A Short Synthetic Route to Novel, Highly Soluble 3,8-Dialkyl-4,7-dibromo-1,10-phenanthrolines

Synlett

Volumn 1997, Issue 9, 1997, Pages 1096-1098

  Schmittel, Michael ^a   Ammon, Horst ^a  

^a UNIVERSITY OF WÜRZBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542735195     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1997-1525     Document Type: Article

References (28)

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12. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
13. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
14. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
15. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
16. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
17. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
18. Kocian, O.; Mortimer, R. J.; Beer, P. D.; J. Chem. Soc., Perkin Trans. 1 1990, 3203; Constable, E. C.; Angew. Chem. Int., Ed. Engl. 1991, 30, 1450; Vögtle, F.; Lüer, I.,; Balzani, V.; Armaroli, N.; Angew. Chem., Int. Ed. Engl. 1991, 30, 1333; Belser, P.; von Zelewsky, A.; Frank, M.; Seel, C.; Vögtle, F.; De Cola, L.; Barigelletti, F.; Balzani, V.; J. Am. Chem. Soc. 1993, 115, 4076; Charbonniere, L. J.; Bernardinelli, G.; Piguet, C.; Sargeson, A. M.; Williams, A. F.; J. Chem. Soc., Chem. Commun. 1994, 1419; Solladié, N.; Chambron, J.-C.; Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Angew. Chem., Int. Ed. Engl. 1996, 35, 906; Ziessel, R.; Suffert, J.; Youinou, M.-T.; J. Org. Chem. 1996, 61, 6535; Hasenkopf, B.; Lehn, J.-M.; Kneisel, B.O.; Baum, G.; Fenske, D.; Angew. Chem. Int., Ed. Engl. 1996, 35, 1838; Tzalis, D.; Tor, Y.; Chem. Commun. 1996, 1043.
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24. 11 (75 mmol) in 100 ml of dichloromethane and kept to reflux in a Dean-Stark apparatus for 2 h. The solvent was evaporated and the oily brown residue used in the following reactions without purification.
25. General procedure for the preparation of 3,8-dialkyl-1,10-phenanthroline-4,7-diones (5b-d): Crude 4b-d (8-12 g) was added under nitrogen to 300 ml of diphenylether at a temperature of 200 °C. The temperature was raised to 240-250 °C for 30 min while a vigorous stream of nitrogen was bubbled through the solution. Thereafter, the reaction mixture was allowed to cool down and a colorless solid started to precipitate. Petroleum ether (50-70 °C) was added (200 ml) to complete precipitation, the solid was filtered off and washed twice with 100 ml of diethylether. To dissolve impurities the colorless residue was suspended in acetone (100 ml) and refluxed for 15 min. The precipitate was filtered off, washed with acetone and dried in vacuo to yield 4a-c as colorless solids in 38-69% in analytically pure form.
26. 4. After evaporation of the solvent and drying in vacuo for 8 h the 3,8-dialkyl-4,7-dibromo-1,10-phenanthrolines 1b-d were obtained as colorless solids in 98-99% yield in analytically pure form.
27. 2 (506.32): calcd. C 56.93, H 5.97, N 5.53; found C 56.65, H 6.29, N 5.50.
28. 3): δ = 14.0 (q, C-6′), 22.5 (t, C-5′), 29.1 (t, C-4′), 30.5 (t, C-3′), 31.6 (t, C-2′), 34.6 (t, C-1′), 84.0 (s, C-2″), 102.3 (s. C-1″), 122.5 (s, C-3″), 125.0 (d, C-6″), 127.6 (d, C-5,-6), 127.9 (s, C-3, - 8), 128.6 (d, C-4′), 129.2 (d, C-5′), 131.8 (s, C-4a, -6a), 138.8 (s, C-4,-7), 144.4 (s, C-1a,-10a), 151.1 (d, C-2, -9).