A.A. Kalinin, et al.
JournalofPhotochemistry&PhotobiologyA:Chemistry386(2020)112125
indolizine), 7.46-7.36 (m, 7.5H, o,p-Ph), 7.15 (d, J = 16.3 Hz, 2.5H,
ethene), 6.90-6.83 (m, 2.5H, H-7 indolizine), 6.78-6.71 (m, 2.5H, H-6
indolizine), 6.63 (d, J = 16.4 Hz, 1H, ethene), 6.44 (d, J = 16.4 Hz,
1.5H, ethene), 6.36 (s, 1H, –CH=C(R)CH(CN)-), 6.02 (s, 1.5H,
-CH=C(R)CH(CN)-), 5.20 (s, 1.5H, =CH(CN)-), 5.06 (s, 1H, =CH
(CN)-), 2.40 (s, 1.5H, CH2), 2.39 (s, 1.5H, CH2), 2.32 (s, 3H, CH2), 2.31
(s, 2H, CH2), 2.25 (s, 1H, CH2), 2.24 (s, 1H, CH2), 1.00 (s, 9H, CH3),
0.96 (s, 6 H, CH3). 13C NMR (100 MHz, CDCl3): δ 158.1, 157.8, 146.1,
145.5, 135.5, 135.3, 133.3, 133.0, 132.0, 131.4, 130.6, 130.5, 128.4,
128.3, 127.2, 127.1, 125.4, 125.1, 124.6, 123.7, 123.1, 122.5, 119.8,
119.1, 119.0, 118.9, 118.8, 118.0, 117.8, 117.78, 117.72, 117.65,
111.9, 111.7, 110.1, 109.8, 91.5, 90.0, 44.8, 42.1, 38.49, 38.46, 31.2,
31.0, 28.2, 28.1, 9.00, 8.97. IR (λmax, cm−1, KBr): 3050 (CH), 2917
(CH), 2198 (C≡N), 1608 (C = C), 1567 (C = C). MALDI-TOF: 379 [M
(d, J = 7.9 Hz, 1H, =CH = CH(O)-), 2.72 (s, 2.5H, CH2), 2.71 (s, 2.5H,
CH2), 2.35 (s, 5H, CH2), 2.33 (s, 2H, CH2), 2.28 (s, 1H, CH2), 2.27 (s,
1H, CH2), 2.21 (s, 3H, CH3), 2.20 (s, 7.5H, CH3), 1.02 (s, 15H, CH3),
0.98 (s, 6 H, CH3). 13C NMR (100 MHz, acetone-d6): δ 190.3, 189.2,
156.8, 156.3, 147.5, 147.4, 136.5, 136.4, 133.7, 132.0, 131.3, 131.2,
129.18, 129.16, 128.2, 127.9, 126.8, 126.7, 125.5, 124.6, 124.5, 121.1,
119.9, 119.8, 119.6, 118.71, 118.67, 118.3, 112.6, 110.6, 110.4, 46.5,
39.4, 39.10, 39.06, 31.5, 31.4, 28.4, 28.3, 9.1, 9.0. IR (λmax, cm−1
,
KBr): 3457 (CH), 2924 (CH), 1651 (C = O), 1561 (C = C). MALDI-TOF:
382 [M+H]+
.
2.2.4. (E,E,E,E)/(E,E,Z,E)
2-(3-Cyano-4-(-3-(5,5-dimethyl-3-(2-(3(1)-
methyl-2-phenylindolizin-1(3)-yl)vinyl)cyclohex-2-en-1-ylidene)prop-1-en-
1-yl)-5,5-dimethylfuran-2(5 H)-ylidene)malononitriles ((MPI-1)-OT-TCF,
(MPI-3)-OT-TCF)
+H]+
.
To solution of aldehyde 7 (0.20 g, 0.52 mmol) in dry ethanol (5 mL)
solution of Me-TCF (0.10 g, 0.50 mmol) in dry ethanol (1 mL) was
added, and combined solution was refluxed for 8 h. After removing the
solvent the residue was purified by column chromatography (eluent:
methylene chloride).
2.2.3. (E,Z)-2-(5,5-Dimethyl-3-((E)-2-(3(1)-methyl-2-phenylindolizin-
1(3)-yl)vinyl)cyclohex-2-en-1-ylidene)acetaldehydes (7a,b)
To the stirred and cooled to −78 °C solution of indolizine 6 (0.37 g,
1 mmol) in dry toluene (8 mL), diisobutylaluminium hydride (1.3 mL,
1.56 mmol) was added dropwise by syringe, then the mixture was
stirred for 2 h at −78 °C and for 1 h at room temperature. Saturated
aqueous NH4Cl solution (5 mL) was added to quench the reaction, and
mixture was stirred for 20 min at room temperature. Organic layer was
separated and washed with water. Toluene was evaporated and the
residue was purified by column chromatography (eluent: methylene
chloride).
2.2.4.1. (E,E,E,E)/(E,E,Z,E) 2-(3-Cyano-4-(3-(5,5-dimethyl-3-(2-(3-methyl
-2-phenylindolizin-1-yl)vinyl)cyclohex-2-en-1-ylidene)prop-1-en-1-yl)-5,5-di-
methylfuran-2(5 H)-ylidene)malononitrile
((MPI-1)-OT-TCF). Yield:
0.16 g (56%). Black powder. Rf = 0.3 (hexane:ethyl acetate = 2:1). 1H
NMR (600 MHz, DMSO-d6): δ 8.22 (d, J = 6.8 Hz, 1H, H-5 indolizine),
8.09 (d, J = 8.9 Hz, 1H, H-8 indolizine), 7.96 (dd, J∼14, 13 Hz, 1H,
=CH-CH = CH-TCF), 7.54 (dd, J = 7.6, 7.4 Hz, 2H, m-Ph), 7.46 (dd,
J = 7.4, 7.4 Hz, 1H, p-Ph), 7.36 (d, J = 7.6 Hz, 2H, o-Ph), 7.29 (d,
J = 15.9 Hz, 1H, ethene), 7.16 (dd, J = 8.9, 6.7 Hz, 1H, H-7 indolizine),
6.96 (dd, J = 6.8, 6.7 Hz, 1H, H-6 indolizine), 6.53 (d, J = 15.9 Hz, 1H,
ethene), 6.41 (d, J ∼13 Hz, 1H, ethene), 6.39 (d, J∼14 Hz, 1H, ethene),
6.27 (br, 1H, -CH=C(R)CH(CH = CHTCF)-), 2.41 (s, 2H, CH2), 2.34 (s,
5H, CH2, CH3), 1.66 (s, 6H, CH3), 0.95 (s, 6H, CH3). 13C NMR (150 MHz,
DMSO-d6): δ 177.0, 172.8, 156.1, 151.5, 143.7, 134.4, 132.6, 130.4,
128.4, 128.1, 127.3, 127.1, 124.9, 124.6, 121.5, 121.6, 118.2, 114.1,
113.7, 113.1, 112.9, 112.8, 109.9, 97.3, 90.1, 49.9, 38.3, 31.0, 27.9,
25.7, 9.6. 1H NMR (400 MHz, CDCl3): δ 8.20 (dd, J∼14, 14 Hz, 1H,
=CH-CH = CH-TCF), 7.99 (dd, J∼14, 14 Hz, 3.3 H, =CH-CH = CH-
TCF), 7.84-7.79 (m, 8.6H, H-5,8-indolizine), 7.53-7.48 (m, 8.6H, m-Ph),
7.46-7.40 (m, 4.3H, p-Ph), 7.38-7.34 (m, 8.6 H, o-Ph), 7.17 (d, J ∼16 Hz,
1H, ethene), 7.16 (d, J = 15.9 Hz, 3.3H, ethene), 7.04-6.98 (m, 4.3 H, H-
2.2.3.1. (E,Z)-2-(5,5-Dimethyl-3-((E)-2-(3-methyl-2-phenylindolizin-1-yl)
vinyl)cyclohex-2-en-1-ylidene)acetaldehyde (7a). Yield: 0.22 g (58%).
Dark red powder, mp 75–77 °C. Rf = 0.33 (hexane:ethyl
acetate = 10:3). 1H NMR (600 MHz, acetone-d6):
δ 10.15 (d,
J = 8.0 Hz, 1H, CHO), 10.02 (d, J = 8.2 Hz, 2.5H, CHO), 7.98 (d,
J = 6.8 Hz, 1H, H-5 indolizine), 7.97 (d, J = 6.8 Hz, 2.5H, H-5
indolizine), 7.89 (d, J = 9.0 Hz, 1H, H-8 indolizine), 7.87 (d,
J = 9.0 Hz, 2.5H, H-8 indolizine), 7.53-7.48 (m, 7H, m-Ph), 7.43-7.39
(m, 3.5H, p-Ph), 7.39-7.36 (m, 7H, o-Ph), 7.09 (d, J = 16.3 Hz, 1H,
ethene), 7.14 (s, 1H, -CH=C(R)CH(CHO)-), 7.08 (d, J = 16.3 Hz, 3.5H,
ethene), 6.94 (dd, J = 9.0, 6.7 Hz, 3.5H, H-7 indolizine), 6.76 (dd,
J = 6.8, 6.7 Hz, 3.5H, H-6 indolizine), 6.69 (d, J = 16.3 Hz, 1H,
ethene), 6.57 (d, J = 16.3 Hz, 2.5H, ethene), 6.07 (s, 2.5H,
-CH=C(R)CH(CHO)-), 5.72 (d, J = 8.2 Hz, 2.5H, =CH-CH(O)-), 5.55
(d, J = 8.0 Hz, 1H, =CH = C(O)-), 2.68 (br, 5H, CH2), 2.37 (s, 3H,
CH3), 2.36 (s, 7.5H, CH3), 2.28 (s, 5H, CH2), 2.26 (s, 2H, CH2), 2.24 (br,
2H, CH2), 1.00 (s, 15H, CH3), 0.96 (s, 6 H, CH3). 13C NMR (150 MHz,
acetone-d6): δ 190.1, 189.3, 157.2, 156.8, 148.1, 147.9, 136.2, 136.1,
131.8, 131.6, 129.1, 128.3, 128.1, 127.8, 127.0, 126.6, 126.1, 126.0,
125.7, 124.1, 124.0, 120.3, 120.1, 120.0, 119.6, 119.0, 118.9, 112.5,
7
indolizine), 6.81-6.77 (m, 4.3H, H-6 indolizine), 6.56 (s, 1H,
-CH=C(R)CH(CH = CHTCF)-), 6.53 (d, J = 16.1 Hz, 4.3 H, ethene),
6.26 (d, J = 12.5 Hz, 3.3H, ethene), 6.15 (d, J = 14.4 Hz, 4.3 H,
ethene), 6.11 (s, 1H, -CH=C(R)CH(CH = CHTCF)-), 6.01 (d, J∼12 Hz,
1H, ethene), 2.39 (s, 6.6H, CH2), 2.38 (br, 12.9 H, CH3), 2.32 (s, 6.6H,
CH2), 2.29 (br, 4H, CH2), 1.68 (s, 6H, CH3), 1.65 (s, 19.8 H, CH3), 1.02 (s,
19.8H, CH3), 0.99 (s, 6H, CH3). 13C NMR (100 MHz, CDCl3): δ 176.5,
173.0, 172.6, 156.3, 155.7, 151.0, 150.2, 144.1, 143.2, 135.0, 134.9,
132.4, 132.3, 130.8, 128.5, 128.4, 128.1, 127.6, 127.5, 127.4, 127.1,
125.8, 125.6, 124.5, 123.1, 123.0, 120.8, 120.5, 120.3, 120.2, 118.3,
118.2, 114.1, 113.5, 113.1, 113.0, 112.6, 112.4, 112.3, 112.2, 110.1,
109.9, 96.5, 96.3, 92.6, 92.1, 53.9, 53.4, 47.1, 39.9, 39.5, 39.1, 31.7,
31.4, 28.5, 28.2, 26.6, 9.9. IR (λmax, cm−1, KBr): 3506 (CH), 2219
109.7, 46.6, 39.5, 39.3, 39.2, 31.5, 31.4, 28.44, 28.37, 9.9. IR (λmax
,
cm−1, KBr): 3452 (CH), 2948 (CH), 1645 (C = O), 1566 (C = C).
MALDI-TOF: 382 [M+H]+
.
2.2.3.2. (E,Z)-2-(5,5-Dimethyl-3-((E)-2-(1-methyl-2-phenylindolizin-3-yl)
vinyl)cyclohex-2-en-1-ylidene)acetaldehyde (7b). Yield: 0.30 g (81%).
Dark red powder, mp 75-770 C. Rf = 0.42 (hexane:ethyl
acetate = 10:3).
(C≡N), 1562 (C = C). MALDI-TOF: 563 [M+H]+
.
1H NMR (500 MHz, acetone-d6): δ 10.10 (d, J = 7.9 Hz, 1H, CHO),
10.03 (d, J = 8.1 Hz, 2.5H, CHO), 8.55 (d, J = 7.0 Hz, 1H, H-5 in-
dolizine), 8.54 (d, J = 7.0 Hz, 2.5H, H-5 indolizine), 7.54-7.48 (m,
10.5H, m-Ph, H-8 indolizine), 7.45-7.43 (m, 3.5H, p-Ph), 7.42-7.38 (m,
7H, o-Ph), 7.15 (d, J = 16.3 Hz, 3.5H, ethene), 7.09 (s, 1H,
-CH=C(R)CH(CHO)-), 7.15 (d, J = 16.3 Hz, 3H, ethene), 7.10 (s, 2.5H,
-CH=C(R)CH(CHO)-), 6.86 (dd, J = 8.9, 6.5 Hz, 3.5H, H-7 indolizine),
6.74 (dd, J = 7.0, 6.5 Hz, 3.5H, H-6 indolizine), 6.64 (d, J = 16.3 Hz,
1H, ethene), 6.52 (d, J = 16.3 Hz, 2.5H, ethene), 6.04 (s, 2.5H,
-CH=C(R)CH(CHO)-), 5.73 (d, J = 8.1 Hz, 2.5H, =CH-CH(O)-), 5.58
2.2.4.2. (E,E,E,E)/(E,E,Z,E) 2-(3-Cyano-4-(3-(5,5-dimethyl-3-(2-(1-methyl
-2-phenylindolizin-3-yl)vinyl)cyclohex-2-en-1-ylidene)prop-1-en-1-yl)-5,5-di-
methylfuran-2(5 H)-ylidene)malononitrile
((MPI-3)-OT-TCF). Yield:
0.20 g (71%). Black powder. Rf = 0.42 (hexane:ethyl acetate = 2:1).
1H NMR (400 MHz, DMSO-d6):
δ 8.81 (d, J = 7.1 Hz, 1H, H-5
indolizine), 7.92 (dd, J∼14, 14 Hz, 1H, =CH-CH = CH-TCF), 7.60 (d,
J = 8.9 Hz, 1H, H-8 indolizine), 7.54 (dd, J = 7.8, 7.5 Hz, 2H, m-Ph),
7.50-7.44 (m, 1H, p-Ph), 7.38-7.35 (m, 2H, o-Ph), 7.34 (d, J∼16 Hz, 1H,
ethene), 7.06 (dd, J = 8.9, 6.8 Hz, 1H, H-7 indolizine), 6.89 (dd, J∼7.1,
3