A2 Organic Reactions / Reagents & Conditions

A2 Organic Reactions / Reagents & Conditions

1. GRIGNARD REAGENTS

Ø  Preparation:

  i.  HALOALKANE + Mg → GRIGNARD

·  Reagents and Conditions:

1)  Heat under reflux

2)  Dry Ether

3)  Single Crystal of Iodine catalyst if needed

Ø  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

Ø  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

Ø  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:

Ø  Preparation:

  i.  CARBOXYLIC ACID + PCl5 → ACID CHLORIDE + HCl + POCl3

Ø  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

4.  ESTERS:

Ø  Preparation:

  i.  CARBOXYLIC ACID + ALCOHOL ↔ ESTER + H2O

·  Reagents and Conditions:

1)  Warmed under reflux

2)  With concentrated H2SO4

  ii.  ACID CHLORIDE + ALCOHOL → ESTER + HCl

Ø  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:

Ø  Preparation – Aldehydes:

  i.  1º ALCOHOL + [O] → ALDEHYDE + H2O

·  Reagents and Conditions:

1)  Heat under DISTILLATION

2)  Potassium Dichromate / H2SO4

Ø  Preparation – Ketones:

  i.  2º ALCOHOL + [O] → KETONE + H2O

·  Reagents and Conditions:

1)  Heat under reflux

2)  Potassium Dichromate / H2SO4

Ø  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

Ø  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

Ø  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

6.  1º AMINES

Ø  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

Ø  Reactions – With ACIDS

  i.  AMINE + HCl → ALKYL AMMONIUM+CHLORIDE-

  ii.  AMINE + CH3COOH → ALKYL AMMONIUM ETHANOATE

Ø  Reactions – With ACID CHLORIDES

  i.  AMINE + ACID CHLORIDE → SUBSTITUTED AMIDE + HCl

7.  NITRILES

Ø  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

Ø  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:

Ø  Preparation:

  i.  ACID CHLORIDE + NH3 → AMIDE + HCl

  ii.  ACID CHLORIDE + AMINE → AMIDE– R + HCl

Ø  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:

Ø  Reactions:

  i.  With Acids:

NH2CH2COOH + H+ → NH3+CH2COOH

  ii.  With Bases:

NH2CH2COOH + OH- → NH2CH2COO - + H2O