CN acrylonitrile(CN2

)C=C(CN)2

tetracyan ethylene

C6 H5 -CH=CH-COOH cinnamic acidO

O

O

maleic anhydrideO

O

benzoquinone


III.4. Phn ng trng hp

CH CH CH CH CH CH CH CH


208/457

12

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

CH3

CH3

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


Ha H c Hu C


209/457

1


K

Thut Ha H c



Chng 7: ALKYNEI Gii thiu chung


210/457

2

I. Gii thiu chungHp cht hydrocarbon khng no, mch h, chalin kt b a C CCng

thc

chung: Cn

H2n-2



211/457

31.2 1.06

180

o


II. Danh phpII 1 Tn thng thng


212/457

4

II.1. Tn thng thng Alkyne n gin nht l HCCH acetylene

Cc

alkyne

n gin khc c

xem

l

dn xut

ca acetyleneHCC-CH2

-CH3

ethylacetylene

CH3

-CC-CH(CH3

)2

isopropylmethylacetylene


II. 2. Tn IUPAC Cch gi tn ging nh alkene, ch i ene thnh yne Mch chnh phi cha CC


213/457

5

Mch chnh phi cha C C Nhng hp cht cha nhiu hn 1 ni badiyne, triyne Hp cht va c ni i va c ni ba enyne

6-methyl-3-octyne

4-methyl-7-nonene-1-yne 1-heptene-6-ynehttp://hhud.tvu.edu.vn

III. Cc phng php iu chIII.1. Thy phn calcium carbide CaC2


214/457

6

y p

CaC2

CaC2

HC CH

CaO + 3C 2000o

C + CO

+ 2H2O + Ca(OH)2

III.2. Oxy ha

methane

6CH4 HC CH+ O21500 oC + 2CO + 10H22


III.3.i t dn xut dihalogenH2C CH2

Br BrHC CH

KOH/EtOH

to


215/457

7

CH3-CH2-CHCl2

Br Br

CH3-CH2-C-CH3

Cl

ClNaNH

2

CH3-C

CH

CH3-CH

C CH3

CH

t

KOH/EtOH

to

KOH/EtO

H

to

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

III.4. Alkyl ha dn xut natri hay c magnesiumca acetyleneHCCNa + R-X HCC-R + NaX


216/457

8

HCC-MgX + R-X HCC-R + MgX2

iu ch

dn xut ca

acetylene

HCCH + NaNH2 HCCNa + NH3

HCCH + CH3

MgX HCC-MgX + CH4

IV. Tnh

cht vt l (t c)


V. Tnh cht ha hcV.1. Phn ng th H u mch


217/457

9

Hu mch th hin tnh acid

HCC-H + NaNH2 HCCNa + NH3HCC-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-HH+ d tch ra Alkene & alkane khng c tnh cht nyhttp://hhud.tvu.edu.vn

V.2. Phn ng cng hydrogenC CR R' + H

2

Ni hay PtR-CH

2

-CH2

-R'


218/457

10

C CR R' + H2

Pd/C

R-CH2-CH2-R'

Pd/CaCO

3

Pd/BaSO4

C C

R

H H

R'

C CR R' + Na/NH3 C C

R

H R'

Hhttp://hhud.tvu.edu.vn

V.3. Phn ng cng halogen

BrBr

Br


219/457

11

H3C C CH H3C C CH

Br

Br2 H3C C CHBr2

Br

+ Br-Br

Sn phm trans trong ln cng th nhtLu : nu ni i & ni ba khng lin hp, X2

scng

vo

ni

i!!!

CH2

=CH-CH2

-CCH + Br2 BrCH2-CHBr-CH2-CCH


V.4. Phn ng cng HX


220/457

12

C C C HH

H

H

H-BrC C CH2H

H

H Br

H-BrC C C H3H

H

H Br

Br

Tun theo quy tc Markonikov



221/457

V.6. Phn ng cng hp alkylborane


222/457

14

C CCH

H

HC

H

HCH3 C CH3C CH2 CH3

H BR2CH3COOH

BHR2

C CH3C CH2 CH3

H OH

CH2 CH3C CH2 CH3

O

C CH

H3C C2H5

H

H2O2/OH-

To

alken: cng

cis


V.7. Phn ng cng hp cht carbonyl Cng

hp

i

nhn


223/457

15

C C HH C O

H

HC CH CH2-OH HCHO C CHO-H2C CH2-OH

C C HH C O

R

R

C CHO-C C-OH

R

R

R

R+ 2


V.8. Phn ng cng hp i nhnR-OH, R-SH, R-COOH, H-CN, amine monomer quan trngHC CH

RO-

150 oCROCH CH- ROH ROCH CH2 + RO-


224/457

16

C CHC6H5CO

R2NH

C C

C6H5CO

H H

NR2

C6H5C CHC2H5ONa

C C

C6H5

H H

OC2H5

CH2 CH C CHROH

CH2 CH CH CHOR

RO-

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

V.9. Phn ng oxy haOxy ha alkyne bng KMnO4 hay ozone to

carboxylic acidR-CC-R + KMnO4 hay ozone RCOOH +


225/457

17

4 y

RCOOH

R-CC-H + KMnO4 hay ozone RCOOH +CO2

V. 10. Phn

ng

trng

hp

C C HHCuCl

CH2-CH=C CH2

Cl

CH2=CH-C CHHCl

CH2=CH-C

Cl

CH22to

chloroprene

n

cao su neoprene


Ha Hc Hu C


226/457

1


K

Thut Ha Hc



Chng 6: HYDROCARBON THM

I Cu to ca benzene


227/457

2

I. Cu to ca benzene Kkul a ra cng thc cu to ca benzenenm 1865

6C, 6H vng 6 cnh c 3 ni i nhng khng

th l cyclotriene

C

CC

C

CC

H

H

H

H

H

H


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


228/457

3

Phn

ng

th

2 ln Br ch

cho

1 sn phm

+ Br2

Br

Br

Br

Br


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


229/457

4

6C nm trong cng 1 mt phng, trng thilai ha

sp2


120 o120 o


230/457

5

120

o

1.09

1.39

121.7o

116.6o

1.33 1.08


II. Tnh thm

Hydrocarbon thm

(arene) nhng hp cht vng

lin hp c cu to phng, c cu to in tgingb kh h h d h h


231/457

6

benzene, kh cho phn ng cng, d cho phn ngth

Br2

CCl4

Br2

CCl4

Br

H

H

Br KMnO4 L

H2

O

OH

OH

H

HKMnO4 L

H2O


Arene thng l vng phng 5, 6, 7 cnh, c hin t lin hp, s t tun theo quy tc Hkel4n + 2, n = 0,1,2,3,4V d h h h d


232/457

7

V d cc hp cht arene thng dng

n=1 n=2 n=3


Mt s trng hp c bit

(-)

cyclopentadienyl

6 in t (i

t

ca

anion

tham

gia

h

lin

hp) n=1 c tnh thm


233/457

8

(+)

cycloheptatrienyl

6 in t (C+ tham

gia

orbital trng p vo h lin hp) c tnhthm

(+)

4 in t khng c tnh thm

(+)

2 in t c tnh thm


(.)

5 in t khng c tnh thm


234/457

9

(.) 7 in t khng c tnh thm

(-) 8 in t khng c tnh thm

NH

Pyrrole

O

Furan

S

Thiophene

6 in t (i in tp tham gia h lin hp)c tnh thmhttp://hhud.tvu.edu.vn

III. Danh php


235/457

10

Hu ht cc arene u c tn thng thng, 1 stn thng thng c chp nhn lm tn IUPAC

Tn IUPAC: benzene c chn lm tn gc, tncc nhm th t trc, nhm th c nh s theo

nguyn

tc tng

ch

s

nh

nht, xp theo

alphabeticalhttp://hhud.tvu.edu.vn

III.1. Dn xut ca benzene


236/457



237/457



238/457

NO2

Cl Br

NH2

Br Br

OH

Cl Cl


239/457

14

C

3-bromo-5-chloronitrobenzene

Br

2,4,6-tribromoaniline

Cl

2,4,6-trichlorophenol

Br

Br

Br

1,2,4-tribromobenzene

OH

NO2

Cl

2-chloro-4-nitrophenol

O2NCH3

NO2

2,6-dinitrotoluene


III.2. Vng a ngng t


240/457

15

Naphthalene Anthracene

1

2

3

45

6

7

8

9

10

1

2

3

45

6

7

8 9

10


III.3. Cc arene c d t trong vng


241/457

16

N

Pyridine

N CH3

2-methylpyridine

NH

Pyrrole

O

Furan

S

Thiophenehttp://hhud.tvu.edu.vn

IV. Cc phng php iu chIV.1. Chng ct mui ca benzoic acid


242/457

17

COONa

+ NaOHto + Na2CO3

IV.2.i t acetylene

HC CH3 Cu hay phc Ni

to


IV.3. Alkyl ha benzene

AlCl3R

R Cl + HCl


243/457

18

IV.4.ng vng & dehydro ha phn on du mC6-C8

CH3(CH2)4CH3Cr2O3 / Al2O3

V. Tnh cht vt l (t c)

3+ R-Cl + HCl


V. Tnh cht ha hcV.1. Phn ng th i in t

V 1 1 C h h


244/457

19

V.1.1. C

ch

phn

ng

+ X+ acid + H+

X

Xc

tc:

H

2 SO

4 , H

3 PO

4 , HF

hay Lewis acid: FeCl3 , AlCl3

, ZnCl2

C6H6 + (CH3)3C-Br /AlBr3 C6H5-C(CH3)3 + HBrhttp://hhud.tvu.edu.vn

C ch phn ng: 2 giai on, lng phn t Giai

on 1: to phc

( benzonium

cation)

t


245/457

20

+ X -Yxt

nhanh

X -Y phc

cham

HX HXHX

+ +

+

HX

+

Trong phc : X khng lin kt trc tip vi C no cPhc

: X c

lin

kt trc tip vi 1 C ca

benzene

phc


Giai on 2: tch proton


246/457

21

HX

+nhanh

X

+ HY


V.1.2. Kh nng phn ng v quy lut tha. Kh nng phn ng: Nhm th y in t (+I, +C, +H) mt

i t t h th t t h i


247/457

22

in t trong nhn thm tng tc nhn iin t cng d tn cng tc phn ngtng

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)


Nhm th ht in t (-C, -I) mt in t canhm thm gim khng thun li cho tc nhn iin t gim tc phn ng

Cc

16 bg hhc ptsnam.pdf

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