The Journal of Organic Chemistry
Page 8 of 10
139.4, 137.3, 131.5, 129.2, 128.8, 126.5, 124.7, 122.8, 101.5; HRMS (ESI+):
1'H,3'H-Spiro[naphtho[2,3-d][1,3]dioxole-2,2'-phenalene]-1',3'-
dione (30). 30 was synthesized following the general procedure A using 2,2-
dichloro-1H-phenalene-1,3(2H)-dione (14, 501 mg, 1.89 mmol,
+
m/z calcd. for C21H13O4 329.0808 [M+H]+, found 329.0806; elemental
1
2
3
4
5
6
7
8
analysis calcd (%) for C21H12O4: C 76.82, H 3.68; found: C 76.94, H 3.80;
UV/Vis (CH2Cl2): ƛmax (log ε) = 367 (2.61), ; mp = 178 °C.
1.0 equiv.), naphthalene-2,3-diol (17, 363 mg, 2.26 mmol, 1.2 equiv.) and
K2CO3 (1.05 g, 7.56 mmol, 4.0 equiv.). Column chromatography (silica gel,
cyclohexane/CH2Cl2: 1/0 to 0/1) afforded 30 (507 mg, 82%) as a white
solid. Rf = 0.73 (CH2Cl2); 1H NMR (500 MHz, CDCl3) δ = 8.55 (dd, J = 7.2,
1.3 Hz, 2H), 8.34 (dd, J = 8.3, 1.2 Hz, 2H), 7.82 (dd, J = 8.3, 7.2 Hz, 2H),
7.70–7.65 (m, 2H), 7.37–7.32 (m, 2H), 7.22 (s, 2H); 13C NMR (126 MHz,
CDCl3) δ = 186.8, 146.9, 136.0, 133.3, 132.1, 130.7, 130.6, 127.5, 127.2,
Spiro[cyclopenta[b]naphthalene-2,2'-naphtho[2,3-d][1,3]diox-
ole]-1,3-dione (26). 26 was synthesized following the general procedure A
using 2,2-dichloro-1H-cyclopenta[b]naphthalene-1,3(2H)-dione (10,
300 mg, 1.13 mmol, 1.0 equiv.), naphthalene-2,3-diol (17, 254 mg,
1.58 mmol, 1.4 equiv.) and K2CO3 (626 mg, 4.52 mmol, 4.0 equiv.). Col-
umn chromatography (silica gel, cyclohexane/CH2Cl2: 1/0 to 0/1) afforded
+
a
yellow solid. Rf = 0.81 (CH2Cl2); 1H NMR
127.1, 125.0, 105.6, 104.9; HRMS (ESI+): m/z calcd. for C23H13O4
26 (343 mg, 86%) as
9
353.0808 [M+H]+, found 353.0807; elemental analysis calcd (%) for
C23H12O4: C 78.40, H 3.43; found: C 76.98, H 3.32; UV/Vis (CH2Cl2): ƛmax
(log ε) = 326 (3.95), ; mp = 319 °C.
(400 MHz, CDCl3) δ = 8.76–8.71 (m, 2H), 8.24–8.16 (m, 2H), 7.88–7.80
(m, 2H), 7.75–7.67 (m, 2H), 7.42–7.33 (m, 2H), 7.24 (s, 2H); 13C NMR
(101 MHz, CDCl3) δ = 190.0, 147.4, 137.4, 134.6, 131.1, 131.0, 130.9,
127.5, 126.8, 125.0, 104.7 (due to low solubility of this compounds, the
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1'H,3'H-Spiro[dibenzo[d,f][1,3]dioxepine-6,2'-phenalene]-1',3'-
dione (31). 31 was synthesized following the general procedure A using 2,2-
+
spiro-C-atom is not visible); HRMS (APCI+): m/z calcd. for C23H13O4
353.0808 [M+H]+, found 353.0808; elemental analysis calcd (%) for
C23H12O4: C 78.40, H 3.43; found: C 76.91, H 4.14; UV/Vis (CH2Cl2): ƛmax
(log ε) = 436 (2.20), ; mp = 293 °C.
dichloro-1H-phenalene-1,3(2H)-dione
(14,
261 mg,
0.98 mmol,
1.0 equiv.), [1,1'-biphenyl]-2,2'-diol (18, 220 mg, 1.18 mmol, 1.2 equiv.)
and K2CO3 (544 mg, 3.94 mmol, 4.0 equiv.). Column chromatography (sil-
ica gel, cyclohexane/CH2Cl2: 1/0 to 1/1) afforded 31 (239 mg, 64%) as a
white solid. Rf = 0.56 (cyclohexane/CH2Cl2: 1/1); 1H NMR (400 MHz,
CD2Cl2) δ = 8.45–8.39 (m, 2H), 8.37–8.30 (m, 2H), 7.88–7.77 (m, 2H),
7.60–7.50 (m, 2H), 7.42–7.30 (m, 4H), 7.18–7.05 (m, 2H); 13C NMR
(101 MHz, CD2Cl2) δ = 189.5, 151.9, 135.6, 133.6, 132.1, 131.8, 129.9,
129.7, 129.2, 128.8, 127.5, 126.7, 123.6, 110.2; HRMS (ESI+): m/z calcd.
for C25H15O4 379.0965 [M+H]+, found 379.0964; elemental analysis calcd
(%) for C25H14O4: C 78.96, H 3.83; found: C 78.28, H 3.77; UV/Vis
(CH2Cl2): ƛmax (log ε) = 319 (3.84); mp = 275 °C.
(R)-1'H,3'H-Spiro[dinaphtho[2,1-d:1',2'-f][1,3]dioxepine-4,2'-
phenalene]-1',3'-dione (32). 32 was synthesized following the general pro-
cedure B using 2,2-dichloro-1H-phenalene-1,3(2H)-dione (14, 210 mg,
0.79 mmol, 1.0 equiv.), (R)-[1,1′-binaphthalene]-2,2′-diol (19, 272 mg,
0.95 mmol, 1.2 equiv.) and K2CO3 (438 mg, 3.17 mmol, 4.0 equiv.). Col-
umn chromatography (silica gel, cyclohexane/EtOAc: 1/0 to 1/1) afforded
32 (353 mg, 93%) as a white solid. Rf = 0.64 (cyclohexane/CH2Cl2: 1/1);
1H NMR (500 MHz, CD2Cl2) δ = 8.39 (dd, J = 7.2, 1.2 Hz, 2H), 8.36 (dd,
J = 8.4, 1.2 Hz, 2H), 7.99–7.93 (m, 4H), 7.84 (dd, J = 8.2, 7.2 Hz, 2H), 7.48
(ddd, J = 8.1, 6.7, 1.2 Hz, 2H), 7.43–7.36 (m, 4H), 7.29 (ddd, J = 8.5, 6.6,
1.3 Hz, 2H); 13C NMR (126 MHz, CD2Cl2) δ = 189.5, 150.2, 135.6, 133.6,
132.5, 132.5, 131.8, 130.3, 129.9, 128.9, 128.8, 127.5, 127.5, 126.7, 126.0,
125.0, 123.0, 111.5; HRMS (ESI+): m/z calcd. for C33H22O4N+ 496.1543
[M+NH4]+, found 496.1541; elemental analysis calcd (%) for C33H18O4: C
82.83, H 3.79; found: C 82.89, H 3.83; UV/Vis (CH2Cl2): ƛmax (log ε) = 312
(4.36); ; mp = 264 °C.
Spiro[cyclopenta[b]naphthalene-2,6'-dibenzo[d,f][1,3]diox-
epine]-1,3-dione (27). 27 was synthesized following the general procedure
A
using 2,2-dichloro-1H-cyclopenta[b]naphthalene-1,3(2H)-dione (10,
300 mg, 1.13 mmol, 1.0 equiv.), [1,1'-biphenyl]-2,2'-diol (18, 295 mg,
1.58 mmol, 1.4 equiv.) and K2CO3 (626 mg, 4.52 mmol, 4.0 equiv.) Column
chromatography (silica gel, cyclohexane/CH2Cl2: 1/0 to 0/1) afforded 27
1
(312 mg, 73%) as a yellow solid. Rf = 0.81 (CH2Cl2); H NMR (500 MHz,
CDCl3) δ = 8.67 (s, 2H), 8.20–8.14 (m, 2H), 7.83–7.77 (m, 2H), 7.61–7.55
(m, 2H), 7.43–7.36 (m, 4H), 7.18–7.12 (m, 2H); 13C NMR (126 MHz,
CDCl3) δ = 191.1, 150.8, 137.3, 134.0, 131.6, 130.9, 130.5, 129.3, 128.9,
+
126.5, 126.4, 122.9, 102.1; HRMS (APCI+): m/z calcd. for C25H15O4
379.0965 [M+H]+, found 379.0966; elemental analysis calcd (%) for
C25H14O4: C 79.36, H 3.73; found: C 79.61, H 3.81; UV/Vis (CH2Cl2): ƛmax
(log ε) = 392 (2.43), ; mp = 253 °C.
(R)-Spiro[cyclopenta[b]naphthalene-2,4'-dinaphtho[2,1-d:1',2'-
f][1,3]dioxepine]-1,3-dione (28). 28 was synthesized following the gen-
eral procedure
B using 2,2-dichloro-1H-cyclopenta[b]naphthalene-
1,3(2H)-dione (10, 309 mg, 1.17 mmol, 1.0 equiv.), (R)-[1,1′-binaphtha-
lene]-2,2′-diol (19, 404 mg, 1.41 mmol, 1.2 equiv.) and K2CO3 (649 mg,
4.70 mmol, 4.0 equiv.). Column chromatography (silica gel, cyclohex-
ane/CH2Cl2: 1/0 to 1/1) afforded 28 (468 mg, 83%) as a yellow crystalline
solid. Rf = 0.49 (cyclohexane/CH2Cl2: 1/1); 1H NMR (500 MHz, CDCl3) δ
= 8.66 (s, 2H), 8.19–8.13 (m, 2H), 8.02–7.99 (m, 2H), 7.99–7.96 (m, 2H),
7.80–7.75 (m, 2H), 7.53–7.50 (m, 2H), 7.49 (ddd, J = 8.1, 6.8, 1.2 Hz, 2H),
7.41 (d, J = 8.7 Hz, 2H), 7.32 (ddd, J = 8.4, 6.8, 1.2 Hz, 2H); 13C NMR
(126 MHz, CDCl3) δ = 191.1, 149.0, 137.3, 134.0, 132.4, 132.3, 130.9,
130.6, 129.9, 128.6, 127.5, 126.4, 126.1, 125.5, 124.6, 122.4, 103.1;
ASSOCIATED CONTENT
+
HRMS (APCI+): m/z calcd. for C33H19O4 479.1278 [M+H]+, found
Supporting Information
479.1281; elemental analysis calcd (%) for C33H18O4: C 82.83, H 3.79;
found: C 82.88, H 3.81; UV/Vis (CH2Cl2): ƛmax (log ε) = 392 (3.16);
mp = 287 °C.
(S)-Spiro[cyclopenta[b]naphthalene-2,4'-dinaphtho[2,1-d:1',2'-
f][1,3]dioxepine]-1,3-dione (29). 29 was synthesized following the gen-
CCDC 1859605 (7), 1874678 (8), 1964046 (13), 1964067 (14),
1864464 (21), 1874255 (23), 1864468 (25), 1912192 (26), 1900045
(27), 1964127 (29), 1886536 (32) contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
NMR spectra, X-ray crystallographic data, TGA and DSC measure-
ments, further cyclic voltammograms, further computational results,
and energies and Cartesian coordinates of calculated structures. The
Supporting Information is available free of charge on the ACS Publica-
tions website.
eral procedure
B using 2,2-dichloro-1H-cyclopenta[b]naphthalene-
1,3(2H)-dione (10, 458 mg, 1.74 mmol, 1.0 equiv.), (S)-[1,1′-binaphtha-
lene]-2,2′-diol (20, 598 mg, 2.09 mmol, 1.2 equiv.) and K2CO3 (962 mg,
6.96 mmol, 4.0 equiv. Column chromatography (silica gel, cyclohex-
ane/CH2Cl2: 1/0 to 1/1) afforded 29 (707 mg, 85%) as a yellow crystalline
solid. Rf = 0.49 (cyclohexane/CH2Cl2: 1/1); 1H NMR (500 MHz, CDCl3) δ
= 8.66 (s, 2H), 8.21–8.13 (m, 2H), 8.01–7.99 (m, 2H), 7.99–7.96 (m, 2H),
7.82–7.75 (m, 2H), 7.53–7.50 (m, 2H), 7.49 (ddd, J = 8.1, 6.8, 1.2 Hz, 2H),
7.41 (d, J = 8.7 Hz, 2H), 7.31 (ddd, J = 8.4, 6.8, 1.2 Hz, 2H); 13C NMR
(126 MHz, CDCl3) δ = 191.1, 149.0, 137.3, 134.0, 132.5, 132.3, 130.9,
130.6, 129.9, 128.6, 127.5, 126.4, 126.1, 125.5, 124.6, 122.4, 103.1;
AUTHOR INFORMATION
Corresponding Author
+
HRMS (APCI+): m/z calcd. for C33H19O4 479.1278 [M+H]+, found
* besser@oc.uni-freiburg.de.
479.1281; elemental analysis calcd (%) for C33H18O4: C 82.83, H 3.79;
found: C 82.89, H 3.83; UV/Vis (CH2Cl2): ƛmax (log ε) = 392 (3.16);
mp = 287 °C.
ORCID
Jan Wössner: 0000-0003-2170-4798
ACS Paragon Plus Environment