Sciencemadness Discussion Board

Pheromones

hodges - 28-7-2006 at 15:46

I probably have more ideas than either time or chemistry ability, but I thought I would throw this out there. I don't see any similar topics.

It seems that some pheromones are not that complicated as far as chemical compounds go. For example, I believe isoamyl acetate is the pheromone that bees release when they sting someone. The scent alert other bees to a threat, and they come to join in the defense. Using this compound as an example someone could synthesize it and have a bit of fun placing some on the clothing of someone they don't like too well. Sorry for the kewl-sounding example but I'm curious if anyone has considered making pheromones in general. It seems this should be within the reach of the amateur chemist.

Hodges

[Edited on 29-7-2006 by chemoleo]

chemoleo - 28-7-2006 at 17:21

Interesting you say this, years ago, at school, a friend wanted me to synth androsterone... and I told him it's wayyy to difficult. Turns out you can buy it over the internet!
http://www.attractant.co.uk/

Structurally, it seems rather difficult to synthesise:



Also have a look at old wiki
http://en.wikipedia.org/wiki/Pheromone



Changed your spelling to 'pheromone. Makes it easier on anyone searching.

solo - 28-7-2006 at 17:49

Here is something to read on the synthesis you're considering.............solo

------------------------------------------------------------------------------------------------


Applications of Sulfenylations of Ester Enolates. Synthesis of Pheromones of the Honey Bee
Barry M, Trost*13 Thomas N. Salzmann
J. Org. Chem., Vol. 40, No. 1, 1975


Summary: By 'the sulferiylation-dehydrosulfenylation
method, the queen substance and the pollen attractant of
honey bees have been synthesized and a new approach to
a-keto esters by direct bissulfenylation has been demonstrated.



[Edited on 29-7-2006 by solo]

Attachment: Applications of Sulfenylations of Ester Enolates. Synthesis of Pheromones of the Honey Bee .pdf (364kB)
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Vitus_Verdegast - 28-7-2006 at 19:05

Androsterone can be synthesized from cholesterol:

"cholesterin" --> 3b-hydroxy-androst-5-en-17-one

Cesk. Farm. 5 (1956) 331; Chem.Abstr. (1957) 8772.
Nippon Nogei Kagaku Kaishi 28, (1954) 317; Chem.Abstr. (1958) 20642.

3b-hydroxy-androst-5-en-17-one ---> 3b-hydroxy-(5a)-androstan-17-one
using a palladium hydrogenation:
Patent US2267759
Hoppe-Seyler's Z. Physiol. Chem. 237, (1935) 57, 71.
J. Am. Chem. Soc. 57 (1935) 1511, 1512.


From 3b-benzoyloxy-5a-cholestane by oxidation (CrO3 or MnO4-):
Helv. Chim. Acta 18, (1935) 210, 215.
Patent US2232735
Patent DE736845
Patent DE699308

3b-benzoyloxy-5a-cholestane is made by treatment of cholestane with benzoyl chloride or benzoic anhydride. Cholestane can be had from cholesterol by hydrogenation of the double bond.

There are also quite some references that use the acetylcholestanol ester for the oxidation.

If I remember correctly straight oxidation of cholesterol (breaking the C-C bond using preferably CrO3) also gives rise to a similar product, androstenedione if I'm not mistaken. I have read a patent on this but am not able to locate it for the moment.

Also, isn't it possible to isolate this from urine? :D:cool:

yes, the Merck Index sez:

"Isolation from male urine after the removal of the phenolic estrogen fraction:

Z. Physiol. Chem. 229, 167 (1934)
Helv. Chim. Acta 25, 998 (1942)

Preparation from cholesterol:
Helv. Chim. Acta 17, 1389 (1934)
J Am. Chem. Soc. 57, 1755 (1935)
patent US 2232735


Now how would one apply this stuff? Use as a deodorant? Spray it in the victim's face?:D

scifly - 28-7-2006 at 20:04

Quote:
Originally posted by Vitus_Verdegast


Now how would one apply this stuff? Use as a deodorant? Spray it in the victim's face?:D


Breath mints?:D

The_Davster - 28-7-2006 at 21:46

Androsterone eh? Hmmm...would make many 'social' experiments quite interesting.:P Perhaps a test is in order.:D

Interesting that that link you supplied Chemoleo, has a very dilute solution (only milligrams in the entire bottle) of androsterone in alcohol for around 50$US. Sigma has 1g of it pure for around 60$. Almost a thousand times more for almost the same price.

Apparently it is applied by spraying it upon clothing, not skin.

hodges - 29-7-2006 at 07:35

Quote:
Originally posted by chemoleo
Interesting you say this, years ago, at school, a friend wanted me to synth androsterone... and I told him it's wayyy to difficult. Turns out you can buy it over the internet!
http://www.attractant.co.uk/


You can also buy oxytocin, the "trust hormone" online:
http://www.verolabs.com/
http://www.oxycalm.com/

Hodges

unionised - 29-7-2006 at 09:00

In the spirit of practical jokes I thought I would mention methyl paraben. A bit unkind to the local dogs though.

Vitus_Verdegast - 29-7-2006 at 10:06

Forget urine.....

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

"Androsterone(ADT) is a steroid hormone with weak androgenic activity. It is made in the liver from the metabolism of testosterone. It was first isolated in 1931, by Adolf Friedrich Johann Butenandt and Kurt Tscherning. They distilled over 17000 liters of male urine, from which they got 50 milligrams of crystalline androsterone, which was sufficient to find that the chemical formula was very similar to estrone.
Androsterone may also act as a pheromone."

In adult humans the average production is about 1 - 2 L per day. So if one is willing to pee in your rotovap every day it would still take 23-46 years.. Make it 50, as at that age one would probably need a whopping dose anyway :P

Vitus_Verdegast - 29-7-2006 at 11:27

Further results on the quest for unlimited amounts of mesmerized beautiful horny ladie.... err.. I mean, androsterone :D

(translation mine, my german is a bit rusty)
According to patent CH221807, the oxidation of cholesterol gives as main products andro-4-ene-3,17-dione and 4-pregnen-3,20-dion. The oxidation agents that may be applied are CrO3, KMnO4, H2O2, Pb(OAc)4, or electrochemical oxidation (if necessary in presence of oxygen or oxygen transferring compounds, such as lead peroxide). Due to partial breaking of cholesterol's sidechain at the 17-position, andro-4-ene-3,17-dione and 4-pregnen-3,20-dion is obtained.

The neutral, non volatile 4-pregnen-3,20-dion (and andro-4-ene-3,17-dione) is obtained e.g. after removal of acidic and volatile components such as monocarbonyl- and dicarbonylcompounds using partly physical and/or chemical separation methods, e.g. by use of ketone-reagentia, by precipitating the polycarbonylcompounds on concentrating the acidic solution, by fractionated crystallization, by high vacuum sublimation etc... to obtain a pure compound.

One can extract the acidic solution using ether, benzene etc... and recover the androstenedione using a derivatisation reagens such as semicarbazide, thiosemicarbazide, aminoguanidin, PhNHNH2...

example:
To a solution of 1 part of cholesterol in 30 parts glacial acetic acid one adds 1.4 parts of chromiumtrioxide dissolved in 90% acetic acid under strong stirring at room temperature, over the course of 4 hours. It was stirred at room temp for an additional 24h, after which the excess CrO3 was neutralized by addition of methanol. The solution was concentrated under vacuum, water was added, and the mixture was steam-distilled under vacuum for one hour. It was then extracted with ether, and the ether washed with dilute H2SO4, dil NaOH and water. When the dil. NaOH washing was evaporated a sodium salt precipitates. The ether was evaporated and the resulting mass was taken up in methanol. Unreacted cholesterol doesn't dissolve and is filtered off.

The resulting mixture of 4-pregnen-3,20-dion and andro-4-ene-3,17-dione can be separated using high vacuum distillation but we will not care and go further to the reduction, as the product has to be applied on the clothes anyway..
Who knows, the structually similar 4-pregnen-3,20-dion (a -COCH3 group on the 17- position) might have similar or potentiating effects ;)


The reduction of andro-4-ene-3,17-dione to androsterone is easily accomplished using Pt in dilute acid at 75°C according to patents US2257137, GB455378 and FR812354. NaBH4 in THF can also be used but the yield is only 40% (see Tetrahedron 38, 12 (1982) 1755-60).


---------------
EDIT: Apparantly when various hydride reagents or electrolytic reduction are applied the selective reduction of the wrong carbonyl (at the 17 position) is preferred, resulting in testosterone :o
see eg. US2356596


[Edited on 29-7-2006 by Vitus_Verdegast]