PAPER
Bis(N-acylamidines) from Amidines and N-Acylbenzotriazoles
1491
solid was collected by filtration and washed with TBME (5 mL) to
give 0.26 g (62%) of 7h as a light-yellow solid; mp 101.3 °C (dec.).
13C NMR (100 MHz, CDCl3): d = 123.9, 126.1, 128.4, 129.4,
129.7, 129.8, 132.6 (CHarom), 137.0, 138.5, 147.7, 151.2 (Cipso),
164.0 (br, C=N), 165.6 (C=N), 179.5 (br, C=O).
IR (ATR): 3333 (m), 3308 (m), 3184 (w), 3088 (m), 1605 (s), 1562
(s), 1530 (s), 1477 (s), 1441 (s), 1369 (s), 1319 (vs), 1290 cm–1 (m).
HRMS (ESI): m/z calcd for C34H26N4O2 + H: 523.2129; found:
523.2116.
1H NMR (400 MHz, DMSO-d6): d = 7.47 (t, 3J = 7.6 Hz, 4 H,
CHarom), 7.56 (t, 3J = 7.3 Hz, 2 H, CHarom), 7.85 (dd, 4J = 2.2,
3J = 8.5 Hz, 2 H, CHarom), 7.98–7.90 (m, 6 Harom), 8.15 (d,
4J = 2.2 Hz, 2 Harom), 9.69 (s, 2 H, NH), 10.24 (s, 2 H, NH).
13C NMR (101 MHz, DMSO-d6): d = 121.1, 124.7, 126.8, 128.2,
128.5, 132.6 (CHarom), 133.5, 134.4, 140.1, 148.0 (Cipso), 167.0
(C=N), 175.4 (C=O).
Anal. Calcd for C34H26N4O2: C, 78.14; H, 5.01; N, 10.72. Found: C,
77.82; H, 5.12; N, 10.55.
X-ray Crystal Structure Analysis for 1114–20
C34H26N4O2·2
0.10 × 0.08 × 0.05
C2H6OS,
mm,
M = 678.84,
a = 5.4554(1),
colorless
crystal
b = 11.5381(2),
c = 13.3390(3) Å, a = 98.112(1), b = 92.331(1), g = 96.284(1)°,
V = 824.88(3) Å3, rcalc = 1.367 g cm–3, m = 1.853 mm–1, empirical
absorption correction (0.836 £ T £ 0.913), Z = 1, triclinic, space
group P1 (No. 2), l = 1.54178 Å, T = 223(2) K, w and j scans, 8843
reflections collected ( h, k, l), [(sin q)/l] = 0.60 Å–1, 2924 inde-
pendent (Rint = 0.050) and 2525 observed reflections [I ≥ 2 s(I)],
239 refined parameters, R = 0.043, wR2 = 0.107, max. (min.) resid-
ual electron density 0.20 (–0.27) e Å–3, hydrogen atom at N5 from
difference Fourier maps, others calculated and refined as riding at-
oms.
HRMS (ESI): m/z calcd for C28H20N6O6S2 + H: 601.0959; found:
601.0957.
Anal. Calcd for C28H20N6O6S2: C, 55.99; H, 3.36; N, 13.99. Found:
C, 55.88; H, 3.73; N, 14.21.
N,N¢-Di(1,3-thiazol-2-yl)-1,3-adamantanedicarboxamide (8)
Prepared from 2-aminothiazole (0.6 g, 6.0 mmol) and bis(N-acyl-
benzotriazole) 6a (1.28 g, 3.0 mmol) according to the general pro-
cedure at r.t. Crystallization from EtOH gave 1.02 g (87%) of 10 as
a light orange solid; mp 275.0–277.6 °C.
IR (ATR): 3186 (w), 3055 (vw), 2911 (m), 2853 (m), 1678 (vs),
1530 (vs), 1487 (s), 1458 (s), 1447 (s), 1435 (s), 1331 (s), 1269
cm–1 (vs).
1H NMR (300 MHz, DMSO-d6): d = 1.68 (br s, 2 H, CHad), 1.82–
2.02 (m, 8 H, CHad), 2.16 (br s, 4 H, CHad), 7.18–7.19 (d,
3J = 3.6 Hz, 2 Harom), 7.48–7.49 (d, 3J = 3.6 Hz, 2 Harom).
Acknowledgment
We thank Dr. Christof Wigbers for preliminary experiments in this
field. This work was supported by the International Research Trai-
ning Group 1444 Münster (DFG) and the Fonds der Chemischen In-
dustrie (Frankfurt).
13C NMR (300 MHz, DMSO-d6): d = 27.6 (CHad), 34.4, 36.6, 38.2
(CH2ad), 41.0 (Cq,ad), 113.4 (SCHthiazolyl), 137.5 (NCHthiazolyl), 158.5
(C=N), 175.3 (C=O).
References
(1) (a) Eberhardt, J. K.; Glaser, T.; Hoffmann, R. D.; Fröhlich,
R.; Würthwein, E.-U. Eur. J. Inorg. Chem. 2005, 1175.
(b) Eberhardt, J. K.; Fröhlich, R.; Würthwein, E.-U. J. Org.
Chem. 2003, 68, 6690. (c) Eberhardt, K.-K.; Würthwein, E.-
U., BASF AG,German Patent, 102 56 854 A1, 2004; Chem.
Abstr. 2004, 141, 46414.
(2) (a) Ley, H.; Werner, F. Ber. Dtsch. Chem. Ges. 1913, 46,
4040. (b) Oehme, G.; Pracejus, H. Z. Chem. 1969, 9, 140.
(c) Bart, J. C. J.; Bassi, I. W.; Calcaterra, M.; Pieroni, M.
Inorg. Chim. Acta 1978, 28, 201.
(3) Lee, I.-M. Characteristics and Applications of Metal
Complexes with b-Ketoiminate Ligands, In Focus on
Organometallic Chemistry Research; Casto, M. A., Ed.;
Nova Science Publishers, Inc.: New York, 2005, Chap. 5,
133.
(4) Böhm, V.; Röper, M.; Würthwein, E.-U.; Wigbers, C.;
Chabanas, M.; Teles, J.-H.; Altenhoff, A. G., BASF AG,
German Patent, 102008000077K1, 2007; Chem. Abstr.
2008, 149, 238276.
HRMS (ESI): m/z calcd for C18H20N4O2S2 + H: 398.1106; found:
398.1100.
Anal. Calcd for C18H20N4O2S2: C, 55.65; H, 5.19; N, 14.42. Found:
C, 55.48; H, 5.03; N, 14.38.
X-ray Crystal Structure Analysis for 814–20
C18H20N4O2S2, M = 388.50, colorless crystal 0.30 × 0.20 × 0.10
mm, a = 7.2609(4), b = 12.1746(7), c = 19.6542(10) Å,
V = 1737.4(2) Å3, rcalc = 1.485 g cm–3, m = 2.963 mm–1, empirical
absorption correction (0.470 £ T £ 0.756), Z = 4, orthorhombic,
space group Pna21 (No. 33), l = 1.54178 Å, T = 223(2) K, w and j
scans, 9365 reflections collected ( h, k, l), [(sin q)/l] = 0.60 Å–1,
2815 independent (Rint = 0.035) and 2801 observed reflections [I ≥
2 s(I)], 242 refined parameters, R = 0.032, wR2 = 0.087, max.
(min.) residual electron density 0.27 (–0.16) e Å–3, refined as race-
mic twin, hydrogen atoms at N3 and N21 from difference Fourier
maps, others calculated and refined as riding atoms.
(5) Pinner, A. Ber. Dtsch. Chem. Ges. 1889, 22, 1600.
(6) Wigbers, C.; Prigge, J.; Fröhlich, R.; Chi, L.; Mu, Z.;
Würthwein, E.-U. manuscript in preparation.
(7) In analogy to a procedure by Cooper et al.: Cooper, F. C.;
Partridge, M. W. Org. Synth. 1956, 36, 64.
(8) Chua, S.-O.; Cook, M. J.; Katritzky, A. R. J. Chem. Soc.,
Perkin Trans. 2 1974, 546.
(9) (a) Hack, V. unpublished results. (b)See: Hack, V. Diploma
Thesis; University of Münster: Germany, 2007, Carpino L.
A.; J. Am. Chem. Soc.; 1993, 115: 4397.
N-(1-Phenylamino-1-{4-[phenylamino(benzoylimino)meth-
yl]phenyl}methylidene)benzamide (11)
Diamidine 921,22(0.31 g, 1.0 mmol) and N-benzoylbenzotriazole
(10; 0.47 g, 2.1 mmol) were suspended in CH2Cl2 (20 mL) and re-
fluxed for 6 h. The solvent was removed under reduced pressure,
TBME (5 mL) was added to the residue and the white precipitate
was collected by filtration after sonication. The solid was dissolved
in CH2Cl2 (50 mL) and the CH2Cl2 layer was washed with aq 0.1 N
NaOH (20 mL). The organic layer was dried (MgSO4), filtered, and
evaporated to give 0.44 g (85%) of a colorless solid; mp 225.7 °C.
(10) Carpino, L. A. J. Am. Chem. Soc. 1993, 115, 4397.
(11) Katritzky, A. R.; Suzuki, K.; Wang, Z. Synlett 2005, 1656.
(12) (a) Katritzky, A. R.; Zhang, Y.; Singh, S. K. Synthesis 2003,
2795. (b) Katritzky, A. R.; Meher, N. K.; Cai, C. S.;
Sandeep, K. Rev. Soc. Quim. Mexico 2004, 4, 275; Chem.
Abstr. 2005, 143, 26540.
IR (ATR): 3267 (w), 3132 (w), 3034 (w), 2984 (w), 1601 (m), 1578
(s), 1522 (s), 1497 (s), 1443 (s), 1406 (m), 1369 (s), 1267 cm–1 (s).
1H NMR (400 MHz, CDCl3): d = 6.94–7.02 (m, 4 Harom), 7.10–7.22
(m, 6 Harom), 7.40–7.47 (m, 4 Harom), 7.52–7.54 (m, 2 Harom), 7.56 (s,
4 Harom,spacer), 8.30–8.31 (m, 4 Harom), 12.27 (s, 2 H, NH).
Synthesis 2010, No. 9, 1485–1492 © Thieme Stuttgart · New York