Angewandte
Chemie
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Due to the clean stoichiometric reactions of 1, the formation
of low volatile and toxic byproducts typically associated with
diisocyanate reactions in polyurethane chemistry, can be
prevented. This is also of interest for the preparation of
polyurethane- and polyurea-based biodegradable polymers
used in biomedical applications.
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Experimental Section
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(DSM N.V.), WO-A1
1-[(2-Oxazepan-1-yl)carbonyl]azepan-2-one (1, CBC) was obtained
from DSM and used as received (purity > 99%). 1-Octylamine
(Merck) and N,N-di(1-octyl)amine (Merck), 1-octanol (Merck), 2-
octanol (Merck), methanol, and toluene were dried over molecular
sieves (4 ) before use. Zirconium tetrapropanolate was obtained
from Aldrich (70 wt.% solution in 1-propanol).
2000017169, 2000 [Chem. Abst. 2000, 132, 238426]; b) J. A.
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f) L. J. Molhoek, J. A. Loontjens, B. M. J. Spoolder, B. J. M.
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2002, 137, 142181].
Reaction of 1 with amines: Table 1, entry 1: Dry 1-octylamine
(11.6 mL, 9.04 g, 70 mmol) was heated under argon to 708C. Then 1
(8.82 g, 35 mmol) was added and the reaction mixture was stirred for
15 min at 708C. The composition of the product mixture was
determined by 1H and 13C NMR spectroscopy. It consisted of
equimolar amounts 2a, caprolactam, and 1-octylamine.
Reaction of 1 with alcohols: Table 2, entry 12: As a typical
example, the reaction of CBC with 1-octanol at 1208C in the presence
of zirconium tetraalcoholate as catalyst is described (entry 12). 1-
Octanol (22.1 mL, 18.23 g, 0.14 mol) was stirred with Zr(On-C3H7)4
(0.229 g, 0.7 mmol, 1 mol% with respect to 1) for 1 h at 408C under
vacuum (oil pump). The solution was then heated under argon to
1208C and preheated 1 (17.65 g, 0.07 mol) was added. The reaction
mixture was stirred for 5 min before the composition was determined
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1
by H and 13C NMR spectroscopy to be 73% (based on 1) 7a, 16%
10a, 3% 9a, and 8% 5a. Residual 1 and 3a were not detected.
See the Supporting Information for H and 13C NMR data.
1
Received: May 12, 2003 [Z51867]
Keywords: carbamates · coupling agents · polyurethane ·
.
synthetic methods
[1] CCDC 201802 (1) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
bridge Crystallographic Data Centre, 12, Union Road, Cam-
bridge CB21EZ, UK; fax: (+ 44)1223-336-033; or deposit@
ccdc.cam.ac.uk).
[13] T. Loontjens, B. Scholtens, S. Maier, R. Mülhaupt, Kunststoffe
2002, 92, 83 – 86. English translation: T. Loontjens, B. Scholtens,
S. Maier, R. Mülhaupt, Kunststoffe Plast Europe 2002, 92, 38 –
40.
[2] H. R. Meyer, Kunstst. Plast. 1956, 3, 160 – 162.
Angew. Chem. Int. Ed. 2003, 42, 5094 –5097
ꢀ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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