like to know if somebody did the "one pot shot from isosafrol to mdma"
 

To clarify, he's referring to Drone's Photoamination which is detailed at my page.

I don't think anyone has because most bees are weary of DCB and it's purchase and handling.  A long time ago there was a lot of discussion on this matter. 

There was some discussion on the production of para-DiCyanoBenzene from OTC mothballs (para-DiChloroBenzene) and NaCN.  The acetonitrile as a solvent was debated as necessary, but I'm not sure if there could be a substitute.  You definitely wouldn't want to have any alcohol or water persent in this reaction because they would add to the alkene. 

This post is for informational purposes only an is not intended to facilitate illegal activity.

Here is a page with a HUGE amount of photoamination references for styrene derivatives:

http://www.crc.miyazaki-u.ac.jp/y1ken/pac.html

This can definatly be done. I have a collection of ref's on this particular subject. 1-Aryl-1-Propene's have been directly aminated with NH₃ in MeCN with p-DCB using a mercury vapour lamp in very high yield. p-DCB can be obtained fairly easily, and is relativly inexpensive.

While this process looks very attractive from a process standpoint, for the average experimentier, peracid -> Ketone then reductive amination with Sodium Triacetoxyborohydride is probably still the easiest route.

Why is the NaBH(OAc)3 reduction easier than the NaBH4 reduction in your opinion? It has far less atom economy, and is thus more expensive.

Why is the NaBH(OAc)3 reduction easier than the NaBH4 reduction in your opinion?
I think because he is talking about preparing the amphetamine, not the methamphetamine thus necessitating the use of a large excess of ammonium acetate and a slightly acidic environment. It seems that he is suggesting using triacetoxyborohydride as a substitue for cyanoborohydride.

Triacetoxy is the shit

Ever consider bubbling ammonia into methanol, forming the imine with a catalytic amount of acid, and then reducing with NaBH4? 

This gets around all of the normal imine formation issues that one must deal with when using NH3-acetate or NH3-HCl.

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something for your mind.......

Catalitic amount of acid?

Use at least enough AcOH to get your soln to pH 4.5 IMO or the imine aint forming at all
ammonia sucks as a nucleophile and usu needs 5-6 eq but it is basic as all get out and Mr Schiff-Base likes 4.5

Nope. Reductive amination via hydrogenation works well without added acid, even with NH3.

That is fine and all

but he is not proposing to do catalytic hydrogenation here is he?

and to some extent, the product may animate better than the ammonia, reacting with the ketone to produce not good things,
although if you swamp it, it should be OK

Generally, I have found it advantageous to hydrogenate catalytically with some acid (AcOH or HCl) around
to get cleaner reactions, especially for ze production of anilines from nitro's, as the free amines can blackify and it is shitty thereby, and/or your compound can glom onto the cat somewhat unless acid is there

I see it as an equilibrium thing, what is the most favorable conditions for forming the imine

b/c, NaBH₄ can reduce the ketone to the alcohol
pretty rapidly

Besides, Triacetoxy is the shit

> That is fine and all
>
> but he is not proposing to do catalytic hydrogenation here is he?

The intermediate is the same.

Sorry, I got my info from someone who should know more than me but in this case he didn't know what the FUCK he was talking about.

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something for your mind.......

Does p-DCB have any OTC uses.  Dcm Is not an alcohol or water would it be a suitable substitute for acetonitrile.  This could be a very attractive way to TMA-2.

p-Dichlorobenzene is used OTC in mothballs. p-Dicyanobenzene has no OTC uses. You can not substitute acetonitrile for alcohol or water here, perhaps if you are lucky DMSO or DMF would work, but before you try any changes to the method, DO try it out as it is written.

This should be golden rule number one:

When attempting an untried synthesis for the first time, follow the original directions to the letter. If it works, then try to change the procedure if you have the desire to do so, one parameter at the time.

Would photoamination work the same with alpha-methylstyrene? Or would the alpha-MS need isomerizing first? I'm unclear about the different depiction of the double bonds when I look at these two molecules.

Have you read this ref. from Tett.Lett. 42 (2001) 2505–2508. I have it as a .pdf file if anyone is interested.
Photoinduced electron transfer oxidation of a-methylstyrene with
molecular oxygen sensitized by dimethoxybenzenes: a non-singlet-oxygen mechanism
Tadashi Mori,a,* Makoto Takamoto,

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Linoleum: the 13th element!  Now available at all good DIY stores... & Walmart.

alpha-methylstyrene would not produce the desired result - you would get the wrong isomeric phenylpropylamine.

Uhhh, while looking around for information on p-DCB, I found this link, in japanese, looks interesting to me, but I don't know what it really means...

Can anyone here translate the top characters? Looks like names to me...

But the ref list is pretty extensive.

EDIT: Forgot to include the link, sheesh:

http://www.crc.miyazaki-u.ac.jp/y1ken/pac.html

                                                   PrimoPyro

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Vivent Longtemps la Ruche!

Post 12408

(CHEM_GUY: "photo-amination help...", Novel Discourse) states that no water should be present, or it will add to the alkene as well, yet the very procedure calls for a 9:1 ratio of MeCN to H2O?

What is correct?

                                                   PrimoPyro

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Vivent Longtemps la Ruche!