[Seanlet]

I've been pondering how to make N-cyanoamines ofr primary amines. BrCN works, but I don't like working with it. I read some 1912-1914 papers in which a halide & sodium cyanamide formed said N-cyanoamine & the sodium salt of the amine.

Has anybody got alternatives, hopefully not using the dreaded (but high-yielding) BrCN. The few hits I get in Reaxys use the disodium or calcium cyanamide on a halide, but I don't see how that balances.

With thanks,
Seanlet

[Dan]

I've been pondering how to make N-cyanoamines ofr primary amines. BrCN works, but I don't like working with it. I read some 1912-1914 papers in which a halide & sodium cyanamide formed said N-cyanoamine & the sodium salt of the amine.

You're talking about two different disconnections here:

You can either form the N-CN bond by cyanation of an amine, or you can form the R-N bond by alkylation of cyanamide.

Has anybody got alternatives, hopefully not using the dreaded (but high-yielding) BrCN.

I think you can make it in situ with NBS + NaCN. That will limit your exposure to BrCN - NaCN is still very toxic of course, but easier to handle than cyanogen bromide.

The few hits I get in Reaxys use the disodium or calcium cyanamide on a halide, but I don't see how that balances.

It's just an S_N2 reaction. This disconnection is going to be the least hazardous as you avoid reagents that easily liberate cyanide.

[Seanlet]

Hi,
    Actually, I have to make the amine from a -Br so is NaHNCN a route for makng -NHCN? Sorry I wasn't clear.

[408]

I have used cyanogen bromide on scales up to 10 g more times than I can count.  Weigh it in a fume hood and you are fine.

[Dan]

If you're going to be making the alkyl bromides anyway, it would make sense to try the cyanamide alkylation strategy first.