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Author: Subject: furfural
Magpie
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[*] posted on 27-4-2011 at 08:12


Quote: Originally posted by blogfast25  

How much did the ribose set you back?


I paid $20/100g at my local health food store. I've seen it on the internet as cheap as $11/100g.

---------------------------------------------------------------------
According to OrgSyn furan can be made easily by the decarboxylation of 2-furoic acid. OrgSyn also shows how to make this acid from furfural. It looks simple enough.

[Edited on 27-4-2011 by Magpie]




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[*] posted on 27-4-2011 at 11:57


Wow. $110/kg. Cheap it ain't!
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[*] posted on 2-6-2011 at 19:02


Here's a few papers on the production of furfural from pentoses. They cover producing useful pentoses from the oxidation of hexoses and the formation of furfuryl from pentoses (the biphasic systems look awfully promising).

Attachment: Fullmer.etal.The.Production.of.Furfural.from.Xylose.Solutions.by.Means.of.Hydrochloric.Acid.Sodium.Solutions.pdf (488kB)
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Attachment: Heines.Microdetermination.of.Pentoses.by.the.Bisulphite.Method.pdf (81kB)
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Attachment: Hockett.Hudson.Improvements.in.the.Preparation.of.d.Arabinose.from.Calcium.Gluconate.pdf (246kB)
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Attachment: Hudson.Harding.The.Preparation.of.Xylose.from.Corn.Cobs.pdf (151kB)
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Attachment: Hurd.Isenhour.Pentose.Reactions.I.Furfural.Formation.pdf (881kB)
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Attachment: Isbell.Holt.Frush.Preparation.of.D.Arabinose.5C14.from.D.Glucose.6C14.pdf (61kB)
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Attachment: Johnson.Upson.The.Oxidation.of.d.Glucose.by.Means.of.Copper.Sodium.Carbonate.Solution.Soldainis.Reagent.pdf (431kB)
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Attachment: Matsushima.D.Arabinose.Hypochlorite.Glucosamine.pdf (258kB)
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Attachment: Weingarten.Kinetics.of.Furfural.Productioni.by.Dehydration.of.Xylose.in.a.Biphasic.Reactor.with.MW.Heating.pdf (348kB)
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[*] posted on 8-6-2011 at 22:46


Xylitol is readily available OTC from health stores, grocery stores, etc as a sugar substitute... I have wondered if it could participate similarly to xylose, except losing 4 moles water per mole of xylitol, instead of 3.

Its been entirely too long since I took Ochem.




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[*] posted on 13-8-2011 at 16:19


I have been drying some corncobs for making furfural per the method in OrgSyn. I'm getting them as they are received from the dinner table. I crushed 4 of them up yielding 114.4g for a 0.076 scale batch.

Dried corn cobs are a bitch to granulate. I eventually settled on using a pair of channel locks but it still took me 2 hours of tough going. The kernel hulls are fragile but the center core is very tough, much like wood. If I ever do this again I will try making them into sawdust using my table saw.

I made up enough H2SO4/NaCl solution for a 0.10 scale batch and since the cob granule slurry looked too dry I added it all. Tomorrow I will set up for steam distillation using a 1000mL RBF, column, and Dean Stark trap, as before.

Here's some pictures:

crushing cobs.JPG - 113kBcob slurry.JPG - 112kB




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[*] posted on 14-8-2011 at 05:26


Someone should contemplate recycling these things into baseball or cricket bats...

Look forward to reading about the rest of this synthesis! :)
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[*] posted on 14-8-2011 at 09:49


Many seed hulls, particularly those from sunflower seeds, are especially rich in hemicellulose (primarily arabinoxylan with almost no cellulose). I expect these to be excellent feedstock for a process like this. I might give it a shot after I get a kg or two of seed hulls.

Cheers,

O3




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[*] posted on 14-8-2011 at 20:57


Quote: Originally posted by Ozone  
... sunflower seeds, are especially rich in hemicellulose (primarily arabinoxylan with almost no cellulose). I expect these to be excellent feedstock for a process like this.


If this converts to arabinose it indeed ought to be a good feedstock & interesting to compare to the oat bran, corn cobs, and d-ribose that I have used.

The steam distillation of the corncob hydrolysis was completed today. I ran it for 4 hours but it was pretty much finished after 3 hours. OrgSyn's preparation says it will take 5-10 hours for their 1.5kg batch.

My yield was 7.5g. Scaled on OrgSyn's expected yield I should have obtained ~15.2 g. But my vastly smaller scale (0.076X) is likely a major factor in my smaller yield.

Again the mash turned black after it started boiling. Pictures are shown below.

This completes my investigation of natural products for the preparation of furfural. If I want any more I'll use d-ribose as available from my neighborhood health food store.



corn cob distillation.JPG - 109kB corn cob furfural.JPG - 67kB

[Edited on 15-8-2011 by Magpie]




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[*] posted on 2-9-2011 at 14:17


Wanting to do some chemistry this week, but nothing too challenging, I decided to purify my crude furfural and then make a derivative of same.

I took the combined lots of furfural that I had made from the various sugar and pentosans, which amounted to about 25mL of straw colored translucent liquid, and vacuum distilled it. Pressure was 50mmHg using an aspirator with the resulting bp at 76C. Being a bit lazy I did not at first set up an ebulliator and a Claisen extension. This proved to be a big mistake due to bumping and carryover so shutdown and reconfigured the right way. Yield was 20mL of clear product with a pleasant aroma - I would call it that of "benzaldehyde light."

Using 1g of homemade semicarbazide, some Na acetate buffer, and 1.5mL of furfural I made the derivative furfural semicarbazone (an imine) according to the method in Brewster. This crystallized out without any help from scratching or cooling. I recrystallized it from 95% ethanol, washing it with same. A melting point was taken of the dried crystals (see picture); it melted at the literature (Wiki) value of 202C.

I find it interesting that furfural is aromatic. Also it is interesting that the terminal nitrogen of the semicarbazide is the only one (of 3) capable of nucleophillic attack due to resonance.

furfural semicarbazone.JPG - 93kB

[Edited on 2-9-2011 by Magpie]




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[*] posted on 2-9-2011 at 21:47


Well, I tried dry distillation of sucrose before, until it carbonized. I obtained very small amount of liquid with the color just like this crude furfural you made, though it had some oily caramel colored dot floating on that yellow liquid. The liquid smelled like burning sugar and caramel (and I wonder why :D). My distillation apparatus was made from aluminium foil so it was really bad one, a lot of fumes escaped. Maybe that liquid contained furfural too?
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[*] posted on 3-9-2011 at 12:13


Good work Magpie!
Quote: Originally posted by Magpie  
I find it interesting that furfural is aromatic.

Aromatic, but not much. If you think furane is much of an aromatic system, then you might be surprised at how easy it undergoes nucleophilic additions. Particularly the reactions with amines and anilines are interesting as they give the corresponding pyrrole compounds from the furanes. For example, furfural itself reacts with anilines such as p-nitroaniline to give 1-(4-nitrophenyl)-1H-pyrrole-2-carbaldehyde. This is a nice looking heterocyclic product which can be further functionalized at the aldehyde group. References:

See DOI: 10.1071/CH9850953

Also, from CA 92:180923
Quote:
Synthesis of 1-arylpyrrole-2-aldehydes from furfural and substituted aromatic amines.
Burmistrov, S. I.; Sannikova, V. M.
Voprosy Khimii i Khimicheskoi Tekhnologii (1979), 54 20-4.

Abstract: Pyrrolecarboxaldehydes I (R = 4-H2NSO2C6H4, Q, 4-nitro-1-naphthyl, 2,5- and 2,4-HO(O2N)C6H3, 2,3,5-HO(Cl)(O2N)C6H2) were prepd. in 23.2-87.6% yield by reaction of furfural with the resp. arom. amine. The semicarbazones, phenylhydrazones, 4-nitrophenylhydrazones, 2,4-dinitrophenylhydrazones, and azines of some I were also prepd.

...and from CA 95:203666
Quote:
Synthesis of 1-(4-nitrophenyl)pyrrole-2-aldehyde from furfural.
Baum, E.; Goldovskaya, T. E.; Kul'nevich, V. G.; Maiorova, O. V.
Khimiya Geterotsiklicheskikh Soedinenii (1981), (8), 1062-6.

Abstract: The condensation of furfural with p-O2NC6H4NH2 in different solvents (e.g., MeOH, EtOH, PrOH, DMF, or HOAc) contg. HCl gave 55% pyrrolealdehyde I and 27% 2,3-bis[(4-nitrophenyl)amino]-4-cyclopentenone. Yields of up to 70% were obtained using methods described earlier (e.g., Liipke, 1939).

...and briefly described in DOI: 10.1007/BF01042479




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[*] posted on 3-9-2011 at 15:16


Bagasse is going to be far easier to work with than corn cobs (given it is already shredded and readily available in most garden stores - it is used as mulch). Rice husk is another easily (and cheaply) acquired source of xylose, there is a paper (here) on the extraction of xylose from Rice Husk/Hulls using 1N H2SO4. Making furfural from the sugar is going to be way easier given the lack of bulk and the reduction in the amount of acid needed.



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[*] posted on 3-9-2011 at 17:48


I agree that it is good to reduce the bulk of the precursor as much as possible. Although expensive, I did this using OTC d-ribose. However, even using this pure sugar the best yield I could get was 45%. When I tried it again I got exactly the same yield. A great deal of the precursor is just turned to carbon.



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[*] posted on 4-9-2011 at 07:41


Just some notes on your alternative feedstocks:

Yes, but bagasse contains 50% w/w water and 2-4% residual cane juice; it is only 20-24% hemicellulose (most of which is arabinoxylan). It is also recalcitrant. I would go for cellulosic ethanol then concentrate and work on the stillage (which contains all sorts of interesting things like aconitic acid, your xylan, etc.)

NIST sugarcane bagasse (from my lab % w/w dry solids):

extractables: 4.4
Cellulose: 40.2
Hemicellulose: Xylan 21.8, Arabinan 1.8 and mannan 0.4
Lignin: Klason 22.3, AS 2.0
Ash: 4.0

Rice hulls come nice and dry, which is a plus for storage and compositionally simple. But, again, these are a rich cellulose source with a composition (La. rice hulls, results from my lab) similar to:

extractables: 2.2
Cellulose: 33.0
Hemicellulose: Xylan 15.8, Arabinan 1.3 and mannan 0.0
Lignin: Klason 24.0, AS 2.7
Ash: 19.0

It should be mentioned that rice hulls are flame retardant (I had a hard time getting them to combust in a Parr bomb under 19 atm O2) and that the huge amount of ash is part of the plant structure; it is at least 94 % silica.

Cheers,

O3

[Edited on 4-9-2011 by Ozone]




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[*] posted on 5-9-2011 at 07:38


Very interesting data, O3. Also that point on > 94 % silica in ash, I wonder how that compares to most plant ashes...



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[*] posted on 5-9-2011 at 20:13


Yes, I thought so, too. When totally combusted to ash, you get a *fine* pure-white silica. I have thought about trying it out (as a stationary phase) in a column.

It would be cool if we could source relatively high-grade silica from rice hulls.

Cheers,

O3




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[*] posted on 7-9-2011 at 04:00


Quote: Originally posted by Ozone  
It would be cool if we could source relatively high-grade silica from rice hulls.
Certain species of horsetail are known as "scouring rushes" because of the high content of silicates; they're a naturally occurring plant abrasive. I would be curious to know what happens when you ash these, but not curious enough to acquire the gear just for this one experiment.
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[*] posted on 12-3-2012 at 01:38


Here is some more - interestingly enough HCl or H3PO4 are the acids of choice for this procedure - with steam distillation being the preferred way of isolating the product from the 'strong' acid before it degrades too much (I suspect your choice of acid would be responsible for much of the charring).

What would be nice is a decent, completely otc route to THF, pyrrole, porphyrins, etc.

[Edited on 12-3-2012 by aliced25]

Attachment: Andrews.Milroy.The.MicroDetermination.of.Pentoses.Free.and.Combined.pdf (474kB)
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Attachment: Duncan.Determination.of.Furfural.pdf (442kB)
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Attachment: Hockett.Guttag.Smith.The.Production.of.Furfural.from.D.Lyxose.and.D.Ribose.pdf (299kB)
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Attachment: Reeves.Munro.Quantitative.Determination.of.Pentoses.pdf (409kB)
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Attachment: Trimble.Dunlop.Recovery.of.Furfural.from.Aqueous.Solutions.pdf (226kB)
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Attachment: Youngburg.Studies.on.Pentose.Metabolism.II.A.Micromethod.for.the.Determination.of.Pentoses.and.Pentosans.pdf (354kB)
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[*] posted on 14-3-2012 at 21:19


Fructose will give one of the best yields. Acid catalyzed hydrolysis of sucrose should give a good supply of it. I don't really think anyone knows why frustose will give a 75% yield or something like that.

You may have to add a little silica jell, though. It seems to facilitate reactions with diols or more ols. When put through GCMS the polyols will kind of rip little bits of the column out.

however if you put any fructose containing mixture(ex. fruit juice) through it, the fructose will read as furfural.


I believe some organization was trying to find a great way to make it for use as an alternative fuel source. Fructose all the way.






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[*] posted on 15-3-2012 at 03:21


Quote:
Acid catalyzed hydrolysis of sucrose should give a good supply of it.


Under what conditions, using what acid? One possible outcome of such hydrolysis is levulinic and formic acids (and plenty of black gunk in an insoluble cake), per Organic Syntheses: http://www.orgsyn.org/orgsyn/prep.asp?prep=CV1P0335
Now maybe with less water, or a dehydrating acid (such as sulfuric acid), or other conditions... do you have a reference?




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