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Michael Wallis Adkins

Synthesis of 1-hexene from 1-octyne

Andrew White  Follow

I guess this is just a paper exercise, since trying to make 1-hexene from octyne means you forget efficiency. A very useful and interesting exercise though. I agree with Ron about potential issues with step 4. I think sulfuric acid is worth trying for step 7 though and if it fails you can try stronger dehydrating agents that are less/non acidic or an indirect method like your tosylate elimination or even selenium chemistry. For step 6 I would use the standard $\ce{NaBH4}$ or $\ce{LiAlH4}$ for reduction.

Alternatively, after step 1, you can apply your ozonolysis-aldehyde reduction - elimination cycle twice to get to the product. Generally you sacrifice 2 of your 8 carbons ie 25% "wasted" from your starting material.

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Chris Myers  Follow

On the plus side, you've clearly thought about this problem and have worked out a detailed synthetic route. I think most of the steps would work as desired. The two steps that concern me the most are 4 and 7. I suspect your step 4 will give a mixture of products. Perhaps with further experimentation you could find reaction conditions that would give you the desired product without other products from undesired side reaction (elimination in the other direction and perhaps some rearrangement products too). I see your step 7 as the most problematical. Aluminum chloride, heat and the alcohol will produce a carbocation and it will undergo significant rearrangement creating a variety of elimination and addition (polymer formation) products. So while your reaction scheme is plausible, in my opinion it is not efficient.

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John Flavin  Follow
That would still proceed through a (primary) carbocation intermediate and be subject to rearrangement and polymerization in addition to the desired elimination. Perhaps dehydration under basic conditions might have a better chance of success.More
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Frederick Pack  Follow
Any nucleophile that favors elimination over substitution.More
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James Warren  Follow
Could I dehydrate the alcohol via heating and sulfuric acid?More
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Jose Carlos Gomes  Follow
You mean NaOH dehydration?More
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