Hydrocarbons & Halohydrocarbons
Unit 8 - NOTE GUIDE
Alkanes
• Saturated hydrocarbons
• Reactivity is less
• Mostly non-polar. Therefore, they have dispersion forces among them
• General formula
• Homologous series
• With branching of the carbon chain, the surface area of molecules decreases and consequently
dispersion forces become weaker and the boiling point decreases
Compound B.P / oC
n-pentane 36
2-methylbutane 28
2,2-dimethylpropane 9
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Covalent bond cleavage during organic reactions
• Heterolytic cleavage
• Homolytic cleavage
Reactions of alkanes
1) Combustion
2) Chlorination (Halogenation)
- Even though alkanes don’t react with common polar reagents, they tend to react with free
radicals by homolytic cleavage of C-H bonds
- This reaction gives rise to a mixture of products formed by a sequence of reactions called as
chain reactions
Steps of the reaction mechanism
1. Chain initiation
2. Chain propagation
3. Chain termination
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Alkenes
C C
• Unsaturated compounds, therefore more reactive than alkanes
• General formula
• Physical property variation is similar to alkanes
Reactions of alkenes
• Reactions of alkenes take place at the C=C
• Typical reaction type is electrophilic addition
Electrophile
- C=C is electron rich. Therefore, it can attract electron deficient species known as
electrophiles
Addition
- As C=C is unsaturated, atoms can get added to those C atoms
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1) Addition of hydrogen halides
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• Why does H go to the carbon with more H atoms when HX is added
Markonikov’s rule
When a protic acid HX adds to an asymmetric alkene, the H adds to the carbon with
higher number of H atoms
Anti-Markonikov’s rule
When there are peroxides in the reaction medium, H adds to the carbon with lower
number of H atoms
Special points
v
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Carbocation Stability
• 3o > 2o > 1o
• Stability of the carbo cation increases when the number of alkyl groups attached to the positively
charged C atom of carbocation increases
Reason
- Alkyl groups release electrons to the positively charged C atom through C – C bond
- It helps to spread the positive charge; thereby stabilize the ion
• If the carbocation can form resonance structures, it will become even more stable
2) Addition of Br2
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3) Addition of H2SO4
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4) Catalytic addition of hydrogen (Hydrogenation)
5) Reactions of alkenes with cold, alkaline, dil. KMnO4
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Alkynes
• C C
• Unsaturated compounds
• General formula (CnH2n-2)
• Physical property variation is similar to alkanes
• Bond length and bond energy variation
Reactions of alkynes
• Characteristic reaction type is electrophilic addition
1) Addition of hydrogen halides (HX)
2) Addition of Br2
3) Addition of H2O
• Enols are unstable. So, they quickly rearrange to a more stable aldehyde or ketone
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4) Catalytic addition of hydrogen (Hydrogenation)
5) Acidic nature of alkynes
- sp orbital has more s character than sp2 / sp3
- Therefore, bonding electron in C – H bonds of alkynes are closer to the nucleus than C – H
bonds in alkanes or alkenes. As a result of that, H in C – H in alkynes has an acidic nature
- However, the acidity of terminal hydrogens in alkynes are less acidic than H2O and alcohol
Conversions
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Benzene
• C6H6 is the molecular formula
• Smallest aromatic compound
• Unsaturated but doesn’t answer tests for unsaturation
Structure of benzene
• Kekule proposed the following structure for benzene
• Draw backs of the proposed structure
- Benzene doesn’t answer to unsaturation tests. However, according to the proposed structure
it should
- Bond length between any 2 adjacent carbons in benzene is same
(C – C in benzene = 1.39×10-10 m)
It is in between a C – C (1.54×10-10 m) and a C=C (1.34×10-10 m)
• The structure of benzene is now considered to be a resonance hybrid of 2 structures given below
- All carbon atoms of benzene are sp2 hybridized
- Each carbon bears an unhybridized p orbital which can overlap with the unhybridized p orbitals
on either side of it
- From this a cyclic delocalized electron cloud common to all six carbon atoms is formed
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Stability of benzene
• The standard enthalpy of hydrogenation of benzene is found to be -208 kJ mol-1, which is -152 kJ
mol-1 less than the expected value for the hydrogenation of 3 double bonds
• Therefore, benzene is more stable than its Kekule structure by an amount of 152 kJ mol-1
• This stability is due to the cyclic delocalization of 6𝜋 electrons. It is termed the resonance
stabilization energy of benzene / aromatic stabilization
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Reactions of benzene
• Characteristic reaction type of benzene is electrophilic substitution
(doesn’t like to undergo addition reaction that destroy the extra stability came from cyclic
delocalization)
1) Nitration
2) Friedel Crafts alkylation
3) Friedel Crafts acylation
4) Halogenation
Nitration
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Friedel Crafts alkylation
• ---- MECHANISM--- (for primary alkyl halides)
• ---- MECHANISM--- (for secondary and tertiary alkyl halides)
- Friedel Crafts doesn’t take place in mono substituted benzenes where the substituent group has
a stronger electron attracting ability than halogen
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Friedel Crafts acylation
v
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Halogenation
v
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Conversions
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Other reactions
v
1) Oxidation of alkyl groups attached to benzene
2) Addition of H2
- Even though benzene doesn’t like to undergo electrophilic addition reactions like alkenes, it can
undergo addition of H2 in the presence of suitable catalysts at hight temperature in comparison
to alkenes
Special points
v
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Directing ability of substituent groups of mono substituted benzene
• The nature of the first substituent will determine the place where the second substituent group attaches
Directors
Ortho/para directors meta directors
activators deactivators
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Conversions
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Alkyl halides
Structure of alkyl halides
v
• Alkyl halides are polar (but not much)
• But their solubilities in water is so poor as they don’t form hydrogen bonds with water
Reactions of alkyl halides
1) Nucleophilic substitutions
2) Elimination
Nucleophilic substitution reactions
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1) One step reaction (SN2 mechanism)
- Primary alkyl halides undergo this mechanism
- Reason – primary carbocations are unstable
2) Two steps reaction (SN1 mechanism)
- Tertiary alkyl halides undergo this mechanism
- Reason – tertiary carbocations are relatively stable
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• Secondary alkyl halides can take both pathways generally
• Vinyl halides and aryl halides do not undergo substitution reactions
Reason
– 2 steps pathway is not working as their carbocations are unstable
– 1 step pathway is blocked as the C – X bond is stronger than alkyl halides due to its double bond
character
Special points
v
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Elimination reactions
• Sometimes nucleophiles can act as a base by reacting with H+ instead of the carbon
• Substitution and elimination are competing reactions in alkyl halides. Solvent used in the reaction
influences one reaction type over the other
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1. i. What is the product you expect to get from the reaction between CH3CH2Br and CH3CH2O-
ii. Is there any other organic product possible to get formed in this reaction
iii. What are the reaction types
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Formation of Grignard
• Due to the high reactivity of alkyl group in Grignard, Grignard reagent cannot be prepared or used in
a medium where even weakly acidic H atoms are present
Conversions
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