phosphorus alternatives -zip

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Author Topic:   phosphorus alternatives
zip
Member   posted 03-06-99 08:31 PM
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Looking through some patents on iodine production, I found some interesting equations from patents -- 1774882 and 2143222:
I2 + NaHSO3 + H20 = 2HI + NaHSO4
I2 + H2SO4 + H2O = 2HI + H2SO4
I2 + H2S = 2HI + S
It seems to me that NaHSO3, H2SO3 and H2S
(poisonous) can be used as a substitute for
red phosphorus in the I2/P reaction.

zip
Member   posted 03-06-99 08:35 PM
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Correction to equation 2:
I2 + H2SO3 + H2O = 2HI + H2SO4

Piglet
Member   posted 03-07-99 06:41 AM
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zip: Hmmmm, yes. I can't help but draw parallels between your first two suggestions & that 'recently descovered' (by the DEA) hypopohosporic route. H2S is widely (an sometimes fatally) used on a big scale. It would seem that the first two might prove to be EXCLELLENT new alternatives.
Rhodium's site links to some DEA stuff concerning both the hypophosphite & H2S routes.
This is some very clever reading. I wonder if one should just throw in the Na2SO3 into the I2/Ephedrine mix, or make HI and add that to the mix, or make ALL your HI beforehand? The impurities should be easy to remove and are fairly non-toxic. In fact, anyone already doing the P/I2 sucessfully should really research it.
I2 can, itself be made from KI. When the cops have to watch KI & H2SO3 (which is SO2 in water,folks). Then the ephedrine itself is the ONLY thing they can then crimp on.

When will we see US ehpedera/Khat fields?

Piglet

PS HS2 Gas could be formed by some routes. Similar risk to the PH3, so play (I mean dream) safe...

Piglet

Piglet
Member   posted 03-07-99 07:13 AM
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There are some interesting amino-alcohol synths. Maybe it may be viable to go via the amino alcohol.
PS I also heard that Zn will replace P @0C, better & better...

Piglet
Member   posted 03-09-99 02:58 AM
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What are you people, stupid! read what the guy says!

Optimus Prime
Member   posted 03-09-99 10:01 AM
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Hmmm.... ummm-hmmmm.... yeeesss.... interesting...
I see what you are saying zip and Piglet but didnt Drone mention the sulfide path before... It would take a temperature in the bounds of 300 dgs to make the H2S if I remember right (prolly dont), so I see the fire depts. getting a workout if that became popular... I dont know about the others and should probably read on them before I opened me mouth One question on the DEA route, having not read it, is it stating that the phosphoric acid reduces the alcohol..?? If so is this because at 150dgs the phosphoric acid becomes anhydrous.. simply put I mean..?? So alcohol+phosphoric at 150-160dgs => reduced alcohol...??
OP

Piglet
Member   posted 03-09-99 11:16 AM
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No, hypophosphorus acid, H3PO2 reduced I2 to HI which reduces the whole thing. H2S made from FeS and bubbled through I2 in an appropriate medium (GAA as I remember) produces HI at RT. So no VFD gonna save me...
The others are similarly strong reducing agents except they are pretty non-toxic solids. Oh, and they are OTC as well...

Piglet
Member   posted 03-09-99 11:17 AM
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PS: drip dilute mineral acid on FeS for H2S. Get the picture now,daddio?

Optimus Prime
Member   posted 03-09-99 11:57 AM
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Yea its getting clearer, but isnt the FeS thing also going back to the high temp H2SO4 discussion? Daddio... hehe... Piglet the blue bloods getting redder by the minute..
OP

Piglet
Member   posted 03-09-99 12:06 PM
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No. You drip dilute H2SO4 onto FeS at RT then bubble the resultant H2S through I2 at RT. Do you need me to draw a lab-prep for this? It seems simple to me...
In mexico, people pull off HUGE batches of HI by bubbling cannisters of H2S through the I2 solution. It's sort of 'industrial' because it is so simple. Just the H2S danger. Now, I'm not frightened of NaHSO3 QUITE as much, although I havn't read the MSDS recently...
I don't see what you can't see?

Piglet
Member   posted 03-09-99 12:58 PM
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I think zip's first post said it all...

MacHeath
Member   posted 03-09-99 01:52 PM
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Premise 1: The HI/RP reduction of a benzyl alcohol involves a substantial amount of time under reflux.
Premise 2: The purpose of RP in this reduction is to regenerate the Iodine anion from the iodine atom, after the anion has reduced the alcohol.

Conclusion: HI, provided in excess, should dramatically reduce the amount of time, the need for reflux, and possibly the odorous byproducts that the HI/RP reaction requires/supplies...

Is this a strong argument?

Mack.

------------------
Drone -- 3.14159265358979323...

Beagle
Member   posted 03-09-99 02:16 PM
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Several comments:
Premise --1: Yes, but if the amount of heat can be increased, as doing the reaction under pressure, the reaction time may be decreased. See Bad Dog!'s post in xtal forum about this.
Premise --2: RP serves more than just to recycle I2 back to HI in this reaction. Evidence of this is that the reaction will not run without P, no matter what the concentration of HI. PI3 and HI/H3PO2 are able to reduce the alcohol, and either may be involved in the mechanism.

Conclusion: The stronger the HI, the faster the reaction. However, reflux appears to be necessary no matter what the concentration.

Optimus Prime
Member   posted 03-09-99 08:26 PM
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Piglet: No lab prep needed... it just seems to me that with what is readily available, the relative ease and wide margin for error the P/I synth has that dripping mineral oil onto FeS to bubble through I2 to use to reduce alcohol just seems like more than one needs to do compared to three trips to the digital scales... not to mention the clean up...
OP

Seedcrystal
Member   posted 03-10-99 01:47 AM
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Well you guys are mostly talking about I2+H2S but I'm more interested in I2+ NaHSO3 it is an industrial reducing bleach which by coincidence I happen to have unlimited amounts of. Although using any procedure with NaHSO3 is going to reek and produce lots of noxous fumes.
Hey MacHeath=Drone?

Piglet
Member   posted 03-10-99 02:57 AM
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OP: You have missed the point. NaHSO3 + I2 --> HI. THATS the new bit. It's OTC. So you can make your HI that way. But What happens if you replace the P with NaHSO3 in the RP/I reduction? You don't need RP. And, as I said, KI+H2SO4--->I2 so that's OTC as well (if messy).
This, easily prepared HI can be used for iodosafrole as well as -OH reductions. My chemistry book says that HI + ZnI2 will reduce that pesky benzyl alcohol without the need for P.
You cannot get P in the UK. We almost NEVER see ----, only DL sulphate made, no doubt, by some ancient route (or simply imported from Holland).

Piglet
Member   posted 03-10-99 03:04 AM
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Overall, I would guess NaHSO3 + I2 to make your HI (which could be bubbled straight into GAA to make iodosafrole, I HOPE).
OR, make your ultrastrong aqueous HI, throw in a little Zn (or any ZnCl2 or ZnBr2) and reflux your sudafed extract as per normal.
There, I've said it. When they make P acquisition harder, you will thank that zip guy (E-Mail me, dude!)
Piglet

MacHeath
Member   posted 03-10-99 09:45 PM
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Actually,
I would really be interested in the actual patents... No slur on zip, but I just spent the last 30 minutes on the IBM patent server looking for the patents. The numbers given are not indexed in their database (not US, WO, or EO). Did you use a different search method, or was it a bug in the IBM system, or was I totally off in my methodology?

Enlighten me, please...

Piglet - I was reading Skinner's report on MeAm synth, and by my interpretation, I don't think the replacement is that cut and dry, as just replacing the RP with the NaHSO3. It seems like it plays a much more integral role than I initially thought (thanks Beagle)... Could you explain your logic, because I'm the first to admit that I misunderstand, quickly...

I would love to hear more about the Zinc, tho.. Where did you dig that rxn out?

Seed - I figure if Rev Drone is/was Drone 342, then by comparison, I approximate Pi. Just my small expression of hero worship...

"When I grow up, I wanna buzz JUST like Drone..."

Mack.

danielsan
Member   posted 03-10-99 10:12 PM
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CHECK IT OUT CHECK IT OUT CHECK IT OUT
alright that was unnecessary (did i spell that right?)

Find JOC 53, '88, p.4477

HI is generated in situ with I2 and alumina. Now this stuff apparently adds to aromatic ring systems, but not before a fucking benzylic alcohol - or a terminal olefin

Optimus Prime
Member   posted 03-11-99 12:54 AM
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All of you are killin me with this multiple personality shiznit... Beagle, whats the scoop with the P.. I remember something about phosphorous reducing ketones but not alcohols other than the HI... is there more to the P.. maybe leading to substituting the acid... ??
OP

Piglet
Member   posted 03-11-99 03:11 AM
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Iodoephedrine is an intermediate in this route, yes? Well Br can be reduced with aq.HI & ZnBr2 @ 0C. (it's a known, general route). So I figure that it may well work here, as well?
You must have seen the 'chloroephedrine using ZnCl2 & HCl?' followed by 'no, it doesn't work'. One is on Rs page. Then someone did 'bromoephedrine with ZnBr2 & HBr' and they did claim results. But not great ones. (low yield).
There was MUCH talk of HI + ZnI2 on ADC, but no one actually did it, mainly because the people discussing it were lame (me for one!). I don't know if the I will form at 0C, but it SHOULD be reduced right away. Maybe heating will still bee needed (but start without. A RT reduction without P takes 1 chemical out of the loop (and I bet you it's already started!). I is easy to make at home. You can EVEN make NaHSO3 easily (but you should never need to. It's OTC).
Response, folks?
Piglet

PS: Where the fuck is this zip guy? If he isn't quick, and this works, I'm going to steal all the credit

zip
Member   posted 03-11-99 08:12 PM
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The patents are US patents. I found them
looking through the paper patents in the US
Patent Office in a class and subclass on
iodine production. The patents used the
above processes for recovering iodine from
activated charcoal which is used to absorb
iodine from sea water or seaweed as far as
I can remember which had been treated with
chlorine to convert iodides to iodine.

zip
Member   posted 03-14-99 07:40 PM
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Hey Piglet, try these rxn out. If they
work take all the credit you want.
Keep us informed!

zip
Member   posted 03-14-99 07:42 PM
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Hey Piglet, try these rxn out. If they
work take all the credit you want.
Keep us informed!

zip
Member   posted 03-14-99 07:42 PM
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Hey Piglet, try these rxn out. If they
work take all the credit you want.
Keep us informed!

Piglet
Member   posted 03-15-99 03:20 AM
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I'm no ---- cook, but maybe I will try it for making iodosafrole soon.
Piglet

PS I was only joking, YOU found the patents!