XC NH CU TRC CC HP CHT HU C BNG CC PHNG PHP PH (Spectrometric Identification of Organic Chemistry)

CHNG I: PH HNG NGOI (IR-INFRARED SPECTROSCOPY) CHNG II: PH CNG HNG T HT NHN (NMRNUCLEAR MAGNETIC RESONANCE) CHNG III: CC BI TP TNG HP PH IR V NMR
GV: ThS. Hong Minh Ho

TI LIU THAM KHO

1. Nguyn Kim Phi Phng (2005), Ph NMR s dng trong phn tch hu c- L thuyt- Bi tp- Bi gii, NXB H Quc 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.

PH HNG NGOI (IR-INFRARED SPECTROSCOPY)

GV: ThS. Hong Minh Ho

CHNG I

I.1. L THUYT CHUNG Theo c hc lng t: Bc x in t c bn cht nh nguyn: Va th hin tnh cht sng, va th hin tnh cht ht. Tnh cht sng: M t bi bc sng hay tn s

Bc sng (Wavelength, ): l khong cch gia hai nt (hay hai bng), o bng n v l m, cm, mm, m, nm.
( di sng hay bc sng) (Bin )

Tn s (Frequency, ): l s bc sng m sng thc hin c trong mt giy (cps: cycles per second), c o bi Hz.

Nng lng ca mt photon (mt lng t):

(h: hng s Planck, h = 6,63.10-34 (J.s); : tn s (Hz)

= h

c: vn tc nh sng trong chn khng, c = 3.108 m/s)

(*)

(*)Bc sng () cng ngn th nng lng (E) cng cao v ngc li.

S sng (Wavenumber):

nh lut Beer:
Trong :

A = .C.l

A = log(1/T) = log(I0/I) gi l hp th (Absorbance)hay mt quang. (T = I/I0 gi l truyn qua, Transmittance, %). C: nng (mol/l). : h s hp th phn t.

l: chiu di bung cha mu (cm)

Trong phn t hu c c mt s dao ng sau:

Ti sao mt phn t hu c hp th IR?

C
H H

Gin i xng

Gin bt i xng

Un trong mt phng

Un ngoi mt phng

Khi mt phn t c chiu x, nng lng bc x in t c hp th nu tn s ca bc x ph hp vi tn s ca dao ng.

Nhng dao ng dn ti s bin i Moment lng cc ca phn t mi quan st c trn ph IR. V d:

Tt c cc dao ng trong phn t hu c u hp th IR?

Bn nguyn t Hydro ca CH4 dao ng mt cch i xng th CH4 khng hp th nng lng IR. Dao ng i xng ca ni i C=C C2H4 v CC C2H2 khng hp th nng lng IR.

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

Mi loi dao ng trong phn t hp th mt tn s xc nh. Ph IR gip ta xc nh c cc loi dao ng c trng ca cc lin kt (bonds) hay cc nhm chc (functional groups) c trong phn t. Cc lin kt hay cc nhm chc: C-C; C=C; C C; C-H; C-O; C=O; C-N; O-H; N-H

 hp th

I.2. PH

S sng

truyn qua S sng

( truyn qua)

(S sng)

Trc honh: Biu th s sng (wavenumber, cm-1) Trc tung: Biu th cng hp th qua truyn quang T (Transmittance), thng dng %T.

I.3. PH IR CA CC HP CHT HU C I.3.1. Ph IR ca cc Hydrocarbon bo I.3.1.1. Alkane Trong Alkane c hai dng lin kt: Lin kt C-H v lin kt C-C.

Lin Kt C-C: Gin C-C (Stretching C-C) v un C-C (Bending C-C).

Dao ng un C-C xut hin di 500 cm-1 nn khng xut hin trn ph . Dao ng gin C-C xut hin 1200-800 cm-1.

Lin kt Csp3-H: Gin C-H (Stretching C-H) v un C-H (Bending C-H) ca 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 mch nhnh (Branched-chain Alkanes)

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

B C

C: Dao ng un C-H ca nhm t-butyl c 1 mi i mnh (strong doublets) 1400-1385 v gn 1370 cm-1.

B: Dao ng un C-H ca nhm isopropyl c 1 mi i mnh (strong doublets) 1385-1380 v 1370-1365 cm-1 vi cng nh nhau.

I.3.1.2. Alkene
C D

A: Gin Csp3-H B: Gin Csp2-H C: Gin C=C (Ni i khng lin hp): 1667-1640 cm-1

D: Un bt i xng Csp3-H ca nhm CH3: 1470 cm-1

Hydro ni vi Csp2 c gi cht hn so vi Alkane, v vy gin tn s cao hn. Di trn 3000 cm-1 c xem nh di ca dao ng Csp2-H. =CH2 3080 cm-1: Gin bt i xng (B) 2975 cm-1: Gin i xng (Cng thp)

=CHR

3020 cm-1: Gin bt i xng

Dao ng gin C=C xut hin tn s cao hn Alkane. Peak ny xung quanh 1650 cm-1. A: Dao 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 xut hin trn di khng no: 3270-3315 cm-1. Tn s gin CC kh yu nhng vn nhn ra: CCu mch: 2100-2140 cm-1 CCgia mch: 2210-2260 cm-1

A: C-H gin: 3314 cm-1 B: CC gin: 2126 cm-1 C: C-H un (C bn): 637 cm-1

I.3.1.4. Hydrocarbon thm

Dao ng un ngoi mt phng C-H 900-675 cm-1 vi cng mnh (Vng c trng ca Hydrocarbon thm). Gin C=C 1430-1600 cm-1, thng l peak i.

Gin bt i xng v i xng C-H 3000-3100 cm-1 (Di khng no).

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: Un C-H vng thm, 741 cm-1 (Peak mnh)

Vng thm th cho cc mu (Pattern) yu nhng rt c trng 1650-2000 cm-1

A: Vng thm th v tr ortho

Vng thm th cho cc mu (Pattern) yu nhng rt c trng 1650-2000 cm-1

A: Vng thm th v tr meta

Vng thm th cho cc mu (Pattern) yu nhng rt c trng 1650-2000 cm-1

A: Vng thm th v tr para

I.3.1.5. Alcohol v Phenol Gin O-H (O-H stretching):

Khi khng c lin kt Hydrogen (Nhm OH t do), gin O-H ca Alcohol v Phenol hp th mnh 3700-3500 cm-1. Khi c lin kt Hydrogen ngoi phn t, gin O-H ca Alcohol v Phenol hp th mnh 3550-3200 cm-1.

A: Gin O-H (Lin kt Hydrogen ngoi phn t), 3329 cm-1

Gin C-O ca Alcohol v Phenol hp th vng 1260-1000 cm-1

A:Gin C-O, 1231 cm-1

Alcohol bc nht: Gin C-O 1060-1020 cm-1

Alcohol bc 2 v bc 3: Gin C-O 1140-1091 cm-1

Gin C-O ca Alcohol bc 1 (1054 cm-1)

I.3.1.6. Ether Eter bo (Aliphatic Ethers) cho hp th mnh ca gin bt i xng C-O-C 1150-1085 cm-1 Aryl Alkyl Ethers cho hp th ca gin bt i xng C-O-C 1275-1200 cm-1 v gin i xng 1075-1020 cm-1.

B C A

A: Gin bt i xng C-O-C: 1254 cm-1. B: Gin i xng C-O-C: 1046 cm-1. C: Gin C=C ca vng: 1601v 1501 cm-1.

I.3.1.7. Ketone

Gin C=O: Dao ng gin C=O ca Ketone, Aldehyde, Carboxylic acid, Ester, Lactone, Acid halide, Alhydride v amide hp th mnh 1870-1540 cm-1. Thng thng xut hin xung quanh 1750 cm-1.

Gin v un ca C-CO-C 1300-1100 cm-1, Ketone bo 1230-1100 cm-1, Ketone thm tn s cao hn. Khi thay i nhm Alkyl ca mt Ketone bo bng mt d nguyn t (hetero atom) s lm thay i dch chuyn ca nhm C=O.

S thay i dch chuyn ca nhm C=O l do hiu ng cm I (Inductive Effect) v hiu ng cng hng R (Resonance Effect).

A: Dao ng gin C=O: 1715 cm-1 B: Dao ng gin v un C-CO-C: 1213 cm-1

Ketone , khng no hp th 1660-1680 cm-1. Ketone thm hp th di 1700 cm-1.

S lin hp lm gim tn s hp th ca nhm carbonyl

A: Dao ng gin C=O, 1686 cm-1

B: Dao ng gin v un ca C-CO-C, 1270 cm-1

I.3.1.8. Aldehyde Aldehyde bo: Gin C=O dao ng tn s cao hn ca Ketone: 1740-1720 cm-1 Aldehyde lin hp v Bezaldehyde: Gin C=O hp th 1710-1685 cm-1 Gin C-H ca nhm CHO 2830-2695 cm-1. Thng thng chnh xc 2720 cm-1 (Peak c trng ca Aldehyde)

A: Dao ng gin C=O, 1728 cm-1 B: Dao ng gin C-H ca nhm -CHO, 2715 cm-1

I.3.1.9. Acid carboxylic Dao ng gin O-H: To lin kt hydrogen mnh (Lng hoc rn/CCl4 (0,01M), lc ny acid tn ti dng dimer

Acid carboxylic cn c peak ca dao ng un 1440-1395 cm-1

C A B

A: Dao ng gin O-H, trn 3000 cm-1 B: Dao ng gin C=O, 1717 cm-1 (Dng dimer) C: Dao ng un C-O-H, 1424 cm-1

I.3.1.10. Ester Ester cho peak nhm C=O tn s cao hn (bc sng ngn) so vi ketone. Ester bo bo ha: 1750-1735 cm-1. Ester , khng no: 1730-1715 cm-1 Gin O-C-C: Khong 1200-1100 cm-1.

A B

A: Gin C=O: 1771 cm-1 B: Gin bt i xng O-C-C cm-1: 1200 cm-1

I.3.1.11. Amine

c trng nht ca Amine l gin N-H ca Amine bc 1 v bc 2. Amine bc 1 (Primary Amines): 3300-3500 cm-1 (Peak i).

Amine bc 2 (Secondary Amines): 3310-3500 cm-1 (Peak n). Gin N-H t do i xng v bt i xng : 3400-3500 cm-1. Nu c lin kt Hydrogene th dao ng gin bc sng di hn (<3400 cm-1).

A: Gin N-H (C lin kt Hydrogene), mi i: gin bt i xng (3368 cm-1) v gin i xng (3291 cm-1).

I.3.1.12. Amide Cc Amide c ph IR ging Amine, nhng c trng nhm C=O 1650-1715 cm-1 (bng amide I), mt di na gi l bng Amide II ngay di vng Carbonyl.

A Amide I Amide II

A: Gin N-H (C lin kt Hydrogene), mi i: gin bt i xng (3352 cm-1) v gin i xng (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 mnh v sc cng: 2260-2240 cm-1 ca gin C N. Nitrile thm v lin hp cho peak ny trong khong 2240-2222 cm-1.

A: Gin CN, 2249 cm-1.