routes to P2P

Elementary · Sun Jul 17, 2005 9:49 pm

EDIT 20/07/05

Since noodle has left and deleted his posts, below is the scheme that he posted that we are discussing.

A lot of the chemicals you are making can be easily purchased, no questions asked !

Reflux toluene with an alkali potassium permangante solution to get Sodium Benzoate, then acidify and extract benzoic acid, benzoic acid + chalk will give you calcium benzoate

I like the beta-methystyrene conversion to P2P route, from here I guess
https://www.synthetikal.com/Rhodiums_pdfs/chemistry/p2p.phenylpropenes.html

EDIT

Let's get rid of the sulphuric acid and the nitric acid

Potassium hydrogen sulphate can be made by heating a solution of oxone (potassium persulphate). 2K2S2O8+2H2O>heat>4KHSO4+O2

Make your Calcium Propionate from Methyl Ethyl Ketone (MEK) and Bleach, MEK is available as PVC pipe cleaner.

Oxalic acid is available OTC as wood bleach

Formic acid is used by beekeepers.

Sodium Benzoate can be bought online, just acidify it to gain benzoic acid, extract and then add to your calcium hydroxide.

Whey Hey !!! and Bob's your Auntie Wink

Elementary · Mon Jul 18, 2005 8:25 pm

MEK is a lot easier to come by than n-propanol, iso-propanol is used in preference to n-propanol in most applications.

I don't like the idear of fucking around with nitric acid, oh and btw heating sulphur and potassium nitrate is not going to be a very tame reaction, think gunpowder !

Sulphuric acid is availble from lead acid batteries, just concentrate it by heating it till it fumes.
If you want to get really ghetto, make your sulphuric acid by burning sulphur to give you sulphur dioxide and bubble it into hydrogen peroxide.

Some of your idears aren't that simple when you come to perform them !

Elementary · Mon Jul 18, 2005 10:45 pm

I agree with your point but I have not been able to find an OTC bulk source for n-propanol except from industrial chemical suppliers, that kinda defeats the point.

The reaction conditions for the oxidation of n-propanol with conc nitric acid need very carefull control as a run away reaction would possibly result in an explosion, the hypochlorite/MEK reaction could be done in bucket fashion just the same as the ghetto prep of chloroform on rhodiums site illustrates, it's the same reaction but you are using MEK rather than acetone.

hahas · Tue Jul 19, 2005 2:08 am

the above reference explored the haloform reaction on MEK, furfuralacetone, and ethyl acetoacetate for the first time, did not say that this was optimized in any way, and is not optimized. if there was more than one experiment with MEK tried, it is not mentioned.

these days, the only OTC hypochlorite sold around here is very cheap and of 78% (min. 74%) purity, which theoretically would give 1/2 mole of Ca propionate and 1 mole of chloroform for every 550 grams. note that the experiment used an excess of ketone.

on the 25 ml scale of the reference, this can be done with 250 ml water and in a 1 L flask, and i assure you that the yields are much higher if done properly. one run takes 30 min.

it is very touchy doing it that way, though, unforgiving of deviation. as usual, much experimentation had to be done, to find the rate of addition that generated the heat necessary to distill the chloroform as it was formed, yet not foam over.

and so it can improved if one actually tries, and the HNO3 and ether were simply what the author chose to use, no solvent is necessary and H2SO4 is more sensible IMHO. i have since heard that the acid can be salted out of solution with CaCl2.

if one wanted large amounts of the acid and didn't care about the chloroform, ozone layer, etc. of course a bucket is all you need. but the chloroform is handy.

and something (reduction to the alcohol) needs to be put in between propiophenone and propenylbenzene.

Elementary · Tue Jul 19, 2005 3:29 pm

See here noodle

https://synthetikal.com/synthforum/viewtopic.php?t=1372

Elementary · Tue Jul 19, 2005 3:38 pm

Just for you noodle

1. Acidic oxidation using Potassium Permanganate

In 500 ml round-bottomed flask equipped with condenser, prepare a mixture of 5,75 ml toluene, 350 ml water and 17 g fine potassium permanganate powder. Couple of ceramic pieces should be added to even out boiling (if magnetic stirrer is unavailable). Reaction mixture is refluxed on a sand-bath for 4 hours.
When reaction is done, solution above MnO2 must be colourless. If not, discolouring may be achieved by addition of 1 ml alcohol or 0,5 g oxalic acid, while heating (this will quickly reduce excess of KMnO4).
Filter hot solution (through coffee filter) and wash solid with some hot water. Evaporate filtrate in a beaker to 50-100 ml and filter from newly formed MnO2. Wash solid with 5 ml hot water and cool combined filtrate to room temperature. Acidify filtrate with concentrated HCl, until it becomes acidic on pH-paper. This will precipitate benzoic acid. Filter and wash it with small amount of cold water, dry.
Yield is 5 g (75% from theoretical)

Benzoic acid appears as white crystals with mp of 122oC. In 100 ml of water, 0,27 g are soluble at 18oC and 5,9 g at 100oC. Also, benzoic acid has good solubility in acetone.

2. Alkaine oxidation using Potassium Permanganate

Toluene 30mL
Potassium Permanganate 10g
Dilute Sodium Hydroxide Solution 200mL

Reflux for 3-4 hours until oily toluene disapears, then cool, filter the manganese (IV) oxide and then acidify with conc hydrochloric acid, which causes the benzoic acid to precipitate. Either filter and recrystalize the benzoic acid from hot distilled water or extract the benzoic acid with ether and evapourate.

Elementary · Tue Jul 19, 2005 7:44 pm

You could always chlorinate the toluene to give you benzotrichloride and then boil it with sodium hydroxide solution to give you sodium benzoate.
Chlorine is easily to make and the only catalyst needed is UV light.

Or via benzyl chloride via Vogel's methods

Have you considered all the routes to p2p via phenylacetic acid ?

I've always kinda liked this idear

Styrene>(Peracid)>Styrene Epoxide>(Rearrangement)>Phenylacetaldehyde>(Oxidation)>Phenylacetic acid

Calcium Phenylacetate + Calcium Acetate >(Dry Distill)>P2P

loki · guinea pig

yeah i knew there was a route using the chlorine to make benzoic acid

that route is neat, elementary. there are other ways to get to phenylacetaldehyde too of course, but probably not so suited to bulk production as styrene.

ooh i just noticed something: would calcium mandelate and calcium acetate dry distill to form phenylacetyl carbinol? does this dry distillation permit substitution with longer acids, such as butyric acid, to produce an alpha-propyl beta-hydroxy phenethylamine (which could be converted to an alpha propyl cathinone)? I recall being told in highschool chem that butyric acid is found in butter... rancid butter, unfortunately (thankyou wikipedia) :/ foul smelling stuff i presume, but sounds like it must be OTC, via oxidation of milk fats.

would sodium phenolate and butyrate form phenyl-1-propanone or is the calcium salt thing compulsory for this kind of reaction?

i ask this because i've become interested in such a compound and wondered how one would go about synthesising it, at least a plain phenethylamine (as opposed to MDPEA) analogue of it (only tricky part then is where to find pyrolidine).

any ideas about whether this dry distillation/addition would adapt to tryptamines? amt anyone? indole acetic acid is easy enough to get.

Elementary · Wed Jul 20, 2005 4:01 pm

Where's noodle gone ???

Could one of the moderators, rename or delete noodle's first post in this thread please.

The dry distillation snyth of ketones is limited by the side reactions such as simple ketones and diketones being formed as well, if it is easy to seperate these then it's not a problem.

Elementary · Wed Jul 20, 2005 5:17 pm

Aldehydes And Ketones - Preparation from Acids

Pyrolysis of Metal Salts

When calcium acetate is heated strongly it undergoes decomposition to acetone and calcium carbonate:

The reaction is like the thermal decomposition of sodium acetate in the presence of sodium hydroxide to give the more stable carbonate and methane. The reaction illustrated once constituted the chief method of manufacturing acetone; the required calcium acetate, known as gray acetate of lime, was obtained from pyroligneous acid. The reation has general application for the synthesis of symmetrical ketones.

(RCOO)2Ca >heat> R2CO + CaCO3

In some instances improved results have been obtained with barium, manganese or thorium salts. Instead of preparing the salt as a dry solid prior to pyrolysis, the acid can be distilled through a heated tube packed with the metal oxide. Thus mananous oxide impregnated on pumice is employed in a catalytic process for conversion of acetic acid into acetone ;

2CH3COOH >MnO,300c> (CH3)2CO + H2O + CO2

The vapourised acid passing through the catalyst tube forms mananous carbonate, which breaks down to the oxide and carbon dioxide.

If a mixture of the calcium salts of two different acids is pyrolyzed, three reaction products are possible because each salt can decompose independantly or interact with the other one.

Such a reaction inevitably gives mixtures and is practical in the preparation of unsymmetrical ketones only when an easy method of separation is at hand. For example, methyl benzyl ketone can be obtained by dropping a mixture of phenylacetic acid and two equivalents of acetic acid through a heated tube of thorium oxide catalyst deposited on pumice. The cheaper reagent, acetic acid, is taken in excess in order to allow for formation of acetone as an easily eliminated by-product.

The other by-product is dibenzyl ketone, C6H5CH2COCH2C6H5, which has a much higher molecular weight than the desired product and is distinctly less volatile (b.p. about 200c at 21mm; methyl benzyl ketone, b.p. 110-115c at 21mm). Similarly, aldehydes can be sythesized by pyrolysis of a mixture of excess calcium formate with the salt of a higher homolog.

A ketone is formed as a by-product, but aldehydes and ketones differ sufficiently in properties to allow fairly sharp separation.

Taken from Fieser & Fieser - Organic Chemistry

Now you've got me thinking about phenylalanine and acetic acid, or am I just Kolbe dreaming again ?

TokenJ · Wed Jul 20, 2005 5:41 pm

no phenylalanine is an amino acid containing the carboxyl group COOH acetic acid also contains COOH so adding an acid to an acid does nothing or atmost rearage phenylalanine to something. I have offten thought about this because phenylalanine is so damn close to amphetamine its to funny. i have thought about using an weak base to remove OOH from COOH leaving C but apparently it doesnt work. people turn phenylalanine into an epoxide and so on.

Elementary · Wed Jul 20, 2005 5:49 pm

Primopyro once sent me an idear he had about making amphetamine via the Kolbe reaction on the hive, it makes good reading, but I can't really post it because it is not my work.

loki · guinea pig

calcium formate and phenylalinate would produce phenylalinal (the aldehyde), which would probably either reduce to phenylalinol or oxidise to phenylalanine. this would be a nice shortcut to phenylalinol if one can make it reduce rather than oxidise.

the acetate would form 2-amino 3-keto phenylbutane. if there is a way to remove formaldehyde from that one would yield amphetamine.

being able to make phenylacetylcarbinol from mandelic acid and acetic acid under these conditions seems a lot more useful. the option of using this to make longer alpha-methyl chains (such as alpha-propyl) with butyric acid sounds useful too.

also, if one has butyric acid this is a route to gbl, which would form from this reaction if butyric acid was the only acid present.

java · Consumer

Well you might consider the Dakin-West reaction( see the tread in the other stimululants) in which both eht COOH and the NH3 get acylated making an oxozolone , now the NHAc can be reduced to get the methylamine group , but the trouble lies onthe ketone made on the COOH, once its removed on has an extra carbon....there lies the problem, and pyridine can be substituded with sodium acetate , hence the starting material is cheap and the process is simple enough but at the end is the challenge...........or look at N-phenylalanine to P2p via the Strecker degradation.....java

http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/p2p.strecker.html