smjp1

place syntheses below



Jule: This has a really nice use of he willsmeier Haak reaction and the wittig reaction. Some of the coupling reactions appear to be transition metal mediated reactions that I am not familiar with. Could you please supply a literature reference? thanks, Bruce Bondurant



The Synthesis of 2,5-bis(4-(diphenylamino)styryl)benzene-1,4-dinitrile Step 1: Cross coupling of phenyl azide (PhN3) with phenylboromic acid via N-arylation promoted by copper. The product formed is diphenylamine. Step 2: Nitration of diphenylamine to protect para positions for further synthesis Step 3: Equal parts of diphenylamine and iodobenzene are stirred and boiled together with nitrobenzene, potassium carbonate and copper powder to produce triphenylamine. Step 4: Addition of POCl3 & DMF forms aldehyde in order to use it for Wittig reaction to form an alkene Step 5: Formation of amide from 2,5-dimethyl-1,4-benzene dicarboxylic acid (formation of acid chloride as intermediate) Step 6: Converting amide to nitrile by POCl3 Step 7: Bromination. N-bromosuccinimide is used to add Br to benzylic position Step 8: Wittig reaction: preparation of ylide Step 9: Reaction of ylide with aldehyde gives a final product but with nitro groups attached that need to be removed Step 10: Removal of NO2 by Fe, HCl and KOH Step 11: Formation of diazonium group that can be removed by H3PO2, which leads to final desired product - __2,5-bis(4-(diphenylamino)styryl)benzene-1,4-dinitrile__

References:

1. Organic synthesis website: []

 2. B.V. Subba Reddy, N. Sivasankar Reddy, Y. Jayasudhan Reddy, Y. Vikram Reddy, Indium/Cu(II)-mediated one-pot synthesis of unsymmetrical diaryl amines from aryl boronic acids and azides, Tetrahedron Letters, Volume 52, Issue 20, 18 May 2011, Pages 2547-2549, ISSN 0040-4039, DOI: 10.1016/j.tetlet.2011.03.022. (http://www.sciencedirect.com/science/article/B6THS-52DC0P6-1/2/ec6a9008bb8d614a04e1f48a4beea0fa) 3. Wade L.G. Organic Chemistry, p.827, 834-837, 906.

Dr.Bondurant, I have changed the reaction for diphenylamine formation. But here is the reference to the previous reaction if you want to take a look at it:

J.S. Yadav, B.V. Subba Reddy, Prashant Borkar, P. Janardhan Reddy, Addition of aryl cuprates to azides: a novel approach for the synthesis of unsymmetrical diaryl amines, Tetrahedron Letters, Volume 50, Issue 48, 2 December 2009, Pages 6642-6645, ISSN 0040-4039, DOI: 10.1016/j.tetlet.2009.09.056. (http://www.sciencedirect.com/science/article/B6THS-4X7GMBP-1/2/866e92f4204df5097297df1878dedd27)