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ALKYLHALIDE By Mrs. Azduwin Khasri 23 rd October 2012.

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Presentation on theme: "ALKYLHALIDE By Mrs. Azduwin Khasri 23 rd October 2012."— Presentation transcript:

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2 ALKYLHALIDE By Mrs. Azduwin Khasri 23 rd October 2012

3 ELIMINATION REACTIONS OF ALKYLHALIDES

4 ELIMINATION REACTION Elimination reactions involve the loss of elements from the starting material to form a new  bond in the product. The product of elimination reaction is an Alkene

5 E1 AND E2 REACTION E1 E-Elimination 1-Unimolecular E2 E-Elimination 2-Bimolecular

6 E2 REACTION Hydroxide cannot act as a nucleophile in this reaction because of the bulky tertiary halide. Rather, hydroxide acts as a base and abstracts a proton.

7 MECHANISM OF E2 REACTION The removal of a proton and a halide ion is called dehydrohalogenation

8 An E2 reaction is also called a  -elimination or a 1,2-elimination reaction MECHANISM OF E2 REACTION Carbon attached to halogen Carbon adjacent to α-carbon

9 The weaker the base, the better it is as a leaving group

10 The Regioselectivity of the E2 Reaction 2 structurally β-carbon base 2 product produce The major product of an E2 reaction is the most stable alkene

11 Reaction coordinate diagram for the E2 reaction 10 2-Butene formed faster than 1-butene

12 The Zaitsev Rule The more substituted alkene product is obtained when a proton is removed from the  -carbon that is bonded to the fewest hydrogens 2-β-Hydrogens3-β-Hydrogens Disubstituted Monosubstituted

13 The more substituted alkene is not always the most stable alkene

14 Conjugated alkene products are preferred over the more substituted alkene product: Do not use Zaitsev’s rule to predict the major product If the alkylhalide has a double bond or a benzene ring. 13

15 Bulky bases affect the product distribution resulting in the Hofmann product, the least substituted alkene Hofmann product Zaitsev product 14 The anti-Zaitsev Rule (Hoffmann Product) Bulky Alkyl halide Less sterically hindered Major product- Most stable product

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17 Another exception to Zaitsev’s rule STRONGEST BASE- POOREST LEAVING GROUP When the halogen is fluorine-The major product of the E2 reaction of alkyl Fluoride is the less substituted alkene. The Fluoride ion does not have as strong a propensity to leave as another halide ion.

18 Consider the elimination of 2-fluoropentane… A carbanion-like transition state Major product- Less substituted alkene

19 Carbocation vs Carbanion Carbocation stability 3° > 2° > 1° Carbanion stability 1° > 2° > 3°

20 CLASS EXERCISE 1-(E2) Which of the alkyl halides is more reactive in an E2 reaction? Br better leaving group Producing more stable alkene

21 Give the major elimination product obtained from an E2 reaction of the following alkyl halides with hydroxide ion: CLASS EXERCISE 2-(E2) ANSWER:

22 E1 REACTION First order elimination reaction Must have at least two step

23 Mechanism of E1 reaction Alkylhalide dissociates,forming carbocation A Base removes a proton from β-carbon

24 How does a weak base like water remove a proton from an sp 3 carbon? 1) The presence of a positive charge greatly reduces the pK a 2) Hyperconjugation weakens the C-H bond by electron density 23

25 The Regioselectivity of the E1 Reaction The major product in an E1 reaction is generally the more substituted alkene Fewest β-Hydrogen (According to Zaitsev rule)

26 Reaction coordinate diagram for the E1 reaction

27 Because the first step is the rate-determining step, the rate of an E1 reaction depends both on the ease with which the carbocation is formed and how readily the leaving group leaves

28 E1 AND E2 REACTION Major product generally the most stable alkene Tertiary alkyl halides are the most reactive and the primary alkyl halides are the least reactive. For alkyl halide with the same alkyl group, alkyl iodide are the most reactive and alkyl fluoride are the least reactive.

29 Because the E1 reaction forms a carbocation intermediate, we need to consider carbocation rearrangement

30 Competition Between E2 and E1 Reactions Competition Between E2 and E1 Reactions An E2 is favored by a high concentration of strong base and an aprotic polar solvent An E1 is favored by a weak base and a protic polar solvent 29 1° Carbocation are too unstable to be formed in E1 reaction

31 Stereochemistry of the E2 Reaction The bonds to the eliminated groups (H and X) must be in the same plane The anti elimination is favored over the syn elimination Parallel on the same side Parallel on the opposite side Syn elimination Anti elimination

32 Consider the stereoselectivity of the E2 reaction The alkene with the bulkiest groups on opposite sides of the double bond will be formed in greater yield, because it is the more stable alkene 31 (E)- : the higher priority groups are on opposite sides of the double bond. (Z)- : the higher priority groups are on the same side of the double bond. (E)- : the higher priority groups are on opposite sides of the double bond. (Z)- : the higher priority groups are on the same side of the double bond. Anti- elimination Syn- elimination

33 Anti- elimination Syn- elimination

34 When only one hydrogen is bonded to the  -carbon, the major product of an E2 reaction depends on the structure of the alkene 33

35 Stereochemistry of the E1 Reaction The major stereoisomer obtained from an E1 reaction is the alkene in which the bulkiest substituents are on opposite sides of the double bond Both syn and anti elimination can occur in an E1 reaction, both E and Z formed In contrast,E2 forms both E and Z only if the β-carbon is bonded to 2 Hydrogen. If β-carbon bonded to only 1 Hydrogen,E2 form only 1 product because anti elimination favored.

36 Competition Between Substitution and Elimination Competition Between Substitution and Elimination Alkyl halides can undergo S N 2, S N 1, E2, and E1 1) HO - is called nu in a substitution reaction (Attack carbon) and a base in elimination reaction (removes proton). 2) Decide whether the reaction conditions favor S N 2/E2 or S N 1/E1 S N 2/E2 reactions are favored by a high concentration of a good nucleophile/strong base S N 1/E1 reactions are favored by a poor nucleophile/weak base 3) Decide how much of the product will be the substitution product and how much of the product will be the elimination product

37 S N 2/E2 conditions 36

38 A bulky alkyl halide or a sterically hindered nucleophile encourages elimination over substitution 37

39 A strong or a bulky base encourages elimination over substitution 38

40 High temperature favors elimination over substitution: Why? Because elimination is entropically favorable. 39

41 Tertiary alkyl halides undergo only elimination under S N 2/E2 conditions: 40

42 S N 1/E1 conditions Primary alkyl halides do not form carbocations; therefore they cannot undergo S N 1 and E1 reactions. The elimination reaction favored at higher temperatures. 41

43 ASSIGNMENT 1 (SUBSTITUTION AND ELIMINATION- ALKYLHALIDE) Submit on 6 th November (Tuesday)

44 -The End-


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