I HC QUC GIA THNH PH H CH MINH

Trng i Hc Khoa hc T nhin Khoa Ha B mn Ha Hc Hu c

GV. NGUYN TH THO TRN

GIO TRNH

Crixivan (Cht c ch HIV)

HA HU C I CNG
CHNG 1: I CNG V HA HC HU C CHNG 2: NG PHN CHNG 3: C CU IN T CHNG 4: HIDROCARBON CHNG 5: HALOGENUR ALKIL, HP CHT GRINARD CHNG 6: ALCOL, PHENOL, ESTER CHNG 7: ALDEHID, CETON CHNG 8: ACID CARBOXILIC V CC DN XUT CHNG 9: AMIN V CC MUI DIAZONIUM CHNG 10: ACID AMIN, HIDRATCARBON, TRIGLICERID CHNG 11: CC HP CHT D HON

CHNG 3 : C CU IN T CA HP CHT HU C

3.1. Vn o nguyn t 3.2. Tp chng vn o 3.3. S to ni 3.4. Hiu ng in t 3.4.1. Moment lng cc 3.4.2. Hiu ng cm 3.4.3. Hiu ng cng hng 3.4.4. Hiu ng siu tip cch 3.5. Acid - baz

CHNG 3
Cu trc mt nguyn t

Ht nhn: Proton + neutron

Electron

CHNG 3
3.1. Vn o nguyn t

Vn o: c 4 loi

Vn o p Vn o s

Vn o d

Vn o f

CHNG 3
3.1. Vn o nguyn t

CHNG 3
3.1. Vn o nguyn t Nguyn tc Aufbau

1 1 1 1 1 1 1 1 Nng lng 1 1 1 1 1 1 1 1 1 1 1 1 1 1

1 1 1 1

1 1 1

1 1 1

CHNG 3
3.2. Tp chng vn o
Theo thuyt loi tr Pauli (Paulis exclusion) - Z=6 - Cu hnh electron: 1s2 2s2 2p2

Trng thi c bn

1 1

Trng thi kch thch

1 1 1

CHNG 3
3.2. Tp chng vn o Vn o phn t
Vn o phn t: cc vn o nguyn t kt hp li to thnh. - a s cc hp cht hu c, cc nguyn t lin kt vi nhau bi lin kt cng ha tr

H2

CH4

CHNG 3
3.2. Tp chng vn o

Tp chng sp3: mt vn o 2s + 3 vn o p

y x x

y x

C: sp3
pz

px

py

Lai ha

sp3,

gc ni 109,5

1
C

1 1

CHNG 3
3.2. Tp chng vn o
Tp chng sp2: mt vn o 2s + 2 vn o p
z z z

y x x

y x

px

py

pz

Lai ha sp2, gc ni 120

CHNG 3
3.2. Tp chng vn o
Tp chng sp: mt vn o 2s + 1 vn o p
z z z

y x x

y x

py

px

pz

Lai ha sp, gc ni 180

CHNG 3
3.3. S to ni
S phi hp gia hai vn o nguyn t to ra mt ni gia hai nguyn t, a n s to thnh mt vn o phn t.

H-H

C hai kiu to ni: ni v ni

CHNG 3
3.3. S to ni Ni

2 vn o nguyn t xen ph theo trc lin nhn: s-s, s-p, p-p, sp3sp3, sp2-sp2, sp-sp, sp3-sp2, sp3-sp, sp2-sp3, s-sp3, s-sp2, s-sp

CHNG 3
3.3. S to ni

Ni

2 vn o nguyn t p c trc song song vi nhau to s xen ph bn : C=C, C=O, C=N, CC, CN, .

CH2=CH2

>C=O

H-CC-H

CHNG 3
3.3. S to ni C: sp3

Ni

Ni

Ni C-H v C-C

C: sp2
H

H C H H C

H H

Ni C-C v C-H

C: sp
H C C H H C C H

CHNG 3
3.4. Hiu ng in t Tnh phn cc v tnh kh phn cc
A

A:A

Cng ha tr khng phn cc (ng cc)

A: B

m in ca A > B Cng ha tr phn cc (ng cc)

Ni C-H c xem nh khng phn cc. Trong cng chu k, m in tng dn t tri sang phI. Trong cng phn nhm, m in gim dn t trn xung di.

CHNG 3
3.4. Hiu ng in t 3.4.1. Moment lng cc
Tnh phn cc ca ni A-B c biu th bng moment lng cc Vector nm trn trc lin nhn, hng t cc dng n cc m v c module

+ B

=xr
r : chiu di nI A-B : thng c tnh bng Debye

Cl

H H + C H Cl Cl

Cl C Cl

Clorometan (=1.87D)

Tetraclorometan (=0D)

CHNG 3
3.4.1. Moment lng cc

A:

+ B

= o

S xut hin tc cht ion gy ra in trng :

' A:

+ B

= o + i

(' > )
o : moment thng trc (do s phn phi cc in t ni ha tr khng ng u trong phn t) i : moment cm ng (do cc hiu ng gy ra) Kh nng phn cc ca mt nI dI tc ng ca in trng gi l tnh kh phn cc. in t cng linh ng, tnh kh phn cc cng cao v i cng ln.

CHNG 3
3.4.1. Moment lng cc

Tnh phn cc ca ni i cao hn ni n

+1 C

1 O

+2 C O

2 O R

1 = 1 x r1 = 2.7D
1 2

2 = 2 x r2 = 1.2D
r2 r1 2.7 x 1.34 1.2 x 1.22

1 2

2.5

Ni i C=O phn cc gp 2.5 ln ni n C-O

CHNG 3
3.4. Hiu ng in t

Hieu ng ien t

Hieu ng cam

Hieu ng cong hng

Hieu ng sieu tiep cach

+I

-I

+R

-R

CHNG 3
3.4. Hiu ng in t 3.4.2. Hiu ng cm I (Inductive)

Hiu ng cm : hin tng nguyn t c m in cao ht in t ca nguyn t c m in thp hn thng qua ni

CHNG 3
3.4. Hiu ng in t Hiu ng cm I : Cc nhm rt in t c hiu ng -I
- Halogen : -F > -Cl > -Br > -I - Nhm mang in tch dng:

-NR3 Amonium

-PR3 Phosphonium

-SR2 Sulfonium

- Nhm trung ha c hiu ng I yu : -NH2

-OH

-OR

-SH, -C6H5, -CH=CH2

- Nhm trung ha c ni lng cc c hiu ng I yu hn nhm mang in tch dng

O N O

O S OH O

- Nhm carbonil c hiu ng I yu : -CHO, -COOH, -COR

CHNG 3
3.4. Hiu ng in t

Hiu ng cm I

Trong cng chu k, -I tng dn t phI qua tri -NR2 < -OR < -F Trong cng phn nhm, -I gim dn t trn xung di

in tch dng cng ln hay tp chng cng c nhiI tnh s, -I cng mnh

-NH3 C CH

> >

-NH2 CH CH2

CHNG 3
3.4. Hiu ng in t

Hiu ng cm +I Cc nhm cho (y) in t c hiu ng +I

sp3 < sp2 < sp :
H H C H H CH3 C H H CH3 C CH3 CH3 CH3 C CH3

Cc nguyn t mang in tch m c hiu ng +I mnh : -O- < -S+I cng ln khi nguyn t mang in tch m c kch thc cng ln Hiu ng cm nh hng n moment lng cc, n tnh acid-baz ca phn t, hat phn ng v nh hng phn ng. Nhm y in t lm gim tnh acid, nhm ht in t lm tng tnh acid.

CHNG 3
3.4. Hiu ng in t 3.4.3. Hiu ng cng hng R (resonance)

S di chuyn in t trng thi tnh trong nhng phn t c ni a tip cch gi l hiu ng cng hng.

NH2

NH2

NH2

NH2

CHNG 3
3.4. Hiu ng in t 3.4.3. Hiu ng cng hng R (resonance) H thng cng hng 1. - - 2. p-- 3. - -C+ 4. p- -C+ 5. in t c thn-
p: i in t t do C+: vn o trng

Qui tc vit cng thc cng hng

Biu din s cng hng gia 2 cng thc Ch chiu di chuyn ca in t

CHNG 3
3.4. Hiu ng in t Qui tc vit cng thc cng hng

Tt c cng thc cng hng phi l cng thc Lewis (cng thc phn t trong mi i in t ni lin 2 nguyn t c biu th bng mt gch ngn (-). V tr tng i, s lng ca cc nguyn t trong phn t y ht nhau. Hai c cu cng hng c cng s in t kt i (hoc cng s in t khng phn chia). Cc nguyn t tham gia vo h thng cng hng phi nm trn cng mt mt phng.

CHNG 3
3.4. Hiu ng in t bn tng i gia cc cng thc cng hng
1. Cng thc c s ni cng ha tr cng nhiu th cng bn. 2. Cng thc c mang in tch km bn hn so vi cng thc khng c in tch. 3. Cng thc no c nguyn t m tng ngoi bin (tn in t ngoi cng) c y in t ging nh kh tr th cng bn. 4. Cng thc no c in tch m nm trn nguyn t c m in mnh th cng bn. 5. Cng thc cng hng vi hai in t cng du trn 2 nguyn t k cn khng bn. 6. Khi cc in tch ngc du cng xa nhau th cng thc cng hng cng km bn.

CHNG 3
3.4. Hiu ng in t Hiu ng cng hng R
Nhm rt in t ca ni i C=C tip cch gy hiu ng -R V d: C=O, -NO2, CN, R-COO-,
O HC CH N O O HC CH C HC CH C HC CH N O O O

O HC CH C O R HC CH C

O O R

Trong 1 chu k, m in cng ln, -R cng mnh (-COR > CNR2). in tch dng trn nguyn t cng ln, -R cng mnh.

CHNG 3
3.4. Hiu ng in t Hiu ng cng hng +R
Nhm cho in t c lp ca mnh v pha ni i C=C tip cch gy hiu ng +R V d: -OR, -X (F, Cl, Br, I)
HC HC CH CH O Cl R HC HC CH CH O Cl R

in tch m cng ln, +R cng mnh (-O- > -OR). m in cng ln, +R cng km (-NR2 > -OR > -F). Vn o p c mc nng lng cng cao, +R cng km (-F>-Cl>-Br>-I).

CHNG 3
3.4. Hiu ng in t

-R, -I

+R, -I

+R, +I
-S-, -O-

-NO2, -CN, -CHO, -NR2, -NH2, -COR, -COOH, -OR, -OH, -COOR, -CONR2, NHCOR, -F, -COCl, -C -Cl, -Br, -I = CR
Hiu ng cng hng nh hng n:

- di ni : hiu ng cng hng lm cho ni n k ni a ngn hn ni n bnh thng v ni a th di hn di bnh thng. - Moment lng cc.

CHNG 3
3.4. Hiu ng in t 3.4.4. Hiu ng siu tip cch
Nhm alkil gn trn C bt bo ha ca mt ni i hoc nhn benzen c th cho in t nh hiu ng cng hng. i in t ca ni n C-H v tr i vi C bt bo ha c tnh linh ng nn c th gy ra hiu ng cng hng tng t nh in t p ca nguyn t halogen trong halogenur vinil.
R R C H H H C H H C H H C H R C CR2 R R C R C CR2

Hiu ng siu tip cch nh hng n di ni, moment lng cc v bn tng i ca alcen.

CHNG 3
4. Acid-baz
Thuyt Brontested Lowry : Acid : cho proton H+ Baz : nhn proton

Acid

Baz lien hp

HCl, phenol, HCOOH, CH3NO2

Baz

Acid lien hp

CH3O-, Ph-NH2, CH3OH Cht lng tnh : va c tnh acid, va tnh baz -OH, -SH, -NH-
H H3C C OH O +H (H2SO4) H3C C OH O -H (H2O) H3C C O O

CHNG 3
4. Acid-baz

Lc acid - baz
AH + H2O
[A-][H3O+] [AH]

H3O

Ka

pKa = -logKa

pKa cng nh, acid cng mnh

B + H2O Kb [BH][OH-] [B-] OH + BH

pKb = -logKb pKb = 14

pKa + pH : pH = -log[H+]

CHNG 3
3.5. Acid-baz Cc yu t nh hng n lc acid - baz
- Nhm I lm tng tnh acid v lm gim tnh baz
H-CH2-C-O-H O pKa = 4,76 O2N-CH2-C-O-H O pKa = 1,68

- Nhm R lm tng tnh acid v lm gim tnh baz - Trong mt chu k t tri sang phi, tnh acid tng v tnh baz gim Tnh acid tng : CH4 < NH3 < H2O < HF Tnh baz gim : CH3- < NH2- < OH- < F- Trong mt phn nhm t trn xung di, tnh acid tng v tnh baz gim Tnh acid : HF < HCl < HBr < HI

CHNG 3
4. Acid-baz
- Hiu ng lp th: s hin din cc nhm c kch thc ln trong phn t c th che khut tm acid hoc tm baz hoc lm tr ngi hiu ng lp th lm nh hng n tnh acid baz. Tnh baz :
Me Me Me N Me Me Me N

- Ni hidrogen
O O H O H O O H O OH COOH

pKa1 = 3,0

pKa2 = 13,4

pKa1 = 4,5 pKa2 = 9,8