Sciencemadness Discussion Board

cyclohexanone

chemrox - 28-10-2007 at 23:18

cyclohexanone is one of those very useful but increasingly hard to obtain chems. Good longstanding relationship with suppliers and faxed memos for the DEA file required. The only reason I can think of is once it was used to make PCP a psychtomimetic/psychotogenic anasthetic and animal tranquilizer. Would you give your dog this shit?

So here's a way I think would work. Cyclohexane -> cyclohexene by KMnO4 or K2Cr2O7. Cyclohexene to cyclohexanone by PdCl2/CuCl2 & DMF. Also formic acid and 30% H2O2. I'm trying to adapt one of these to MW. Maybe a clay substrate?

evil_lurker - 28-10-2007 at 23:40

Sorry don't mean to burst your hypothetical bubble, but I'm pretty damn sure you can order it without much fuss from these guys:

http://store.hvchemical.com/browse.cfm/4,506.htm

Antwain - 29-10-2007 at 00:22

Quote:

Cyclohexane -> cyclohexene by KMnO4 or K2Cr2O7.


What???

Maya - 29-10-2007 at 12:12

Quote:

Cyclohexane -> cyclohexene by KMnO4 or K2Cr2O7.


What???


Same....... Anyways, cyclohexanone is not hard to get at all

I've ordered liters, it has a huge number of industrial uses.

its also used in PVC pipe cement extensively, so if worse comes to worst, distill from there

Fleaker - 29-10-2007 at 18:15

I think I have some that I can spare you. I know I have a lot of either that or cyclohexanol. I only have a few hundred mL of cyclohexene though so tough luck there :P

What are you planning on doing with it?

evil_lurker - 29-10-2007 at 19:25

Quote:
Originally posted by Fleaker
I think I have some that I can spare you. I know I have a lot of either that or cyclohexanol. I only have a few hundred mL of cyclohexene though so tough luck there :P

What are you planning on doing with it?


He gonna cook some space dope with it, what else? :P

chemrox - 30-10-2007 at 14:33

That's funny but untrue "lurker." One time many moons ago I did just that and didn't much care for the results. Earning your name I see. I was going to make a few things that might react with either the fatty acids or the glycerins in biodiesel to make them absorb in the visible or UV range. It's a total crap shoot. Make it, check it on the IR and try to react it in oil and then run the oil up on the UV/vis machine. After six months or so we ought to know if anything is working and what its reacting with and maybe what it is.

I don't think the reaction I suggested would work anyway.. did it again, dammit. I was remebering cyclohexene from the alcohol by way of acid. Forget the cyclohexene. Just oxidize the alcohol. Is there a way to oxidize the alkane? I think peroxide, peracetic acids and catalysts are involved.

[Edited on 30-10-2007 by chemrox]

Sandmeyer - 23-2-2008 at 19:12

Quote:
Originally posted by chemrox


So here's a way I think would work. Cyclohexane -> cyclohexene by KMnO4 or K2Cr2O7. Cyclohexene to cyclohexanone by PdCl2/CuCl2 & DMF. Also formic acid and 30% H2O2. I'm trying to adapt one of these to MW. Maybe a clay substrate?


In practice the Wacker process works good only for terminal alkenes (i.e. to obtain methyl ketones).

edit:
How is cyclohexane supposed to give cyclohexene using those oxidants? Did you mean cyclohexanol or what?

There are countless recipes on the net regarding epoxide/pinacol rearrangement method of converting alkenes to ketones. utfg.

must be very boring to make simple aliphatic compounds, buy them if possible.

[Edited on 24-2-2008 by Sandmeyer]

chemrox - 24-2-2008 at 00:51

Yeah- I had mis-remembered and should have looked it up first. "It must be boring.." tell me about it, I'm making propionyl chloride this week as I just ran out of the supply I made last year. Why? either unavailable or too dear. Me-am has wide application and is another waste of time to make. The alternative is having too many regulators asking about ones business. Did I mention that having been away from wet chem for decades I need the practice? I distill hardware solvents to hold costs down and fine tune my ditillation practices at the same time. I'm getting ready to 'graduate' though and start playing around with catlysts for coupling reactions.

grind - 24-2-2008 at 07:16

Quote:
Originally posted by chemroxIs there a way to oxidize the alkane?

Very difficult. But you can make this:

C6H12 + SO2Cl2 ---> C6H11Cl + HCl + SO2

Cyclohexylchloride is a good precursor for Cyclohexanol and Cyclohexene.

Ozone - 24-2-2008 at 13:52

I am procrastinating from dissertation writing (dreaded background chapter). Shame, that.

Seems to me that, IIRC, we used alkaline KMnO4 to make adipic acid from cyclohexanone. I can't find my ancient lab manual so:

http://members.aol.com/profchm/chap22-6.html

Anyhow, I don't think cyclohexanone will react in any way with either fatty acids or glycerol (they just use brute force with the GC to get the quantitation on the fatty acids and HPLC/DRI for the glycerol).

You can get cyclohexanone in small, unsuspicious quantities from HACH as standard material to go with their test kits.

Your chromic acid (Jone's reagent) route should work from cyclohexanol:

http://wwwchem.uwimona.edu.jm:1104/lab_manuals/c10expt21.htm...

Which (cyclohexanol) is also a nice source of cyclohexene via dehydration w/ 85% H3PO4.

http://wwwchem.uwimona.edu.jm:1104/lab_manuals/c10expt8.html

Which, of course, has the snake biting its tail. However, this looks interesting (catalysis):

http://www.wipo.int/pctdb/en/wo.jsp?WO=1997%2F08119&IA=W...

I'd elaborate, but I have to push hard and try to spew another page of scientific diarrhea.

Cheers,

O3

Sandmeyer - 1-3-2008 at 00:14

Even a legitimate well equipped lab tries to avoid working with reagents like chromic acid, (IMO kind of a last resort reagent). I don't follow the logic of going through the trouble of obtaining, working with and disposing stuff such as chromic acid just to prepare something as cheap, non-toxic and readily available as cyclohexanone.

[Edited on 1-3-2008 by Sandmeyer]

Jor - 1-3-2008 at 02:45

chromic acid should be prety easy to dispose of by simply reducing it with acidified sodium sulphite.

not_important - 1-3-2008 at 03:18

Quote:
Originally posted by Jor
chromic acid should be prety easy to dispose of by simply reducing it with acidified sodium sulphite.


But still consuming expensive Cr(VI), which in some locals may even have a surcharge on it because of its toxicity and disposal problems (there are people who will say "we'll I only have a little bit, I'll just pour it down the drain). And you add the cost of the sulfite on top of that.

I believe that chlorine bleach and Ni(OH)2 or NiCl2, as documented by Sauron and others, will do just fine at oxidising cyclohexanol to cyclohexanone in 70% yield or so, and much less hassle in the workup as the nickel oxides/whatever can just be filtered out. Just plain old NaCl as a waste product, bleach is cheap and still readily accessible.

That WIPO patent is basically creating Fenton's reagent on the fly, Fe(II) and H2O2, and assumable optimising the conditions for best yield of cyclohexanol and cyclohexanone.

jamit - 21-2-2015 at 01:34

I have a chance to obtain about 1 liter of cyclohexanone. What can I used this for? What kind of synthesis? Should I get it? I did a search ...but it's not clear on what it can be used for... Except adipic acid?





[Edited on 21-2-2015 by jamit]

Magpie - 21-2-2015 at 10:56

cyclohexanone > adipic acid > nylon 66

The tricky part is coming up with some adipoyl chloride.

jamit - 21-2-2015 at 16:11

Thanks magpie! I'll look into both these products!

Pickardjr - 21-2-2015 at 17:29

I had an order stolen off the truck in route, it just disappeared from tracking. I called the company and they sent a new one, it made it. You can buy it with no issues.

Magpie - 21-2-2015 at 20:24

Quote: Originally posted by Magpie  
cyclohexanone > adipic acid > nylon 66

The tricky part is coming up with some adipoyl chloride.


Sorry jamit I think I oversimplified here. You are also going to need some hexamethylenediamine.

We made the nylon 66 in an organic lab at college. It's a simple & fun experiment once you have the 2 precursors.



[Edited on 22-2-2015 by Magpie]

plante1999 - 21-2-2015 at 20:31

He could also make caprolactam and then turn that into nylon.

turd - 22-2-2015 at 01:29

Obligatory: https://www.erowid.org/archive/rhodium/chemistry/pcp/
(A nicely written document even for those not planning any of the included syntheses)

Magpie - 22-2-2015 at 12:02

adipic acid > cyclopentanone

I have done this one.

Chemosynthesis - 22-2-2015 at 13:22

Old thread, but to something the OP mentioned, while cyclohexanone was probably most cracked down on due to PCP synthesis, there are other narcotics which use derivatives in their scaffold, just as with piperidine, which was obviously also scrutinized.

Magpie, presuming you used something on orgsyn?
http://www.orgsyn.org/demo.aspx?prep=CV1P0192

Too bad reducing strong enough agents to use on carboxylic acids aren't commonly OTC. I could potentially see a Dieckmann condensation, reducing the beta keto acid, aminating to yield 1-aminomethyl-cycloalkanol, and then finally performing a Tiffeneau–Demjanov ring expansion rearrangement to cyclohexanone as a mechanistically interesting synthesis.

Magpie - 22-2-2015 at 14:43

Here's my post on cyclopentanone. It looks like my attempt wasn't all that successful, but that of garage chemist was.

http://www.sciencemadness.org/talk/viewthread.php?tid=5564#p...

CuReUS - 23-2-2015 at 01:21

Quote: Originally posted by Chemosynthesis  

Too bad reducing strong enough agents to use on carboxylic acids aren't commonly OTC.

to what stage do you want to reduce it? if you esterify the COOH and treat that with DIBAL,you could reduce it to the aldehyde.then to get alcohol,you could treat it with dithionite and to get hydrocarbon,you could do clemmenson.I think DIBAL can be made at home,as isobutanol is available
http://en.wikipedia.org/wiki/Diisobutylaluminium_hydride#Pro...
Quote:
I could potentially see a Dieckmann condensation, reducing the beta keto acid, aminating to yield 1-aminomethyl-cycloalkanol, and then finally performing a Tiffeneau–Demjanov ring expansion rearrangement to cyclohexanone as a mechanistically interesting synthesis.

I couldn't follow your reaction as you haven't mentioned your starting product,but if you are starting off with an ester of acid lower than adipic acid,there might be a problem:(
Quote: Originally posted by Sandmeyer  
Quote:
Originally posted by chemrox


So here's a way I think would work. Cyclohexane -> cyclohexene by KMnO4 or K2Cr2O7. Cyclohexene to cyclohexanone by PdCl2/CuCl2 & DMF. Also formic acid and 30% H2O2. I'm trying to adapt one of these to MW. Maybe a clay substrate?


In practice the Wacker process works good only for terminal alkenes (i.e. to obtain methyl ketones).

see this
http://www.sciencemadness.org/talk/viewthread.php?tid=10007#...

[Edited on 23-2-2015 by CuReUS]

Chemosynthesis - 23-2-2015 at 06:11

Magpie, I always enjoy your experimentals.
Quote: Originally posted by CuReUS  

to what stage do you want to reduce it?

I don't want to reduce anything. I don't even expect worthwhile yields from that, but it utilizes some interesting chemical reactions.
Quote:
if you esterify the COOH and treat that with DIBAL,you could reduce it to the aldehyde.then to get alcohol,you could treat it with dithionite and to get hydrocarbon,you could do clemmenson.I think DIBAL can be made at home,as isobutanol is available
http://en.wikipedia.org/wiki/Diisobutylaluminium_hydride#Pro...

I know about DIBAL. It's a commonly taught in sophomore organic chemistry. I'd love to see an experimental of you synthesizing it at home.
Quote:
I couldn't follow your reaction as you haven't mentioned your starting product,but if you are starting off with an ester of acid lower than adipic acid,there might be a problem:(
The ring expansion gives it away in a retrosynthetic analysis.

Crowfjord - 23-2-2015 at 12:00

There are ways to reduce carboxylic acids or their esters to the corresponding alcohols using modified sodium borohydride systems. These methods are probably safer than LAH or its modifications. See attached for some examples.



Attachment: enhancing.nabh4.reactivity.and.selectivity.pdf (315kB)
This file has been downloaded 652 times

Attachment: Reduction of Carboxylic Acids with Sodium Borohydride and an Electrophile.pdf (104kB)
This file has been downloaded 516 times

Attachment: Chemoselective Reduction of Esters by Sodium Borohydride.pdf (3.2MB)
This file has been downloaded 2754 times

Chemosynthesis - 23-2-2015 at 13:12

Probably also worth noting, to anyone interested but not yet familiar, that respective acyl halides are easily reduced to aldehydes and alcohols. Yields in my example DOI were excellent. Sometimes this allows for different solvent systems, such as DCM/water, which might be more available than THF for some.
However, this presumes the use of home agents such as thionyl chloride or alternatives discussed elsewhere in the forum with accompanying experimentals. Not sure how available NaBH4 is everywhere, but there are a few potential OTC avenues I'm aware of.

Example in DOI:10.1080/00397910903340645

chemrox - 23-2-2015 at 13:30

Hey Crowfjord-nice set of refs-thank you!

Magpie - 23-2-2015 at 13:31

I don't know of any OTC source of NaBH4, which is a little surprising as it is used by the ton for paper bleaching. Fortunately we can buy it from Elemental Scientific. I have not used it since organic class at college where we made isoborneol from camphor (a ketone).

There's another way to make alcohols from esters: the classic Bouveault-Blanc synthesis, which uses elemental Na. It's somewhat tedious but it does work:

http://www.sciencemadness.org/talk/viewthread.php?tid=18625#...

[Edited on 23-2-2015 by Magpie]

[Edited on 24-2-2015 by Magpie]

[Edited on 24-2-2015 by Magpie]

Darkstar - 23-2-2015 at 19:57

Since we're on the topic of over-the-counter chemistry, adipic acid, novel cyclohexanone syntheses and ester reductions using elemental Na, what about something like this: Adipic acid is first converted to a diester, which then undergoes intramolecular cyclisation on reduction by Na to give a cyclic α-hydroxyketone via acyloin condensation. The 2-hydroxycyclohexanone is then reduced to cyclohexanone using hydroiodic acid and red phosphorous. (should work due to the adjacent pi-system of the carbonyl group)

Obviously this wouldn't be a very practical way to make it, however, as elemental sodium, red phosphorous and iodine are way more valuable than cyclohexanone, and are a hell of a lot harder for most people to obtain anyway. I guess you could try to recover your iodine during the work-up, though.

Maybe I'll try it on a small scale one of these days just for the hell of it. :)

thingy.bmp - 224kB

Chemosynthesis - 24-2-2015 at 04:44

I like that.

CuReUS - 24-2-2015 at 05:16

Quote: Originally posted by Chemosynthesis  

I know about DIBAL. It's a commonly taught in sophomore organic chemistry. I'd love to see an experimental of you synthesizing it at home.

I might have mis understood,are you mocking me ?
Quote:
The ring expansion gives it away in a retrosynthetic analysis.

yes,I know the ring expansion,but what I was trying to say was that if lower acid than adipic acid is used,then cyclohexadione will form instead of the expected product,because a six carbon ring is more stable

IIRC,NaBH4 is a watched chemical

I had this crazy idea,suppose you did a birch reduction of acetanilide.you would normally get a 1,4 dihydro product,but if you carried out the reduction at high temp,the 1,4 will isomerise to 1,2 and the reduction will take place again to give (hopefully) N-(1-cyclohexene) acetamide,which can be hydrolysed to get cyclohexanone
or you could start off from nitrobenzene
http://en.wikipedia.org/wiki/Birch_reduction#Second_step_of_...

cyclohexanone.bmp - 1.5MB

[Edited on 24-2-2015 by CuReUS]

DJF90 - 24-2-2015 at 06:48

Quote: Originally posted by Darkstar  
Since we're on the topic of over-the-counter chemistry, adipic acid, novel cyclohexanone syntheses and ester reductions using elemental Na, what about something like this: Adipic acid is first converted to a diester, which then undergoes intramolecular cyclisation on reduction by Na to give a cyclic α-hydroxyketone via acyloin condensation. The 2-hydroxycyclohexanone is then reduced to cyclohexanone using hydroiodic acid and red phosphorous. (should work due to the adjacent pi-system of the carbonyl group)

Obviously this wouldn't be a very practical way to make it, however, as elemental sodium, red phosphorous and iodine are way more valuable than cyclohexanone, and are a hell of a lot harder for most people to obtain anyway. I guess you could try to recover your iodine during the work-up, though.

Maybe I'll try it on a small scale one of these days just for the hell of it. :)



Treatment of the adipate ester with sodium in ethanol will yield the b-ketoester; ethyl 2-oxo-cyclopentanoate (Dieckmann condensation). Hydrolysis and decarboxylation would afford cyclopentanone. If you want the acyloin product, you'd need to use 4 eq. TMS-chloride avoid the Dieckmann.

[Edited on 24-2-2015 by DJF90]

Darkstar - 24-2-2015 at 07:07

@ CuReUS:

If you're going to go that route, why not just do a Benkeser on phenol? Should give well over 90% cyclohexanone if you don't screw up the hydrolysis at the end.

Darkstar - 24-2-2015 at 07:19

Quote: Originally posted by DJF90  

Treatment of the adipate ester with sodium in ethanol will yield the b-ketoester; ethyl 2-oxo-cyclopentanoate (Dieckmann condensation). Hydrolysis and decarboxylation would afford cyclopentanone. If you want the acyloin product, you'd need to use 4 eq. TMS-chloride avoid the Dieckmann.


The reduction isn't done in ethanol, it's done in an inert, aprotic solvent. The acyloin will be the primary product.

Chemosynthesis - 24-2-2015 at 07:23

Quote: Originally posted by CuReUS  

I might have mis understood,are you mocking me ?

Not mocking. Just not sure how on earth you'd make DIBAL or really any metal hydride at home.
Quote:

yes,I know the ring expansion,but what I was trying to say was that if lower acid than adipic acid is used,then cyclohexadione will form instead of the expected product,because a six carbon ring is more stable

Not a problem, even though you're not being specific. Take succinic acid, for example. Proceed through Dieckmann cyclization and decarboxylation to the dione, protect with one equivalent ketal, and then (the part I haven't done to this substrate) reduce via Wolf-Kishner or similar.
Quote:
IIRC,NaBH4 is a watched chemical

Watched doesn't mean not sold.

DJF90 - 24-2-2015 at 08:01

Quote: Originally posted by Darkstar  
Quote: Originally posted by DJF90  

Treatment of the adipate ester with sodium in ethanol will yield the b-ketoester; ethyl 2-oxo-cyclopentanoate (Dieckmann condensation). Hydrolysis and decarboxylation would afford cyclopentanone. If you want the acyloin product, you'd need to use 4 eq. TMS-chloride avoid the Dieckmann.


The reduction isn't done in ethanol, it's done in an inert, aprotic solvent. The acyloin will be the primary product.


Sorry, the mention of ethanol was meant for the dieckmann route. Even in xylenes (typical solvent) you need the TMS-chloride to favour the acyloin, as the byproduct ethoxide will otherwise lead to the dieckmann product.

Darkstar - 24-2-2015 at 08:45

Quote: Originally posted by DJF90  

Sorry, the mention of ethanol was meant for the dieckmann route. Even in xylenes (typical solvent) you need the TMS-chloride to favour the acyloin, as the byproduct ethoxide will otherwise lead to the dieckmann product.


I'm not arguing that using TMSCl won't improve overall yields, because it certainly will. It's just that the whole point was to come up with a novel synthesis that uses OTC reagents.

DJF90 - 24-2-2015 at 09:05

Quote: Originally posted by Darkstar  
Quote: Originally posted by DJF90  

Sorry, the mention of ethanol was meant for the dieckmann route. Even in xylenes (typical solvent) you need the TMS-chloride to favour the acyloin, as the byproduct ethoxide will otherwise lead to the dieckmann product.


I'm not arguing that using TMSCl won't improve overall yields, because it certainly will. It's just that the whole point was to come up with a novel synthesis that uses OTC reagents.



Of course, and I'm glad that we agree. But, I have a feeling that you're going,to struggle getting even 1:1 acyloin:dieckmann in the absence of a trapping reagent.even if you're wiling to take the low yield, you're going to have to separate that mixture somehow. First guess would be distillation, but I'm not sure without checking literature values that they'd be easily separable.

[Edited on 24-2-2015 by DJF90]

CuReUS - 3-3-2015 at 01:21

Quote: Originally posted by Darkstar  
@ CuReUS:
If you're going to go that route, why not just do a Benkeser on phenol? Should give well over 90% cyclohexanone if you don't screw up the hydrolysis at the end.

the literature says that birch reduction cannot be done on phenols.I don't know why.and benkeser is a modified birch reduction.the phenol would have to be esterified or etherified first.
also phenol is a very bad chemical to work with.Its hard to get out of the bottle,freezes up in the test tube and also burns you if you aren't careful.It also loves to get oxidised and polymerises rapidly to give tarry crap.last but not the least,its not OTC.
Also,doing an acyloin condensation is no joke because the reaction must be done in an N2 environment as traces of O2 reduces the yield

[Edited on 3-3-2015 by CuReUS]

Darkstar - 3-3-2015 at 01:26

I have a reference claiming that cyclohexanone was obtained via a Benkeser on phenol at 96% yield. I'll try to dig it up.

Darkstar - 3-3-2015 at 01:36

Reference

Page 16 of .pdf, bottom paragraph, left side:

"Furthermore, phenol and β-phenylethyl alcohol have been reduced under Benkeser conditions. Thus, phenol is converted to cyclohexanone in 96% yield by lithium in methyl- or ethylamine provided the hydrolysis of the reaction mixture is carried out rapidly with little lithium remaining."

Don't be so quick to assume! :)