Abstract
The peraza analogue of polyether cryptand [2.2.2], 1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane, has been synthesized in 70% yield via a two-step one-pot procedure by the condensation of tris(2-aminoethyl)amine (tren) with glyoxal in isopropanol at -78 °C followed by reduction of the intermediate with Na/liquid NH3 . This preparation is significantly faster, simpler, and higher yielding than the previously reported two-step procedure, with its lengthy isolation process and 45% overall yield.
Key words
macropolycyclic - polyamine - complexant - imines - sodium
References 1 IUPAC name of 1 : 1,4,7,10,13,16,21,24-octaaza-bicyclo[8.8.8]hexacosane.
2 Organic-based alkalides and electrides are crystalline salts in which the cation is encapsulated by one or more saturated complexants (e.g. cryptands, crown ethers, or aza-crowns); the negative partner is an alkali metal anion (Na- to Cs- ) or a trapped electron.
3a Wagner MJ.
Dye JL.
Comprehensive Supramolecular Chemistry
Vol. 1:
Elsevier;
Oxford:
1996.
p.477-510
3b Dye JL.
Inorg. Chem.
1997,
36:
3816
4 Cauliez PM.
Jackson JE.
Dye JL.
Tetrahedron Lett.
1991,
32:
5039
5 Vlassa M.
Huang R.
Jackson JE.
Dye JL.
Tetrahedron
2002,
58:
5849
6 Kim J.
Ichimura AS.
Huang RH.
Redko M.
Phillips RC.
Jackson JE.
Dye JL.
J. Am. Chem. Soc.
1999,
121:
10666
7 Redko MY.
Vlassa M.
Jackson JE.
Misiolek AW.
Huang RH.
Dye JL.
J. Am. Chem. Soc.
2002,
124:
5928
8 Redko MY.
Huang RH.
Jackson JE.
Harrison JF.
Dye JL.
J. Am. Chem. Soc.
2003,
125:
2259
9a Redko MY.
Jackson JE.
Huang RH.
Dye JL.
J. Am. Chem. Soc.
2005,
127:
12416
9b The new material, which also is the first Na+ electride, is the formal adduct of Na0 and 1,4,7,10,13,16,21,24-octaazapentacy-clo[8.8.8.2
[4 7 13 16 21 24 1 . A publication is in preparation describing synthesis, structural details, and ab initio calculations for this new ligand.
10 McKee V.
Nelson J.
Speed DJ.
Town RM.
J. Chem. Soc., Dalton Trans.
2001,
3641
11 Al-Obaidi A.
Baranovic G.
Coyle J.
Coates CG.
McGarvey JJ.
McKee V.
Nelson J.
Inorg. Chem.
1998,
37:
3567
12 Coyle J.
Drew MGB.
Harding CJ.
Nelson J.
Town RM.
J. Chem. Soc., Dalton Trans.
1997,
1123
13 De Santis G.
Fabbrizzi L.
Perotti A.
Sardone N.
Taglietti A.
Inorg. Chem.
1997,
36:
1998
14 Harding C.
Nelson J.
Symons MCR.
Wyatt J.
J. Chem. Soc., Chem. Commun.
1994,
2499
15 Qin L.
McCann M.
Nelson J.
J. Inorg. Biochem.
1993,
51:
633
16 Barr ME.
Smith PH.
Antholine WE.
Spencer B.
J. Chem. Soc., Chem. Commun.
1993,
1649
17 Ragunathan KG.
Bharadwaj PK.
J. Chem. Soc., Dalton Trans.
1992,
1653
18 Chand DK.
Ghosh P.
Shukla R.
Sengupta S.
Das G.
Bandyopadhyay P.
Bharadwaj PK.
Proc.-Indian Acad. Sci., Chem. Sci.
1996,
108:
229
19 Nelson J.
McKee V.
Morgan G.
Prog. Inorg. Chem.
1998,
47:
167
20 Miskowski VM.
Franzen S.
Shreve AP.
Ondiras MR.
Wallace-Williams SE.
Barr ME.
Woodroof WH.
Inorg. Chem.
1999,
38:
2546
21 Thompson JA.
Barr ME.
Ford DK.
Silks LA.
McCormick J.
Smith PH.
Inorg. Chem.
1996,
35:
2025
22 Martin N.
McKee V.
Nelson J.
Inorg. Chim. Acta
1994,
218:
5
23 Dietrich B.
Dilworth B.
Lehn J.-M.
Souchez J.-P.
Cesario M.
Guilhem J.
Pascard C.
Helv. Chim Acta
1996,
79:
569
24 Hossain MA.
Llinares JM.
Miller CA.
Seib L.
Bowman-James K.
Chem. Commun.
2000,
2269
25 Reilly SD.
Khalsa GRK.
Ford DK.
Brainard JR.
Hay BP.
Smith PH.
Inorg. Chem.
1995,
34:
569
26 Dietrich B.
Lehn J.-M.
Guilhem J.
Pascard C.
Tetrahedron Lett.
1989,
30:
4125
27 Clifford T.
Danby A.
Llinares JM.
Mason S.
Alcock NW.
Powell D.
Aguilar JA.
Garcia-Espana E.
Bowman-James K.
Inorg. Chem.
2001,
40:
4710
28 Jost P.
Schurhammer R.
Wipff G.
Chem. Eur. J.
2000,
6:
4257
29 Smith PH.
Barr ME.
Brainard JR.
Ford DK.
Frieser H.
Muralidharan S.
Reilly SD.
Ryan RR.
Silks LA.
Yu WH.
J. Org. Chem.
1993,
58:
7939
30 Chassonnery D.
Chastrette F.
Chastrette M.
Blanc A.
Mattioda G.
Bull. Soc. Chim. Fr.
1994,
131:
188
31 Ferruti P.
Pere A.
Zetta L.
J. Chem. Soc. C
1970,
2512
32 Willer RL.
Moore DW.
Lowe-Ma CK.
J. Org. Chem.
1985,
50:
2368
33 Bracco SPA. inventors; International Patent WO 97/49691.
34 An anonymous reviewer has kindly offered the following suggestion: ‘As source of glyoxal for the Schiff-base condensation, some workers use the trimeric solid, which is depolymerized by reflux for 15 mins or so in the intended alcohol: perhaps the new synthesis of 2 could be extended to include this route to the starting dialdehyde, which might indeed present less hazard than the 40% aqueous solution which is described.’ Though we have not tested this suggestion, it appears sensible and we include it here for completeness.
