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Problem of spectroscopy

Teacher: Nguyen Thien Thao

Students: Group 7
Pham Van Trung
Duong Thi Hai Hoa
Contents

 Mass spectroscopy
 Problem 1
 Problem 2
 Problem 3
 Problem 4
Summary

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Mass spectrum

 Molecular ion peak (M+) m/z corresponds to molecule

weight of singly-charged molecule.
 In general the following group of compounds will, in
order of decreasing ability, give prominent molecular
ion peaks: aromatic compounds> conjugated alkenes
> cyclic compounds > organic sulfides > short, normal
alkanes > mercaptans.
 Fragment peak m/z less than molecule weight of
singly-charged molecule.
 Base peak most intense m/z
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Mass spectrum

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Mass spectrum
 Isotopes: present in their usual abundance.
 Hydrocarbons contain 1.1% C-13, so there will be a
small M+1 peak.
 If Br is present, M+2 is equal to M+.
 If Cl is present, M+2 is one-third of M+.
 If iodine is present, peak at 127, large gap.
 If N is present, M+ will be an odd number (The
nitrogen rule)
 If S is present, M+2 will be 4% of M+.
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Mass spectrum

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Problem 1

 A organic compound consists 68.5% C, 4.92%

H and 26.23% O.
 Following are MS,1H-NMR, 13C-NMR, and IR
spectrum for a compound.
 Determine the structural formula of organic
compound.

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Solution
 Using for CxHyOzNt
%C % H %O % N
x : y : z : t  nC : nH : nO : nN  : : :  a:b:c:d
12 1 16 14

 A organic compound consists 68.5% C, 4.92% H and

26.23% O have
68.5 4.93 26.23
: :  5.7 : 4.93 :1.64
12 1 16
 We have ratio 3.5: 3:1 and the simple formula is
(C3.5H3O)n
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Mass spectrum
Base peak

M+

M+ +1

-CHO
M+ +2
-OH

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Solution
 Most intense m/z at 121 is base peak.
 The presence fragment peak m/z at 77  aromatic
compounds the molecular-ion peak M is strong.
 We can determine molecular-ion peak m/z at 122
because it is usually the peak of highest mass number
except for the isotope peaks.
 Molecule weight is 122 (C3.5H3O)n = 122  n = 2
 Molecular formula is C7H6O2

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Solution
 Degree of unsaturated a compound C7H6O2

(2.7  2)  6
S  5
2
 Look for an aromatic ring in IR spectrum.
 Also look for a carbonyl, a double bond, or a ring because
the degree of unsaturated is 5

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IR spectrum

C-H stretch of
Aldeheyde

O-H C-H stretch of

stretch Aromatic C=O C- C in ring C-O

A compound have Aromatic ring, O-H group and H-C=O group

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H-NMR of spectrum
1

RCHO

Aromatic C-H
OH
Phenol

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13
C-NMR of spectrum
A compound have seven type
RCHO
of carbon one of C=O and six
carbon in aromatic ring.
OH

CHO

2-hydroxybenzaldehyde

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Problem 2 C10H15N

 A organic compound have a molecule formula

C10H15N .
 Following are IR, 1H-NMR, 13C-NMR, and
DEPT spectrum for a compound.
 Determine the structural formula of organic
compound.

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Solution
 Degree of unsaturated a compound C10H15N
(2.9  2)  12
S 4
2
 Look for an aromatic ring in IR spectrum because the
degree of unsaturated is 4.

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IR spectrum of C10H15N

C-H stretch C-H stretch

of Aromatic of Alkanes

C-N stretch of
C- C in C-H oop
Aromatic
ring
amine
C-H bend of
Alkanes
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Solution
 A compound have N and C-N stretch aromatic amines
but hasn’t the absorption at 3400 - 3250cm-1
corresponds to a N-H stretch of primary, secondary
amines, amide.
 A compound is a tertiary amine and have one
aromatic ring.
N

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H-NMR of spectrum
1

6H
A compound have 15 H.
From the integration, the
hydrogens in the ratio 2:3:4:6
Alkanes
Aromatic
4H

3H
2H

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13
C-NMR of spectrum
Alkanes
In 13C-NMR of spectrum
have 6 types of two in e c
b a
region alkanes and 4 in
Aromatic.

Aromatic d

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 DEPT spectrum

CH2

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Structure formula

b b
a N a

c f c

e d e

N,N-diethylbenzenamine

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Problem 3

 A organic compound consists 90% C, 10% H.

 Following are 1H-NMR, 13C-NMR, IR and mass
spectrum for a compound.
 Determine the structural formula of organic
compound.

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Solution
 A organic compound consists 90% C, 10% H and have
90 10
:  7.5 :10
12 1

 We have ratio 1:4/3 and the simple formula is (CH4/3)n

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Problem 3: C9H12

Base peak

M+
M+- 29
- C2H5

C6H+5
M+- 15 M++1
- CH3

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Solution for test
 Most intense m/z at 91 is base peak.
 The presence fragment peak m/z at 77  aromatic
compounds the molecular-ion peak M is strong.
 We can determine molecular-ion peak m/z at 120 have
an isotopic peak at (M+ + 1) is 121  Molecular ion
peak (M+) m/z = 120 corresponds to molecule weight
is 120. Using for(CH4/3)n = 120  n = 9
 Molecular formula is C9H12

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Solution for test

 Degree of unsaturated a compound C9H12

(2.9  2)  12
S 4
2
 Look for an aromatic ring in IR spectrum because the
degree of unsaturated is 4.

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IR spectrum of C9H12

C-H stretch C-H stretch

of Aromatic of Alkanes C-H rock of
C-C stretch in Alkanes or
ring aromatic C-H oop
aromatic

C-H bend of Alkanes

A compound have aromatic and anlkanes ( C-H oop aromatic)

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1
H-NMR of spectrum

Alkanes
Aromatic

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1
H-NMR of spectrum

CH3
Aromatic

CH2-CH2 -CH3
Ar-CH2

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13
C-NMR of spectrum

A compound
have seven type Alkanes
of carbon.

Aromatic 1-propylbenzene

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Problem 4

 A compound: %C = 55.17, %H = 8.06, %O = 36.78

 Following are H-NMR, C-NMR and MS for a
compound.
 Determine the structural formula of organic
compound.

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Problem 4

 Using for CxHyOz

55.17 8.06 36.78

: :  4.6 : 8.06 : 2.3
12 1 16

 Ratio 2: 4: 1  the simple formula is

(C2H4O)n

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Mass of spectrum

M+

M++1

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 Mass spectrum

 Most intense m/z at 129 is base peak.

 Don’t presence fragment peak m/z at 77  Don’t
have aromatic compounds.
 We can determine molecular-ion peak m/z at 174 have
an isotopic peak at (M+ + 1) is 175  Molecular ion
peak (M+) m/z = 174 corresponds to molecule weight
is 174. Using for (C2H4O)n = 174  n = 4
 Molecular formula is C8H14O4

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Solution

 Degree of unsaturated a compound C8H14O4

(2.8  2)  14
S 2
2

 A compound can has two total carbonyl, and/or

double bond, and/or triple bond

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IR C8H14O4

C-H
(alkane)

C-H
bend
Alkanes
C=O C-O

A compound have C=O and C-H alkanes

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H-NMR of spectrum C8H14O4
1

There are four types of hydrogen

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 C8H14O4

R-CH2-CH3

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 C8H14O4

R-CH-CH3

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 C8H14O4
R-CH-CH3

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 C8H14O4

R-CH2-CH3

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 C8H14O4
 1H NMR show four signals:
 6H: triplet
 3H: doublet
 2H: multiplet
 1H: tetraplet
 1.21 – 1.26 ppm: RCH2CH3
 1.36 – 1.4 ppm: RCHCH3
 3.36 – 3.42 ppm: -OOCCHCH3
 4.1 – 4.22 ppm: -OCH2CH3

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 C-NMR of spectrum C8H14O4
13

RCH3

R3CH
RCH2R

RCOOR

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 C8H14O4
 13C NMR shows four signals:
 13.5, 13.9: RCH3
 46.1: RCH2R
 61.2: R3CH
 170.1: RCOOR

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 C8H14O4
 Propose a structure:

O O
CH3CH2O C CH C OCH2CH3
CH3

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Summary
Six step Analyze the spectra
 Step 1: Determine the simple formula;
 Step 2: Using mass spectroscopy determine the molecule formula
of organic compound;
 Step 3: Calculate the degree of unsaturated a organic compound;
 Step 4: Using IR spectroscopy detecting certain functional groups
in a molecule;
 Step 5: Using NMR (1H-NMR and 13C-NMR spectroscopy,
DEPT) gives valuable data about the carbon chain.
 Step 6: Put this information together to arrive at the following
structural formula.
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 References
 [1]. Các phương pháp phân tích quang phổ trong Hóa học Hữu cơ. Tiến sĩ
Nguyễn Thanh Hồng, Nhà xuất bản khoa học và kỹ thuật.
 [2]. GS-TS Khoa học Nguyễn Đình Triệu, Các phương pháp phân tích vật
lý và hóa lý- tập 1
 [3]. A Handbook of Spectroscopic Data CHEMISTRY (UV, IR, PMR,
13CNMR and Mass Spectroscopy) B.D. Mistry B.K.M. Science
College.Valsad - (Gujarat)
 [4]. Brooks Cole - Organic Chemistry 5edition by Brown; Foote; Iverson
and Anslyn. Chapter 12, 13 and 14. page 456-540
 [5] Dr. Walt Volland, Bellevue Community College All rights reserved
1999, Bellevue, Washington
 http://orgchem.colorado.edu/hndbksupport/spectprob/problems.html
 http://www.chem.ucla.edu/~webspectra/

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