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m1tanker78
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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
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NurdRage
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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... 
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m1tanker78
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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]
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blogfast25
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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)…
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blogfast25
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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]
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garage chemist
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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.
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blogfast25
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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]
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garage chemist
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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.
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blogfast25
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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.
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garage chemist
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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.
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bbartlog
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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?
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Picric-A
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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.)
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blogfast25
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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]
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ChemistryGhost
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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?
"Imagination is more important than knowledge" ~Einstein
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blogfast25
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| 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.
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Nicodem
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Thread Split
18-4-2013 at 14:09 |
bfesser
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Thread Topped
7-8-2013 at 20:21 |
hyfalcon
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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]
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halogen
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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]
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CuReUS
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| Quote: Originally posted by NurdRage |
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.
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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]
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CuReUS
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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
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Crowfjord
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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]
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CuReUS
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| 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]
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CuReUS
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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
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hyfalcon
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Don't think I want to attempt to handle methyl lithium at home.
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CuReUS
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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
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hyfalcon
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msds still lists it as pyrophoric when exposed to air.
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