Efficient Synthesis of Novel N-Substituted Bulky Diphosphinoamines

Abstract

A convenient procedure for the facile preparation of electron-rich bulky diphosphinoamines from alkylamines and chlorodiphenylphosphine has been developed. The choice of solvent proved to be critical to the successful synthesis of the diphosphinoamine (PNP) products.

alkylamines - ethylene oligomerisation catalysis - solvent effects - diphoshinoamine ligands - steric hindrance

References

<A NAME="RP09307SS-1">1</A> Al-Jarallah AM. Anabtawi JA. Siddiqui MAB. Aitani AM. Al-Sa’doun AW. Catal. Today  1992,  14:  1 

<A NAME="RP09307SS-2">2</A> Keim W. Kowaldt FH. Goddard R. Krueger C. Angew. Chem., Int. Ed. Engl.  1978,  17:  466 ; Angew. Chem. 1978, 90, 493

<A NAME="RP09307SS-3A">3a</A> Wass DF. inventors; (BP Chemicals Ltd) Pat. Appl. WO  02/04119.  ; Chem. Abstr. 2001, 136, 86240

<A NAME="RP09307SS-3B">3b</A> Carter A. Cohen SA. Cooley NA. Murphy A. Scutt J. Wass DF. Chem. Commun.  2002,  858 

<A NAME="RP09307SS-3C">3c</A> Skupinska J. Chem. Rev.  1991,  91:  613 

<A NAME="RP09307SS-4A">4a</A> Bollmann A. Blann K. Dixon JT. Hess FM. Killian E. Maumela H. McGuinness DS. Morgan DH. Nevelling A. Otto S. Overett MJ. Slawin AZM. Wasserscheid P. Kuhlmann S. J. Am. Chem. Soc.  2004,  126:  14712 

<A NAME="RP09307SS-4B">4b</A> Overett MJ. Blann K. Bollmann A. Dixon JT. Haasbroek D. Killian E. Maumela H. McGuinness DS. Morgan DH. J. Am. Chem. Soc.  2005,  127:  10723 

<A NAME="RP09307SS-4C">4c</A> Blann K, Bollmann A, Neveling A, Morgan DH, Maumela H, Killian E, Hess FM, Otto S, Pepler L, Mohamed HA, and Overett MJ. inventors; [Sasol Technology (Pty) Ltd.] Pat. Appl. WO  2004/056479.  ; Chem. Abstr. 2004, 141, 89548

<A NAME="RP09307SS-4D">4d</A> Blann K, Bollmann A, Neveling A, Morgan DH, Maumela H, Killian E, Hess FM, Otto S, Pepler L, Mohamed HA, and Overett MJ. inventors; [Sasol Technology (Pty) Ltd.], Pat. Appl. WO  2004/056477.  ; Chem. Abstr. 2004, 141, 89536

<A NAME="RP09307SS-4E">4e</A> Blann K. Bollmann A. Dixon JT. Hess FM. Killian E. Maumela H. Morgan DH. Neveling A. Otto S. Overett MJ. Chem. Commun.  2005,  620 

<A NAME="RP09307SS-4F">4f</A> Overett MJ. Blann K. Bollmann A. Dixon JT. Hess FM. Killian E. Maumela H. Morgan DH. Neveling A. Otto S. Chem. Commun.  2005,  622 

<A NAME="RP09307SS-4G">4g</A> Walsh R. Morgan DH. Bollmann A. Dixon JT. App. Catal. A: Gen.  2006,  306:  184 

<A NAME="RP09307SS-4H">4h</A> Kuhlmann S. Dixon JT. Haumann M. Morgan DH. Ofili J. Spuhl O. Taccardi N. Wasserscheid P. Adv. Synth. Catal.  2006,  348:  1200 

<A NAME="RP09307SS-5">5</A> An excellent general overview is provided by: Vogt D. In Applied Homogeneous Catalysis with Organometallic Compounds   Vol. 1:  Cornils B. Herrmann WA. Wiley-VCH; New York: 2002.  p.240 

<A NAME="RP09307SS-6A">6a</A> Blann K. Bollmann A. de Bod H. Dixon JT. Killian E. Klaas P. Maumela MC. Maumela H. McConnell AE. Morgan DH. Overett MJ. Prétorius M. Kuhlmann S. Wasserscheid P. J. Catal.  2007,  249:  242 

<A NAME="RP09307SS-6B">6b</A> Kuhlmann S. Blann K. Bollmann A. Dixon JT. Killian E. Maumela MC. Maumela H. Morgan DH. Prétorius M. Taccardi N. Wasserscheid P. J. Catal.  2007,  245:  277 

<A NAME="RP09307SS-6C">6c</A> Killian E. Blann K. Bollmann A. Dixon JT. Kuhlmann S. Maumela MC. Maumela H. Morgan DH. Nongodlwana P. Overett MJ. Pretorius M. Höfener K. Wasserscheid P. J. Mol. Catal. A: Chem.  2007,  270:  214 

<A NAME="RP09307SS-7A">7a</A> Appleby T. Woollins DJ. Coord. Chem. Rev.  2002,  235:  121 

<A NAME="RP09307SS-7B">7b</A> Balakrishna MS. Sreenivasa Reddy V. Krishnamurthy SS. Nixon JF. Burckett St. Laurent JCTR. Coord. Chem. Rev.  1994,  129:  1 

<A NAME="RP09307SS-7C">7c</A> Dyson PJ. Coord. Chem. Rev.  2005,  2056 

<A NAME="RP09307SS-7D">7d</A> Woollins DJ. Polyhedron  1995,  14:  3367 

<A NAME="RP09307SS-7E">7e</A> Balakrishna MS. Prakasha TK. Krishnamurthy SS. Siriwardane U. Hosmane NS. J. Organomet. Chem.  1990,  203 

<A NAME="RP09307SS-7F">7f</A> Ewart G. Lane P. McKenzie JC. Payne DS. J. Chem. Soc.  1964,  1543 

<A NAME="RP09307SS-7G">7g</A> Cross RJ. Green TH. Keat R. J. Chem. Soc.  1976,  1425 

<A NAME="RP09307SS-7H">7h</A> Gaw KG. Smith MB. Slawin MZ. New J. Chem.  2000,  24:  429 

<A NAME="RP09307SS-7I">7i</A> Elowe PR. McCann C. Pringle PG. Spitzmesser SK. Bercaw JE. Organometallics  2006,  25:  5255 

<A NAME="RP09307SS-7J">7j</A> Gaw KG. Smith MB. Steed JW. J. Organomet. Chem.  2002,  664:  294 

<A NAME="RP09307SS-7K">7k</A> Schmidbaur H. Lauteschlager S. Kohler FH. J. Organomet. Chem.  1984,  271:  1 

<A NAME="RP09307SS-8">8</A> Foss VL. Veits YuA. Chernykh TE. Lutsenko IF. Zh. Obshch. Khim.  1984,  54:  2670 ; Chem. Abstr. 1985, 103, 37537

<A NAME="RP09307SS-9">9</A>

¹H NMR (CDCl₃): δ = 1.35 (s, 9 H, t-C₄H₉), 2.10 (d, J = 11.6 Hz, 1 H, NH), 7.27-7.36 (m, 6 H, ArH), 7.40-7.45 (m, 4 H, ArH).

<A NAME="RP09307SS-10">10</A> Fei Z. Scopelliti R. Dyson PJ. J. Chem. Soc., Dalton Trans.  2003,  2772 

<A NAME="RP09307SS-11">11</A> Biricik N. Fei Z. Scopelliti R. Dyson PJ. Helv. Chim. Acta  2003,  86:  3281 

<A NAME="RP09307SS-12">12</A>

N,N-Bis(diisopropylphosphanyl)ethylamine: ³¹P NMR (162 MHz, CDCl₃): δ = 83.9 (s).