Structural analysis of 2-arylidene-1-indanone derivatives by electrospray
tandem mass spectrometry†
José C. J. M. D. S. Menezes*, José A. S. Cavaleiro, M. Rosário M. Domingues*
Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal
†
Dedicated to Dr. Shashikumar K. Paknikar on the occasion of his 78th birthday
SUPPORTING INFORMATION
INDEX
1. Experimental procedures and NMR data of 2-arylidene indanones
S2-S6
2. MS2 of 2-[3',4'-Dimethoxybenzylidene]-4-methoxy-7-methyl-1-indanone 3
S7
3. MS2 of 2-[3',4',5'-Trimethoxybenzylidene]-4-methoxy-7-methyl-1-indanone 4
S7
4. MS2 of 2-[4'-Hydroxybenzylidene]-4-methoxy-7-methyl-1-indanone 5
S8
5. MS2 of 2-[4'-Cyanobenzylidene]-4-methoxy-7-methyl-1-indanone 6
S9
6. MS2 of 2-[4'-Nitrobenzylidene]-4-methoxy-7-methyl-1-indanone 7
S9
7. MS2
of
2-[4'-Methoxy-2',3',5',6'-tetrafluoro
benzylidene]-4-methoxy-7-methyl-1-
indanone 10
S10
8. MS2 of 2-[(1'-methyl-1H-imidazol-2'-yl)methylene]-4-hydroxy-7-methyl-1-indanone
11
S10
9. MS2 of 2-[4'-(1''H-imidazol-1''-yl)benzylidene]-4-hydroxy-7-methyl-1indanone 12
S11
10. MS2 of 2-methylene-4-methoxy-7-methyl-1-indanone 13
S11
*Correspondence to: J. C. J. M. D. S. Menezes; M. R. M. Domingues, QOPNA, Department of Chemistry,
University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: josemenezes@ua.pt; mrd@ua.pt; Tel: +351 234 401
505; Fax: +351 234 370 084.
S1
Experimental
Melting points were measured with a Büchi B-540 melting point apparatus (heating rate
10°C/min) and are uncorrected. 1H NMR spectra were recorded at 300 or 500 MHz and 13C
NMR spectra were recorded at 75.5 or 125.8 MHz with Bruker Avance 300 and Bruker DRX
500 spectrometers.
19
F NMR spectra were obtained on a Bruker Avance 300 at 282 MHz.
CDCl3 was used as solvent in most cases; otherwise is stated. Chemical shifts () are
expressed in parts per million (ppm) relative to tetramethylsilane. The coupling constants (J)
are given in Hertz (Hz). Unequivocal 1H assignments were made using 2D COSY and
NOESY experiments (mixing time of 800 ms) while 13C assignments were made on the basis
of DEPT-135 and 2D HSQC and HMBC experiments (delay for long-range J C/H couplings
were optimized for 7 Hz). Elemental analysis were recorded in duplicate on LECO Truspec
630-200-200 micromass (Sample size-upto 1.66 mg per measurement; Combustion furnance
temp.- 1075°C; Afterburner temp.-850°C; Detection method used for C, H, S-Infrared
absorption; N-Thermal conductivity) at Department of Chemistry, University of Aveiro. All
yields refer to isolated products unless stated. Preparative thin layer chromatography was
carried out on 20 × 20 cm glass plates coated with silica gel (1 mm thick, Merck). Analytical
TLC was carried out on precoated sheets with silica gel (0.2 mm thick, Merck). Petroleum
ether (PE) refers to hydrocarbon fraction boiling in the range 60–80°C. All other solvents and
reagents were used without further purification.
General procedure for the synthesis of 2-arylidene indanones (1-12)
To a mixture of 4-methoxy (or hydroxy)-7-methyl-1-indanone (57 µmol of A or 62 µmol for
B), benzaldehyde derivative (68 µmol or 74 µmol) in MeOH (2 mL), was added KOH (2.5 g)
and the reaction mixture was stirred overnight. The mixture was evaporated and the residue
diluted with water (10 mL) and neutralized with dil. HCl. The solution was extracted with
CHCl3 or ethyl acetate (4 × 5 mL). The combined extracts were washed with water, brine and
dried over Na2SO4, they were then filtered and concentrated to give a solid. The solvent
system used for crystallization or purification by prep-TLC is outlined with the respective
compounds.
S2
2-[2'-Methoxybenzylidene]-4-methoxy-7-methyl-1-indanone 1
Purified by prep-TLC; CH2Cl2: PE (1:1); Colorless solid; m.p. 218.1-220oC (CHCl3:PE);
yield- 82%; 1H NMR (300 MHz, CDCl3) δ 2.67 (s, 3H, Ar-CH3), 3.86 (d, 2H, J = 2.2 Hz, H3), 3.89 (s, 3H, 4-OCH3), 3.91 (s, 3H, OCH3), 6.94 (d, 2H, J = 8.2 Hz, H-5 & 3'), 7.00 – 7.06
(m, 1H, Ar-H-5'), 7.11 (dd, 1H, J = 8.1, 0.8 Hz, H-6), 7.36 (ddd, 1H, J = 8.3, 7.5, 1.7 Hz, H4'), 7.73 (dd, J = 7.7, 1.7 Hz, 1H, H-6'), 8.08 (t, 1H, J = 2.1 Hz, =CH). 13C NMR (75 MHz,
CDCl3) δ 17.7 (Ar-CH3), 28.8 (C-3), 55.5 (OCH3), 55.6 (OCH3), 110.9, 114.5, 120.5, 124.6,
127.7, 129.7, 130.2, 130.4, 130.9, 134.9, 136.6, 138.8, 154.4 (C-4), 159.0 (C-2'), 195.5 (C-1).
Elemental Analysis: for C19H18O3 Calcd; C, 77.53; H, 6.16; O, 16.31. Found; C, 77.53; H,
5.87; O, 16.63. C19H18O3. ¼ H2O.
2-[4'-Methoxybenzylidene]-4-methoxy-7-methyl-1-indanone 2
Light yellow solid; m.p. 163.8oC (CHCl3:PE); yield- 92%; 1H NMR (300 MHz, CDCl3) δ
2.67 (s, 3H, Ar-CH3), 3.87 (s, 5H, H-3 & OCH3), 3.92 (s, 3H, OCH3), 6.95 (d, 1H, J = 8.9
Hz, H-5), 6.98 (d, 2H, J = 9.0 Hz, H-3', 5'), 7.11 (dd, 1H, J = 8.1, 0.7 Hz, H-6), 7.57 (t, 1H, J
= 2.0 Hz, =CH), 7.67 (d, 2H, J = 8.8 Hz, H-2', 6'). 13C NMR (75 MHz, CDCl3) δ 17.7 (ArCH3), 29.0 (C-3), 55.4 (OCH3), 55.5 (OCH3), 114.39 (C-3', 5'), 114.45, 128.3, 130.3, 130.4,
132.5 (C-2', 6'), 132.8, 133.1, 136.6, 138.6, 154.4 (C-4), 160.7 (C-4'), 195.6 (C-1). Elemental
Analysis: for C19H18O3 Calcd; C, 77.53; H, 6.16; O, 16.31. Found; C, 77.60; H, 5.84; O,
16.56. C19H18O3. ¼ H2O.
2-[3',4'-Dimethoxybenzylidene]-4-methoxy-7-methyl-1-indanone 3
Purified by prep-TLC; CHCl3: PE (2:1); Colorless solid; m.p. 170.3-171oC (CHCl3:PE);
yield- 98%; 1H NMR (300 MHz, CDCl3) δ 2.67 (s, 3H, Ar-CH3), 3.88 (d, 2H, J = 1.9 Hz, H3), 3.92 (s, 3H, OCH3), 3.95 (s, 3H, OCH3), 3.97 (s, 3H, OCH3), 6.96 (d, 2H, J = 8.3 Hz, H-5
& 5'), 7.12 (dd, 1H, J = 8.1, 0.7 Hz, H-6), 7.20 (d, 1H, J = 2.0 Hz, H-2'), 7.35 (dd, 1H, J =
8.4, 2.0 Hz, H-6'), 7.55 (t, 1H, J = 2.0 Hz, =CH). 13C NMR (75 MHz, CDCl3) δ 17.7 (ArCH3), 28.8 (C-3), 55.5 (OCH3), 55.99 (OCH3), 56.04 (OCH3), 111.2, 113.6, 114.5, 124.3,
128.6, 130.3, 130.4, 133.1, 133.3, 136.6, 138.5, 148.9, 150.4, 154.4 (C-4), 195.5 (C-1).
Elemental Analysis: for C20H20O4 Calcd; C, 74.06; H, 6.21; O, 19.73. Found; C, 74.2; H,
5.88; O, 19.92. C20H20O4.¼ H2O.
S3
2-[3',4',5'-Trimethoxybenzylidene]-4-methoxy-7-methyl-1-indanone 4
Colorless solid; m.p. 159.2-160.2oC (CHCl3:PE); yield- 98%; 1H NMR (300 MHz, CDCl3) δ
2.67 (s, 3H, Ar-CH3), 3.89 (d, 2H, J = 1.9 Hz, H-3), 3.92 (s, 6H, OCH3), 3.95 (s, 6H, OCH3),
6.93 (s, 2H, H-2',6'), 6.96 (d, 1H, J = 8.1 Hz, H-5), 7.13 (dd, 1H, J = 8.1, 0.7 Hz, H-6), 7.51
(t, 1H, J = 2.1 Hz, =CH). 13C NMR (75 MHz, CDCl3) δ 17.7 (Ar-CH3), 28.6 (C-3), 55.5
(OCH3), 56.3 (2  OCH3), 61.0 (OCH3), 108.0 (C-2',6'), 114.6, 130.4 (2Cs), 131.1, 133.4,
134.2, 136.4, 138.5, 139.5, 153.3, 154.4, 195.3 (C-1). Elemental Analysis: for C21H22O5
Calcd; C, 71.17; H, 6.26; O, 22.57. Found; C, 70.9; H, 5.92; O, 23.18. C21H22O5.¼ H2O.
2-[4'-Hydroxybenzylidene]-4-methoxy-7-methyl-1-indanone 5
Yellow solid; m.p. 276.4-277.8oC (EtOH); yield- 71%; 1H NMR (500 MHz, DMSO-d6): δ
2.56 (s, 3H, Ar-CH3), 3.83 (s, 2H, J = 1.1 Hz, H-3), 3.89 (s, 3H, OCH3), 6.91 (d, 2H, J = 8.5
Hz, H-3', 5'), 7.16 (d, 1H, J = 8.2 Hz, H-5), 7.19 (d, 1H, J = 8.2 Hz, H-6), 7.39 (s, 1H, =CH),
7.64 (d, 2H, J = 8.5 Hz, H-2', 6'), 10.14 (bs, 1H, OH). 13C NMR (75 MHz, DMSO-d6): δ 17.1
(Ar-CH3), 28.6 (C-3), 55.5 (OCH3), 115.3 (C-5), 116.1 (C-3', 5'), 126.0 (C-1'), 128.8 (C-7),
130.4 (C-6), 131.6 (C-2), 132.9 (C-2', 6' and =CH), 135.8 (C-8), 138.1 (C-9), 154.3 (C-4),
159.3 (C-4'), 194.3 (C-1). Elemental Analysis: for C18H16O3 Calcd; C, 77.12; H, 5.75; O,
17.12. Found; C, 76.6; H, 5.72; O, 17.68. C18H16O3.¼ H2O.
2-[4'-Cyanobenzylidene]-4-methoxy-7-methyl-1-indanone 6
Colorless solid; m.p. 264.6-265.7oC (CHCl3:PE); yield- 94%; 1H NMR (300 MHz, CDCl3) δ
2.66 (s, 3H, Ar-CH3), 3.90 (d, 2H, J = 2.0 Hz, H-3), 3.93 (s, 3H, OCH3), 6.99 (d, 1H, J = 8.2
Hz, H-5), 7.15 (dd, 1H, J = 8.2, 0.7 Hz, H-6), 7.55 (t, 1H, J = 2.2 Hz, =CH), 7.73 (d, 1H, J =
8.7 Hz, H-2',6'), 7.78 (d, 1H, J = 8.7 Hz, H-3',5'). 13C NMR (75 MHz, CDCl3) δ 17.6 (ArCH3), 28.9 (C-3), 55.5 (OCH3), 112.3 (C-4'), 115.1 (C-5), 118.6 (CN); 130.6(C-6, CH, C-7),
130.7 (C-2',6'), 132.5 (C-3',5'), 136.0 (C-8), 138.2 (C-9), 138.4 (C-2), 139.9 (C-1'), 154.4 (C4), 194.8 (C-1). Elemental Analysis: for C19H15NO2 Calcd; C, 78.87; H, 5.23; N, 4.84; O,
11.06. Found; C, 78.3; H, 5.03; N, 4.75; O, 11.92. C19H15NO2.¼ H2O.
2-[4'-Nitrobenzylidene]-4-methoxy-7-methyl-1-indanone 7
Yellow solid; m.p. 267.2-268.3oC (CHCl3:PE); yield- 94%; 1H NMR (300 MHz, CDCl3 +
Acetone-d6) δ 2.66 (s, 3H, Ar-CH3), 3.95 (s, 5H, H-3 & OCH3), 7.03 (d, 1H, J = 8.2 Hz, H-5),
7.17 (dd, 1H, J = 8.1, 0.7 Hz, H-6), 7.60 (t, 1H, J = 2.2 Hz, =CH), 7.87 (d, 2H, J = 8.8 Hz, H2',6'), 8.32 (d, 2H, J = 8.9 Hz, H-3',5'). 13C NMR (75 MHz, CHCl3 + Acetone-d6) δ 17.3 (ArS4
CH3), 28.6 (C-3), 55.2 (OCH3), 115.0 (C-5), 123.7 (C-3',5'), 129.8 (=CH, C-7), 130.2 (C-6),
130.3, 130.5, 130.8 (C-2',6'), 138.2 (C-9), 141.6 (C-1'), 146.0 (C-4'), 154.3 (C-4), 194.4 (C1). Elemental Analysis: for C18H15NO4 Calcd; C, 69.89; H, 4.89; N, 4.53; O, 20.69. Found; C,
68.4; H, 4.69; N, 4.45; O, 22.46. C18H15NO4.⅓ H2O.
2-[2'-Bromobenzylidene]-4-methoxy-7-methyl-1-indanone 8
Colorless solid; m.p. 213.2-214.7oC (CHCl3:PE); yield- 84%; 1H NMR (300 MHz, CDCl3) δ
2.67 (s, 3H, Ar-CH3). 3.82 (d, 2H, J = 2.0 Hz, H-3), 3.90 (s, 3H, OCH3), 6.96 (d, 1H, J = 8.2
Hz, Ar-H), 7.13 (d, 1H, J = 8.1 Hz, Ar-H), 7.22 (dt, 1H, J = 7.6, 1.5 Hz, Ar-H), 7.39 (dt, 1H,
J = 7.8, 1.5 Hz,Ar-H), 7.67 (dd, 1H, J = 8.0, 1.2 Hz, Ar-H), 7.73 (dd, 1H, J = 7.8, 1.4 Hz, ArH), 7.92 (t, 1H, J = 2.1 Hz, =CH). 13C NMR (75 MHz, CDCl3) δ 17.6 (Ar-CH3), 28.2 (C-3),
55.5 (OCH3), 114.8, 126.5, 127.4, 130.0, 130.3, 130.4, 130.6, 131.8, 133.4, 135.3, 136.3,
137.2, 138.8, 154.4 (C-4), 194.9 (C-1). Elemental Analysis: Calcd; C, 62.99; H, 4.41; Br,
23.28; O, 9.32. Found; C, 63.3; H, 4.27; C18H15BrO2
2-[4'-Bromobenzylidene]-4-methoxy-7-methyl-1-indanone 9
Colorless solid; m.p. 219.2-219.8oC (CHCl3:PE); yield- 87%; 1H NMR (300 MHz, CDCl3) δ
2.66 (s, 3H, Ar-CH3), 3.86 (d, 2H, J = 2.0 Hz, H-3), 3.93 (s, 3H, OCH3), 6.97 (d, 1H, J = 8.2
Hz, Ar-H), 7.13 (dd, 1H, J = 8.2, 0.7 Hz, Ar-H), 7.52 (t, 1H, J = 2.1 Hz, =CH), 7.53 – 7.61
(m, 4H, H-2',3',5',6'). 13C NMR (75 MHz, CDCl3) δ 17.6 (Ar-CH3), 28.8 (C-3), 55.5 (OCH3),
114.8, 123.8, 130.4, 130.5, 131.8, 132.0, 132.1, 134.4, 135.6, 136.2, 138.5, 154.4 (C-4),
195.2 (C-1). Elemental Analysis: Calcd; C, 62.99; H, 4.41; Br, 23.28; O, 9.32. Found; C,
62.9; H, 4.46; C18H15BrO2
2-[4'-Methoxy-2',3',5',6'-tetrafluoro benzylidene]-4-methoxy-7-methyl-1-indanone 10
Purified by prep-TLC; CH2Cl2: PE (1:1); Colorless solid; m.p. 171.7-173.1oC (CHCl3:PE);
yield- 73%; 1H NMR (300 MHz, CDCl3) δ 2.65 (s, 3H, Ar-CH3), 3.67 (d, 2H, J = 0.9 Hz, H3), 3.88 (s, 3H, OCH3), 4.14 (t, 3H, J = 1.6 Hz, 4'-OCH3), 6.96 (d, 1H, J = 8.1 Hz, H-5), 7.12
(dd, 1H, J = 8.1, 0.7 Hz, H-6), 7.47 (tt, 1H, J = 2.3, 1.2 Hz, =CH). 19F NMR (282 MHz,
CDCl3) δ -162.23 (dd, 2F, J = 20.4, 7.4 Hz), -181.54 (dd, 2F, J = 20.8, 7.7 Hz). 13C NMR (75
MHz, CDCl3) δ 17.6 (Ar-CH3), 28.5 (t,C-3), 55.5 (OCH3), 62.2 (t, 4'-OCH3), 115.0, 115.2 (C5, 2Ar-Cs), 118.3 (=CH), 130.4 (C-6, 2Ar-Cs), 130.5, 130.7, 136.1, 138.7, 141.9, 154.4 (C4), 193.9 (C-1). Elemental Analysis: for C19H14F4O3 Calcd; C, 62.30; H, 3.85; F, 20.75; O,
13.10. Found; C, 61.0; H, 3.75; C19H14F4O3.½ H2O.
S5
2-[(1'-methyl-1H-imidazol-2'-yl)methylene]-4-hydroxy-7-methyl-1-indanone 11
Yellow solid; m.p. 258.9-260.2oC dec.; yield- 85%; 1H NMR (300 MHz, DMSO-d6) δ 2.51
(s, 3H, N-CH3), 3.84 (s, 3H, N-CH3), 3.91 (d, 2H, J = 1.4 Hz, H-3), 6.95 (d, 1H, J = 8.0 Hz,
H-5), 7.03 (d, 1H, J = 8.0 Hz, H-6), 7.23 (s, 1H, H-4'), 7.31 (t, 1H, J = 1.9 Hz, =CH), 7.40 (d,
J = 0.7 Hz, 1H, H-3'), 9.73 (s, 1H, OH). 13C NMR (75 MHz, DMSO-d6) δ 17.2 (Ar-CH3),
29.9 (C-3), 32.7 (N-CH3), 115.9 (=CH), 120.2 (C-5), 124.4 (C-3'), 127.9 (C-7), 130.2 (C-6),
130.4 (C-4'); 136.1, 136.3 (C-8, 2), 137.2 (C-9), 143.4 (C-1'), 152.5 (C-4), 194.5 (C-1).
Elemental Analysis: for C15H14N2O2 Calcd; C, 70.85; H, 5.55; N, 11.02; O, 12.58. Found; C,
69.8; H, 5.71; N, 9.97; O, 14.48. C15H14N2O2.⅓ H2O.
2-[4'-(1''H-imidazol-1''-yl)benzylidene]-4-hydroxy-7-methyl-1-indanone 12
Yellow solid; m.p. >330oC dec.; yield- 88%; 1H NMR (300 MHz, DMSO-d6) δ 2.54 (s, 3H,
Ar-CH3), 3.92 (s, 2H, H-3), 6.98 (d, 1H, J = 8.0 Hz, H-5), 7.06 (d, 1H, J = 8.0 Hz, H-6), 7.16
(s, 1H, H-5''), 7.50 (s, 1H, =CH), 7.82 (d, 2H, J = 8.6 Hz, H-3', 5'), 7.87 (s, 1H, H-4''), 7.92
(d, 2H, J = 8.6 Hz, H-2', 6'), 8.40 (s, 1H, H-2''), 9.82 (s, 1H, OH). 13C NMR (75 MHz,
DMSO-d6) δ 17.2 (Ar-CH3), 28.7 (C-3), 117.9 (C-4''), 120.2 (C-5), 120.4 (C-3', 5'), 128.0 (C7), 130.2 (C-5''), 130.5 (C-6), 131.0 (=CH), 132.2 (C-2', 6'), 133.5 (C-1'); 135.6, 135.68,
135.7 (C-2'', C-8, C-2), 136.7 (C-9), 137.4 (C-4'), 152.5 (C-4), 194.6 (C-1). Elemental
Analysis: for C20H16N2O2 Calcd; C, 75.93; H, 5.10; N, 8.86; O, 10.11. Found; C, 68.3; H,
4.75; N, 7.75; O, C20H16N2O2.2.5 H2O.
2-methylene-4-methoxy-7-methyl-1-indanone 13
1
H NMR (300 MHz, CDCl3) δ 2.62 (s, 3H, Ar-CH3), 3.61 (s, 2H, H-3), 3.89 (s, 3H, OCH3),
5.61 (dd, J = 2.7, 1.7 Hz, 1H, =CH), 6.30 (td, J = 2.2, 1.0 Hz, 1H, =CH), 6.95 (d, J = 8.1 Hz,
1H, H-5), 7.10 (dd, J = 8.1, 0.7 Hz, 1H, H-6). 13C NMR (75 MHz, CDCl3) δ 17.6 (Ar-CH3),
28.3 (C-3), 29.7, 55.5 (OCH3), 114.8 (C-5), 118.6 (=CH2), 130.2 (C-6,7), 130.6 (C-2), 139.1,
143.6, 154.6, 179.1 (CO). ESI-MS: [M+H]+ 189.
S6
(21, 1')A+
187.0
100
3
[(21, 1')A-HCHO-CO] +
[(2, 21)B- CH3 ]+
[P-CH3OH-HCHO] +
[P-CO-HCHO] +
(2, 21)B+
136.0
%
151.0
[(21, 1')A-CO] +
278.0
263.0
[(21, 1')A-HCHO]+
[P-CO-HCHO-H2O]+
(1,2)(3,9)B+
[P-CH3OH+CH3]+
[P-CH3OH] +
267.0
157.0
[P-3HCHO] +
159.0 175.0
235.0 249.0
[P-CH3]+
[M+H] +
310.0
292.0
221.1 233.0
129.0
293.1
279.0
325.1
0
m/z
140
160
180
200
220
240
260
280
300
320
Figure SF1- MS2 of 2-[3',4'-Dimethoxybenzylidene]-4-methoxy-7-methyl-1-indanone 3
(21, 1')A+
187.0
100
4
(2, 21)B+
181.0
%
[(2, 21)B- CH3 ] +
166.0
[P-CH3O - CH3] +
[P-CH3O -CH3OH]+
[(21, 1')A-CO]+
[M+H]+
[P-CH3OH]+
355.1
159.0
(1,2)(3,9)B +
292.0
0
140
309.0
323.0
205.0
[P-CH3]+
340.0
m/z
160
180
200
220
240
260
280
300
320
340
360
Figure SF2- MS2 of 2-[3',4',5'-Trimethoxybenzylidene]-4-methoxy-7-methyl-1-indanone 4
S7
[P-H2O-CH3]+
5
248.0
100
[P-H2O-CH3-CH4]+
[P-HCHO-CO-H2O] +
[P-HCHO-CO]+
[P-CO-CH4]+
[P-H2O-CH3-CO] +
223.0
%
[(21, 1')A-HCHO]+
[P-HCHO-2CO] +
[(21, 1')A-CO]+
[(21, 1')A-HCHO-CO] +
(1,2)(3,9)B +
(1,8)(3,9)B+
-H2O
131.0
129.0
145.0
128.0
121.0
0
100
110
120
130
140
150
(21, 1')A +
237.0
251.0
195.0
(2,21)A+
220.0
175.0 187.0
205.0
157.0
(2, 21)B+
107.0
[P-HCHO]+
232.0
[P-CH4]+
159.1
263.0
[M+H] +
281.0
178.0
160
170
180
190
200
210
220
230
240
250
260
270
280
m/z
290
Figure SF3- MS2 of 2-[4'-Hydroxybenzylidene]-4-methoxy-7-methyl-1-indanone 5
The combined loss of 33 Da (H2O+CH3), observed in compound 5 also gives rise to
further combined loss of 48 Da (CH3OH+CH4), 49 Da (H2O+CH3+CH4), 50 Da
(H2O+CH3OH), 61 Da (H2O+CH3+CO), 62 Da (HCHO+CH3+OH) and 76 Da
(H2O+2CH3+CO) (Figure SF3). The combined loss of 48 and 62 Da in case of compound 5
with respect to neutral loss of CH3OH is considered as combined radical loss of CH3 and
OH.
S8
[P-HCHO-CO] +
6
232.0
100
[P-CO-CH4] +
246.0
[P-CO-CH3]+
247.1
[P-HCHO-CO-HCN- H]+
204.0
[(21, 1')A-HCHO-CO] +
[P-HCHO] +
%
(2, 21)B+
116.0
(1,8)(3,9)B +
-HCN
[P-CH3]+
[(21, 1')A-HCHO]+
[M+H]+
(1,2)(3,9)B +
230.1
140.0 145.0
105.0
0
100
129.0
120
140
260.0
(21, 1')A+
157.0
187.1
[(21, 1')A-CO]+
159.0
160
180
275.0
258.0
274.0
288.0
242.0
200
220
240
290.0
260
m/z
300
280
Figure SF4- MS2 of 2-[4'-Cyanobenzylidene]-4-methoxy-7-methyl-1-indanone 6
[P-HNO2] +
7
263.0
100
[P-CO-HCHO-CH3]+
[P-HNO2-CH3]+
[P-NO2-CH3]+
[P-CO-CH3 -NO2]+
[P-NO2]+
%
221.0
264.1
249.0
[P-2CO-CH3 -NO2]+
193.1
248.0
220.0
[M+H] +
[P-HCHO-CH3]+
265.0
237.0
310.0
178.0 187.0
0
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
Figure SF5- MS2 of 2-[4'-Nitrobenzylidene]-4-methoxy-7-methyl-1-indanone 7
S9
m/z
320
10
193.0
100
%
(2, 21)B+
[P-HF-CH3] +
[M+H]+
[P-HF-HCHO]+
[P-HF]+
309.0
293.0
367.1
347.1
352.1
332.0
0
180
[P-CH3]+
317.0
m/z
200
220
240
260
280
300
320
340
360
Figure SF6- MS2 of 2-[4'-Methoxy-2',3',5',6'-tetrafluoro benzylidene]-4-methoxy-7-methyl-1indanone 10
(21, 1')A+
11
173.0
%
100
[P-CH3OH] +
[(21, 1')A-CO]+
[P-H2O] +
145.0
[P-CO-CH3]+
[M+H] +
[P-CH3]+
223.0
255.1
240.0
[(21, 1')A-2CO] +
237.1
212.1
117.0
0
110
m/z
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
Figure SF7- MS2 of 2-[(1'-methyl-1H-imidazol-2'-yl)methylene]-4-hydroxy-7-methyl-1-indanone 11
S10
[(21, 1')A-CO] +
[P-CH4] +
[P-H2O]+
301.0
299.0
12
145.0
100
[P-2CO-CH4]+
[P-CH3-OH-CO] +
(21, 1')A+
245.0
173.0
[(21, 1')A- CH4]+
%
[P-CO-CH4]+
273.0
[P-2CO-CH3]+
[(21, 1')A-CH3]+
[P-HCHO] +
246.0 257.0
220.0
[(21, 1')A-2CO] +
157.0
202.0
182.0
158.0
117.0
205.0
219.0
287.0
[P-2H]+
[M+H]+
317.0
315.0
259.1
231.0
218.0
288.0 302.0
191.0
0
m/z
120
140
160
180
200
220
240
260
280
300
320
Figure SF8- MS2 of 2-[4'-(1''H-imidazol-1''-yl)benzylidene]-4-hydroxy-7-methyl-1-indanone 12
[P-CH3-CO]+
13
146.1
100
%
[P-CO-CH4]+
145.1
[P-HCHO]+
[P-CH3]+
174.1
[P-CO-HCHO]+
161.1
105
157.0
135.1
110
115
120
125
130
135
140
145
150
155
160
[P-2H] +
[P-CH4]+
173.1
159.1
129.1
0
100
189.1
[P-CO] +
131.0
105.1
[M+H] +
[P-CH3OH] +
165
170
187.1
175
180
Figure SF9- MS2 of 2-methylene-4-methoxy-7-methyl-1-indanone 13
S11
185
190
195
m/z
200