Organic Chemistry AS

1. Hydrocarbons

(a)Nomenclature (I.U.P.A.C)

(b)Functional Group: Alkane, Alkene, Alkyne, Alkyl, Alcohol, Alkyl Halides(Halageno Alkanes),
Aldehyde & Ketone(Carbonyl), Carboxylic Acid, Acyl, Ester, Ether, Amine and Amides.

(c) Representation of chain

(i) Structure:

(ii) Condensed:

OR CH3(CH2)2CH3

(iii) Molecular:

C5H10O3

(iv) Skeletal:

* Aliphatic Compounds = Organic compounds with open chains of carbon atoms which may be branched or
unbranched

*Alicyclic Compounds = Organic compounds with closed rings of carbon atoms

* Aromatic compounds (Arene) = Organic compounds that contain at least one Benzene ring (A2 Syllabus)

* = Bond in the plane of paper

* = Bond going back into paper away from you

* = Bond coming out of paper towards you

* Electrons sufficient species are called Nucleophile ( NU)

* Electrons deficient species are called Electrophile (E+)

* Atom or Group of atoms having an unpaired electron is called Free Radical

* A substance formed during a reaction and can be isolated from reaction mixture called Intermediate

* A substance formed during a reaction and cannot be isolated is called Transition State

* An organic molecule in which Carbon is positively charged is called Carbonium or Carbocation

* An organic molecule in which Carbon is negatively charged is called carbanion

(d) Isomerism

Structure Chain C-C-C -C / C-C-C

Position C=C-C-C/C-C=C-C

Functional Group alcohol ether

Isomerism carboxylic Ester

aldehyde ketone

Ring - Chain C=C-C /

Stereo Geometrical (cis trans)

✓ 2n Isomers
✓ Probability (Double bonds at same position at both side
of chain)

✓ 2n Isomers
✓ Chiral centre / Chiral Carbon
Optical ✓ Optical Activity
✓ Enantiomers
✓ Super and Non-super impossible
✓ Dextro and Levo rotatory

2. Alkane CnH2n+2

(a) Cracking: Source of Alkane, Alkene and Hydrogen

Conditions: Catalyst Al2O3 or SiO2 (Thermal and Catalytic)

Temperature 400 ⁰C - 500 ⁰C
Absence of Oxygen

(b) Combustion: Complete, CO2 , H2O

(Energy Source)
Incomplete, C, CO, H2O

(c) Free Radical Substitution: Initiation Cl - Cl Cl● + Cl●

Propagation Cl● + CH4 CH3● + HCl

Termination CH3● + CH3● C2 H6

Initiation = Only halogen free radicals formed

Propagation = A free radical substitutes a substance into a free radical
Termination = Two free radicals combine to form a substance
* Homolytic Fission results free radicals while Homolytic Fission results ions

* shows the movement of single electron

* shows the movement of an electron pair

3. Alkene CnH2n

Dehydration / Elimination CH3 - CH2 - OH CH2 = CH2 + H2O

(Condition: Conc. H2SO4 + 170 ⁰C OR Al2O3(s) + 300 ⁰C)

Preparations Dehydrogenation
C2H6 C2H4 + H2
Cracking
OH- Alcohol
Elimination CH3 - CH2 - X CH2 = CH2 + H2O + X-
reflux

Ni + 150⁰C
Hydrogenation CH2 = CH2 + H2 CH3 - CH3

Cone. H3 PO4 + 300⁰C + 70atm

Hydration CH2 = CH2 + H2 O CH3 - CH2 - OH

CCl4
Reactions Bromination (a) CH2 = CH2 + Br2 CH2 - CH2
(With Electrophilic
addition Mechanism) Br Br

(b) CH2 = CH2 + Br2 (aq) CH2 - CH2 + CH2 - CH2

Br Br Br OH
r.t.p
Hydrohalogenation CH3 - CH = CH2 + HBr(g) CH3 - CH2 - CH2-Br
(With Markonioves Rule) (20%)
+

CH3 - CH - CH3

Br (80%)
(i) Cold dil. KMnO4
MnO4- / OH-
Oxidation CH2 = CH2 + [O] + H2O CH2 - CH2
r.t.p
OH OH (Diol)
{Observation: Purple to Colourless and Brown ppt (MnO2)}

O
MnO4- / H+
(ii) Hot Cone. KMnO4 CH2 = CH-R + [O] CO2 + H2O + R - C -OH
Heat

R R
MnO4- / H+
R - C = CH2 + [O] R - C = O + CO2 + H2O
Heat
* used to find out position of C=C in alkenes.
* If the double bonded carbon attached to one carbon directly, Carboxylic acid produces
* If the double bonded carbon attached to two more carbons directly, Ketone produces
* If the double bonded carbon attached to no more carbon, Carbon dioxide and water produce
4. Alcohols CnH2n+1OH

Primary (1⁰) C - C - OH

Types Secondary (2⁰) C - C - OH

C
C

Tertiary (3⁰) C - C - OH

Hydration of alkene

Preparation Fermentation C6 H12 O6 2C2 H5OH + 2CO2

(Condition: yeast, 18⁰C - 40⁰C, Absence of Oxygen)

Reduction of Carboxylic acid

With Na, CH3 - CH2 - OH + Na CH3 - CH2 - O-Na+ + 1⁄2H2

(use to find no. of OH group) (Basic solution) Bubbles/Fizzing)

SN reaction R - OH R - X + HX (Steamy fumes)

(Conditions PCl5 or PCl3 + Heat or SOCl2 or I2 + P4 + Heat)

with HBr R - OH R - Br + H2O

(Conditions HBr(g) or NaBr + Cone. H2SO4 + Heat)

Reactions Dehydration

1⁰ mild
Oxidation CH3 - CH2 - OH + [O] CH3 - CHO
Oxidation
(Conditions: H+ / K2Cr2O7 + Heat or H+ / KMnO4 + Heat)

O
1⁰ Oxidation
CH3 - CH2 - OH + [O] CH3 - C - OH
(Conditions: H+ / K2Cr2O7 + reflux or H+ / KMnO4 + reflux)

CH3 CH3
2⁰ Oxidation
CH3 - CH - OH CH3 - C = O

Esterification RCOOH + ROH RCOOR + H2O

(Condition: Heat + Any one Conc. HCl or Conc. H2SO4)

* 3⁰ do not oxidise

5. Halogeno alkane, R-X, Alkyl Halides CnH2n+1X

Alkane (free radial substitution)

Preparation Alkene (Electrophilic addition)

Alcohol (SN reaction)

 Hydrolysis CH3 - CH2 - X CH3 - CH2 - OH + HX
(Conditions: Aq NaOH + reflux)
(Nucleophilic substitution)

CH3 - CH2 - X CH3 - CH2 - CN + X-

Reaction (Conditions: KCN or NaCN in Alcohol + reflux)

Elimination CH3 - CH2 - X CH2 = CH2 + H2O + X-

(Conditions: Alcoholic NaOH + reflux)

Amine formation, R-X R - NH2 + HCl

(Conditions: Conc. NH3 in ethanol + Heat)

* Primary Alkyl halides undergo SN 2 reactions

* Secondary Alkyl halides undergo both SN 1 and SN 2 reaction

* Tertiary Alkyl halides undergo SN 1 reaction

* Higher temperature, Higher concentration of Nucleophile and Ethanol as a solvent will favour
Elimination reaction

* Lower temperature, Dil solution of nucleophile and Water as a solvent will favour Substitution reaction

* SN mechanism with ease of hydrolysis depending on C - Hal bond length.

6. Carboxylic Acid CnH2n+1COOH

[O]
Preparation Oxidation 1⁰ alcohol R-CH2 - OH R - COOH
[O]
aldehyde R - CHO R - COOH

H+ + reflux
Hydrolysis R - CN R - COOH + NH4+
(Oxidation of Nitriles) (Acidic Hydrolysis)

OH- + reflux
R - CN R - COO- + NH3
(Alkaline Hydrolysis)
* After alkaline hydrolysis Acidifying with any strong acid will produce carboxylic acid again
* Reduction of Nitriles will produce amine

r.t.p
Reactions With NaOH: RCOOH + NaOH RCOO-Na+ + H2O

r.t.p
With NaHCO3 / Na2CO3 RCOOH + Na2CO3 RCOO-Na+ + H2O + CO2

r.t.p
With Na: RCOOH + Na RCOO-Na+ + 1⁄2H2
(used to identify COOH Groups)

warm
With SOCl2 , RCOOH + SOCl2 ROCl + SO2 + HCl

warm
With PCl5 , RCOOH + PCl5 RCOCl + POCl3 + HCl

dry ether/r.t.p
With LiAlH4 , RCOOH R - CH2 - OH

Esterification can be done both with Alcohol and Acyl halides

* For Reduction of carboxylic acid Sodium boron hydride cannot be used

* Ni + H2 can be used to reduce carboxylic acid industrially
7. Aldehydes and Ketones / Carbonyl

Test for Carbonyl: Condensation reaction

NO2 NO2

Test for Aldehyde

(i) Tollen's Reagent

O O O O
Heat
R - C - H + 2Ag(NH3)2OH R - C - OH or R - C - O- or R - C - O-NH4+ + 2Ag(s) + 3NH3 + H2O

colourless (Silver ppt)

(ii) Fehling's Solution

O O O O
Heat
R - C - H + 2Cu(OH)2 + NaOH R - C - OH or R - C - O- or R - C - O-Na+ + Cu2O(s) + 3H2O

Blue Solution (Brick red ppt)

* Both are redox reaction

* Ketones and Bezaldehyde do not react with Fehling's solution

(Iodo form test) / Triiodomethane test / Test for methyl ketones

*Test for methyl ketone, Ethanal, Ethanol, and 2⁰ alcohol with CH3 - CH Group

OH

O O
warm
CH3 - C - CH3 + NaOH + 3I2 CH3 - C - O- + CHI3(s) + 3H2O + 3NaI

(Yellow ppt)

Preparations Alcohols (done)

Alkenes (done)

O (10 0C - 20 0C)/ KCN OH

Reaction Cyanohydrin R-C- + HCN(g) R - C - CN

(with Nucleophilic addition mechanism)

Oxidation of aldehyde (done)

* Ketones don't oxidise.

*The carbonyl compounds can be converted back into alcohols by reduction

*Hydrogen cyanide dissociate in water to form the cyanide ion, CN-, which is nucleophile. However, HCN is weak
acid and thus a poor source of cyanide ions, a trace of sodium or potassium cyanide is added in order to accelerate
the reaction:
8. Polymerisation

Addition Polyethene, Poly propene, PVC, PTFE etc.