Sciencemadness Discussion Board

Succinaldehyde from THF

Crypto - 18-11-2013 at 16:20

Wikipedia states that:
Quote:

Succinaldehyde is generated by the oxidation of THF with chlorine followed by hydrolysis...

https://en.wikipedia.org/wiki/Succinaldehyde

I have looked for some reference about it but found nothing.

Anyone of you guys have anything about it?

Marvin - 19-11-2013 at 09:40

Think of the hydrolysis like this,

-CH2Cl -> -CH2OH
-CHCl2 -> -CH(OH)2 -> -CHO + H2O
-CCl3 -> -C(OH)3 -> -COOH + H2O

An ether is just two ends of an alcohol. So if you chlorinate to -CHCl-O-CHCl- then hydrolysis will produce the dialdehyde.

Crypto - 19-11-2013 at 14:54

I'd love to try but I can't find any info about reaction and wiki gives no reference.

DraconicAcid - 19-11-2013 at 15:06

For the chlorination, I found this:

http://www.chempap.org/file_access.php?file=311a109.pdf

The chlorination must be done at temperatures under -10 oC to prevent getting beta-chlorination (you want your chlorines alpha to the oxygen), with UV light to get the chlorine to react.

Crypto - 20-11-2013 at 01:22

What product exactly should be hydrolysed to yield succinaldehyde?

[Edited on 20-11-2013 by Crypto]

bfesser - 20-11-2013 at 09:24

<del>The primary geminal dihalide.</del>

You seem to be solely interested in the product and not the reaction, which leads me to suspect that you're seeking it for illicit syntheses. Just a warning; we don't take kindly to cooks requesting spoon-feeding. If this is not the case, disregard.

[edit] Don't know what I was thinking... must need more coffee.

[Edited on 20.11.13 by bfesser]

Crypto - 20-11-2013 at 10:27

The reaction can yield different compounds, depending on the temperature it's kept. That's why I'm asking. Is this path a viable path to the dialdehyde? Wiki states so but I can't find any reference or experimental procedure.

PHILOU Zrealone - 25-11-2013 at 12:15

THF is a dehydrated form of succinaldehyde...
O=CH-CH2-CH2-CH=O <==> HO-CH=CH-CH=CH-OH
HO-CH=CH-CH=CH-OH <--==> cyclo (-CH=CH-CH=CH-O-) + H2O

A special reaction occurs between THF and hydroxylamine (NH2-OH) to yield HO-N=CH-CH2-CH2-CH=N-OH (the dioxime of succinaldehyde (butandial dioxime)). So it is a convenient way to open the ring!

The reaction does not work with amonia what produces pyrrole (oxygen is replaced by N-H in the THF molecule) while H2S forms thiophene (oxygen is replaced by S in the THF molecule).

DJF90 - 25-11-2013 at 13:41

Philou, You're getting confused between THF and Furan.

PHILOU Zrealone - 25-11-2013 at 14:51

Quote: Originally posted by DJF90  
Philou, You're getting confused between THF and Furan.

You are right! My mistake. That's what happens when watching TV while answering/typing :( .

DJF90 - 27-11-2013 at 10:44

Succinaldehyde is an unstable compound and practically not used. The 2,5-dimethoxyTHF is the common in situ source.

Crypto - 27-11-2013 at 12:37

My chem supply doesn't have 2,5-dimethoxytetrahydrofuran but I'm almost 100% sure i read once something about preparing it from malic acid by electrochemical means.

DJF90 - 27-11-2013 at 13:25

http://www.orgsyn.org/Content/pdfs/procedures/cv5p0403.pdf

This procedure describes preparation of the 3,4-dehydro compound, which can be hydrogenated to the desired 2,5-dimethyoxyTHF. There are surely other ways, and although the paper describes raney nickel at 1800psi, I'm sure a more active catalyst could do it at STP.

kristofvagyok - 27-11-2013 at 16:05

Quote: Originally posted by DJF90  
http://www.orgsyn.org/Content/pdfs/procedures/cv5p0403.pdf

This procedure describes preparation of the 3,4-dehydro compound, which can be hydrogenated to the desired 2,5-dimethyoxyTHF. There are surely other ways, and although the paper describes raney nickel at 1800psi, I'm sure a more active catalyst could do it at STP.


I done this OrgSyn recipe a few times not long ago and it also works with chlorine, however the yield will drop by 50%. But since furan is much cheaper than bromine, it is worth. And the benzene is also totally useless. The short recipe is:

Mix the methanol with the sodium carbonate, cool it down with salt/ice bath to 0 °C, add the furan and start to bubble chlorine through the solution, while keeping the temperature of the mixture under 5 °C. After 3-5 hour (till the mixture won't absorb more chlorine) filter out the insoluble salts, evaporate the methanolic solution under vacuum.
Extract the participated salt and oil mixture with cyclohexane, wash it with concentrated NaCl, evaporate and distill under vacuum to get the dimethoxy dihydro furan.

Easy and well working recipe.

Crypto - 28-11-2013 at 08:41

I did some reading about TCCA oxidation of ethers.

Trichloroisocyanuric Acid - A Safe and Efficient Oxidant

Oxidation of THF at 0 C, with TCCA yields trans-2,5-dichlorotetrahydrofuran. I assume that this compound after hydrolysis yields the dialdehyde.

Does anyone have any experimental data about such oxidation?

DJF90 - 28-11-2013 at 10:00

I found this with google. Not what you're looking for but something to keep in mind as a competing reaction...
http://www.tandfonline.com/doi/abs/10.1080/00304947109356057...

SHADYCHASE54 - 28-11-2013 at 19:11

I found this patent online perhaps it would be of interest to some

US2710883A

Mush - 23-11-2020 at 15:51

CN107417548

Example 1: Preparation of 1,4-butanedialdehyde (4)

Compound 3

1,4-butanediol (50 g, 0.55 mol, 1 eq) was dissolved in 500 ml of dichloromethane. A solution of TEMPO in dichloromethane (10 ml, 0.02 mmol, 0.2 mol %) was added in sequence and the ice bath was allowed to cool.An aqueous solution (200 ml) containing 20 g of NaClO was slowly added dropwise at 010° C., and the mixture was stirred for 1 h and allowed to stand for stratification.The aqueous layer was extracted with DCM (200 ml), the organic layers combined, dried over anhydrous sodium sulfate, concentrated and the residue used directly in the next step.About 42.3 g of an oil was obtained (yield 88.6%). 1HNMR(CDCl3, 400MHz)：δ9.80(t,2H)；2.75-2.73(m,4H)；.ESI-MS(m/z):87.1[M+H]+

zed - 26-11-2020 at 19:45

Ummm. Usta produce succindialdehyde by the simple acid hydrolysis of Pyrrole.

[Edited on 27-11-2020 by zed]

zed - 9-12-2020 at 14:06

Ummm. Maybe it is the action of hydroxylamine on pyrrole.

And, pyrrole, can be produced from furan.

Since furan might be easier to acquire than THF. Is that the way to go?


This is a Furfural link.

This is the correct link: http://www.orgsyn.org/demo.aspx?prep=CV1P0280

Furfural to the Carboxylic Acid: http://www.orgsyn.org/demo.aspx?prep=CV1P0276

The Carboxylic acid to Furan: http://www.orgsyn.org/demo.aspx?prep=CV1P0274


[Edited on 9-12-2020 by zed]

[Edited on 9-12-2020 by zed]

[Edited on 9-12-2020 by zed]

[Edited on 9-12-2020 by zed]