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Supplementary Material 2

A new entry to phenanthridine ring system Poulomi Mandal, Latibuddin Thander and Shital K Chattopadhyay* Department of Chemistry, University of Kalyani, Kalyani-741235, West Bengal, India

Contents:

1. Table 2 ……………………………………………………………….page 2 2. General experimental procedure for the compounds 16a-f……………page 3

3. General experimental procedure for the compounds 18a-f …………..page 4

4. General experimental procedure for the compounds 19a-f ………… page 5

5. General experimental procedure for the compounds 20a-f ………… page 6

6. Copies of 1H and 13C-NMR spectra of the compounds 15a-f, 16a-f, 18a-f, 19bc, 20a-f …………………………………. pages 7-58

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Table 2: List of new compounds 15a-f, 16a-f, 18a-f, 19b-c, 20a-f

Entry R R1 Compound (% of yield )

1 H Et 15a (88)

Mp 110 ˚C

16a (86)

Mp76 ˚C

18a (69)

Mp 135 ˚C

19a (66)

20a (68)

Mp 104 ˚C

2 Me Me 15b (85)

Mp 116 ˚C

16b (79)

Mp 111 ˚C

18b (72)

Mp 122 ˚C

19b (78)

Mp 132 ˚C

20b (66)

Mp 142 ˚C

3 OMe Et 15c (90)

Mp 122 ˚C

16c (89)

Mp 118 ˚C

18c (66)

Mp 120 ˚C

19c (81)

Mp 108 ˚C

20c (74)

Mp 90 ˚C

4 Cl Me 15d (75)

Mp 124 ˚C

16d (78)

Mp 130 ˚C

18d (71)

Mp 105 ˚C

19d (65)

20d (80)

Mp 126 ˚C

5 Br Et 15e (65)

Mp 146 ˚C

16e (94)

Mp 102 ˚C

18e (75)

Mp 110 ˚C

19e (70) 20e (77)

Mp 104 ˚C

6 F Et 15f (70)

Mp 102 ˚C

16f (74)

Mp 105 ˚C

18f (87)

Mp 126 ˚C

19f (74)

20f (90)

Mp 96 ˚C

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General procedure for the preparation of the enynes 16a-f

Propargyl bromide (2 equiv) and K2CO3 (3 equiv) were added to a solution of the

compound 15 (0.5 mmol) in dry acetone (5 ml) and the reaction mixture was heated

to reflux for 6 hrs. It was then filtered and the filter cake was washed with EtOAc (2

x 10 ml). The combined filtrate was concentrated under reduced pressure to leave a

residue which was purified by chromatography over SiO2 using EtOAc-PE (1:19)

as eluent to give the product.

Selected data: Compound 16c: Mp: 118-119˚C (EtOAc + hexane). IR (KBr) ʋmax

3292, 2935, 2300, 1602,1498, 1350, 1162 cm-1.1H NMR (400 MHz, CDCl3): δ =

7.66 (2H, d, J = 8.4 Hz), 7.27 (2H, d, J = 7.6 Hz), 7.03 (1H, d, J = 2.8 Hz), 6.79

(1H, d, J = 7.6 Hz), 6.62 (1H, dd, J = 3.2 Hz,8.8 Hz), 6.58 (1H, dd, J = 1.6 Hz,16

Hz), 6.19 (1H, dq, J = 6.4 Hz, 16 Hz), 4.63 (1H, d, J = 17.2 Hz), 4.11 (1H, d, J =

17.4 Hz), 3.80 (3H, s), 2.43 (3H, s), 2.15 (1H, t, J = 2.4 Hz), 1.84 (3H, dd, J = 1.6

Hz,6.4 Hz).13C NMR (100 MHz, CDCl3): δ = 159.6, 143.6, 139.7, 136.6, 130.9,

129.3, 128.6, 128.1, 126.3, 112.9, 110.7, 78.1, 73.6, 55.3, 41.5, 21.6, 18.8. Anal.

Calcd for C20H21NO3S: C, 67.58; H, 5.95; N, 3.94; Found: C, 67.64; H, 6.03; N,

3.83. MS (QTOF MS ES+) m/z 378 [M+Na]+

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General procedure for the preparation of the dienes 18a-f

Grubbs’ catalyst 17 (5 mol %) was added to a solution of compound 16 (0.4

mmol) in dry degassed toluene (40 ml) under argon and the reaction mixture was

heated at 90 ˚C for 24-48 h. It was then concentrated under reduced pressure and the

residue was chromatographed over SiO2 using EtOAc-PE (1:19) as eluent to give the

product 18. Selected data: Compound 18c: Mp: 121-122˚C (EtOAc + hexane). IR

(KBr): 2964, 1598, 1569, 1490, 1344, 1279, 1223, 1157, 1077, 1037 cm-1. 1H NMR

(400 MHz, CDCl3): δ = 7.62 (1H, d, J = 8.8 Hz), 7.18 (2H, d, J = 8.4 Hz), 7.00 (2H, d,

J = 8.4 Hz), 6.78 (1H, dd, J = 2.8 Hz, 8.4 Hz), 6.43 (1H, d, J = 2.8 Hz), 5.95-5.82

(2H, m), 5.70 (1H, s), 4.48 (2H, s), 3.80 (3H, s), 2.32 (3H, s), 1.85 (3H, d, J = 6.0

Hz).13C NMR (100 MHz, CDCl3):δ = 158.2, 143.2, 135.3, 134.2, 131.8, 130.1, 128.7,

128.1, 127.3, 127.2, 127.1, 121.9, 112.5, 111.3, 55.4, 45.4, 21.5, 18.7. Anal. Calcd for

C20H21NO3S: C, 67.58; H, 5.95; N, 3.94; Found: C, 67.79; H, 6.12; N, 4.11. MS

(QTOF MS ES+) m/z 378 [M+Na]+

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General procedure for the preparation of the Diels-Alder adducts 19a-f

Diethyl acetylenedicarboxylate / Dimethyl acetylenedicarboxylate (2.5 equiv) was

added to a solution of compound 18 (0.3 mmol) in dry toluene (2 ml) under nitrogen

and the reaction mixture was refluxed for 48 h. It was then concentrated under

reduced pressure and the residue was chromatographed over SiO2 using EtOAc-PE

(1:9) as eluent to give the product 19. Selected data: Compound 19c: Mp: 108-109˚C

(EtOAc + hexane). IR (KBr) ʋmax 2978, 1734, 1718, 1641, 1613, 1581, 1487, 1351,

1255, 1167, 1051 cm-1.1H NMR (400 MHz, CDCl3): δ = 7.61 (1H, d, J = 8.8 Hz), 7.47

(2H, d, J = 7.6 Hz), 7.21 (2H, d, J = 8.0 Hz), 6.79 (1H, dd, J = 2.4 Hz, 8.8 Hz), 6.43

(1H, s), 5.39 (1H, s), 4.58 (1H, d, J = 14.8 Hz), 4.31-4.23 (2H, m), 4.15-4.05 (3H, m),

3.76 (3H, s), 3.05-3.01 (2H, m), 2.38 (3H, s), 1.31 (3H, t, J = 7.2 Hz), 1.19 (3H, t, J =

7.2 Hz), 1.00 (3H, d, J = 6.8 Hz).13C NMR (100 MHz, CDCl3): δ = 168.4,165.8,

158.1, 145.2, 143.6, 139.6, 136.0, 132.1, 129.8, 128.9, 128.5, 127.6, 126.8, 122.0,

111.3, 110.3, 61.4, 61.1, 55.4, 51.5, 38.7, 34.3, 21.6, 20.5, 14.1. HRMS (EI) m/z =

calcd for [M+Na]+ 548.1719; found 548.1723.

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General procedure for the preparation of the phenanthridine derivatives 20a-f

1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) (0.3 mmol, 2 equiv) was added

to a solution of compound 19 (0.15 mmol) in dry toluene (2 ml) under nitrogen and

the reaction mixture was refluxed for 24 hrs. It was then concentrated under reduced

pressure and the residue was chromatographed over SiO2 using EtOAc-PE (1:9) as

eluent to give the product 20. Selected data: Compound 20c: Mp: 94-95˚C (EtOAc

+hexane). IR (KBr) ʋmax 1719, 1732, 1282, 1224, 1195, 1236 cm-1.1H NMR (400

MHz, CDCl3): δ = 9.08 (1H, s), 8.11 (1H, d, J = 8.8 Hz), 7.92 (1H, s), 7.61 (1H,s),

7.38 (1H, d, J = 8.8 Hz), 4.55-4.45 (4H, m), 3.93 (3H, s), 2.61 (3H, s), 1.46-1.37 (6H,

m).13C NMR (100 MHz, CDCl3): δ = 170.0, 167.9, 158.2, 150.3, 140.7, 135.2, 134.5,

131.8, 131.5, 129.3, 127.6, 126.8, 123.7, 118.7, 106.3, 62.4, 62.2, 55.6, 20.2, 14.2,

13.9. Anal. Calcd for C21H21NO5: C, 68.65; H, 5.76; N, 3.81; Found: C, 68.59; H,

5.83; N, 3.74. MS (QTOF MS ES+) m/z 368 [M+H]+.

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