A2 Organic Reactions / Reagents & Conditions

1. GRIGNARD REAGENTS
 Preparation:
i. HALOALKANE + Mg → GRIGNARD
 Reagents and Conditions:
1) Heat under reflux
2) Dry Ether
3) Single Crystal of Iodine catalyst if needed
 Reactions:
i. GRIGNARD + CO2(cold/solid) → (+1C)CARBOXYLIC ACID + MgBrCl
(+1C = the addition of one Carbon molecule to the chain)
ii. GRIGNARD + METHANAL → (+1C) 1º ALCOHOL + MgBrCl
iii. GRIGNARD + Other ALDEHYDES → (+1C) 2º ALCOHOL +MgBrCl
iv. GRIGNARD + KETONE → (+1C)3º ALCOHOL + MgBrCl
 Reagents and Conditions:
1) Dry Reagents
2) With HCl

2. CARBOXYLIC ACIDS
 Preparation:
i. 1º ALCOHOLS + 2[O] → CARBOXYLIC ACID + WATER
 Reagents and Conditions:
1) Heat under Reflux
2) Potassium Dichromate / H2SO4
ii. Hydrolysis of Nitriles
NITRILE + 2H2O + HCl → CARBOXYLIC ACID + NH4Cl
 Reagents and Conditions:
1) Heat under reflux
2) With dilute HCl
 Reactions:
i. CARBOXYLIC ACID + NaOH → CARBOXYLATE SALT + H2O
ii. CARBOXYLIC ACID + Na2CO3/NaHCO3 → CARBOXYLATE SALT + H2O + CO2
iii. CARBOXYLIC ACID + ALCOHOL ↔ ESTER + H2O
 Reagents and Conditions:
1) Warmed under reflux
2) With concentrated H2SO4
iv. CARBOXYLIC ACID + PCl5 → ACID CHLORIDE + POCl3 + HCl
 Reagents and Conditions:
1) Dry / room temperature
v. CARBOXYLIC ACID + 4[H] → ALCOHOL + H2O
 Reagents and Conditions:
1) LiAlH4 in dry ether
2) With HCl

3. ACID CHLORIDES:
 Preparation:
i. CARBOXYLIC ACID + PCl5 → ACID CHLORIDE + HCl + POCl3
 Reactions:
i. ACID CHLORIDE + H2O → CARBOXYLIC ACID + HCl
ii. ACID CHLORIDE + ALCOHOL → ESTER + HCl
iii. ACID CHLORIDE + (concentrated)AMMONIA → AMIDE + NH4Cl
iv. ACID CHLORIDE + AMINE → SUBSTITUTED AMIDE + HCl

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4. ESTERS:
 Preparation:
i. CARBOXYLIC ACID + ALCOHOL ↔ ESTER + H2O
 Reagents and Conditions:
1) Warmed under reflux
2) With concentrated H2SO4
ii. ACID CHLORIDE + ALCOHOL → ESTER + HCl
 Reactions:
i. ESTER + NaOH → ALCOHOL + CARBOXYLATE SALT
 Reagents and Conditions:
1) Heat under reflux
ii. ESTER + H2O ↔ CARBOXYLIC ACID + ALCOHOL
 Reagents and Conditions:
1) Warmed under reflux
2) With concentrated H2SO4

5. CARBONYL COMPOUNDS:
 Preparation – Aldehydes:
i. 1º ALCOHOL + [O] → ALDEHYDE + H2O
 Reagents and Conditions:
1) Heat under DISTILLATION
2) Potassium Dichromate / H2SO4
 Preparation – Ketones:
i. 2º ALCOHOL + [O] → KETONE + H2O
 Reagents and Conditions:
1) Heat under reflux
2) Potassium Dichromate / H2SO4
 Reactions – Both Aldehydes and Ketones:
i. CARBONYL + 2,4-DNPH → YELLOW/ORANGE PPT. + H2O
ii. Aldehyde + HCN → n-HYDROXY ALKYLNITRILE
 Reagents and Conditions:
1) HCN / KCN in pH 8 buffer solution
iii. Ketone + HCN → n-HYDROXY-n-METHYL ALKYLNITRILE
 Reagents and Conditions:
1) HCN / KCN in pH 8 buffer solution
iv. CARBONYL + 2[H] → ALCOHOL (Aldehyde = 1º / Ketone = 2º)
 Reagents and Conditions:
1) LiAlH4 in dry ether
v. CARBONYL + GRIGNARD → ALCOHOL (Methanal=1ºAld=2º/Ket=3º) + MgBrCl
 Reagents and Conditions:
1) In dry ether
2) HCl
 Iodoform of Ethanal and Methyl Ketones (-COCH3):
i. ETHANAL + 3I2 + 4NaOH → CHI3 + 3NaI + SODIUM METHANOATE + 3H2O
ii. METHYL KETONE + 3I2 + 4NaOH → CHI3 + 3NaI + SODIUM CARBOXYLATE + 3H2O
 Reactions – Aldehydes ONLY:
i. Aldehyde + [O] + OH- → RED PPT. + CARBOXYLATE SALT + H2O
 Reagents and Conditions:
1) Warmed with Fehling’s Solution
ii. Aldehyde + [O] + OH- → SILVER MIRROR + CARBOXYLATE SALT + H2O
 Reagents and Conditions:
1) Warmed
2) With Silver Nitrate in dilute Ammonia

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6. 1º AMINES
 Preparation:
i. NITRILE + 4[H] → AMINE
 Reagents and Conditions:
1) LiAlH4 in dry ether
ii. HALOALKANE + NH3 → AMINE + HX
 Reagents and Conditions:
1) Heated in a sealed tube
2) Concentrated NH3
 Reactions – With ACIDS
i. AMINE + HCl → ALKYL AMMONIUM+CHLORIDE-
ii. AMINE + CH3COOH → ALKYL AMMONIUM ETHANOATE
 Reactions – With ACID CHLORIDES
i. AMINE + ACID CHLORIDE → SUBSTITUTED AMIDE + HCl

7. NITRILES
 Preparation:
i. HALOALKANE + KCN → (+1C)NITRILE + KX
 Reagents and Conditions:
1) Heat under reflux
2) Aqueous Ethanol
ii. CARBONYL + HCN → HYDROXY NITRILE
 Reagents and Conditions:
1) HCN / KCN in pH 8 buffer solution
 Reactions:
i. NITRILE + H+ + 2H2O → CARBOXYLIC ACID + AMMONIUM+ (hydrolysis)
 Reagents and Conditions:
1) Heat under reflux
2) With acid / HCl
ii. NITRILE + 4[H] → 1º AMINE
 Reagents and Conditions:
1) LiAlH4 in dry ether

8. AMIDES:
 Preparation:
i. ACID CHLORIDE + NH3 → AMIDE + HCl
ii. ACID CHLORIDE + AMINE → AMIDE– R + HCl
 Reactions:
i. Dehydration:
6AMIDE + P4O10 → 6NITRILE + 4H3PO4
Simplified: AMIDE - H2O → NITRILE
 Reagents and Conditions:
1) With warm P4O10
ii. Hoffman’s Degradation:
AMIDE + Br2 + 4NaOH → (-1C) AMINE + Na2CO3 + 2NaBr + 2H2O
Simplified: RCONH2 → RNH2
 Reagents and Conditions:
1) Warmed under DISTILLATION
2) Br2 / NaOH

9. AMINO ACIDS:
 Reactions:
i. With Acids:
NH2CH2COOH + H+ → NH3+CH2COOH
ii. With Bases:
NH2CH2COOH + OH- → NH2CH2COO- + H2O

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