Solve the following spectral problems as far as possible give possible

justifications. Also predict the fragmentation pattern.

1. An organic compound C6H10O4 shows the following spectral data.
UV: No significance absorbance above 210nm
IR: Significant absorption band at 1760, and 2950 cm -1.
PMR:  1.5 (3H, d, J = 7cps),  2.2 (6H, s)and 6.8 (1H, q,J = 7cps).
CMR (Proton decoupled): Four signals at  = 18, 20, 88, 168.
CMR (Off resonance decoupled): two overlapping quartets at  19, One doublet at  88, One singlet  168.
Mass: Prominent peaks at m/e 146, 87 and 43.
Deduce the structure of the compound.

2. An organic compound C3H5O2Br shows the following spectral data.

UV: max 223 nm, max100
IR: Significant absorption band at 2900-3125, 2690, 2600, 1715, and 1440 cm -1.
PMR:  1.83 (3H, d, J = 7cps), 4.52 (1H, q, J = 7cps) and4.93 (1H, s,exchange with D2O).
Mass: Prominent peaks at m/e 151/154, in the ratio 1:1.
Deduce the structure of the compound.

3. An organic compound C6H10O2 shows the following spectral data.

UV: max 250 nm
IR: Significant absorption band at 3000-2900, 1705, and 1180 cm -1.
PMR: 2.2 (6H, s), 2.7 (4H, s) and  4.93 (1H, s, exchange with D2O).
CMR (Proton decoupled): Three signals at  = 28, 36, 208.
CMR (Off resonance decoupled): One quartet at  28, One Triplet at  36, One singlet  208.
Mass: Prominent peaks at m/e 214, 99 and 43.
Deduce the structure of the compound.

4. An organic compound containing C, H, and Oxygen shows the following spectral data.
UV: max 274 nm, max17
IR: Significant absorption band at 2900, 1705, and 1460 cm -1.
PMR:  2.48( q, J = 7.2cps),  2.12(s) and 1.07 (t, J = 7.2cps)In the intensity ratio 2:3:3
CMR (Proton noise decoupled): Four signals.
CMR (Off resonance decoupled): One quartet at 8.00, One quartet at  38, One singlet  209.
Mass: Prominent peaks at m/e 72, 57, 43and 29.
Deduce the structure of the compound.

5. An organic compound containing C 9H10 O2 shows the following spectral data.

UV: max 257 nm, max 194
IR: Significant absorption band at 3040, 2950, 1740, 1480, 1440, 1220, 750 and 700 cm -1.
PMR: 1.96( 3H, s), 5.00(2H, s) and 7.22 (5H, s)
CMR (Off resonance decoupled): Two singlets, One triplet, One quartet and three doublets. One of
singlet is at  171 and other is at  136.
Mass: Prominent peaks at m/e 150, 108, 91, 79, 78 and 77.
Deduce the structure of the compound.

6. An organic compound containing C 5H11Cl shows the following spectral data.

IR: Significant absorption band at 2950, and 800 cm -1.
PMR:  1.00( 3H, t, J = 7cps), 1.6(6H, s) and 1.8 (2H, q, J = 7cps)
CMR (Off resonance decoupled): Two quartets, tripletand Onesinglet, singlet is at  70.
CMR (Proton decoupled): four singlets
Mass: Prominent peaks at m/e 106/108(3:1 ratio), 70 and 55.
Deduce the structure of the compound.
7. Explain the spectral data and deduce the structure of the compound from the given spectra
8. Explain the spectral data and deduce the structure of the compound from the given spectra
9. Explain the spectral data and deduce the structure of the compound from the given spectra
Answers:

O 5.
O C O
CH3
H3C HC CH2 O C CH3
O C CH3 Cl
1. O
H3C C CH2 CH3

6. CH3
H3C CH COOH

2. Br
O
CH2 C CH3
7.

O O

3. H3C C CH2 CH2 C CH3

O
C CH2 CH3
8.

4. H3C C CH2 CH3 (solved problem) OH

9. H3C CH CH2 CH3

Solved Problem 4 :

UV:  max 274nm, max 17

IR: band 2900, 1705, and 1460Cm-1
PMR:  2.48 (q, J= 7.2 cps), 2.12 (s) and 1.07 (t, J=7.2 cps) in the intensity ratio of 2:3:3.
13C NMR: (proton noise decoupled): Shows four signals.
13CNMR (Off resonance decoupled):  = 8.00 (q), 29 (q), 38(t) and 209 (s)
Mass: Prominent peak 72(M+), 57, 43, and 29.

Solution:

Analyzing the UV spectra: 


- Absorbance at UV region with low molar absorptivity shows the
presence of C=O chromophore and n to * transition. n n transtion


Analyzing the IR spectra: 

- Presence of band at 2900cm-1 indicates the presence of C-H stretch.(Most of hydrocarbon gives
this absorption).
- Presence of band at 1705cm-1 indicates the presence of C=O stretch.
- Presence of band at 1460cm-1 indicates the presence of C-H bending.

Analyzing the PNMR,C13 spectraand C13 off resonance decoupled spectra:

- Three peaks at ,…… , …, represents three types of non equivalent protons.

- Quartet, Triplet, and singlet peaks shows the presence of 3, 2, and no neighboring protons.
- The intensity ratio of 2:3:3
- Presence of 4 kinds of non equivalent carbons.
- It also shows that two of the carbon is linked with 3hree protons, one carbon is linked with two
proton and one of the carbon with singlet has no proton in it.
- The positions are also indicated by chemical shift values. (presence of electronegative species
and anisotropic nature affects the chemical shift values)
Tentative NMR spectras:
Analyzing the Mass spectra.

- Mass of the molecular ion peak 72, 57,

- Peak at 29, may predict the presence of CH 3CH2
- Peak at 57, shows the loss of 72 – 57 = 15 mass, which suggest the presence of CH 3 loss.
- Peak at 43, shows the loss of 72 – 43 = 27 mass, which suggest or confirms the presence of
CH3CH2.

Fragmentation patterns

O + O
+ +
H3C C CH2 CH3 H3C C O H3C C H2C CH3
m/z = 43
stable ions/radicals
m/z = 72

O O
+ +
H 3C C CH2 CH3 O C CH2 CH3 H3C C

m = 72 H2C
+
CH3
m/z = 57
m/z = 29

O + O
+ +
H3C C CH2 CH3 H3C C O H3C C H2C CH3
m/z = 43
stable ions/radicals
m/z = 72

O O
+ +
H 3C C CH2 CH3 O C CH2 CH3 H3C C

m = 72 H2C
+
CH3
m/z = 57
m/z = 29

The compound is: Butanone

 O
H3C C CH2 CH3