XC NH C U TRC CC H P CH T H U C B NG CC PHNG PHP PH (Spectrometric Identification of Organic Chemistry)

CHNG I: PH H NG NGO I (IR-INFRARED SPECTROSCOPY)

CHNG II: PH C NG H NG T H T NHN (NMRNUCLEAR MAGNETIC RESONANCE)

CHNG III: CC BI T P T NG H P PH

IR V NMR

GV: ThS. Hong Minh H o

TI LI U THAM KH O
1. Nguy n Kim Phi Ph ng (2005), Ph NMR s d ng trong phn tch h u c- L thuy t- Bi t p- Bi gi i, NXB H Qu c Gia TP. HCM. 2. Robert M. Silverstein, Francis X. Webster (1996), Spectrometic Identification of Organic Compounds, John Wiley & Sons, Sixth Edition. 3. James. V. Cooper (1980), Spectroscopic Techniques for Organic Chemist, John Wiley & Sons. 4. John McMurry (2004), Organic Chemistry, Physical Sciences, Seventh Edition.

CHNG I PH H NG NGO I (IR-INFRARED SPECTROSCOPY)

GV: ThS. Hong Minh H o

I.1. L THUY T CHUNG Theo c h c l ng t : B c x i n t c b n ch t nh nguyn: V a th hi n tnh ch t sng, v a th hi n tnh ch t h t. Tnh ch t sng: M t b i b c sng hay t n s

B c sng (Wavelength, ): l kho ng cch gi a hai nt (hay hai b ng), o b ng n v l m, cm, mm, m, nm.
( di sng hay b c sng) (Bin )

T n s (Frequency, ): l s b c sng m sng th c hi n c trong m t giy (cps: cycles per second), c o b i Hz.

Nng l ng c a m t photon (m t l ng t ):

= h
(h: h ng s Planck, h = 6,63.10-34 (J.s); : t n s (Hz)

c: v n t c nh sng trong chn khng, c = 3.108 m/s)

(*)

(*)B c sng () cng ng n th nng l ng (E) cng cao v ng c l i.

S sng (Wavenumber):

nh lu t Beer:
A = .C.l Trong : A = log(1/T) = log(I0/I) g i l quang. (T = I/I0 g i l : h s h p th phn t . C: n ng (mol/l). h p th (Absorbance)hay m t

truy n qua, Transmittance, %).

l: chi u di bu ng ch a m u (cm)

T i sao m t phn t h u c h p th IR?

Trong phn t h u c c m t s dao ng sau:

C
H H

Gin

i x ng

Gin b t x ng

U n trong m t ph ng

U n ngoi m t ph ng

Khi m t phn t c chi u x , nng l ng b c x i n t c h p th n u t n s c a b c x ph h p v i t n s c a dao ng.

T t c cc dao

ng trong phn t h u c

u h p th IR?

Nh ng dao ng d n t i s bi n t m i quan st c trn ph IR.

i Moment l ng c c c a phn

V d : B n nguyn t Hydro c a CH4 dao CH4 khng h p th nng l ng IR. ng m t cch i x ng th

Dao ng i x ng c a n i i C=C h p th nng l ng IR.

C2H4 v CC

C2H2 khng

Vai tr c a ph IR:
IR spectrum What molecular motions? What functional groups?

M i lo i dao nh.

ng trong phn t h p th

m t t n s xc

Ph IR gip ta xc nh c cc lo i dao ng c trng c a cc lin k t (bonds) hay cc nhm ch c (functional groups) c trong phn t . Cc lin k t hay cc nhm ch c: C-C; C=C; C C; C-H; C-O; C=O; C-N; O-H; N-H

h p th

I.2. PH

S sng

truy n qua S sng

truy n qua)

(S sng)

Tr c honh: Bi u th s sng (wavenumber, cm-1)

Tr c tung: Bi u th c ng h p th (Transmittance), th ng dng %T.

qua

truy n quang T

I.3. PH

IR C A CC H P CH T H U C

I.3.1. Ph IR c a cc Hydrocarbon bo I.3.1.1. Alkane

Trong Alkane c hai d ng lin k t: Lin k t C-H v lin k t C-C. Lin K t C-C: Gin C-C (Stretching C-C) v u n C-C (Bending C-C). Dao ng u n C-C xu t hi n trn ph . Dao ng gin C-C xu t hi n d i 500 cm-1 nn khng xu t hi n 1200-800 cm-1.

Lin k t Csp3-H: Gin C-H (Stretching C-H) v u n C-H (Bending C-H) c a nhm Methyl (-CH3) v nhm Methylene (-CH2-)

A: C-H stretching (asymmetrical: as v symmetrical: s): 3000-2800 cm-1.

B: C-H bending (asymmetrical: as v symmetrical: s): 1470-1300 v 720 cm-1.

Alkane m ch nhnh (Branched-chain Alkanes)

A: C-H stretching and bending (asymmetrical: as v symmetrical: s): 3000-2800 cm-1.

B C

B: Dao ng u n C-H c a nhm isopropyl c 1 mi i m nh (strong doublets) 1385-1380 v 1370-1365 cm-1 v i c ng nh nhau. C: Dao ng u n C-H c a nhm t-butyl c 1 mi (strong doublets) 1400-1385 v g n 1370 cm-1. i m nh

I.3.1.2. Alkene
C D

A: Gin Csp3-H B: Gin Csp2-H C: Gin C=C (N i i khng lin h p): 1667-1640 cm-1 D: U n b t i x ng Csp3-H c a nhm CH3: 1470 cm-1

Hydro n i v i Csp2 c gi ch t hn so v i Alkane, v v y gin t n s cao hn. D i trn 3000 cm-1 c xem nh d i c a dao ng Csp2-H. =CH2 3080 cm-1: Gin b t 2975 cm-1: Gin =CHR i x ng (B) th p)

i x ng (C ng i x ng

3020 cm-1: Gin b t

Dao ng gin C=C xu t hi n ny xung quanh 1650 cm-1. A: Dao

t n s cao hn Alkane. Peak

ng gin C=C: 1640 v 1601 cm-1.

Group RCH=CH2 R2C=CH2 cis-RCH=CHR trans-RCH=CHR Tri and tetra substituted

Stretching Frequency (cm-1) 1645 1655 1660 1675 1670

Intensity Medium

Weak

I.3.1.3. Alkyne

Dao ng gin Csp-H xu t hi n trn d i khng no: 3270-3315 cm-1.

T n s gin CC kh y u nhng v n nh n ra: CC CCgi : 2100-2140 cm-1 u m ch : 2210-2260 cm-1 a m ch

A: C-H gin: 3314 cm-1 B: CC gin: 2126 cm-1 C: C-H u n (C b n): 637 cm-1

I.3.1.4. Hydrocarbon thm Gin b t no). i x ng v i x ng C-H 3000-3100 cm-1 (D i khng

Dao ng u n ngoi m t ph ng C-H 900-675 cm-1 v i c ng m nh (Vng c trng c a Hydrocarbon thm). Gin C=C 1430-1600 cm-1, th ng l peak i.

C A

A: Gin C-H vng thm, 3017 cm-1 B: Gin C-H nhm CH3, 2970, 2940, 2875 cm-1 C: Gin C=C, 1605, 1497, 1466 cm-1 D: U n C-H vng thm, 741 cm-1 (Peak m nh)

Vng thm th cho cc m u (Pattern) y u nhng r t 1650-2000 cm-1

c trng

A: Vng thm th

v tr ortho

Vng thm th cho cc m u (Pattern) y u nhng r t 1650-2000 cm-1

c trng

A: Vng thm th

v tr meta

Vng thm th cho cc m u (Pattern) y u nhng r t 1650-2000 cm-1

c trng

A: Vng thm th

v tr para

I.3.1.5. Alcohol v Phenol Gin O-H (O-H stretching): Khi khng c lin k t Hydrogen (Nhm OH t do), gin O-H c a Alcohol v Phenol h p th m nh 3700-3500 cm-1. Khi c lin k t Hydrogen ngo i phn t , gin O-H c a Alcohol v Phenol h p th m nh 3550-3200 cm-1.

A: Gin O-H (Lin k t Hydrogen ngo i phn t ), 3329 cm-1

Gin C-O c a Alcohol v Phenol h p th

vng 1260-1000 cm-1

A:Gin C-O, 1231 cm-1

Alcohol b c nh t: Gin C-O

1060-1020 cm-1 1140-1091 cm-1

Alcohol b c 2 v b c 3: Gin C-O

Gin C-O c a Alcohol b c 1 (1054 cm-1)

I.3.1.6. Ether Eter bo (Aliphatic Ethers) cho h p th m nh c a gin b t i x ng C-O-C 1150-1085 cm-1

Aryl Alkyl Ethers cho h p th c a gin b t i x ng C-O-C 1275-1200 cm-1 v gin i x ng 1075-1020 cm-1.

B C A

A: Gin b t B: Gin

i x ng C-O-C: 1254 cm-1.

i x ng C-O-C: 1046 cm-1.

C: Gin C=C c a vng: 1601v 1501 cm-1.

I.3.1.7. Ketone Gin C=O: Dao ng gin C=O c a Ketone, Aldehyde, Carboxylic acid, Ester, Lactone, Acid halide, Alhydride v amide h p th m nh 1870-1540 cm-1. Thng th ng xu t hi n xung quanh 1750 cm-1.

Gin v u n c a C-CO-C 1300-1100 cm-1, Ketone bo 1230-1100 cm-1, Ketone thm t n s cao hn.

Khi thay i nhm Alkyl c a m t Ketone bo b ng m t d nguyn t (hetero atom) s lm thay i d ch chuy n c a nhm C=O.

S thay i d ch chuy n c a nhm C=O l do hi u ng c m I (Inductive Effect) v hi u ng c ng h ng R (Resonance Effect).

A: Dao B: Dao

ng gin C=O: 1715 cm-1 ng gin v u n C-CO-C: 1213 cm-1

S lin h p lm gi m t n s h p th c a nhm carbonyl

Ketone , khng no h p th 1660-1680 cm-1. Ketone thm h p th d i 1700 cm-1.

A: Dao

ng gin C=O, 1686 cm-1

B: Dao

ng gin v u n c a C-CO-C, 1270 cm-1

I.3.1.8. Aldehyde Aldehyde bo: Gin C=O dao Ketone: 1740-1720 cm-1 ng t n s cao hn c a

Aldehyde lin h p v Bezaldehyde: Gin C=O h p th 1710-1685 cm-1

Gin C-H c a nhm CHO 2830-2695 cm-1. Thng th ng chnh xc 2720 cm-1 (Peak c trng c a Aldehyde)

A: Dao B: Dao

ng gin C=O, 1728 cm-1 ng gin C-H c a nhm -CHO, 2715 cm-1

I.3.1.9. Acid carboxylic Dao ng gin O-H: T o lin k t hydrogen m nh (L ng ho c r n/CCl4 (0,01M), lc ny acid t n t i d ng dimer

Acid carboxylic cn c peak c a dao 1440-1395 cm-1

ng u n

C A B

A: Dao B: Dao C: Dao

ng gin O-H, trn 3000 cm-1 ng gin C=O, 1717 cm-1 (D ng dimer) ng u n C-O-H, 1424 cm-1

I.3.1.10. Ester Ester cho peak nhm C=O ng n) so v i ketone. t n s cao hn (b c sng

Ester bo bo ha: 1750-1735 cm-1. Ester , khng no: 1730-1715 cm-1 Gin O-C-C: Kho ng 1200-1100 cm-1.

A B

A: Gin C=O: 1771 cm-1 B: Gin b t i x ng O-C-C cm-1: 1200 cm-1

I.3.1.11. Amine c trng nh t c a Amine l gin N-H c a Amine b c 1 v b c 2.

Amine b c 1 (Primary Amines): 3300-3500 cm-1 (Peak i).

Amine b c 2 (Secondary Amines): 3310-3500 cm-1 (Peak n). Gin N-H t do i x ng v b t N u c lin k t Hydrogene th dao hn (<3400 cm-1). i x ng : 3400-3500 cm-1. ng gin b c sng di

A: Gin N-H (C lin k t Hydrogene), mi i: gin b t x ng (3368 cm-1) v gin i x ng (3291 cm-1).

I.3.1.12. Amide Cc Amide c ph IR gi ng Amine, nhng c trng nhm C=O 1650-1715 cm-1 (bng amide I), m t di n a g i l bng Amide II ngay d i vng Carbonyl.

A Amide I Amide II

A: Gin N-H (C lin k t Hydrogene), mi i: gin b t x ng (3352 cm-1) v gin i x ng (3198 cm-1).

B: Bng Amide I: 1679 cm-1 C: Bng Amide II: 1617 cm-1

I.3.1.13. Nitrile Nitrile c bng m nh v s c c a gin C N. cng: 2260-2240 cm-1

Nitrile thm v lin h p cho peak ny trong kho ng 2240-2222 cm-1.

A: Gin CN, 2249 cm-1.