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1 Chapter 11 Alkynes. 2 general molecular formula C n H 2n-2 the triple bond introduces two degrees of unsaturation. Introduction—Structure and Bonding.

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Presentation on theme: "1 Chapter 11 Alkynes. 2 general molecular formula C n H 2n-2 the triple bond introduces two degrees of unsaturation. Introduction—Structure and Bonding."— Presentation transcript:

1 1 Chapter 11 Alkynes

2 2 general molecular formula C n H 2n-2 the triple bond introduces two degrees of unsaturation. Introduction—Structure and Bonding

3 3 Cf.  bond in CH 2 CH 2 : 64 Kcal/mol Both  bonds of a C-C triple bond are weaker than the C- C double bond for homolytic cleavage. Alkynes are more polarizable than alkenes. Cyclooctyne is the smallest isolable cycloalkyne, though it decomposes upon standing at room temperature after a short time.

4 4 Alkynes Alkynes are named in the same general way that alkenes are named. In the IUPAC system, change the –ane ending of the parent alkane name to the suffix –yne. Choose the longest continuous chain that contains both atoms of the triple bond and number the chain to give the triple bond the lower number. Compounds with two triple bonds are named as diynes, those with three are named as triynes and so forth. Compounds both a double and triple bond are named as enynes. The chain is numbered to give the first site of unsaturation (either C=C or C  C) the lower number. The simplest alkyne, H-C  C-H, named in the IUPAC system as ethyne, is more often called acetylene, its common name. The two-carbon alkyl group derived from acetylene is called an ethynyl group. Nomenclature

5 5 Alkynes Nomenclature

6 6 Alkynes The physical properties of alkynes resemble those of hydrocarbons of similar shape and molecular weight. Alkynes have low melting points and boiling points. Melting point and boiling point increase as the number of carbons increases. Alkynes are soluble in organic solvents and insoluble in water. Physical Properties

7 7 Alkynes Acetylene and Other Interesting Alkynes Acetylene (H-C  C-H) is a colorless gas that burns in oxygen to form CO 2 and H 2 O. Closest hydrocarbon to charcoal and is an excellent fuel.

8 8 Acetylene and Other Interesting Alkynes

9 9 Alkynes Acetylene and Other Interesting Alkynes Ethynylestradiol and norethindrone are two components of oral contraceptives that contain a carbon-carbon triple bond. Both molecules are synthetic analogues of the naturally occurring female sex hormones estradiol and progesterone, but are more potent so they can be administered in lower doses. Most oral contraceptives contain both of these synthetic hormones. They act by artificially elevating hormone levels in a woman, thereby preventing pregnancy.

10 10 Alkynes Acetylene and Other Interesting Alkynes blocks the effects of progesterone, thus preventing pregnancy and inducing abortions interferes with ovulation, and so it prevents pregnancy

11 11 Alkynes Preparation of Alkynes

12 12 Alkynes Preparation of Alkynes

13 13 Introduction to Alkyne Reactions—Additions

14 14 Introduction to Alkyne Reactions—Acids & Nucleophile

15 15 Hydrohalogenation—Electrophilic Addition of HX hydrohalogenation

16 16 Alkynes Hydrohalogenation—Electrophilic Addition of HX

17 17 Alkynes Electrophilic addition of HX to alkynes is slower than electrophilic addition of HX to alkenes Introduction to Alkyne Reactions Markovnikov addition

18 18 Alkynes Carbocation A is stabilized by resonance, but B is not. Introduction to Alkyne Reactions

19 19 Alkynes Halogenation—Addition of Halogen

20 20 Alkynes Halogenation—Addition of Halogen

21 21 Alkynes In the presence of strong acid or Hg 2+ catalyst, the elements of H 2 O add to the triple bond. Hydration—Electrophilic Addition of Water

22 22 Alkynes Hydration—Electrophilic Addition of Water Internal alkynes undergo hydration with concentrated acid terminal alkynes require the presence of an additional Hg 2+ catalyst—usually HgSO 4 —to yield methyl ketones by Markovnikov addition of water.

23 23 Tautomerism : the conversion of a general enol A to the carbonyl compound B. A and B are tautomers: A is the enol form and B is the keto form of the tautomer. Hydration—Electrophilic Addition of Water Equilibrium favors the keto form largely because the C=O is much stronger than a C=C. Tautomerization (the process of converting one tautomer into another), is catalyzed by both acid and base.

24 24 Alkynes Hydration—Electrophilic Addition of Water

25 25 Alkynes Hydration—Electrophilic Addition of Water

26 26 Alkynes Hydroboration—Oxidation Hydroboration—oxidation is a two step reaction sequence that converts an alkyne to a carbonyl compound.

27 27 Alkynes Hydroboration—Oxidation

28 28 Alkynes Introduction to Alkyne Reactions—Acetylide anions

29 29 Alkynes Reactions of Acetylide Anions Acetylides are strong nucleophiles the mechanism of substitution is S N 2, and thus the reaction is fastest with CH 3 X and 1 0 alkyl halides.

30 30 Alkynes Reactions of Acetylide Anions nucleophilic substitution with acetylide anions forms new carbon-carbon bonds in high yield only with unhindered CH 3 X and 1 ° alkyl halides.

31 31 Alkynes Reactions of Acetylide Anions

32 32 Alkynes Reactions of Acetylide Anions

33 33 Alkynes Reactions of Acetylide Anions Carbon—carbon bond formation with acetylide anions is a valuable reaction used in the synthesis of numerous natural products.

34 34 Alkynes Reactions of Acetylide Anions Acetylide anions are good nucleophiles that open epoxide rings by an S N 2 mechanism. Backside attack occurs at the less substituted end of the epoxide.

35 35 Alkynes Synthesis You can now begin to consider (for example) how to prepare a five-carbon product from three smaller precursor molecules using the reactions you have learned. To plan a synthesis of more than one step, we use the process of retrosynthetic analysis : working backwards from a desired product to determine the starting materials from which it is made.

36 36 Alkynes Synthesis In designing a synthesis, reactions are often divided into two categories: 1. Those that form new carbon-carbon bonds. 2. Those that convert one functional group into another—that is, functional group interconversions.

37 37 Alkynes Synthesis

38 38

39 39

40 , 11.37, 11.40, 11.41, 11.44, 11.46, 11.47, 11.50, 11.51, Homework

41 41 Preview of Chapter 12 Oxidation and Reduction Reduction What is the reaction condition for reducting alkyne to cis-double bond? What is the reaction condition for reducting alkyne to trans-double bond? Oxidation How can you make epoxide from olefin? What is ozonolysis?


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