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Kurdyukova et al.
centration of 1•10–5 mol L–1 in DMSO. The crimson color of the
solution indicates the formation of the anionic dye. The comꢀ
pound is stable in DMSO in a closed vessel under argon for 1 h.
2,7ꢀBis(phenoxysulfonyl)ꢀ9Hꢀfluorene (6). A mixture of
fluoreneꢀ2,7ꢀdisulfochloride16 (1.8 g, 4.95 mmol), phenol (2.35 g,
0.025 mol), and pyridine (2 mL) was heated for 30 min at
110—120 C. Propanꢀ2ꢀol (15 mL) and water (5 mL) were addꢀ
ed, and the mixture was refluxed for several minutes. After coolꢀ
ing, the precipitate was filtered off and treated with hot water.
A substance with m.p. 200—202 C was obtained in a yield of
1.75 g (73%). The obtained precipitate was dissolved in boiling
dioxane (8 mL), and the solution was diluted with propanꢀ2ꢀol
(8 mL). Compound 6 was obtained as lustrous white lamellae
with m.p. 202—203 С in a yield of 1.6 g (68%). 1Н NMR
(DMSOꢀd6), : 4.22 (s, 2 H, CH2); 7.07 (d, 4 H, phenoxyl proꢀ
tons, J = 8.4 Hz); 7.28—7.43 (m, 6 H, phenoxyl protons); 7.91
(d, 2 H, H(4), H(5), J = 8.4 Hz); 8.22 (s, 2 H, H(1), H(8)); 8.34
(d, 2 H, H(3), H(6), J = 8.4 Hz).
2,3,4,6,7,8,9,10ꢀOctahydropyrimido[1,2ꢀa]azepinꢀ1ꢀium
(E)ꢀ9ꢀ[3ꢀ(2,7ꢀbis(phenoxysulfonyl)ꢀ9Hꢀfluorenꢀ9ꢀylidene)propꢀ
1ꢀenyl]ꢀ2,7ꢀbis(phenoxylsulfonyl)ꢀ9Hꢀfluorenꢀ9ꢀide (10). A mixꢀ
ture of compound 6 (100 mg, 0.21 mmol), Nꢀ(3ꢀanilinopropꢀ2ꢀ
enylidene)anilinium chloride (8) (26 mg, 0.1 mmol), and pyridꢀ
ine (3.2 mL) was heated to complete dissolution, 3 droplets of
DBU were added, and the mixture was heated for 2 h in a water
bath (125 C) (spectrophotometric monitoring*). The reaction
mixture was cooled and the solvent was evaporated under reꢀ
duced pressure. The residue was triturated in water and filtered
off. The yield was 60 mg (52%), m.p. 126 C. Found (%):
С, 64.89; Н, 4.40; S, 11.02. C62H52N2O12S4. Calculated (%):
C, 65.07; Н, 4.49; S, 11.21. 1Н NMR (acetoneꢀd6), : 1.58—1.73
(m, 6 H, CH2 groups of cation); 2.72—2.80 (m, 2 H, CH2 group
of cation); 3.19—3.27 (m, 2 H, CH2 group of cation); 3.27—3.39
(m, 2 H, CH2 group of cation); 3.52—3.61 (m, 4 H, CH2 groups
of cation); 6.81 (t, 1 H, ꢀproton of chain, J = 12.0 Hz); 7.01—7.19
(m, 8 H, phenoxyl protons); 7.24—7.46 (m, 12 H, phenoxyl
protons); 7.91 (d, 2 H, ꢀprotons of chain, J = 13.2 Hz); 8.07
(d, 8 H, Ar—H, J = 8.0 Hz); 8.27 (br.s, 4 H, Ar—H).
2,3,4,6,7,8,9,10ꢀOctahydropyrimido[1,2ꢀa]azepinꢀ1ꢀium
9ꢀ[(1E,3E)ꢀ5ꢀ(2,7ꢀbis(phenoxysulfonyl)ꢀ9Hꢀfluorenꢀ9ꢀylidene)ꢀ
pentaꢀ1,3ꢀdienyl]ꢀ2,7ꢀbis(phenoxysulfonyl)ꢀ9Hꢀfluorenꢀ9ꢀide
(11). A mixture of compound 6 (128 mg, 0.27 mmol), Nꢀ(5ꢀ
anilinopentaꢀ2,4ꢀdienylidene)anilinium chloride (9) (40 mg,
0.14 mmol), and pyridine (2.5 mL) was heated to complete disꢀ
solution, and 3 droplets of DBU were added. The reaction mixꢀ
ture was heated for 40 min in an oil bath (125 C) (spectrophotoꢀ
metric monitoring). The solvent was evaporated under reduced
pressure, and the residue was triturated in ethanol, filtered off,
and washed with anhydrous diethyl ether (3×10 mL). The yield
was 120 mg (83%), m.p. 111 C. Found (%): С, 65.35; Н, 4.50;
S, 10.78. C64H54N2O12S4. Calculated (%): C, 65.68; Н, 4.56;
S, 10.96. 1Н NMR (CD3CN), : 1.71—1.73 (m, 4 H, CH2 groups
of cation); 2.81—2.83 (m, 4 H, CH2 groups of cation); 3.39 (t, 2 H,
CH2 group of cation, J = 6.0 Hz); 3.61 (t, 2 H, CH2 group of
cation, J = 6.0 Hz); 3.64—3.66 (m, 4 H, CH2 groups of cation);
6.13 (d, 2 H, ꢀprotons of chain, J = 14.4 Hz); 6.82 (t, 2 H,
ꢀprotons of chain, J = 12.0 Hz); 6.95—7.20 (m, 8 H, phenoxyl
protons); 7.23—7.45 (m, 1 Н, proton of chain, 12 H, Ar—H
phenoxyl protons); 8.18 (d, 4 H, Ar—H, J = 8.0 Hz); 8.28 (d, 4 H,
Ar—H, J = 8.0 Hz); 9.16 (s, 4 H, Ar—H).
2,3,4,6,7,8,9,10ꢀOctahydropyrimido[1,2ꢀa]azepinꢀ1ꢀium
2,7ꢀdinitroꢀ9ꢀ[(1E,3E)ꢀ5ꢀ(2,7ꢀdinitroꢀ9Hꢀfluorenꢀ9ꢀylidene)ꢀ
pentaꢀ1,3ꢀdienyl]ꢀ9Hꢀfluorenꢀ9ꢀide (12). A mixture of 2,7ꢀdiꢀ
nitroꢀ9Hꢀfluorene (7) (256 mg, 1 mmol) (see Ref. 17) and comꢀ
pound 9 (150 mg, 0.52 mmol, 10% excess) was dissolved in DMF
(5 mL) and heated to boiling, and DBU (200 mg, 1.32 mmol)
was added (spectrophotometric monitoring). The reaction mixꢀ
ture was cooled to ambient temperature and treated with anꢀ
hydrous diethyl ether. The precipitate that formed was filtered
off after sedimentation. The yield was 450 mg (96%), m.p. 132 C.
Found (%): С, 65.92; Н, 4.44; N, 11.27. C40H34N6O8. Calculatꢀ
1
ed (%): C, 66.20; Н, 4.58; N, 11.58. Н NMR (DMSOꢀd6), :
1.53—1.62 (m, 6 H, CH2 groups of cation); 1.94—2.02 (m, 2 H,
CH2 group of cation); 2.58—2.63 (m, 4 H, CH2 groups of cation);
3.46—3.51 (m, 2 H, CH2 group of cation); 3.53—3.57 (m, 2 H,
CH2 group of cation); 7.61 (t, 1 H, ꢀproton of chain, J = 12.0 Hz);
7.98 (t, 2 H, ꢀprotons of chain, J = 12.9 Hz); 8.29 (d, 2 H,
ꢀprotons of chain, J = 13.5 Hz); 8.88 (s, 8 H, H(3), H(4) of
fluorene); 8.96 (br.s, 4 H, H(1), H(8) of fluorene).
9ꢀ(Ethoxymethylidene)ꢀ2,4,5,7ꢀtetranitroꢀ9Hꢀfluorene.
A mixture of 2,4,5,7ꢀtetranitroꢀ9Hꢀfluorene (13) (105 mg,
0.3 mmol) (see Ref. 18) and triethyl orthoformate (~0.7 mL) in
acetic anhydride (1.5 mL) was refluxed for several minutes, while
the product precipitated from the hot reaction mixture. The preꢀ
cipitate was filtered off, washed with acetic anhydride and ethanol,
and recrystallized from acetone. The yield was 90 mg (75%),
m.p. >250 C. Found (%): С, 47.32; Н, 2.44; N, 13.78. C16H10N4O9.
Calculated (%): C, 47.77; Н, 2.51; N, 13.93. 1Н NMR (DMSOꢀd6),
: 1.06 (t, 3 H, O–CH2СН3, J = 6.9 Hz); 3.44 (q, 2 H,
O—CH2СН3, J = 6.9 Hz); 8.41 (s, 2 H, H(3), H(6)); 9.57 (br.s, 2 H,
H(1), H(8)); 10.25 (s, 1 H, methinic proton).
Triethylammonium 2,4,5,7ꢀtetranitroꢀ9ꢀ[(2,4,5,7ꢀtetranitroꢀ
9Hꢀfluorenꢀ9ꢀylidene)methyl]ꢀ9Hꢀfluorenꢀ9ꢀide (14). A mixture
of
9ꢀ(ethoxymethylidene)ꢀ2,4,5,7ꢀtetranitroꢀ9Hꢀfluorene
(80 mg, 0.2 mmol) and compound 13 (70 mg, 0.2 mmol) was
heated in a minimum amount of acetic anhydride until dissoluꢀ
tion, several droplets of triethylamine were added, and the mixꢀ
ture was heated for several minutes more. A precipitate of the
product formed was filtered off and washed with Ac2O and EtOH.
The yield was 150 mg (93%), m.p. >270 C. Found (%): С, 49.03;
Н, 3.01; N,15.27. C33H25N9O16. Calculated (%): C, 49.32; Н, 3.14;
N, 15.69. 1Н NMR (DMSOꢀd6), : 1.17 (t, 9 H, NCH2СН3,
J = 7.2 Hz); 3.06—3.14 (m, 6 H, NCH2СН3); 8.52 (d, 4 H, Ar—H
of fluorene, J = 2.1 Hz); 8.96 (br.s, 4 H, Ar—H of fluorene);
9.75 (s, 1 H, proton of chain).
Triethylammonium (E)ꢀ2,4,5,7ꢀtetranitroꢀ9ꢀ[3ꢀ(2,4,5,7ꢀ
tetranitroꢀ9Hꢀfluorenꢀ9ꢀylidene)propꢀ1ꢀenyl]ꢀ9Hꢀfluorenꢀ9ꢀide
(15). A mixture of compound 13 (138 mg, 0.4 mmol), compound
8 (52 mg, 0.2 mmol), acetic anhydride (1.5 mL), and several
droplets of triethylamine was refluxed for 3 min, and the product
precipitated from the reaction mixture. The precipitate was filꢀ
tered off and washed with a minimum amount of acetic anhyꢀ
dride and ethanol. The yield was 150 mg (90%), m.p. >270 C.
Found (%): С, 50.42; Н, 3.16; N, 14.93. C35H27N9O16. Calcuꢀ
lated (%): C, 50.67; Н, 3.28; N, 15.19. 1Н NMR (DMSOꢀd6), :
1.20 (t, 9 H, NCH2СН3, J = 7.2 Hz); 3.05—3.13 (m, 6 H,
NCH2СН3); 7.71 (t, 1 H, ꢀproton of chain, J = 13.2 Hz); 8.28
(s, 4 H, Ar—H of fluorene); 8.50 (d, 2 H, ꢀproton of chain,
J = 13.2 Hz); 9.04 (s, 4 H, Ar—H of fluorene).
* The reaction was spectrophotometrically monitored at the
longestꢀwavelength absorption band of the product formed.