Angewandte
Chemie
4
, a = 12.250(4), b = 12.373(4), c = 22.192(5) , a = 81.041(9),
3
[
[
1] Reviews: a) C. Knapp, J. Passmore, Angew. Chem. 2004, 116,
938 – 4941; Angew. Chem. Int. Ed. 2004, 43, 4834 – 4836; b) H.-J.
Himmel, B. Hoge, Nachr. Chem. 2005, 53, 225 – 235.
2] a) T. M. Klapötke, B. Krumm, P. Mayer, I. Schwab, Angew.
Chem. 2003, 115, 6024 – 6026; Angew. Chem. Int. Ed. 2003, 42,
b = 82.336(9), g = 85.500(11)8, V= 3287.1(18) ,
1
=
calcd
À3
3
4
1.238 gcm , T= 298 K, crystal size 0.30 0.30 0.30 mm , R =
0.0762 (I > 2s(I), Rw = 0.2545, GOF = 1.048. CCDC-619288 and
-619287 (4a and 4b, respectively) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
5
843 – 5846; b) R. Haiges, J. A. Boatz, A. Vij, M. Gerken, S.
Schneider, T. Schroer, K. O. Christe, Angew. Chem. 2003, 115,
027 – 6031; Angew. Chem. Int. Ed. 2003, 42, 5847 – 5851; c) R.
6
[10] Because the yield of 1 could not be determined by weighing (see
1
3
Haiges, J. A. Boatz, A. Vij, V. Vij, M. Gerken, S. Schneider, T.
Schroer, M. Yousufuddin, K. O. Christe, Angew. Chem. 2004,
the Safety Precautions), the integration of the C NMR signal
(without decoupling, delay of 60 s between the pulses) relative to
those of weighed amounts of CCl , CBr , and tetrachloroethene
116, 6844 – 6848; Angew. Chem. Int. Ed. 2004, 43, 6676 – 6680;
4
4
d) R. Haiges, A. Vij, J. A. Boatz, S. Schneider, T. Schroer, M.
Gerken, K. O. Christe, Chem. Eur. J. 2004, 10, 508 – 517; e) R.
Haiges, J. A. Boatz, S. Schneider, T. Schroer, M. Yousufuddin,
K. O. Christe, Angew. Chem. 2004, 116, 3210 – 3214; Angew.
Chem. Int. Ed. 2004, 43, 3148 – 3152; f) R. Haiges, J. A. Boatz, R.
Bau, S. Schneider, T. Schroer, M. Yousufuddin, K. O. Christe,
Angew. Chem. 2005, 117, 1894 – 1899; Angew. Chem. Int. Ed.
was used. This resulted in a yield of 1–2% for the synthesis of 1
from 2h including isolation by gas chromatography and a yield
of 60–87% for the generation of 1 from 3a and NaN or LiN3
3
without workup. As the method described above for determi-
nation of the yield is very laborious and inaccurate, the yields of
the stable succeeding products of 1 (Schemes 1 and 2) were
based on precursor 2h. Thus, we obtained 6 in 3% yield (based
on 2h) as well as 8 in 2%, 9a in 2%, 9b in 0.1%, 10a in 0.7%,
and 10b in 0.1% yield.
2005, 44, 1860 – 1865; g) I. C. Tornieporth-Oetting, T. M. Kla-
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M. Warchhold, Angew. Chem. 2000, 112, 2197 – 2199; Angew.
Chem. Int. Ed. 2000, 39, 2108 – 2109; i) A. C. Filippou, P. Portius,
D. U. Neumann, K.-D. Wehrstedt, Angew. Chem. 2000, 112,
[11] U. Müller, K. Dehnicke, Angew. Chem. 1966, 78, 825; Angew.
Chem. Int. Ed. Engl. 1966, 5, 841 – 842.
[12] R. K. Howe, M. L. Rueppel, Chem. Eng. News 1983, 61 (Jan. 17),
4.
[13] L. A. Burke, Chem. Eng. News 1983, 61 (April 25), 2.
[14] a) W. Beck, J. Geisenberger, Chem. Eng. News 1984, 62 (March
5), 39; b) J. Geisenberger, I. Eble, I. Neibrich, U. Nassel, W.
Beck, Z. Naturforsch. B 1987, 42, 55 – 64.
[15] M. A. Petrie, J. A. Sheehy, J. A. Boatz, G. Rasul, G. K. S.
Prakash, G. A. Olah, K. O. Christe, J. Am. Chem. Soc. 1997,
119, 8802 – 8808, and references therein.
4
524 – 4527; Angew. Chem. Int. Ed. 2000, 39, 4333 – 4336; j) M.-J.
Crawford, A. Ellern, P. Mayer, Angew. Chem. 2005, 117, 8086 –
090; Angew. Chem. Int. Ed. 2005, 44, 7874 – 7878.
8
[
[
3] Q. S. Li, H. X. Duan, J. Phys. Chem. A 2005, 109, 9089 – 9094.
4] A. Hassner, M. Stern, H. E. Gottlieb, F. Frolow, J. Org. Chem.
1990, 55, 2304 – 2306.
[
[
5] We prepared triazidomethane from iodoform and a concen-
trated solution of tributylhexadecylphosphonium azide in
chloroform.
[16] W. Kesting, Ber. Dtsch. Chem. Ges. B 1924, 57, 1321 – 1324, and
references therein.
I
6] We treated 2a–c with reagents such as NaN in N,N-dimethyl-
[17] The sensitivity of 1 to hydrolysis may be the reason that Cu -
3
formamide or acetonitrile and tributylhexadecylphosphonium
catalyzed treatment with terminal alkynes (click chemistry)
[
18]
azide in different solvents. The starting materials 2d–g were
according to the Sharpless protocol
was not successful.
+
À
reacted with these reagents as well as (Me N) C=NH N3 in
2
2
2
However, variants of this click reaction in water-free solvents
have also hitherto failed.
CH Cl or acetonitrile and HN in chloroform.
2
2
3
[
7] a) H. G. Viehe, Z. Janousek, Ger. Offen., Patent DE2033276,
972 [Chem. Abstr. 1972, 76, 85425]; b) G. Barany, A. L. Schroll,
[18] Review on click reaction (azide/alkyne): V. D. Bock, H. Hiem-
stra, J. H. van Maarseveen, Eur. J. Org. Chem. 2006, 51 – 68.
[19] Synthesized from N,N,N’,N’-tetramethylguanidine and the acid
1
A. W. Mott, D. A. Halsrud, J. Org. Chem. 1983, 48, 4750 – 4761;
c) C. Bolln, H. Frey, R. Mülhaupt, Macromolecules 1996, 29,
1
5
15
H N , which was generated from Na N and concentrated
3
3
3111 – 3116; d) E. E. Gilbert, Tetrahedron 1969, 25, 1801 – 1806.
aqueous hydrochloric acid (59% yield over the two steps).
[20] D. M. Kanjia, J. Mason, I. A. Stenhouse, R. E. Banks, N. D.
Venayak, J. Chem. Soc. Perkin Trans. 2 1981, 975 – 979.
[21] The spectroscopic data for 4a,b, 6, 8, 9a,b, and 10a,b as well as
(further) suggestions of reaction mechanisms to explain the
formation of 6, 9a,b, and 10a,b are collected in the Supporting
Information.
[
[
8] L. F. Tietze, T. Eicher, Reaktionen und Synthesen im organisch-
chemischen Praktikum und Forschungslaboratorium, 2nd ed.,
Thieme, Stuttgart, 1991, pp. 39 – 40.
9] Crystallographic data for 4a: C H N , M = 504.66, monoclinic,
2
5
36 12
space group P2 /c, Z = 4, a = 11.1484(6), b = 11.0673(5), c =
1
3
2
1
0
1.2600(13) ,
b = 90.153(5)8,
V= 2623.1(2) ,
1
=
calcd
À3
3
.278 gcm , T= 298 K, crystal size 0.40 0.35 0.20 mm , R =
.0605 (I > 2s(I), Rw = 0.2078, GOF = 1.023. Crystallographic
[22] a) F. D. Marsh, M. D. Hermes, J. Am. Chem. Soc. 1964, 86, 4506 –
4507; b) F. D. Marsh, J. Org. Chem. 1972, 37, 2966 – 2969.
¯
data for 4b: C H N , M = 612.83, triclinic, space group P1, Z =
3
3
48 12
Angew. Chem. Int. Ed. 2007, 46, 1168 –1171
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1171