ORGANIC OPTION -G

1. ORGANIC OPTION -G

2. IB Core Option Objective Electrophilic Addition Reactions • G.1.1 Describe and explain the electrophilic addition mechanisms of the reactions of alkenes with halogens and hydrogen halides.

3. Terms • Electrophile: • Carbocation: • Carbocationstabalization: • Nucleophile: (Loves positives) Any molecule or ion that has a lone pair of electons

4. G.1.1 Describe and explain the electrophilic addition mechanisms of the reactions of alkenes with halogens and hydrogen halides. • Alkene double bond is attacked by an electrophile Cl Cl – Cl Cl H H + C C H H 1-Chloroethane

5. IB Core Option Objective • G.1.2 Predict and explain the formation of the major product in terms of the relative stabilities of the carbocations.

6. G.1.2 Predict and explain the formation of the major product in terms of the relative stabilities of the carbocations. • Markovnikov’s Rule • H-X when added to a multiple bond molecule, hydrogen will always add to the carbon with the most hydrogen's. Primary Secondary Tertiary Increasing stability

7. Carbocation stabilization • Iodine monochloride: • Identify the more electronegative group • Is the molecule polar? • Draw the steps for how the product is formed, and name the product. Iodine monochloride + propene

8. IB Core Option Objective Nucleophilic Addition Reactions • G.2.1 Describe, using equations, the addition of hydrogen cyanide to aldehydes and ketones. • G.2.2 Describe and explain the mechanism for the addition of hydrogen cyanide to aldehydes and ketones.

9. G.2.1 Describe, using equations, the addition of hydrogen cyanide to aldehydes and ketones. • HCN + OH-  H2O + CN- (Requires a base catalyst to make CN- which is a better nucleophile) • Significance: Increases carbon chain length by one carbon Cyanide ion + Propanone

10. G.2.1 Describe, using equations, the addition of hydrogen cyanide to aldehydes and ketones. Which end is slightly positive and negative? C C • Draw the VSEPR diagram for CN- H O O R R R

11. G.2.2 Describe and explain the mechanism for the addition of hydrogen cyanide to aldehydes and ketones. • CH3CHO + HCN with OH- • Get in partners, use the molecular model kits and make the structures for each. • Play out the steps for this reaction in pairs. • While working the steps in 3D, show the steps for this reaction on paper, showing the intermediate step and the product. Use curly arrows to show electron transfer.

12. IB Core Option Objective • G.2.3 Describe, using equations, the hydrolysis of cyanohydrins to form carboxylic acids.

13. G.2.3 Describe, using equations, the hydrolysis of cyanohydrins to form carboxylic acids. • The Nitrogen group can be removed by: • 1) Adding a base to produce carboxylic acid & NH3 • 2) By adding an acid to produce NH4+ O C R C N R Acid (H+) O Base (OH-) O- C R NH4+ NH3 OH

14. G.2.3 Describe, using equations, the hydrolysis of cyanohydrins to form carboxylic acids. Hydrolysis • Take the product you made from the previous reaction (2-hydroxypropanenitrile) and react it with water and acid. What are your products? • A: 2-hydroxypropanoic acid (lactic acid) and NH4+.

15. G.2.3 Describe, using equations, the hydrolysis of cyanohydrins to form carboxylic acids. H H C C C C H H H H H H H C O O O O H H

16. IB Core Option Objective • G.4.1 Describe, using equations, the reactions of 2,4-dinitrophenylhydrazine with aldehydes and ketones.

17. G.4.1 Describe, using equations, the reactions of 2,4-dinitrophenylhydrazine with aldehydes and ketones. • Addition: 2,4 –dinitrophenylhydrazine acts as a nucleophile (non-bonding pair of electrons). • Elimination: The two hydrogens bonded to the nitrogen will bond with the oxygen on a ketone or aldehyde, causing atoms to be eliminated to form water. NO2 N N H H H NO2

18. G.4.1 Describe, using equations, the reactions of 2,4-dinitrophenylhydrazine with aldehydes and ketones. Significance: Creates an orange-yellowprecipitate which can be melted to test what ketones or aldehydes are present in solution based on its MP. N N H NO2 H H NO2 + Propanone Note: Products from these reactions are called 2,4-dinitrophenylhydrazones. You do not need to know how to name specific products for this reaction.

19. You don’t need to know every step!

20. G.4.1 Describe, using equations, the reactions of 2,4-dinitrophenylhydrazine with aldehydes and ketones.

21. IB Core Option Objective • G.3.1 Describe, using equations, the dehydration reactions of alcohols with phosphoric acid to form alkenes. • G.3.2 Describe and explain the mechanism for the elimination of water from alcohols.

22. G.3.1 Describe, using equations, the dehydration reactions of alcohols with phosphoric acid to form alkenes. • What would the equation be for the dehydration of ethanol? • A: C2H5OH → C2H4 + H2O • What would be needed to protonate the hydroxyl group? Is it a catalyst or part of the products? • A: Strong acid, preferably phosphoric (V) acid, H3PO4. It is a catalyst, since a proton is donated back to regenerate the acid.

23. G.3.2 Describe and explain the mechanism for the elimination of water from alcohols. Dehydration of alcohols to form alkenes using acids. Concentrated phosphoric acid Butan-1-ol 180 oC Concentrated phosphoric acid Butan-2-ol 180 oC

24. G.3.2 Describe and explain the mechanism for the elimination of water from alcohols. Mechanism Butan-1-ol Phosphoric acid Carbocation H O PO3H2 Conjugate Base Carbocation Butene

25. IB Core Option Objective • G.5.1 Describe and explain the structure of benzene using physical and chemical evidence. • For physical evidence, include a comparison of carbon–carbon bond lengths in alkanes, alkenes and benzene, and the number of structural isomers with the formula C6H4X2. • For chemical evidence, include a comparison of the enthalpies of hydrogenation of benzene, cyclohexene, 1,3‑cyclohexadiene and 1,3,5-cyclohexatriene, and the tendency of benzene to undergo substitution rather than addition reactions.

26. G.5.1 Describe and explain the structure of benzene using physical and chemical evidence. What do you know? You already know some things about benzene. Brainstorm with a partner what you already know! Think back to Topic 4 or 10!

27. G.5.1 Describe and explain the structure of benzene using physical and chemical evidence. • Arenes: Compounds that contain benzene ring. • How do we know: Three separate double bonds with localized electrons or resonance structure with delocalized electrons? OR

28. Booya double bond I’m gonna react you good!! Arenes What the? ? • Evidence: • 1) Will not react with bromine water • Significance: There must be no double bonds • 2) Six equal bond lengths • Significance: No alternating double/ single bonds as double bonds are shorter, single bonds are longer. • 3) Benzene is more thermodynamically stable • Significance: Combustion of cyclohexatriene should result in more energy released then predicted. Double bonds are shorter than single!!! Br Br

29. G.5.1 Describe and explain the structure of benzene using physical and chemical evidence. 4) There are no second structural isomers for 1,2 disubstituted benzene compounds. (There is only one) 5) Look at the study guide for the enthalpy of hydrogenation of cyclohexene. What would you expect if you hydrogenated two more double bonds, compared to what happens in benzene?

30. IB Core Option Objective • G.5.2 Describe and explain the relative rates of hydrolysis of benzene compounds halogenated in the ring and in the side-chain. • Only the reactions with the OH– ion will be assessed.

31. G.5.2 Describe and explain the relative rates of hydrolysis of benzene compounds halogenated in the ring and in the side-chain. • Arenes can be halogenated directly on the benzene ring: • Or they can be halogenated on a side chain to the ring:

32. G.5.2 Describe and explain the relative rates of hydrolysis of benzene compounds halogenated in the ring and in the side-chain. • If it is on the side chain, it undergoes nucleophilic substitution just like a halogenoalkane. What is needed as a reagent and what would the mechanism be? ? + → ? A: Aqueous NaOH, SN2

33. G.5.2 Describe and explain the relative rates of hydrolysis of benzene compounds halogenated in the ring and in the side-chain. • If the halogen atom is directly attached, nucleophilic substitution does not occur, or it occurs very slowly. • This is due to the dense cloud of electrons surrounding the arene ring, thus the nucleophile is repelled. • It is also due to the stronger C-Br bond from the benzene than the C-Br bond in halogenoalkanes.

34. IB Core Option Objective • G.6.1 Outline the formation of Grignard reagents. • G.6.2 Describe, using equations, the reactions of Grignard reagents with water, carbon dioxide, aldehydes and ketones.

35. G.6.1 Outline the formation of Grignard reagents. • Using halides to create longer carbon chains by Nucleophilic addition, particularly using electron deficient carbons on ketones and aldehydes • Grignard Reagents δ- δ+ Mg + R-X R-Mg-X Carbon anion formed due to the electronegativity difference between C-Mg

36. G.6.2 Describe, using equations, the reactions of Grignard reagents with water, carbon dioxide, aldehydes and ketones. H H – δ- C C H H H H δ- δ+ R--Mg--X R H+ -- + H Acid removes remaining part of Grignard reagent in the intermediate step C Mg--X O

37. Reactions and Products • 1) R-Mg-Cl + CO2  R-COOH • Carbon dioxide  Carboxylic acid • 2) R-Mg-Cl + H2O  R-H + Mg(OH)Cl • Ketone  Alkane • 3) R-Mg-Cl + C=O  R-C-OH • Methanal  Primary alcohol • 4) R1-Mg-Cl + R2-CHO  R1-CH(R2)-OH • Aldehyde  Secondary alcohol • 5) R1-Mg-Cl + R2-CO-R3  R1-C(R2R3)-OH • Ketone  Tertiary alcohol

38. Questions • Mg + 1-Chloroethane • 1) Grignard + Water  • 2) Grignard + Carbon dioxide  • 3) Grignard + Methanal  • 4) Grignard + Propanal  • 5) Grignard + Propan-2-one  • 6) Make the Grignard 2-Chlorobutane

39. IB Core Option Objective • G.8.1 Describe and explain the acidic properties of phenol and substituted phenols in terms of bonding. • Review: If an acid has a weak conjugate base, is it a strong or weak acid? A: It is strong.

40. G.8.1 Describe and explain the acidic properties of phenol and substituted phenols in terms of bonding. • Phenols are weakly acidic, but stronger than ethanol. • This is because the negative charge on the conjugate base can be spread out over the entire benzene ring (resonance). Can you figure out the other resonance structures?

41. G.8.1 Describe and explain the acidic properties of phenol and substituted phenols in terms of bonding. • Negative charge can be spread even further when nitro groups are added. • They are electron withdrawing, leading to an even weaker conjugate base. • Thus, 2,4,6-trinitrophenol is a strong acid. • A group that donates electrons, such as CH3, will make the anion less stable (stronger conjugate base) and the acid weaker. • Q: What would the order of pKa, from largest to smallest, be for ethanol, phenol, 2-methylphenol, and 2,4,6-trinitrophenol? • A: Ethanol: pKa=16, 2-methylphenol pKa = 10.26, Phenol pKa=10.0, 2,4,6-trinitrophenol pKa=0.42

42. IB Core Option Objective • G.8.2 Describe and explain the acidic properties of substituted carboxylic acids in terms of bonding.

43. G.8.2 Describe and explain the acidic properties of substituted carboxylic acids in terms of bonding. • The conjugate base of carboxylic acids has two resonance forms. • Adding more methyl groups will have a positive inductive effect, making the acid weaker. • Adding electron withdrawing substituents such as chlorine will make the acid stronger.

44. IB Core Option Objective • G.8.3 Compare and explain the relative basicities of ammonia and amines.

45. G.8.3 Compare and explain the relative basicities of ammonia and amines. • Like ammonia, amines will act as weak bases when dissolved in water: R-NH2 + H2O R-NH3 + OH- • Alkyl amines are stronger bases than ammonia (positive inductive effect). • The longer the alkyl group, the more basic the amine. • The base strength increases from a primary amine to a tertiary amine.

46. G.8.3 Compare and explain the relative basicities of ammonia and amines. • What would the equation be if ethylamine reacted with hydrochloric acid? • A: C2H5NH2 + HCl→ C2H5NH3+Cl- (ethylammonium chloride) • What would happen if you were to react the ethylammonium chloride with warm sodium hydroxide? • A: C2H5NH3+Cl- + NaOH→ C2H5NH2+ NaCl + H2O

47. Advanced Question • How can you make 2,3 dimethyl-pent-3-ol • Using only Propan-1-ol and Butan-1-ol • Press for hint # 1 • Press for hint # 2 • Press for hint # 3 • Press for hint # 4 • Press for hint # 5 • Press for hint # 6 • Press for hint # 7 OH Cl MgCl OH OH