Sciencemadness Discussion Board - Selenium, phosphorous & arsenic mustards?

Selenium, phosphorous & arsenic mustards?

Ritter - 25-6-2008 at 08:24

There is a lot of literature on the N, O & S mustard agents. I'm curious as to why there appears to be little or no literature on the title compounds. Tris(2-chloroethyl)phosphine is a known compound. Tris(2-chloroethenyl)arsine is Lewisite L3 but what about tris(2-chloroethyl)arsine? And I'm sure someone has prepared bis(2-chloroethyl)selane to test its properties as a CW agent. I would expect all of these compounds to be toxic but I've been wrong before!

ScienceSquirrel - 25-6-2008 at 08:32

Don't forget my favourite, sneezing gas

http://en.wikipedia.org/wiki/Diphenylchlorarsine

Ritter - 25-6-2008 at 08:39

Here is an interesting historical document: a list of all (?) the candidate vesicant agents tested at Porton Down in the U.K. during WWII: http://www.mod.uk/NR/rdonlyres/F2012484-2472-4B04-8C9D-E3DA7...

I did a fast scan but did not find any of the compounds I was curious about.

ScienceSquirrel - 25-6-2008 at 08:46

Sap of wild parsnip?

Sadly giant hogweed had failed to reach these shores by then.

Bloody horrible stuff!

Ritter - 25-6-2008 at 08:52

Quote:

Originally posted by ScienceSquirrel
Sap of wild parsnip?

Sadly giant hogweed had failed to reach these shores by then.

Bloody horrible stuff!

The NY Times on wild parsnip dermal phototoxicity:

Quote:

. The flowers might belong to any of several common weeds, but wide leaves make me fear your plant could be wild parsnip, Pastinaca sativa.

If so, yes, it would take over, and probably burn you as well. Wild parsnip sap is not dangerous by itself, but when it is on your skin and it is exposed to ultraviolet light, it destroys skin cells.

Even on cloudy days, the sun provides enough ultraviolet to provoke the reaction, which begins with redness and pain, then raises blisters. Healing takes place at about the same rate as recovery from other surface burns, but the affected skin often darkens and can remain dark for a year or more.

The burns may not appear until a few days after exposure, so they are often attributed to poison ivy or to an allergic reaction. Brushing against unbroken plants is safe, and washing up promptly can forestall problems, so wild parsnip's mean side is seldom obvious. But there are few wild plants less worthy of adoption.

ScienceSquirrel - 25-6-2008 at 09:02

Giant hogweed be similar stuff, it be, arr

http://en.wikipedia.org/wiki/Giant_hogweed

Ritter - 25-6-2008 at 10:07

Quote:

Pharmazie. 2000 Aug;55(8):618-20.

Furanocoumarins in Pastinaca sativa L. in vitro culture.

Ekiert H, Gomółka E.

Department of Pharmaceutical Botany, Collegium Medicum of Jagiellonian University, Kraków, Poland. mfekiert@cyf-kr.edu.pl

Callus cultures of Pastinaca sativa L. (parsnip), Apiaceae, were cultivated on variants of Linsmaier-Skoog's medium, containing varying quantities (0.1-10.0 mg/l) of phytohormones: NAA-BAP and IBA-BAP which allowed to obtain 1.5-3-fold fresh biomass growth during 6-week subcultures. HPLC analyses showed that tissues cultured in vitro produced psoralen, bergapten, xanthotoxin, isopimpinellin and umbelliferone which are well known metabolites in plants growing under natural conditions. Total content of coumarins depended on the nature and quantity of phytohormones present in the medium, and ranged from 115.7 to 408.5 mg/100 g of the dry weight, isopimpinellin being the metabolite which dominated quantitatively (maximum content of 238.9 mg/100 g). Psoralen was also accumulated in callus tissues at considerable amounts (maximum content of 108.8 mg/100 g). This metabolite dominated in vegetative plant parts that have been analysed in our study (leaves, stems, roots) but its contents were lower than in the material from in vitro culture (48.9 mg/100 g 10.6 mg/100 g and 14.9 mg/100 g, respectively). Imperatorin was not detected in callus tissues although it dominated in the analysed fruits of the studied plant (200.0 mg/100 g). The best of the tested media in respect of promoting tissue biosynthetic capabilities was that which contained 3 mg/l NAA and 1 mg/l BAP. The studies showed that in vitro cultures of Pastinaca sativa L. can be a convenient model to study the biosynthesis of furanocoumarins and also a potential rich source of these compounds, particularly isopimpinellin.

ScienceSquirrel - 25-6-2008 at 15:03

Yuzzem, you chemically toipes jest know about about this book stuff.

But them there giant hogweeds seem to have gone out there and made those substituted furocoumarins for themselves

http://en.wikipedia.org/wiki/Furocoumarin

Sauron - 25-6-2008 at 16:44

Going by memory:

There was a professor of chemistry at one of the Florida universities, now deceased, one of their science buildings is named for him. IIRC his name was Fred Lee Heath. In a short bio I ran across he was described as having been the "father of selenium mustard" in the WWI period.

Based on at least one Ministry of Defense list of proscribed substances, the following were most certainly prepared and evaluated:

Br and I and F analogs of H (sulfur mustard)

Se and Te analogs of H

The arsenicals generally analogous to H were of course the Lewisites. Many other arsenical CW agents were proposed but IIRC not as vesicants per se.

I have never heard of any phosphorus "mustard". Any P analog of H would be pyrophoric and any P analog of HN3 would oxidize to the phosphine oxide. Ditto for P analogs of the L series.

If you want a nasty vesicant then H is still scary, if you want something more exotic, try phosgene oxime.

My recollection is that the other halogen sulfur mustards were dead ends and so were the Se and Te analogs.

ScienceSquirrel - 26-6-2008 at 02:45

Quote:

Originally posted by ScienceSquirrel
Yuzzem, you chemically toipes jest know about about this book stuff.

But them there giant hogweeds seem to have gone out there and made those substituted furocoumarins for themselves

http://en.wikipedia.org/wiki/Furocoumarin

On a more sane and sober note I think I should point out that wild parsnip and giant hogweed are moderately closely related species and the genes and biochemical pathways for the synthesis of furocoumarins are probably similar.

Morgan - 8-8-2015 at 19:09

I was perusing information on this plant because it happened to be mentioned in an article on my news page.
https://www.youtube.com/watch?v=YrXlVZ172T8
https://www.youtube.com/watch?v=lKMBURu_zig

And there was this article which may or may not be all that important.

"There may be higher quantities of furocoumarins in fresh fruits with peel and pulp than in processed juices."
https://news.brown.edu/articles/2015/06/citrus

kecskesajt - 8-8-2015 at 20:38

Giant hogweed is painful enoung to be a warfare agent :mad:

Last year I had experience with one.

halogen - 16-8-2015 at 14:50

A White man stained himself Black with psoralen in the late 50s, went to the South, and wrote a book about this.

ave369 - 19-8-2015 at 02:06

Quote: Originally posted by kecskesajt

Giant hogweed is painful enoung to be a warfare agent :mad:

Last year I had experience with one.

This plant monster is extremely common in Central and Northern Russia, where it is known as "Stalin's revenge". One plant even grows in my garden, despite my best attempts to get rid of it. Right now I've tried to entomb its roots under an iron drum lid to prevent another iteration of hogweed growing from them.

Morgan - 19-4-2016 at 05:20

Quote: Originally posted by Morgan

I was perusing information on this plant because it happened to be mentioned in an article on my news page.
https://www.youtube.com/watch?v=YrXlVZ172T8
https://www.youtube.com/watch?v=lKMBURu_zig

And there was this article which may or may not be all that important.

"There may be higher quantities of furocoumarins in fresh fruits with peel and pulp than in processed juices."
https://news.brown.edu/articles/2015/06/citrus

I came across this (inacurate?) article yesterday and it made me wonder if it's the citric acid that does this or if it's something else in the lime juice or a synergistic combination of the two.
http://www.usatoday.com/story/news/nation-now/2015/06/02/ski...

For review
PROVIDENCE, R.I. [Brown University] — Physicians have known for a while that compounds called psoralens make skin more sensitive to light exposure. Psoralens are abundant in citrus fruits. These facts are documented in the scientific literature and are apparent in anecdotes about lime-squeezing bartenders with sunburned hands or kids with streaks of sunburn matching where a citrus-flavored popsicle dripped down the chin.
https://news.brown.edu/articles/2015/06/citrus

unionised - 19-4-2016 at 12:51

Can we ban Earl grey tea?
https://en.wikipedia.org/wiki/Bergamot_orange#Toxicology

Theoretic - 22-4-2016 at 05:22

Quote: Originally posted by Morgan

Well, you've answered your own question! It's the psoralens. Citric acid doesn't have the structure to absorb UV light and cause these effects. Psoralens do, and they also are heavier and greasier, and can stick around in the body.
"kids with streaks of sunburn matching where a citrus-flavored popsicle dripped down the chin"- for some reason makes me think of using with lime juice on friends asleep in the sun (like a twisted version of doodling with sunblock).

Quote: Originally posted by unionised

Can we ban Earl grey tea?
https://en.wikipedia.org/wiki/Bergamot_orange#Toxicology

"Potential side effects of drinking large amounts of bergamot oil can include convulsions and death in children."
...
NO! I take it back! I take it all back! Save the childrunz

a nitrogen rich explosive - 24-4-2016 at 10:14

What's the LD50 of S mustard?

careysub - 24-4-2016 at 13:38

Quote: Originally posted by a nitrogen rich explosive

What's the LD50 of S mustard?

About the same as hydrogen cyanide, about 25 mg.