Author Topic: 1,4-butanediol to GBL - Will this work?  (Read 13575 times)

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Prefix

  • Guest
1,4-butanediol to GBL - Will this work?
« on: July 20, 2000, 03:43:00 PM »
This was originally posted by assholium (Feb 18 1999):

For my pleasure - I think, that that fckn' DEA have a problem here. Gamma-butyrolactone can be simply prepared by heating & stirring of 1,4-butandiol with copper chromite catalyst at 195-200°C. 2-3 hrs, quant. yield. This is

Patent US5110954

- Dehydrogenation of diols.

Experimental procedure 
Example 1.
A 250 ml RGB flask fitted with a stirrer and a Vigaraux condenser was charged with 150 of 1,4-butandiol and 7.5 g of copper chromite catalyst. The reactor was heated to 195C and samples were periodically taken and analysed by GC. At 180 min point analysis shows 99% conversion of diol to GBL, catalyst was filtered off and GBL of 99.16 purity was recovered - 156.1 g, bp 205C. Catalyst can be reused up to 10 times without loss of activity.

Simple preparation of copper chromite - JACS 71, 1130 (1949).


Is this possible?

foxy2

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #1 on: July 20, 2000, 06:01:00 PM »
You will get more answers on the methods board

This sounds very possible, why don't you get the reference and check it out.

"The best place for a pig is in the fryin pan"

Prefix

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #2 on: July 20, 2000, 07:25:00 PM »
I'm going to check out that reference on my next visit to the library for sure.  But really, I wanted to know if anyone had had any success with it before I wasted a trip. 

I also came across this in reading the archives - "72.1 grams of THF, C4H8O, added to 78.4 grams of Calcium Hypochlorite, CaCl2O2, should yield 86.1 grams of GBL C4H6O2 and 64.4 grams of CaCl2H2O." The GBL could then be distilled off right? 

Would one of you moderators please move this thread to the Methods Forum? 

 


placebo

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Re: 1,4-butanediol to GBL - Will this work?
« Reply #3 on: July 23, 2000, 10:19:00 PM »
How could one make this copper chromite catalyst?
SWIM has access to:
Copper chloride
Copper nitrate2
Copper nitrate
Copper oxide
Copper sulphate
Copper sulphide
Copper turnings
But no Copper Chromite, so how can one make it?

One horny Bee!

placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #4 on: July 23, 2000, 10:56:00 PM »
Ok, here is all I found on it on the old board:



Author  Topic:   copper chromite AKA Assholium catalyst 
Torch
--------------------------------------------------------------------------------
A quick preparation question:
Can CuSO4*5H2O be used as a substitute for Cu(NO3)2*3H2O in the preparation of this catalyst?

(The use of CuSO4 would make this an OTC thing for me)
 
assholium
--------------------------------------------------------------------------------
Torch:
Sorry, no - it's impossible.
What's happen here:
copper nitrate + ammonium dichromate -> copper-ammonium-chromate + ammonium nitrate
if someone want to use copper sulphate, then obviously traces of ammonium sulphate must exists in deposited copper-ammonium-chromate, and under heating (remember - you must decompose chromate to chromite, hexavalent chromium to 3-valent) this shit can produce sulphyric acid, catalyst poison.
So... only nitrate acceptable, because heated ammonium nitrate cleanly decomposes to nitrogen suboxide, elemental nitrogen and water.
 
Torch
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Damnit damnit damnit!!
I read US Pat# 5,210,229 and thought it might work.
They prepared a Cu-Cr + Mn or Br & Na or K catalyst for gaseous phase dehydrogenation.
It sez' the catlips can be prepared as follows: copper nitrate, copper sulfate, copper chloride or copper acetate may be used as a copper source.
The Chromium soln is made basic by ammonium and admixed with the copper soln to form the prcpt. (I thought I could use their method up to this point prepare a Cr+Mn+Cr catlip)...It goes on..wash it, dry it & pyrolize it. Then wash with dil aq acid, water wash, dry and add the Na or K soln, dry it then calcinate, and finally reduce activate it with hydrogen reduction.
I couldn't just wash that kitten real good before I harvest the lips?
 
assholium
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>It sez' the catlips can be prepared as >follows: copper nitrate, copper sulfate, >copper chloride or copper acetate may be >used as a copper source.
Hm. According to my experience, Cu-Cr catalyst sensitive to halogens and strong acids, only 20 ppm of chlorine in hydrogenated substrate - and it's enough for catalyst death...
>I couldn't just wash that kitten real good >before I harvest the lips?
Of course, you can. But there is some risk to obtain shit instead of candy. This risk can be minimized by washing with diluted barium or calcium nitrate soln, for conversion of traces of ammonium sulphate to the thermally stable and inactive calcium or barium sulphate...
 
Torch
--------------------------------------------------------------------------------
Okay so I can make Cu(NO3)2 with nitric and copper..it's worth the extra work if it means the difference between shit and candy.
Just to make sure I'm on the right page here, it wouldn't hurt to add a pinch of Mn(NO3)2 if available or is it better to stick to the straight Cu-Cr?
Also if I have fumed silica would this be beneficial or is this just good for spray drying?
Finally I imagine stirring during the pyrolysis helps eliminate the gases and gives a nice powder. I have a standard 110V glasscloth heating mantle, if this doesn't get me up to temperature can I use a shallow crucible and kiln dry it w/o stirring or do I hafta' bust out a pot of molten lead?
 
Torch
--------------------------------------------------------------------------------
I don't get it... This seems like the purrfect catlips to transform sec alcs into ketones and primary alcs into aldehydes.
I can think of tons of uses..hasn't anyone else tried this cat befor?
grignard->alcohol->ketone->amine


This catalyst sounds like it is worthy of much more discussion and not just for 1,4B

Any more info on this catalyst and preperation!


One horny Bee!


placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #5 on: July 24, 2000, 12:42:00 AM »
I found a patent for a catalyst that was designed to replace the copper chromite and the associated pitfalls in producing it and am wondering if one of you smart bees can check it out and see if it is suitable for this rxn! It looks pretty simple to make but WTF do I know?

http://www.water-cooler.com/WC/patentviewer/patent-4252689.html



Please look into this, we may have a small victory in the war, when everybody can make their own GBL very simply at home! As 1,4BDO is widely available!

Also, in the above posts they are assuming copper chromite is a pure product but all the chem companys I look up, sell a mix,
ie.Copper chromite, catalyst, Item # 31272
CAS Number 11104-65-7 
Formula Approx 43% CuO   39% Cr2O3
$60/100gm 

Shouldn't this be in chemistry forum?

 

One horny Bee!

foxy2

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #6 on: July 24, 2000, 04:58:00 AM »
It may work however i am very skeptical, they don't list any reactions that are even close to the 1,4-bd to GBL.  It seems effective at reduceing an aldehyde to an alcohol if anyone has a use for that.  Maybe ill make up a batch of this stuff, im not sure if i have an Al salts around.
Anyone have any ideas on how i could calcine this???
My oven only goes up to maybe 300C.  Maybe heating a metal crucible wityh a torch will work.

"The best place for a pig is in the fryin pan"

Osmium

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #7 on: July 24, 2000, 11:41:00 AM »
Copper chromite, catalyst, Item # 31272
               CAS Number 11104-65-7
               Formula Approx 43% CuO 39% Cr2O3
               $60/100gm

This catalyst is not just a mixture, it is an inorganic compound consisting of 43% CuO and 39% Cr2O3. If you mixed CuO and Cr2O3 in that proportion it wouldn't work.

There are many different varieties of copper chromite catalysts. They are usually specifically produced for the intended purpose, like hydrogenation or dehydrogenation etc. So that patent stuff might be useless for our purpose. But I think that it might work, maybe not most efficiently but better to have a so-so easy to make catalyst than none at all!

Note that in the patent placebo mentioned it says that the most active catalyst is made at 550°C.
Ask your local potter for heating sources.


Rhodium

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #8 on: July 24, 2000, 03:44:00 PM »
Preparation of the dehydrogenation catalyst from copper nitrate, sodium dichromate and NH3:

http://rhodium.lycaeum.org/chemistry/copperchromite.txt




http://rhodium.lycaeum.org


placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #9 on: July 24, 2000, 04:21:00 PM »
Sorry Rhodium, I didn't even look on your page for this as I was certain you wouldn't have something like this! hahahaa
So is this what you would suggest for this?

One horny Bee!

Rhodium

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #10 on: July 24, 2000, 04:53:00 PM »
Yes, definitely. Assholium tells us he has had very good experiences with this catalyst.

http://rhodium.lycaeum.org


placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #11 on: July 24, 2000, 05:05:00 PM »
Thankyou Rhodium, just so happens I can buy both these chems:
Sodium Dichromate.....500gm/$40
Copper(11) Nitrate....250gm/$60
from a company, totally unwatched!

Any ideas on a 350c bath?

I am on this like shit on a rug!




One horny Bee!

foxy2

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #12 on: July 24, 2000, 06:24:00 PM »
Yea 350C is tough to hit.  Hmm

"The best place for a pig is in the fryin pan"

Rhodium

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #13 on: July 24, 2000, 06:46:00 PM »
I would use a large crucible, a bunsen burner and a high-temp thermometer.

http://rhodium.lycaeum.org


Bwiti

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #14 on: July 25, 2000, 10:13:00 AM »
I don't know about you folks, but I'm definately interested in what Prefix had to say: "I also came across this in reading the archives - "72.1 grams of THF, C4H8O, added to 78.4 grams of Calcium Hypochlorite, CaCl2O2, should yield 86.1 grams of GBL C4H6O2 and 64.4 grams of CaCl2H2O." The GBL could then be distilled off right?"
   Every chemical used is very easy to get. It seems too good to be true ! Can anyone verify that GBL is the result of this method? Thank you kindly ! 

                                   

   If there really was a God, I would have been forwarded to Hell a long time ago.

placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #15 on: July 25, 2000, 11:00:00 AM »
I think not!
Where SWIM is....
THF....$250/2.5L
BDO....$4/L

Maybe real easy but not cheap

One horny Bee!

Osmium

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #16 on: July 25, 2000, 12:49:00 PM »
Maybe SWIM shouldn't try to buy the most expensive grade of THF. It is absolutely not an exotic solvent and can be bought for 20$/l from a chem supply, or for way less OTC in some hardware stores. Unless you don't glue PVC in Oz...


placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #17 on: July 25, 2000, 01:52:00 PM »
No we don't... :P
Now what is this OTC source of THF you speak of?

One horny Bee!

Bwiti

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #18 on: July 25, 2000, 02:40:00 PM »
Would it help if the THF/hypochlorite was gently heated to make sure everything has reacted? Should the solution be filtered before it is distilled? In my dreams, I have a shit-load of sodium hypochlorite that I'd like to replace the calcium hypo with----how many grams should be used? Sorry for all the questions. Thanks !

   If there really was a God, I would have been forwarded to Hell a long time ago.

Osmium

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #19 on: July 25, 2000, 03:27:00 PM »
> Now what is this OTC source of THF you speak of?

Well, as I said, PVC glue and solvents for it, and I found pure THF in 5L drums for vulcanizing rubber for roofs.