10.1002/adsc.202000082
Advanced Synthesis & Catalysis
ESI/MS negative mode: m/z 237 [M-H]-; MS2 m/z 173 [M- 131.5 (C7), 131.2 (C10), 131.1 (C9), 130.5 (C11), 128.1
H-SO2]-; MS3 145 [M-H-SO2-CO]-.
(C8), 127.6 (C12,16), 123.8 (C5), 114.7 (C13,15), 99.8 (C3)
and 55.3 (CH3). UV/Vis: 475 nm, ε = 5 389 M−1cm−1
(Ethanol). ESI-MS positive mode: 280 [M+H]+, MS2 (m/z):
General procedure for the cross-coupling reactions:
4-amino-3-hydroxynaphthalene-1-sulfonic acid (12 mg, 252 [M+H-CO]+; ESI-MS negative mode: 278 [M-H]-.ESI-
0.05 mmol) and the different aromatic amines (2a-g) (0.05 HRMS: m/z calcd. for [C17H13NO3+H]+: 280.0968; found
mmol) were dissolved in 10 mL of an ethanol: 20 mM 280.0969.
phosphate buffer (pH 7) solution (1:9) in a 25 mL round-
bottom flask. After the solubilisation of the starting 4-(Aminodiphenylamino)naphtalene-1,2-dione (3d)
materials, 1 U.mL-1 of CotA-laccase was added and an Purple solid (13.3 mg, 78%), mp = 247.6 – 248.2 ºC. 1H
immediate change of colour was observed in all assays. NMR (400 MHz, DMSO-d6): δ (ppm) = 9.91 (bs, 1H, NH),
Reactions proceed with stirring, at room temperature, under 8,39 (s, 1H, NH), 8.33 (d, 1H, J = 7.9 Hz, H5), 8.04 (d, 1H,
aerobic conditions and progress was monitored by TLC. The J = 7.7 Hz, H8), 7.86 (t, 1H, J = 7.6 Hz, H6), 7.73 (t, 1H, J
final products were isolated by filtration or by extraction = 7.5 Hz, H7), 7.27 (t, 2H, J = 7.7 Hz, H19,21), 7.18 (s, 4H,
with ethyl acetate followed by solvent removal. Whenever H13,15,18,22), 7.13 (d, 2H, J = 7.9 Hz, H12,16), 6.87 (t, 1H,
necessary the crude residues were purified by J = 7.3 Hz, H20) and 5.81 (bs, 1H, H3). 13C NMR (DMSO-
preparative/column chromatography.
d6) δ (ppm) = 181.4 (C1), 154.6 (C4), 142.9 (C14,17), 134.1
(C6), 131.4 (C7), 131.2 (C9,10), 129.3 (C12,16,19,21),
127.6 (C8), 123.8 (C5), 120.2 (C20), 117.2 (C11,18,22),
116.7 (C13,15) and 100.6 (C3). UV/Vis: 520 nm, ε = 4 979
M−1 cm−1 (Ethanol). ESI-MS positive mode: 341 [M+H]+,
MS2 (m/z): 313 [M+H-CO]+, ESI-MS negative mode: 339
Characterization of the 4-arylamino-1,2-naphthoquino-
ne products:
4-(Aminophenylamino)naphthalene-1,2-dione (3a)
Purple solid (10.2 mg, 79%), mp = 212.0 - 212.9 ºC. H [M-H]-; MS2 (m/z): 311 [M-H-CO]-, MS3 (m/z): 283 [M-H-
NMR (400 MHz, CD3OD-d4): δ (ppm) = 8.19 (d, 1H, J = 8.8 CO-CO]-. ESI-HRMS: m/z calcd. for [C22H15N2O2+H]+:
Hz, H5), 8.16 (d, 1H, J = 7.6 Hz, H8), 7.83 (t, 1H, J = 8.8 341.1285; found 341.1279.
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Hz, H6), 7.73 (t, 1H, J = 8.8 Hz, H7), 7.10 (d, 2H, J = 8.8
Hz, H12,16), 6.83 (d, 2H, J = 8.8 Hz, H13,15) and 5.92 (s, 4-(Dimethylphenylamino)naphtalene-1,2-dione (3e)
1H, H3).
Dark purple solid (11.1 mg, 76%), mp = 215.3 – 216.0 ºC.
13C NMR (DMSO-d6) δ(ppm) = 181.8 (C1), 175.2 (C2), 1H NMR (400 MHz, DMSO-d6): δ (ppm) = 8.04 (bs, 1H,
155.0 (C4), 148.0 (C14), 134.2 (C6), 131.4 (C7), 130.7 H5), 7.72 (bs, 1H, H8), 7.62 (bs, 1H, H6), 7.48 (d, 1H, J =
(C10), 130.6 (C9),128.0 (C8), 127.1 (C12,16), 125.4 (C11), 7.8 Hz, H7), 7.40 (d, 2H, J = 8.3 Hz, H12,16), 6.85 (d, 2H,
123.6 (C5), 114.1 (C13,15), 99.8 (C3). UV/Vis: 500 nm, ε = J = 8.3 Hz, H13,15), 6.30 (s, 1H, H3) and 3.01 (s, 6H, CH3).
2 428 M−1 cm−1 (ethanol). ESI-MS positive mode: 287 13C NMR (DMSO-d6) δ(ppm) = 179.5 (C1), 179.4 (C2),
[M+Na]+; 265 [M+H]+, MS2 (m/z): 237 [M+H-CO]+, MS3 155.7 (C4), 151.4 (C14), 134.8 (C8), 134.7 (C10), 132.0
(m/z): 209 [M+H-CO-CO]+; ESI-MS negative mode: 263 (C9), 130.6 (C6), 129.8 (C12,16), 129.4 (C7), 129.3 (C5),
[M-H]-. ESI-HRMS: m/z calcd. for [C16H13N2O2+H]+: 125.5 (C3), 122.9 (C11), 111.8 (C13,15) and 40.0 (CH3,
265.0972; found 265.0974.
under the solvent peak). UV/Vis: 525 nm, ε = 6 529 M−1cm−1
(Ethanol). ESI-MS positive mode: 293[M+H]+, MS2 (m/z):
265 [M+H-CO]+, ESI-HRMS: m/z calcd. for
4-(Hydroxyphenylamino)naphtalene-1,2-dione (3b)
Red solid (10.6mg, 80%), mp = 310.7 – 311.2 ºC. 1H NMR [C18H16N2O2+H]+: 293.1285; found 293.1283.
(400 MHz CD3OD-d4): δ (ppm) = 8.22 (d, 1H, J = 7.6 Hz,
H5), 8.14 (d, 1H, J = 7.2 Hz, H8), 7.80 (t, 1H, J = 7.2 Hz, 4-(Acetaminophenylamino)naphtalene-1,2-dione (3f)
H6), 7.70 (t, 1H, J = 7.2 Hz, H7), 7.12 (d, 2H, J = 8.0 Hz, Dark red solid (10.8 mg, 71 %), mp = 349.9 – 350.3 ºC. 1H
H12,16), 6.90 (d, 2H, J = 8.4 Hz, H13,15) and 5.91 (s, 1H, NMR (400 MHz, DMSO-d6): δ (ppm) = 10.08 (s, 1H, NH),
H3).13C NMR (DMSO-d6) δ(ppm) = 181.5 (C1), 175.4 (C2), 9.88 (bs, 1H, NH), 8.30 (d, 1H, J = 6.9 Hz, H5), 8.02 (d, 1H,
156.4 (C4), 155.1 (C14), 134.3 (C6), 131.5 (C7), 131.4 J = 6.9 Hz, H8), 7.84 (bs, 1H, H6), 7.77-7.60 (m, 3H, H7,
(C10), 130.8 (C9), 128.7 (C8), 128.1 (C11), 127.7 (C12,16), H13,15), 7.20 (bs, 2H, H12,16), 5.73 (bs, 1H, H3) and 2.05
123.7 (C5), 116.0 (C13,15) and 99.9 (C3). UV/Vis: 480 nm, (s, 3H, CH3). 13C NMR (DMSO-d6) δ (ppm) = 181.2 (C1),
ε = 4 936 M−1cm−1 (Ethanol). ESI-MS positive mode: 288 168.6 (C=O), 154.7 (C4), 134.1 (C6), 131.5 (C7), 131.2
[M+Na]+; 266 [M+H]+, MS2 (m/z): 238 [M+H-CO]+, MS3 (C9,10), 128.4 (C8), 126.7 (C12,16), 123.9 (C5), 119.6
(m/z): 210 [M+H-CO-CO]+; ESI-MS negative mode: 264 (C11,13,15) and 23.8 (CH3). UV/Vis: 465 nm, ε = 4 456
[M-H]-. ESI-HRMS: m/z calcd. for [C16H11NO3+H]+: M−1cm−1 (Ethanol). ESI-MS positive mode: 307[M+H]+,
266.0812; found 266.0810.
MS2 (m/z): 279 [M+H-CO]+, MS3 (m/z): 251 [M+H-CO-
CO]+. ESI-HRMS: m/z calcd. for [C18H14N2O3+H]+:
307.1077; found 307.1078.
4-(Methoxyphenylamino)naphtalene-1,2-dione (3c)
Dark red solid (10.9 mg, 78%), mp = 249.8 – 250.4 ºC. H
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NMR (400 MHz, DMSO-d6): δ (ppm) = 9.82 (bs, 1H, NH),
8.31 (bs, 1H, H5), 8.04 (d, 1H, J = 8.0 Hz, H8), 7.87 (t, 1H, 4-(Cyanophenylamino)naphtalene-1,2-dione (3g)
J = 7.6 Hz, H6), 7.74 (t, 1H, J = 7.6 Hz, H7), 7.31 (bs, 2H, Red solid (7.1 mg, 52%), mp = 250.3 – 250.8 ºC. 1H NMR
H12,16), 7.07 (d, 2H, J = 8.4 Hz, H13,15), 5.54 (s, 1H, H3) (300 MHz, DMSO-d6): δ(ppm) = 8.31 (d, 1H, J = 7.8 Hz,
and 3.81 (s, 3H, CH3). 13C NMR (DMSO-d6) δ (ppm) = H5), 8.06 (d, 1H, J = 7.8 Hz, H8), 7.89 (d, 2H, J = 7.8 Hz,
181.2 (C1), 175.4 (C2), 158.0 (C14), 154.9 (C4), 134.0 (C6), H13,15), 7.83 (m, 1H, J = 7.2 Hz, H6), 7.73 (t, 1H, J = 7.8
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