(Stranger)
07-20-00 15:43
No 30904
(Rated as: excellent)
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?
(Hive Bee)
07-20-00 18:01
No 30951
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"
(Stranger)
07-20-00 19:25
No 30973
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?
(Hive Addict)
07-23-00 22:19
No 32181
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!
(Hive Addict)
07-23-00 22:56
No 32187
(Rated as: good read)
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
------------------------------------------------ -------- -------- -------- --------
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
------------------------------------------------ -------- -------- -------- --------
>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!
(Hive Addict)
07-24-00 00:42
No 32235
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/patentvie
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!
(Hive Bee)
07-24-00 04:58
No 32336
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"
(Moderator)
07-24-00 11:41
No 32475
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.
(Chief Bee)
07-24-00 15:44
No 32540
Preparation of the dehydrogenation catalyst from copper nitrate, sodium dichromate and NH3:
http://rhodium.lycaeum.org/chemistry/cop
http://rhodium.lycaeum.org
(Hive Addict)
07-24-00 16:21
No 32559
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!
(Chief Bee)
07-24-00 16:53
No 32566
Yes, definitely. Assholium tells us he has had very good experiences with this catalyst.
http://rhodium.lycaeum.org
(Hive Addict)
07-24-00 17:05
No 32570
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!
(Hive Bee)
07-24-00 18:24
No 32587
Yea 350C is tough to hit. Hmm
"The best place for a pig is in the fryin pan"
(Chief Bee)
07-24-00 18:46
No 32595
I would use a large crucible, a bunsen burner and a high-temp thermometer.
http://rhodium.lycaeum.org
(Hive Bee)
07-25-00 10:13
No 32776
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.
(Hive Addict)
07-25-00 11:00
No 32793
I think not!
Where SWIM is....
THF....$250/2.5L
BDO....$4/L
Maybe real easy but not cheap
One horny Bee!
(Moderator)
07-25-00 12:49
No 32818
Maybe SWIM shouldn't try to buy the most expensive grade of THF. It is absolutely not an exotic solvent and can be bought for 20$/l from a chem supply, or for way less OTC in some hardware stores. Unless you don't glue PVC in Oz...
(Hive Addict)
07-25-00 13:52
No 32837
No we don't...
Now what is this OTC source of THF you speak of?
One horny Bee!
(Hive Bee)
07-25-00 14:40
No 32849
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.
(Moderator)
07-25-00 15:27
No 32858
> 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.
(Hive Bee)
07-25-00 21:58
No 32977
From Rhodiums site
A solution of 260 g of Copper(II)nitrate trihydrate in 900 ccm of tap water at 80°C was added while stirring to a soln 178 g of sodium dichromate dihydrate and 225 ml of 28% NH4OH made up to 900 ml at 25°C.
Had no copper nitrate so i used copper sulfate(praying the sulfur is not a fucking nasty poison for this catalyst)and i fucked up and added the ammonia to the dam copper instead of the cromate(this could also be a good thing, form ammonium sulfate to get rid of that dam sulfur).
Well i have a big mass of reddish ppt that has been wased about 5 times with dh2o. I am about to dry then make a half assed attempt to get the temp up to 350C. Will pyrex withstand 350C???
"Vote Libertarian"
(Chief Bee)
07-25-00 22:56
No 32998
No, pyrex will probably bust at that temperature. Use metal or high-temp ceramics.
http://rhodium.lycaeum.org
(Hive Bee)
07-26-00 00:22
No 33029
Well i might go for it anyway. Since some guy somewhere said.
"The glass used in oven doors is a borosilicate type product, which includes that sold under the name of "Pyrex". The softening properties of glass are time/temperature dependent. According to Principles of Fire Investigation which is published by the Institute of Fire Engineers here is the termperature effects on borosilicate glass
very slight distortion 750 degrees C 1352 degrees F
slight distortion 800 degrees C 1442 degrees F
Considerable distortion and rounding of corners 850 degrees C 1562 degrees F
Flows retaining only slight evidence of original form 900 degrees C 1652 degrees F
Flows forming a liquid like pool 950 degrees C 1712 degrees F "
"Vote Libertarian"
(Hive Addict)
07-26-00 05:32
No 33167
I agree Foxy, as you know boro glass is used in a tube furnace.
But the trouble is trying to heat it evenly at 350c. Because trying with bunsen burner will be too un-even and I think breakage will be inevitable.
One horny Bee!
(Moderator)
07-26-00 12:03
No 33297
That reaction has to be done at 350°C? Does that mean under pressure? GBL BP is lower than that.
Edit: Nevermind, you guys are talking about the catalyst... oops
I have heating mantles with a big hole, when you take two of them you can easily cover a flask completely. And they work up to 400-450°C.
(Hive Addict)
07-26-00 15:56
No 33343
Thanks Os, I know what you mean, unfortunately, I don't even have one heating mantle and to buy two of the ones you speak of will cost me about $4000, sorta self-defeating! hahahaha
But I will figure something out!
One horny Bee!
(Stranger)
07-26-00 16:33
No 33357
I know the yields for the THF and CaCl2O2 reaction are only around 68% and maybe THF is expensive in some areas, but why isn't this reaction being seriously considered as an alternative method of producing GBL?
Bwiti - You asked about using sodium hypochlorite instead of calcium? Here is what was posted in an old thread: "The instability of sodium hypochlorite solutions however led us to consider other hypochlorite reagents which would be more stable and easier to handle. Calcium hypochlorite is a commercially available solid and is inexpensive. Since this reagent does not decompose significantly when stored without light in a desiccator, carrying out oxidations by weighing the required amount of solid oxidant represented a more convenient method than using solutions which would frequently have to be titrated. We now wish to report our results concerning the use of Ca(OCl)2 as an oxidant.
Oxidations of secondary alcohols with calcium hypochlorite proceed smoothly, and in excellent yield at 0 degrees in a solvent containing acetic acid. Our results are given in Table 1 [Mellifex: I haven't included it; its just yields for various alcohols>ketones] for twelve compounds along with our initial results using sodium hypochlorite. A general procedure is outlined for the oxidation of l-methol to l-menthone. Thus l-menthol (3g, 19mmol) was dissolved in acetonitrile:acetic acid (3:2 25ml) and added dropwise over a period of ten minutes to a cooled (0oC) and stirred solution of Ca(OCl)2 (1.84g, 12.7mmol) in water (40ml). Stirring was continued for 1 hr after which water (40ml) was added. The solution was extracted with CH2Cl2 (4 x 30ml) and the organic layers washed with 10% NaHCO3 followed by an aqueous wash. After drying with MgSO4 and evaporating the CH2Cl2 the crude product was distilled affording l-menthone (2.89g, 98%) The spectra (ir and nmr) were identical with those of authentic material.Oxidation of primary alcohols under identical conditions gave an aldehyde only in the case of benzyl alchohol. Other primary alcohols gave esters as tabulated in Table 2. This table also includes our results on the oxidation of ethers to esters. [relevant extract from Table 2: tetrahydrofuran > gamma-butyrolactone yield 68% using Ca(OCl)2]. Though the yields were not nearly as good as for the alcohols, the data is reported because of the unusual and potentially useful transformation. The ethers were oxidised under similar conditions as the alcohols except that the reactions were carried out at room temperature for from 4-16 hrs. Heating does not seem to increase the yield.
We are presently carrying out studies to improve the yields on the ether to ester transformation and to utilise the primary alcohol oxidation for the preparation of lactones from alpha-omega diols."
(Hive Addict)
07-27-00 00:35
No 33523
How bout these ones?
Reaction Details 40 of 111
Reaction Classification Preparation
Yield 70 percent (BRN=105248)
Reagent potassium dichromate
Solvent dimethylformamide
Time 20 hour(s)
Other Conditions Ambient temperature
Ref. 1 5611749; Journal; Kim, Kwan Soo; Szarek, Walter A.; CRBRAT; Carbohydr.Res.; EN; 104; 1982; 328-333;
Ref. 1 5611749; Journal; Kim, Kwan Soo; Szarek, Walter A.; CRBRAT; Carbohydr.Res.; EN; 104; 1982; 328-333;
----------------------------------------
Or this one...
Reaction Classification Preparation
Yield 92 percent (BRN=105248)
Reagent sodium bromite
Solvent H2O,acetic acid
Time 10 hour(s)
Other Conditions Ambient temperature
Ref. 1 5666548; Journal; Kageyama, Toshifumi; Kawahara, Shuji; Kitamura, Kohji; Ueno, Yoshio; Okawara, Makoto; CMLTAG;Chem.Lett.; EN; 1983; 1097-1100;
Q's, is sodium bromite made from sodium bromide? How? Huge temp, I bet?
----------------------------------------
or this one...
Reaction Classification Preparation
Yield 95 percent (BRN=105248)
Reagent (bipy)H2CrOCl5
Solvent CH2Cl2
Time 4 hour(s)
Other Conditions Ambient temperature
Ref. 1 5574719; Journal; Chakraborty, T. K.; Bhushan, Vidya; Chandrasekaran, S.; IJSBDB; Indian J.Chem.Sect.B; EN; 22; 1;1983; 9-11;
Q's, what is H2CroC15?
----------------------------------------
another...
Reaction Classification Preparation
Yield 95 percent (BRN=105248)
Reagent (1,10-phenanthroline)H2CrOCl5
Solvent CH2Cl2Time 8 hour(s)
Temperature 25 C
Ref. 1 5555229; Journal; Chakraborty, T. K.; Chandrasekaran, S.; TELEAY; Tetrahedron Lett.; EN; 21; 1980; 1583-1586;
Q's, reagent sounds a little obscure..
----------------------------------------
or this...
Reaction Classification Preparation
Yield 80 percent Chromat (BRN=105248)
Catalyst CuO
Time 15 hour(s)
Temperature 200 C
Note 1 Further byproducts given
Ref. 1 5549295; Journal; Berthon, Bruno; Forestiere, Alain; Leleu, Gerard; Sillion, Bernard; TELEAY; Tetrahedron Lett.; FR; 22; 41; 1981; 4073-4076;
Looks too easy, heat at 200c with copper oxide for 15 hours and distill! Am I missing something?
----------------------------------------
another....
Reaction Classification Preparation
Yield 86 percent (BRN=105248)
Reagent AcOOH/NaBr
Solvent ethyl acetate
Time 2 hour(s)Temperature 39.9 C
Ref. 1 5647691; Journal; Morimoto, Takashi; Hirano, Masao; Hamaguchi, Takayoshi; Shimoyama, Masahide; Zhuang, Xiumin; BCSJA8; Bull.Chem.Soc.Jpn.; EN; 65; 3; 1992; 703-706;
Sodium bromide and ethyl acetate is easy to get....
----------------------------------------
Where can I go to look up these refs on the net?
Oh and Rhodium....you need to fix that page of references on your site coz there aint no 111 refs its about 80 with 40 of them repeated! You will see where Rev Drone signs out and then they are repeated from there.
One horny Bee!
(Hive Addict)
07-27-00 19:33
No 33867
Yes!, I am bringing it to the top!
One horny Bee!
(Hive Bee)
07-27-00 19:47
No 33878
Beautiful placebo
If my fucked up catalyst don't work then i know where to go!!!
"Vote Libertarian"
(Stranger)
07-27-00 21:16
No 33892
I'd like to know where to go for references on the net as well. My local library doesn't have shit. Just looking at JOC online reveals that their entries only go back to 1997. Plus, it costs a damn fortune to view any full-length article. Suggestions, hints, flames???
(Hive Bee)
07-27-00 23:40
No 33934
Go to your local research institution
"Vote Libertarian"
(Hive Addict)
07-28-00 00:44
No 33959
Wal-mart or McDonald's??
One horny Bee!
(Hive Bee)
07-28-00 01:43
No 33979
A prefer best buy. Plug myself in and all the articles pop into my brain.
Warning if you stay pluged in to long there won't be any brain left to recover the articles!!!
I prefer to grease up the digestive tract at McDonalds
"Vote Libertarian"
(Hive Addict)
07-29-00 23:26
No 34538
Rhod or Os, somebody can we have a comment on any of these or my Q's?
One horny Bee!
(Stranger)
08-02-00 16:29
No 35771
Fuck. There has to be a way to make GBL cheaply and easily. These shady overseas companies are making a damn fortune ripping us off. I for one, am NOT going to take it anymore! Come on placebo, put your nose to the grindstone and head to the library.
(Stranger)
08-03-00 20:34
No 36245
Guys and gals, please let me direct you to a thread located in the Chemistry Forum called Extraction of g-butyrolactone from THF. Making GBL is not as hard as you all are making it out to be!
(Hive Addict)
08-05-00 03:05
No 36756
Yes, but for SWIM, maybe BDO can be had easily and cheaply where as THF can't.
I have read your thread (I read every thread here) and it is very interesting but not for SWIM!
<--If I put this here, people think I'm joking instead of a cunt!
(Freelance Moderator)
08-25-00 05:20
No 44936
Ok, for all the G fans, I thought I'd bring this back up.
Take note of the other refs I put in above.
SWIM shall be trying the copper chromite synth very soon.
Where is my delete button?? huh?
(Hive Bee)
08-25-00 14:32
No 45096
SWIM tried his fucked CuCr catalyst and a GC analysis indicated about a 25% conversion, but swim didn't heat the reaction mixture hot enought or long enough due to sketching out. He will attempt to run this rxn hotter and longer to see if the results are more favorable.
The GABA method may be the way of the future, ill update everyone once i get that reference.
foxy out
(Hive Bee)
09-02-00 21:34
No 48188
So there has been some trials with the THF route being discussed, has this route(BDO) been proven one way or the other yet...?
(i always talk like this!!)
09-03-00 06:51
No 48332
I have the reagents to make the catalyst and will be trying it soon. Just waiting on some more equipment! Don't worry I will post all details of course!
It's people like me that make Unobtanium look like a dick!
(Moderator)
03-05-04 01:50
No 493049
(Rated as: good read)
From CA 59 538 (1963):
New catalysts for obtaining tetrahydrofuran and y-butyrolactone from 1,4-butanedioL V. I. Ivanskii and B. N. Dolgov (State Univ., Leningrad). Kinetika i Kataliz 4, 165-6(1963); cf. Shostakovskii, et al., CA 51, 12826i. Catalysts with the compositions. Cu 60%, Al2O3 15%, SiO2 25% (1) and NiO 60%, Al2O3 15%, SiO2 25% (II) are prepared by adding NaOH and Na silicate to hot solutions of the metal nitrates, drying the preciptates., heating at 250-450°, and reducing in an H2 stream. At 190-200°, catalyst I converts 1,4-butanediol (III) quantitatively to gamma-butyrolactone at a space velocity of 60 without carrier gas; at 300°, the yield of IV is only 18% and a complex mixture is formed. Between 190° and 260°, II converts III quantitatively to tetrahydrofuran at a space velocity of 60 without carrier gas; at 300°, AcH appears in the product. HO(CH2)3CHO is suggested as intermediate in the formation of IV.
Perhaps one of the members of Hyperlab can come up with the original journal article, this seems to bee a good alternative to the chromite catalyst
Chemistry is our Covalent Bond