Author Topic: Short Questions Thread  (Read 10820 times)

zzhuchila_clocker

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Re: Short Questions Thread
« Reply #20 on: April 22, 2009, 07:27:16 AM »
other potential method:
Quote
Electrolytic reduction of phenol in aqueous solutions gave high yields of benzene at 80°C and atmospheric pressure.
form  http://www.publish.csiro.au/paper/CH9802565.htm , but there is no full text (if you wonder how i have taken a cite without access to full text, that was because this cite was saved by google)
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Sedit

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Re: Short Questions Thread
« Reply #21 on: April 22, 2009, 05:21:27 PM »
Will this work on substituted phenols? Say if someone wanted to demethoxylate anethole or 4-MA would there be interferance from the other functional groups?
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zzhuchila_clocker

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Re: Short Questions Thread
« Reply #22 on: April 22, 2009, 05:58:07 PM »
It is better to seek in literature, i can not predict.  btw, probably in google while searching for reduction of phenol i've seen some info about direct demethoxylation of aromatic compounds, with alkyl substituents. i dont remember what reagent they used, but the yields were not so poor like Zn method and conditions not harsh (probably)
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Enkidu

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Re: Short Questions Thread
« Reply #23 on: April 22, 2009, 06:16:30 PM »
From Electrolytic hydrogenation and hydrogenolysis of phenols at platinum black electrodes:

Quote
Non-electrolytic catalysed hydrogenation of phenols at platinum is well documented'-3 and there are at least four types of processes:

(i) Partial ring reduction to form cyclohexanones.
(ii) Complete ring reduction without hydrogenolysis to form cyclohexanols.
(iii) Hydrogenolysis without ring reduction to form benzenes.
(iv) Hydrogenolysis with ring reduction to form cyclohexanes.

Under mild conditions hydrogenolysis without ring reduction, process (iii), is rarely observed but the other three major processes are common. The amount of hydrogenolysis to cyclohexanes is usually enhanced in acidic media and polyhydric phenols hydrogenolyse more readily than monophenols.

Enkidu

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Re: Short Questions Thread
« Reply #24 on: April 22, 2009, 07:33:18 PM »
Quote
Other procedures include zinc-dust distillation, not generally useful except for exhaustive degradation of phenols to hydrocarbons, and various sodium and liquid ammonia cleavages of phenol ethers.3,4,5,6,7 These latter reactions lack generality and are often unpredictable. They require conditions too harsh for certain aromatic substituents, and the yields are frequently low.

As I said before...

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Re: Short Questions Thread
« Reply #25 on: April 22, 2009, 07:51:10 PM »
Ok maybe I worded my question wrong. Is there a means that is effective with substituted phenols. Thats the problem I seem to be running into with most methods is the substitution get in the way of any effective means of the hydroxyl removal. Allmost all seem very harse conditions required to remove it.
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Vesp

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Re: Short Questions Thread
« Reply #26 on: April 22, 2009, 10:23:15 PM »
Electrolysis of phenol produces benzene? That makes sense and I think it is worth trying. Wonderful!
I wish I had that reference in full. Do you think it needs some special electrodes, or would carbon suffice?
Looks like it just might be time to hydrolyze, decarboxylate and perform electrolysis on some aspirin!
In order to increase solubility think it would work to use the sodium salt of phenol?
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Enkidu

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Re: Short Questions Thread
« Reply #27 on: April 22, 2009, 10:40:55 PM »
^ Dude, I attached it.

Sedit

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Re: Short Questions Thread
« Reply #28 on: April 22, 2009, 10:59:48 PM »
According to the paper that Enkidu posted the production of benzene by this method is not going to happen although this caught my eye a little bit.

Quote
Indirect electroreductive elimination of phenolic hydroxy groups can be accomplished in wet dimethylformamide at lead cathode but the hydroxy group must first be esterified with diethyl phosphite.

Two questions on this if anyone has the answer.
Number one: Would another solvent such as DMSO be a viable option here and
Number two: Does anyone know of alternatives to DEP for the esterfication?
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Re: Short Questions Thread
« Reply #29 on: April 22, 2009, 11:16:31 PM »
Sorry about that, I didn't see it attached.
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Enkidu

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Re: Short Questions Thread
« Reply #30 on: April 23, 2009, 03:32:24 AM »
Sedit, there's a paper by Huffmann (of JWH fame) that talks about dehydroxylating some cannabinoid. I think he uses like six steps, and there are no OTC friendly reagents (I think he uses a triflate).... Honestly, you're wasting your time with aromatic dehydroxylation. I know, it looks soo tempting!!

Sedit

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Re: Short Questions Thread
« Reply #31 on: April 23, 2009, 03:40:40 AM »
I know Iv been wasting my time for a while now looking for an efficiant means but some people may have a mass of substrate that no one wants. It adds up after performing different test and it is very tempting to find a safe means of getting that methoxy off of 4-MA or anethol for any further experiments so atlest when there done it'll produce something worthwhile then Highblood pressure and a foggy head. Do you forsee any other option for 4-MA or anethole to something else?
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Enkidu

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Re: Short Questions Thread
« Reply #32 on: April 23, 2009, 04:54:51 AM »
Hmm, maybe demethylation followed by amine protection, ortho-hydroxylation, and then ring closure? Or maybe you could make some trimethoxyamphetamine if you live in a country where it's legal...
« Last Edit: April 23, 2009, 04:57:18 AM by Enkidu »

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Re: Short Questions Thread
« Reply #33 on: May 02, 2009, 04:33:58 AM »
Ammonium persulfate is readily available for numerous places on line. It is used to make sequencing gels, if i remember right. Any biotech supply store should have it.  There are a bunch that sell to individuals w/ a CC. How much are you trying to source?  Are you trying to make it as a cost saving measure?

Depending on the amount you need it runs like 20-30$ /100 or like 50$ a Kg. 


Sedit

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Re: Short Questions Thread
« Reply #34 on: May 02, 2009, 04:45:29 AM »
If you speaking with me, I attempted to make it because of ease and.... well Im a mad scientist what can I say. I converted it in one pot to sodium persulfate but later spilled it right after slow and painful condensation as not to destroy it(oh the irony). Im a fan of Ecells for inorganic synthesis and when I want a chemical I go for it. This one had to be in an Ecell so im more then happy to play with a little sparks.

Best source of NH3 persufate would be circuit bord cleaners.
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Vesp

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Re: Short Questions Thread
« Reply #35 on: June 21, 2009, 05:13:10 AM »
I was wondering, if it would be safe/workable to use glycerol as a substitute for ethylene glycol when making terephthalic acid from PETE using this probably well known method.. http://www.sciencemadness.org/member_publications/terephthalic_acid_from_PET.pdf
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Sedit

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Re: Short Questions Thread
« Reply #36 on: June 22, 2009, 11:33:01 PM »
Heres a short question which may turn into a new threed depending....


What do yall make of this?
Do you think the yeilds may compair when using a secondary bromide and something like methylamine?


Full table right here: http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=2531286&rendertype=table&id=T1

99% yeilds on the above process :o


Also another paper that shows its use with ammonia as the amine to get 90% yeilds from the halogen:
« Last Edit: June 22, 2009, 11:44:04 PM by sedit »
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Re: Short Questions Thread
« Reply #37 on: June 23, 2009, 09:27:35 PM »
Got another quick question but please lets not over look the last.

Formic acid can be used to reduce enamines as per the paper I will attach.

Heating Pseudo ephedrines and is derivitives with H2SO4 dehydrates the ephedrines to a reversible state between an enamine and an imine. After the dehydration would the addition of concentrated Formic acid reduce the enamine to the amine without the amine reversing to the previous states due to the highly acetic H2SO4.

If this would not work how could one go about isolating the formed enamine or amine?
« Last Edit: June 23, 2009, 09:29:36 PM by sedit »
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Vesp

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Re: Short Questions Thread
« Reply #38 on: July 14, 2009, 08:28:32 AM »
Does anyone know the concentration of Bromonitropropane diol in the "natural" campa chem cleaner stuff?

It seems like this might be useful, but I don't know how.
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zzhuchila_clocker

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Re: Short Questions Thread
« Reply #39 on: July 14, 2009, 10:47:43 AM »
sedit: I suppose the yields will not compair. I'm not sure, but i think Cu(I) can catalyse only aryl halides reactions. This surely should have been known, if it could work same with alkylhalides. I don't know why this is like that, maybe alkylcuprates are less stable. Besides, any NH3 or methylamine would fly away at that T.
The second paper's reaction which uses NH3 does not need any catalyst at all (i don't know why they used Cu), because it is having different mechachanism: addition of ammonia takes place prior to Br- elimination, because the negative charge is accepted by ring nitrogen and is stabilized. In case of usual aromatic halides(if there were C instead of N in ring) such addition could not be possible, and the temperature required would be too high to keep NH3 in solution.
And alkylhalides reaction with amines has another mechanism, called SN2 (synchronous addition of amine and elimination of bromine).
As for isolation of imine, i suppose it is impossible - they are unstable and any traces of free water would kill them. Better to isolate corresponding ketone and make enamine with methylamine(sorry, forgot that there is a problem with MA in US). Formic acid reacts with H2SO4 producing CO gas, but i dont know if that would be a problem for enamine reduction or not.
« Last Edit: July 14, 2009, 10:54:17 AM by zz-zhuchila »
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