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Author: Subject: Butyric Acid - Synthesis/Extraction
roamingnome
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[*] posted on 18-11-2006 at 14:42


while skimming the post here saw the,

butanol from electroysis of ethanol. just was looking into that elsewhere as a substatute for octanol which is hard to come buy unless you have coconuts laying around...

anyway theres no excuse for exspirmentation on my part but what do you recomend put some electrodes into ethanol?, or is there some pH issue or secrete acetate ion to add.. i cant seem to find any solid refs on it....
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[*] posted on 19-11-2006 at 04:39


@mericad193724
The procedure worked for me, but it shows the disadvantages of following " cooking-book recipes": I don't know exactly why. I got a slightly lower yield, but I think that's due to the fact that I did not have a 4l RBF, so I had to distill in several batches. The original recipe did not give any explanation or rationale beyond the bare steps, but here are some thoughts:
As for the " fertilizer" I believe any phosphate salt will do. The phosphate is after all the nutrient needed by the bacteria. The addition of calcium carbonate was a mystery to me until wikipedia told me (under "butyric acid") that there are strains of bacteria that start producing acetone rather than butyric acid if the pH gets too low (<= 5), so an alkaline must be added. I also think that calcium butyrate will be formed, but before the destillation the liquid must be made slightly acidic (I used diluted HCl), which helps releasing the butyric acid. The difference in boiling points makes the destillation rather easy, but I used a short colum nevertheless.
As for any fermentation cleanliness is very important. I desinfected all the gear before use and it worked out ok.

No experience with the electrolysis of ethanol to get butanol, but I'll see what I can find in the literature. 10A at 6V looks plenty to me, though. I don't think the problem lies there.
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[*] posted on 19-11-2006 at 08:33


Thanks for all the help fractional...I found the ethanol electrolysis problem...the liquid is not conductive! I feel like an idiot:P! I used my multimeter and I got a reading of around 200K ohms, I had less than a 1 milliAmp flowing! Now all I need to do is make it very conductive and I will try again. What should I add that will not effect the final product or react with it? CaCl2 is soluble in ethanol, but won't that form CaOH? My electrochemistry knowledge is close to zippo.


Could someone please give me some advice or adding some kind of electrolyte to ethanol so I can make Butanol.

I could run the cell tonight

Mericad
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[*] posted on 20-11-2006 at 06:11


I did some research on the electrolysis of ethanol to get butanol with close to zero result. Lund, " Organic Electrochemistry" hints at an "electroenzymatic" production of butanol: a bit exotic, I think. Loeb, " Electrochemistry of organic compounds" mentions butanol as a rather insignificant by-product of other reactions. Bochris " Modern Electrochemistry", a more recent book, says nothing.
Wikipedia does not give a reference, not uncommon, but rather annoying, all the same.
So I have no idea where this reaction comes from and personnally I would not give it much hope. Worth trying, nevertheless, because it's so simple. You can try in acidic or alkaline conditions. The results will be different for the two setups! Sulfuric acid and HCl are used to acidify. "A little alkali" (Loeb) to do the opposite. Potassium acetate was used to increase the conductivity of pure alcohols without changing the pH.

[Edited on 20-11-2006 by fractional]
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[*] posted on 24-11-2006 at 14:53


I added NaOH to alcohol but couldn't dissolve enough to make it very conductive. I don't want to use an acid like Sulfuric acid so I won't make Diethyl Ether and get the peroxides as well:o! If it was so easy to make butanol by electrolysis, it probably would have been very well documented and known, so I am assuming it is hard.

I know you can convert Butanol --> Butyric Acid, but can you convert Butyric acid --> Butanol???

Butanol has low solubility in cold water so if we can change the butyric acid in the fermentation to butanol, separation would be very easy! No need to distill 2L!

Mericad
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[*] posted on 9-11-2010 at 08:24


I took like 1 kg of very ripe ginkgo fruit that smelled bad (so thats good). I squeezed the juice out of them, then filtered it few times (juice didn't smell so bad or I started to like butyric acid smell?). After that I put ca(oh)2 in it. The smell disappeared. After that I put HCl in it and there started to form some insoluble particles floating on top, yellow and orange separated pieces, some were big as 1.5 cm. MAybe there is now oily layer, but I didn't check, but from top, the solution smells bad when wind blows it into my nose :) What are those insoluble particles and should there be butyric acid salted out as oily layer? (maybe I didn't notice it immediately because of those particles.)
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[*] posted on 9-11-2010 at 09:22


Quote: Originally posted by Random  
What are those insoluble particles and should there be butyric acid salted out as oily layer? (maybe I didn't notice it immediately because of those particles.)



30 Minutes in the libary (or 2.4 seconds on la net) can often
save 30-days in the lab.


Ginkgo biloba
Teris André van Beek

Provides a ref to a publication of the putrid aroma compounds
from GB.

Think butanuic (butyric) & hexanoic (caproic) acids.

Parts of la book can be read at the usual URL place.

Ginko fruits always smelled like old socks to me.


[442]
ANNUAL REPORT SMITHSONIAN INSTITUTION, 1938
GINKGO BILOBA
MAIDENHAIR TREE SEWARD

Male and female reproductive organs are borne on separate trees. It is possible to obtain both kinds of "flower" on one tree by grafting a female branch on to a male tree: this operation was successfully performed some years ago on the large male tree at Kew. My friend the Rev. Prof. A. C. Moule of Cambridge, tells me he discovered a passage in an old Chinese book advising the planting of female seeds close together in order to ensure fertilization at a later stage. This implies an uncanny power of distinguishing female even in the seeds. The male flowers as it is convenient to call the reproductive shoots are loose catkins bearing on a slender axis several short stamens, each of which has two or rarely three or even four pollen sacs. The female shoots are longer and la usually bearing a pair of ovules which develop into fleshy yellow seeds as large as cherries. In the Far East the maidenhair tree of as the silver apricot. Within the fleshy covering a hard shell, generally with a prominent median keel, encloses and protects the embryo and the store of food prepared by parent for offspring. The kernel (embryo and food) is eaten in China and Japan as a delicacy: the outer flesh is nauseous.

----------
Srurtevant’s Edible Plants of the World 1919
Dover Reprint


Ginko biloba Linn. Coniferae. GINKO. MAIDEN HAIR TREE.
China and Japan. The fruit of the ginko is sold in the markets in all Chinese towns and is not unlike dried almonds, only whiter, fuller and more round. The natives seem very fond of it, although it is rarely eaten by Europeans.(7) In Japan, the seeds furnish an oil used for eating and burning. (8) The fruit of the maiden hair tree is called in China pa kwo. The Chinese consume the nuts of this tree at weddings, the shells being dyed red; they have a fishy taste. (9) This tree is largely cultivated as an ornamental in Europe, Asia and North America.

7 Fortune,R. Wand.China 118. 1847.
8 Pickering,C. Chron.Hist.Pls. 797. 1879.
9 Smith, F. P. Contrib. Mat. Med. China 103. 1871


eaten in China and Japan as a delicacy... well
the French eat each other so who am I to criticize?


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[*] posted on 9-11-2010 at 11:21


But butyric and caproic acids have melting point of -7 and -2 celsius degrees, so it should be oily layer then and not insoluble solid particles floating on top. I don't think butyric acid should look like that, or is that actually oily layer?
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[*] posted on 12-4-2011 at 13:01


I left that jam jar with all that ginkgo stuff outside during the winter until now. It looks I got some success.

Today I checked the solution, it smelled like a successful reaction. I saw some brown stuff at the bottom (it could be some iron oxides because of the jam jar cap and some stuff from ginkgo which was destroyed by HCl during few months). But, there was something more interesting. I think I noticed very thin like 1.5-2mm colorless layer on that brown solution which is floating like oil. It was in smaller jam jar bottle so up to the lid so I transferred it then into a bigger one. Everything mixed so I think I need to leave it until tomorrow to break the emulsion. Maybe there is even more butyric acid in solution, because I did this:

Extracted the ginkgo juice, filtered it and added Ca(OH)2.
Added HCl to make it highly acidic. This made some CaCl2 to salt out butyric acid from the solution, though maybe not everything what's in is salted out. Maybe saturating it with NaCl would make it more insoluble if there is more.
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[*] posted on 13-4-2011 at 09:53


Is the subtilis fermentation aerobic or anaerobic?

[Edited on 13-4-2011 by 12332123]
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[*] posted on 9-6-2011 at 04:37


Hydrolize acid chloride like butyryl chloride (cheap) with water in the present of base like pyridine or NaOH to consume evolving HCl
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[*] posted on 9-6-2011 at 12:06


If you want butyric acid, take 1-butanol, which is common, and oxidize the s**t out of it! :D Try jones' reagent (dichromate + acid + acetone), or alkaline potassium permanganate. When you smell the tell-tale smell, you're done!



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[*] posted on 9-6-2011 at 12:49


The easiest, cheapes method is what redox said , Jones will do job but hot alkaline solution of KMnO4 too ! but it's not carcogenic like Jones
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[*] posted on 9-6-2011 at 13:12


Another low cost method, discussed several times on other threads, is NaOCL bleach plus a nickle salt as catalyst. You get a solution of the acid as its sodium salt, plus NaCL, with the nickle as insoluble oxides which are easily filtered off and converted back to NiCl2.

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[*] posted on 10-6-2011 at 12:47


Quote: Originally posted by not_important  
Another low cost method, discussed several times on other threads, is NaOCL bleach plus a nickle salt as catalyst. You get a solution of the acid as its sodium salt, plus NaCL, with the nickle as insoluble oxides which are easily filtered off and converted back to NiCl2.



Yes, I remember you advising nickel salt + hypochlorite to ‘break’ the emulsion of a zirconium containing roll on anti-perspirant. I didn’t have any nickel but I have now…

For the oxidation of n-butanol this way, do you have anything resembling a recipe? And should this also work with iso-amyl alcohol (3-methyl butan-1-ol)?

In that reaction the ClO<sup>-</sup> is reduced to Cl<sup>-</sup>, right? Wouldn’t that require ridiculous volumes of commercial bleach, given how dilute the latter is and (at least!) two ions of hypochlorite per molecule of alcohol?
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[*] posted on 11-6-2011 at 14:36


Quote: Originally posted by blogfast25  
...

For the oxidation of n-butanol this way, do you have anything resembling a recipe? And should this also work with iso-amyl alcohol (3-methyl butan-1-ol)?

In that reaction the ClO<sup>-</sup> is reduced to Cl<sup>-</sup>, right? Wouldn’t that require ridiculous volumes of commercial bleach, given how dilute the latter is and (at least!) two ions of hypochlorite per molecule of alcohol?



http://www.sciencemadness.org/whisper/viewthread.php?action=...

The JOC article there reports isbutyric acid from the alcohol with an isolated yield of 89%, neopentyl alcohol to the acid with 88% isolated, n-octanol to the acid at 68% isolated.

Yeah, it's not real concentrated. But you can extract, or acidify then steam distill an acid-water mix for the more volatile acids, or make sure the solution is alkaline (NaHCO3 or Na2CO3) then evaporatively concentrate followed by acidification and extraction or steam distillation. Bleach can be had cheaply if you look a like, or wait for sales. Common bleach is 0.8 to 0.9 M, so it does take a bit of it but the OTC nature and cheapness makes up for that.


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[*] posted on 12-6-2011 at 05:03


Quote: Originally posted by not_important  
Quote: Originally posted by blogfast25  
...

For the oxidation of n-butanol this way, do you have anything resembling a recipe? And should this also work with iso-amyl alcohol (3-methyl butan-1-ol)?

In that reaction the ClO<sup>-</sup> is reduced to Cl<sup>-</sup>, right? Wouldn’t that require ridiculous volumes of commercial bleach, given how dilute the latter is and (at least!) two ions of hypochlorite per molecule of alcohol?



http://www.sciencemadness.org/whisper/viewthread.php?action=...

The JOC article there reports isbutyric acid from the alcohol with an isolated yield of 89%, neopentyl alcohol to the acid with 88% isolated, n-octanol to the acid at 68% isolated.

Yeah, it's not real concentrated. But you can extract, or acidify then steam distill an acid-water mix for the more volatile acids, or make sure the solution is alkaline (NaHCO3 or Na2CO3) then evaporatively concentrate followed by acidification and extraction or steam distillation. Bleach can be had cheaply if you look a like, or wait for sales. Common bleach is 0.8 to 0.9 M, so it does take a bit of it but the OTC nature and cheapness makes up for that.




Thanks! I wonder if it would work on that vinyl-gloves-extracted 2-ethyl hexan-1-ol,,,
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[*] posted on 17-6-2011 at 07:57


Isn't butyric acid used by all the pro lifers?! You don't want to use the same foul shi as them, do you?! Besides, although I think butyric acid does indeed smell foul, I think methyl mercaptan smells like a pepporoni and meat sub which Tony Soprano ate too fast, and is therfore bein anaerobically fermented in his intestines, and results in a deadly fart. Seriously. I have smelt both. It is far worst.
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[*] posted on 17-6-2011 at 10:14


Quote: Originally posted by blogfast25  
...
Thanks! I wonder if it would work on that vinyl-gloves-extracted 2-ethyl hexan-1-ol,,,


Should, given that they reported the yield for n-octanol. Clean-up likely requires extraction with aqueous alkali from something like DCM or toluene to separate unreacted alcohol from the acid, then regeneration of the acid.

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[*] posted on 28-6-2014 at 02:48


I tried the synthesis using KMno4 and it worked!

I made a video on it: https://www.youtube.com/watch?v=M8VSKqPYdHI
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[*] posted on 28-6-2014 at 06:18


Nice work, nb198! Good video too. Even yield wasn't too shabby. But it does take the patience of an angel, this method...

So are you going to make some pineapple flavoured ester with it? ;)

How bad does this pure butyric acid really smell?

Wouldn't the oxidation proceed more quickly in acid conditions? The formed Mn<sup>2+</sup> could be precipitated as Mn(OH)2 (which fairly quickly oxidises to MnO2 anyway) with NaOH, which would also form sodium butyrate. From there on the work up would be very similar...

[Edited on 28-6-2014 by blogfast25]




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[*] posted on 28-6-2014 at 11:13


Very nice work, showing good technique and excellent purity of product! I take it that you were using university facilities?



The single most important condition for a successful synthesis is good mixing - Nicodem
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[*] posted on 2-7-2014 at 05:56


Quote: Originally posted by blogfast25  
Nice work, nb198! Good video too. Even yield wasn't too shabby. But it does take the patience of an angel, this method...

So are you going to make some pineapple flavoured ester with it? ;)

How bad does this pure butyric acid really smell?

Wouldn't the oxidation proceed more quickly in acid conditions? The formed Mn<sup>2+</sup> could be precipitated as Mn(OH)2 (which fairly quickly oxidises to MnO2 anyway) with NaOH, which would also form sodium butyrate. From there on the work up would be very similar...

[Edited on 28-6-2014 by blogfast25]


I don't plan to makes esters with it actually. I am going to keep the stinky concoction!

I honestly don't think it smells that bad. For some reason, bad smells don't affect me too much though. Coworkers think it's awful, but I don't mind it.
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[*] posted on 2-7-2014 at 05:59


Quote: Originally posted by Magpie  
Very nice work, showing good technique and excellent purity of product! I take it that you were using university facilities?


You are right. I work in a university lab as a technician. Unfortunately, this is only for he next 2 days, as I will be leaving. So some future videos might be in a ghetto home lab. Until I return as a grad student
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[*] posted on 4-2-2021 at 14:46


What is the procedure for isolating butyric acid from a solution? I had performed a Sandemeyer reaction to produce GBL and I wanted to extract the butyric acid and then purify it to at least 95%.

I have seen people discuss salting it out of solution then collecting the oil fraction and purifying by distillation.

I'm having trouble finding a procedure for isolating butyric acid. Thanks!
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