Amine Chemistry PDF

# Cyanide When alkyl group is attached with carbon atom and that carbon atom is attached to nitrogen with triple bond is known as alkyl cyanide (R-C≡N). ## Nomenclature: * General Formula: R-CN or R-C≡N * Functional Group: -CN or -C≡N * Common Name: Alkyl cyanide * IUPAC Name: Alkane nitrile ##...

# Cyanide When alkyl group is attached with carbon atom and that carbon atom is attached to nitrogen with triple bond is known as alkyl cyanide (R-C≡N). ## Nomenclature: * General Formula: R-CN or R-C≡N * Functional Group: -CN or -C≡N * Common Name: Alkyl cyanide * IUPAC Name: Alkane nitrile ## Cyanide | Cyanide | Common Name | IUPAC Name | |---|---|---| | CH₃CN | Methyl cyanide | Ethane nitrile | | C₂H₅CN | Ethyl cyanide | Propane nitrile | | C₃H₇CN | Propyl cyanide | Butane nitrile | | C₄H₉CN | Butyl cyanide | Pentane nitrile | | C₅H₁₁CN | Pentyl cyanide | Hexane nitrile | **Note**: In IUPAC naming of cyanide, carbon is attached in the long chain that's why carbon is counted in the total number of carbons. ## Method of Preparation of Cyanide ### From Alkyl Halide * R-X + LiCN → RCN + LiX * R-X + MeCN → RCN + MX, M= alkali metal * R-X + KCN → RCN + KX * R-X + NaCN → RCN + NaX When alkyl halide react with AgCN, then alkyl isocyanide is formed. * RX + AgCN → RNC + AgX ### From Acid Amide * RCONH₂ P₂O₅ → RCN + H₂O ### From Diazonium Salt * C₆H₅N₂Cl + KCN Cu powder → C₆H₅CN + N₂ + KCl ## Industrial Manufacturing * RCOOH + NH₃ → RCONH₂ * RCONH2 △ → RCN + H₂O ## By Acetaldioxime * CH₃ C=N-OH △ → CH₃C≡N + H₂O * 500°C * B₀₅ # Chemical Properties of Cyanide ### Mendius Reduction Rx: When reduction is carried out with SnCl₂/HCl or LiAlH₄, alkyl cyanide gives primary amine (aliphatic/aromatic) and this reaction is known as Mendius reduction reaction: * R-C≡N + 4[H] SnCl₂/HCl → RCH₂NH₂ * or LiAlH₄ **But on reduction of alkyl iso cyanide, secondary amine is obtained:** * R-NC + 4[H] SnCl₂/HCl → CH₃NH₂ * RNH₂ (secondary amine) ### Stephen Reduction Reaction: Aliphatic as well as aromatic aldehyde can be prepared by this method. When partial reduction of R-CN is carried out with the help of SnCl₂/HCl then aldimine is obtained which on hydrolysis with boiled water gives aldehyde. * R-C≡N + 2[H] SnCl₂/HCl → R-CH=NH + H₂O * Aldimine * CH₃-C≡N + 2[H] SnCl₂/HCl → CH₃-CH=NH + H₂O * Hydrolysis * CH₃CHO + NH₃ * C₆H₅-C≡N + 2[H] SnCl₂/HCl → C₆H₅-CH=NH + H₂O * Benzaldimine * Note: Iso cyanide does not give this reaction. ### Reaction with Grignard Reagent Alkyl cyanide reacts with Grignard reagent to form firstly additional compound which on hydrolysis gives aliphatic and aromatic ketone. * R-C≡N + R-Mg-X → R-C=N-MgX * R * R-C=0 + H₂O → R-C=O + NH₃ + Mg(OH)X * R ### Hydrolysis Alkyl cyanide are hydrolyzed in acidic medium to form carboxylic acid and ammonia. * R-C≡N + 2H₂O Acidic Medium → RCOOH + NH₃ # Uses of Cyanide * Cyanide is used to make paper, textiles, plastics, killing ants, rat poison, pesticides etc. * Cyanide salts are used in metallurgy for electroplating, metal cleaning and removing gold from its ore. # Isocyanides When alkyl group is attached with nitrogen atom and this nitrogen is attached with a carbon atom with double bond and one co-ordinate bond (R-N≡C). ## Nomenclature * General Formula: R-NC * Functional Group: -NEC * Common Name: Alkyl isocyanide * IUPAC Name: Alkane iso nitrile **Note**: In isocyanide, long chain is attached with N-atom that's why C-atom is not counted in the total number of carbon atom ## Isocyanide | Compound | Common Name | IUPAC Name | |---|---|---| | CH₃-NC | Methyl isocyanide | Methane isonitrile | | CH₃-CH₂-NEC | Ethyl isocyanide | Ethane isonitrile | | C₃H₇-NC | Propyl isocyanide | Propane iso nitrile | ## Method of Preparation of Isocyanide ### From Alkyl Halide * R-X + AgCN → RNC + AgX ### By Carbyl amine RXn * RNH₂ + CHCl₃ + 3KOH → RNC + 3KCl + 3H₂O # Chemical properties ### Stephen RXn Isocyanide does not give Stephen reaction ### Rx with Grignard Reagent Isocyanide does not react with Grignard reagent ### Hydrolysis RNC on hydrolysis in acidic medium gives primary amine and carboxylic acid * RNC + 2H₂O Acidic Medium → RNH₂ + HCOOH ### Effect of Heat When less stable alkyl iso cyanide is heated, it's converted into more stable alkyl cyanide * RNC △ → R-CN ### Mendius Reduction RXn When reduction of alkyl isocyanide is done with the help of SnCl₂/HCl then secondary amine is formed. * R-NEC + 4[H] SnCl₂/HCl → CH₃NH₂ * RNH₂ # Uses of Isocyanide Isocyanides are used in pesticides, paint, and plastics. # Properties of Alkyl Cyanide vs. Alkyl Isocyanide | Properties | Alkyl cyanide | Alkyl isocyanide | |---|---|---| | Definition and Formula | When alkyl group is attached with carbon atom and that carbon atom is attached to nitrogen with triple bond is known as alkyl cyanide. R-C≡N | When Alkyl group is attached with nitrogen atom and this nitrogen atom is attached with carbon double bond and coordinate bond. R-N≡C | | Mendius Reduction Rx | When reduction is carried out with the help of SnCl₂/HCl then Primary amine is obtained. R-C≡N + 4[H] SnCl₂/HCl → RCH₂NH₂ | When reduction is carried out with the help of SnCl₂/HCl then Secondary amine is formed. R-NEC + 4[H] SnCl₂/HCl → CH₃NH₂| | Method of preparation | (a) From RX b/w R-X and alkali metal cyanide | (a) By carbyl amine Rx (b) By Rxn b/w RX and AgCN (c) By acetamide (d) by diazonium salt | | Stephen Rx | Alkyl cyanide gives aldehydes on Stephen rx. R-C≡N + 2[H] SnCl₂/HCl → R-CH=NH + H₂O | Alkyl isocyanide does not give Stephen reaction. | | Reaction with Grignard reagent | Alkyl cyanide react with Grignard reagent to form ketones. R-C≡N + R-Mg-X → R-C=N-MgX | Alkyl isocyanide does not react with Grignard reagent. | | Hydrolysis | In acidic medium it gives carboxylic acid and ammonia. RCN+2H₂O → RCOOH + NH₃ | In acidic medium it gives primary amine and formic acid. RCN+2H₂O → RINH₂ + HCOOH | | Thermal Stability | Alkyl cyanide is stable and it can not be converted into isocyanide. | Alkyl isocyanide are unstable which on heating are converted in alkyl cyanide. RNC → RCN | # Matching Columns ## Matching Column 1 | I | II | |---|---| | Explosive | TNT | | Nitrobenzene | Oil of Mirbane | | Hinsberg Reagent | C₆H₅SO₂Cl | | Carbyl amine RXn | Primary amine | | Diazonium Salt | C₆H₅N₂Cl | | Mustard Oil Rxn | Alkyl isothiocyanate | ## Matching Column 2 | I | II | |---|---| | C₆H₅SO₂Cl | Hinsberg Reagent | | C₆H₅CH=N-C₆H₅ | Schiff Base | | CCl₃-NO₂ | Chloropicrine | | (CH₃-CH₂)₂-N-N=O | Nitroso amine | | Diazotization | Aromatic primary amine | | TNB | Explosive | | CH₃-NCS | Smells mustard oil | | CH₃NH + CH₃I | Primary amine | ## Matching Column 3 | I | II | |---|---| | Hinsberg Reagent | C₆H₅SO₂Cl | | TNT | Explosive | | CCl₃-NO₂ | Chloropicrine | | Diazonium Salt | C₆H₅N₂Cl | | Primary amine + HNO₂ | Alcohol | ## Matching Column 4 | I | II | |---|---| | Explosive | TNT | | Nitrobenzene | Oil of Mirbane | | Hinsberg Reagent | C₆H₅SO₂Cl | | Carbyl amine Test | Primary amine | | Mustard Oil Rxn | Alkyl isothiocyanate | | Nitrating mixture | Conc. HNO₃ + Conc. H₂SO₄ | | Isocyanide | R-N≡C | | Ammonolysis | Rxn of RX and NH₃ | # Answer in One Word/Sentence 1. **Write the name of reaction:** C₆H₅NaCl + CuCl/HCl → C₆H₅Cl + NaCl + HCl * **Sandmeyer reaction** 2. **Write the name of reaction:** C₆H₅NH₂ + HNO₂ 0°C → C₆H₅N₂Cl * **Diazotisation** 3. **Reduction of nitrobenzene in acidic medium, what is formed?** * **Aniline** 4. **Write the name of this reaction:** C₆H₅NO₂ + 6[H] Sn/HCl → C₆H₅NH₂ + 2H₂O * **Mendius reduction reaction** 5. **On heating acetamide in the presence of P₂O₅, what is formed?** * **CH₃CN** 6. **Write the name of reaction:** CH₃COOH + NaN₃ → CH₃NH₂ + CO₂ + N₂ * **Schmidt reaction** 7. **In which Rx primary amine is heated with CS₂ and HgCl₂?** * **Mustard oil reaction** 8. **Dyes are formed by which reaction?** * **Coupling reaction** 9. **On heating aniline with KOH and CHCl₃, what is formed?** * **Phenyl isocyanide** 10. **C₆H₅N₂Cl + HCl Cu powder → C₆H₅NH₂ + N₂ + HCl** * **Gatterman reaction** 11. **Write the chemical formula and chemical name of the Hinsberg reagent?** * **C₆H₅SO₂Cl, benzene sulphonyl chloride** 12. **Which amine gives diazotization reaction?** * **Aromatic primary amine** 13. **What is nitrating mixture?** * **Conc. H₂SO₄ + conc. HNO₃** 14. **What is oil of mirbane?** * **Nitrobenzene** 15. **What is diazotization reaction?** * **Conversion of aromatic primary amine into diazonium salt with the help of HNO₂ or NaNO₂/HCl at 0°C. It is called diazotization.** 16. **Secondary amine is tested by which method?** * **Liebermann nitrosoamine test** 17. **On exposing in air, aniline turns black. Why?** * **Aniline exposed in air then it reacts with oxygen and turns brown-black. It is due to the formation of aniline oxide.** 18. **Acetylation is not given by tertiary amine. Why?** * **Due to absence of active H-atom** 19. **For differentiating primary, secondary, and tertiary amine, which reagent is used?** * **Hinsberg reagent** 20. **Write the formula of 'X':** C₆H₅NO2 + 6[H] Sn/HCl → X + 2H₂O * **C₆H₅NH₂** 21. **Methyl orange indicator is formed by which reaction?** * **Coupling reaction** 22. **By which reaction methyl isocyanide is formed?** * **Carbyl amine reaction** 23. **Aldehyde or ketone reacts with primary amine then what is formed?** * **Schiff’s base** 24. **The Rxn of diazonium salt with phenol/amine is called?** * **Coupling reaction** 25. **Write down the decreasing order of aromatic amine, ammonia, and aliphatic amine on the basis of basicity:** * **Aliphatic amine > NH3 > Aromatic amine** 26. **In nitrating mixture which type of electrophile is present.** * **Nitronium ion (NO₂⁺)** 27. **In the aqueous solution of aniline on adding bromine water which ppt is formed?** * **2,4,6- tribromo aniline** 28. **Write the nature of amines.** * **Basic nature** # Fill in the Blanks 1. **Carbyl amine test gives only _______ amine.** * **Primary** 2. **By reduction of cyanide _______ and by the reduction of isocyanide _______ is formed.** * **Primary amine**, **secondary amine** 3. **The reaction of benzoic acid and hydrazoic acid, _______ is formed.** * **aniline** 4. **All aliphatic amine are more _______ in nature than ammonia.** * **basic** 5. **Primary and secondary amine reacts with grignard reagent to form _______** * **alkane** 6. **Trinitro toluene (TNT) is _______ substance.** * **explosive** 7. **Ethylamine/methylamine are more _______ than ammonia.** * **more** 8. **In the presence of NaOH, the benzylation of amine is done and is called _______ rxn.** * **Schotten-Baumann reaction** 9. **The basic nature of amine is due to the presence of _______ on Nitrogen atom.** * **lone pair of electron** 10. **The mixture of TNT and ammonium nitrate is called ______.** * **Amatol** 11. **On heating primary amine with _______ and _______ to obtain RNC.** * **CHCl₃**, **KOH** 12. **On heating alkyl isocyanide at 200°C, ______ is obtained.** * **Alkyl cyanide** 13. **On reaction of aniline with HCl and NaNO₂ at 0°C to form C₆H₅N₂Cl and this reaction is called ______.** * **Diazotisation** 14. **The main product of mustard oil reaction is ________.** * **Alkyl isothiocyanate** 15. **C₆H₅N=C=S reacts with H₂O to form ______.** * **Phenol** 16. **_______ is identified by the Liebermann nitroso amine rxn.** * **Secondary amine** 17. **Oil of Mirbane is also called ______.** * **Nitrobenzene** 18. **C₆H₅COOH + ______ → C₆H₅NH₂ + CO₂ + N₂** * **NaN₃** 19. **On reduction of nitrobenzene, _______ is obtained.** * **Aniline** 20. **Amines are _______ in nature.** * **Basic** 21. **The general formula of diazonium salt is ______.** * **ArN₂⁺X^-** 22. **Aromatic amines are ______ in water.** * **Insoluble**