Synthesis (5) – Reactions of Alkynes
Last updated: November 15th, 2022 |
A Reaction Map For Alkynes (PDF)
Today, we’re going to add the reactions of alkynes to our reaction map, which will bring to a close all the major reactions we’ve discussed so far in a typical first semester course.
- Summary of Alkyne Reactions: Addition, Deprotonation (+ SN2), And Oxidative Cleavage
- Key Reactions of Alkynes
- Visualizing The Addition and Oxidative Cleavage Reactions of Alkynes With A Reaction Map
- A Full Reaction Map PDF For First-Semester Organic Chemistry: Alkanes, Alkyl Halides, Alkenes, and Alkynes
1. Summary of Alkyne Reactions: Addition, Deprotonation (+ SN2), And Oxidative Cleavage
Like alkenes, the main pathway found in the reactions of alkynes is “addition” – that is, breaking the C-C π bond and forming two new single bonds to carbon. The product of an addition reaction to an alkyne is an alkene – and, as we just mentioned, alkene reactions undergo addition reactions too. The upshot of this is that since alkynes possess two π bonds, one must always be alert to the possibility of two addition reactions occurring. Furthermore, should only one addition occur, the stereochemistry of the addition should be well noted, as it can lead to the formation of geometric isomers (see post: E and Z Notation for Alkenes).
Finally, there is an additional complexity in certain alkyne reactions that is not found in the reactions of alkenes. When water is added across an alkyne, the resulting product is an “enol”. (See post: Hydroboration and Oxymercuration of Alkynes)
And enols, as you’ll learn more about in Org 2, tend to be fairly unstable species. Through a process called tautomerism, (See post: Keto-Enol Tautomerism)they convert to their constitutional isomers containing carbonyl (C=O) groups such as aldehydes and ketones.
Another reaction not present in the reactions of alkenes is deprotonation. Alkynes are unusually acidic hydrocarbons, with a pKa of about 25 (compare that to alkenes (pka = 43) and alkanes (pKa = 50). The deprotonation of alkynes leads to its conjugate base, an “acetylide”, which is an excellent nucleophile (See post: Acetylides from Alkynes)
The reaction of acetylides with alkyl halides (in SN2 reactions) is one of the few carbon-carbon bond forming reactions learned in Org 1, which makes it arguably the most important reaction to learn for synthesis this semester.
Finally, alkynes also undergo oxidative cleavage reactions. Treatment of alkynes with either ozone or KMnO4 leads to carboxylic acids [terminal alkynes give carbonic acid, which decomposes to CO2 and water].
2. Key Reactions of Alkynes
Here’s a list of the key reaction types:
3. Visualizing The Addition and Oxidative Cleavage Reactions of Alkynes With A Reaction Map
One useful way to help visualize these reactions is to make a “spiderweb” diagram, showing how alkynes are transformed into a variety of functional groups. This is what it looks like for alkynes.
The previous post in the series on alkynes was entitled, “Alkynes Are A Blank Canvas“. Alkynes are a blank canvas because on top of their own transformations, through partial reduction (Na/NH3 or Lindlar) alkynes can also be transformed to alkenes, (which themselves have a host of reactions) or even alkanes (which can then be transformed to alkyl halides, which also have a host of reactions).
4. A Full Reaction Map PDF For First-Semester Organic Chemistry: Alkanes, Alkyl Halides, Alkenes, and Alkynes
This updated reaction map shows all the key reactions of alkanes, alkyl halides, alkenes, and alkynes covered in this and previous blog posts. One note – in a large map such as this, compromises had to be made: it is impossible to maintain complete self-consistency between all the structures drawn for each functional group and the resulting reactions. For example, on the sheet, alkynes are depicted as R-C≡C-R, (internal alkyne) while the products of certain reactions clearly come from a terminal alkyne. Each functional group should be interpreted figuratively (i.e. including its common variations) and not literally.
See if you can use the map to find ways to do these transformations (in any number of steps):
- alkane to alkyne
- alkyne to an alcohol (4 ways)
- alkyne to an alkyl halide
- alkene to an alkyne
- (challenging) go from a cis-alkene to a trans-alkenePRINTABLE (PDF) VERSION OF THIS IMAGE – CLICK HERE
19 thoughts on “Synthesis (5) – Reactions of Alkynes”
Urgh, the pictures are so small, I can barely see…
PDF available for free – just download it!
This is wonderful. Thank You!
This is wonderful. Thank You!
also noted: A PDF is a “raster” type image, so you can resize.
Sir, my professor told me that you can dehydrogenate an alkane to an alkene with the use of a metal catalyst like Pt. Also, I read in a book that you can reduce an alkyl halide to an alkane with LiAlH4. Why are these not in your map?
(Please disregard the first comment I gave :) )
Your website is wonderful!
Interestingly, I did a postdoc at McGill in 2012-2014. Now I’m working at a University in China with a bit of a struggle. Recently I’m working on a total synthesis project. Your summary of alkyne transformations is very helpful.
So glad to hear it. I hope your time back in China is fruitful – James
Actually, in oxidation clevage, ozone makes either a ketone and a aldehyde,
in your problem, it is a non-terminal alkyne, therefor it has to be ketone when reacted with O3
No, you need to go up an oxidation state.
Just curious, when transforming a terminal alkyne specifically to an alkene, either with H2, Lindlar’s catalyst or Na, NH3 (l), does the reagent matter. If you the desired product is a terminal alkene with a double bond on one end of the compound, cis- and trans- specificity does not really matter. So can either of the above reagents be used?
Lindlar is milder and is probably the best choice. Na/NH3 would involve formation of a terminal acetylide ion and trying to pump electrons into a negatively charged species is not the easiest thing to do.
Hey James, does NH3 always have to be the solvent to create an acetylide anion from an alkyne? Can one just use water as a solvent and add NaNH2 to the alkyne to create the acetylide anion?
No, it doesn’t. There’s lots of other options. Alkyllithiums will do the job nicely, as will LDA in ethereal solvents and many other strong bases. Water is a no-go, though – it’s too acidic to use as a solvent for the deprotonation of alkynes.
This is sooooo clear and useful! Thank you SO MUCH!!
Awesome. Thanks Donna!
Thanks for this site; it is very helpful to my work.
Please could you describe the mechanism for the reaction between Alkynes and benzene to form PAH’s? Thank you.
Do you have a specific example?
I haven been taught that whenever we use alcoholic KOH for the formation of unsaturated compounds ,rearrangement of double or triple bond will take place leading to more substituted unsaturated compounds.In case of Alkynes ,I thought the added heat will favour rearrangement not the KOH itself but this is not the case.So plz can you tell how KOH favours rearrangement in detail?