Sciencemadness Discussion Board

1-butanol synthesis

quest - 12-4-2005 at 11:15

I wana make 1-butanol.
I know only one methood to make this alcohol - fermentation of starch, but for this I need special bacterium.

Any other ways to make this alcohol? maybe from other smaller alcohols like methanol and ethanol?


Esplosivo - 12-4-2005 at 11:33

Other methods I know of require non-common lab reagants and are not useful for large productions. Maybe other can help in this.

Fermentation of sugar (sucrose) with normal backer's yeast Saccharomyces cerevisae can produce fussel oils, which are discussed in some other thread. This fussel oil is rich in long-chain aliphatic alcohols, such as butanols. I am currently fermenting a batch to test for this property, together with the yields obtained, and if the process can be manipulated to obtain higher yields by varying nutrients/environment. My 2.5lt batch fermentation will be ready in a month. I have already processed one smaller batch, and after distillation I obtained a mixture of alcohols of which I still cannot determine the composition. Must look up how after the exams. Anyways, just giver a look to the 'fussel oils' thread by Polverone.

JohnWW - 12-4-2005 at 13:51

What about methods of making 1,4-n-butanediol? This is the 4-carbon alcohol that everyone wants, but unfortunately, in recent years, the jackbooted anti-drug government mafia has pulled it from the shelves.

BromicAcid - 12-4-2005 at 14:05

Reduction of butyric acid prepared by allowing butter to sit around exposed to the air for awhile.

Reaction of butane with chlorine in the presence of light at 35C and careful fractioning of the resulting products (very unlikely to fraction well) and followed by reaction of the 1-chlorobutane with basified water to give the 1-butanol.

Then of course there are pain in the butt methods involving Grignard reagents.

I can try to think of something else though as nothing so far is reasonable.

sparkgap - 12-4-2005 at 21:42

The answer to JohnWW's question is implicitly in BromicAcid's answer:

Now, if a cheap way of producing hydride reagents, or a cheap/OTC way of reducing carboxylic acids in general, can be found, you can reduce succinic acid (can be bought without question, I believe) to butanediol.

As to butanol, maybe the "fusel oil" route may be the most viable for quest. Ask Polverone; I believe he's still working on it now, although the thread mentioned by Esplosivo hasn't been touched for weeks.

sparky (^_^)

Esplosivo - 12-4-2005 at 22:33

Does anyone know any direct test which can lead to the identification of butanols? I have a 500mL amount of distillate from my previous run of 'fusel oil' production, where I started by excluding amino acids and using a highish conc. of ammonium salts. There is a mixture of alchols (turns acidified dichromate green), and i found no substantial amounts of carbonyl compounds (by 2,4-DNPH). analysis is practically impossile because of such a mixture of compounds in there. (Strange thing I noticed is that the distillate is sort of milky. Seems like a suspension of long-chain aliphatic alcohols, but none tends to form a layer after settling. Will post more details in the fusel oil thread when I will have the time and more results).

S.C. Wack - 12-4-2005 at 23:45

Crotonaldehyde is easily made via aldol condensation of acetaldehyde. Reduction of this with Ni/H2, etc. gives the saturated alcohol. Butyraldehyde can be obtained by dry distillation of butyrate and formate, and I would think that a number of reducing agents would give the alcohol.

There is a high yielding electroreduction of crotonaldehyde in JCS 101, 1016 (1912) if anyone is interested.

Go back to your first thought

fizzy - 13-4-2005 at 07:33

"Industrial Fermentations" by Paul Allen, c. 1926 (available here, I think, from the ftp or on the net via emule) page 107 tells how to isolate the yeast that produces butyl alcohol. Basically it can survive 90 C for 1-2 minutes where as most other yeasts are killed.

I found a book on the FTP

quest - 14-4-2005 at 04:56

his called: "Vogel, Henry - Fermentation and Biochemical Engineering Handbook.pdf"

On page 130 it wrote about butanol, but I can't understand how they made it.

I can take a screen shot of page 130 if you dont want to look for the book on the FTP....

Esplosivo - 14-4-2005 at 06:28

It is basically stating that the Embden-Meyerhof Pathway, also more commonly known as Glycolysis, leads to the production of 2 pyruvate molecules (from every glucose molecule, although this is not exactly correct due to an equilibrium rxn in one step of the pathway between dihydroxyacetonephosphate and glyceraldehyde-3-phosphate. The latter produce pyruvat and therefore the equil. shifts more towards it, but some dihyroxyacetonephosphate still remains). The pyruvat can then be converted, under anaerobic conditions in an anoxic environment (i.e. no oxygen) to produce the alcohols, acid and ketone named. A mixture is formed, usually the majority of pyruvate is metabolised to ethanol by the yeast, since the pyruvate is first decarboxylated and then the resulting acetaldeyhde molecule is reduced to ethanol, but under certain conditions the concentration of one or a mixture of the other products may be increased. These properties are being discussed in the 'fusel oil' thread. Experimentation on my behalf is being carried out but I must stop for a month now, and resume later on. If anyone finds anything interesting please post. Hope this helps.

Dave Angel - 14-4-2005 at 17:08

Originally posted by BromicAcid

Reaction of butane with chlorine in the presence of light at 35C and careful fractioning of the resulting products (very unlikely to fraction well) and followed by reaction of the 1-chlorobutane with basified water to give the 1-butanol.

I like this method on paper as the reagents are very easy to come by, but I would convert the mixed chlorobutanes to alcohols before fractionation as this seems to give better separation between boiling points. For example; 11°C between the 1- and 2-chloro derivatives but 20°C between the respective alcohols. Naturally, the products are unlikely to be as simple as this but conditions could be set up to favour monosubstitution, ie. excess butane.

Of course, there is the issue of azeotropes, which will decide at what stage to fractionate. I shall try to find any relevant azeotropic data during my next trip to the library.

Dave Angel - 21-4-2005 at 15:18

Hmm, sorry but I couldn't find any relevant azeotropic data on the compounds in the library, despite having found a wonderful book which seemed to have any possible combination!

I still think the process has theoretical merit and is worth an experiment.

BromicAcid - 26-4-2005 at 08:14

Is butanol restricted or watched in any way? I found a method to THF via butanol today but it is quite the pain in the butt, involving first converting the butanol to the hypochlorite ester and allowing that to decompose in the presence of sodium bicarbonate with benzene under reflux for an hour. You end up with ClCH2CH2CH2CH2OH in a 17% yield which can then be reacted with aqueous NaOH or KOH to give THF which can then be distilled off, as the author of the article did.

The paper is from The Journal of Organic Synthesis, Vol 27, 1032, Intramolecular Hydrogen Abstraction in a Primary Alkoxy Radical I'd try it for novelty purposes if it weren't for the fact that I have no acetic acid besides vinegar, although there are other methods to form butylhypochlorite....

Esplosivo - 26-4-2005 at 08:52

Very interesting reaction. Well I don't know what occurs in the States but where I live nothing is totally illegal (but everything is expensive :P). Can the butylhypochlorite be formed by a similar procedure as that used by Axt to produce ethylhypochlorite? It would be quite simple as I see it.

Could you elaborate on the synthesis of the hypochlorite with the use of ethanoic acid. I've got quite a lot of it, and would gladly find some good use for it.

[Edited on 26-4-2005 by Esplosivo]

BromicAcid - 26-4-2005 at 09:02

Experimental:n-Butyl hypochlorite was prepared by adding 67 ml of n-butyl alcohol, 400 ml benzene, and 67 ml. of acetic acid to a mixture of 1000 ml of 0.76 M sodium hypochlorite and 200 g. of ice. The benzene solution of n-butyl hypochlorite was separated, and the aqueous fraction washed twice with 50 ml portions of benzene. The combined benzene solution was washed with aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The resulting dry benzene solution (550 ml.) was 1.14 M in n-butyl hypochlorite, as determined by iodometric titration. Seventy grams of dry powdered sodium bicarbonate was added and the resulting slurry was heated under reflux until the evolution of carbon dioxide gas ceased (1 hr). The solids were removed by filtration and the benzene was distilled. Butanol was detected by gas chromatography in the distillate. The residue was fractionally distilled and the fractions were assayed by gas chromatography.

The caluclated yield of tetramethylene chlorohydrin was 16%. The infrared spectrum of Fraction 3 confirmed that it was chiefly tetramethylene chlorohydrin. When a portion of Fraction 3 was treated with hot aqueous 10 M sodium hydroxide, tetrahydrofuran, bp 60-68C was obtained.....

In a similar experiment, condusted in the absence of sodium bicarbonate, the total reaction mixture was treated with potassium hydroxide and tetrahydrofuran was obtained directly.

Just a fun an interesting synthesis taking advantage of an organic hypochlorite compound.

As for just the formation of hypochlorites in general the orgnic synthesis website has I think two preparations for t-butyl hypochlorite that are worth checking out.

[Edited on 4/26/2005 by BromicAcid]

Esplosivo - 26-4-2005 at 09:36

Thanks BromicAcid. After the exams I will try this out. I guess that the benzene can be substituted by toluene (I see no other role for it except for being a solvent). Butanol I can buy, and hopefully produce by fermentation till the end of summer, assuming I can find and isolate the fungus (yeast).

you deviating a little from thwe subject

quest - 2-5-2005 at 08:21

The only thing that will react with butane is halogen?

I'm looking maybe to some chemical that I can bubble the butane into, and synthesis my self some "butane-derivative"

It will be very hard if I need to use butane and chlorine because they both gases and take alot of room for a little mas (In ordinary pressure)

Esplosivo - 2-5-2005 at 08:35

You could try passing the two gases from a transparent tube (glass would be best, plastic could also be OK). With a large excess of butane, you could maybe ensure the formation of chlorobutanes only, instead of the di, tri, etc... butanes. The gases can then be passed through a cooling jacket, the chlorobutanols should condense and then you could use these for the substitution with sodium hydroxide to produce butanols (which can further be separated).

And about the deviation from the subject, you should thank BromicAcid rather, he provided a pretty synthesis pathway to carry out with butanol ;)

Other halogens which can be used in the liquid state as in bromine, or iodine in solution would give more than one substitution since they would be present in excess when compared to the butane being bubbled. After rxn with NaOH soln you would therefore obtain a miture of butanols with a varying number of -OH groups. Hope this helps.

sparkgap - 3-5-2005 at 21:55

I'm not too sure of that working, Esplosivo. The two secondary carbons of butane are the more likely places where the chlorine will go, if I rmemeber my reactivities correctly. If he wanted 2-butanol, though, that might be good.

BromicAcid, how about continuing your research on magnesium boride; this may be the solution to his problem! ;)

sparky (^_^)

Esplosivo - 4-5-2005 at 02:25

Yes sparkgap, most of the the product will be 2-chlorobutane, up to over 70%. Borane/diborane is indeed a nice reducing agent, can be used to reduced butanoic acid, and that one could probably make by oxidation of butter - not that straight-forward but it can be done with a little research you know...