Synthesis of Bis- and Tris(3-H-1,3-azaphospholo)benzenes
9
from CH3CN (16 mL) to give 16 1.15g (65%). Mp
187–189◦С. 31P NMR (Et2O), δ: 65.1. 1Н (CDCl3,
500 MHz), δ: 5.71 (s, 3H, CHAr), 2.87 (s, 18H, NCH3),
2.30 (d, 36H, J 11.0 Hz, NCH3). 13C (CDCl3): δ 151.05
(d, J 147 Hz, CN), 150.2 (d, J 20 Hz, i-CAr), 105.7,
41.1 (d, J 2.5 Hz), 38.1 (d, J 1.3 Hz). Anal. calcd for
C27H57N12P3Se3 N 19.11, P 10.56. Found: N 19.45, P
10.73.
filtration. The mother liquor was evaporated under
reduced pressure and the residue was recrystallized
from CH3CN (25 mL) to give yellow solid (414 mg,
67%). Mp 330–332◦С. 31P (CDCl3): δ 59.7. 1Н (CDCl3,
300 MHz): δ 2.73 (dd, 18H, J1 9.0 Hz, J2 13.0 Hz,
NCH3), 3.23+3.24 (s, 9H, C-NCH3), 3.41+3.42 (s,
9H, C-NCH3).
Anal calcd. for C21H36N9P3S3 N 20.88, P 15.39.
Found: N 21.09, P 15.54.
N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ
Dodecamethyl-1,4,7-triaza-3,6,9-triphosphatrindene-
2,3,5,6,8hexaamine 17. To stirred solution
-
REFERENCES
a
of amidine 16 (2.93 g, 3.3 mmol) in benzene
(15 mL), hexamethylphosphorus triamide (1.96 g,
12 mmol) was added in one portion and the reaction
mixture was left at 15◦С for 5 min. Then, the
volatiles were removed under reduced pressure
and tris(dimethylamino)phosphane selenide was
distilled off in vacuo (bp 120–130◦С/ 0.05 mmHg).
The residue was placed in a pressure tube and
the product was extracted with pentane at 100◦С
(80 mL). The resulting solution was concentrated
to 50 mL and cooled to 17◦С to give an orange
precipitate. The precipitate was filtered and dried
under reduced pressure to give yellow solid 17
(1.0 g, 59%). 31P (C6D6, 202 MHz): δ 61.7, 61.4,
61.3. 1Н (C6D6, 300 MHz): δ 2.63, 2.67, 2.70 td,
2.61–2.72 m (18H, J 10.2 Hz, NCH3), 2.89 (9H, m,
NCH3), 2.99 (br s, 9H, NCH3).
[1] (a) Bansal, R. K.; Heinicke, J Chem Rev 2001, 101,
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Curr Org Chem 2007, 11, 33; (c) Bansal, R. K. Top.
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[2] (a) Heinicke, J.; Gupta, N.; Surana, A.; Peulecke, N.;
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R. K.; Karaghiosoff, K.; Vogt, M. Z Anorg Allg Chem
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lan, T. H.; Elsegood, M. R. J.; Clegg, W. J Organomet.
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(h) Aluri, B. R.; Niaz, B.; Kindermann, M. K.; Jones,
P. G.; Heinicke, J. Dalton Trans 2011, 40, 211.
[3] Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M.
Chem Rev 2012, 112, 1001.
[4] Choi, H.-J.; Park, Y. S.; Yun, S. H.; Kim, H.-S.; Cho,
C. S.; Ko, K.; Ahn K. H. Org Lett 2002, 4(5), 795.
[5] Wilkens, H.; Ostrowski, A.; Jeske, J.; Ruthe, F.; Jones,
P. G.; Streubel, R. Organometallics 1999, 18, 5627.
[6] (a) Marchenko, A.; Koidan, G.; Hurieva, H.;
Merkulov, A.; Pinchuk, A. Y.; Kostyuk, A. Tetrahe-
dron 2010, 66, 3668; (b) Marchenko, A.; Koidan, H.;
Hurieva, H.; Merkulov, A.; Pinchuk, A. Y.; Rozhenko,
A. B.; Jones, P. G.; Tho¨nnesen, H.; Kostyuk, A. Tetra-
hedron 2011, 67, 7748.
N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ
-
Dodecamethyl-3,6,9-trioxo-6,9-dihydro-3H-1,4,7-tri-
aza-3λ5,6λ5,9λ5-triphospha-trindene-2,3,5,6,8 hexaa-
mine 18a. To a stirred solution of 17 (100 mg,
0.2 mmol) in CH2Cl2 (2 mL), H2O2 (0.1 mL, 30%
aqueous) was added in one portion and the reaction
mixture was left at 17◦С for 10 min. The solvent was
evaporated under reduced pressure and the residue
was recrystallized from Et2O (5 mL) to give yellow
solid (21 mg, 20%). Mp 212–213◦С.
31P (CDCl3): δ 32.7 (88.5%); 18.8 (11.5%). 1Н
(CDCl3, 300 MHz): δ 2.62–2.72 (m, 18H, NCH3), 3.20
(m, 9H, C-NCH3), 3.34 (m, 9H, C-NCH3).
[7] Sheldrick, G. M. SADABS: Program for scaling
and correction of area detector data; University of
Go¨ttingen: Go¨ttingen, Germany, 1996.
[8] Sheldric, G. M. SHELXS97. Program for the solu-
tion of crystal structure; University of Go¨ttingen:
Go¨ttingen, Germany, 1997.
N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ
-
Dodecamethyl-3,6,9-trithioxo-6,9-dihydro-3H-1,4,7-
triaza-3λ5,6λ5,9λ5-triphospha-trindene-2,3,5,6,8hexa
amine 18b. To a stirred solution of 17 (520 mg,
1.02 mmol) in benzene (6 mL), finely powdered
elemental sulfur (100 mg, 3.11 mmol) was added
in one portion and the reaction mixture was left at
70◦С for 1 h. After cooling to ambient temperature,
benzene (45 mL) was added to the reaction mix-
ture and insoluble components were separated by
[9] Sheldric, G. M. SHELXL97. Program for the refine-
ment of crystal structures; University of Go¨ttingen:
Go¨ttingen, Germany, 1997.
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Betteridge, P. W. CRYSTALS Issue 10. Oxford: Chem-
ical Crystallography Laboratory, University of Ox-
ford, 1996.
[11] Carruthers, J. R.; Watkin, D. J. Acta Crystallogr, Sect
C: Cryst Struct Commun 1979, 35, 698.
[12] Flack, H. D. Acta Crystallogr 1983, A39, 876.
Heteroatom Chemistry DOI 10.1002/hc