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Author: Subject: Acetaldehyde synthesis
clearly_not_atara
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[*] posted on 16-9-2020 at 06:21


In reality producing acetaldehyde isn't all that hard. What is hard is producing acetaldehyde in significant quantities and in such a way that it can be separated from the reaction mixture, condensed, and isolated.

It's difficult, for example, to condense a compound with bp 20 C when that compound is co-produced in the efflux stream with much larger quantities of water, bp 100 C, and when said gas stream emerges at nearly 200 C.

It is likewise not very easy to isolate acetaldehyde from aqueous rxn mixtures since its bisulfite adduct is not as insoluble as those of larger aldehydes, and it may polymerize under the alkaline conditions typically used for bisulfite adduct deprotection. Bisulfite adducts may also be deprotected with acid, but this produces copious SO2.

As such, the great majority of syntheses posted in this thread are not really solving the right problem. IMHO, if you want a practical synth of acetaldehyde, what you're really after is an oxidation of ethanol that produces 1,1-diethoxyethane -- acetaldehyde diethyl acetal -- in situ. This compound can easily be separated from the reaction mixture and pure acetaldehyde obtained by acidic cleavage under relatively mild conditions with few co-products. It is stable and can be stored.

To that end, I offer the direct photocatalytic oxidation of ethanol to 1,1-diethoxyethane over two catalysts: 1% Pt-doped TiO2 nanorods and Cd-Ni-Mo sulfide.

https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10...

https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10....

While the photocatalysts take a little work -- hardly impractical IMO -- they offer the possibility of one-step large-scale production of DEE qua acetaldehyde in a form that is stable and easy to isolate and store.

But be aware that while acetals such as DEE usually do not form peroxides, the risk must not be ignored.

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[Edited on 04-20-1969 by clearly_not_atara]
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Triflic Acid
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[*] posted on 5-11-2020 at 17:53


I see this threads been dead for a while :P, but this paper outlines a way of oxidizing alcohols using O2 over some Pd/C like catalysts. https://pubs.acs.org/doi/pdf/10.1021/cr0200116

[Edited on 6-11-2020 by Triflic Acid]
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[*] posted on 24-11-2020 at 13:54


Quote: Originally posted by Corrosive Joeseph  
Quote: Originally posted by S.C. Wack  
Page 4686 of JCS (1956) claims a 50% yield by reflux of EtOH with excess MnO2 for 20 min. No explicit experimental is given in this case. A number of aldehydes and a few ketones are prepared, but my copy (from microfilm) is of poor quality.


Barakat et al. - Oxidation of Organic Compounds by Solid Manganese Dioxide - Notes, Journal of the Chemical Society (1956) Pages 4685-4687


CJ


Did anyone try this method yet? It seems like the most convinient method...
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[*] posted on 2-12-2020 at 12:43


It might just be easier to attempt to partially dehydrate ethylene glycol. An enol will form and tautomerize. It could be done pretty easily with say H2SO4, H3PO4 or Al2O3. Though if there if there is a reason why it wouldn't work someone let me know.
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[*] posted on 14-4-2021 at 10:33


Quote: Originally posted by EverythingAl2O3  
It might just be easier to attempt to partially dehydrate ethylene glycol. An enol will form and tautomerize. It could be done pretty easily with say H2SO4, H3PO4 or Al2O3. Though if there if there is a reason why it wouldn't work someone let me know.

Forgive me for not reading this thread, but what about NurdRage's YouTube videos for producing sodium? He purifies sodium by boiling it in dioxane, which he produces from ethylene glycol and sulfuric acid. And the side product in that production is the ethylene glycol acetal of acetaldehyde. He vents a ton of acetaldehyde saying to get rid of that nasty carcinogen. Opportunity abounds. I plan to use this myself as a way to produce dioxane plus the acetaldehyde I require.
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draculic acid69
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[*] posted on 14-4-2021 at 17:41


Quote: Originally posted by Jenks  
Quote: Originally posted by EverythingAl2O3  
It might just be easier to attempt to partially dehydrate ethylene glycol. An enol will form and tautomerize. It could be done pretty easily with say H2SO4, H3PO4 or Al2O3. Though if there if there is a reason why it wouldn't work someone let me know.

Forgive me for not reading this thread, but what about NurdRage's YouTube videos for producing sodium? He purifies sodium by boiling it in dioxane, which he produces from ethylene glycol and sulfuric acid. And the side product in that production is the ethylene glycol acetal of acetaldehyde. He vents a ton of acetaldehyde saying to get rid of that nasty carcinogen. Opportunity abounds. I plan to use this myself as a way to produce dioxane plus the acetaldehyde I require.


Many ppl have done this rxn for the dioxane but no one yet has done this for the purpose of capturing and measuring the yeild of the acetaldehyde. If U do this
please report back with yeild.it would contribute to this thread greatly
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EverythingAl2O3
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[*] posted on 28-4-2021 at 16:56


Have we also considered the Corey-Kim oxidation? N-chlorosuccinimide with a unhindered thioether and a tertiary amine/hindered amine like triacetoneamine. Yes DMS would be pretty smelly, but if one can make a long chain sulfide (Wikipedia says dodecyl methyl sulfide was used as a less noxious sulfide) it wouldn't be as much of an issue. NCS can be regenerated by reacting Succinimide with bleach. Only downside is cooling to around -40 to -25C and 10h ish reaction time. But the reagents can be regenerated with cheap chemicals.
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