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M.E. Wright et al. / Journal of Organometallic Chemistry 637–639 (2001) 837–840
4.3. Preparation of compound 3a
in an aluminum DSC pan (no lid). The sample was
placed in the DSC, allowed to purge for ꢀ2 min under
nitrogen, and then heated quickly (200 °C min−1) to
100 °C and maintained at that temperature for the
duration of the experiment.
A THF (50 ml) solution of m-aminophenol (2.10 g,
19.2 mmol) was treated with sodium ethoxide (1.09 g,
16 mmol) and allowed to react for 15 min with stirring.
Compound 2 (5.00 g, 6.41 mmol) was added directly to
the reaction vessel in small portions and the mixture
was diluted with DMF (30 ml). The resulting mixture
was heated to 60 °C for 30 min, the heating bath
removed, and then allowed to react for an additional 1
h. The mixture was diluted with benzene–ether (200 ml,
1:1, v/v) and the organic layer washed with aqueous
K2CO3, water (2×100 ml), brine, and then dried over
anhydrous K2CO3. The solvents were removed under
reduced pressure and crude product purified by column
chromatography on silica gel (gradient elution:
CHCl3 [ 2% MeOH in CHCl3) to afford compound 3a
4.6. X-ray analysis sample preparation
Samples were prepared by mixing Epon 828, MDA,
and a CH2Cl2 solution of either 3a or 3b. The mol-
equivalents wt of Epon 828 is 340 g mol−1 and is used
to determine the needed amounts of diamine. The mol
ratio of bis(epoxide) to diamine used was always 1:1.
Hence in a typical experiment to prepare a 20 mol%
ferrocene resin was as follows: Epon 828 (3 g, 8.8
mmol), MDA (1.40 g, 7.1 mmol), and a CH2Cl2 (1 ml)
solution of 3a (1.16 g, 1.7 mmol) were combined and
mixed thoroughly. The sample was placed under re-
duced pressure for a few minutes and then transferred
to a curing oven maintained at 80 °C for ꢀ16 h.
Samples that contained engineered defects had them
placed in the samples after treatment under reduced
pressure.
1
as an orange solid (3.50 g, 80%). H-NMR (CDCl3):
l=7.06 (apparent t, J=8.3 Hz, 1H), 6.40–6.25 (m,
3H), 4.11 (s, 4H, Cp), 4.04 (s, 5H, Cp), 3.91 (t, J=5.8
Hz, 2H, CH2O), 3.5–3.1 (brs, 2H, NH2), 2.15–1.95 (m,
4H, CH2s). 13C-NMR (CDCl3): l=160.2 (ArC1), 147.7
(ArC3), 130.0 (ArC5), 107.7 (ArC4), 104.5 (ArC6),
101.7 (ArC2), 99.2 (ipso-Cp), 68.7 (Cp), 68.3 (CH2O),
66.6, 66.4 (C5H4s), 38.7 (CH2), 35.2 (CFc2), 24.7 (CH2).
Anal. Found: C, 68.55; H, 6.10; N, 3.94. Calc. for
C39H42Fe2N2O2: C, 68.64; H, 6.20; N, 4.10%.
Acknowledgements
We wish to thank the Boeing Aircraft Corporation
for partial funding of this work.
4.4. Preparation of compound 3b
Compound 3b was prepared in a manner similar to
3a utilizing p-aminophenol (3.56 g, 32.6 mmol), sodium
ethoxide (1.85 g, 27.2 mmol), and compound 2 (8.52 g,
10.9 mmol) and isolated as an orange solid (6.54 g,
References
[1] (a) T.J. Kealy, P.L. Pauson, Nature 168 (1951) 1039;
(b) For a general review of ferrocene chemistry see: M. Rosen-
blum, Chemistry of the Iron Group Metallocenes, Wiley, New
York, 1965;
1
88%). H-NMR (CDCl3): l=6.77 (d, J=8.8 Hz, 2H),
6.64 (d, J=8.8 Hz, 2H), 4.10 (s, 5H, Cp), 4.03 (s, 4H,
Cp), 3.92 (t, J=6.1 Hz, 2H, CH2O), 3.6–3.2 (brs, 2 H,
NH2), 2.12–1.95 (m, 4H, CH2s). 13C-NMR (CDCl3):
l=152.4 (ArC1), 139.9 (ArC4), 116.5 (ArC2,6), 115.8
(ArC3,5), 99.4 (ipso-Cp), 69.3 (CH2O), 68.8 (Cp), 66.8,
66.4 (C5H4s), 38.8 (CH2), 35.4 (CFc2), 24.9 (CH2).
Anal. Found: C, 68.33; H, 6.44; N, 3.99. Calc. for
C39H42Fe2N2O2: C, 68.64; H, 6.20; N, 4.10%.
(c) W.E. Watts, Organomet. Chem. Rev. 2 (1967) 231;
(d) A. Tagni, T. Hayashi, Ferrocenes-Homogenous Catalysis,
Organic Synthesis, Materials Science, VCH, New York, 1995.
[2] For example see: E.W. Neuse, J.R. Woodhouse, G. Montaudo, C.
Puglisi, Appl. Organomet. Chem. 2 (1988) 53;
(b) J.E. Sheats, C.E. Carraher, C.U. Pittman Jr. (Eds.), Metal
Containing Polymer Systems, Plenum, New York, 1985.
[3] (a) J.W. Harwood, Industrial Applications of Organometallic
Compounds, Reinhold, New York, 1963;
(b) J.C. Johnson Jr., Metallocene Technology, Noyes Data Cor-
poration, Park Ridge, NJ, 1973.
[4] M.E. Wright, Organometallics 9 (1990) 853.
4.5. DSC analysis of the curing reaction
[5] (a) M.E. Wright, E.G. Toplikar, R.F. Kubin, M.D. Seltzer,
Macromolecules 25 (1992) 1838;
Samples were prepared by combining Epon® Resin
828 (cas c25068-38-6), MDA, and a CH2Cl2 solution
of the appropriate ferrocene monomer. The mixture
was subjected to reduced pressure (ꢀ0.3 mm) for
several minutes at ambient temperature and then placed
(b) M.E. Wright, E.G. Toplikar, Macromolecules 25 (1992) 6050;
(c) M.E. Wright, M.S. Sigman, Macromolecules 25 (1992) 6055.
[6] J.M. Winter, R.E. Green Jr., A.M. Waters, W.H. Green, Res.
Nondestructive Eval. 11 (1999) 199 (and references cited therein).
[7] W.P. Norris, J. Org. Chem. 43 (1978) 2200.