Megatherium (Hive Bee)
02-12-03 20:02
No 407115
      1-phenyl-1-propenyl-3-amine synth, proc needed  Bookmark   

Dear bees,

I need a synthesis for 1-phenyl-1-propenyl-3-amine ( Ph-CH=CH-CH2-NH2).  Ideas of synthetic scemes are wellcome, and even better: lab procedures would be VERY appreciated.

Thanks smile
 
 
 
 
    Rhodium
(Chief Bee)
02-13-03 00:59
No 407207
      trans-cinnamylamine  Bookmark   

The compound you are looking for is 3-phenyl-allylamine, or trans-cinnamylamine.
Chemical data: bp 71-74C/1mmHg, 84-87C/1.8mmHg. HCl salt mp 246-250C (Experientia; 21; 1965; 506.), HCl salt mp 235-236C (Chem.Abs. 64; 9635d; 1966.)

There are a lot of synthetic methods for it, and to be able to provide you with a good experimental, you'll have to say how many steps you are willing to perform. Let me know which route you'd like to have more detailed.

The immediate precursors for trans-cinnamylamine include the following:

N-trans-cinnamyl-phthalimide (Hydrazine hydrate/MeOH reflux, JACS 77; 1955; 3262. or J.Org.Chem.; 57; 7; 1992; 2105-2114.)
trans-cinnamaldehyde-(E)-oxime (LAH/Ether reflux, JACS 74; 1952; 5185.)
N-trans-cinnamyl-azide (FeCl3/Zn/EtOH @ RT, Synthesis 1978; 24-26. - Fe/NiCl2/THF @ 0C, Tet Lett. 37; 26; 1996; 4559-4560. - SnCl2/MeOH @ RT, Tet Lett. 27; 13; 1986; 1423-1424.)
3-phenyl-acrylonitrile (LAH/AlCl3/Ether @ RT, JMC 35; 6; 1992; 1042-1049.)

N-trans-cinnamyl-phthalimide can in turn be made from potassium phtalimide and 3-chloro-allylbenzene (Ber.; 26; 1893; 1860.) or 3-bromo-propenylbenzene (J.Pharm.Sci. 72; 11; 1983; 1344-1347.). The latter can for example be had from propenylbenzene/CCl4/NBS (Ann. Chem.; 551; 1942; 115.) or by brominating cinnamic alcohol (which can be bought or synthesized in a myriad of ways. The oxime above is of course made from trans-cinnamaldehyde and the azide is made from any of the 3-halo-propenylbenzenes.
 
 
 
 
    Megatherium
(Hive Bee)
02-13-03 01:30
No 407224
      Thank you Rhodium for these references.  Bookmark   

Thank you Rhodium for these references.  Wow, this really helps alot.  Since I can access almost all the refs, I 'll check those out in the library.

You just made my day smile.

I like the trans-cinnamaldehyde-(E)-oxime  route the most.  I wonder, is cinnamaldehyde a 'suspicious' chemical?  In Vogel, 5 th ed, p 1036 - 1041, there is a nice piece of text about the Perkin and Doeber reactions to make the cinnamic acid.
 
 
 
 
    Rhodium
(Chief Bee)
02-13-03 02:21
No 407244
      N-cinnamyl-4-piperidone?  Bookmark   

It is hardly suspicious. The only suspicious use I can think of for it would be the practically never used transformation to allylbenzene: ../rhodium/chemistry /cinnamaldehyde.html

Please tell, what do you want the amine for? N-cinnamyl-4-piperidone?
 
 
 
 
    Megatherium
(Hive Bee)
02-13-03 02:41
No 407249
      Well, my goal is the synthesis of a ...  Bookmark   

Well, my goal is the synthesis of a phenoperidine analogue, where the Ph-CHOH-CH2-CH2- group is replaced by a 2-thienyl-CH=CH-CH2- group.

According to Dorvault, L 'officine, 23 th ed., p 1263: phenoperidine = 25 - 50 x morphine in humans.

No piperidone will be needed: Post 404354 (Megatherium: "1-(2-phenethyl)-4-phenyl-4-acetoxypiperidine synth", Chemistry Discourse)