Author Topic: 1,4-butanediol to GBL - Will this work?  (Read 13569 times)

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foxy2

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Am i Fucked?
« Reply #20 on: July 25, 2000, 09:58:00 PM »
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???





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Rhodium

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Re: Am i Fucked?
« Reply #21 on: July 25, 2000, 10:56:00 PM »
No, pyrex will probably bust at that temperature. Use metal or high-temp ceramics.

http://rhodium.lycaeum.org


foxy2

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Re: Am i Fucked?
« Reply #22 on: July 26, 2000, 12:22:00 AM »
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 "



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placebo

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Re: Am i Fucked?
« Reply #23 on: July 26, 2000, 05:32:00 AM »
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!

Osmium

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Re: Am i Fucked?
« Reply #24 on: July 26, 2000, 12:03:00 PM »
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.


placebo

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Re: Am i Fucked?
« Reply #25 on: July 26, 2000, 03:56:00 PM »
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!

Prefix

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Back to the original question....
« Reply #26 on: July 26, 2000, 04:33:00 PM »
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."





placebo

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Re: Back to the original question....
« Reply #27 on: July 27, 2000, 12:35:00 AM »
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!

placebo

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Re: Back to the original question....
« Reply #28 on: July 27, 2000, 07:33:00 PM »
Yes!, I am bringing it to the top!

One horny Bee!

foxy2

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Re: Back to the original question....
« Reply #29 on: July 27, 2000, 07:47:00 PM »
Beautiful placebo
If my fucked up catalyst don't work then i know where to go!!!

"Vote Libertarian"

Prefix

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Re: Back to the original question....
« Reply #30 on: July 27, 2000, 09:16:00 PM »
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???


foxy2

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Re: Back to the original question....
« Reply #31 on: July 27, 2000, 11:40:00 PM »
Go to your local research institution

"Vote Libertarian"

placebo

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Re: Back to the original question....
« Reply #32 on: July 28, 2000, 12:44:00 AM »
Wal-mart or McDonald's??

One horny Bee!

foxy2

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Re: Back to the original question....
« Reply #33 on: July 28, 2000, 01:43:00 AM »
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"

placebo

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Re: Back to the original question....
« Reply #34 on: July 29, 2000, 11:26:00 PM »
Rhod or Os, somebody can we have a comment on any of these or my Q's?


One horny Bee!

Prefix

  • Guest
Re: Back to the original question....
« Reply #35 on: August 02, 2000, 04:29:00 PM »
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.

Obgynium

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Re: 1,4-butanediol to GBL - Will this work?
« Reply #36 on: August 03, 2000, 08:34:00 PM »
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!

placebo

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Re: 1,4-butanediol to GBL - Will this work?
« Reply #37 on: August 05, 2000, 03:05:00 AM »
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!


:P <--If I put this here, people think I'm joking instead of a cunt!

placebo

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #38 on: August 25, 2000, 05:20:00 AM »
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?

foxy2

  • Guest
Re: 1,4-butanediol to GBL - Will this work?
« Reply #39 on: August 25, 2000, 02:32:00 PM »
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