Okay, what's up with this? I have had several people vehemently insist that heat in the Hoffman is what is killing the yield. I've also had several people vehemently insist that you must have heat to effect the rearrangement. I have no idea, as I am but a lowly uneducated hick who does what smart people do and hope I have the same or atleast favorable results.

What some guys on Mattlock did
20gms of amide were placed in 250ml of -2C bleach and stirred until a uniform consistency was achieved. This was stirred in an ice/acetone bath for about 2 hours as the idiot doing it forgot all about the lye. Finally a solution of 200ml of water and 20gms of lye were added. The ice bath was replenished as needed for 24 hours to maintain 0-2C and stirring set as high as it could go without slinging the stir bar loose. The progression of colors in this reaction has thus far been very consistent, being loosely tied to temperature and time. As expected the color never changed during it's time in the ice, it never does. Usually upon hitting room temperature it will get white, then brown/tan and with heat it will go into darker brown and finally to red. None of this happened. Upon letting the solution warm up to room temperature on it's on it stayed the exact same color. After 18 hours or so it turned yellow and a brown precipitate began to show. After another full 24 hours (three days from start to finish) heat was added to bring it up to 60-63C and was held there for 30 minutes. After the 30 minutes it was allowed to cool on it's on. Then the yellow liquid was decanted off of the waxy brown chunk in the bottom of the flask. 150-200ml of fresh xylene were added to the solid and it was stirred vigorously for an hour. The resultant xylene was filtered and washed with HCl water as usual.

Now, what's weird.

6.18gms of unreacted amide were recovered, this has never happened. That means only 13.82gms of the amide participated in the reaction. The recovered amide was as white as the day it was born, and apparently unaltered. Sparkly, soft and white (like Sedit's girlfriend)
The xylene then shat out 4.3gms of amine for a total yield of 31.11%

I'm inclined to believe that the heat is definitely an issue, especially considering that blahblahblah's monkey is obviously a pro and he didn't use heat. I have also came to another conclusion, to hell with bleach. TCICA to get the chloramide before hand from now on.

One person in particular who has chose to not join this conversation, so I'm not sayin' names, claims steady 70% yields using no heat over two days sometimes more.

What else can I say?

There it is.

ETA: as for yieid calculation- at the end of the day I got 6.18gms of amide back, so......

Edit2: Dnigbow, I have less than zero interest in a pissing contest. If you get better yields in 6 hours, then I commend you, well done. I am an experimenter, plain and simple. I change things and note what happens. You won't see people posting write ups about the 'cold method' because it's anti to the info in the patent. Heat is generally just an accelerant for a reaction, not always, but usually. I've said numerous times that I don't understand the mechanism here, what do you want me to say to justify my not using heat? The people who have taken me under their wing are not people who blow these boards up and participate in these conversations, therefore I won't be saying so and so told me this or that. If you'd like me to keep my results to myself you can always ignore me. But, I'm hoping someone sees something in my procedure and makes a connection of some sort and says 'AHA, the XXX, that seems to be using a greater percentage of your amide and shitting out what it doesn't use" I dunno, this is fun to me, 4.3 grams of amine is more than I need for a year, so I don't give two fucks. I'm here to figure out a mystery, now where's my dog?

It was passed on in private by more than one person and I have gotten the overwhelming impression that's how it should stay. I don't know why, but that's what I take away from it.

I think mostly anything that is gonna spoonfeed people these guys don't want it on their boards. I'm just guessing, but there again, that's my take away. I think talking about how the mechanism can run better cold would be okay.

I usually get some nasty looking shit too, but one wash in acetone usually brightens it up quite a bit. What's weird about that last time when it gave back all the unreacted amide, the amine that came out was WHITE AS FUCK. This pic is as it came out, no wash.

thanks for the fries that's what i been saying for a long time.
that method seems to yeild no better than say 70-80 c.

Run it cold over night. Work up is a bitch. So thats why heat was added. But it is not needed. 50+ % w/ consistent and thorough work up. Off white, a tone wash brings out the white.

Thanks fries, appreciate the write up. I might try and mish mash your method with mine, say run it in a bottle in the fridge with shaking overnight then heat it as per the 'usual' method.

Im going to try the TCCA method first though, should be done in a few days. If that works out, it could turn out better then the 'cold' or 'hot' method. Hopefully it works, I need more amine to try the monomethylation again...

that method seems to yeild no better than say 70-80 c.

Yeah i know that, but its pretty simple and doesn't need any fancy schmancy stuff like decadent hot plates and thermometers

I don't find workup difficult, my only sep funnel is 100ml, so i'm separating layers more manually from beaker to beaker... just clean the result as i mentioned.

I'd love to know what Waz is doing right to get those 50% + w/w yields... running 200g batches or something?

No I meant did you TLC your aldehyde as soon as you received it, to obtain its original purity for comparison to the aged sample? Or did you purify it then store it?

Alice just ran the TCCA method for prep of N-Chloroamides:

-Fully dissolved 10g amide into 100ml MeOH (took tiny bit of heat to speed things up)
-Added 4.1g TCCA, stirred for an hour (some evolution of heat occurred)
-Solid precipitate formed fairly quickly after addition of TCCA, assuming this precipitate is CYA
-CYA filtered
-Instead of boiling off solvent (pita to setup and timely) to obtain N-Chloroamide solid, I precipitated it by addition of H20, seemed to work great.

Few things work mentioning, my TCCA was a solid block that had copper sulfate mixed in. This was removed by powdering the block and stirring in H20, which dissolved the copper sulfate, then filtered and dried it as much as I could be bothered. MeOH was not dried. The final product obtained is a very clean white powder with no smell what so ever. Currently drying, so when thats done I will post yield.

I'll get a MP test for this substance too. Im pretty excited to see how this stuff goes in the rearrangement.