El_Zorro (Hive Bee)
04-07-02 18:07
No 293918
      performic oxidation & boro reduction  Bookmark   

Just a few Q's relating to the performic.

1.Does formic acid form an azeotrope(sp.?) with water?  As in reacting sodium formate with HCl, or H3PO4, then distilling?  Could pure formic be isolated by simple distillation?

2.After the glycolization step in the performic, the products are mostly the monoformyl glycol, correct?  So would the strong acid hydrolysis give the ketone and formic acid, among other things?

3.Anyone have ref's for using an acid besides sulfuric for the hydrolysis step?


And now for the boro reduction.

1.Couldn't the boro be dissolved in anhydrous methanol and dripped in, so you wouldn't have to sit around for fucking HOURS dropping it in teaspoon by teaspoon.  All you would have to do is maintain strong stirring and adjust the drip rate to keep the temp acceptable.  Could it work?

Well, that's the only question for the boro bit, but can anyone give me some insights?

Edit: Oh, shit!  I was just looking up the density of formic on chemfinder, and it said the boiling point was 100.7.  Shit!  I don't entirely trust chemfinder, though, so somebody, please, tell me it aint so!


I sell crack for the CIAfrown
 
 
 
 
    LaBTop
(Daddy)
04-07-02 18:23
No 293924
      Answers  Bookmark   

1.Yes, but you don't have to worry about that, the buffered performic doesn't need distillation of formic acid.
2.Yes, and if done well, you should get a near quantitative yield of monoformyl glycol, the 15% H2SO4 treatment is the culprit, if done too hot or too long, many sideproducts (2 to 2.5 hrs max), if done to short or too cold, not enough conversion to ketone.
3.Yes, but that will come up soon, when consistent yields have been obtained. The Hive laboratories Inc. is working on it, hehhe.

1.No. Don't even try it, boro reacts with methanol. LT/

WISDOMwillWIN
 
 
 
 
    Rhodium
(Chief Bee)
04-07-02 18:45
No 293946
      And as always, my page...  Bookmark   

What you need to know about the modified performic acid oxidation: ../rhodium/chemistry /peracid.html
 
 
 
 
    El_Zorro
(Hive Bee)
04-07-02 20:10
No 293991
      Just the guys I was lookin' for!  Bookmark   

LaBTop-

1.What do you mean?  If I react sodium formate with the acid of my choice, I would think that it would need some cleanup before the reaction.
2.With the monoformyl glycol bit, I was just wondering if the formic acid could be distilled and reused, eliminating a precurser for future reactions.  I realize the yeild losses lie in the hydrolyzation step, I've been following your work.wink
3.Maybe someday there'll be a quantitative safrole oxidation.laugh

4.Then why is methanol used?  Wouldn't it tie up boro that should go to the imine?  I guess I'm just a fatass and want to do as little work as possible.crazy


And Rhod-

I could probably recite that page by heart by now.  Your page is always the first place I look, next to the Hive.

Anyone-

Is formic's BP really 100.7 C?  That would be a bitch to distill from water.mad

I sell crack for the CIA
 
 
 
 
    cheeseboy
(I'm not Cheesie)
04-07-02 23:14
No 294088
      eww  Bookmark   

Plus cheese heard that Formic acid is nasty smelling and it takes a coon's age to distill. Is H2SO4 hard for you to get EZ or do you have an excess of other 'strong' acids you want to use up?

<Cheeseboy-a whiteboy with soul, like a black guy without soul
May De Sorce Bee Wit Chu-Always
 
 
 
 
    LaBTop
(Daddy)
04-08-02 01:01
No 294145
      Answers:  Bookmark   

1. Keep that sodium formate in a safe, and guard it as a diamond, for better days to come. Formic acid can be obtained from beekeepers.
2. Don't even concider it.
3. Yes, there will be.
4. It's the needed solvent to let the reaction proceed, the boro hitting it when spooned in is directly used for the good work, but if stocked up in a dripping funnel all together with an amount of methanol, it will decompose fairly fast, and your yield will be near zero.
Btw, endless discussions on this topic can be found in TFSE.

BP formic acid: fill in Formic acid in Chemfinder search, then note the CAS number at their page only, do NOT pay attention to their crappy data, then click Physical Properties, then you get a new screenshot, click there the first top long link to InternationalPhysicalProperties Data, it's the first link on top, then fill in there -only the CAS number- (like 11-22-33 as an example only, not all those 0000 in front of them from Chemfinder), and these guys have reliable data!
I found a bp of a chem yesterday in Chemfinder which was about 200C OFF the real one in IPP! Messy data. LT/


WISDOMwillWIN
 
 
 
 
    El_Zorro
(Hive Bee)
04-08-02 12:43
No 294314
      how's this for a meaningful subject??  Bookmark   

cheese-

I could get H2SO4, but I was only intersted in the yeild side of the equation.

LaBTop-

1.Why is sodium formate so precious?  Are you preparing for formic becoming a List 1?wink

2.Why not?  Does it have to do with what cheese mentioned before, smell and time?

3.Let's hope so.

I sell crack for the CIA
 
 
 
 
    El_Zorro
04-14-02 14:20
      how about this whimsical idea?
(Rated as: UTFSE!)
 Bookmark   
 
 
 
    El_Zorro
(Hive Bee)
04-14-02 18:13
No 296980
      touche  Bookmark   

after U'ingTFSE, All I could come up with was [No 209961], which said that the acetate ion is used to buffer the reaction somewhat.  I found this post by searching for "methylammonium acetate", and when I searched for "methylamine acetate", TFSE found two posts, but they wouldn't come up.  Has anybee actually tried using methylammonium acetate in the boro reduction?

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas
 
 
 
 
    Rhodium
(Chief Bee)
04-14-02 18:46
No 296991
      Freebase  Bookmark   

The methylamine freebase must be used, as the acetate ion would react with the sodium borohydride if it was left in solution. However, something that has been used successfully in the past is an equimolar mixture of methylamine hydrochloride and triethylamine, which in solution creates methylamine freebase and triethylamine hydrochloride. Post 188868 (SuperAssman: "Repost: BzCl ---> meth    (for "Andrew"??)", Stimulants)
 
 
 
 
    El_Zorro
(Hive Bee)
04-14-02 19:03
No 296996
      I guess there is no lazy way.[frown]  Bookmark   

Thanks anyway, but I was looking for more along the lines of a methylamine salt that could actually be used in the boro.  I just don't wanna have to dick around with the freebase.

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas