S1 PHOTOINDUCED SKELETAL REARRANGEMENT OF ...
PHOTOINDUCED SKELETAL REARRANGEMENT OF DIARYLETHENES COMPRISING OXAZOLE AND PHENYL RINGS Andrey G. Lvov, Valerii Z. Shirinian,* Vadim V. Kachala, Alexey M. Kavun, Igor V. Zavarzin, Mikhail M. Krayushkin N. D. Zelinsky Institute of Organic Chemistry, RAS, 47, Leninsky prosp., 119991 Moscow, Russian Federation, e-mail: [email protected]
Supporting Information Table of Contents
I. General information, synthesis and characterization of starting compounds...........................S2 II. General procedure and analytical data for photoproducts 2 and compound 3.......................S7 III. NMR monitoring of photoreaction........................................................................................S12 VI. UV-vis spectra of compounds 1a,b,e,f,g and 2a,b,e,f,g.........................................................S13 V. Absorption spectra of photoinduced form of diarylethenes 1b and 1f ...................................S18 VI. 2D NMR spectra of compounds 2a,b,f...................................................................................S19 VII. Temperature dependent NMR spectra of compound 2g.......................................................S44 VIII. References...........................................................................................................................S45 IX. Copies of 1H NMR and 13C NMR spectra..............................................................................S46
S1
I. General information, synthesis and characterization of starting compounds Proton nuclear magnetic resonance spectra (1H NMR) and carbon nuclear magnetic resonance spectra (13C NMR) were recorded in deuterated solvents on a spectrometers working at 300 MHz or 400 MHz or 600 MHz for 1H, 75 MHz or 101 MHz or 151 MHz for 13C. Data are represented as follows: chemical shift, multiplicity (s, singlet; d, doublet; m, multiplet; br, broad), coupling constant in hertz (Hz), integration, and assignment. Infrared spectra were measured on a FT-IR spectrometer in KBr pellets or abs. CHCl3 solutions and are reported in terms of frequency of absorption (cm−1). Melting points (Mp) were recorded using an apparatus and not corrected. Mass spectra were obtained on a mass spectrometer (70 eV) with direct sample injection into the ion source. High resolution mass spectra were obtained from a TOF mass spectrometer with an ESI source. All chemicals and solvents were purchased from commercial sources and used without further purification. Silica column chromatography was performed using silica gel 60 (70−230 mesh); TLC analysis was conducted on silica gel 60 F254 plates. Photochemical studies. UV−Vis spectra were recorded in 1.0 cm quartz cuvettes. The experimental measurements were performed at 293 K in the presence of air in solutions of acetonitrile. The irradiation was carried out using a 6W Vilber Lourmat (France) UV-lamp model VL-6.LC (365 nm light). Synthesis of the starting diarylethenes. 2,3-Diarylcyclopent-2-en-1-ones 1a-e were prepared according previously reported method[S1] from corresponding ketoesters[S2,S3] and bromoketones[S4] (Scheme S1). Cyclopentene 1f was synthesized from diarylethene 1a by the reduction with triethylsilane in the presence of trifluoromethanesulfonic acid (Scheme S2).[S5] Diarylethene 1g was prepared by Robinson type reaction of ethyl 3-oxo-4-phenylbutanoate[S2] with chalcone 9 (this compound was prepared according to the literature protocol[S6] and was used without additional purification) with subsequent hydrolysis and decarboxylation (Scheme S3).[S7] Diarylethene 1h was prepared from (5-methyl-2-phenyl-1,3-oxazol-4-yl)acetic acid[S8] and benzaldehyde with subsequent esterification (Scheme S4).[S9]
S2
N
1a: Ar1 = Ph; Ar2 = Me
O 1
Ar
CO2 Et
1b: Ar1 = Br
2
Ar
N Me
Ph
O
O
Ph
O
; Ar2 = Ph N
1c: Ar1 = Ph; Ar2 =
O
1
Me
2
Ar
Ar
O OMe
1a-e
1d:
Ar1 =
Ph;
N
Ar2 = Me
O CF 3
1e: Ar1 =
N
; Ar2 = Me
O
Ph
Scheme S1. Synthesis of the diarylethenes of cyclopentenone series.
O Et3SiH, CF3SO3H N
N DCM
O
Me
Ph
Me 1f
1a
O
Ph
Scheme S2. Synthesis of diarylethene 1f.
Ph
EtO2C O
Ph
CO2Et
Ph
O
O
O
N
Ph Me
O
-CO2 -EtOH
N
Ph Me
9
O
N
Ph
Me 1g
Scheme S3. Synthesis of diarylethene 1g.
O
HO2C
EtO2C
HO2C C2H5OH
Ph N Ph
N
N O
Me
Ph
O
Me
Ph
O
Me 1h
Scheme S4. Synthesis of diarylethene 1h.
S3
O
Ph
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one (1a). Yield 35%, yellow crystals. Mp 210-212 °C. IR (KBr), cm-1: 3068, 1697, 1636, 1600, O
1158, 698. 1H NMR (300 MHz, CDCl3): δ = 1.70 (s, 3H, CH3), 2.63N Ph
O
2.79 (m, 2H, CH2), 3.06-3.20 (m, 2H, CH2), 7.27-7.58 (m, 8H, Harom), 7.94-8.08 (m, 2H, Harom). 13C NMR (75 MHz, CDCl3): δ = 11.6, 29.2,
1a
34.7, 126.1, 127.0, 127.7, 128.5, 128.8, 129.1, 130.4, 132.4, 132.9, 139.4, 148.0, 160.5, 160.9, 207.3. MS (EI, 70 eV): m/z (%) = 315 (100) [M]+, 300 (15) [M-CH3]+, 286 (25). HRMS (ESITOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1323.
2-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylcyclopent-2-en-1-one (1b). Yield 27%, yellow crystals. Mp 148-150 °C. IR (KBr), cm-1: 2919, 1700, 1557, 1444,
O
1373, 929. 1H NMR (300 MHz, CDCl3): δ = 2.15 (s, 3H, CH3), 2.66N Ph
2.79 (m, 2H, CH2), 3.08-3.20 (m, 2H, CH2), 7.31-7.48 (m, 6H, Harom),
O 1b
7.50-7.63 (m, 2H, Harom), 7.92-8.07 (m, 2H, Harom).
13
C NMR (75
MHz, CDCl3): δ = 11.1, 29.7, 34.6, 126.1, 127.6, 128.0, 128.3, 128.4, 128.6, 129.9, 130.4, 131.8, 135.2, 147.2, 160.4, 170.8, 206.8. MS (EI, 70 eV): m/z (%) = 315 (100) [M]+, 286 (20). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1337.
3-[2-(4-methoxyphenyl)-5-methyl-1,3-oxazol-4-yl]-2-phenylcyclopent-2-en-1-one
(1c).
Yield
40%, yellow crystals. Mp 150-152 °C. IR (KBr), cm-1: 2931,
O
1694, 1627, 1505, 1259, 1154, 1030. 1H NMR (300 MHz, N
CDCl3): δ = 1.68 (s, 3H, CH3), 2.65-2.74 (m, 2H, CH2),
O 1c
OMe
3.07-3.17 (m, 2H, CH2), 6.98 (d, J = 8.8 Hz, 2H, Harom),
7.27-7.41 (m, 5H, Harom), 7.94 (d, J = 8.8 Hz, 2H, Harom). 13C NMR (75 MHz, CDCl3): δ = 11.6, 29.2, 34.7, 55.4, 114.2, 119.8, 127.7, 127.8, 128.4, 129.1, 132.5, 132.7, 139.2, 147.4, 160.5,
S4
161.1, 161.4, 207.4. MS (EI, 70 eV): m/z (%) = 345 (100) [M]+, 330 (17) [M-CH3]+, 316 (25). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20NO3: 346.1438; Found: 346.1436.
3-{5-methyl-2-[4-(trifluoromethyl)phenyl]-1,3-oxazol-4-yl}-2-phenylcyclopent-2-en-1-one (1d). Yield 27%, orange crystals. Mp 168-170 °C. IR (KBr), cm-1: O
3054, 1697, 1621, 1326, 1166, 1073. 1H NMR (300 MHz, N
CDCl3): δ = 1.73 (s, 3H, CH3), 2.68-2.75 (m, 2H, CH2), 3.09-
O CF3
1d
3.19 (m, 2H, CH2), 7.29-7.41 (m, 5H, Harom), 7.73 (d, J = 8.1
Hz, 2H, Harom), 8.12 (d, J = 8.1 Hz, 2H, Harom).13C NMR (75 MHz, CDCl3): δ = 11.7, 29.2, 34.7, 125.8, 126.4, 127.9, 128.5, 128.7, 129.1, 129.4, 130.2, 132.3, 133.4, 139.8, 148.8, 159.1, 160.2, 207.2. MS (EI, 70 eV): m/z (%) = 383 (100) [M]+, 368 (50) [M-CH3]+, 354 (45). HRMS (ESITOF) m/z: [M + H]+ Calcd for C22H17F3NO2: 384.1206; Found: 384.1203.
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-(1-naphthyl)cyclopent-2-en-1-one (1e). Yield
26%,
yellow crystals. Mp 224-226 °C. IR (KBr), cm-1: 3046, 1687,
O
1628, 1191, 1155, 775. 1H NMR (300 MHz, CDCl3): δ = 1.34 (s, N O 1e
Ph
3H, CH3), 2.78-2.88 (m, 2H, CH2), 3.28-3.39 (m, 2H, CH2), 7.317.56 (m, 7H, Harom), 7.64 (d, J = 8.2 Hz, 1H, Harom), 7.80-7.97 (m,
4H, Harom). 13C NMR (75 MHz, CDCl3): δ = 11.5, 29.5, 34.7, 125.4, 125.5, 125.8, 126.0, 126.1, 126.9, 127.8, 128.4, 128.5, 128.7, 130.3, 130.7, 131.4, 132.9, 133.7, 138.7, 149.0, 160.0, 162.8, 207.6. MS (EI, 70 eV): m/z (%) = 365 (80) [M]+, 262 (30), 219 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H20NO2: 366.1489; Found: 366.1485.
S5
5-Methyl-2-phenyl-4-(2-phenylcyclopent-1-en-1-yl)-1,3-oxazole (1f). Yield 65%, yellow crystals. Mp 81-83 °C. IR (KBr), cm-1: 2951, 2842, 1602, 1493, 1447, 1333, 770, 691. 1H NMR (300 MHz, CDCl3): δ = 1.76 (s, 3H, CH3), 2.03N Ph
O
2.18 (m, 2H, CH2), 2.84-3.02 (m, 4H, 2 x CH2), 7.117.33 (m, 5H, Harom), 7.38-7.50 (m, 3H, Harom), 7.99-8.08 (m, 2H, CH2).
1f 13
C NMR (75 MHz, CDCl3): δ = 10.9, 22.3, 38.0, 126.0, 126.6, 127.4, 127.8, 128.1, 128.6,
129.2, 129.7, 133.9, 138.3, 140.1, 144.2, 159.6. MS (EI, 70 eV): m/z (%) = 301 (40) [M]+, 196 (10), 155 (35). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO: 302.1539; Found: 302.1533.
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2,5-diphenylcyclohex-2-en-1-one (1g). Yield 19%, yellow crystals. Mp 130-132 °C. IR (KBr), cm-1: 3058, 3029, 2920, 1737,
Ph
1672, 1596, 1492, 1289, 696. 1H NMR (300 MHz, CDCl3): δ = 1.58 (s,
O
3H, CH3), 2.88-3.05 (m, 3H, CH2 + ½ CH2); 3.44-3.71 (m, 2H, CH +
N Ph
O
½ CH2), 7.12-7.53 (m, 13H, Harom), 7.90-8.05 (m, 2H, CH2). 13C NMR
1g
(75 MHz, CDCl3): δ = 11.1, 38.6, 39.9, 45.2, 126.0, 126.8, 126.9, 127.1, 127.2, 127.9, 128.7, 130.2, 130.8, 135.2, 135.3, 137.6, 143.2, 146.3, 148.1, 160.0, 197.4. MS (EI, 70 eV): m/z (%) = 405 (100) [M]+, 390 (45) [M-CH3]+, 301 (40). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H24NO2: 406.1802; Found: 406.1806.
Ethyl 2-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylprop-2-enoate (1h). Yield 45%, yellow oil. IR (KBr), cm-1: 2982, 1713, 1251, 1035, 694. 1H NMR (300 MHz, CO2 Et
CDCl3): δ = 1.33 (t, J = 7.1 Hz, 3H, CH3), 2.01 (s, 3H, CH3), 4.31 (q, J
N O 1h
Ph
= 7.1 Hz, 2H, CH2), 7.21-7.33 (m, 5H, Harom), 7.40-7.49 (m, 3H, Harom), 7.99 (s, 1H, CH), 8.01-8.10 (m, 2H, Harom). 13C NMR (75 MHz,
CDCl3): δ = 10.6, 14.3, 61.3, 123.3, 126.2, 127.7, 128.4, 128.6, 129.4, 130.0, 131.0, 134.6, S6
143.9, 146.2, 160.1, 166.9. MS (EI, 70 eV): m/z (%) = 333 (70) [M]+, 287 (40) [M-EtOH]+, 259 (55). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO3: 334.1438; Found: 334.1434.
II. General procedure and analytical data for photoproducts 2 and compound 3 Diarylethene 1 (0.3 mmol) was dissolved in CHCl3 (3 ml) and the reaction mixture in a quartz vessel (1 x 1 x 4 cm3) was irradiated with UV-light (UV lamp, λ = 365 nm, 6W). After completion of the reaction (TLC control) the solution was evaporated under vacuum, the residue was purified by flash chromatography eluting by light petroleum - ethyl acetate 10:1 (compounds 2b,f,h) or by recrystallization from small amount of mixture CH2Cl2/petroleum ester 1:1 (compounds 2a,c-e,g).
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2a). Irradiation time 4 h. Yield 76 mg (80%), white crystals. Mp 248-250 °C. IR O
(KBr), cm-1: 3294 (NH), 1703, 1638, 1505, 1484, 1279. 1H NMR (400
H N Ph
MHz, DMSO-d6): δ = 2.65 (s, 3H, CH3), 2.72-2.78 (m, 2H, CH2),
O 2a
3.06-3.13 (m, 2H, CH2), 7.56-7.77 (m, 5H, Harom), 8.09 (d, J = 7.2 Hz,
2H, Harom), 8.23 (d, J = 8.3 Hz, 1H, Harom), 9.13 (d, J = 8.0 Hz, 1H, Harom), 10.30 (s, 1H, NH). 13
C NMR (101 MHz, DMSO-d6): δ = 15.0, 24.4, 36.7, 123.6, 125.7, 127.2, 127.9, 128.2, 128.8,
129.0, 129.6, 132.2, 132.3, 132.5, 134.4, 140.1, 157.8, 166.2, 207.1. MS (EI, 70 eV): m/z (%) = 315 (60) [M]+, 210 (20) [M-PhCO]+, 105 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1332.
N-(5-Methyl-3-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2b). Irradiation time 15 h. Yield 52 mg (55%), white crystals. Mp 174-176 °C. IR
O
(CHCl3), cm-1: 3340 (NH). IR (KBr), cm-1: 2925, 1686, 1487, 1412,
H N
1265, 1027, 706. 1H NMR (400 MHz, CDCl3): δ = 2.60 (s, 3H, CH3),
Ph O 2b
S7
2.83-2.87 (m, 2H, CH2), 3.38-3.43 (m, 2H, CH2), 7.52-7.60 (m, 3H, Harom), 7.60-7.64 (m, 1H, Harom), 7.73-7.79 (m, 1H, Harom), 8.04 (J = 7.6 Hz, 1H, Harom), 8.13 (J = 6.8 Hz, 2H, Harom), 8.20 (J = 8.5 Hz, 1H, Harom), 10.05 (s, 1H, NH).
13
C NMR (101 MHz, CDCl3): δ = 15.7, 23.8, 36.4,
124.7, 125.7, 126.1, 127.2, 127.7, 128.3, 128.5, 128.8, 129.8, 129.9, 131.9, 134.4, 137.1, 155.7, 165.8, 208.3. MS (EI, 70 eV): m/z (%) = 315 (10) [M]+, 210 (100) [M-PhCO]+. HRMS (ESITOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1330.
4-Methoxy-N-(5-methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide
(2c).
Irradiation time 4 h. Yield 71 mg (69%), yellow crystals. Mp
O
225-227 °C. IR (KBr), cm-1: 3204 (NH), 1692, 1629, 1606,
H N OMe O 2c
1495, 1260, 1174. 1H NMR (300 MHz, DMSO-d6): δ = 2.62 (s, 3H, CH3), 2.65-2.75 (m, 2H, CH2), 3.00-3.13 (m, 2H,
CH2), 3.85 (s, 3H, CH3), 7.10 (d, J = 8.2 Hz, 2H, Harom), 7.60-7.78 (m, 2H, Harom), 8.06 (d, J = 8.2 Hz, 2H, Harom), 8.20 (d, J = 7.9 Hz, 1H, Harom), 9.11 (d, J = 7.9 Hz, 1H, Harom), 10.13 (s, 1H, NH).
13
C NMR (75 MHz, DMSO-d6): δ = 15.0, 24.3, 36.7, 55.9, 114.2, 123.6, 125.6, 126.5,
127.2, 128.1, 128.7, 129.5, 130.1, 132.5, 140.0, 157.9, 162.5, 165.6, 207.0. MS (EI, 70 eV): m/z (%) = 345 (45) [M]+, 135 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20NO3: 346.1438; Found: 346.1433.
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)-4-(trifluoromethyl)benzamide (2d). Irradiation time 8 h. Yield 75 mg (65%). Mp 305-307 O
°C. IR (KBr), cm-1: 3231 (NH), 1698, 1648, 1522, 1499,
H N CF3 O 2d
1327, 1163, 1118. 1H NMR (300 MHz, DMSO-d6): δ = 2.64 (s, 3H, CH3), 2.69-2.80 (m, 2H, CH2), 3.02-3.16 (m, 2H,
CH2), 7.62-7.80 (m, 2H, Harom), 7.90-8.02 (m, 2H, Harom), 8.17-8.34 (m, 3H, Harom), 9.07-9.16 (m, 1H, Harom), 10.54 (s, 1H, NH).
13
C NMR (75 MHz, DMSO-d6): δ = 15.0, 24.3, 36.7, 123.6, S8
125.7, 126.0, 126.0, 127.3, 128.2, 128.9, 129.1, 129.7, 131.8, 132.4, 138.2, 140.0, 157.5, 165.1, 207.0. MS (EI, 70 eV): m/z (%) = 383 (40) [M]+, 210 (35), 173 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H17F3NO2: 384.1206; Found: 384.1199.
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[c]phenanthren-4-yl)benzamide (2e). Irradiation time 4 h. Yield 81 mg (74%), white crystals. Mp 263-265 °C. IR O
(KBr), cm-1: 3351 (NH), 1687, 1665, 1509, 1481, 1278. 1H NMR
H N Ph
(300 MHz, DMSO-d6): δ = 2.69 (s, 3H, CH3), 2.78-2.91 (m, 2H,
O
CH2), 3.07-3.22 (m, 2H, CH2), 7.51-7.45 (m, 5H, Harom), 7.95-8.20
2e
(m, 5H, Harom), 9.16 (d, J = 8.1 Hz, 1H, Harom), 10.34 (s, 1H, NH). 13C NMR (75 MHz, DMSOd6): δ = 15.6, 23.9, 36.9, 123.4, 125.4, 127.7, 127.9, 128.1, 128.2, 128.4, 128.5, 129.0, 130.5, 132.1, 132.3, 133.0, 134.4, 140.2, 156.5, 166.2, 205.0. MS (EI, 70 eV): m/z (%) = 365 (100) [M]+, 260 (30) [M-PhCO]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H20NO2: 366.1489; Found: 366.1475.
N-(5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2f). Irradiation time 9 h. Yield 45 mg (50%), white crystals. Mp 243-245 °C. IR (KBr), cm-1: 3289 (NH), 1639, 1509, 1486, 1281. 1H NMR (600 MHz, CDCl3): δ =
H N Ph
2.21-2.28 (m, 2H, CH2), 2.62 (s, 3H, CH3), 3.08 (t, J = 7.3 Hz, 2H,
O 2f
CH2), 3.32 (t, J = 7.4 Hz, 2H, CH2), 7.49-7.55 (m, 4H, Harom), 7.58-
7.62 (m, 1H, Harom), 7.72 (s, 1H, NH), 7.82 (d, J = 8.3 Hz, 1H, Harom), 7.99 (d, J = 7.3 Hz, 2H, Harom), 8.07 (d, J = 7.3 Hz, 1H, Harom). 13C NMR (151 MHz, CDCl3): δ = 13.8, 24.0, 31.7, 32.4, 124.9, 125.1, 125.2, 125.6, 127.3, 128.8, 128.8, 129.6, 129.8, 131.8, 132.5, 134.6, 138.6, 138.9, 166.1. MS (EI, 70 eV): m/z (%) = 301 (40) [M]+, 196 (60) [M-PhCO]+, 180 (35), 105 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO: 302.1539; Found: 302.1539.
S9
N-(10-methyl-5-oxo-7-phenyl-5,6,7,8-tetrahydrophenanthren-9-yl)benzamide (2g). Irradiation time 12 h. Yield 83 mg (68%), white crystals. Mp 259-261 °C. IR
Ph
(KBr), cm-1: 3233 (NH), 1665, 1637, 1503, 1485, 1287. 1H NMR (600
O H
MHz, DMSO-d6): δ = 2.61, 2.64 (s, 3H, CH3),1 2.85-2.94 (m, 1H, ½
N Ph
CH2), 3.04-3.21 (m, 2H, CH2), 3.41-3.51 (m, 2H, CH + ½ CH2), 7.22
O 2g
(t, J = 7.3 Hz, 1H, Harom), 7.29-7.34 (m, 2H, Harom), 7.35-7.39 (m, 2H, Harom), 7.51-7.56 (m, 2H, Harom), 7.58-7.62 (m, 1H, Harom), 7.62-7.67 (m, 1H, Harom), 7.68-7.72 (m, 1H, Harom), 8.04 (d, J = 7.2 Hz, 2H, Harom), 8.21 (d, J = 8.3, 1H, Harom), 9.41 (d, J = 8.7 Hz, 1H, Harom), 10.17, 10.23 (s, 1H, NH). 13C NMR (75 MHz, DMSO-d6): δ = 15.3, 15.4, 34.4, 34.7, 47.0, 47.3, 125.3, 126.7, 127.1, 127.3, 128.0, 128.7, 129.0, 130.0, 132.0, 132.3, 132.6, 134.1, 139.5, 139.8, 144.1, 145.0, 166.1, 199.8. MS (EI, 70 eV): m/z (%) = 405 (100) [M]+, 300 (15) [M-PhCO]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H24NO2: 406.1802; Found: 406.1803.
Ethyl 4-methyl-3-[(phenylcarbonyl)amino]naphthalene-2-carboxylate (2h). Irradiation time 13 h. Yield 45 mg (45%), white crystals. Mp 75-76 °C. IR (KBr), cm-1: CO2 Et H N
3331 (NH), 2987, 1696, 1512, 1478, 1296, 1272, 1208, 1024. 1H NMR Ph
O 2h
(300 MHz, CDCl3): δ = 1.42 (t, J = 7.0 Hz, 3H, CH3), 2.62 (s, 3H, CH3), 4.40 (q, J = 7.0 Hz, 2H, CH2), 7.49-7.60 (m, 4H, Harom), 7.63-7.70 (m,
1H, Harom), 7.92 (d, J = 8.1 Hz, 1H, Harom), 8.05-8.16 (m, 3H, Harom), 8.47 (s, 1H, Harom), 10.32 (s, 1H, NH). 13C NMR (75 MHz, CDCl3): δ = 14.2, 15.6, 61.6, 122.2, 124.7, 126.0, 127.6, 128.7, 129.6, 130.3, 130.9, 131.1, 131.5, 131.8, 134.6, 135.4, 165.4, 167.9. MS (EI, 70 eV): m/z (%) = 333 (14) [M]+, 228 (30) [M-PhCO]+, 105 [PhCO]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO3: 334.1438; Found: 334.1442.
1
Double set of some signals in the 1H and Supporting Information)
13
C NMR spectra indicates dynamic NMR effect (see section VII in
S10
Reduction of compound 2a. Naphthalene 2a (100 mg, 0.32 mmol) was suspended in dry Et2O (5 ml), LiAlH4 (LAH, 122 mg, 3.2 mmol) was added and the solution was refluxed for 10 h. The resulting mixture was cooled to 0 °C with ice-water bath and was quenched very carefully with addition of ethyl acetate (10 ml). The resulting suspension was poured carefully into ice water (100 ml) and extracted with ethyl acetate (2 x 20 ml). The combined organic phases was filtered through thin layer of silica gel (2 cm) and concentrated in vacuum. The residue was purified by column chromatography on silica gel (light petroleum - ethyl acetate, 20:1) to give 47 mg (51 %) of compound 3 as yellow viscous oil.
N-benzyl-5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-amine (3). IR (KBr), cm-1: 2950, 2926, 1588, 1453, 1384, 1188, 1116, 751, 699. 1H NMR (300 MHz, CDCl3): δ = 2.15-2.30 (m, 2H, CH2), 3.01 (t, J = 7.1 Hz, 2H, CH2), ),
H N Ph 3
3.28 (t, J = 7.3 Hz, 2H, CH2), 4.30 (s, 2H, CH2), 7.27-7.50 (m, 7H, Harom), 7.75 (d, J = 8.0 Hz, 1H, Harom), 7.95 (d, J = 8.4 Hz, 1H, Harom).
13
C NMR (75 MHz, CDCl3): δ = 13.2, 24.4, 31.6, 32.4, 53.6, 119.4, 123.2, 124.0, 124.8, 124.9,
127.0, 127.3, 127.9, 128.6, 133.4, 135.2, 138.7, 140.5, 142.1. MS (EI, 70 eV): m/z (%) = 287 (100) [M]+, 272 (25) [M-CH3]+, 196 (95) [M-C7H7]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H22N: 288.1747; Found: 288.1744.
S11
III. NMR monitoring of photoreaction
Figure S1. 1H NMR (200MHz) stacked plot of solution of diarylethene 3a (10 mg in 0.5 ml of CDCl3) during irradiation with UV light (365 nm, 6W lamp) at 298 K. S12
IV. UV-vis spectra of compounds 1a,b,e,f,g and 2a,b,e,f,g O
O
UV
H N
N O
Ph
Ph
O
1a
2a
Figure S2. UV absorption spectra during the course of isomerization of diarylethene 1a in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S3. UV absorption spectrum of naphthalene 2a in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S13
O
O
UV
H N
N Ph
Ph O
O 2b
1b
Figure S4. UV-Vis absorption spectra during the course of isomerization of diarylethene 1b in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S5. UV absorption spectrum of naphthalene 2b in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S14
O
O
UV
H N
N O
Ph
Ph
O
1e
2e
Figure S6. UV-Vis absorption spectra during the course of isomerization of diarylethene 1e in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S7. UV absorption spectrum of naphthalene 2e in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section. S15
UV
H N
N Ph
Ph O
O 2f
1f
Figure S8. UV-Vis absorption spectra during the course of isomerization of diarylethene 1f in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S9. UV absorption spectrum of naphthalene 2f in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S16
Ph
Ph O
UV
O H N
N O
Ph
Ph
O
1g
2g
Figure S10. UV-Vis absorption spectra during the course of isomerization of diarylethene 1g in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S11. UV absorption spectrum of naphthalene 2g in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S17
V. Absorption spectra of photoinduced form of diarylethenes 1b and 1f
Figure S12. UV-Vis absorption spectra of diarylethene 1b in MeCN (C ≈ 3 × 10-4 M) before and after irradiation with UV light (λ = 365 nm) and thermal decomposition of colored intermediate observed at 540 nm at 293 K.
Figure S13. UV-Vis absorption spectra of diarylethene 1f in MeCN (C ≈ 3 × 10-4 M) before and after irradiation with UV light (λ = 365 nm) and thermal decomposition of colored intermediate observed at 470 nm at 293 K.
S18
VI. 2D NMR spectra of compounds 2a,b,f N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2a)
H
H H
O
H
H
3 4
5
H 7
2
1 6
N
13 11
14
H
9 10
H
H
H
19
H
17 16 18
12
8
20
H 15
O
H
H
H
Table S1. Assignment of NMR signals and 2D NMR correlations for compound 2a № 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1
H (ppm)
2.72-2.78 (m) 3.06-3.13 (m) 9.13 (d, J = 8.0 Hz) 7.72-7.77 (m) 7.66-7.72 (m) 8.23 (d, J = 8.3 Hz) 2.65 (s) 10.3 (s) 8.09 (d, J = 7.2 Hz) 7.56-7.62 (m) 7.62-7.66 (m)
13
C (ppm) 207.1 36.7 24.4 157.9 129.6 128.0 123.7 128.8 127.3 125.7 132.5 140.1 132.2 15.0 166.2 134.5 128.2 129.0 132.3
S19
NOESY HMBC {1H-1H} {1H-13C} 2, 3 3 1, 3, 4 2, 15 1, 2, 4, 5, 13 2, 3, 14, 15 3, 7 8 5, 9, 11 6, 10 7, 11 14 8, 12 7, 9, 14 10, 14, 15 3, 14 10, 15 4, 11, 12, 13 3, 14, 18 4, 12, 16 15, 18 19 15 16, 20 17 18
1
H NMR spectra (400.16 MHz; DMSO-d6) of compound 2a
13
C DEPTQ NMR spectra (100.62 MHz; DMSO-d6) of compound 2a
S20
{1H-1H}NOESY (400.16 MHz; DMSO-d6)
H
H H
O
5
H 7
H
2
1
H
3 4
20
6
N
13
17 18
12
O
14
H
9 10
H
19
16
11 8
H
H
H
H 15
H
S21
H
H
{1H-13C}HSQC (400.16 MHz; DMSO-d6)
S22
{1H-13C}HMBC (400.16 MHz; DMSO-d6)
H
H H
O
2
H
20
4
5 6 11
12
8
H
O
14
H
9 10
H
H
H
H 15 N 16 13
7
H
H
3
1
H
S23
17
19 18
H
H
1
H-13C}HMBC (400.16 MHz; DMSO-d6)
H 1
H 8
3 4
5 7
H
20
15
N 16 13
H
O
14
H H
17
19 18
12
10
H
H
6 11
9
H H
2
O
H
H
H
S24
H
H
{1H-13C}HMBC (400.16 MHz; DMSO-d6)
H
H H
O
5
H 7 8
H
2
1
H
3 4
N 16 13
6 11
12
9
14
H
10
H
20
15
H
H
H
H
H
S25
O
17
19 18
H
H
{1H-1H}COSY (400.16 MHz; DMSO-d6)
S26
N-(5-Methyl-3-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2b)
H H H H
O
2 1
H 7
H 3 4
5 6
N
13
8
17 18
12 14
H
10
H
H
H
O
H
19
16
11 9
20
H 15
H
H
H
Table S2. Assignment of NMR signals and 2D correlations for compound 2b № 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1
H (ppm)
3.38-3.43 (m) 2.83-2.87 (m) 8.04 (J = 7.6 Hz) 7.60-7.64 (m) 7.73-7.79 (m) 8.20 (J = 8.5 Hz) 2.60 (s) 10.05 (s) 8.13 (J = 6.8 Hz) 7.52-7.60 (m) 7.52-7.60 (m)
13
C (ppm) 23.8 36.4 208.3 127.2 155.7 128.3 124.7 126.1 129.8 125.7 137.1 128.5 129.9 15.7 165.8 134.4 127.7 128.8 131.9
S27
NOESY HMBC {1H-1H} {1H-13C} 2, 7 2, 3, 4, 5, 6, 13 1 1, 3, 4, 5 1, 2 1, 2 1, 2, 7 1, 8, 10 1 5, 9, 11 6, 10 7, 11 14 6, 8, 12 7, 9, 14 10, 14, 15 1, 14 10, 15, 18 11, 12, 13 14, 18 12 18 19 14, 15 16, 20 17 18
1
H NMR spectra (400.16 MHz; CDCl3) of compound 2b
13
C DEPTQ NMR spectra (100.62 MHz; CDCl3) of compound 2b
S28
{1H-1H}ROESY (400.16 MHz; CDCl3)
H
H
H H
H 7
H
O
2 3 4
1 5
H 15
6 13
11
8
N
18
12 9
H
14
H
10
H
H
17 16
H
S29
O
H
{1H-13C}HSQC (400.16 MHz; CDCl3)
S30
{1H-13C}HMBC (400.16 MHz; CDCl3)
H H H 7
H
1
H
H 2
5
O
3 4
H 15
6
N 16 13
18
11 12
8
H
O
14
H
9 10
H
17
H
S31
H
H
{1H-13C}HMBC (400.16 MHz; CDCl3)
H H H
H
7
3 4
5 6
20
12 10
H
O
14
H H
H
H 15 N 16 13
9
H
O
2
11
8
H
1
H
H
S32
17
19 18
H
H
{1H-13C}HMBC (400.16 MHz; CDCl3) H H H
H 7
H
8
1
H O
2 3 4
5
H 15
6
N
13 11
18 12 14
H
9 10
H
17 16
H
H
S33
H
O
H
{1H-13C}HMBC (400.16 MHz; CDCl3) H H H
H 7
H
H 2
1 5
O
3 4
H 15
6
N 16
13
8
18
11 12 9
H
17
14
H
10
H
H
S34
H
O
H
{1H-1H}COSY (400.16 MHz; CDCl3)
S35
N-(5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2f)
H
H H
H 2
1
H
H 7
H
H
3 4
5 6
N
13
8
17 18
12
H
14
H
10
H
O
H
19
16
11 9
20
H 15
H
H
H
H
Table S3. Assignment of NMR signals and 2D correlations for compound 2f №
1
H (ppm)
1 3.32 (t, J = 7.4 Hz) 2 2.21-2.28 (m) 3 3.08 (t, J = 7.3 Hz) 4 5 6 7 7.82 (d, J = 8.3 Hz) 8 7.49-7.55 (m) 9 7.49-7.55 (m) 10 8.07 (d, J = 7.3 Hz) 11 12 13 14 2.62 (s) 15 7.72 (s) 16 17 18 7.99 (d, J = 7.3 Hz) 19 7.49-7.55 (m) 20 7.58-7.62 (m)
13
C (ppm) 31.7 24.0 32.4 138.6 138.9 129.8 124.9 125.6 125.1 125.2 132.6 128.8 129.6 13.8 166.0 134.6 127.3 128.8 131.8
S36
NOESY HMBC {1H-1H} {1H-13C} 7 2, 3, 4, 5, 13 1, 3, 4, 5 15 1, 2, 4, 5, 13 1, 2, 3, 14 1, 2, 3, 7 7, 10 1 5, 6, 9, 11 10 7 14 6, 8, 11, 7, 10, 14 14 1, 3, 14 10, 15 4, 11, 12, 13 3, 14, 18 18 19 15 16, 20 17 18
1
H NMR spectra (600.13 MHz; CDCl3) of compound 2f
13
C DEPTQ NMR spectra (150.90 MHz; CDCl3) of compound 2f
S37
{1H-1H}NOESY (600.13 MHz; CDCl3)
H
2
H H
H
3
1 7H
H
H
4
5
H 15
6
N
13 8
16
11
H
18
12
H 9H
H
H
O 14
H
10
S38
H
{1H-13C}HSQC (600.13 MHz; CDCl3)
S39
{1H-13C}HMBC (600.13 MHz; CDCl3)
H H
H 2
H 3
1
H
H 6
5
N
13
8
H H 15
4 7
H
H 17 16 18
11 12 9
H
14
H
10
H
H
20
H
S40
O
H
19
H
{1H-13C}HMBC (600.13 MHz; CDCl3)
H H
2
H H
1
3
H
H 5
H 6
7
H
4
20
N 16 13 12
9
H
17
19 18
11 8 10
H
H
H 15
14
H
H H
S41
O
H
H
{1H-13C}HMBC (600.13 MHz; CDCl3)
H
H H
H H
2
H
3
1
H
4 6 5
H
8
13
7 11
H
N 16
12
H
O
14
H
9 10
H
20
H
19
H
H 15
H
S42
17
18
H
{1H-1H}COSY (600.13 MHz; CDCl3)
S43
VII. Temperature dependent NMR spectra of compound 2g Naphthalene 2g shows double set of signals belonging to methyl
Ph
1
(2.61 and 2.64 ppm) and amide (10.17 and 10.23 ppm) groups in the H
O H
NMR spectrum at 303 K (Figure S14). At 343 K there is only one set of
N Ph
the signals (2.66 and 10.06 ppm, Figure S15), which clearly indicates dynamic NMR effect, related to restricted rotation of amide group.
O 2g
Figure S14. 1H NMR (600.13 MHz) spectrum of compound 2g in DMSO-d6 at 303 K.
Figure S15. 1H NMR (600.13 MHz) spectrum of compound 2g in DMSO-d6 at 343 K. S44
VIII. References
[S1] Shirinian, V. Z.; Shimkin, A. A.; Lonshakov, D. V.; Lvov, A. G.; Krayushkin, M. M. J. Photochem. Photobiol. A: Chem. 2012, 233, 1. [S2] Shimkin, A. A.; Shirinian, V. Z.; Mailian, A. K.; Lonshakov, D. V.; Gorokhov, V. V.; Krayushkin, M. M. Russ. Chem. Bull. 2011, 60, 139. [S3] Shirinian, V. Z.; Lvov, A. G.; Krayushkin, M. M.; Lubuzh, E. D.; Nabatov, B. V. J. Org. Chem., 2014, 79, 3440. [S4] a) Sohda, T.; Mizuno, K.; Momose, Y.; Ikeda, H.; Fujita, T.; Meguro, K. J. Med. Chem. 1992, 35, 2617; b) Lvov, A. G.; Shirinian, V. Z.; Kavun, A. M.; Krayushkin, M. M. Mendeleev Commun. submitted. [S5] Olah, G. A.; Arvanaghi, M.; Ohannesian, L. Synthesis 1986, 770. [S6] Chang, M.-Y.; Tsai, C.-Y.; Wu, M.-H. Tetrahedron 2013, 69, 6364. [S7] García-Raso, A.; García-Raso, J.; Campaner, B.; Mestres, R.; Sinisterra J. V. Synthesis 1982, 1037. [S8] Hulin, B; Clark, D. A.; Goldstein, S. W.; McDermott, R. E.; Dambek, P. J.; Kappeler, W. H.; Lamphere, C. H.; Lewis, D. M.; Rizzi, J. P. J. Med. Chem. 1992, 35, 1853. [S9] Karminski-Zamola, G.; Bajić, M. Synth.Commun. 1989, 19, 1325.
S45
IX. Copies of 1H NMR and 13C NMR spectra2 3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one (1a)
O N O
Ph
1a
O N O
Ph
1a
2
Copies of 1H NMR and Information.
13
C NMR spectra of compounds 2a,b,f are presented in section VI of Supporting
S46
2-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylcyclopent-2-en-1-one (1b)
O N Ph
O 1b
O N Ph
O 1b
S47
3-[2-(4-Methoxyphenyl)-5-methyl-1,3-oxazol-4-yl]-2-phenylcyclopent-2-en-1-one (1c)
O N O OMe
1c
O N O 1c
OMe
S48
3-{5-Methyl-2-[4-(trifluoromethyl)phenyl]-1,3-oxazol-4-yl}-2-phenylcyclopent-2-en-1-one (1d)
O N O CF3
1d
O N O 1d
CF3
S49
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-(1-naphthyl)cyclopent-2-en-1-one (1e)
O N O 1e
O N O
Ph
1e
S50
Ph
5-Methyl-2-phenyl-4-(2-phenylcyclopent-1-en-1-yl)-1,3-oxazole (1f)
N O 1f
N O
Ph
1f
S51
Ph
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2,5-diphenylcyclohex-2-en-1-one (1g)
Ph O N O
Ph
1g
Ph O N O
Ph
1g
S52
Ethyl 2-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylprop-2-enoate (1h)
CO2 Et N O
Ph
1h
CO2 Et N O 1h
S53
Ph
4-Methoxy-N-(5-methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2c)
O H N OMe O 2c
O H N OMe O 2c
S54
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)-4(trifluoromethyl)benzamide (2d)
O H N CF3 O 2d
O H N CF3 O 2d
S55
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[c]phenanthren-4-yl)benzamide (2e)
O H N Ph O 2e
O H N Ph O 2e
S56
N-(10-Methyl-5-oxo-7-phenyl-5,6,7,8-tetrahydrophenanthren-9-yl)benzamide (2g)
Ph O H N Ph O 2g
Ph O H N Ph O 2g
S57
Ethyl 4-methyl-3-[(phenylcarbonyl)amino]naphthalene-2-carboxylate (2h)
CO2 Et H N Ph O 2h
CO2 Et H N Ph O 2h
S58
N-benzyl-5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-amine (3)
H N Ph 3
H N Ph 3
S59
Supporting Information Table of Contents
I. General information, synthesis and characterization of starting compounds...........................S2 II. General procedure and analytical data for photoproducts 2 and compound 3.......................S7 III. NMR monitoring of photoreaction........................................................................................S12 VI. UV-vis spectra of compounds 1a,b,e,f,g and 2a,b,e,f,g.........................................................S13 V. Absorption spectra of photoinduced form of diarylethenes 1b and 1f ...................................S18 VI. 2D NMR spectra of compounds 2a,b,f...................................................................................S19 VII. Temperature dependent NMR spectra of compound 2g.......................................................S44 VIII. References...........................................................................................................................S45 IX. Copies of 1H NMR and 13C NMR spectra..............................................................................S46
S1
I. General information, synthesis and characterization of starting compounds Proton nuclear magnetic resonance spectra (1H NMR) and carbon nuclear magnetic resonance spectra (13C NMR) were recorded in deuterated solvents on a spectrometers working at 300 MHz or 400 MHz or 600 MHz for 1H, 75 MHz or 101 MHz or 151 MHz for 13C. Data are represented as follows: chemical shift, multiplicity (s, singlet; d, doublet; m, multiplet; br, broad), coupling constant in hertz (Hz), integration, and assignment. Infrared spectra were measured on a FT-IR spectrometer in KBr pellets or abs. CHCl3 solutions and are reported in terms of frequency of absorption (cm−1). Melting points (Mp) were recorded using an apparatus and not corrected. Mass spectra were obtained on a mass spectrometer (70 eV) with direct sample injection into the ion source. High resolution mass spectra were obtained from a TOF mass spectrometer with an ESI source. All chemicals and solvents were purchased from commercial sources and used without further purification. Silica column chromatography was performed using silica gel 60 (70−230 mesh); TLC analysis was conducted on silica gel 60 F254 plates. Photochemical studies. UV−Vis spectra were recorded in 1.0 cm quartz cuvettes. The experimental measurements were performed at 293 K in the presence of air in solutions of acetonitrile. The irradiation was carried out using a 6W Vilber Lourmat (France) UV-lamp model VL-6.LC (365 nm light). Synthesis of the starting diarylethenes. 2,3-Diarylcyclopent-2-en-1-ones 1a-e were prepared according previously reported method[S1] from corresponding ketoesters[S2,S3] and bromoketones[S4] (Scheme S1). Cyclopentene 1f was synthesized from diarylethene 1a by the reduction with triethylsilane in the presence of trifluoromethanesulfonic acid (Scheme S2).[S5] Diarylethene 1g was prepared by Robinson type reaction of ethyl 3-oxo-4-phenylbutanoate[S2] with chalcone 9 (this compound was prepared according to the literature protocol[S6] and was used without additional purification) with subsequent hydrolysis and decarboxylation (Scheme S3).[S7] Diarylethene 1h was prepared from (5-methyl-2-phenyl-1,3-oxazol-4-yl)acetic acid[S8] and benzaldehyde with subsequent esterification (Scheme S4).[S9]
S2
N
1a: Ar1 = Ph; Ar2 = Me
O 1
Ar
CO2 Et
1b: Ar1 = Br
2
Ar
N Me
Ph
O
O
Ph
O
; Ar2 = Ph N
1c: Ar1 = Ph; Ar2 =
O
1
Me
2
Ar
Ar
O OMe
1a-e
1d:
Ar1 =
Ph;
N
Ar2 = Me
O CF 3
1e: Ar1 =
N
; Ar2 = Me
O
Ph
Scheme S1. Synthesis of the diarylethenes of cyclopentenone series.
O Et3SiH, CF3SO3H N
N DCM
O
Me
Ph
Me 1f
1a
O
Ph
Scheme S2. Synthesis of diarylethene 1f.
Ph
EtO2C O
Ph
CO2Et
Ph
O
O
O
N
Ph Me
O
-CO2 -EtOH
N
Ph Me
9
O
N
Ph
Me 1g
Scheme S3. Synthesis of diarylethene 1g.
O
HO2C
EtO2C
HO2C C2H5OH
Ph N Ph
N
N O
Me
Ph
O
Me
Ph
O
Me 1h
Scheme S4. Synthesis of diarylethene 1h.
S3
O
Ph
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one (1a). Yield 35%, yellow crystals. Mp 210-212 °C. IR (KBr), cm-1: 3068, 1697, 1636, 1600, O
1158, 698. 1H NMR (300 MHz, CDCl3): δ = 1.70 (s, 3H, CH3), 2.63N Ph
O
2.79 (m, 2H, CH2), 3.06-3.20 (m, 2H, CH2), 7.27-7.58 (m, 8H, Harom), 7.94-8.08 (m, 2H, Harom). 13C NMR (75 MHz, CDCl3): δ = 11.6, 29.2,
1a
34.7, 126.1, 127.0, 127.7, 128.5, 128.8, 129.1, 130.4, 132.4, 132.9, 139.4, 148.0, 160.5, 160.9, 207.3. MS (EI, 70 eV): m/z (%) = 315 (100) [M]+, 300 (15) [M-CH3]+, 286 (25). HRMS (ESITOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1323.
2-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylcyclopent-2-en-1-one (1b). Yield 27%, yellow crystals. Mp 148-150 °C. IR (KBr), cm-1: 2919, 1700, 1557, 1444,
O
1373, 929. 1H NMR (300 MHz, CDCl3): δ = 2.15 (s, 3H, CH3), 2.66N Ph
2.79 (m, 2H, CH2), 3.08-3.20 (m, 2H, CH2), 7.31-7.48 (m, 6H, Harom),
O 1b
7.50-7.63 (m, 2H, Harom), 7.92-8.07 (m, 2H, Harom).
13
C NMR (75
MHz, CDCl3): δ = 11.1, 29.7, 34.6, 126.1, 127.6, 128.0, 128.3, 128.4, 128.6, 129.9, 130.4, 131.8, 135.2, 147.2, 160.4, 170.8, 206.8. MS (EI, 70 eV): m/z (%) = 315 (100) [M]+, 286 (20). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1337.
3-[2-(4-methoxyphenyl)-5-methyl-1,3-oxazol-4-yl]-2-phenylcyclopent-2-en-1-one
(1c).
Yield
40%, yellow crystals. Mp 150-152 °C. IR (KBr), cm-1: 2931,
O
1694, 1627, 1505, 1259, 1154, 1030. 1H NMR (300 MHz, N
CDCl3): δ = 1.68 (s, 3H, CH3), 2.65-2.74 (m, 2H, CH2),
O 1c
OMe
3.07-3.17 (m, 2H, CH2), 6.98 (d, J = 8.8 Hz, 2H, Harom),
7.27-7.41 (m, 5H, Harom), 7.94 (d, J = 8.8 Hz, 2H, Harom). 13C NMR (75 MHz, CDCl3): δ = 11.6, 29.2, 34.7, 55.4, 114.2, 119.8, 127.7, 127.8, 128.4, 129.1, 132.5, 132.7, 139.2, 147.4, 160.5,
S4
161.1, 161.4, 207.4. MS (EI, 70 eV): m/z (%) = 345 (100) [M]+, 330 (17) [M-CH3]+, 316 (25). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20NO3: 346.1438; Found: 346.1436.
3-{5-methyl-2-[4-(trifluoromethyl)phenyl]-1,3-oxazol-4-yl}-2-phenylcyclopent-2-en-1-one (1d). Yield 27%, orange crystals. Mp 168-170 °C. IR (KBr), cm-1: O
3054, 1697, 1621, 1326, 1166, 1073. 1H NMR (300 MHz, N
CDCl3): δ = 1.73 (s, 3H, CH3), 2.68-2.75 (m, 2H, CH2), 3.09-
O CF3
1d
3.19 (m, 2H, CH2), 7.29-7.41 (m, 5H, Harom), 7.73 (d, J = 8.1
Hz, 2H, Harom), 8.12 (d, J = 8.1 Hz, 2H, Harom).13C NMR (75 MHz, CDCl3): δ = 11.7, 29.2, 34.7, 125.8, 126.4, 127.9, 128.5, 128.7, 129.1, 129.4, 130.2, 132.3, 133.4, 139.8, 148.8, 159.1, 160.2, 207.2. MS (EI, 70 eV): m/z (%) = 383 (100) [M]+, 368 (50) [M-CH3]+, 354 (45). HRMS (ESITOF) m/z: [M + H]+ Calcd for C22H17F3NO2: 384.1206; Found: 384.1203.
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-(1-naphthyl)cyclopent-2-en-1-one (1e). Yield
26%,
yellow crystals. Mp 224-226 °C. IR (KBr), cm-1: 3046, 1687,
O
1628, 1191, 1155, 775. 1H NMR (300 MHz, CDCl3): δ = 1.34 (s, N O 1e
Ph
3H, CH3), 2.78-2.88 (m, 2H, CH2), 3.28-3.39 (m, 2H, CH2), 7.317.56 (m, 7H, Harom), 7.64 (d, J = 8.2 Hz, 1H, Harom), 7.80-7.97 (m,
4H, Harom). 13C NMR (75 MHz, CDCl3): δ = 11.5, 29.5, 34.7, 125.4, 125.5, 125.8, 126.0, 126.1, 126.9, 127.8, 128.4, 128.5, 128.7, 130.3, 130.7, 131.4, 132.9, 133.7, 138.7, 149.0, 160.0, 162.8, 207.6. MS (EI, 70 eV): m/z (%) = 365 (80) [M]+, 262 (30), 219 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H20NO2: 366.1489; Found: 366.1485.
S5
5-Methyl-2-phenyl-4-(2-phenylcyclopent-1-en-1-yl)-1,3-oxazole (1f). Yield 65%, yellow crystals. Mp 81-83 °C. IR (KBr), cm-1: 2951, 2842, 1602, 1493, 1447, 1333, 770, 691. 1H NMR (300 MHz, CDCl3): δ = 1.76 (s, 3H, CH3), 2.03N Ph
O
2.18 (m, 2H, CH2), 2.84-3.02 (m, 4H, 2 x CH2), 7.117.33 (m, 5H, Harom), 7.38-7.50 (m, 3H, Harom), 7.99-8.08 (m, 2H, CH2).
1f 13
C NMR (75 MHz, CDCl3): δ = 10.9, 22.3, 38.0, 126.0, 126.6, 127.4, 127.8, 128.1, 128.6,
129.2, 129.7, 133.9, 138.3, 140.1, 144.2, 159.6. MS (EI, 70 eV): m/z (%) = 301 (40) [M]+, 196 (10), 155 (35). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO: 302.1539; Found: 302.1533.
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2,5-diphenylcyclohex-2-en-1-one (1g). Yield 19%, yellow crystals. Mp 130-132 °C. IR (KBr), cm-1: 3058, 3029, 2920, 1737,
Ph
1672, 1596, 1492, 1289, 696. 1H NMR (300 MHz, CDCl3): δ = 1.58 (s,
O
3H, CH3), 2.88-3.05 (m, 3H, CH2 + ½ CH2); 3.44-3.71 (m, 2H, CH +
N Ph
O
½ CH2), 7.12-7.53 (m, 13H, Harom), 7.90-8.05 (m, 2H, CH2). 13C NMR
1g
(75 MHz, CDCl3): δ = 11.1, 38.6, 39.9, 45.2, 126.0, 126.8, 126.9, 127.1, 127.2, 127.9, 128.7, 130.2, 130.8, 135.2, 135.3, 137.6, 143.2, 146.3, 148.1, 160.0, 197.4. MS (EI, 70 eV): m/z (%) = 405 (100) [M]+, 390 (45) [M-CH3]+, 301 (40). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H24NO2: 406.1802; Found: 406.1806.
Ethyl 2-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylprop-2-enoate (1h). Yield 45%, yellow oil. IR (KBr), cm-1: 2982, 1713, 1251, 1035, 694. 1H NMR (300 MHz, CO2 Et
CDCl3): δ = 1.33 (t, J = 7.1 Hz, 3H, CH3), 2.01 (s, 3H, CH3), 4.31 (q, J
N O 1h
Ph
= 7.1 Hz, 2H, CH2), 7.21-7.33 (m, 5H, Harom), 7.40-7.49 (m, 3H, Harom), 7.99 (s, 1H, CH), 8.01-8.10 (m, 2H, Harom). 13C NMR (75 MHz,
CDCl3): δ = 10.6, 14.3, 61.3, 123.3, 126.2, 127.7, 128.4, 128.6, 129.4, 130.0, 131.0, 134.6, S6
143.9, 146.2, 160.1, 166.9. MS (EI, 70 eV): m/z (%) = 333 (70) [M]+, 287 (40) [M-EtOH]+, 259 (55). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO3: 334.1438; Found: 334.1434.
II. General procedure and analytical data for photoproducts 2 and compound 3 Diarylethene 1 (0.3 mmol) was dissolved in CHCl3 (3 ml) and the reaction mixture in a quartz vessel (1 x 1 x 4 cm3) was irradiated with UV-light (UV lamp, λ = 365 nm, 6W). After completion of the reaction (TLC control) the solution was evaporated under vacuum, the residue was purified by flash chromatography eluting by light petroleum - ethyl acetate 10:1 (compounds 2b,f,h) or by recrystallization from small amount of mixture CH2Cl2/petroleum ester 1:1 (compounds 2a,c-e,g).
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2a). Irradiation time 4 h. Yield 76 mg (80%), white crystals. Mp 248-250 °C. IR O
(KBr), cm-1: 3294 (NH), 1703, 1638, 1505, 1484, 1279. 1H NMR (400
H N Ph
MHz, DMSO-d6): δ = 2.65 (s, 3H, CH3), 2.72-2.78 (m, 2H, CH2),
O 2a
3.06-3.13 (m, 2H, CH2), 7.56-7.77 (m, 5H, Harom), 8.09 (d, J = 7.2 Hz,
2H, Harom), 8.23 (d, J = 8.3 Hz, 1H, Harom), 9.13 (d, J = 8.0 Hz, 1H, Harom), 10.30 (s, 1H, NH). 13
C NMR (101 MHz, DMSO-d6): δ = 15.0, 24.4, 36.7, 123.6, 125.7, 127.2, 127.9, 128.2, 128.8,
129.0, 129.6, 132.2, 132.3, 132.5, 134.4, 140.1, 157.8, 166.2, 207.1. MS (EI, 70 eV): m/z (%) = 315 (60) [M]+, 210 (20) [M-PhCO]+, 105 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1332.
N-(5-Methyl-3-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2b). Irradiation time 15 h. Yield 52 mg (55%), white crystals. Mp 174-176 °C. IR
O
(CHCl3), cm-1: 3340 (NH). IR (KBr), cm-1: 2925, 1686, 1487, 1412,
H N
1265, 1027, 706. 1H NMR (400 MHz, CDCl3): δ = 2.60 (s, 3H, CH3),
Ph O 2b
S7
2.83-2.87 (m, 2H, CH2), 3.38-3.43 (m, 2H, CH2), 7.52-7.60 (m, 3H, Harom), 7.60-7.64 (m, 1H, Harom), 7.73-7.79 (m, 1H, Harom), 8.04 (J = 7.6 Hz, 1H, Harom), 8.13 (J = 6.8 Hz, 2H, Harom), 8.20 (J = 8.5 Hz, 1H, Harom), 10.05 (s, 1H, NH).
13
C NMR (101 MHz, CDCl3): δ = 15.7, 23.8, 36.4,
124.7, 125.7, 126.1, 127.2, 127.7, 128.3, 128.5, 128.8, 129.8, 129.9, 131.9, 134.4, 137.1, 155.7, 165.8, 208.3. MS (EI, 70 eV): m/z (%) = 315 (10) [M]+, 210 (100) [M-PhCO]+. HRMS (ESITOF) m/z: [M + H]+ Calcd for C21H18NO2: 316.1332; Found: 316.1330.
4-Methoxy-N-(5-methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide
(2c).
Irradiation time 4 h. Yield 71 mg (69%), yellow crystals. Mp
O
225-227 °C. IR (KBr), cm-1: 3204 (NH), 1692, 1629, 1606,
H N OMe O 2c
1495, 1260, 1174. 1H NMR (300 MHz, DMSO-d6): δ = 2.62 (s, 3H, CH3), 2.65-2.75 (m, 2H, CH2), 3.00-3.13 (m, 2H,
CH2), 3.85 (s, 3H, CH3), 7.10 (d, J = 8.2 Hz, 2H, Harom), 7.60-7.78 (m, 2H, Harom), 8.06 (d, J = 8.2 Hz, 2H, Harom), 8.20 (d, J = 7.9 Hz, 1H, Harom), 9.11 (d, J = 7.9 Hz, 1H, Harom), 10.13 (s, 1H, NH).
13
C NMR (75 MHz, DMSO-d6): δ = 15.0, 24.3, 36.7, 55.9, 114.2, 123.6, 125.6, 126.5,
127.2, 128.1, 128.7, 129.5, 130.1, 132.5, 140.0, 157.9, 162.5, 165.6, 207.0. MS (EI, 70 eV): m/z (%) = 345 (45) [M]+, 135 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20NO3: 346.1438; Found: 346.1433.
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)-4-(trifluoromethyl)benzamide (2d). Irradiation time 8 h. Yield 75 mg (65%). Mp 305-307 O
°C. IR (KBr), cm-1: 3231 (NH), 1698, 1648, 1522, 1499,
H N CF3 O 2d
1327, 1163, 1118. 1H NMR (300 MHz, DMSO-d6): δ = 2.64 (s, 3H, CH3), 2.69-2.80 (m, 2H, CH2), 3.02-3.16 (m, 2H,
CH2), 7.62-7.80 (m, 2H, Harom), 7.90-8.02 (m, 2H, Harom), 8.17-8.34 (m, 3H, Harom), 9.07-9.16 (m, 1H, Harom), 10.54 (s, 1H, NH).
13
C NMR (75 MHz, DMSO-d6): δ = 15.0, 24.3, 36.7, 123.6, S8
125.7, 126.0, 126.0, 127.3, 128.2, 128.9, 129.1, 129.7, 131.8, 132.4, 138.2, 140.0, 157.5, 165.1, 207.0. MS (EI, 70 eV): m/z (%) = 383 (40) [M]+, 210 (35), 173 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H17F3NO2: 384.1206; Found: 384.1199.
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[c]phenanthren-4-yl)benzamide (2e). Irradiation time 4 h. Yield 81 mg (74%), white crystals. Mp 263-265 °C. IR O
(KBr), cm-1: 3351 (NH), 1687, 1665, 1509, 1481, 1278. 1H NMR
H N Ph
(300 MHz, DMSO-d6): δ = 2.69 (s, 3H, CH3), 2.78-2.91 (m, 2H,
O
CH2), 3.07-3.22 (m, 2H, CH2), 7.51-7.45 (m, 5H, Harom), 7.95-8.20
2e
(m, 5H, Harom), 9.16 (d, J = 8.1 Hz, 1H, Harom), 10.34 (s, 1H, NH). 13C NMR (75 MHz, DMSOd6): δ = 15.6, 23.9, 36.9, 123.4, 125.4, 127.7, 127.9, 128.1, 128.2, 128.4, 128.5, 129.0, 130.5, 132.1, 132.3, 133.0, 134.4, 140.2, 156.5, 166.2, 205.0. MS (EI, 70 eV): m/z (%) = 365 (100) [M]+, 260 (30) [M-PhCO]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H20NO2: 366.1489; Found: 366.1475.
N-(5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2f). Irradiation time 9 h. Yield 45 mg (50%), white crystals. Mp 243-245 °C. IR (KBr), cm-1: 3289 (NH), 1639, 1509, 1486, 1281. 1H NMR (600 MHz, CDCl3): δ =
H N Ph
2.21-2.28 (m, 2H, CH2), 2.62 (s, 3H, CH3), 3.08 (t, J = 7.3 Hz, 2H,
O 2f
CH2), 3.32 (t, J = 7.4 Hz, 2H, CH2), 7.49-7.55 (m, 4H, Harom), 7.58-
7.62 (m, 1H, Harom), 7.72 (s, 1H, NH), 7.82 (d, J = 8.3 Hz, 1H, Harom), 7.99 (d, J = 7.3 Hz, 2H, Harom), 8.07 (d, J = 7.3 Hz, 1H, Harom). 13C NMR (151 MHz, CDCl3): δ = 13.8, 24.0, 31.7, 32.4, 124.9, 125.1, 125.2, 125.6, 127.3, 128.8, 128.8, 129.6, 129.8, 131.8, 132.5, 134.6, 138.6, 138.9, 166.1. MS (EI, 70 eV): m/z (%) = 301 (40) [M]+, 196 (60) [M-PhCO]+, 180 (35), 105 (100). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO: 302.1539; Found: 302.1539.
S9
N-(10-methyl-5-oxo-7-phenyl-5,6,7,8-tetrahydrophenanthren-9-yl)benzamide (2g). Irradiation time 12 h. Yield 83 mg (68%), white crystals. Mp 259-261 °C. IR
Ph
(KBr), cm-1: 3233 (NH), 1665, 1637, 1503, 1485, 1287. 1H NMR (600
O H
MHz, DMSO-d6): δ = 2.61, 2.64 (s, 3H, CH3),1 2.85-2.94 (m, 1H, ½
N Ph
CH2), 3.04-3.21 (m, 2H, CH2), 3.41-3.51 (m, 2H, CH + ½ CH2), 7.22
O 2g
(t, J = 7.3 Hz, 1H, Harom), 7.29-7.34 (m, 2H, Harom), 7.35-7.39 (m, 2H, Harom), 7.51-7.56 (m, 2H, Harom), 7.58-7.62 (m, 1H, Harom), 7.62-7.67 (m, 1H, Harom), 7.68-7.72 (m, 1H, Harom), 8.04 (d, J = 7.2 Hz, 2H, Harom), 8.21 (d, J = 8.3, 1H, Harom), 9.41 (d, J = 8.7 Hz, 1H, Harom), 10.17, 10.23 (s, 1H, NH). 13C NMR (75 MHz, DMSO-d6): δ = 15.3, 15.4, 34.4, 34.7, 47.0, 47.3, 125.3, 126.7, 127.1, 127.3, 128.0, 128.7, 129.0, 130.0, 132.0, 132.3, 132.6, 134.1, 139.5, 139.8, 144.1, 145.0, 166.1, 199.8. MS (EI, 70 eV): m/z (%) = 405 (100) [M]+, 300 (15) [M-PhCO]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H24NO2: 406.1802; Found: 406.1803.
Ethyl 4-methyl-3-[(phenylcarbonyl)amino]naphthalene-2-carboxylate (2h). Irradiation time 13 h. Yield 45 mg (45%), white crystals. Mp 75-76 °C. IR (KBr), cm-1: CO2 Et H N
3331 (NH), 2987, 1696, 1512, 1478, 1296, 1272, 1208, 1024. 1H NMR Ph
O 2h
(300 MHz, CDCl3): δ = 1.42 (t, J = 7.0 Hz, 3H, CH3), 2.62 (s, 3H, CH3), 4.40 (q, J = 7.0 Hz, 2H, CH2), 7.49-7.60 (m, 4H, Harom), 7.63-7.70 (m,
1H, Harom), 7.92 (d, J = 8.1 Hz, 1H, Harom), 8.05-8.16 (m, 3H, Harom), 8.47 (s, 1H, Harom), 10.32 (s, 1H, NH). 13C NMR (75 MHz, CDCl3): δ = 14.2, 15.6, 61.6, 122.2, 124.7, 126.0, 127.6, 128.7, 129.6, 130.3, 130.9, 131.1, 131.5, 131.8, 134.6, 135.4, 165.4, 167.9. MS (EI, 70 eV): m/z (%) = 333 (14) [M]+, 228 (30) [M-PhCO]+, 105 [PhCO]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H20NO3: 334.1438; Found: 334.1442.
1
Double set of some signals in the 1H and Supporting Information)
13
C NMR spectra indicates dynamic NMR effect (see section VII in
S10
Reduction of compound 2a. Naphthalene 2a (100 mg, 0.32 mmol) was suspended in dry Et2O (5 ml), LiAlH4 (LAH, 122 mg, 3.2 mmol) was added and the solution was refluxed for 10 h. The resulting mixture was cooled to 0 °C with ice-water bath and was quenched very carefully with addition of ethyl acetate (10 ml). The resulting suspension was poured carefully into ice water (100 ml) and extracted with ethyl acetate (2 x 20 ml). The combined organic phases was filtered through thin layer of silica gel (2 cm) and concentrated in vacuum. The residue was purified by column chromatography on silica gel (light petroleum - ethyl acetate, 20:1) to give 47 mg (51 %) of compound 3 as yellow viscous oil.
N-benzyl-5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-amine (3). IR (KBr), cm-1: 2950, 2926, 1588, 1453, 1384, 1188, 1116, 751, 699. 1H NMR (300 MHz, CDCl3): δ = 2.15-2.30 (m, 2H, CH2), 3.01 (t, J = 7.1 Hz, 2H, CH2), ),
H N Ph 3
3.28 (t, J = 7.3 Hz, 2H, CH2), 4.30 (s, 2H, CH2), 7.27-7.50 (m, 7H, Harom), 7.75 (d, J = 8.0 Hz, 1H, Harom), 7.95 (d, J = 8.4 Hz, 1H, Harom).
13
C NMR (75 MHz, CDCl3): δ = 13.2, 24.4, 31.6, 32.4, 53.6, 119.4, 123.2, 124.0, 124.8, 124.9,
127.0, 127.3, 127.9, 128.6, 133.4, 135.2, 138.7, 140.5, 142.1. MS (EI, 70 eV): m/z (%) = 287 (100) [M]+, 272 (25) [M-CH3]+, 196 (95) [M-C7H7]+. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H22N: 288.1747; Found: 288.1744.
S11
III. NMR monitoring of photoreaction
Figure S1. 1H NMR (200MHz) stacked plot of solution of diarylethene 3a (10 mg in 0.5 ml of CDCl3) during irradiation with UV light (365 nm, 6W lamp) at 298 K. S12
IV. UV-vis spectra of compounds 1a,b,e,f,g and 2a,b,e,f,g O
O
UV
H N
N O
Ph
Ph
O
1a
2a
Figure S2. UV absorption spectra during the course of isomerization of diarylethene 1a in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S3. UV absorption spectrum of naphthalene 2a in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S13
O
O
UV
H N
N Ph
Ph O
O 2b
1b
Figure S4. UV-Vis absorption spectra during the course of isomerization of diarylethene 1b in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S5. UV absorption spectrum of naphthalene 2b in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S14
O
O
UV
H N
N O
Ph
Ph
O
1e
2e
Figure S6. UV-Vis absorption spectra during the course of isomerization of diarylethene 1e in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S7. UV absorption spectrum of naphthalene 2e in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section. S15
UV
H N
N Ph
Ph O
O 2f
1f
Figure S8. UV-Vis absorption spectra during the course of isomerization of diarylethene 1f in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S9. UV absorption spectrum of naphthalene 2f in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S16
Ph
Ph O
UV
O H N
N O
Ph
Ph
O
1g
2g
Figure S10. UV-Vis absorption spectra during the course of isomerization of diarylethene 1g in MeCN (C ≈ 3.0 × 10-5 M), induced by irradiation with UV light (λ = 365 nm).
Figure S11. UV absorption spectrum of naphthalene 2g in MeCN (C ≈ 3 × 10-5 M) prepared by method, described in the experimental section.
S17
V. Absorption spectra of photoinduced form of diarylethenes 1b and 1f
Figure S12. UV-Vis absorption spectra of diarylethene 1b in MeCN (C ≈ 3 × 10-4 M) before and after irradiation with UV light (λ = 365 nm) and thermal decomposition of colored intermediate observed at 540 nm at 293 K.
Figure S13. UV-Vis absorption spectra of diarylethene 1f in MeCN (C ≈ 3 × 10-4 M) before and after irradiation with UV light (λ = 365 nm) and thermal decomposition of colored intermediate observed at 470 nm at 293 K.
S18
VI. 2D NMR spectra of compounds 2a,b,f N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2a)
H
H H
O
H
H
3 4
5
H 7
2
1 6
N
13 11
14
H
9 10
H
H
H
19
H
17 16 18
12
8
20
H 15
O
H
H
H
Table S1. Assignment of NMR signals and 2D NMR correlations for compound 2a № 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1
H (ppm)
2.72-2.78 (m) 3.06-3.13 (m) 9.13 (d, J = 8.0 Hz) 7.72-7.77 (m) 7.66-7.72 (m) 8.23 (d, J = 8.3 Hz) 2.65 (s) 10.3 (s) 8.09 (d, J = 7.2 Hz) 7.56-7.62 (m) 7.62-7.66 (m)
13
C (ppm) 207.1 36.7 24.4 157.9 129.6 128.0 123.7 128.8 127.3 125.7 132.5 140.1 132.2 15.0 166.2 134.5 128.2 129.0 132.3
S19
NOESY HMBC {1H-1H} {1H-13C} 2, 3 3 1, 3, 4 2, 15 1, 2, 4, 5, 13 2, 3, 14, 15 3, 7 8 5, 9, 11 6, 10 7, 11 14 8, 12 7, 9, 14 10, 14, 15 3, 14 10, 15 4, 11, 12, 13 3, 14, 18 4, 12, 16 15, 18 19 15 16, 20 17 18
1
H NMR spectra (400.16 MHz; DMSO-d6) of compound 2a
13
C DEPTQ NMR spectra (100.62 MHz; DMSO-d6) of compound 2a
S20
{1H-1H}NOESY (400.16 MHz; DMSO-d6)
H
H H
O
5
H 7
H
2
1
H
3 4
20
6
N
13
17 18
12
O
14
H
9 10
H
19
16
11 8
H
H
H
H 15
H
S21
H
H
{1H-13C}HSQC (400.16 MHz; DMSO-d6)
S22
{1H-13C}HMBC (400.16 MHz; DMSO-d6)
H
H H
O
2
H
20
4
5 6 11
12
8
H
O
14
H
9 10
H
H
H
H 15 N 16 13
7
H
H
3
1
H
S23
17
19 18
H
H
1
H-13C}HMBC (400.16 MHz; DMSO-d6)
H 1
H 8
3 4
5 7
H
20
15
N 16 13
H
O
14
H H
17
19 18
12
10
H
H
6 11
9
H H
2
O
H
H
H
S24
H
H
{1H-13C}HMBC (400.16 MHz; DMSO-d6)
H
H H
O
5
H 7 8
H
2
1
H
3 4
N 16 13
6 11
12
9
14
H
10
H
20
15
H
H
H
H
H
S25
O
17
19 18
H
H
{1H-1H}COSY (400.16 MHz; DMSO-d6)
S26
N-(5-Methyl-3-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2b)
H H H H
O
2 1
H 7
H 3 4
5 6
N
13
8
17 18
12 14
H
10
H
H
H
O
H
19
16
11 9
20
H 15
H
H
H
Table S2. Assignment of NMR signals and 2D correlations for compound 2b № 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1
H (ppm)
3.38-3.43 (m) 2.83-2.87 (m) 8.04 (J = 7.6 Hz) 7.60-7.64 (m) 7.73-7.79 (m) 8.20 (J = 8.5 Hz) 2.60 (s) 10.05 (s) 8.13 (J = 6.8 Hz) 7.52-7.60 (m) 7.52-7.60 (m)
13
C (ppm) 23.8 36.4 208.3 127.2 155.7 128.3 124.7 126.1 129.8 125.7 137.1 128.5 129.9 15.7 165.8 134.4 127.7 128.8 131.9
S27
NOESY HMBC {1H-1H} {1H-13C} 2, 7 2, 3, 4, 5, 6, 13 1 1, 3, 4, 5 1, 2 1, 2 1, 2, 7 1, 8, 10 1 5, 9, 11 6, 10 7, 11 14 6, 8, 12 7, 9, 14 10, 14, 15 1, 14 10, 15, 18 11, 12, 13 14, 18 12 18 19 14, 15 16, 20 17 18
1
H NMR spectra (400.16 MHz; CDCl3) of compound 2b
13
C DEPTQ NMR spectra (100.62 MHz; CDCl3) of compound 2b
S28
{1H-1H}ROESY (400.16 MHz; CDCl3)
H
H
H H
H 7
H
O
2 3 4
1 5
H 15
6 13
11
8
N
18
12 9
H
14
H
10
H
H
17 16
H
S29
O
H
{1H-13C}HSQC (400.16 MHz; CDCl3)
S30
{1H-13C}HMBC (400.16 MHz; CDCl3)
H H H 7
H
1
H
H 2
5
O
3 4
H 15
6
N 16 13
18
11 12
8
H
O
14
H
9 10
H
17
H
S31
H
H
{1H-13C}HMBC (400.16 MHz; CDCl3)
H H H
H
7
3 4
5 6
20
12 10
H
O
14
H H
H
H 15 N 16 13
9
H
O
2
11
8
H
1
H
H
S32
17
19 18
H
H
{1H-13C}HMBC (400.16 MHz; CDCl3) H H H
H 7
H
8
1
H O
2 3 4
5
H 15
6
N
13 11
18 12 14
H
9 10
H
17 16
H
H
S33
H
O
H
{1H-13C}HMBC (400.16 MHz; CDCl3) H H H
H 7
H
H 2
1 5
O
3 4
H 15
6
N 16
13
8
18
11 12 9
H
17
14
H
10
H
H
S34
H
O
H
{1H-1H}COSY (400.16 MHz; CDCl3)
S35
N-(5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2f)
H
H H
H 2
1
H
H 7
H
H
3 4
5 6
N
13
8
17 18
12
H
14
H
10
H
O
H
19
16
11 9
20
H 15
H
H
H
H
Table S3. Assignment of NMR signals and 2D correlations for compound 2f №
1
H (ppm)
1 3.32 (t, J = 7.4 Hz) 2 2.21-2.28 (m) 3 3.08 (t, J = 7.3 Hz) 4 5 6 7 7.82 (d, J = 8.3 Hz) 8 7.49-7.55 (m) 9 7.49-7.55 (m) 10 8.07 (d, J = 7.3 Hz) 11 12 13 14 2.62 (s) 15 7.72 (s) 16 17 18 7.99 (d, J = 7.3 Hz) 19 7.49-7.55 (m) 20 7.58-7.62 (m)
13
C (ppm) 31.7 24.0 32.4 138.6 138.9 129.8 124.9 125.6 125.1 125.2 132.6 128.8 129.6 13.8 166.0 134.6 127.3 128.8 131.8
S36
NOESY HMBC {1H-1H} {1H-13C} 7 2, 3, 4, 5, 13 1, 3, 4, 5 15 1, 2, 4, 5, 13 1, 2, 3, 14 1, 2, 3, 7 7, 10 1 5, 6, 9, 11 10 7 14 6, 8, 11, 7, 10, 14 14 1, 3, 14 10, 15 4, 11, 12, 13 3, 14, 18 18 19 15 16, 20 17 18
1
H NMR spectra (600.13 MHz; CDCl3) of compound 2f
13
C DEPTQ NMR spectra (150.90 MHz; CDCl3) of compound 2f
S37
{1H-1H}NOESY (600.13 MHz; CDCl3)
H
2
H H
H
3
1 7H
H
H
4
5
H 15
6
N
13 8
16
11
H
18
12
H 9H
H
H
O 14
H
10
S38
H
{1H-13C}HSQC (600.13 MHz; CDCl3)
S39
{1H-13C}HMBC (600.13 MHz; CDCl3)
H H
H 2
H 3
1
H
H 6
5
N
13
8
H H 15
4 7
H
H 17 16 18
11 12 9
H
14
H
10
H
H
20
H
S40
O
H
19
H
{1H-13C}HMBC (600.13 MHz; CDCl3)
H H
2
H H
1
3
H
H 5
H 6
7
H
4
20
N 16 13 12
9
H
17
19 18
11 8 10
H
H
H 15
14
H
H H
S41
O
H
H
{1H-13C}HMBC (600.13 MHz; CDCl3)
H
H H
H H
2
H
3
1
H
4 6 5
H
8
13
7 11
H
N 16
12
H
O
14
H
9 10
H
20
H
19
H
H 15
H
S42
17
18
H
{1H-1H}COSY (600.13 MHz; CDCl3)
S43
VII. Temperature dependent NMR spectra of compound 2g Naphthalene 2g shows double set of signals belonging to methyl
Ph
1
(2.61 and 2.64 ppm) and amide (10.17 and 10.23 ppm) groups in the H
O H
NMR spectrum at 303 K (Figure S14). At 343 K there is only one set of
N Ph
the signals (2.66 and 10.06 ppm, Figure S15), which clearly indicates dynamic NMR effect, related to restricted rotation of amide group.
O 2g
Figure S14. 1H NMR (600.13 MHz) spectrum of compound 2g in DMSO-d6 at 303 K.
Figure S15. 1H NMR (600.13 MHz) spectrum of compound 2g in DMSO-d6 at 343 K. S44
VIII. References
[S1] Shirinian, V. Z.; Shimkin, A. A.; Lonshakov, D. V.; Lvov, A. G.; Krayushkin, M. M. J. Photochem. Photobiol. A: Chem. 2012, 233, 1. [S2] Shimkin, A. A.; Shirinian, V. Z.; Mailian, A. K.; Lonshakov, D. V.; Gorokhov, V. V.; Krayushkin, M. M. Russ. Chem. Bull. 2011, 60, 139. [S3] Shirinian, V. Z.; Lvov, A. G.; Krayushkin, M. M.; Lubuzh, E. D.; Nabatov, B. V. J. Org. Chem., 2014, 79, 3440. [S4] a) Sohda, T.; Mizuno, K.; Momose, Y.; Ikeda, H.; Fujita, T.; Meguro, K. J. Med. Chem. 1992, 35, 2617; b) Lvov, A. G.; Shirinian, V. Z.; Kavun, A. M.; Krayushkin, M. M. Mendeleev Commun. submitted. [S5] Olah, G. A.; Arvanaghi, M.; Ohannesian, L. Synthesis 1986, 770. [S6] Chang, M.-Y.; Tsai, C.-Y.; Wu, M.-H. Tetrahedron 2013, 69, 6364. [S7] García-Raso, A.; García-Raso, J.; Campaner, B.; Mestres, R.; Sinisterra J. V. Synthesis 1982, 1037. [S8] Hulin, B; Clark, D. A.; Goldstein, S. W.; McDermott, R. E.; Dambek, P. J.; Kappeler, W. H.; Lamphere, C. H.; Lewis, D. M.; Rizzi, J. P. J. Med. Chem. 1992, 35, 1853. [S9] Karminski-Zamola, G.; Bajić, M. Synth.Commun. 1989, 19, 1325.
S45
IX. Copies of 1H NMR and 13C NMR spectra2 3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one (1a)
O N O
Ph
1a
O N O
Ph
1a
2
Copies of 1H NMR and Information.
13
C NMR spectra of compounds 2a,b,f are presented in section VI of Supporting
S46
2-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylcyclopent-2-en-1-one (1b)
O N Ph
O 1b
O N Ph
O 1b
S47
3-[2-(4-Methoxyphenyl)-5-methyl-1,3-oxazol-4-yl]-2-phenylcyclopent-2-en-1-one (1c)
O N O OMe
1c
O N O 1c
OMe
S48
3-{5-Methyl-2-[4-(trifluoromethyl)phenyl]-1,3-oxazol-4-yl}-2-phenylcyclopent-2-en-1-one (1d)
O N O CF3
1d
O N O 1d
CF3
S49
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2-(1-naphthyl)cyclopent-2-en-1-one (1e)
O N O 1e
O N O
Ph
1e
S50
Ph
5-Methyl-2-phenyl-4-(2-phenylcyclopent-1-en-1-yl)-1,3-oxazole (1f)
N O 1f
N O
Ph
1f
S51
Ph
3-(5-Methyl-2-phenyl-1,3-oxazol-4-yl)-2,5-diphenylcyclohex-2-en-1-one (1g)
Ph O N O
Ph
1g
Ph O N O
Ph
1g
S52
Ethyl 2-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-3-phenylprop-2-enoate (1h)
CO2 Et N O
Ph
1h
CO2 Et N O 1h
S53
Ph
4-Methoxy-N-(5-methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)benzamide (2c)
O H N OMe O 2c
O H N OMe O 2c
S54
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-yl)-4(trifluoromethyl)benzamide (2d)
O H N CF3 O 2d
O H N CF3 O 2d
S55
N-(5-Methyl-1-oxo-2,3-dihydro-1H-cyclopenta[c]phenanthren-4-yl)benzamide (2e)
O H N Ph O 2e
O H N Ph O 2e
S56
N-(10-Methyl-5-oxo-7-phenyl-5,6,7,8-tetrahydrophenanthren-9-yl)benzamide (2g)
Ph O H N Ph O 2g
Ph O H N Ph O 2g
S57
Ethyl 4-methyl-3-[(phenylcarbonyl)amino]naphthalene-2-carboxylate (2h)
CO2 Et H N Ph O 2h
CO2 Et H N Ph O 2h
S58
N-benzyl-5-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-4-amine (3)
H N Ph 3
H N Ph 3
S59
