Natural Science Forum / Chemistry / Organic Synthesis / January 2004

You may have problems with conjugate addition - and will certainly
have problems with the extra mole of acrylic acid.  You might do
better by polymerizing the acid chloride (anhydride) and then reacting
the dissolved polymer (absolutely anhydrous!) with the aniline to make
the anilides (aniic acids, then anililimides under forcing dehydrative
conditions).

For the monomer, I'd take pyridine or triethylamine in anhydrous ether
plus the acryloyl chloride, and slowly add the aniline with cooling as
needed.

I am sorry to tell you that puting acryloyl on anilines is not going
to be easy, because of the conjugate addition problem and because of
poor stability of the products. As mentioned by Al.

First, make sure that your acrylate starting material is pure (as
opposed old and partly polymerised) and that you have added inhibitors
of polymerisation, like BHT or hydroquinone. Keep your products from
light and air, store them in fridge. Add extra inhibitors if needed.
Second, tell your professor that you do not want to use poorly rective
anilines (like p-nitroaniline) and that you would much prefer to work
with the reactive ones, like p-methoxyaniline.

Then,

A)If you can buy a good-quality isocyanate, you can try a reaction of
anhydrous acrylic acid with aryl isocyanate in a presence of a trace
(catalytic ammount) of a weak base, like pyridine. (CO2 evolution.
Isocyanates have tear-gas like properties.)

B)You can also try to buy or make acrylic acid activated ester with
N-hydroxysuccinimide
(acrylic acid + DCC + hydroxysuccinimide in anh. acetonitrile at room
temp, after few hours remove the urea-sideproduct by filtration)
and use this activated ester to put acryloyl on anilines at 0C in
aqueous THF or acetonitrile with some KHCO3 as a base.

C)If that does not work, you can use 3-chloropropionyl chloride as
acylating agent, isolate the chloropropionyl anilide and then
eliminate HCl by heating it with DABCO.

(By the way, can you make the analogous vinylsulfonanilide instead?
The  elimination of 2-chloroethylsulfonates is spontaneous, and if you
use 2-chloroethylsulfonyl chloride in 2,6-collidine at 0C, you get
vinylsulfonanilides right away, without necessity to perform
additional elimination step)

(Also, Beata - are you beautiful? It is Friday night and I feel very
lonely!)