7428
S. Bittner et al. / Tetrahedron 57 (2001) 7423±7429
standard Bruker SMART 6K CCD diffractometer
Ê
130.7 'C-7 and C-18), 131.5'C-3 and C-13), 133.9 'C-8
and C-14), 134.8 'C-1 and C-11), 145.5 'C-10 and C-16),
177.0 'C-2 and C-12), 178.3 'C-9 and C-20). m/z 488 'MH1,
100), 406 'M12Br, 66).
[l'MoKa)0.711069 A, graphite monochromator, a scan
width of 0.38 and exposure time of 10 s/frame, detector-
crystal distance 4.95cm]. Data were corrected for absorp-
tion using SADABS program. The structures were solved by
direct methods and re®ned by least squares in full-matrix
approximation. Hydrogen atoms were placed to the calcu-
lated positions and were re®ned using the `riding model'.
SHELXTL [Bruker AXS, 1998] software package were
used for calculations and drawings. The angles between
planes and lattice packs were calculated using Oscail
Version 8 software. Crystallographic data 'excluding
structure factors) for the structures in this paper have
been deposited with the Cambridge Crystallographic Data
Center as supplementary publication numbers 161188-
161190. Copies of the data can be obtained, free of
charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK [fax: 144-01223-336033 or
e-mail: deposit@ccdc.cam.ac.uk].
3.2.3. N-Methyl-N,N-bis ꢀ3-chloro-1,4-naphthoquinonyl)-
amine ꢀ5c). '2.5g, 61%) was obtained from 2,3-dichloro-
1,4-naphthoquinone '2.72 g) and 2-methylamino-3-chloro-
1,4-naphthoquinone '2.22 g). The product was obtained as
red needles and melted at 229±2318C. nmax'KBr) 2960,
1666, 1651 cm21; dH '500 MHz) 3.58 's, 1H), 7.66 'dt,
2H, J7.4, 1.3 Hz), 7.70 'dt, 2H, J7.5, 1.3 Hz), 8.05
'dd, 2H, J7.8, 2.1 Hz), 8.12 'dd, 2H, J7.5, 1.5 Hz); dC
'125MHz) 'according to X-ray diagram of 5a, Fig. 5) 41.6
'CH3), 127.1 'C-6 and C-15), 127.4 'C-5 and C-16), 130.7
'C-7 and C-14), 131.3 'C-4 and C-17), 131.4 'C-8 and
C-13), 133.9 'C-3 and C-18), 134.4 'C-10 and C-11),
148.8 'C-1 and C-20), 176.0 'C-9 and C-12), 179.8 'C-2
and C-20). HRMS 'CI/i-bu) 'm/z): 411.002176 'MH1,
calcd. 411.006513 for C21H11Cl2NO4), 376 'M12Cl).
3.2. General procedure for the synthesis of 5a±d
3.2.4. N-ꢀ3,5,6-trichloro-1,4-benzoquinon-2-yl)-N-ꢀ3-chloro-
1,4-naphthoquinonyl)amine ꢀ5d). '3.3 g, 79%) was
obtained from chloranil '2.95g) and 2-amino-3-chloro-
1,4-naphthoquinone '2.07 g) as dark red needles melting
at 231±2328C. 'Found: C, 46.01; H, 1.24; Cl, 33.89, N,
3.42. C16H5Cl4NO4 required C, 46.08; H, 1.21; Cl, 34.01;
N, 3.36%); nmax'KBr) 3277, 1683, 1673, 1665cm 21; dH
'500 MHz) 6.83 'brs, 1H), 7.70 'dt, 1H, J7.5, 1.2 Hz),
7.75'dt, 1H, J7.5, 1.2 Hz), 7.98 'dd, 1H, J7.5,
1.3 Hz), 8.13 'dd, 1H, J7.6, 1.3 Hz), dC '125MHz)
'according to the X-ray diagram of 5d, Fig. 7) 121.2
'C-6), 126.2 'C-5), 127.3 'C-7), 127.6 'C-4), 130.3 'C-8),
131.3 'C-3), 134.5'C-10), 135.2 'C-11), 138.6 'C-1), 140.8
'C-16), 141.5'C-13), 148.9 'C-14), 170.3 'C-9), 172.4
'C-2), 176.7 'C-12), 178.6 'C-15). m/z 417 'M1), 380
'M12Cl, 100), 352 'M12Cl±CO).
Haloquinone '12.0 mmol) and aminoquinone '10 mmol)
were added to a solution of approximately 1 g of potassium
carbonate in DMF '50 mL, pH12) and the mixture was
allowed to stir for 2 h at room temperature. Addition of HCl
'2% ice-water solution, 100 mL) caused precipitation of the
crude product. This was ®ltered off, dissolved in CH2Cl2 and
puri®ed by silica gel column chromatography with methyl-
ene chloride as eluant. The products were recrystallized
from glacial acetic acid to yield orange to red ®ne crystals.
It is interesting to note that a typical feature of compounds
5a, 5b, and 5d is their color changes to strong blue upon
exposure to ammonia vapors.
3.2.1. N,N-Bisꢀ3-chloro-1,4-naphthoquinonyl)amine ꢀ5a).
'2.3 g, 58%) was obtained from 2,3-dichloro-1,4-naphtho-
quinone '2.72 g) and 2-amino-3-chloro-1,4-naphthoquinone
'2.07 g) as bright orange needles melting at 273±2748C,
'Found: C, 60.04; H, 2.28; Cl, 17.50, N, 3.39
C20H9Cl2NO4 requires C, 60.33; H, 2.28; Cl, 17.81; N,
3.3. General procedure for the synthesis of 8a±c
The quinone '20.0 mmol) and 2-amino-3-chloro-1,4-
naphthoquinone '2.08 g, 10 mmol) were added to a solution
of approximately 1 g of potassium carbonate in DMF
'50 mL, pH12) and the mixture was allowed to stir for
12 h at room temperature. Addition of HCl '2% ice-water
solution, 100 mL) caused precipitation of the crude product.
It was ®ltered off and puri®ed by silica gel column chroma-
tography with methylene chloride as eluant. The products
were recrystallized from glacial acetic acid. A change of
color to strong blue was observed upon exposure to
ammonia vapors.
3.52%); nmax 'KBr) 3318, 1676, 1660 cm21
;
dH
'500 MHz) 7.08 'brs, 1H), 7.76 'dt, 2H, J7.5, 1.8 Hz),
7.81 'dt, 2H, J7.5, 1.5 Hz), 8.05 'dd, 2H, J7.2,
1.8 Hz), 8.21 'dd, 2H, J7.2, 1.8 Hz). dC '125MHz)
'numbering of the carbons according to the X-ray diagram
of 5a, Fig. 5) 125.0 'C-6 and C-15), 127.2 'C-5 and C-16),
127.4 'C-7 and C-14), 130.6 'C-4 and C-17), 131.5'C-8 and
C-13), 133.9 'C-3 and C-18), 134.8 'C-10 and C-11), 142.4
'C-1 and C-20), 176.9 'C-9 and C-12), 178.8 'C-2 and
C-20). m/z 403 'M115, 100), 401 'M113, 74), 364
'M12Cl, 66).
3.3.1. N-ꢀNaphthoquinonyl)-N-ꢀ3-chloro-1,4-naphtho-
quinonyl)amine ꢀ8a). This compound was prepared from
1,4-naphthoquinone '3.16 g) and obtained as yellow needles
'1.49 g, 41%) melting at 246±2488C. 'nmax'KBr) 3304,
1681, 1662 cm21; dH '500 MHz) 5.88 's, 1H), 7.74 'dt,
1H, J7.5, 1.3 Hz), 7.80 'm, 2H), 7.83 'td, 1H, J7.4,
1.5Hz), 8.12 'dd, 1H, J7.6, 1.3 Hz), 8.16 'dd, 1H,
J7.2, 2.3 Hz), 8.18 'dd, 1H, J7.3, 2.6 Hz), 8.23 'dd,
1H, J7.5, 1.5 Hz), 8.31 'brs, 1H). dC '125MHz)
'according to Fig. 2) 110.4 'C-13), 115.3 'C-12), 126.5
'C-2), 126.8 'C-17), 127.2'C-18), 127.4 'C-8), 127.6
3.2.2. N,N-Bisꢀ3-bromo-1,4-naphthoquinonyl)amine ꢀ5b).
'3.5g, 69%) was obtained from 2,3-dibromo-1,4-naphtho-
quinone '3.7 g) and 2-amino-3-bromo-1,4-naphthoquinone
'2.52 g) as bright orange needles melting at 240±2428C.
nmax 'KBr) 3300, 1673 cm21; dH '500 MHz) 7.00 'brs,
1H), 7.67 'dt, 2H, J7.5, 1.3 Hz), 7.72 'dt, 2H, J7.6,
1.4 Hz), 7.95'dd, 2H, J7.5, 1.3 Hz), 8.16 'dd, 2H,
J7.8, 2.0 Hz). dC '125MHz), 'numbering of carbons
according to the X-ray diagram of 5b, Fig. 6) 119.0 'C-5
and C-19), 127.1 'C-6 and C-17), 127.4 'C-4 and C-15),