BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 30 (30-03-2020)

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 1H and 13C-NMR technique
13C-NMR provides information on:
• Number of chemically different carbons: The number of distinct kinds of carbons
atoms present equals the number of peaks in a proton decoupled 13C spectra.
• The All carbon peaks appears as singlets when decoupled from protons.
• Chemical shift information: The chemical environment of the carbon
• chemical shift (dc) is given in ppm, the usual range = 0-250 ppm with the zero being
the methyl carbon in TMS.
• 13C are shielded and deshielded (chemical shift) due to the same factors as for 1H-
NMR.
• Electron withdrawing ability of the nearby group
• Hybridization
• Electron current effects
• Information from 1H and 13C-NMR
1. Number of signals (chemically different nucleus)
2. Chemical shift of signals (shielded or deshielded w.r.t reference)
3. Intensity of signals (population difference, number of nuclei)
4. Spin-spin splitting of signals (interaction with nearby nucleus, only for 1H)
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 Topics to be covered

30-31 Conformations Rotation around sigma bonds, T2: 4.8-4.9, • Conformation and
conformational analysis of butane, 4.10 (SS), configuration of acyclic
cyclohexane, and di-substituted 4.11-4.12, and cyclic i.e.
cyclohexanes 4.13 substituted cyclohexane
32-34 Stereochemistry Isomerism, chirality, origin of T2: 5.1-5.14, • Concept of chirality and
optical activity, stereochemistry of 5.15-5.18, optical activity, learn to
cyclic & acyclic saturated and 7.2 stereochemistry for
unsaturated, resolution. compound having chiral
carbon and resolution of
enantiomers
35-37 Aromaticity & Huckel rule, aromatic compounds, T2: 14.7- • Concept of aromaticity
Pericyclic electrocyclic and cycloaddition 14.8B; 15.1- and related rules.
reactions reactions 15.11 Different pericyclic
reactions including
cycloaddition
38-41 Reaction Nucleophilic (SN1, SN2, SNAr etc.) T2: 6.2-6.13; • Nucleophilic and
Mechanisms and electrophilic substitution 7.5-7.9, electrophilic substitution
reactions; electrophilic addition 20.12 reactions
reactions; Elimination reactions T2: 8.1 (SS), • Different addition and
(E1, E2 and Hoffmann and Cope 8.2-8.9, 8.12- elimination reactions
elimination) 8.15, 10.9
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Organic Chemistry: Chemistry of Carbon Compounds

Chemists invent molecules. Biologists apply molecules.

Physicists study molecules. Engineers fabricate molecules.
Public enjoys molecules.
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 Isomers: The Same But Not The Same
Constitutional Stereoisomers
or structural isomers (spatial isomers)
The compounds that have identical The compounds that have identical
molecular formulas but different molecular formulas and same
connectivity of atoms and connectivity of atoms but different
properties: arrangement of atoms in space:
1) Chain isomers. 1) Conformational isomers
2) Positional isomers. (conformers).
3) Tautomers. Rotating about bonds (Bond breaking
not required)
(Bond breaking required)

2) Configurational isomers: (Bond

breaking required)
▪Enantiomers.
▪Diastereomers

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CONFORMATIONS
➢ Two methyl groups in ethane are not fixed in a single position.
➢ They rotate about the sigma bond connecting two carbon atoms,
maintaining the linear bonding overlap.
➢ The different arrangements formed by rotation about single bond
are called conformations and a specific conformation is called a
conformer.

Since conformations differ from each other only in the way their
atoms are oriented in space, they are stereoisomers.
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 Conformations
Conformations are represented by two kinds of formulas
(1) Sawhorse formula & (2) Newman projection formula

sawhorse Newman projection

Dihedral angle (θ): Angle between the C-H bond on the front
carbon atom and C-H bond on the back carbon atom in
Newman projection.
Eclipsed conformation: (θ= 00)
Staggered conformation: (θ= 600)
Skew conformation: (θ= anything else)
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CONFORMATIONS

Sawhorse

Newman

Eclipsed Staggered Skew

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CONFORMATIONS
Conformational analysis: study of energetics of different
conformations.
Potential energy of the molecule changes as the groups within
rotate about C-C bond.
❑ Minimum for the staggered conformation
❑ Increases with rotation
❑ Maximum at the eclipsed conformation
Torsional Strain: It is the resistance to twisting (torsion) as
molecule rotates toward an eclipsed conformation.
The energy difference between staggered and eclipsed
conformers is called torsional energy.
At any given moment all molecules do not exist in most stable
conformation; rather a higher percentage of molecules are present
in a more stable conformation than any other arrangement.
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Conformational analysis
For ethane molecule torsional energy is about 12.6 kJ/mol

For propane molecule torsional energy is about 13.8 kJ/mol

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Conformational analysis of n-Butane
Rotation about the C2-C3 single bond

❑ The barriers to rotation are far too small to allow isolation of the different
staggered conformations or conformers, even at temperatures considerably
below rt.
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Conformational analysis of n-Butane
Free rotation around C2-C3 bond in n-butane
• Highest energy has methyl groups eclipsed.
• Lowest energy has methyl groups anti.
• In between, methyl-methyl gauche
& methyl-H eclipsed.

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CONFORMATIONS
• Anti conformation is lowest in energy.
• “Straight chain” actually is zigzag.
• A staggered conformation with two larger groups 180° from each
other is called anti.
• A staggered conformation with two larger groups 60° from each
other is called gauche.
• In most of the cases staggered conformations are lower in energy
than the eclipsed conformations.
• The relative energies of the individual staggered conformations
depend on their steric strain.
• Steric strain is an increase in energy resulting when atoms are
forced too close to one another.
• Gauche conformations are generally higher in energy than anti
conformations because of steric strain.
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Conformational analysis
• Increase in torsional strain (from 12.6 kJ/mol to 13.8 kJ/mol)
from ethane to propane is due to more bulky methyl group.
• Other factors such as van der Waals attraction or repulsion,
dipole-dipole interaction, hydrogen bonding etc. also affect the
stability of conformations.
• The tendency for the bond orbitals on adjacent carbons to be
staggered remains, and any rotation away from staggered
conformation is accompanied by torsional strain.

3.0

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Conformational analysis
The gauche effect: X-C-C-Y containing compounds (where X
and Y are electronegative groups) adopt gauche rather than anti
conformations – despite this conformation having a larger overall
dipole. For example, for 1,2-difluoroethane the gauche
conformation is more stable by 2.4 to 3.4 kJ/mole in the gas
phase.
– Stabilization accrues from σ → σ* interactions between the best
combinations of anti-periplanar donor and acceptor bonds.

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Conformational analysis
Hydrogen bonding affect
In the case of 1,2-ethanediol an
intramolecular H-bond also
stabilizes the gauche form.

Compounds with the general formula OHCH2CH2X are found to

be stable in their gauche conformation when X = OH, NH2, F, Cl,
Br, OR, NHR, NR2 etc.

Solvent polarity affect

What about NH2CH2CH2CHO or NH2CH2CH2CO2H or +XCH2CH2Y- ?

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