Phn tch cu trc hp cht hu c

1. t vn
Con ng ti u nht xc nh cu trc mt cht thng khng nh trc c.
Thng thng phi kt hp 4 phng php : UV, IR, MS, NMR, i khi c s tr

gip ca phng php nh sc trn (CD) hoc tn sc quay cc (ORD).

2. Phng php chung
T MS xc nh ion phn t v suy ra cng thc tng.
Trong trng hp MS khng cho ion phn t th dng phn tch nguyn t.
Xc nh s lin kt i v vng c hnh dung v khung phn t.
Nu mt phn t ch cha C, H, O th s tng ng ni i v vng c tnh
theo cng thc:
CaHbOc : DBE =

(2a + 2) b
2

(1)

DBE = s tng ng ni i
(2a + 2) l s nguyn t H trong hydrocacbon no c a nguyn t C. V ni i hoc
vng s lm gim i 2H nn khi tr i b ta c s H thc c ca (2a + 2), chia 2 ta c s
ni i v vng.
+ V d : Benzen c 4 tng ng ni i (3 ni i v 1 vng). Nhng nguyn t
c 1 hoc 2 ho tr nh Cl, Br, O, S, ... khng nh hng n phng trnh (1). Cl, Br...
c coi nh H v cng vo b.
|

+ Khi c nguyn t ho tr 3 nh N hoc P ... th phi s dng phng trnh (2) :

CaHbOcNd : DBE =

(2a + 2) (b d)
2

(2)

V d : C5H11N : cha 1 tng ng ni i. y c th l cht isopropylimin ca

acetandehit (1 ni i) hoc cyclopentylamin (1vng). Ngoi ra cn c th l nhiu cht
khc na. Nhng khi 1 trong 4 phng php ph xc nh c 1 ni i (C=C, C= N,
C=O) th kh nng vng b loi. Ngc li nu khng xc nh c ni i tc l phi
c 1 vng. iu u tin ngh ti l ph UV. Nu nghi ng c hai hoc nhiu ni i
tng ng trong phn t th s thy hp th mnh trong ph UV. Song, khi bt u
cng vic xc nh cu trc ca mt cht th cha nn ly qu nhiu thng tin t ph UV.
Thay vo l xc nh cc nhm chc trong phn t thng qua ph IR.

Ph NMR ( 1H v 13C) s gip ta dng nn khung cacbon ca cht cn tm v kh

nng v v tr ca cc nhm chc trong phn t.
Ph khi (MS) cng gip ta xc nh s b khung C, H ca phan t da vo phn
mnh.
giai on ny cha c nh c th t cc thng tin thu c t cc phng php

ph.
Mt s v d :
V d 1 : Phn tch nguyn t v MS cho bit cng thc C4H8O cha 1 tng
ng ni i.

UV : max = 295 nm
Tnh hng s hp th :
=

Hp th . TLPT (trng lng phn t)

Lng cn trong 100 ml . dy cuvet bng cm

Trng hp ny : =

0,28.72.100
= 19
106.1

Nh vy l yu n * ca keton hoc andehyt no (cng c th tp cht c hp

th mnh ?)
IR : * = 1715 cm

(mnh) carbonyl

khng c vch 2700 2900 cm

trong IR ( *C H andehyt) khng c andehyt.

1

khng c tn hiu = 9 10 ppm trong HNMR (H andehyt)

V ch c 1 tng ng ni i v 1 d nguyn t nn l keton carbonyl.

Xc nh khung cacbon
13C-NMR cho bit 4C l khc nhau, mt trong s l C=O v : = 208,79 ppm v
cng yu (cacbon bc 4)
1H-NMR : = 2,4 q CH2
2,09 s CH3 nh vi C bc 4

H 3C C
O

1,04 t CH3
CH3 C
||

Tch phn (Intergral) : 2 : 3 : 3

29,37

H3C

36,80

7,86 ppm

CH2

CH3

43

MS :

m/z : 72, 57, 43, 29

29

57

V d 2 :
Cng thc cng : C11H20O4 tnh c hai tng ng ni i.
UV : khng cho hp th ca hai ni i lin hp.
1

IR : + nh C=O mnh ti 1740 cm

( keton vng 5 hoc ester no)

+ nh >C=C< khng thy trong IR hai tng ng ni i phi l hai nhm

carbonyl hoc 1C=O v 1 vng.
+ khng c OH 4 O l ca keton, ester hay ete.

13

C-NMR : ch c 8C khc nhau, nh vy c mt s C xut hin cng v tr do cu

trc i xng trong phn t.
1

H-NMR : + Tn hiu thp nht = 4,12 ppm (q) OCH2CH3. = 1,3 ppm (t)

thy r, tuy t l cng 1 : 2 : 1 khng r do trng lp.

+ Cng ca OCH2 quartet tng ng 4 H c th c hai nhm
OCH2CH3 ging nhau.
+ Kt lun : OCH2CH3 thuc nhm ester (COOCH2CH3)
+ = 3,2 ppm (t) tch phn cho bit l 1 H, v ht O ( 2 COOEt),
2 tng ng ni i

O
C
O

Triplett 3,2 ppm l ca nhm CH2CH(COOC2H5)2

+ Quartet ca 2 H : = 1,88 l ca : CH2CH(CO2C2H5)2

c 1 nhm CH2 na cnh ta c
CH2CH2CH(CO2C2H5)2

+ Triplett = 1,00 l ca CH3CH2.

3

+ Tn hiu ca CH3CH2 c l b trng vi triplett = 1,3 ppm.

171

173

O
O
O

13

C-NMR : + Hai CH3 : 13,81 v 14,10. 14,10 tn hiu gp 2 v cng .

+ H2CCH2CH2 : 22,38 ; 28,49 ; 29.53.

COOH

: 52,03

HC
COOH

+ 61,12 ppm:

+ 169,32 ppm:

CH2
COOEt

OH

OC2H5

m* = 83

m/z = 115

OEt
C2H5CH CH2

OEt

m/z = 13

COOEt

COOEt

- MS :

C2H3

m/z = 160 (pic c s)

Phn ct v chuyn dch

m* = 110,5

V d 3 :
L ho cht trong kho c ghi nhn l metylpropylxeton. Kim tra xem c ng cht

y khng ?
Ph s 5 -7
*) IR : + 1720 cm

O
R C
R'

+ 1380, 1360 khung CH2, CH3 IR ph hp vi cu trc ghi trn nhn.

71

+.

*) MS : m/z = 86 M ion phn t

m/z = 71 [ M- CH3]

H 3C

CH 2

CH2

CH 3

O
43

m/z = 43 mnh nht [H3CCO]+ ( base peak, pic c s)

m/z = 57 mnh [MC2H5]+ kh gii thch

m/z = 58 [MC2H4]+
*) 1H-NMR :
H3C C

: ~
~ 2,4;
~ 2,11; C CH2 : ~
O

C CH2 CH2

: ~
~ 1,0ppm
~ 1,6; H2C CH3 : ~

bi, v t l ng tch phn : khng tht ph hp .

V d : T l 2,4/2,11/1,6/1,0 c tch phn : 3,04/3,00/2,01/4,65 H trong khi ng l

phi l 3/2/2/3 H.
Triplett 1,00 ppm l 2 triplett trng nhau. Triplett th nht l : tn hiu 1,11 ; 1,03

v 0,95 ; triplett th hai l 0,98 ; 0,90 ; 0,81. Hai triplett c J = 7 Hz.

Triplett 2,4 ppm : 2,49 ; 2,41 ; 2,32 ppm km theo quartet 2,55 ; 2,46 ; 2,38 ;

2,30.
Tn hiu 6 vch 1,6 ppm (t l cng 1 : 5 : 10 : 10 : 5 : 1) v singulet 2,11

ppm l sch.
Cht ghi trn nhn l metylpropylxeton c ln mt ng phn. ng phn ny cha

nhm carbonyl ( > C= O) v nhm CH 2 gn trc tip vi CH3 (2,4 ppm) cc kh

nng nh sau c th xem xt:
O

Ta c th loi cu trc 4, 5 v 6 ra v khng ph hp d kin ph. Trong ph IR v

1

H- NMR khng c nhm andehit (IR: * 2600-2830cm-1. 1H- NMR: 8-10 ppm) khng
phi 4. Cn 5 khng cha nhm - CH2 -; 6 khng cha nhm xeton.
*) 1H-NMR : cho thng tin v t l hai ng phn :
Ta tr gi tr tch phn : 3,04 H (chun 2,11 ppm = 3H) ca tn hiu 2,4 ppm c

2H th cn 1,04H. Gi tr ny tng ng (l ca) 4H v tr - ca ng phn

T l 2/3 = 1 : 0,26 (1.04 4H, vy 1H tng ng 0,26)
1,26 = 100% 79% (2)
1,00 = X 21% (3)
0,26 = Y
V d 4 :
5

 MS : khng c ion phn t. T phn tch nguyn t ta c cng thc C5H11NO4. C

mt tng ng ni i nhng khng phi C=O, v

IR : 1600 1900 cm

1545 cm

khng c nh no.

: nh mnh, c th ca NO2 ; 3350 cm

: OH.

UV : = 275 nm ( = 24) c th n (khng c pic ion phn t trong MS,

thng thy vi cc hp cht NO2, mch thng, no).

13

C-NMR : C 4 nhm C : 2C trong cng mt mi trng t v chng trng nhau

(cng ln). Nh vy rt c th c hai nhm ging nhau, i xng trong phn t.
1

H-NMR : 4H = 4,12 ppm

2H = 3,32 (t)
2H = 2,00 (q)
3H = 1,00 (t)
|

C nhm C2H5 (CH2CH3) v nhm CH2 nh vi cacbon bc 4 C

|

13

C-NMR (khng kh tng tc proton) :

Nhm CH2CH3 cho 1 quartet 7.66 ppm v mt trong hai triplett 25,77 hoc
63,51.
Nguyn t C bc 4 cho mt tn hiu yu 94,23 ppm.
Hai C ging nhau nh vy phi l mt trong hai triplett. Triplett 63,51 c cng
gn gp 2 triplett kia, nh vy n thuc v 2C ging nhau. N trng thp nn phi
gn vi d nguyn t.

H-NMR sau khi lc vi D2O (nhn ph trn) th triplet ca 2H 3,32 bin mt

tn hiu ny do hai nhm OH gy ra v 2 OH ny gn vi CH2.

Nh vy hai nhm ging nhau ny l CH2OH. Ta c cc phn nh sau
NO 2
NO 2 ,

HO

OH

( CH 2

OH) 2

 Sau khi lc vi D2O, CH2OH cho mt quartet ca h AB : A = 4,00 ppm, B =

4,24, JAB = 12 Hz Nhm CH2OH c gn vo mt trung tm "gi bt i" (prochiral):
HA

CH2 CH3

HA

CHAHBOH HO

OH
HB NO2

HB

V d 5 : *) T MS v phn tch nguyn t thu c C8H8O2 5 tng ng ni

i.
*) UV : h thng khng no mnh : max = 316 nm (max = 22000).
4 hoc 5 ni i.
*) IR : Ch c t lin kt CH no 2880 2980 cm

Hai nh 1695 v 1675 cm

Aryl, C=CH 3100.

hoc , -keton khng no, andehit hoc COOH,

loi COOH v khng c nh 2500 3000 (OH). Loi c andehit, v 1H-NMR vng 9
10 ppm khng c tn hiu c th l mt keton.
1

1615 cm

1555 v 1480 : nhn thm.

: C=C lin hp hoc aryl lin hp.

*) 13C-NMR : 8 tn hiu, tr mt metyl 27,83 (q) cn li 7 tn hiu vng khng no

( > 100 ppm), 1 carbonyl 193,36 ppm.
*) 1H-NMR : 2,29 s sc CH3CO, mnh [M15]+ m/z = 121 (pic c s) ng h
iu .
C6H5O C CH3

O
(Keten)
H2C C
C6H5O
m/z = 94

- CH3

C6H5O C O

m/z = 121

- CO

C6H5O

m/z = 93

+
H3C C O+
m/z = 43

*) 13C-NMR (off resonance) : H phn chia ra cc C

*) 1H-NMR trong dung mi CCl4 khng phn gii tt. Khi cho thm 10% benzen vo
th ph phn gii tt hn.
7

- C dublet vi J = 16 Hz H AB ni i trans hai ln th (IR : 970 mnh).

Chc c cc phn :
H
H3C

C
O

Y
C

, X v Y khng c proton

Phn cn li l C4H3O, khng cha carbonyl v OH, 3 H nh

vi C khc nhau.

Vn cn li : th hay
3 H cn li c cc tn hiu : 6,46 ; 6,62 ; 7,48[rpm l mt
furan th .
H : J = 1,5 Hz (d) ; H = d, J, ' = 3,5 Hz (vch 2, 3)

H '
O

H = (q) (vch 5 8) J' = 3,5 Hz, J = 1,5 Hz.

V d v kt hp cc phng php ph

1. V d 1 : Ph 1 4
Bi ton : Xc nh cu trc ca cht 1.
MS : + m/z = 215 v 217 cng bng nhau c Br trong phn t (79 v 81).
m/z = 169 v 171
m/z = 136 pic c s (base peak) khng cn Br- do ct mnh
+ cn cha 1 N trong phn t (s l trong TLPT)
[M16]+. : m/z = 199, [M46]+ m/z = 169

C NO2

[MBr16]+ : m/z = 120, [MBr 30]+ : m/z = 106

IR : + hai nh mnh : * = 1530 v 1345 cm

- c trng cho nhm NO2 v

lin hp (v NO2 no : 1560 cm 1)

+ 1610 : nhn thm lin hp vi NO2.
1

Vch 1600, 1450, 1400 cm

ca nhn thm khng thy, c th do yu qu.

+ *C H : 3100 3300 ca nhn thm (dao ng ln, xung vi mt phng vng

thm ).
8

+ 855 cm

: mnh th para nhn thm

NO2

NO2

c th c kh nng cu trc A:
B

Br

Nh vy gc R phi cha Br : d on R = CH2Br (m/z = 215).

Cn chng minh l p-aromat :

UV : ging UV ca p-nitrotoluen [max = 272 nm, log = 3,99 trong EtOH]

1H-NMR : ph hp vi cu trc B v c 3 nhm tn hiu nh sau :
+ Singulet = 4,52 ppm
+ Dublet 7,62 v 8,25
+ ng tch phn cho t l cng : 1 : 1 : 1
+ CH2 cho singulet (tnh ton l 4,45 ppm, thc nghim : 4,52 ppm).
+ H v tr ortho vi NO2 : tnh ton : 8,21, tm thy 8,25
H m-NO2 : tnh ton 7,52, tm thy 7,62
O

O N O

NO2

- NO

- Br

Br

m/z = 136

+
- CO

m/z = 106

Xc nh cu trc bng phng php NMR hin i

1. T trng cao

Nam chm siu dn c lm lnh bng He lng (cryomagnet)

Hin c n thit b c nam chm 700 MHz hoc cao hn.

Nam chm in t thng thng c cng t trng ti a l 100 MHz.

*) u th ca t trng cao :
nhy tng do tng hiu s phn b trng thi ht nhn
Ghi ph nhanh hn
phn gii tt hn

2. 13C-NMR mt chiu (DEPT)

DEPT : Distortionles Enhancement by Polarization Transfer) cho thng tin v s

proton gn vi (

CH3

, CH2 ,

CH

), v cacbon bc 4 (

APT : Attached Proton Test: Thy cc tn hiu ca cacbon gn vi proton (CH3 ,

CH2 , CH), cacbon bc 4

10