GENERAL ORGANIC CHEMISTRY – EXTENDED MASTER NOTES
(With Diagrams + Examples + Detailed Orders)
---------------------------------------------------------
1. INDUCTIVE EFFECT (+I / –I)
---------------------------------------------------------
Definition: Electron displacement through sigma (σ) bonds due to electronegativity differences.
Distance effect: Operates up to 3 carbon atoms effectively.
ASCII Diagram (How –I works):
δ– δ+ δ+
X —— C —— C —— C ——
(EWG pulls electron density)
ASCII Diagram (How +I works):
δ+ δ– δ–
R —— C —— C —— C ——
(EDG pushes electron density)
FULL –I ORDER (Strongest → Weakest):
NO2 > CF3 > CCl3 > CN > SO3H > COOH > COOR > CHO > COR > F > Cl > Br > I > OH > OR >
NH3+ > NR3+ > Vinyl > Aryl > H
FULL +I ORDER (Strongest → Weakest):
–SiR3 > –Li > –MgX > –CR3 > –SR > –SH > –OR > –OH > –NH2 > –NHR > –NR2 > Alkyl groups
Alkyl group order:
tert-butyl > isopropyl > ethyl > methyl
Applications:
• Acidity ↑ with –I
• Basicity ↑ with +I
• Carbocation stability ↑ with +I
• Carbanion stability ↑ with –I
• Bond polarization changes reaction pathways
---------------------------------------------------------
2. RESONANCE (CONJUGATION)
---------------------------------------------------------
ASCII Diagram of π–σ–π Conjugation:
C=C – C – C=C
πσπ
ASCII Diagram of lone pair → π:
:O — C=C
(Lone pair delocalizes into π-system)
Rules for resonance:
1. Octet rule must not be violated (except stable exceptions).
2. Charge positioned on correct atom (negative on EN atom).
3. More covalent bonds in structure = more stable.
4. Resonance hybrid = real structure, not any single form.
+R (Electron donating by resonance):
–OH, –OR, –NH2, –NHR, –NR2, –O–, –C6H5
–R (Electron withdrawing):
–NO2, –CN, –SO3H, –CHO, –COOR, –COR, –CONH2
Examples showing resonance in phenoxide ion:
O– O
| ||
C6H5–O(–) ↔ C6H5=O
Stability increases due to charge spreading over aromatic ring.
---------------------------------------------------------
3. HYPERCONJUGATION ("No Bond Resonance")
---------------------------------------------------------
ASCII Diagram:
CH3–C+
|
(Hyperconjugation: C–H bond → empty p orbital)
More α-hydrogens = more hyperconjugation structures.
Carbocation stability (via hyperconjugation):
3° > 2° > 1° > CH3+
Free radical stability:
3° > 2° > 1° > CH3•
Alkene stability:
Tetra > Tri > Di > Mono substituted
Reason: More hyperconjugation donors.
Example diagram:
CH3–CH=CH2
3 hyperconjugative structures from α-H of CH3.
---------------------------------------------------------
4. MESOMERIC EFFECT (+M / –M)
---------------------------------------------------------
ASCII Diagram of +M:
:OH → C=C
(Arrow pushes electron density toward ring)
ASCII Diagram of –M:
NO2 ← C=C
(Arrow pulls electron density)
+M increases basicity, activation of benzene.
–M increases acidity, deactivation.
Stability in carboxylate ion due to –M:
O=C–O(–) ↔ O(–)–C=O
Negative charge delocalized → strong acid.
---------------------------------------------------------
5. AROMATICITY
---------------------------------------------------------
Hückel Rule: (4n + 2)π electrons → aromatic (n = 0,1,2...).
ASCII Diagram of benzene:
■
(6 π electrons, cyclic, planar, conjugated)
Conditions:
1. Cyclic
2. Planar
3. Fully conjugated
4. (4n+2) π electrons
Examples:
Aromatic: Benzene, pyridine, pyrrole, furan
Anti-aromatic: Cyclobutadiene (4π)
Non-aromatic: Cyclohexadiene (non-planar)
Stability Order:
Aromatic >> Non-Aromatic >> Anti-Aromatic
Example diagram of anti-aromaticity:
Square with 4 π-electrons → highly unstable.
---------------------------------------------------------
6. REACTION INTERMEDIATES (Detailed)
---------------------------------------------------------
A. Carbocations:
Structure: sp2, planar, empty p orbital
Stability: 3° > 2° > 1° > CH3+
Effects increasing stability:
+I, +M, hyperconjugation, resonance, aromaticity
B. Carbanions:
Structure: sp3, pyramidal, lone pair
Stability: CH3– > 1° > 2° > 3°
Stabilized by –I and –M
C. Free Radicals:
Stability: 3° > 2° > 1°
Stabilized by resonance + hyperconjugation.
D. Carbenes:
Singlet carbene = sp2 (paired electrons)
Triplet carbene = sp (unpaired electrons)
Represented as:
:C: (singlet)
•C• (triplet)
---------------------------------------------------------
7. STABILITY RULES BY ELECTRON EFFECTS
---------------------------------------------------------
Carbocation:
+I ↑
+R ↑
Hyperconjugation ↑
Aromaticity ↑
Carbanion:
–I ↑
–R ↑
Resonance (negative on EN atom) ↑
Free Radical:
Hyperconjugation ↑
Resonance ↑
Mixed-effect priority:
Resonance > Hyperconjugation > Inductive
---------------------------------------------------------
8. IMPORTANT ORDERS FOR JEE
---------------------------------------------------------
Acidity (Phenols):
NO2–phenol > CN–phenol > F–phenol > phenol > CH3–phenol
Basicity of Amines (Aqueous):
2° > 1° > 3° > NH3
Reason: Solvation effects.
Basicity (Gas Phase):
3° > 2° > 1° > NH3
Electrophilic substitution activation order:
–NH2 > –NHR > –NR2 > –OH > –OR > –R > H
Deactivating:
–F > –Cl > –Br > –I > –CHO > –COOH > –NO2
Alkene stability:
Tetra > Tri > Di > Mono
---------------------------------------------------------
9. COMBINED GOC JEE TRAPS
---------------------------------------------------------
1. –M > –I in acidic strength decisions.
2. +R dominates over +I in reactivity control.
3. Aromaticity beats all stabilization effects.
4. Hyperconjugation beats weak +I.
5. Resonance beats hyperconjugation.
6. Carbanions destabilized strongly by alkyl groups.
Common example:
CH3–CH2–CO–O(–) is more stable than CH3–CH2–CH2–O(–) due to –M of carbonyl.
---------------------------------------------------------
10. EXTRA DIAGRAMS + PRACTICE CONCEPT MAPS
---------------------------------------------------------
Arrow Pushing Basics (ASCII):
A lone pair attacking:
:O: → C=O
Carbocation formation:
C–Br → C+ + Br–
Free radical homolysis:
Cl–Cl → Cl• + Cl•
Resonance in benzyl carbocation:
Ph–CH2+ ↔ Ph+=CH2
Hyperconjugation diagrams:
CH3–C+=CH2 shows 3 C–H sigma bonds donating.
More Aromaticity Test Map:
1. Check cycle
2. Check planarity
3. Check conjugation
4. Count π-electrons
5. Apply (4n+2)