cyclohexane-1,2,3,4,5,6-hexone;octahydrate

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound was synthesized according to a modified literature procedure.30 Hexaketocyclohexane octahydrate (10.0 g, 32.0 mmol) and 1,2-phenylenediamine SM17 (10.4 g, 96.0 mmol) were refluxed in 500 ml of glacial acetic acid:ethanol (1:1) at 140° C. for 24 hours. The reaction mixture was then filtered and washed with ca. 200 ml of hot glacial acid. The solid was then refluxed with 200 ml of 30% nitric acid for 3 hours at 140° C. The yellow solid (12.6 g) was filtered and dried under vacuum. An amount 2.0 g was sublimed at high vacuum (3.2×10−6 torr and t=350° C.) to yield 0.77 g (estimated extrapolated yield=40%) of yellow solid. The yield could be increased with prolonged sublimation time. This compound is slightly soluble in CHCl3. 1H NMR (CDCl3, 300 MHz) δ 8.73-8.69 (dd, J=6.6 Hz; J2=3.6 Hz, 6H), 8.08-8.043 (m, 6H). 13C NMR (CDCl3, 75 MHz), 143.57, 132.30, 130.65, 119.05, 98.58. Anal. Calcd. for C24H12N6: C, 74.99; H, 3.15; N, 21.86. Found: C, 74.76; H, 3.11; N, 21.66. The reaction mixture was then filtered washed with ca. 200 ml of hot glacial acid The yellow solid (12.6 g) was filtered dried under vacuum was sublimed at high vacuum (3.2×10−6 torr and t=350° C.) to yield 0.77 g (estimated extrapolated yield=40%) of yellow solid The yield could be increased with prolonged sublimation time

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the course of the synthesis of hexaazatristriphenylene HATT (also referred to as “Mickey-Mouse” HATNA), BK3—31, a different product was observed, Scheme 2. The three-fold condensation of hexaketocyclohexane octahydrate SM4 with 9,10-diaminophenanthrene SM7 in acetic acid/ethanol under air resulted in an orange solid phenanthrazine BK2—97E, which was sublimed under high vacuum. Phenanthrazine was confirmed by 1H NMR and E1 mass analysis. In this regard, 9,10-diaminophenanthrene SM7 may have been partially oxidized to phenanthrene-9,10-dione SM34 under air. The double bond (9=10) in 9,10-diaminophenanthrene SM7 behaves more like a single double bond rather than one in an aromatic system, i.e. it can be oxidized more easily. Condensation of SM7 and SM34 led to BK2—97E. To give evidence for the proposed mechanism, two control experiments were performed. 9,10-diaminophenanthrene SM7 was refluxed in acetic acid/ethanol for 24 hours. E1 mass analysis showed the presence of phenanthrazine, BK3—29. Hexaazatristriphenylene HATT, BK3—31 was obtained when the condensation was performed in acetic acid under nitrogen (MALDI TOF measurement confirmed the presence of HATT). In the course of the synthesis of hexaazatristriphenylene HATT (