| Molbank 2004, M386 |
7,10-Diazafluoranthene (Acenaphtho[1,2-b]pyrazine)
Jørgen Eskildsen, Jørn B. Christensen*
Chemical Laboratory II, Department of Chemistry, University
of Copenhagen, Copenhagen, Denmark,
Tel.: 45-35320194, fax: 45-3530212
E-mail:
[email protected]
Received: 10 January 2004 / Accepted: 23 February 2004 / Published: 29 March 2004
Keywords: Heterocyclic chemistry, mutagenic activity, 7,10-diazafluoranthene
7,10-Diazafluoranthene has been reported to be strongly mutagenic in an Ames-test [1], but no details regarding neither the synthesis nor other properties have been published.
7,10-Diaza-8,9-dihydrofluoranthene (1).(Compare to [2])
Acenaphtene quinone (4.1g; 23 mmol) was dissolved in refluxing MeOH (170 mL), a small portion of the quinone sometimes remained undissolved. Ethane-1,2-diamine (1.7 mL; 25 mmol) was slowly added. This mixture was refluxed for 1h, cooled to room temperature and evaporated to dryness.
The dark brownish powder was dissolved in a small portion of MeOH and cooled in an ice bath. Water was slowly added until a fog of colloid precipitate became visible, which was removed by filtration. The filtrate was extracted twice with CH2Cl2 (1 ´ 70, 1 ´ 50 mL). The combined organic solutions were dried over MgSO4, filtered and concentrated in vacuo to give almost pure 1 in quantitative yield. Yellow powder. Mp 94.4-96.0 ＜C.
M/z: M+ = 206 (70) ); 178 (90); 151 (20); 125 (5); 103 (3).
1H NMR (400 MHz, CDCl3, d, ppm): 7.96 (d, J = 8.4 Hz); 7.94 (d, J = 7.0 Hz); 7.69 (dd, J1 = 7.2 Hz; J2 = 7.0 Hz); 3.91 (s, 4 H).
13C NMR (100 MHz, CDCl3, d, ppm): 158.6; 141.5; 131.7; 130.7; 128.5; 128.4; 118.7; 45.0.
7,10-Diaza-8,9-dihydrofluoranthene (1) (5.35 g ; 26 mmol) was dissolved in dioxane (270 mL). A solution of DDQ (6.0g; 26.5 mmol) in dioxane (150 mL) was added, and the mixture was refluxed for 30 min. After evaporation to dryness, the mixture was dissolved in CH2Cl2 (200 mL) and washed with a 0.3 M solution of Na2SO3 in water (40 mL). The solid material was removed by filtration, and dried in vacuo. The organic phase was evaporated to dryness, and combined with the material from the filtration. This mixture was subjected to Soxhlet-chromatography [3] on Aluminium oxide (Woelm, basic activity I) with CH2Cl2 as eluent to give 7,10-diazafluoranthen as yellow crystals in 74% yield (3.92 g) melting 145.0-147.1＜C.
M/z: M+ = 204 (100); 178 (74); 151 (24); 102 (9); 75 (16).
An analytical sample obtained by sublimation. (100 ＜C/ 0.01 mmHg) had:
Calcd. for C14H8N2: 82.34% C; 3.95% H; 13.72% N
Found 82.36% C; 4.07% H; 13.47% N
Mp:
145.0-147.1 ºC.
1H NMR (400 MHz, CDCl3, d, ppm):
8.46 (s, 2 H); 8.28 (d, J = 7.0 Hz); 8.04 (d, J = 8.2 Hz);
7.78 (dd, J1 = 7.0 Hz; J2 = 7.0 Hz)
13C
NMR (100 MHz, CDCl3, d, ppm): 153.6; 141.1; 132.3; 131.4; 129.6;
129.4; 128.3; 122.7.
References and notes:
1. Gatehouse, D. Mutagenicity of 1,2-ring-fused acenaphthenes against Salmonella typhimurium TA1537 and TA1538: structure-activity relationships. Mutation Res. 1980, 78, 121-35.
2. van Asselt, Rob; Elsevier, Cornelis J.; Smeets, Wilberth J. J.; Spek, Anthony L.; Benedix, Roland. Rigid bidentate nitrogen ligands in organometallic chemistry and homogeneous catalysis. V. Synthesis and characterization of rigid bidentate nitrogen ligands and some examples of coordination to divalent palladium. X-ray crystal structures of bis(p-tolylimino)acenaphthene and methylchloro[bis(o,o'-diisopropylphenyl-imino)acenaphthene]palladium(II). Rec. Trav. Chim. Pays-Bas 1994, 113, 88-98.
3. Faldt, Andre; Pedersen, Morten J.; Krogh, Thomas P.; Hviid, Lene; Christensen, Jørn B.. Preparation and properties of some new extended tetrathiafulvalene (TTF) derivatives. Synth. Met. 1998, 94, 307-310.
Sample availability: Available from MDPI
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