ISC Class 11 Organic Chemistry - GOC (with Structures)

1. FUNDAMENTAL CONCEPTS
Organic Chemistry: Study of carbon compounds and their properties.

Tetravalency of Carbon: Carbon has 4 valence electrons, forms 4 covalent bonds.

H
|
H-C-H
|
H

Methane (CH₄) - simplest organic compound

Catenation: Carbon forms long chains

C - C - C - C - C - C (straight chain)

C
|
C - C - C - C (branched chain)
|
C

2. HYBRIDIZATION & GEOMETRY

sp³ Hybridization (Tetrahedral, 109.5°)

H
|
H - C - H (Methane)
|
H

H H
| |
H - C - C - H (Ethane)
| |
H H
sp² Hybridization (Trigonal planar, 120°)

H H
\ /
C=C (Ethene)
/ \
H H

All atoms in same plane

One π bond + one σ bond = double bond

sp Hybridization (Linear, 180°)

H - C ≡ C - H (Ethyne)

Linear molecule
Two π bonds + one σ bond = triple bond

3. STRUCTURAL REPRESENTATIONS

Chain Isomers Example: C₅H₁₂

(1) n-Pentane:
HHHHH
|||||
H - C-C-C-C-C - H
|||||
HHHHH

(2) Isopentane:
H
|
H-C-H
|
HHH | HH
||| | ||
H-C-C-C-C-C-H
|||||
HHHHH

(3) Neopentane:
H
|
 H-C-H
|
C - (CH₃)₃
/\
H₃C CH₃

Bond-line (Skeletal) Formula

Butane: \/\/

Pentane: \/\/\/

2-methylbutane: \/\/
|

Each vertex = Carbon

Each line end = Carbon
Hydrogens are implied

4. FUNCTIONAL GROUPS (Key Structures)

Alcohol: R - OH

Aldehyde: R - C = O
|
H

Ketone: R-C=O
|
R'

Carboxylic O
Acid: R - C - OH
‖
O

Ester: O
R - C - O - R'
‖
O

Amine: R - NH₂
 Halide: R - X (X = F, Cl, Br, I)

5. ISOMERISM WITH STRUCTURES

Chain Isomerism (C₄H₁₀)

Butane: C-C-C-C

Isobutane: C
|
C-C-C

Position Isomerism (C₃H₈O)

1-Propanol: HO - C - C - C

2-Propanol: C - C - C
|
OH

Functional Isomerism (C₂H₆O)

Ethanol: CH₃ - CH₂ - OH

Dimethyl CH₃ - O - CH₃

ether:

Geometrical Isomerism

Cis-2-butene: CH₃ CH₃

\ /
C=C
/ \
H H

Trans-2-butene: CH₃ H
\ /
C=C
/ \
H CH₃
Optical Isomerism (Chirality)

Chiral carbon (*):

W
|
X - C* - Y
|
Z

Four different groups attached to carbon

Non-superimposable mirror images

6. REACTIVE INTERMEDIATES

Carbocation (C⁺)

Primary (1°): R - CH₂⁺

Secondary (2°): R - CH⁺- R

|

Tertiary (3°): R
|
R - C⁺- R

Stability: 3° > 2° > 1° > CH₃⁺

Structure: Planar, sp² hybridized

Carbanion (C⁻)

Primary (1°): R - CH₂⁻

Secondary (2°): R - CH⁻- R

Tertiary (3°): R
|
R - C⁻- R

Stability: CH₃⁻ > 1° > 2° > 3° (OPPOSITE of carbocation)

Structure: Pyramidal, sp³ hybridized

Free Radical (C•)

Primary (1°): R - CH₂•

Secondary (2°): R - CH•- R

Tertiary (3°): R
|
R - C•- R

Stability: 3° > 2° > 1° > CH₃• (same as carbocation)

Structure: Planar, sp² hybridized

7. ELECTRONIC EFFECTS

Inductive Effect (-I and +I)

-I Effect (Electron Withdrawing):

CH₃ - CH₂ - Cl
←←←
Electron density shifts toward Cl

+I Effect (Electron Donating):

CH₃ - CH₂ - CH₂⁺

→→→
Alkyl groups push electrons toward positive charge

Order of -I effect:

F > Cl > Br > I > OH > NH₂ > C₆H₅ > H

Order of +I effect:

(CH₃)₃C- > (CH₃)₂CH- > CH₃CH₂- > CH₃- > H

Resonance/Mesomeric Effect

Resonance in Benzene:
 H H
| |
H-C C-H H - C•• ••C - H
‖ ‖ ↔ | |
H-C C-H H-C C-H
| ‖ ‖
H H

+M Effect (e.g., Aniline):

NH₂ NH₂⁺
| |
⌽ ↔ ⌽⁻

Lone pair delocalizes into ring

-M Effect (e.g., Nitrobenzene):

NO₂ NO₂
| |
⌽ ↔ ⌽⁺

Withdraws electrons from ring

Hyperconjugation

H H⁺
| |
H - C - CH₂⁺ ↔ H - C = CH₂
| |
H H

C-H σ bond electrons delocalize to stabilize carbocation

8. TYPES OF ORGANIC REACTIONS (DETAILED)

A. SUBSTITUTION REACTIONS

One atom/group replaced by another

1. Free Radical Substitution (in Alkanes)

 CH₄ + Cl₂ → CH₃Cl + HCl
(UV light/heat)

Mechanism:
Initiation: Cl₂ → 2Cl• (UV)
Propagation: CH₄ + Cl• → CH₃• + HCl
CH₃• + Cl₂ → CH₃Cl + Cl•
Termination: CH₃• + Cl• → CH₃Cl

2. Nucleophilic Substitution (SN1 and SN2)

SN1 (Unimolecular) - Two steps:

Step 1: R-Br → R⁺ + Br⁻ (slow, rate-determining)

Step 2: R⁺ + OH⁻ → R-OH (fast)

Example:
CH₃ CH₃
| |
CH₃-C-Br → CH₃-C-OH
| |
CH₃ CH₃
(tert-butyl bromide → tert-butyl alcohol)

- Works best with 3° > 2° halides

- Carbocation intermediate
- Racemization occurs

SN2 (Bimolecular) - One step:

OH⁻ + CH₃-Br → HO-CH₃ + Br⁻

(Backside attack)

- Works best with 1° > 2° halides

- No intermediate
- Inversion of configuration (Walden inversion)

3. Electrophilic Substitution (in Benzene)

 + Cl₂/FeCl₃ Cl
⌽ → ⌽ + HCl

Benzene Chlorobenzene

Other examples:
- Nitration: ⌽ + HNO₃/H₂SO₄ → ⌽-NO₂
- Sulphonation: ⌽ + H₂SO₄ → ⌽-SO₃H
- Friedel-Crafts Alkylation: ⌽ + RCl/AlCl₃ → ⌽-R

B. ADDITION REACTIONS

Two molecules combine to form one

1. Electrophilic Addition (in Alkenes)

Addition of HBr (Markovnikov's Rule):

CH₃
|
CH₃-C=CH₂ + HBr → CH₃-C-CH₃
|
Br
(2-methylpropene) (2-bromo-2-methylpropane)

Rule: H adds to carbon with MORE H atoms

Br adds to carbon with FEWER H atoms

Mechanism:

Step 1: π electrons attack H⁺

CH₃-CH=CH₂ + H⁺ → CH₃-CH⁺-CH₃ (more stable 2° carbocation)

Step 2: Br⁻ attacks carbocation

CH₃-CH⁺-CH₃ + Br⁻ → CH₃-CHBr-CH₃

Anti-Markovnikov Addition (Peroxide Effect):

CH₃-CH=CH₂ + HBr → CH₃-CH₂-CH₂Br

(Peroxide)
Only with HBr, not HCl or HI
Free radical mechanism
2. Addition of Halogens (X₂)

H H H H
\ / | |
C=C + Br₂ → H-C - C-H
/ \ | |
H H Br Br
(Ethene) (1,2-dibromoethane)

- Reddish-brown Br₂ decolorizes

- Test for unsaturation

3. Addition of H₂O (Hydration)

CH₂=CH₂ + H₂O → CH₃-CH₂-OH

(H⁺ catalyst)
Follows Markovnikov's rule

4. Hydrogenation

H H H H
\ / | |
C=C + H₂ → H-C - C-H
/ \ (Ni/Pt/Pd) | |
H H H H

C. ELIMINATION REACTIONS

Removal of atoms/groups to form multiple bonds

1. Dehydration of Alcohols (E1 mechanism)

H H
| | H H
H - C - C - H → H-C = C-H + H₂O
| | (H₂SO₄,170°C)
H OH
(Ethanol) (Ethene)

Saytzeff Rule: Major product is more substituted alkene

Example with Saytzeff Rule:

 CH₃ H CH₃ H
| | | |
CH₃-C - C-H → CH₃-C = C-H (Major)
| | (H₂SO₄)
H OH

+ CH₂=C-CH₃ (Minor)
|
H

2. Dehydrohalogenation

H H
| | H H
H - C - C - H → H-C = C-H + HBr
| | (alc. KOH)
H Br
(Bromoethane) (Ethene)

D. REARRANGEMENT REACTIONS

Atoms reorganize within molecule

1. Carbocation Rearrangement (Hydride shift)

CH₃ H CH₃ H
| | | |
CH₃-C - C⁺ → (H⁻ shift) CH₃-C⁺-C-H
| | | |
H H H H
(1° carbocation) (2° carbocation - more stable)

2. Carbocation Rearrangement (Methyl shift)

CH₃ CH₃ CH₃

| | |
CH₃-C - C⁺ → (CH₃ shift) CH₃-C⁺-CH₂-CH₃
| | |
H H CH₃
(2° carbocation) (3° carbocation - more stable)
E. OXIDATION REACTIONS

1. Oxidation of Alcohols

Primary Alcohol:
RCH₂OH → RCHO → RCOOH
[O] [O]
(Aldehyde) (Carboxylic acid)

Secondary Alcohol:
R₂CHOH → R₂C=O
[O]
(Ketone - stops here)

Tertiary Alcohol:
R₃COH → No oxidation (no H on C-OH)

2. Oxidation of Alkenes

With cold dil. KMnO₄ (Baeyer's Test):

R-CH=CH-R + [O] + H₂O → R-CH(OH)-CH(OH)-R
(Glycol/diol)
Purple KMnO₄ decolorizes - test for unsaturation

With hot conc. KMnO₄:

R-CH=CH-R → R-COOH + R-COOH
(Breaks double bond)

F. REDUCTION REACTIONS

1. Reduction of Aldehydes/Ketones

RCHO + H₂ → RCH₂OH
(Ni/LiAlH₄)
(Aldehyde) (1° Alcohol)

R₂C=O + H₂ → R₂CHOH
(Ni/LiAlH₄)
(Ketone) (2° Alcohol)

2. Reduction of Carboxylic Acids

 RCOOH + 4[H] → RCH₂OH + H₂O
(LiAlH₄)

G. CONDENSATION REACTIONS

Two molecules combine with elimination of small molecule (H₂O, NH₃, etc.)

Esterification:

O O
‖ ‖
R-C-OH + HO-R' → R-C-O-R' + H₂O
(H⁺ catalyst)
(Acid) (Alcohol) (Ester)

9. REACTION CONDITIONS - QUICK REFERENCE

Reaction Type Common Reagents/Conditions

Free Radical Substitution UV light, heat, Cl₂/Br₂

Nucleophilic Substitution OH⁻, CN⁻, NH₃, ROH

Electrophilic Substitution HNO₃/H₂SO₄, Cl₂/FeCl₃

Electrophilic Addition HBr, H₂SO₄, Br₂, H₂O/H⁺

Anti-Markovnikov HBr + Peroxide

Elimination Alc. KOH, conc. H₂SO₄ at 170°C

Oxidation KMnO₄, K₂Cr₂O₇, [O]

Reduction H₂/Ni, LiAlH₄, NaBH₄

Hydrogenation H₂ with Ni/Pt/Pd catalyst

9. BOND FISSION

Homolytic Fission

CH₃ - CH₃ → CH₃• + •CH₃

(UV)
Each gets one electron
Forms free radicals

Heterolytic Fission

CH₃ - Br → CH₃⁺ + Br⁻

Or

CH₃ - Li → CH₃⁻ + Li⁺

One atom gets both electrons

Forms ions

10. ELECTROPHILES & NUCLEOPHILES

Electrophiles (E⁺)

H⁺, Br⁺, NO₂⁺, Cl⁺

R
|
R - C⁺ (carbocations)
|
R

Nucleophiles (Nu:)

OH⁻, CN⁻, NH₃, H₂O

R
|
R - C⁻ (carbanions)
|
R
11. ACIDITY COMPARISON

Acidity Order (Common Examples)

R-COOH > ArOH > H₂O > R-OH > R-H

(Carboxylic (Phenol) (Alcohol)

acid)

Why phenol is more acidic than alcohol:

Phenoxide ion: O⁻
|
⌽
Resonance stabilizes negative charge

Alkoxide ion: R - O⁻
No resonance stabilization

12. IMPORTANT REACTIONS TO REMEMBER

KEY NAMED REACTIONS

1. Markovnikov's Rule

CH₃-CH=CH₂ + HBr → CH₃-CHBr-CH₃

(Major product)

H goes to carbon with MORE hydrogens

Br goes to carbon with FEWER hydrogens
Forms more stable carbocation intermediate

2. Anti-Markovnikov (Kharasch Effect/Peroxide Effect)

CH₃-CH=CH₂ + HBr → CH₃-CH₂-CH₂Br

(Peroxide) (Major product)

Free radical mechanism

Only works with HBr
3. Saytzeff Rule (Zaitsev's Rule)

In elimination: More substituted alkene is major product

CH₃ H CH₃
| | |
CH₃-C - C-H → CH₃-C = CH₂ (Major - more substituted)
| |
H OH

4. Baeyer's Test (for Unsaturation)

R-CH=CH-R + KMnO₄ (cold, dil.) → R-CH(OH)-CH(OH)-R

Purple color Colorless
(Positive test)

QUICK REVISION CHECKLIST ✓

STRUCTURES TO REMEMBER:

✓ Hybridization: sp³ (tetrahedral), sp² (planar), sp (linear)

✓ All functional groups with structures

✓ Carbocation (planar), Carbanion (pyramidal), Free radical (planar)

STABILITY ORDERS:

✓ Carbocation & Free Radical: 3° > 2° > 1° > CH₃⁺/CH₃•

✓ Carbanion: CH₃⁻ > 1° > 2° > 3° (OPPOSITE!)

✓ Alkenes: More substituted = more stable

EFFECTS:

✓ -I Effect: F > Cl > Br > I > OH > NH₂ (withdrawing)

✓ +I Effect: (CH₃)₃C > (CH₃)₂CH > CH₃CH₂ > CH₃ (donating)

✓ +M Effect: -NH₂, -OH, -OR (donate electrons via π)

✓ -M Effect: -NO₂, -CN, -COOH, -CHO (withdraw via π)

REACTIONS TO MEMORIZE:

1. Substitution: SN1 (3° best), SN2 (1° best)

 2. Addition: Markovnikov (H to more H side), Anti-Markovnikov (with peroxide)

3. Elimination: Saytzeff rule (more substituted alkene)

4. Tests: Br₂ water (decolorizes), KMnO₄ (decolorizes)

IMPORTANT REAGENTS:

✓ Oxidation: KMnO₄, K₂Cr₂O₇

✓ Reduction: H₂/Ni, LiAlH₄

✓ Elimination: Alc. KOH, conc. H₂SO₄ 170°C

✓ Addition: Br₂, HBr, H₂O/H⁺

ISOMERS:

✓ Chain, Position, Functional, Metamerism

✓ Geometrical (cis-trans), Optical (chiral carbon)

COMMON EXAM MISTAKES TO AVOID ⚠️

1. ❌ Confusing carbocation and carbanion stability orders
2. ❌ Forgetting that Anti-Markovnikov ONLY works with HBr + peroxide
3. ❌ Not showing proper bond angles in hybridization
4. ❌ Mixing up SN1 (carbocation) and SN2 (backside attack)
5. ❌ Forgetting to show electron movement arrows in mechanisms
6. ❌ Writing wrong major product in elimination (remember Saytzeff!)
7. ❌ Not knowing which alcohols can be oxidized (3° cannot!)

EXAM STRATEGY 💡
For Structure Questions:

1. Draw all bonds clearly

2. Show correct geometry (planar/tetrahedral)

3. Mark chiral centers with *

4. Use curved arrows for electron movement

For Mechanism Questions:

1. Identify type of reaction first

2. Show all intermediates

3. Draw electron movement arrows

4. Write complete structures (not shortcuts)

For Comparison Questions:

1. Always give reason/explanation

2. Compare stability using factors (I, M, hyperconjugation)

3. Draw structures if needed

LAST-MINUTE FORMULAS
Degree of Unsaturation:

DBE = (2C + 2 + N - H - X) / 2

C = carbons, N = nitrogens
H = hydrogens, X = halogens

Homologous Series:

Alkanes: CₙH₂ₙ₊₂
Alkenes: CₙH₂ₙ
Alkynes: CₙH₂ₙ₋₂

EXAM TIPS
1. Draw clear structures with proper bonds

2. Show electron movement with curved arrows

3. Remember stability orders

4. Identify functional groups correctly

5. Practice drawing resonance structures

Best of luck! Stay calm and confident! 🎯📚