13 Alkynes: The Carbon—Carbon Triple Bond Now chat the properties of carbon-carbon double bonds have been examined in detail, it's time to have a brief look at their relatives. carbon-carbon triple bonds. Not surprisingly, what you will find will be very simiker 0 What you've just seen, Addition reactions will make up the main portion of triple bond chemistry, An impor- tant feature is the hydrogen attached to triply bonded carbon: It is unusually acidic, allowing ready removal by strong bases to form a new and synthetically useful class of earbanions called alkynyl anions. Outline of the Chapter 13-1 Nomenclature 13-2 Structure and Bonding 13-3. Spectroscopy of the Alkynes An urusual effect in the NMR due to electron motion. 13-4 Preparation of Alkynes by Double Elimination 13-5 Preparation of Alkynes by Alkylation of Alkynyl Anions A. synthesis of internal alkynes stating from terminal alkynes, 13-6, 137, 13-8 Reactions of Alkynes 13.9 Alkeny! Halides A brief description of these compounds, and an introduction to reactions of organic compounds catalyzed by transition metals. 13-10 Ethyne as an Industrial Starting Material 13-11 Naturally Occurring and Physiologically Active Alkynes Keys to the Chapter 13-1 and 13-2, Nomenclature, Structure, and Bonding ‘The alkyne functional group has a geometry simpler than that of the alkenes: Its linear. Thus, no cis-trans iso: merism is possible; and in naming the alkynes it is necessary only to indicate the position of the triple bond. ‘When the triple tond is at the end of a chain, itis said to be terminal, and it thus possesses a —C=C—H unit, This hydrogen is characterized by unexpectedly high-field absorption in the proton NMR spectrum and by a very strong, polarized carbon-hydrogen bond, making it relatively acidic. Section 13-5 examines some conse- quences of that acidity268 * Chapter 13 AIKYNES: THE CARBON-CARBON TRILE BOND 13-3. Spectroscopy of the Alkynes ‘The high-field position of the hydrogen resonance is surprising at first, but it is the logival result of the eylin- Grical symmetry of the triple bond, which allows electrons to rotate in tight circle about its axis, These alkyne signals are often easy to spot because of their characteristic splitting patterns, which arise from long-range cou- pling to the neighboring nucle across the triple bond (see, for instance, the alkynyl hydrogen triplet in Fig, 13-5), Other NMR properties of these compounds are pretty normal. Diagnestie bands for C=C and =C—H in the IR spectra of terminal alkynes complement the NMR data, especially when the latter beeome more com- plex as a result of overlapping signals. Take note, however, of the weakness or even absence of an IR band for triple bonds. 13-4, Preparation of Alkynes by Double Elimination ‘The elimination woute to alkynes involves removal of two moles of hydrogen halide by strong base from a dihaloalkane. The most common kind of sequence involves forming the dihaloalkane by addition of halogen to-an alkene double bond. Because you already know how to make alkenes, you now have a in the following way: cess to alkynes or iin ee Bes ss see cH, cur *# KOC Haloatkane Adon ctiati cucu 8", — cur cHpr SE, cae Alkene 1.2-Dihatostkane Alkyne 13-5. Preparation of Alkynes from Alkynyl Anions The other major alkyne preparation is based on the easy accessibility of nucleophilic curbanions from termi- nal alkynes (Section 13-2). So, a Wide variety of internal alkynes may be made from any terminal alkyne, via the scheme R-C=C-H ROC Nucleophile where is the electrophi arbon in a primary haloalkane, a strained cyclic ether, or a carbony\ compound, 13-6, 13-7, and 13-8. Reactions of Alkynes Just as you saw with alkenes, alkynes are subject to a variety of addition reactions. These can occur in two stages: a single addition to make an alkene, and then a second addition to give an alkane derivative. The mech- anisms, stereochemistry and regiochemistry, are essentially analogous to those you've already seen. So, you can Jook back to the reactions of the previous chapter as points of reference. Only an occasional detail or two will be different. When you choose to stop the addition reaction at the alkene stage, there is often the possi bility of picking reagents and conditions to allow for specific formation of either the trans or cis alkene prod uct, This flexibility further contributes to the usefulness of alkynes in synthesis. A special note should be made concerning hydration reactions of alkynes. Remember that hydration of alkenes leads to alcohols. Alkynes can be hydrated, too. Markovnikov addition is achieved with an aqueousSolutions to Problems * 269° acidic Hg(I1) catalyst. Anti-Markovnikov addition ovcurs via modified hydroboration-oxidation sequence. Both initially give vinylic alcohols (or enols) as products, but these are kinetically and thermodynantically un- stable and isomerize to carbonyl compounds in a reaction called tautomerism o-H 1 6 Z ‘The latter is thermodynamically favorable because of the very strong carbon-oxygen double bond that is formed. It is Kizetically rapid because the enol OH bond is acidic and readily deprotonated, allowing the proton eventually to find its way to the nearby carbon, More details concerning the process will be upcoming when carbonyl compounds are discussed. Note that the hydration of alkynes is a new synthesis of aldehydes and ketones, 13-9. Alkeny| Halides Although the carbon—halogen bonds in alkenyl halides do not participate in the usual substitution reactions. they may be converted into carbon—metal honds. thus allowing formation of lithium and Grignard reagents that can be used in the synthesis of allylic alcohols by exposure to ketones and aldehydes. The alkeny! halide carbon-halogen bond is also reactive in a variety oF transformations involving transition metals. The Heck reaction utilizes this property to enable the coupling of the halogen-hearing carbon oF an alkenyl halide to one of the double-bonded carbons of a second alkene, giving rise to dienes as products. We ‘won't be exploring this kind of chemistry in much depth, partly because it falls outside the scope of main- stream mechanistic organic chemistry. However, take note of the fact that such processes aow make Up an important part of the so-called synthetic toolbox of the pharmaceutical and medicinal chemist: Reactions such as these have made the syntheses of many types of compounds of therapeutic value much easier than was the cease before their discovery and development Solutions to Problems 27. (a) I= (by = © wo ~~ F# 28. (a) 3-Chloro-3-methyl-I-butyne (b) 2-Methyl-2-batyn-2-01 (©) 4-Propyl-S-hexyn-I-ol (A) srans-3-Penten-|-yne (e) E-5-Methyl-4-(1-methylbutyl)-4-hepten-2-yne (1) cis-1-Ethenyl-2-ethynyleyclopentane 29. Bond strengths: ethyne > ethene > ethane. Ethyne C—H bond uses the sp orbital from carbon, which overlaps best with the Ly orbital on hydrogen. The high (50%) s character strongly attracts the bonding, electrons to the carbon nucleus. This effect shifts these electrons closer to carbon, thereby enhancing the bond polarity, which follows the same order: °-C—H®" greatest in ethyne. In turn, the greater bond polarity