Crypto
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Succinaldehyde from THF
Wikipedia states that:
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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?
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Marvin
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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.
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Crypto
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I'd love to try but I can't find any info about reaction and wiki gives no reference.
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DraconicAcid
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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.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Crypto
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What product exactly should be hydrolysed to yield succinaldehyde?
[Edited on 20-11-2013 by Crypto]
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bfesser
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<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]
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Crypto
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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.
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PHILOU Zrealone
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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).
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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DJF90
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Philou, You're getting confused between THF and Furan.
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PHILOU Zrealone
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You are right! My mistake. That's what happens when watching TV while answering/typing  .
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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DJF90
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Succinaldehyde is an unstable compound and practically not used. The 2,5-dimethoxyTHF is the common in situ source.
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Crypto
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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.
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DJF90
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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.
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kristofvagyok
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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.
I have a blog where I post my pictures from my work: http://labphoto.tumblr.com/
-Pictures from chemistry, check it out(:
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Crypto
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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?
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DJF90
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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...
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SHADYCHASE54
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I found this patent online perhaps it would be of interest to some
US2710883A
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Mush
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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]+
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zed
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Ummm. Usta produce succindialdehyde by the simple acid hydrolysis of Pyrrole.
[Edited on 27-11-2020 by zed]
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zed
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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]
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