R. Huisgen, R. Temme
FULL PAPER
[1]
[2]
with MgSO4, vinyltriphenylphosphonium bromide[42] (37, 3.80 g,
10.3 mmol) was added; the red color of 2a turned to yellow-brown.
After removal of the solvent, the residue (39a) was shaken with 12
ml of 7% aqueous NaOH for 45 min at room temp. The dark sticky
mixture was extracted with 3 ϫ 50 ml of ether; after concentration,
triphenylphosphane oxide crystallized from the ether solution after
seeding. The mother liquor was put on a column of basic alumina
and eluted with petroleum ether. The first fraction (Rf ϭ 0.89) was
followed by an unidentified substance which turned brown on air;
the first fraction (0.66 g) crystallized from petroleum ether at
Ϫ10°C: 0.17 g (7%) of colorless 34a, m.p. 74Ϫ76°C, was obtained.
Ϫ IR (KBr): ν˜ ϭ 692 cmϪ1, 752, 763, 782 st (cis-CHϭCH and
arom. CH out-of-plane def.); 1492, 1603 st, 1569 m (arom. ring
vibr.), 1623 st (CϭCϪN). Ϫ 1H NMR (100 MHz, CDCl3, fresh
solution): Table 4; δ ϭ 6.81Ϫ7.18 (m, 9 arom. H). Ϫ 13C NMR
(25.2 MHz, CDCl3): δ ϭ 35.3 (t, C-1), 50.0 (t, C-2), 58.8 (d, C-
10b), 102.2 (d, C-6), 113.6 (d, C-2Ј/C-6Ј of NϪC6H5), 119.6 (d, C-
4Ј), 124.4, 125.3, 126.4, 127.7 (4 d, C-7 to C-10), 128.9 (d, C-3Ј/C-
5Ј); 130.2, 131.8 (2 s, C-6a, C-10a), 139.4 (d, C-5), 151.3 (s, C-1Ј);
smaller signals for the product of the hydrazo rearrangement were
visible. Ϫ C17H16N2 (248.3): calcd. C 82.22, H 6.50, N 11.28; found
C 82.13, H 6.26, N 11.30.
R. Sustmann, Pure Appl. Chem. 1974, 40, 569Ϫ593.
Review: R. Huisgen in 1,3-Dipolar Cycloaddition Chemistry
(Ed.: A. Padwa), J. Wiley, New York, 1984, vol. 1, p. 99Ϫ128.
[3a] K. Bast, Ph. D. Thesis, Univ. of Munich, 1962. Ϫ [3b] Experi-
[3]
[3c]
ments by T. Durst, Univ. of Munich, 1964/1965. Ϫ
Experi-
ments by R. Schiffer, Univ. of Munich, 1967. Ϫ [3d] Experiments
by K. Lindner, Univ. of Munich, 1977. Ϫ [3e] R. Temme, Ph. D.
[3f]
Thesis, Univ. of Munich, 1980. Ϫ
Experiments by M.
J. Finke, Ph. D. Thesis,
[3g]
Behrens, Univ. of Munich, 1980. Ϫ
Univ. of Munich, 1984.
[4]
[5]
[6]
[7]
R. Huisgen, Chimia 1981, 35, 344Ϫ346; Wiss. Z. Karl Marx
Univ. Leipzig, Math.-Naturwiss. R. 1983, 32, 395Ϫ406.
K. Bast, M. Behrens, T. Durst, R. Grashey, R. Huisgen, R.
Temme, Eur. J. Org. Chem. 1998, preceding paper.
K. Bast, T. Durst, R. Huisgen, K. Lindner, R. Temme, Tetra-
hedron, submitted.
E. Pretsch, Th. Clerc, J. Seibl, W. Simon, Tabellen zur Struktur-
aufklärung organischer Verbindungen mit spektroskopischen
Methoden, Springer-Verlag, Berlin, 1976.
[8]
J. Streith, J. M. Cassal, Ang. Chem. 1968, 80, 117; Ang. Chem.,
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7, 129; J. Streith, A. Blind, J. M. Cassal, C. Sigwalt, Bull. Soc.
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Commun. 1969, 831: T. Tsuchiya, M. Enkaku, J. Kurita, H. Sa-
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M. Ikeda, N. Tsujimoto, Y. Tamura, Org. Mass. Spectrom. 1971,
5, 61Ϫ71.
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[13]
I. L. Karle, J. L. Flippen-Anderson, R. Huisgen, Acta Cryst.
1985, C 41, 1095Ϫ1100.
T. Durst, J. Finke, R. Huisgen, R. Temme, manuscript in prep-
aration.
K. Kohata, T. Fukuyama, K. Kutchisu, J. Phys. Chem. 1982,
86, 602Ϫ606.
S. F. Nelsen, G. R. Weisman, J. Am. Chem. Soc. 1976, 98,
3281Ϫ3287; G. R. Weisman, S. F. Nelsen, ibid. 1976, 98,
7007Ϫ7013.
Review: R. S. Atkinson, “Derivatives of Hydrazine and Related
Compounds” in Comprehensive Organic Chemistry (Eds.: D. H.
R. Barton, W. D. Ollis, I. O. Sutherland), Pergamon Press, Ox-
ford, 1979; Vol. 2, p. 225Ϫ227.
M. E. Kuehne, S. J. Weaver, P. Franz, J. Org. Chem. 1964, 29,
1582Ϫ1586.
K. Bast, M. Christl, R. Huisgen, W. Mack, R. Sustmann,
Chem. Ber. 1973, 106, 3258Ϫ3274.
K. Bast, M. Christl, R. Huisgen, W. Mack, Chem. Ber. 1973,
106, 3312Ϫ3344.
G. A. Berchtold, G. F. Uhlig, J. Org. Chem. 1963, 28,
1459Ϫ1464; K. C. Brannock, R. D. Burpitt, V. W. Goodlett, J.
G. Thweatt, J. Org. Chem. 1963, 28, 1464Ϫ1468.
Reviews: D.N. Reinhoudt, Adv. Het. Chem. 1977, 21, 264Ϫ275;
J. D. Cook in Enamines, 2nd. ed., Marcel Dekker, New York
1988, pp. 384Ϫ388.
C. W. Haigh, Ann. Rep. NMR Spectrosc. 1971, 4, 311Ϫ362.
H. Beyer, E. Thieme, J. Prakt. Chem. 1966, 303, 293Ϫ303.
A. Eckell, R. Huisgen, R. Sustmann, G. Wallbillich, D. Gra-
shey, E. Spindler, Chem. Ber. 1967, 100, 2192Ϫ2213.
R. Huisgen, H. Knupfer, R. Sustmann, G. Wallbillich, V. We-
berndörfer, Chem. Ber. 1967, 100, 1580Ϫ1592.
G. P. Schiemenz, Angew. Chem. 1968, 80, 559Ϫ561; Angew.
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C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165Ϫ195.
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K. B. Wiberg, Computer Programming for Chemists; W. A.
Benjamin, New York 1965.
1,2,3,10b-Tetrahydro-3-(2-pyridyl)pyrazolo[5,1-a]isoquinoline
(34b): 2b (2.21 g, 10.0 mmol) was dissolved in 50 ml of CH2Cl2;
the deep-red color faded upon addition of 3.80 g (10.3 mmol) of
37 within 2 min. The work-up with alkaline hydrolysis of the or-
ange primary adduct followed the description for 34a. Colorless
crystals of 34b (0.34 g, 14%), m.p. 75Ϫ78°C, came from ether/
petroleum ether at Ϫ18°C. Ϫ IR (KBr): ν ϭ 710 cmϪ1, 740 m, 765,
˜
[14]
785 st (cis-CHϭCH- and arom. CH out-of-plane def.), 1430, 1460
st (pyridyl vibr.), 1563 m, 1595 st (arom. ring vibr.), 1625 m
(CϭCϪN). Ϫ 1H NMR (100 MHz, CDCl3): Table 4; δ ϭ
6.44Ϫ8.16 (m, 8 arom. CH); (C6D6, 60 MHz): δ ϭ 1.40Ϫ2.58 (m,
1-H2), 3.26 (m, 2α-H), 3.76 (dd, 10b-H), 4.27 (m, 2β-H), 5.29, 6.01
(AB, J5,6 ϭ 8.0 Hz, 6-H and 5-H), 6.30Ϫ7.33 (m, 7 arom. CH),
8.25 (m, 6Ј-H of pyridyl). Ϫ 13C NMR (25.2 MHz, CDCl3, com-
parison of H-decoupled and off-resonance spectrum): δ ϭ 34.6 (t,
C-1), 45.7 (dd, C-2), 59.7 (C-10b), 103.3 (d, C-6), 108.4 (d, C-3Ј of
pyridyl), 114.9 (d, C-5Ј); 124.5, 125.5, 126.3, 127.7 (4 d, C-7 to C-
10); 129.9, 131.9 (2 s, C-6a, C-10a), 137.3 (d, C-5), 138.9 (d, C-4Ј),
147.5 (d, C-6Ј), 161.3 (s, C-2Ј). Ϫ C16H15N3 (249.3): calcd. C 77.08,
H 6.06, N 16.86; found C 77.10, H 6.18, N 16.83.
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[1,1-D2]-34b: The above procedure for 34b was followed on the
same 10 mmol scale, but a 7% solution of NaOD in D2O was used
for the hydrolysis of 39b; 0.30 g (12%), m.p. 78Ϫ80°C, crystallized
[23]
[24]
from ether/petroleum ether. Ϫ IR (KBr): ν˜ ϭ 2003 cmϪ1 w (CϪD).
1
Ϫ H NMR (60 MHz, CDCl3): δ ϭ 3.25 and 4.01 (AB, J2α,2β
ϭ
10.8 Hz, 2α-H, 2β-H), 3.92 (s, 10b-H, coincides with the high-field
signal for the d of 2β-H), 5.32, 5.98 (AB, J5,6 ϭ 8.0 Hz, 6-H and
5-H). (C6D6, 60 MHz): δ ϭ 3.25, 4.28 (AB, J2α,2β ϭ 10.8 Hz, 2α-
H, 2β-H), 3.75 (s, 10b-H), 5.31, 6.02 (AB, J5,6 ϭ 8.0 Hz, 6-H, 5-
H). Ϫ C16H13D2N3 (251.3): calcd. C 76.46, H/D 6.81, N 16.72;
found C 76.54, H/D 6.17, N 16.49.
[25]
[26]
[27]
[28]
[29]
[30]
Statistical Analysis: The increments Is of equation (1) were calcu-
lated by standard matrix algebra leading to a minimal least-squares
fit of the model equation to the experimental data. In order to
find out the standard errors, the Variance-Covariance matrix was
determined. The square root of its diagonal elements are the stand-
R. Zurmühl, Praktische Mathematik für Ingenieure und Phy-
siker, Springer-Verlag, Berlin, 1961. H. Bandemer, A. Bellmann,
Statistische Versuchsplanung, 4th edition, Teubner, Leipzig,
1994.
H. Mayr, R. Huisgen, Tetrahedron Lett. 1975, 16, 1349Ϫ1352.
M. Karplus, J. Chem. Phys. 1959, 30, 11Ϫ15; J. Am. Chem. Soc.
1963, 85, 2870Ϫ2871.
R. C. Cookson, T. A. Crabb, J. J. Frankel, J. Hudec, Tetrahedron
1966, Suppl. 7, 355Ϫ390.
Th. Zincke, G. Weisspfenning, Liebigs Ann. Chem. 1913, 396,
103Ϫ131.
[31]
[32]
ard errors of the fitted parameters[32]
.
[33]
[34]
Ƞ
Dedicated to Emanuel Vogel, Köln, on the occasion of his
70th birthday.
400
Eur. J. Org. Chem. 1998, 387Ϫ401