P2P

[Mastermind]

Anyone ever see one of these bottles.

[Mastermind]

It really helped FOAF develop his skills with this type of chemistry.  FOAFOAF got three bottles for him around 20 years ago.  More pics to come (ie. chems used to make p2p, etc.).  Stay tuned.  Lots of tips, too.

[Rhodium]

Wonderful! I want one of those, I want one of those! (empty is all right).

http://rhodium.lycaeum.org

[Mastermind]

Here's some more pics.  Ten bottles of benzyl chloride and 5 lbs of NaCN.  FOAF had 5 lbs of PAA at one time but all he has left is an IR spectrum.  FOAF'll get the references together and tell what he thinks is the best processes (that he tried).

[obituary]

swim has access to a broader range or a little more common chemicals of less proportions and is very envious.  esp. the phenyl compouns, the BzCl is nice too esp in that quantity- all swim has to say is damn your good luck
good lunch

[Mastermind]

I've been busy and couldn't get back sooner.  So maybe I'll post a little at a time (looks like I'm on a roll here so I'll keep going; edited 3 hrs later).  FOAF discovered after much experience with the acetic anhydride process and the Thoria tube furnace reaction (Organic Synthesis Vol 2 pages 389-391) that the magnesia tube furnace he developed on his first try was the holy grail of P2P, in his opinion (assuming you have PAA).  This was discussed by someone using the username OTC on the old Hive board (talking to oilman and I think CHEMMAN; others seem to know about the tube furmace,too).  The rest of the references are:

Vogels mentioned here a lot, and
US patents:
2108156
2612524
2697729
2811559
3075016
3660491
4172097
4754074
5750795

You can download these patents from

http://www.micropat.com

Patents issued in 1976 and later can be viewed at the IBM (I think) and USPTO web sites.

[Mastermind]

The magnesia catalyst was made using pea sized pumice (some patents were seen supporting similar catalytic materials using perlite for cracking petroleum hydrocarbons; other art).  Enough pea sized pumice to fill FOAF's combustion (now catalyst) tube was covered with enough Milk of Magnesia so that the pumice 'had looked like it had been white washed' (good description) and at the same time the pores were not clogged (for maximum catalytic surface area).  A 98% silica combustion tube was used which was wrapped with a heating tape (max temp 800 degrees C) and was covered with glass wool as insulation.  2-3 teaspoons of calamine lotion (ZnO and Fe oxide; see US patent 5750795, for example, especially tables 1 and 2) was added to the catalyst and it was heated, alternately, on a gas stove and in a microwave oven to dry it and convert it to MgO.  It was found that when the catalyst was placed in the tube and heated to about 500+ degrees C (with air pumped through it) that the Mg(OH)2 could more easily be dehydrated (H2O given off and condensed) and converted to MgO.

*Note: add calamine lotion before putting in combustion tube (maybe a little sloppy here, have to read over it some more, questions must be in chemical language as formally taught in college, nothing else will be understood (I did get a couple private messages))

[Mastermind]

A mixture of PAA and acetic acid was passed through the tube at around 400-450 C (see the Organic Synthesis article for setup of the apparatus; heating tape used in place of the electric furnace).  An aqueous layer and organic layer was obtained (smelled sweet like P2P and maybe a little like burnt rubber, too).  The next night some Mn carbonate (see Vogels, etc) was added to the rest (last half) of the PAA and acetic acid, as well as some being placed in the tube (no effervesence was seen from the Mn carbonate; see also US patent 4754074 which uses decomposable Mn salts, such as the acetate).  The process was continued and it was found that after the addition of the Mn carbonate that the product smelled a lot sweeter like pure P2P (see bottle above).  The organic layer was washed with NaHCO3 solution, centrifuged using an old centrifuge bought for $18 in an antique store to seperate the emulsion, distilled at atmospheric pressure to check its boiling range (good range) and reacted with formamide in the Leukart reation to get the amine in good yield.  The aqueous layers mentioned above should be extracted with solvent to recover more ketone.

[Mastermind]

Its well known that phenylacetonitrile (refered to here as PAN) can be made from benzyl chloride (BzCl) and NaCN.  FOAF found that when trying to distill PAN under a vacuum according the Organic Synthesis article (another article on PAN from BzCl and NaCN) it bumped so badly that it was almost impossible to do, even using a distilling column and claisen adapter.  The use of a capillary tube leading into the distilling flask was not tried.  Later, FOAF realized he could probably distill it at atmospheric pressure and tried it.  It worked very well and the PAN distilled in a narrow 10-12 degree range without bumping (most of it distilled at around 208 C, I think, which is its boiling point, ie. at least 95% distilled at this temperature.  It was found that if a clear distillate is obtained (smells something like BzCl except less pungent and more cinnamon-like) and hydrolyzed with dilute H2SO4 according to another Organic Synthesis article that the resulting PAA comes out off white or yellow and can be used in the tube furnace without purifying it by vacuum distillation.

[Mastermind]

Now getting to the PAA.  As is known it melts at about 77 C.  The Organic Synthesis article that describes its synthesis from PAN includes vacuum distillation in its purification.  FOAF found this to be impractical since it seems to boil at such a high temperature, as well as the fact that the constant sound of his vacuum pump drives him nuts sometimes.  So he decided that going with freshly distilled (at 1 atm) PAN for making PAA is the best way, and not distilling the PAA for use in the tube furnace.

[Mastermind]

Also, for some reason, FOAF found that when he tried to hydrolyze the PAN with dilute H2SO4 (according to Organic Synthesis) for some reason it would not solidify when cooled (mp of PAA is 77 C).  He thought about this, visualized the triple bond between the C and N and decided to try adding HCl.  It worked.  The organic layer above the aqueous layer solidified when cooled.  Later, FOAF read in a chemistry book in the library that HCl works better when hydrolyzing nitriles compared to H2SO4.

[Mastermind]

Conclusions:  After years of experimentation FOAF finally decided that maybe it is true that some of the most respected publications in chemistry don't necessarily have the best syntheses. 
For example, he found that the magnesia tube furnace (it is patented, by the way) is superior to both the acetic anhydride process and the thoria tube furnace reaction in Organic Synthesis.  Also, distilling PAN at atm P is better than distilling under a vacuum and using HCl is better than H2SO4 when hydrolyzing PAN.  The Organic Synthesis article also mentions in the notes the use of a mixture of acetic acid and I think HCl and H2SO4, for small scale production, which gives a yield of  about 100%.  My xerox copies are a mess.

[Mastermind]

FOAF developed these techniques for 15+ years without the knowledge of the I2/RP process discussed here (other forums) and was surprised when he found out about the extensive use of pfed.  The experience gained here might be best applied to other analogs or if the precursors are easily available or if pfed becomes restricted, the techniques described here could be used.

[Mastermind]

The process(es) described above is/are probably the most well known or "industrial" process(es).  It definitely facilitates large scale production.

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posts made possible by phenethylamines
everything in moderation

[oilman]

Well mastermind,I'm fuckin astonished at the info that you have presented.I too have all available chems to dream this method and I can say that the route that you prescribe is the exact same route which I researched years ago before there was such a thing as the hive.I am currently dreamin the seudo way and plan on dustin the ol' bottles from the shelf to go the tube furnac route.Your thread here is of great value to me ,especially since I have 200l of benzyl chloride available(yes thats right!!).Thanks for the insight to my future dreams
Oilman
I take my hat off to ya !!

[Osmium]

I think this post should be moved to the chemistry or serious chemistry forum.
Please give a more detailed writeup. I'm sure Rhodium will post it at his site.
This really needs more discussion (which it will not get here in the newbee board).

[Mastermind]

Another thing I should mention is to keep a bucket of ice water around when making PAN from BzCl and NaCN.  The reaction is exothermic but not as bad as the Grignard reaction.  If it starts heating up too much by itself stop stirring and put the reaction flask in the bucket of ice water just like you would do to control a Grignard reaction.  The reaction slows down a lot after about 3 hours.  Its best to stir it for about 8 hrs, too, to make sure the reaction is complete.

[oilman]

The conversion of benzyl chloride to benzyl cyanide was quite a simple process for me except that it should be done with extereme care(fume cupboard!!,gloves etc).I have about a pound of NaCN left so I intend on doin the conversion in time.I have been an advocate of the tube furnace since I realised this method but it doesn't seem to catch on to well.By the way my first experience with NaCN kinda had me staggering out of the room with numbness creeping up to me and bloodshot eyes,quite an experience I will never forget!!
I also have crude PAN stored in a container(kept in the dark).Would you know the shelf life of this product.
Also do you have experience in Grignard to PAA??

Oilman

[Mastermind]

OK, Osmium.  I'll look into doing that.  It might be a little tricky writing up the process without a drawing of the apparatus, though.  If you look at both the Organic Synthesis article and in Vogels you'll notice that they both have drawings of tube furnaces.  This seems to be necessary since it isn't a commonly used setup.  I found one thing on Rhodium's site that has a drawing; the aspirator pump.  If a drawing isn't possible, then I'll have to think about how to describe the apparatus and how it's setup as well as the process.

I was just at the library today to check the volume numbers.  The three Organic Synthesis articles refered to here are:

Benzyl Cyanide, Organic Synthesis Collective vol. I pg. 107-109 (from benzyl chloride and sodium cyanide)

Phenyl Acetic Acid, Organic Synthesis Collective vol. I pg. 436-438 (by hydrolysis of benzyl cyanide)

Methyl Benzyl Ketone, Organic Synthesis Collective vol. II pg 389-391 (from phenyl acetic acid and acetic acid using the tube furnace method with thoria catalyst on pea sized pumice)

Note:  Benzyl cyanide is also known as phenylacetonitrile (the nitrile theoretically from phenyl acetic acid) and methyl benzyl ketone is also known as phenyl-2-propanone (P2P) or phenyl acetone.

[Mastermind]

Oilman, I sent you a private message.  Some more tips I can think of are the need for glasswool and a buchner funnel when filtering out the NaCl when making PAN (benzyl cyanide).  Filter paper tends to clog up. Also I recommend weighing out the NaCN in a large oil pan that will hold the NaCN bottle and scale and then add the NaCN to the flask in the oil pan.  The oil pan should catch anything that falls (NaCN gives off HCN when exposed to H2O and CO2). I found, also, If you do everything in front of a window fan you can keep fumes down to a minimum.  After the apparatus is set up, a length of rubber tubing can be connected to it using an adapter or a one hole rubber stopper and glass tubing(ie. top of condenser in a reflux system) and the rubber tubing can be led through the window to the outside.  The speed of some window fans can be controlled (ie. variac or motor speed control) which allows you to slow them down to keep the noise down (do this after the reflux or distillation apparatus is set up).