BDO

[fierceness]

Not sure if this is the right forum, but here goes.  SWIF recently came into possession of a bottle of 1,4-BDO.  He expected it to be a liquid, but it turns out there is a TON of crystallization in the bottle in a big chunk so he cannot even get it out.  Is this really BDO?  If so, will adding H2O get rid of the crystals?

Thanks.

[Osmium]

This is a good sign. The melting point of pure BDO is about 22°C.
Yes, H2O will depress the melting point.

[armageddon]

May I suggest you don't add water to your 1,4-BDO!? Unless you plan on using it in aequous suspension of course...

To get it out of your flask, simply let it sit in a warm place for some hours - it will melt slowly.

(the only things to avoid when storing BDO for long time are water and iron vessels)

Post 516012 (missing)

(Quality: "Applications 1,4-BDO is a versatile chemical...", General Discourse) (don't know where he got his info from, though)


Greetz A

[GOD]

heating pad...
(electric blankets work good for large containers)

avoid using H2O as swiy may want to use it for other things later in life....but its plenty good all by itself

[armageddon]

Well sure - of course it's better to post everything twice - at least noone will miss the important parts, eh??

..and heating blankets/pads DO NOT work very well when it comes to heating BOTTLES (unless they have stainless steel bottoms or thick-walled pyrex maybe, heat transfer is bad nevertheless) - better use a hot water bath (or simply put in warm place for a few hours, saves work)...

and for the sake of completeness: 1,4-BDO will melt exactly at 19.95°C, regardless whether a heating pad, heating bath or the place on top of your irradiator is the heat source - if you are not one of those guys preferring living in siberian climate (room temp. preferably below 18°C - I really know someone who likes this!), leaving it outside the freezer for a few hours will suffice.

...adding water is bad 'cuz it is difficult to separate from afterwards...

(please don't repeat any of these statements anymore - three times is really enough   )

Greetz A

[placebo]

Try reacting with copper chromite catalyst on Rhod's page to convert to GBL.
BDO is nasty shit, especially if taken any more then a couple times a year.

[armageddon]

What about simply heating 1,4-BDO to 200°C (i.e. reflux) for 15 hours over a CuO catalyst to yield 80% GBL which is separated by distillation?


Journal; Berthon, Bruno; Forestiere, Alain; Leleu, Gerard; Sillion, Bernard; TELEAY; Tetrahedron Lett.; FR; 22; 41; 1981; 4073-4076

https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.cuo.pdf

...Or maybe with hypochlorite  - although it seems to evolve a lot of nasty gas (Cl2, HCl)...


McDonald C.E., Nice L.E., Shaw A.W., Nestor N.B., Calcium hypochlorite-mediated oxidation of primary alcohols to methyl esters,
Tetrahedron Lett., 34 (17) , (1993) 2741–2744

https://www.thevespiary.org/rhodium/Rhodium/pdf/alcohols2methyl-esters.hypochlorite.pdf

(and with NaOCl too)

https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.pdf

Or just go ahead and prepare your wierd, dirty "chromite catalysts" as usual...
(I wonder if some bees refrain from visiting rhodium's archive because they're "hive addicts" - does the title imply you guys are only searching at the hive, nowhere else?   )


Greetz A

[fierceness]

[placebo]

armageddon,
It was suggested as it has been tried, I am not in the habit of speaking shit about stuff unless I know it for a fact, not because I read it somewhere. Have you tried any method whatsoever of converting BDO to GBL? I don't like your tone.

[armageddon]

[armageddon]

OK I really didn't try the CuO oxidation on 1,4...

But anyway, here's a translated key sentence from the original article I cited (hope you believe me I'm able of translating french   ):

"In case of the diols 1-4, 1-5 and 1-6, (entries 6,7 and the conversion is quantitative and the reaction results in formation of lactone and/or polyesters, as the formed lactones are prone to polymerisation. With benzyl alcohol, ester formation couldn't be observed, but rather a disproportionating reaction leading to equimolar amounts of benzaldehyde, toluene and water."

Do you still think the CuO oxidation is bogus, placebo???

A

[Quality]

[Rhodium]

Armageddon: From now on every single post you make with any snide remarks or other childish stuff found anywhere (including subject line/signature) will be downrated. You are disturbing the calm atmosphere here at the Hive...

Oh, could you please explain to me: why are you allowed to suggest routes for 1,4-BDO oxidation, whereas I am not allowed to suggest other, easier methods as well??

Reputation. A good track record of providing correct and useful information and little in the way of useless/incorrect stuff.

Also, if you had UTFSE for placebo's username and some well chosen keywords, you would find out that he indeed possesses intimate knowledge of the chromite dehydrogenation. Don't be so quick to jump the gun when you haven't even checked the archives first.

[armageddon]

You are disturbing the calm atmosphere here at the Hive...

Sure, MY posts contain the word "Dick" in the subject line... really disturbing! And bit childish indeed...

Reputation. A good track record of providing correct and useful information and little in the way of useless/incorrect stuff

I really fail to see the usefulness in telling me to shut up with proposing easier methods!??

Sure, Placebo has far more reputation (I was able to find 4 up-rated posts all placed in stimulants or general discourse and containing words as "Fuck" and insults, his good karma amounts to 5.0 while the total number of posts is above 3000... ), therefore my thoughts are automatically not as right as his are, hm!???

Tell me, what was incorrect with suggesting to use CuO???
It is from a scientific article that is archieved on your page! So you are archieving incorrect, useless information (a.k.a. bogus) or what?? Would be new to me...

And without checking any archives or searching for placebo's posts about the subject, I just know that the preparation of copper chromite catalyst simply is time-consuming, whereas the CuO can be bought!
And even if placebo had founded the HIVE and I was not even newbee but stranger, I would again post about CuO being better, cuz it is easier!!!!!!!!!!!!!!

..you would find out that he indeed possesses intimate knowledge of the chromite dehydrogenation. Don't be so quick to jump the gun when you haven't even checked the archives first If you would know about me, you might notice that I posess quite a bit of knowledge about CuO dehydrogenation of 1,4 (at least I've read a *lot* about it, including a 120page dissertation about the subject - dunno if this can be called "knowledge" though   )...


Now come on, rate this post down, too!

A

[armageddon]

BTW I checked the archives before I suggested using CuO...

https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.cuo.pdf

"Abstract: Linear primary alcohols with at least 7 carbon atoms are quite quantitatively transformed in esters, by CuO, at temperatures >170°C, without air in liquid phase. Preponderant influence of Carbon 2 is evidenced. In the same conditions lactones are obtained from diols, and benzylic alcohols undergoes, by hydride transfer, a disproportionation into toluene, benzaldehyde and water."

Really, what's wrong with this article? I thought every scientific paper you provide us with could  - at least to some extent - be taken for being reliable?

A

[Rhodium]

Sure, MY posts contain the word "Dick" in the subject line... really disturbing! And bit childish indeed...

When there is a quarrel going on, a single person is never at fault. However, there has been several instances lately where you have been one of the opponents/participants, and that makes me target you with this warning.

I really fail to see the usefulness in telling me to shut up with proposing easier methods!?? Tell me, what was incorrect with suggesting to use CuO???

There is nothing wrong with suggesting the use of CuO, I haven't commented upon your argument at all this far as it was perfectly all right. What I dislike is your slandering of placebo and the chromite dehydrogenation, two entities which deserve no such treatment.

I just know that the preparation of copper chromite catalyst simply is time-consuming, whereas the CuO can be bought! [...] I would again post about CuO being better, cuz it is easier! [...] wierd copper chromite catalysts aren't necessary, just use CuO and heat to 200°C for 14 hours, then distill.

Don't be so self-centered - ready-made copper chromite is easily available to a lot of people and thus it doesn't have to be prepared first. With the catalyst in hand, the copper chromite procedure only requires 3-4 hours of reflux (~200°C) after which time the GBL is distilled directly from the reaction mixture (and the reaction is not overly sensitive to air and moisture, as opposed  to the chromite dehydrogenation).

Different procedures have different virtues, and which ones are the most important depends heavily on the chemist's main constraints (availability of chemicals, money, time or equipment). For some, the chromite dehydrogenation is the shit, for others (you, among others) it would be the CuO dehydrogenation. Neither procedure is the "best" one, they are just suitable for different people. Therefore neither is to be unfairly critizised, especially not by someone who have tried neither.

We are supposed to be scientists! We can present arguments for our favorite methods and against those which we find less attractive - but please be objective - name-calling and derogatory remarks shouldn't be cast upon either people or scientific procedures.

[biffman]

One of the great things about the Hive is that it is an amazing forum for like-minded inquisitive people to exchange ideas and experiences with each other.
  Until recently this has gone on with a limited amount of bitch slapping taking place although there does seem to be an increase of it recently.
  I'm sure I'm not alone in that I tend to skip over these entertaining but ultimately depressing little posts and I am certainly not going to blame anyone involved since in between the ocassional name calling and dick size comparisons all participants usually contribute valuable information for the discussion at hand.
  I know sometimes egos can get in the way, especially when you are typing anonymously behind a keyboard, but hey, we're here ultimately for all the same reason.  To furthur out knowledge and to screw the Man. Not each other.  mmmmkay?