Sciencemadness Discussion Board - Synthesis of longer chain tertiary alcohols

"Citrusy" sounds like you are making limonene. Terpineol should smell like lilac or hyacynth. I'm having a go at using various acid catalysts to make terpin hydrate, then dehydrate to terpineol. Will post if I get anything promising.

It has occurred to me. Limonene, itself a hydratable terpene, is listed in the original paper’s by-products. But alfa-terpineol is supposed to be the main reaction product…

Not sure though what you mean by ‘dehydrating’ in this context.

Your help would certainly be appreciated.

There’s also the reaction of limonene (very OTC) with trichloroacetate to synth. the alfa-terpineol trichloroacetate that can be considered…

blogfast25 - 3-4-2011 at 07:43

http://www.scielo.br/scielo.php?script=sci_arttext&pid=S...

... for that reaction between limonene and trichloroacetic acid (courtesy of Eclectic, above).

[Edited on 3-4-2011 by blogfast25]

Eclectic - 3-4-2011 at 07:57

I've found many references that indicate that both limonene and pinene will add water to form terpin hydrate with dilute mineral acids, and possibly some alcohol to improve solution of H2O in the terpene phase.
Terpin Hydrate has low odor and can be isolated nicely crystalline. From there, boiling with dilute mineral acids removes water to form terpineol.

I'm thinking 1 cup turpentine, 1 cup 70% isopropanol (rubbing alcohol), and about a tsp (5ml) H2SO4. I'm also trying it with isopropanol/HCl, and Methanol/H2SO4 (water 25-30%)

blogfast25 - 3-4-2011 at 11:41

I've found many references that indicate that both limonene and pinene will add water to form terpin hydrate with dilute mineral acids, and possibly some alcohol to improve solution of H2O in the terpene phase.
Terpin Hydrate has low odor and can be isolated nicely crystalline. From there, boiling with dilute mineral acids removes water to form terpineol.

I'm thinking 1 cup turpentine, 1 cup 70% isopropanol (rubbing alcohol), and about a tsp (5ml) H2SO4. I'm also trying it with isopropanol/HCl, and Methanol/H2SO4 (water 25-30%)

Great! Could you post one or two of these references? Googling only points to medical info, not even what 'terpin hydrate really is'. If it can indeed be crsytallised, that would be a great advantage for work up...

Edit:

Oh, I get you now: terpin hydrate:

http://drugstoremuseum.com/sections/level_info2.php?level_id...

I can see how that could be dehydrated to terpineol...

"In making terpin hydrate a mixture of four parts of rectified oil of turpentine, three parts of alcohol (sp. gr. 0.863), and one part of nitric acid is put in large, shallow porcelain dishes and allowed to stand for three or four days. The crystals which have formed are then collected and allowed to drain thoroughly; they are then pressed between sheets of absorbent paper, and recrystallized in a cold solution of 95 per cent, of alcohol. The product is about 12 per cent, of the original turpentine oil. E. T. Hahn proposed the use of methyl alcohol (sp. gr. 0.801) in place of alcohol, in making terpin hydrate. ( A. J. P., 1897, 73.) Terpin hydrate is officially described as in "colorless, lustrous, rhombic prisms, nearly odorless, and having a slightly aromatic and somewhat bitter taste. Permanent in the air. Soluble in about 200 parts of water, and in 10 parts of alcohol at 25° C. (77° F.); in 32 parts of boiling water, and in 2 parts of boiling alcohol; also soluble in about 100 parts of ether, 200 parts of chloroform, or 1 part of boiling glacial acetic acid. Terpin Hydrate melts when quickly heated at 116° to 117° C. (240.8° to 242.6° F.), with the loss of water, and, at the temperature of boiling water, sublimes in fine needles. When heated in a flask adapted for distillation, it first loses water. At 258° C. (496.4° F.) anhydrous terpin distils over without decomposition, soon solidifying to a crystalline, hygroscopic mass, which melts at 102° to 105° C. (215.6° to 221° F.). When strongly heated on platinum foil, it burns with a bright, smoky flame, leaving no residue. If to its hot, aqueous solution a few drops of sulphuric acid be added, the liquid will become turbid and develop a strongly aromatic odor. Terpin Hy-drate should not have the odor of turpentine, and its hot, aqueous solution should not redden blue litmus paper." U.S. The anhydrous terpin obtained from it by the loss of water has the characters of a glycol. Dipentene dihydrochloride is its hydrochloric acid ether. By the loss of water the terpin then becomes terpineol and finally yields dipentene, terpinene, or terpinolene, according to the conditions of its treatment. Bouchardat and Voiry obtained terpineol in crystals which melt at 35° C. and remain in superfusion for long periods. (Ann. Ch. Ph., 1893, 103.) For Wallach's researches on crys-tallized terpineol, see P. J., 1893, 2."

[Edited on 3-4-2011 by blogfast25]

MrHomeScientist - 3-4-2011 at 19:19

Today I did a run of the terpineol synthesis at 4x what I did before:

18.4mL turpentine
6.4mL H2SO4
100mL Acetone

I ran this for about 3 hours, with some strange results.

First, the initial mix was three layers, instead of the two I'd previously observed.

I set this one up with my new ground glass setup - a 250mL RBF in a hot water bath and a Liebig condenser connected to some cold water for the jacket.

I ran this for 3 hours with the standard color change to yellow. The volume didn't change at all, so my condenser setup is working beautifully. However, when I stopped the reaction and took everything apart, the product only had one layer!

Product before Neutralization.jpg - 343kB

This was before neutralizing. Even after neutralizing there didn't appear to be any change. Actually I added the stoichiometric amount of base to neutralize it, but it was still acidic. I decided to leave it to see if it does anything overnight. Blogfast, have you ever seen anything like this in your trials? It seems my oil layer has disappeared, even though volume has not decreased. Maybe the large amounts I'm using require a longer time to settle into layers? I'll check again tomorrow.

blogfast25 - 4-4-2011 at 05:29

MrHS:

Firstly, the three layers is bizarre. Are you sure the ratios used are these in the paper? 18.4 ml turps sounds mighty high for 100 ml acetone, off the top of my head. And the H2SO4: was it 15 v/v% (if not you’ve no water in there!)

But the disappearance of the layers into 1 layer I think may be a good sign. Here’s why. What’s always bothered me is that in the paper they claim to dilute their sample for analysis (taken every 30’, IIRW) with more acetone (after meutralisation), then directly inject it in their MS and GC. Well, with what I saw that wouldn’t make any sense: you can’t reliable inject a two phase system into the evaporator of a MS or GC! That would strongly point to the authors having obtained a single phase too, like you have. Sadly the point about the number of phases isn’t touched upon in the paper.

Re. neutralisation: on both accounts I had the stoichiometric amount of NaOH at hand as NaOH 5%, on both accounts it turned out not to be enough! Like you…

Re. work up: your new system seems more that robust enough to go for direct distillation: crank up the heat to 100 C and acetone should be coming over swiftly (56 - 57 C). At some point though I’m sure the bottom will split up again. You could stop there and attempt liquid-liquid extraction with water to get the last bit of acetone into the added water. Or you could attempt to distil till almost dry, then wash with water…

I’m convinced now that my product is too contaminated with limonene, as eclectic suggests: the smell is just too strong and not in accordance with the literature described delicate lilac flagrance of terpineol.

With the new information about terpin hydrate it would appear that the conversion of alfa-pinene would be like this: alfa pinene > limonene > terpin hydrate > alfa-terpineol. I think the last step in my case wasn’t completed.

Good work, MrHS!

%$%$%$%$%$%

Terpin Hydrate Synth:

I’ve also started an attempt to synth. terpin hydrate from turpentine using roughly the recipe above. It says ‘nitric acid’ but indicates no strength. Instead I’ve used 50 v/v% H2SO4 because I can’t really see how this hydration can be achieved without some water present (alcohol being a poor hydration agent). I used:

80 ml straight turps
60 ml alcohol (well, ‘methylated spirits’)
20 ml H2SO4 50/50 v%

.. so 160 ml total volume, poured out in a clean 1 L PE ice cream tub, so that maximum contact area between the two phases exists. Patience is a virtue...

I imagine the reaction to go as:

Alfa pinene (l) < === > limonene (l) (isomerisation)

Limonene (l) === > terpin hydrate (cr) (hydration), catalysed by acid.

… with the first reaction being ‘pulled’ to the right by the second.

The hydration itself, say for instance on the dangling methyl ethenyl group, I imagine to go as follows. Electrophylic attack by a proton on the ethenyl double bond, turning the =CH2 group into a -CH3 group and the tertiary carbon into a carbenium ion. Water then approaches the carbenium ion with its partially negatively charged O atom, leaving behind an OH group on the tertiary carbon and freeing a proton (thus showing the acid is indeed catalytic and isn’t used up). Similar for the hexene double bond and its tertiary carbon in position 1.

Eclectic is right: there are quite a few references to terpin hydrate, many short on details though. Here’s a google book reference:

http://books.google.co.uk/books?id=07g30rxCA0EC&pg=PA495...

… which suggests stirring turpentine wik 2 -3 times its volume of 30 % H2SO4 at RT for 4 - 6 day to get the hydrate.

So I’ve initiated another test of 56 ml turps + 72 ml water and 32 ml of conc. H2SO4 (total = 160 ml) into the same type of ice cream 1 L container. I’ll stir it regularly but I reckon the large contact area between the phases and enough time should make the reaction happen, provided the turps contain enough alfa pinene.

Update:

Eclectic is right: there are quite a few references to terpin hydrate, many short on details though. Here’s a google book reference:

http://books.google.co.uk/books?id=07g30rxCA0EC&pg=PA495...

… which suggests stirring turpentine wik 2 -3 times its volume of 30 % H2SO4 at RT for 4 - 6 day to get the hydrate.

So I’ve initiated another test of 56 ml turps + 72 ml water and 32 ml of conc. H2SO4 (total = 160 ml) into the same type of ice cream 1 L container. I’ll stir it regularly but I reckon the large contact area between the phases and enough time should make the reaction happen, provided the turps contain enough alfa pinene.

[Edited on 4-4-2011 by blogfast25]

MrHomeScientist - 4-4-2011 at 20:20

Blogfast:

Thanks for the encouragement! The ratios should be the same, I just multiplied everything from my initial run by 4. My first post used 4g turpentine, which came out to 4.6mL so I just used 4x that volume in this one (along with 4x acetone and H2SO4 volumes). My H2SO4 is 4.4M, so about 20% concentrated. It's battery electrolyte from the local Sears auto shop. I adjusted the volume so there's the same amount of acid in the mix, of course, but I guess a little less water.

You comment on the single phase is interesting. It's strange that it would appear in this one run and not any of the others. Mine unfortunately still smells of turpentine though :/ I never have gotten that pleasant scent you've described.

----

I neutralized my products tonight, and ended up having to use almost twice as much NaOH as I stoichiometrically should have. Ah well. The color changed a bit, becoming more of a cloudy yellow. A new phase has appeared at the bottom, which is the water from my NaOH solution. You can sort of see it in this picture.

Product After Neutralization.jpg - 329kB

I decanted it off into a sep funnel (another of my new glassware pieces I was excited to use), and you can see the aqueous layer clearly on the bottom. The line in the middle isn't another layer, just some crap on the inside of the funnel that I can't get off until I get a proper bottle brush.

Like you did, I also found some sodium sulfate crystals that formed from the neutralization, leftover in the reaction flask. Hopefully no more will form in the funnel and cause that nuisance you mentioned!

Sodium Sulfate from Aq Layer.jpg - 363kB

I suppose the next step, then, is to boil off the acetone and see what I'm left with of my upper layer. It's strange that it's not already in a separate oil layer though, as I thought it wasn't soluble in acetone. Turpentine certainly wasn't.

Good luck with your terpin hydrate synthesis! That'd make a pretty simple alternative route, if a bit slower. The fact that it crystallizes would be great to ensure you're getting what you want, rather than the soup that the reflux method ends up with.

[Edited on 4-5-2011 by MrHomeScientist]

blogfast25 - 5-4-2011 at 08:24

MrHomeScientist:

It remains strange that you don’t get that characteristic smell that I get. No idea how to explain that. But go right ahead with the distillation and see what you obtain. More transformations may take place during the distillation process…

I’ve made some strange observations in the mean time.

When I started the second run at terpin hydrate, the one that called for turps + 30% H2SO4, I was a little careless and got a curious little side show.

I measured the turps in a 100 ml PP measuring cylinder, emptied it into the ice cream tub, then measured the water (w/o cleaning the measuring cylinder), added it to the turps and the finally measured the conc. H2SO4 (w/o cleaning the measuring cylinder) and added it to the turps/water mixture. Well, well: on measuring the H2SO4 the remains on the measuring cylinder (MC) underwent a marked colour change to almost red! It needs to be said that my ‘Knockout Drain Cleaner!’ sulphuric acid is 94.5 w% H2SO4 (titrated) but slightly amber in colour to begin with.

I then filled up the MC with water for a soak and didn’t think much more about it. Until I washed up my stuff for the day: the MC had a white substance (the red had gone by then) on its walls and it was clearly water insoluble (and quite hard to remove too) Well, terpin hydrate is almost water insoluble and this resource:

http://drugstoremuseum.com/sections/level_info2.php?level_id...

… claims:

”Terpin hydrate may be identified by the color reaction of Petenkoefer. A drop of sulfuric acid is added to a crystal of terpin hydrate. This produces a yellow color which changes to orange on heating. If a solution of levulose, 0.5 Gm. in 100 cc. of 25 per cent alcohol, is added a carmine red color develops. {Bull. Soc. Pharm. Bordeaux, 1922, 60, 49.)”

(levulose is fructose, BTW. Very OTC.)

Well, my solution had of course heated up a bit due to the solvation of the conc. H2SO4. All seems to fit the formation of a bit of terpin hydrate.

Today I replicated the observation, first with a glass test tube but that didn’t work too well because the turps don’t cling to glass much (surface tension). But using a small PP MC, I got the same phenomenon alright. And adding some water to the emptied MC, the red colour disappeared and a strong milkyness appeared, I’m sure it’s a suspension and not an emulsion. It’s been transferred to a test tube for possible decantation later on and maybe checking alcohol solubility or repeating the ‘Petenkoefer test’ (with fructose).

$%$%$%$%$

On the terpineol front, I’ve left my reaction product (from the 2 runs combined) with a good dollop of anh. MgSO4 to dry for a few days and obtained 6 ml of a pale yellow, oily citrussy liquid. Like eclectic I believe it contains too much limonene to be considered alfa-terpineol. The limonene may also be responsible for the positive test with K2Cr2O7.

To test that hypothesis, the product is now being treated with 30% H2SO4, at RT in a shallow plastic dish. If limonene can be hydrated to terpin hydrate over the course of the next days the citrussy odour should disappear 9and crystals should appear): terpin hydrate is almost odourless, apparently…

On a side note: having by now read and learned a lot about terpene chemistry, you could safely call turpentine ’Evidence of Evolution in a Bottle’!, because it’s amazing how many of these very similar derivatives (also carveol, carvone etc) are found in so many, often quite disparate plant species and essential oils derived from them!

Even tetrahydro myrcenol, another t-alcohol with that 2-methyl-2-ol structure, typical of t-butanol and t-amyl alcohol (the two t-alcohols that work for K synth) that has been discussed above as a possible candidate for K/Na catalysis, seem structurally related to alfa-terpineol:

http://www.iff.com/Ingredients.nsf/0/D40CD91FB557A2B78025699...

TH myrcenol wouild have been one of my first choices to test as a catalyst but despite its widespread use in flagrant OTC applications, it's remarkably hard to get hold of...

%$%$%$%$%

And here’s another claimed method for the synth. of alfa-terpineol, this onr from limonene:

http://chestofbooks.com/health/aromatherapy/The-Volatile-Oil...

When perfectly dry, limonene absorbs one molecule of hydrohalogen with the formation of limonene monochlorhydrate which, when treated with sodium acetate, yields active a-terpineol.

[Edited on 5-4-2011 by blogfast25]

Eclectic - 8-4-2011 at 07:05

http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...

Terpine chemistry makes my head hurt. I suspect production of terpin hydrate is driven by the product crystallizing out of solution of equilibrating products.

blogfast25 - 8-4-2011 at 13:22

http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...

Terpine chemistry makes my head hurt. I suspect production of terpin hydrate is driven by the product crystallizing out of solution of equilibrating products.

Eclectic:

I get a

Error
Sorry, you are not permitted to view this forum

... message when clicking that link. Have you got the correct url there?

Polverone - 8-4-2011 at 20:57

Eclectic:

I get a

Error
Sorry, you are not permitted to view this forum

... message when clicking that link. Have you got the correct url there?

That's a link to a thread in References. I have given you access to that subforum now. If you normally use the /whisper/ site you will need to log in separately for /talk/ links to protected subforums.

blogfast25 - 9-4-2011 at 03:47

Polverone:

Yes, it works now, thanks!

blogfast25 - 10-4-2011 at 11:50

Both papers are interesting. The first part’s conclusions run very similar to those of the paper (above) MrHomeScientist and me did some experiments with: alfa-pinene gets converted to alfa-terpineol, limonene and some other by-products, catalysed by a strong acid and in the presence of water at 70 - 80 C. It shows also how the ratios of the product mix vary with experimental conditions. This variability is a limitation for those who can’t afford a rectification to isolate the alfa-terpineol as a reasonably pure substance.

The route of hydrating pinene to terpin hydrate crystals (which can at least be isolated easily) at RT, followed by dehydration to mainly alfa-terpineol seems more attractive in that sense. But the three experiments that I’m running for terpin hydrate are now in their sixth day have yet to yield the first crystal…

I’ve a feeling that I’ll end up using the ‘Spanish method’: esterification of limonene (readily available - eBay) with trichloro acetic acid, followed by alkaline de-esterification to alfa-terpineol (extraction with hexane)…

Eclectic - 10-4-2011 at 13:23

Careful with the Trichloroacetic...it causes liver tumors. But I'm tempted by that route also. It's a shame trifluoroacetic is so expensive. I also have yet to see any Terpin Hydrate, using isopropanol and 5% H2SO4. I may separate the top organics layer from my 4 different batches and use just 10-20% H2SO4 with a mag stirrer and bar. It may be that the current source of turpentine is byproduct of sulfite process papermaking and is not as good a source of pinene as distillation from pine resin.

I'll also try terpin hydrate from limonene.
http://www.greenterpene.com/

[Edited on 4-10-2011 by Eclectic]

blogfast25 - 11-4-2011 at 05:55

Your mention of ‘sulfite process’ rings a bell: the very first paper on hydration of pinenes was actually mentioned ‘sulphate turpentine’. A typo? But they got comparable results with that kind of turps as with pure pinene…

So you’re not getting any terpin hydrate crystals either, huh? Even my experiment with just turps + dilute H2SO4 (no solvent) isn’t working so far (a week now) but I’ll give it more time.

One possibility is to get some ‘essential pine oil’, that might be higher in pinenes but they tend to be expensive and it’s impossible to tell whether in this ‘New Age’ world of ‘aromatherapy’ and assorted nonsense these products has been adulterated for profit or not… But I might try that.

Thanks for the link and the health warning on TCAA. And they use that stuff for chemical peels!

It’s not only expensive; it’s also hard to get, at least anhydrous. And I don’t see an easy way to extract it from a watery solution… Neutralise with Ca(OH)2 to Ca(TCA)2, crystallise and treat with an equivalent amount of conc. H2SO4 to displace the acid? Sounds messy!

Eclectic - 11-4-2011 at 06:59

You may be able to make it from hexachloroethane by refluxing with 25% H2SO4, and maybe some iron.

I have 3-4 gallons of Freon 113 I stashed away 20 years ago...If it has not evaporated, conversion to 1,1,1,trifluoro-2,2,2,trichloroethane and hydrolysis to trifluoroacetic acid is looking very worthwhile.

[Edited on 4-11-2011 by Eclectic]

blogfast25 - 11-4-2011 at 08:27

Hmm… that sounds like a lot of messing, assuming you’ve got any Freon left, of course. And how would you go about isomerising it?

But I imagine trichloroacetic acid may not be too hard to get in the US. eBay.co.uk sellers of watery solutions (for chemical peels) are mainly US sellers (but all are watery solutions and laced with lactic/salicylic acids).

blogfast25 - 11-4-2011 at 09:37

Holy moly:

Scavenging through the Kremer Pigmente site (the guys most of us in Europe got their Shellsol D for K synth. from!) for some solvents, there’s terpineol:

http://www.kremer-pigmente.de/shopint/index.php?cat=0301&...

Clicking through to ‘Details’, this looks like the real deal: 62.3 % α-terpineol, terpineol (total) > 98 %...

[Edited on 11-4-2011 by blogfast25]

Eclectic - 11-4-2011 at 14:32

Well, hell, Blogfast, if all you want is to buy it, I don't even want to know you :-D (reference to "The West Wing" TV show).
I have 2 liters of Tert-Amyl alcohol and could send you some.

I'm kinda pissed off USA site doesn't offer it.

[Edited on 4-11-2011 by Eclectic]

MrHomeScientist - 11-4-2011 at 20:19

Yeah I've had a lot of trouble finding a source for a useable alcohol for the K-synth here in the US. That's why I'm interested in this whole terpineol synthesis (plus it's a pretty neat process).

I haven't gotten much work done on it lately though, because I've been rather busy with stuff at work. I'm co-starring in an educational outreach program that takes science demonstrations to local elementary schools, to get kids interested in science at an early age. This month is full of shows, so that's taking up much of my time. It's lots of fun!

I'll see if I can't distill my latest product (as mentioned in my last post) this weekend.

blogfast25 - 12-4-2011 at 06:12

Well, hell, Blogfast, if all you want is to buy it, I don't even want to know you :-D (reference to "The West Wing" TV show).
I have 2 liters of Tert-Amyl alcohol and could send you some.

I'm kinda pissed off USA site doesn't offer it.

[Edited on 4-11-2011 by Eclectic]

No, no, no, Eclectic, of course I want to be able to synth. it but please do remember the purpose of this thread: to find other t-alcohols that could work for the reduction of KOH with Mg and in particular for the synth. of Na by the same process (it’s suspected that poor solubility of the alkoxides of Na and t-butanol and t-amyl alcohol in high alkanes is the problem).

In an ideal world where sourcing wasn’t a problem I would have tested maybe up to ten such alcohols by now but getting hold of the ones of interest has proved difficult, hence the look out for stuff that can possibly be home synthesised, like alfa-terpineol.

There’s also tetrahydro myrcenol (2,6 dimethyl octan-2-ol) I find very hard to get, despite it being widely used in OTC flagrance systems (plenty of patents on ‘bleach resistant perfumes’ out there - LOL)

And this one we thought would cure all our woes (US only)(courtesy Unintentional Chaos):

http://www.newdirectionsaromatics.com/dimethyl-benzyl-carbin...

… but Nurdrage wanted to get it and there was a long backlog (or something like that anyway). It got a bit forgotten after that. Shame, because it’s a 2-methyl-2-ol type alcohol too…

I do have some t-amyl alcohol and it’s the one I use for K (but Nurdrage tested it for Na and it didn’t work).

How about we swap? 0.5 l of your t-amyl alcohol for 0.5 l of terpineol? Or another type of swap even? I’ll be ordering it this afternoon. Even if we do get to synth. it, it’d be nice to have a baseline. Also, using the TCA or TFA route with limonene, it’s likely to be very expensive compared to commercially available product. The TCA here is about £10 for (pure) 25 g TCA. And it’s basically non-recoverable…

Enjoy the shows, MrHomeScientist!

blogfast25 - 19-4-2011 at 01:43

Well over two weeks now and still no terpin hydrate crystals at RT. The mixtures (all three of them) have clearly darkened somewhat but that's about it.

Eclectic - 19-4-2011 at 03:05

Same here. Now I'm REALLY determined to make terpin hydrate.
I'll tap a pine tree and use nitric acid if I have to.

Um....maybe there is a peroxide intermediate and air oxidation is part of the process?

[Edited on 4-19-2011 by Eclectic]

blogfast25 - 19-4-2011 at 09:38

On the plus side my Kremer terpineol got here today. Will U2U U tomorrow.

It really smells a bt like my second attempt at synthesising it but more musky and less citrussy. Subjectively, of course...

blogfast25 - 20-4-2011 at 07:14

I tested the Kremer terpineol with potassium dichromate today. Remember that dichromate is only supposed to oxidise primary and secondary alcohols, not tertiary ones.

10 ml each of 0.1 M K2Cr2O7 in 0.1 M H2SO4 was added to 3 test tubes. To #1, 8 drops of methylated spirits (methanol denaturated ethanol) was then addedand to #2, 8 drops of terpineol, to #3, 8 drops of 2-methyl butan-2-ol (t-amyl alcohol or 2M2B).

At RT there’s not much going on: #1 darkens slightly, in #2 the floating terpineol darkens quite quickly, #3 was unaffected.

Then they were kept on a steam bath for a while. #1 reacts way fastest and oxidation runs to completion (only green/blue Cr3+ to be seen).

#3 also runs to complete reduction of the Cr2O7(2-) but it takes a much longer time (about half an hour).

Surprisingly #2 started to darken in colour at 100 C too. But that took even longer and didn’t run to completion. But green/blue Cr3+ can be noticed. Is this due to small quantities of primary/secondary alcohols accompanying the t-amyl alcohol? Not sure…

I noted also the #2 test behaved very much like the home made ‘hydrated turpentine’ described (and tested) above.

So although it seems the commercial terpineol does contain some dichromate oxidisable stuff it’s probably at a level that’s acceptable for a test in making K with the terpineol as a catalyst under test… Time allowing I should be conducting such a test tomorrow.

Lambda-Eyde - 20-4-2011 at 20:42

Isn't it possible for dichromate to break the double bond under harsh conditions, thus giving a false positive for secondary/primary alcohol? Potassium permanganate, a slightly more powerful oxidant, is used to cleave double bonds to give alcohols under basic conditions and carboxylic acids under acidic conditions.

blogfast25 - 21-4-2011 at 02:43

The thought has certainly occurred to me. But are the described conditions 'harsh'? I don't really know enough about organic to answer that.

blogfast25 - 22-4-2011 at 08:40

Commercial terpineol tested negative as a catalyst for making potassium. No use testing it for sodium then.

http://www.sciencemadness.org/talk/viewthread.php?tid=14970&...

Another potential precursor for a t-alcohol (type “2-methyl-2-ol”) is OTC (but not cheap) Ibuprofen:

http://www.sciencemadness.org/talk/viewthread.php?tid=16085

Extract with hexane (I’m told), esterify to methyl ester and double Grignard with MeI. Simple really

[Edited on 22-4-2011 by blogfast25]

m1tanker78 - 28-4-2011 at 11:23

In the context of this thread and sodium, which is more problematic?

1. Lack of catalytic activity?
2. Low or no solubility of NaOH in the target alcohol?

My understanding of these reactions is very limited but aren't #1 and #2 basically the same in this context?

blogfast25 - 28-4-2011 at 11:40

Tanker:

It probably helps to understand the latest proposal for a reaction mechanism for K reduction, you’ll find it here:

http://www.sciencemadness.org/talk/viewthread.php?tid=14970&... (scroll up to my post of 2:41)

It’s suspected that for Na the problem is poor solubility of the sodium alkoxide (NaOR) in the HC, hence the search for longer chain t-alcohols…

[Edited on 28-4-2011 by blogfast25]

m1tanker78 - 28-4-2011 at 13:55

I see. I assume you're still using Shellsol for the reaction medium? Why not substitute (or augment) it with something like triethylene glycol monobutyl ether? It's one of the only HC's that I know of which is miscible with both water and most other HC's. A quick look at the data sheet puts the density at 0.984 g/ml, BP ~ 272C. I should mention that it's a major component in DOT3 brake fluid.

Brake fluid by itself (although hygroscopic) seems like it can serve as the reaction medium AND produce clean, floating potassium (maybe even sodium) - eliminating the need for the additional and expensive step of heating the K (or Na) in i.e. dioxane to clean and coalesce. It isn't terribly viscous either.

I did a quick experiment last night which was nothing more than heating some sodium ore in brake fluid. Unfortunately, I don't have the proper equipment for reflux. I was delighted when I saw CLEAN sodium spherelets as well as some larger globules rise to the surface, leaving the block residue at the bottom. Of course, the hot sodium quickly oxidized at the surface so I didn't have a chance to test the ease of coalescence. Based on what I witnessed, either Na or K should coalesce just fine if protected from air and moisture.

The figures for the particular BF I used are: BP ~ 232C; Specific Gravity ~ 1.05; Viscosity = 'Not Determined' but subjectively very low.

BTW BlogFast, your reaction writeup was very helpful. The K thread is so long that I completely forgot about it by the time I got to the last page.

m1tanker78 - 29-4-2011 at 05:45

Hmmm well, I was unable to reproduce the favorable conditions I outlined in my previous post. The sodium readily popped up to the surface but came up white and oxidized away fairly quickly. The only real change I made was to mostly drain the mineral oil from the ore before I added it to the hot BF. I also pre-heated the BF some in an attempt to drive off moisture. This leads me to believe that on the first experiment, there was probably an ideal blend of BF/MO which balanced the rate of oxidation and the overall density. I suppose the -O- bonds are what give BF a favorable specific gravity. It's hard to tell if moisture is the culprit or if the hot sodium is breaking down the ether by stripping the bonding -O-. At RT, Na remains clean and shiny in a BF/MO blend. I wish I could test this in an inert environment with proper reflux.

BF isn't off the bench just yet. I'm going to attempt to blend it with a HC to increase the overall SG and reduce the metal interaction with the glycol ether.

blogfast25 - 29-4-2011 at 08:03

Triglycol Monobutyl Ether hardly qualifies as a hydrocarbon in my book: it has four oxygen hetero atoms in it, one of them present as a primary alcohol function!

The latter function alone would disqualify it both as a reaction medium and as a coalescing medium. The oxidation you observed may well be nothing more than the reaction of the primary alcohol group with the sodium, forming an alcoholate (alkoxide). Certainly at reaction temperatures that is precisely what would happen.

Still, I’m glad you brought up this material because it’s fairly OTC and if esterified, e.g. to its ethyl ester, it might be much more suitable as a coalescing liquid. The many oxygen atoms in it would make it less suitable as a reaction medium because of potassium’s affinity for oxygen.

And it does have a high density and may have high surface tension due to some polarity.

A whole range of solvents have been tested for K by several experimenters, including me. Currently I use a medium-heavy kerosene (lamp oil, in plain English) because it’s cheap and works well. Shellsol D is quite expensive by comparison and offers no great advantages. Basically anything that’s inert to potassium and has a boiling point of no less than 180 C is suitable.

[Edited on 29-4-2011 by blogfast25]

m1tanker78 - 29-4-2011 at 22:46

BlogFast: Point taken about it not being a HC and about the unsuitability at higher temps.

As far as BF being a potential coalescing fluid..... I leave you with this video. They are sodium spherelets in a BF/HC blend - enough BF to where they just barely float to the surface at BP. If I can eliminate all the 'x-factors' to make it reliable, this will drastically improve the way I do my post processing! I don't want to get my hopes up too high yet.....

<iframe sandbox width="640" height="510" src="http://www.youtube.com/embed/mw-lhQiO2WY?rel=0" frameborder="0" allowfullscreen></iframe>

Tank

blogfast25 - 30-4-2011 at 04:45

Okay, the video is a bit inconclusive but I was thinking last night that it would be worth trying DOT 3 anyway. I should be able to get some today. Thanks for the information!

m1tanker78 - 30-4-2011 at 05:55

Sorry about that. T'was late and I got caught up in the half-asleep excitement.

Sadly, I wind up throwing away a good portion of Na because it takes more time to refine than it takes to make a little more. The hard-to-refine stuff sort of piles up in a can with oil until I get fed up and just toss it (after incinerating). It's hard to explain but I'll leave that for another thread.

The point of the video was to show that:

1. A BF/HC blend can float Na (and hence, K) at elevated temps with minimum oxidation. The soda can was used to prolong the blend since the BF volatilizes at that temp.

2. The same can coalesce Na (assume K). In the video clip, some coalescence had already taken place.

3. The Na that came up from 2 teaspoons worth of [otherwise] garbage is virtually free of crusty impurities.

BlogFast, I brought this up with the hope that it will be of good use for the people who are now making K. I'm eager to see your results and help out in any way I can (with my limited resources). Something tells me the blend might work OK as the reaction medium (to float ALL the K and thus, increase yield). I'll leave that up to you guys...

Tom

blogfast25 - 30-4-2011 at 09:47

Thanks Tom, the result of a simple test with K, using DOT 4, are reported in the K thread. The test wasn't positive but the K did float (but it also reacted briskly with the brake fluid, Na has lower reactivity and may be much more suitable...)

In your video, I seem to see Na globules bobbing up and then down again: that's often a sign that H2 is being generated; they pick up hydrogen, come to float, then 'offload' the hydrogen and nosedive again...

[Edited on 30-4-2011 by blogfast25]

m1tanker78 - 30-4-2011 at 10:46

In your video, I seem to see Na globules bobbing up and then down again: that's often a sign that H2 is being generated[...]

Blog, the globules are bobbing up and over because of the gentle boiling of the blend. This isn't possible with Na in straight mineral oil. The higher SG of the blend permits them to 'ride the currents'.

Tom

blogfast25 - 30-4-2011 at 12:25

You got that stuff to boil? At about 232 C, no wonder it's fuming!

Hmm. Try coalescing at much lower temps. Just an idea...

[Edited on 30-4-2011 by blogfast25]

m1tanker78 - 30-4-2011 at 15:46

Blog, I coalesce Na slightly beyond the MP. After coalescence, it's good practice to ramp up the oil temp to boiling, if possible. Doing so promotes the separation of surface contaminants.

I was concerned more with the SG than with coalescence in the vid. I found it interesting that they coalesced at all at such a high temp. Then again, the blend's viscosity at BP is similar to water (subjectively).

Tom

blogfast25 - 1-5-2011 at 05:55

And you don't lose much Na to Na alcoholate? That must be good progress to recover bits and pieces from 'dirty' sodium, right?

m1tanker78 - 1-5-2011 at 10:04

You got that right! Last night, I took the same batch from the video and heated it up to just under boiling and kept it that way for ~ 90 minutes. Throughout the first 5 or 10 minutes, I added BF drop by drop until the Na bits began to surface with the circulating effect (similar to the video but with a little less buoyancy). I replenished BF as necessary. I couldn't observe any appreciable loss. The bits remained shiny (not white). A little further coalescence may have taken place but I wasn't really paying attention to that aspect. It goes without saying, all of this is strictly subjective observation at this point. After a total of ~ 2 or 3 hours @ BP, there SHOULDN'T be any nascent Na left.

This is [potentially] a large leap for me to increase Na recovery and, thus, total yield. This may also prove to be VERY useful for the 'sodium-by-thermite' crew. If/when the K process is successfully implemented to make Na, there should be some good use in wringing out the fine Na from the junk. Still speculation at this point for all of the above.

The esterification process you propose sounds very interesting indeed. Not easy but not impossible.

Tom

[Edited on 5-1-2011 by m1tanker78]

blogfast25 - 1-5-2011 at 12:40

Yes, for those who wish to recover their relatively meager yields from magnesiothermic or aluminothermic sodium this should be very useful. Ping Nurdrage, he should be interested...

NurdRage - 2-5-2011 at 00:03

no need to, i already came across using brake fluid a couple of months ago.

i'll share my findings in a video after i've perfected the process.

[Edited on 2-5-2011 by NurdRage]

blogfast25 - 2-5-2011 at 13:11

Look forward to watching that.

m1tanker78 - 2-5-2011 at 14:02

no need to, i already came across using brake fluid a couple of months ago.

i'll share my findings in a video after i've perfected the process.

[Edited on 2-5-2011 by NurdRage]

Hehehe....

NurdRage - 2-5-2011 at 15:37

Quote: Originally posted by m1tanker78

no need to, i already came across using brake fluid a couple of months ago.

i'll share my findings in a video after i've perfected the process.

[Edited on 2-5-2011 by NurdRage]

Hehehe....

?????

m1tanker78 - 2-5-2011 at 16:51

A little off topic:

NurdRage, your comment came off sounding arrogant. Don't get me wrong, I enjoy your videos and the ultimate goal here is to get this stuff out to as many enthusiasts as possible. There's always room for improvement but the legwork is always done behind the scenes. Wouldn't you agree?

Keep the concept of collaboration alive. I look forward to the video!

Tank

NurdRage - 2-5-2011 at 17:00

Sorry if it did, i've been known to be a dick.

my apologies if it sounded that way.

As for the actual work, I have no idea when such a video will be ready. Improvements have been..... incremental at best...

m1tanker78 - 2-5-2011 at 17:53

i've been known to be a dick.

Well that makes 2 of us then.

I started this thread to help iron out the process(es) of refining and coalescing the alkalis. Stop in and let us know how it's going and if you need someone to test something. I've already offered to do so and BlogFast has done some testing of his own.

Tanker78

[Edited on 5-3-2011 by m1tanker78]

blogfast25 - 9-5-2011 at 03:32

Here are two links to highly interesting academic papers (pdf) that thoroughly investigate the reactivity of monoalkenes in hydration reaction to alcohols, acid catalysed, in function of various alkene substituents (alkyl groups):

http://www.sciencemadness.org/talk/files.php?pid=209214&...

http://www.sciencemadness.org/talk/files.php?pid=209214&...

Among other things, based on these results, I wonder if it’s worth attacking turpentine (alfa and beta pinenes) with much stronger H2SO4 (50 % or higher)…

blogfast25 - 15-5-2011 at 13:45

It’s been proved difficult so far to find OTC feedstocks of C6/C7/C8…/C10 materials that could be converted to longer chain tertiary alcohols. One idea that was floated much higher up in the thread was medium chain fatty acids from certain weed killers.

‘Bayer garden 3 hour’ is claimed to contain a mixture of ammonium octanoate and decanoate, at about 30 g/L total. ‘Weedol Max’ claims to contain about the same amount of pelargonic acid (nonanoic acid).

So I bought a bottle of the ‘Bayer garden 3 hour’. It’s a slightly turbid watery solution that smells a little of diesel oil and feels very soapy to the touch. It forms bubbles easily, all points indeed to ammonium soap solution.

100 ml of it was treated with 10 ml 37 % HCl and the solution immediately became very milky and an organic phase started floating on top. To ensure maximum separation, the emulsion was very slightly simmered for a few minutes, then separated with a separation funnel. About 2.2 g of what is presumably the mixture of C8 (caprylic) and C10 (capric) fatty acids was obtained (which when hot stinks accordingly!) Calculated back ammonium pergolate (C9) gave a value of about 2.5 g/L, so that’s about right as some of the material was lost to the watery phase.

The product was esterified with 1.5 ml ethanol and about 5 drops of conc. H<sub>2</sub>SO<sub>4</sub> and yielded a few ml of pleasant smelling ethyl esters. On effective work-up these could be double Grignarded with MeI to the corresponding 2-methyl-2-alkanols…

************

Today I extracted the pelargonic acid (nonanoic acid) from ‘Weedol MAX’. It appears that this product is very similar to the Bayer product: a slightly turbid solution, slightly smelling of diesel oil, soapy and keen to form bubbles.

I added 20 ml of 37 % HCl to a litre of Weedol and immediately the liquid goes very milky and a smelly oily substance starts to float on the watery phase. Presumably Weedol MAX is a clone of the Bayer product and the nonanoic acid is in solution as a soap (Na, K or ammonium).

Heating the emulsion to close to BP for about half an hour made the watery phase steadily clear up and a slightly yellow oil to form on top. It smells very much like the mixture of octanoic and decanoic acid obtained yesterday.

After the watery phase had much cleared up I siphoned it off carefully and transferred the remaining about 100 ml of two phase system to a separating funnel. Here it is immediately after transfer:

There’s an estimated 38 ml of crude pelargonic acid there, more or less in line with the advertised content (30 g/L). 38 ml is roughly 0.2 mol of the acid.

Methyl esterified to methyl nonanoate and properly worked up it will be a precursor to 2-methyldecan-2-ol (2-methyl-2-decanol) by means of grignard.

[Edited on 16-5-2011 by blogfast25]

garage chemist - 12-6-2011 at 15:28

Today I cooked up a 0,3 mol batch of 2-methyl-2-hexanol, tertiary heptanol, or compound tC7 (tertiary C7 alcohol) as I will call it from now on.

About half of the 1-bromobutane that I made in january was reacted with magnesium in Na/K dried diethyl ether to form a 2 mol/L solution of butylmagnesium bromide and to this was added the correct amount of pure acetone, diluted with an equal amount of dry ether.
Hydrolysis was done with water containing acetic acid, and after washing with aqueous alkali, the ethereal solution is now being dried over K2CO3. Tomorrow it will be distilled to hopefully isolate pure tC7.
Pictures have been made, stay tuned for the complete synthesis soon appearing in Prepublication.

blogfast25 - 13-6-2011 at 04:24

That’s brilliant, garagechemist, congrats! You must feel quite excited: you’re the first here to synth significant quantities of a 2-methyl alkan-2-ol other than the ones we know work for sure! I never thought of that route: C4 alkylating agent + C3 ketone, smarter than MeI + long chain methyl ester (which is what I’m aiming to do). You’ve got quite a bit of it there: about 34 g?

Do you have a link to your bromobutane synthesis?

Will you test the t-C7 alcohol as catalyst for KOH reduction?

[Edited on 13-6-2011 by blogfast25]

garage chemist - 13-6-2011 at 04:35

The bromobutane synthesis is on page 2 of this thread.

I used 0,3 moles of starting materials, how much tC7 I will get from that is a different story. I once made 2-methyl-2-butanol from EtMgBr and acetone and yield was like 45%.
I have quite a bit of experience with running grignards at home, but yields never come near the literature ones.

blogfast25 - 14-6-2011 at 06:25

I'm very tempted to try this starting from isoamyl alcohol (3-methyl 1-butanol) but my experience with Grignard is zero (apart from a uni practicum 30 years ago!) but I have all the materials, including ether. The bromination to 3-methyl 1-bromobutane should be well within my envelope. So I wait with anticipation for your detailed write up.

garage chemist - 14-7-2011 at 14:50

Sorry for the lack of updates, I had some problems with internet (no connection for the last two weeks). I will eventually post the t-C7 synthesis with pictures.

bbartlog - 4-10-2011 at 17:48

Would it be possible to perform reductive dechlorination on 1,1,1-trichloro-2-methyl-2-propanol (aka 'chlorobutanol') as a way of obtaining tert-butanol? The chlorobutanol is easily synthesized from OTC materials (acetone, bleach and lye as reagents, plus maybe ethanol for purification - see e.g. http://www.erowid.org/archive/rhodium/chemistry/chlorobutano... ). Unfortunately most of the references I find on such dechlorination involve its use in decontamination (destruction of chlorine pollutants) and not on any possible value as a preparative technique. Still, there is a lot of literature on dechlorination using zero-valent zinc and iron (google scholar using 'reductive dechlorination iron' turns up over 5000 hits, covering such diverse substrates as ddt, carbon tetrachloride, and chlorophenol). Can anyone see a reason why it *wouldn't* work?

Picric-A - 4-10-2011 at 23:59

Quote: Originally posted by bbartlog

Would it be possible to perform reductive dechlorination on 1,1,1-trichloro-2-methyl-2-propanol (aka 'chlorobutanol') as a way of obtaining tert-butanol? The chlorobutanol is easily synthesized from OTC materials (acetone, bleach and lye as reagents, plus maybe ethanol for purification - see e.g. http://www.erowid.org/archive/rhodium/chemistry/chlorobutano... ). Unfortunately most of the references I find on such dechlorination involve its use in decontamination (destruction of chlorine pollutants) and not on any possible value as a preparative technique. Still, there is a lot of literature on dechlorination using zero-valent zinc and iron (google scholar using 'reductive dechlorination iron' turns up over 5000 hits, covering such diverse substrates as ddt, carbon tetrachloride, and chlorophenol). Can anyone see a reason why it *wouldn't* work?

Out of personal experiencel; Sodium in ethanol can dechlorinate chlorobutanol to t-butanol.

Yields are not amazing and you will have trouble distilling the product t-butanol from the remainding chlorobutanol (i always found my t-butanol smelt a bit like the chlorobutanol, despite double fractional dist.)

blogfast25 - 25-12-2011 at 13:51

After quite a long search for tetrahydro myrcenol, I’ve now finally located a Dutch supplier of ‘aroma chems’ for dihydro myrcenol (2,6-dimethyloct-7-en-2-ol), a tertiary alcohol of sufficient length (C8). The entire ‘fragrance business’ feels quite secretive to me and nearly all suppliers contacted didn’t deem it necessary (or polite) to acknowledge my existence. Said company (not the one linked too) is a wholesaler + retailer and has been recommended for service by a knowledgeable source. Price seems OK, but they’re shut till Jan 3. Wait and see…

I’ve no idea whether this will work for K or Na synth catalysis, especially considering the terminal double bond, which would be hard to get rid of w/o further hydrogenation (halogenation would reduce paraffin solubility and make it prone for any K to snatch the halogen).

BP nearly 200 C.

[Edited on 25-12-2011 by blogfast25]

ChemistryGhost - 5-4-2013 at 12:16

How about dehydrating 2-methyl-1-butanol using phosphoric acid and using the resulting 2-methyl2-butene and 2-methyl-1-butene in an Markovnikov hydration to obtain tert-amyl alcohol?

blogfast25 - 9-4-2013 at 03:17

Quote: Originally posted by ChemistryGhost

How about dehydrating 2-methyl-1-butanol using phosphoric acid and using the resulting 2-methyl2-butene and 2-methyl-1-butene in an Markovnikov hydration to obtain tert-amyl alcohol?

Elaborate on the reaction paths? t-amyl alcohol is of course fairly easily obtained w/o jumping through hoops.

hyfalcon - 10-8-2013 at 17:01

Is this a t-alcohol? Terpinen-4-ol. It's a primary active ingredient in tea tree oil.

Would be great if it is. BP of 212⁰C.

[Edited on 11-8-2013 by hyfalcon]

[Edited on 11-8-2013 by hyfalcon]

halogen - 10-8-2013 at 19:26

Trouble finding long carbon? If you felt desperate enough - "The Wurtz Coupling is one of the oldest organic reactions, and produces the simple dimer derived from two equivalents of alkyl halide."

The destructive distillation of polyisobutene yields some isobutene, wink wink, and also large amounts of an olefin that I forget which it is, dimethylheptene sounds right, but I ain't found the paper yet - but the hydration of that too might be relevant to you.

A shame if phenol is definitely out. I imagine you guys'd be jumpin' and chirping if that worked, which being so simple must have been tried.

Aha! Just remembered: a Zinc copper couple will produce dialkyl zinc with alkyl halide; which adds to ketones. So indeed Eclectic's suggestion was not far off.

edit - no, in fact it's polypropene which yields some dimethylheptene amid a sloo of hydrocarbons.

double edit: In fact you'll love the pyrolysis of polypropylene, just what you're looking for.

Monomer - you get some, not sure what good it is. Higher temperatures are increasingly selective for it.

Dimer - 2-methyl-1-pentene (bingo) CH3(CH2)2C(=CH2)CH3 in rather lower quantity than propylene, but significant.

Trimer - The major product, CH3(CH2)2CH(CH3)CH2C(=CH2)CH3 ie. 2,4-dimethyl 1-heptene is a prime candidate for your purposes, about 20-27% of the pyrolysate.

Other contaminants may or may not yield tertiary alcohols on hydration. Some are longer, others are even saturated. A process for refinement is concievable, but may, if you are rough, gamble. or are impatient, not need separation to be tested.

"Other reports [82] indicate up to 25% monomer, 2,4-dimethyl-l-heptene (27-32%), pentane (about 8%), 2,4,6,8-teytamethyl-l-undecene (7-18%), 2,4,6-trimethyl-l-nonene (4-10%) upon heating at 700 ~ C."

M. T. Sousa Pessoa de Amorim, C. Comel, P. Vermande, J. Anal. Appl. Pyrol., 4 (1982) 73.

For further information consult Moldovenogh's Analitical Pyrolysis of Synthetic Organic Polymers. A wonderfully interesting information-full book.

Also worth examining

http://www3.ntu.edu.sg/r3c/PDF/News/R3C_International_Sympos...

Which I find disturbing, that it mentions something 20% aromatic content in PE and PP pyrolysate. Either oxygen is being introduced in the studies based on, likely, and very relevant to amateur, or...? But disturbing - either no mention in Analytical Pyrolysis, or "trace".

I don't know, I'm tired. Will look further into later. Lot of people researching pyrolys what with oil and so. But the consensus seems to be you get more dimethylheptene than anything else, unless, if I understand and it can be trusted, there's some kind of catalyst? So give it a whack. Thomas Anderson distilled bones and his name is in the books.

edit 3

I think I see what's up. Kaminski was using a "fluidized bed" on a kilogram scale. If anything lets O2 in, or other weird shit (metal catalyzsed dehydrogenation??) it's large scale fluidized bed. Heck of a way to make benzene though.

[Edited on 11-8-2013 by halogen]

[Edited on 12-8-2013 by halogen]

[Edited on 12-8-2013 by halogen]

CuReUS - 9-10-2014 at 09:13

coming in from a completely different direction: could we make crown ethers by amateur means? t-butanol and a crown ether (say 15-crown-5) might do the trick and solvate sodium ions... assuming the ether remains stable under these harsh conditions.

actually although crown ethers are good electron donors,they can easily undergo a beta-elimination,thats why tert butoxide is the best base

btw ,nurdrage i am a huge fan of yours,and your videos are amazing,pls make more

[Edited on 9-10-2014 by CuReUS]

CuReUS - 9-10-2014 at 09:34

i know i am coming late to the party but could you make tertiary alcohol from sugar

sucrose(table sugar ) has 5 secondary OH groups and 3 primary OH groups
couldnt we acetylate the OH with acetyl chloride or acetic anhydride or any anhydride or acid chloride to get a huge ester which could be treated with methyl,ethyl or isopropyl lithium to get tertiary alcohol(organolithium resemble grignards in their reactions but are more reactive and work even for bulky or sterically hindered groups unlike grignards

also lithium can be easily obtained(from batteries) and is less expensive than Mg

also instead of making ester ,we could oxidise all the secondary and primary OH to ketones and aldehydes respectively with fenton's reagent and then treat that with the organolithium to get tertiary alcohol

till now every one has made compounds with one tertiary OH group
what if there are many tertiary OH groups like in my product

more info on sucrose esters
http://en.wikipedia.org/wiki/Sucrose_acetate_isobutyrate

http://en.wikipedia.org/wiki/Sucrose_octaacetate

Crowfjord - 9-10-2014 at 10:04

As far as your first idea is concerned, it seems like it would be more economical/easier to start with ethyl acetate or the like, but the second one is pretty interesting. If one could feasibly oxidize a sugar (or maybe a sugar alcohol or other polyol) to a poly ketone/aldehyde, the product from a grignard or other organometallic addition could potentially form a good metal ligand, with relatively high melting and boiling points.

[Edited on 9-10-2014 by Crowfjord]

CuReUS - 10-10-2014 at 01:41

Quote: Originally posted by Crowfjord

As far as your first idea is concerned, it seems like it would be more economical/easier to start with ethyl acetate or the like

yes you are right,i also realised a few hours ago that if we make an ester with the sugar OH and acetyl chloride,the grignard or other organometallic would attack the acetyl part not the sucrose because sucrose is contributing the OH not the carbonyl carbon.

Quote:

If one could feasibly oxidize a sugar (or maybe a sugar alcohol or other polyol) to a poly ketone/aldehyde, the product from a grignard or other organometallic addition could potentially form a good metal ligand, with relatively high melting and boiling points.

yes we can oxidise the OH to aldehydes and ketones using fenton's reagent.but we cannot use grignard because grignard hydrogenates the carbonyl carbon and to give secondary alcohol instead of adding to it if the ketone is sterically hindered(like in sugars) that's why i suggested organolithium

my new idea is that we can treat sucrose(or glucose) with KMNO₄ (or even bromine water or dilute nitric acid) so that all the secondary OH groups get oxidised to ketones.

the primary OH will be oxidised to carboxylic acid and the lactone ring will obviously break to give another carboxylic acid as well.

so we end up with 4 keto groups and 2 carboxylic groups
now we can esterify both the carboxylic groups with a suitable alcohol

after that we treat the whole compound with organolithium
the organolithium adds to the ketones as well as the esters to give tertiary alcohol

Quote:

with relatively high melting and boiling points

if you want high mp and bp then you can just leave the two carboxylic acids the way they are instead of esterifying them
that will surely increase the boiling point

i thought that they wanted exclusively tertiary alcohols so i suggested the esterification idea

[Edited on 10-10-2014 by CuReUS]

[Edited on 10-10-2014 by CuReUS]

CuReUS - 14-10-2014 at 04:42

actually i dont think we need to even esterify it ,if we directly treat it with say,methyl lithium,the organolithim would attack both the ketones and the carboxylic acids to give tertiary alcohols

hyfalcon - 14-10-2014 at 04:50

Don't think I want to attempt to handle methyl lithium at home.

CuReUS - 16-10-2014 at 10:07

Quote: Originally posted by hyfalcon

Don't think I want to attempt to handle methyl lithium at home.

methyllithium is much more safe to handle than tert butyl lithium(which bursts into flames in contact with air)

also ,we dont need to make it so that we can isolate it
we could generate it in situ

hyfalcon - 16-10-2014 at 10:12

msds still lists it as pyrophoric when exposed to air.

CuReUS - 17-10-2014 at 08:32

but we have to use lithium ,as your grignard is too heavy and bulky ,not Lively and Light like Lithium

but about using organo zinc?

maleic - 4-1-2015 at 01:22

Depending on what did you use sodium alcoholate with corresponding alcohol solvent. Sodium alcohol itself is alkaline, so we shouldn't use alkali. Directly drops allyl chloride into the sodium alcohol, and allyl chloride activity was so high, reaction would be very quickly.

blogfast25 - 15-2-2015 at 08:49

Quote: Originally posted by maleic

Depending on what did you use sodium alcoholate with corresponding alcohol solvent. Sodium alcohol itself is alkaline, so we shouldn't use alkali. Directly drops allyl chloride into the sodium alcohol, and allyl chloride activity was so high, reaction would be very quickly.

I've kind of lost track of this thread a bit.

What is the projected reaction product between sodium ethoxide and allyl chloride?

Metacelsus - 15-2-2015 at 10:59

Sounds like a Williamson ether synthesis to me.

Alice - 13-5-2015 at 15:00

So did anybody have success in manufacturing higher tertiary alcohols and use in making potassium?
I don't see any reason why it shouldn't work.
When I think about tertiary alcohols, camphor and some alkyl grignard comes to my mind. Ketones in general would be less reagent consuming than esters.
How many moles are required for one mole of potassium?

blogfast25 - 13-5-2015 at 15:31

Quote: Originally posted by Alice

So did anybody have success in manufacturing higher tertiary alcohols and use in making potassium?
I don't see any reason why it shouldn't work.
When I think about tertiary alcohols, camphor and some alkyl grignard comes to my mind. Ketones in general would be less reagent consuming than esters.
How many moles are required for one mole of potassium?

No, no success has been reported so far.

About 0.1 mol alcohol is needed per mol of K.

Alice - 13-5-2015 at 16:23

No, no success has been reported so far.

About 0.1 mol alcohol is needed per mol of K.

Thank you very much for the answer.
10 mol% is a fairly good efficiency.

Here I found a reference for camphor reactions with grignards: http://onlinelibrary.wiley.com/doi/10.1002/ffj.2730060102/abstract

Yields don't seem fantastic. The authors claim that grignard reduction is a major side reaction. Interesting to know, though.

[Edited on 14-5-2015 by Alice]

blogfast25 - 13-5-2015 at 18:07

Quote: Originally posted by Alice

10 mol% is a fairly good efficiency.

Here I found a reference for camphor reactions with grignards: http://onlinelibrary.wiley.com/doi/10.1002/ffj.2730060102/abstract

Well, it is a catalyst.

I'll have a look at your link later.

blogfast25 - 14-5-2015 at 10:08

Alice:

A ‘bulky’, camphor-like t-alcohol could be a great idea.

Remember that the purpose [in this context] of these ‘longer C’ t-alcohols is mainly to prepare sodium t-alkoxides of higher solubility in paraffinic solvents. We believe that lower solubility of sodium alkoxides (compared to K equivalents) is the cause of the very long reaction times (in the case of the reduction of NaOH with Mg in inert solvent)

The obvious potential drawback is steric hindrance: the reduction rate of a bulky sodium alkoxide (by Mg to Na and Mg alkoxide) may be slower than with a smaller Na t-alkoxide. That would be swings and roundabouts.

A request for access to the paper you linked to has now been made.

[Edited on 14-5-2015 by blogfast25]

blogfast25 - 15-5-2015 at 05:42

From that paper:

http://www.sciencemadness.org/talk/viewthread.php?tid=62326#...

Preparations of Alkyl Isoborneols and Alkyl Borneols

Quote:

Preparation of the Alkyl Isoborneols 9a-19a,
21a-26a and Alkyl Borneols 19&22b, 24b, General
Procedure

2.43 g (100 mmol) of Mg turnings were covered
with 10ml of ether, and some drops of the total
amount of 100 mmol of the respective alkyl halide
(see above) was added. After starting the reaction
the mixture was cooled with ice-water, and the
alkyl halide solution in 25 ml of ether was added
with stirring in such a manner that the temperature
remained below 15°C. After stirring for 30 min at
room temperature a solution of 35mmol of the
respective ketone 1-4 in 25 ml of ether was added
dropwise. The mixture was heated under reflux for
one day, then cooled with ice-water, and poured
into 50 ml of saturated NH4Cl solution. Work-up
as above afforded the product which was purified
by FC. Analytical data: see Table 2; 'H-NMR data:
see Table 3; 13C-NMR data: see Table 4.

Quote:

Work up

The mixture was neutralized with dilute hydrochloric acid, the phases were
separated, and the aqueous phase was extracted
three times with ether. The combined organic
phases were washed with water and brine, dried
over MgSO, and concentrated. The product was
purified by FC and distilled (KRD).

9a: 2-methyl isoborneol

http://en.wikipedia.org/wiki/Borneol

[Edited on 15-5-2015 by blogfast25]

Alice - 16-5-2015 at 09:45

Here are the literature yields for the camphor derived alcohols:

2-methyl-: 64 %
2-ethyl-: 29 %
2-butyl-: 23 %

I did a little literature research about t-butoxides, and found KOt-Bu forms tetramers with a cubic core made of K and O. NaOt-Bu has two structures, nonamer and hexamer. The hexamer has a hexagonal prism with sodium and oxygen alternating, nonamer has a more complicated irregular structure. http://onlinelibrary.wiley.com/doi/10.1002/cber.19771101018/abstract. The authors state that the bulkyness of the alcohol leads to these ball-like oligomers. In comparison NaOMe gives plane like structures, thus insoluble solids.
This might be a hint why these t-alkoxides have some solubility in nonpolar organic solvents.
The procedure used by the authors for making NaOt-Bu is dissolving Na in a solution of t-BuOH in hexane which gives a cloudy solution.

Now my guess is for 2-metyl-2-hydroxyalkanes the structure might be similar.
This means there might be more than just a difference in basicity and solubility in the K and Na reactions.

The interesting fact is for both structures, hexamer (Na) and tetramer (K) ions and O- are buried. For further reaction with Mg it has to dissociate.

-------------------------------------------------------------------------------------------------------------------

An obvious reason why making sodium takes much longer is NaOH beeing a weaker base than KOH and therefor following equilibrium is not favorable for NaOR/nNaOR:

ROH + NaOH -> NaOR + H2O -> NaOR (cluster)

Some further speculations:

O- is the basic agent in alkoxides. The counterion just draws more or less electron density from O- and makes it therefor more or less basic. For all clusters described above O- is completely buried. Once a cluster is formed it will be more difficult (even for water) to access and reprotonate one of the O-. This might be the reason why tertiary alcohols are required. So equilibrium is shifted more towards alkoxide because of said cluster formation.

Which cluster is more stable, K or Na?

For energetic reasons, I'd say Na-clusters are more stable because Na-O ionic bond energy is bigger than K-O.
Kinetics are less favorable for tNa clusters. It takes longer (lower probability) for more alkoxides to meet. Lower solubility for Na alkoxide contributes additionally, of course.

Considering sterics it is hard to believe to get hexamers or nonamers with a camphor derived t-alcohol, because it would be highly crowded. Smaller clusters may be forced, because the angle between alkyl moieties is bigger.

[Edited on 16-5-2015 by Alice]

blogfast25 - 16-5-2015 at 10:09

That's very interesting Alice, thanks for your thoughts on that.

So in your estimation, would pursuing the alkoxides of 2-methyl camphor derived t-alcohols be worth doing? The first test would of course be on K itself. Failure there would render this catalyst unusable for Na.

And on a minor point, when can you start preparing some?

Alice - 16-5-2015 at 11:36

That's very interesting Alice, thanks for your thoughts on that.

Your welcome.

Quote:

So in your estimation, would pursuing the alkoxides of 2-methyl camphor derived t-alcohols be worth doing? The first test would of course be on K itself. Failure there would render this catalyst unusable for Na.

Good thinking just to change one parameter. From a chemical point of view 2-methyl- would be most interesting, but I won't deal with MeI and I don't want to encourage anyone to deal with it. So 2-ethyl- would most likely be the best choice.

Quote:

And on a minor point, when can you start preparing some?

I need some dry ether.

Any ideas how to separate borneol and 2-ethyl borneol?

[Edited on 16-5-2015 by Alice]

[Edited on 16-5-2015 by Alice]

blogfast25 - 16-5-2015 at 12:24

Borneol as a side-product? Blimey, good question. I'm not that much of an OC, I'm afraid. Column chromatography? Plenty of possible solvents at least!

Would it even hurt to leave it in there? Secondary alcohols might not be very stable in those conditions though.

Ether: a lot of car starter fluids contain it. Or used to at least.

Are EtI or EtBr that much safer than MeI? No idea...

Different approach: tetrahydromyrcenol. Any thoughts? I have some dihydromyrcenol, so it needs hydrogenating, haven't 'gotten round' to that 'yet' (and now in quite poor health, for the foreseeable future)...

[Edited on 16-5-2015 by blogfast25]

Alpha-pinene distillation from OTC turpentine

aga - 20-12-2015 at 12:59

Today some OTC Turpentine was distilled in order to extract a quantity of alpha-pinene as a reagent for an upcoming synthesis.

One reference said that 155 C is the boiling point, yet another stated between 90 C and 105 C in a vacuum distillation (torr unstated).

Firstly a 500ml RBF was tried with a Vigreux column and a 300mm Liebig condenser.

When boiling, the turpentine simply refluxed in the boiling pot, with barely any condensation front seen in the column, despite insulation.

Interestingly the condensate ran back to the liquid down the inner wall of the RBF in thin, evenly spaced rivulets, which at times flash-boiled at the top end before re-forming.

Next a 250ml RBF was charged with 190ml of turpentine in a 'normal' distillation setup (no column) with aluminium foil insulation around the RBF and stillhead.

With this apparatus the distillate started coming over at 142 C (25 minutes), although there was still significant refluxing, and the vapour was condensing before it reached the condenser.

The vapour temperature stabilised at 155 C (30 minutes) at which point the distillate was literally pouring into the receiver flask.

Armed with these parameters, it was decided to re-run the distillation with the 'heads' being anything under 155 C, the reference range of 15 C used to determine that the 'bulk' would be distillate between 155 C and 170 C and the 'tails' being anything over 170 C.

The receiving flask was swapped at each of these cut-off points.

More insulation was added to cover the entire stillhead and the side arm, right up to the condenser, then the distillation repeated.

The results were (left to right) :-

20ml 'heads', a clear liquid smelling slightly of emulsion paint.
143ml 'bulk, a sparklingly clear liquid smelling faintly of pine.
14ml 'tails', a clear liquid smelling of nothing apart from a faint hint of alcohol.
4ml 'dregs' (left in the boiling pot) a yellow liquid smelling faintly of pine resin.

blogfast25 - 20-12-2015 at 13:16

Very nice work and write up.

Full disclosure: this is the α-pinene that will hopefully be converted to α-terpineol and its fully saturated equivalent 2-(4-methylcyclohexyl)propan-2-ol.

Hopefully this will make the work-up of the crude α-terpineol easier because of fewer by-products/impurities.

aga - 20-12-2015 at 13:25

Thanks !

Is 143ml enough, and should that 143ml be re-distilled ?

gdflp - 20-12-2015 at 13:47

Nice job aga, 143ml should be plenty for a run of mixed high MW tertiary alcohols. It's actually quite a lot, I wouldn't use more than 25ml for a test run to make sure that everything works as expected. As for redistillation, unless you can push enough heat into the mixture to fractionate it, I don't think it's worth it unless you have some sort of obvious contaminant. Worst case, the trial run is unsuccessful and you can redistill the main batch.

blogfast25 - 20-12-2015 at 14:16

Quote: Originally posted by aga

Thanks !

Is 143ml enough, and should that 143ml be re-distilled ?

The plan (in your email inbox) calls for 20 ml for the initial test. I don't see a great need for re-distilling what you have there because we have no serious means of determining α-pinene content on it but it's a very reasonable assumption that this distillation increased the α-pinene content in that fraction. That could prove very useful.

blogfast25 - 20-12-2015 at 14:23

For gdflp's information:

The plan is now to go straight to α-terpineol via refluxing of dilute α-pinene in acidic acetone solution. We have an authoritative paper with detailed procedure on it. Will post some more on it when aga starts converting.

j_sum1 - 20-12-2015 at 14:26

Thanks for the latest report from shedworld.

Given that this thread started as a support resource for thhe potassium thread, how suitable will your product be for extracting K? What other uses will you put it to?

edit
Cross post. Thanks for answer anyway. Looking forward to seeing how it all works out.

[Edited on 20-12-2015 by j_sum1]

blogfast25 - 20-12-2015 at 15:53

Quote: Originally posted by j_sum1

Thanks for the latest report from shedworld.

Given that this thread started as a support resource for thhe potassium thread, how suitable will your product be for extracting K?

[Edited on 20-12-2015 by j_sum1]

The purpose is to test the saturated one as a catalyst in the KOH/Mg reduction, which is why I asked aga to post his distillation results (which were entirely his own initiative) here. And in the case of success, also testing for catalysis of NaOH/Mg reduction.

A second derivative from α-terpineol, i.e. tetrahydro myrcenol (2,6-dimethyl octan-2-ol) may also be attempted to synthesize, for the same purposes.

There's no other goal apart from perhaps a bit of shed-fun!

[Edited on 21-12-2015 by blogfast25]

blogfast25 - 20-12-2015 at 16:18

Oh and the procedure for the conversion of α-pinene to α-terpineol you can find here, second *.pdf linked to by UC235:

http://www.sciencemadness.org/talk/viewthread.php?tid=64560#...

Suggestions for work-up are welcome.

aga - 21-12-2015 at 12:12

Will post some more on it when aga starts converting.

Oh ! Right.

That was my Cue then.

Best get started.

blogfast25 - 21-12-2015 at 14:08

Quote: Originally posted by aga