Chem110 Notes

Block 1: Unit 1
Differences between ionic and covalent bonding
Ionic bond
Covalent bonding
o Bonds
End on overlap of AO
bond
Sideways overlap of AO
bond
o bond weaker than bond
addition reaction occur in bond
o Tetravalent
Carbon forms 4 bonds in neutral compound
o Single bond
( 2 electrons)
o Double bond
+ (4 electrons)
o Triple bond
+ 2 (6 electrons)
o Valence: number of bonds to an atom in a stable neutral (uncharged) molecule.
Carbon=4
Nitrogen=3
Oxygen/sulphur=2
Halogen=1
o Single bond>double bond>triple bond (decrease bond length, increase bond
number, increase number of electrons)
Rotation
Not possible in a C-C multiple bond.
Possible in C-C single bond (not in rings)

Bonding in organic compounds
Completely filled outer shell of electrons is a stable arrangement
Atoms
o Loss or gain electrons to achieve completely filled outer shell
Form ions
o Share electrons
By atomic orbital (AO) overlap covalent bonds
Covalent bond
Bonds
o End on overlap of AO
bond
o Sideways overlap of AO
bond
bond weaker than bond
o addition reaction occur in bond
Tetravalent
o Carbon forms 4 bonds in neutral compound
Single bond
o ( 2 electrons)
Double bond
o + (4 electrons)
Triple bond
o + 2 (6 electrons)
Valence: number of bonds to an atom in a stable neutral (uncharged) molecule.
o Carbon=4
o Nitrogen=3
o Oxygen/sulphur=2
o Halogen=1
Single bond>double bond>triple bond (decrease bond length, increase bond number,
increase number of electrons)
Rotation
Not possible in a C-C multiple bond.
Possible in C-C single bond (not in rings)
Functional groups
Is an atom (not H) or a group of atoms (not alkyl) attached to carbon(s) in an organic
compound. It can also be a carbon to carbon multiple bond, which is part of the
molecular framework.
Where reactions usually happen (hydrocarbon chain quite unreactive)
Geometry about carbon


Notation (hybridization state)
Non-hybridised state
sp
3

o s+p+p+p
o 4 equivalent bonds
sp
2

o s+p+p
o 3 sp
2
orbitals + p
sp
o s+p
o 2 sp orbitals +2p
Nomenclature
Meth(1), Eth(2), Prop(3), But(4), Pent(5), Hex(6), Hept(7), Oct(8), Non(9), Dec(10)
Longest straight chain is the parent name
o *name must contain C=C for alkene
Identify and give lowest possible sum of numbers for substituents (alkyl, alkoxy,
chloro, etc)
Prefix contains the number of substituents
o *add cyclo- for cycloalkanes
C=C + oxygen containing functional group
o *Alk-#-en
Primary, secondary, tertiary alcohol, amino
Aliphatic: group not attached to aromatic ring.
Thiol: alkane thiol, thioether
Aromatic
Mono-substituted= substituent + benzene
Di-substituted
o Ortho (O-1,2), Meta (M-1,3), Para (P-1,4)
o *Use lowest sum of numbers.

Block 1: Unit 2
Constitutional isomerism
Isomer
o Same molecular formula
Same molecular formula but different atom to atom bonding sequence.
Types
o Position of functional group
o Type of functional group (alcohol vs ether)
Double bond equivalents (DBE)
o Degree of unsaturation
o DBE= # + # rings (even rings containing O)
o *N
1
= hydrogen of halogen
o

Stereoisomerism
Same molecular formula, same atom to atom bonding sequence, but different
arrangement of their atoms in space.
Conformational
o Interconvert by rotation about C-C single bond
o Interconversion requires no bond breaking
o Conformation: the particular shape the molecule adopts as a result of rotation
about bonds.
o 0= methyl group


Main example: Cyclohexane
o Chair
Each carbons wants 109.5
Not planar
2 distinct sets of bonds
Lowest energy conformer
Ring flip: all axial groups become equatorial and vice versa.
o Boat
No axial/equatorial classification



o Substituted
Steric interference: unfavourable interaction between groups
Favoured conformer
Largest atom/ groups in equatorial position.
Not possible to have all substituents in equatorial position
Largest groups in axial is more stable than both in equatorial position


Configurational
o Can only interconvert if a covalent bond is broken and reformed.
o Cis-Trans isomers
Atoms/groups held in different positions by ring or C=C
*1 atoms/group common to both sp
2
/sp
3

o E-Z system
Developed by Cahn, Ingold, Prelog
1. Atom with higher atomic number directly attached to carbon has
higher priority
2. If directly attached atom is the same go to the next atom until priority
can be assigned at the first point of difference.
Cis-trans in chair conformer
Draw the conformer to if
substituents are cis or trans to
each other
E.g. both axial= trans
Left is a general formula for
substituents in the same
orientation
3. Groups with double bonds are considered as being bonded to 2 of the
atoms by single bonds (e.g C=C has higher priority to C-C)
Z (zusammen)
o 2 higher (Hi) priority groups on the same side.
E (entgegen)
o Hi on opposite sizes
Enantiomer
Contains an asymmetric carbon with 4 different groups.
Molecule cannot be superimposed on it mirror image.
*Enzymes have enantiomers at its active site (specific)
Chiral: molecule contains stereogenic centre
Achiral
o has 2 identical atoms/groups
o plane of symmetry
o superimposable on its mirror image
Enantiomer differs in their interaction with a chiral medium/reagent (e.g plane
polarized light [PPL])
o Rotates to right
Dextrorotatory (+)
o Rotates to left
Laevorotatory (-)
Racemic mixture
o Equal amount of two enantiomers
o Has zero rotation of PPL
*sign, magnitude of rotation not convey configuration
Configuration conveyed by
o Fischer projection


o Steering wheel approach

Diastereomers: stereoisomers that have a non-mirror image relationship.

Block 1: Unit 3
Physical properties
Properties in relation to structure
Molecular size/ molar mass
o Increase molecular size increases boiling point
Due to increased van der Waals forces
Molecular shape
o Increasing branching decreases boiling point
Functional groups
o Degree of unsaturation
Little effect on boiling point
o Types (boiling point lowest to highest)
Alkanes-ether-halogeno-ketone-aldehyde-amino-alcohol-carboxylic
acid
Assume similar molar mass
Boiling point increases due to more polar bonds increasing
intermolecular interactions
Bond polarity
Overall polarity of a molecule depends on
o Size of hydrocarbon portion
o Nature of functional group
In organic molecules most bonds are covalent
Bonds range from strictly covalent (C-C) to polar bonds (O-H)
Polar bonds
o Electrons comprising bonds are not equally shared between bonded atom
One bonded atom carries
Partial positive charge (
+
)
Partial negative charge (
-
)
*Bond polarity measures the difference in electronegativity of bonded atoms
Electronegativity
Measure of ability of a bonded atom to attract electrons to itself
*Electrostatic potential maps

Increase electronegativity of bonded atoms increase polarity of bond
Partial negative charge
o More electronegative atom of the bond
Partial positive charge
o More electropositive atom of the bond
Trends
o Electronegativity C>H>B



Hydrogen bonding
Presence of O-H group
Lesser extent in N-H
C=O more polar than C-O
o More electrons available in bond
o Mobility of electrons
More H-bond
o Increase boling point
o Increase water solubility

Ionic bonds
More polar than H-bonds
Present in amine/ carboxylic acid salt
Water solubility
Functional group Relative polarity Water solubility
Hydrocarbon, halide, ether Low Insoluble
Ester, aldehydes, ketones,
amides, amines, alcohol,
acids
Intermediate Soluble up to 5 carbons

Amine/ carboxylic acid salts High Soluble up to 7 carbons
*Increasing hydrocarbon portion decreases water solubility
o Reverse in non-polar solvents
Chromatography
Polar
o Solute is more strongly attracted to polar stationary phase
Move slowly
Non-polar
o Solute is more soluble in mobile phage (relatively non-polar)
Move rapidly
Reaction classification
Substitution
o One atom or group is replaced by another
o Same DBE
Addition
o 2 atoms or groups added to a molecule with double/triple bond
o Decrease DBE
o More saturated
Elimination
o 2 or more groups removed from a molecule
o Increase DBE
o Less saturated
Electron movement

Homolytic
o Homolysis
o symmetrical
o One electron of pair in the bond ends up on each of the atoms that were
bonded
o A-B A + B
o Form free radicals
Neutral species with unpaired electrons
E.g. carbon centred free radical
Heterolytic
o Heterolysis
o Unsymmetrical
o Both electrons of bonding pair end up on one of the bonded atoms
o Direction of electron pair movement depend on relative electronegativity of
bonded atoms
o Electron move toward more electronegative atom of bond
o Carbocation or carbanion formed
Formal charges
Lose ownership of shared bonding electrons
o One unit of charge more positive
Gain ownership of shared bonding electrons
o One unit of charge more negative
Carbocation

Stability
o Carbocation attached to aryl ring>3>2 >1 > methyl
Lower energy intermediate is favoured
Charge delocalisation over more atoms
o Lower energy
o More stable
Covalent bond formation
Heterogenesis
o C
+
+ A
-
= C-A
o C
-
+ A
+
= C-A
o Polar reactions
Nucleophiles
Electron rich
Provide an electron pair to an electron deficient centre to form
a new bond
N for Negative
electrons
Electrophiles
Electron deficient
Accept electron pair to form a new bond
Positive atoms
Electropositive atom in polar bond

Homogenesis
o C + A = C-A


o Non-polar reaction
Bond breaking
Homolytic
Bond making
Homogenic