Electronic Supplementary Information
Iodine promoted α- hydroxylation of ketones
Yogesh Siddaraju and Kandikere Ramaiah Prabhu*
Department of Organic Chemistry
Indian Institute of Science
Bangalore 560 012, Karnataka, India
Fax: (+)91-80-23600529
*e-mail: [email protected]
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015
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Contents
1. General experimental 3
2. Optimization table 4
3. Typical experimental procedures and characterization data for starting
material synthesis
5 – 15
4. Typical experimental procedure for α-hydroxylation of aryl ketones 16
5. Characterization data for α-hydroxy aryl ketones 17 – 31
6. References 32
7. 1H,
13C NMR Spectra of unknown starting materials 33 – 74
8. 1H,
13C NMR Spectra of products
72 – 155
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General experimental
NMR spectra were recorded on a 400 MHz NMR spectrometers in CDCl3, tetramethylsilane (TMS; δ
= 0.00 ppm) served as an internal standard for 1H NMR. The corresponding residual non-deuterated
solvent signal (CDCl3; δ = 77.00 ppm) was used as internal standard for 13
C NMR. IR spectra were
measured using FT/IR spectrometers. Mass spectra were measured uisng Q-Tof (ESI-HRMS).
Column chromatography was carried out on Silica gel 100-200 mesh (commercial suppliers) and thin-
layer chromatography was carried out using SILICA GEL GF-254.
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Table 1. Optimization studiesa
entry Catalyst (mol%) Oxidant (3 equiv) solvent conversionb
1 I2 (50) aq.TBHP DMSO 58%
2 I2 (50) aq.TBHP ACN NR
3 I2 (50) aq.TBHP DCE NR
4 I2 (50) aq.TBHP EtOAc NR
5 I2 (50) aq.TBHP toluene NR
6 I2 (50) aq.TBHP DMF NR
7 I2 (50) aq.TBHP DMA NR
8 KI (30) aq.TBHP DMSO NR
9 NaI (30) aq.TBHP DMSO NR
10 TBAI (30) aq.TBHP DMSO NR
11 TBAB (30) aq.TBHP DMSO NR
12 NIS (30) aq.TBHP DMSO NR
13 NCS (30) aq.TBHP DMSO NR
14 I2 (50) TBHP in decane DMSO 70%
15 I2 (50) O2 DMSO 41%
16 I2 (50) H2O2 DMSO 36%
17 I2 (50) oxone DMSO 18%
18 I2 (50) TBPB DMSO NR
19 I2 (50) m-CPBA DMSO NR
20 I2 (50) K2S2O8 DMSO NR
21 I2 (50) CHP DMSO NR
22 I2 (100) TBHP in decane DMSO 70%
23 I2 (30) TBHP in decane DMSO 60%
24 I2 (50) TBHP in decane DMSO 68% c
25 I2 (50) TBHP in decane DMSO 58% d
26 I2 (50) TBHP in decane DMSO NR e
27 I2 (50) TBHP in decane DMSO 60% f
28 I2 (50) ( None) Ar atmosphere DMSO 37% g
aReaction conditions: 1a (0.75 mmol), I2 (0.37 mmol), oxidant (2.24 mmol) in of DMSO (1 mL) at 80 °C.
bIsolated yield.
c4
Equiv of TBHP. d2 Equiv of TBHP.
e20 mol% of p-TSA was used.
f20 mol% piperidine was used.
g The reaction was performed
for 12h. DMA = N,N, Dimethyl acetamide. TBAI = tetra-n-butylammonium iodide, TBAB = tetra-n-butyl ammonium
bromide, NIS = N- iodosuccinimide, NCS = N-chlorosuccinimide, TBPB= tert-butyl peroxy benzoate, CHP = Cumene hydro
peroxide, NR = no reaction.
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Experimental Section
Typical experimental procedure for Friedel Crafts acylation of arenes, starting material
synthesis
To a solution of anhydrous aluminium trichloride (1.1 equiv) in DCE (10 mL) at 0°C was added acid
chloride (1.1 equiv), slowly, the reaction mixture was stirred at 0 °C for 10 min, followed by addition
of a solution of arene in DCE (500 mg – 1g in 10 mL DCE, 1equiv) during 10 min, the reaction
mixture was slowly warmed to 50 °C and allowed to stir at 50 °C for completion of the reaction
(monitored by TLC), the reaction mixture was cooled to 0 °C and quenched with ice cold water (20
mL). The reaction mixture was extracted with ethyl acetate (3 x 20 mL), and combined organic layer
was washed with dilute HCl (25 mL, 2N), dilute sodium carbonate solution (25 mL, 5% aq solution)
and finally with water. The organic layer was dried over anhydrous Na2SO4 and concentrated under
reduced pressure. The crude product was purified on a silica gel column using hexane/EtOAc to get
the pure product.
1-Phenylbutan-1-one (1b).1 Yellow oily liquid; Yield 90%; Rf (hexane) 0.2. Prepared
as shown in the general experimental procedure (reaction completion time 2 h at 50
°C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H),
7.46 (t, J = 7.6 Hz, 2H), 2.95 (t, J = 7.2 Hz, 2H), 1.81 – 1.72 (m, 2H), 1.01 (t, J = 7.2
Hz, 3H).
1-Phenylpentan-1-one (1c).1 Yellow oily liquid; Yield 90%; Rf (hexane) 0.2.
Prepared as shown in the general experimental procedure (reaction completion time 2h
at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.6 Hz, 2H), 7.55 (t, J = 7.2 Hz,
1H), 7.45 (t, J = 7.6 Hz, 2H), 2.97 (t, J = 7.2 Hz, 2H), 1.76 – 1.69 (m, 2H), 1.46 – 1.37
(m, 2H), 0.95 (t, J = 7.2 Hz, 3H).
6-methyl-1-phenylheptan-1-one (1d).2 Colorless oily liquid; Yield 76%; Rf
(hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
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completion time 2 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.2
Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 2.97 (t, J = 7.2 Hz, 2H), 1.76 – 1.68 (m, 2H), 1.60 – 1.50 (m, 1H),
1.42 – 1.34 (m, 2H), 1.25 – 1.19 (m, 2H), 0.87 (d, J = 6.4 Hz, 6H).
1-Phenyldecan-1-one (1e).3
Colorless oily liquid; Yield 70%; Rf (hexane) 0.3.
Prepared as shown in thr general experimental procedure (reaction completion time
2 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t, J =
7.2 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 2.96 (t, J = 7.2 Hz, 2H), 1.77 – 1.70 (m, 2H),
1.34 – 1.27(m, 12H), 0.88 (t, J = 6.4 Hz, 3H).
1-(4-Ethylphenyl)butan-1-one (1f). Colourless oily liquid; Yield 92%; Rf (hexane) 0.3. Prepared as
shown in the general experimental procedure (reaction completion time 1 h at 50 °C): IR (Neat, cm−1
)
3348, 3032, 2965, 2933, 2874, 1682, 1606, 1568; 1H NMR (400 MHz, CDCl3) δ
7.89 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 2.70 (q,
J = 7.6 Hz, 2H), 1.81 – 1.72 (m, 2H), 1.26 (t, J = 7.6 Hz, 3H), 1.00 (t, J = 7.2 Hz,
3H). 13
C NMR (100 MHz, CDCl3) δ 200.13, 149.74, 134.81, 128.24, 128.00,
40.41, 28.89, 17.85, 15.19, 13.89; HRESI-MS (m/z) Calculated for C12H16O (M+ + Na) 199.1099,
found (M+ + Na) 199.1094.
1-(4-(tert-butyl)phenyl)butan-1-one (1g).4 Colourless oily liquid; Yield 91%; Rf
(hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 1 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.4 Hz,
2H), 7.47 (d, J = 8.4 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.81 – 1.72 (m, 2H), 1.34
(s, 9H), 1.00 (t, J = 7.2 Hz, 3H).
1-(4-(tert-butyl)phenyl)pentan-1-one (1h).5
Colorless oily liquid; Yield 85%; Rf
(hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 1 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.0 Hz,
2H), 7.47 (d, J = 8.0 Hz, 2H), 2.94 (t, J = 7.2 Hz, 2H), 1.75 – 1.69 (m, 2H), 1.45 –
1.40 (m, 2H), 1.34 (s, 9H), 0.95 (t, J = 7.2 Hz, 3H).
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1-(4-decylphenyl)butan-1-one (1i). Pale yellow oily liquid; Yield 88%; Rf (hexane) 0.4. Prepared as
shown in the general experimental procedure (reaction completion time 1 h at 50 °C): IR (Neat, cm−1
)
;3085, 3031, 2926, 2854, 1684, 1808, 1684, 1606, 1569; 1H NMR (400 MHz,
CDCl3) δ 7.88 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 7.6 Hz, 2H), 2.92 (t, J = 7.2 Hz,
2H), 2.65 (t, J = 7.6 Hz, 2H), 1.81 – 1.71 (m, 2H), 1.66 – 1.58 (m, 2H), 1.31 –
1.25 (m, 14H), 1.00 (t, J = 7.2 Hz, 3H), 0.88 (t, J = 6.8 Hz, 3H); 13
C NMR (100
MHz, CDCl3) δ 200.11, 148.53, 134.80, 128.54, 128.16, 40.40, 35.95, 31.87,
31.11, 29.57, 29.53, 29.43, 29.30, 29.24, 22.66, 17.85, 14.09, 13.90; HRESI-MS (m/z) Calculated for
C20H32O (M+ + Na) 311.2351, found (M
+ + Na) 311.2353.
1-(4-benzylphenyl)pentan-1-one (1j). Pale yellow oily liquid; Yield 61%; Rf (5% EtOAc/hexane)
0.2. Prepared as shown in the general experimental procedure (reaction completion time 2 h at 50
°C): IR (Neat, cm−1
) 3582, 3346, 3059, 3027, 2957, 2867, 1681, 1603, 1569; 1H
NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 2H), 7.30 – 7.20 (m, 5H), 7.17
(d, J = 7.6 Hz, 2H), 4.01 (s, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.74 – 1.66 (m, 2H),
1.44 – 1.34 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ
200.14, 146.45, 140.03, 135.10, 129.02, 128.88, 128.56, 128.38, 128.33, 126.33,
41.82, 38.20, 26.49, 22.44, 13.90; HRESI-MS (m/z) Calculated for C18H20O (M+ + Na) 275.1412,
found (M+ + Na) 275.1411.
1-(5,6,7,8-tetrahydronaphthalen-2-yl)pentan-1-one (1k). Pale yellow oily liquid; Yield 62%; Rf
(5% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction
completion time 2 h at 50 °C): IR (Neat, cm−1
) 3348, 3021, 2931, 2864, 2661, 1680,
1604, 1570; 1H NMR (400 MHz, CDCl3) δ 7.66 – 7.65 (m, 2H), 7.12 (d, J = 8.4 Hz,
1H), 2.92 (t, J = 7.2 Hz, 2H), 2.80 – 2.79 (m, 4H), 1.81 – 1.77 (m, 4H), 1.74 – 1.66
(m, 2H), 1.45 – 1.35 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3)
δ 200.52, 142.80, 137.30, 134.55, 129.20, 128.89, 125.11, 38.16, 29.54, 29.33,
26.62, 22.93, 22.79, 22.46, 13.90; HRESI-MS (m/z) Calculated for C15H20O (M+ + Na) 239.1412,
found (M+ + Na) 239.1416.
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1-(9H-fluoren-2-yl)butan-1-one (1l). Pale yellow solid; mp: 120−122°C; Yield 53%; Rf (5%
EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion
time 3 h at 50 °C): IR (Neat, cm−1
) 3317, 3044, 2957, 2862, 2647, 1662,
1603, 1460; 1H NMR (400 MHz, CDCl3) δ 8.13 (s, 1H), 8.00 (d, J = 7.6
Hz, 1H), 7.83 – 7.80 (m, 2H), 7.56 (d, J = 7.2 Hz, 1H), 7.42 – 7.34 (m, 2H),
3.93 (s, 2H), 2.99 (t, J = 7.2 Hz, 2H), 1.85 – 1.75 (m, 2H), 1.03 (t, J = 7.2
Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 200.28, 146.15, 144.43, 143.24,
140.50, 135.52, 127.89, 127.37, 126.99, 125.20, 124.67, 120.79, 119.60, 40.63, 36.86, 17.95, 13.93;
HRESI-MS (m/z) Calculated for C17H16O (M+ + Na) 259.1099, found (M
+ + Na) 259.1094.
1-(5'-phenyl-[1,1':3',1''-terphenyl]-4-yl)butan-1-one (1m). White solid; Yield 52%; mp 109 −
111°C; Rf (5% EtOAc/hexane) 0.5. Prepared as shown in the general experimental procedure
(Reaction completion time 2 h at 50 °C): IR (KBr, cm−1
) 3337, 2959, 2931, 2868,
1674, 1597, 1495; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.0 Hz, 2H), 7.81 –
7.75 (m, 5H), 7.69 – 7.67 (m, 4H), 7.49 – 7.45 (m, 4H), 7.39 (t, J = 7.2 Hz, 2H),
2.97 (t, J = 7.2 Hz, 2H), 1.85 – 1.75 (m, 2H), 1.03 (t, J = 7.2 Hz, 3H); 13
C NMR
(100 MHz, CDCl3) δ 199.95, 145.37, 142.53, 140.80, 135.98, 128.87, 128.67,
127.67, 127.37, 127.30, 125.98, 125.12, 40.55, 17.80, 13.90; HRESI-MS (m/z) Calculated for
C28H24O (M+ + Na) 399.1725, found (M
+ + Na) 399.1728.
1-(4-benzhydrylphenyl)butan-1-one (1n). Pale yellow oily liquid; Yield 66%; Rf (5%
EtOAc/hexane) 0.5. Prepared as shown in the general experimental procedure (Reaction completion
time 2 h at 50 °C): IR (Neat, cm−1
) 3346, 3058, 3026, 2962, 2874, 1682,
1601, 1493, 1451; 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 2H),
7.29 – 7.27 (m, 4H), 7.22 – 7.18 (m, 4H), 7.09 (d, J = 7.2 Hz, 4H), 5.57 (s,
1H), 2.89 (t, J = 7.2 Hz, 2H), 1.79 – 1.69 (m, 2H), 0.98 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 199.89, 149.13, 142.94, 135.22, 129.54,
129.29, 128.38, 128.08, 126.52, 56.67, 40.36, 17.70, 13.83; HRESI-MS (m/z) Calculated for C23H22O
(M+ + Na) 337.1568, found (M
+ + Na) 337.1566.
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1,1'-(5'-phenyl-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(butan-1-one) (3a). White solid; Yield 48%; mp
155 – 157; 122°C; Rf (5% EtOAc/hexane) 0.1. Prepared as shown in the general experimental
procedure (2.2 equiv of acid chloride and 2.2 equiv of aluminium
trichloride used) (reaction completion time 4 h at 50°C): IR (Neat,
cm−1
) 3330, 3040, 2956, 2498, 2044, 1977, 1917, 1673, 1594, 1495;
1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 8.0 Hz, 4H), 7.82 – 7.77
(m, 7H), 7.68 (d, J = 7.2 Hz, 2H), 7.49 (t, J = 7.2 Hz, 2H), 7.41 (t, J
= 7.2 Hz, 1H), 2.99 (t, J = 7.2 Hz, 4H), 1.85 – 1.76 (m, 4H), 1.03 (t, J
= 7.2 Hz, 6H). 13
C NMR (100 MHz, CDCl3) δ 199.88, 145.04, 142.74, 141.24, 140.49, 136.09,
128.92, 128.69, 127.82, 127.36, 127.27, 125.94, 125.10, 40.54, 17.76, 13.87. HRESI-MS (m/z)
Calculated for C32H30O2 (M+ + Na) 469.2143, found (M
+ + Na) 469.2148.
1,1'-((phenylmethylene)bis(4,1-phenylene))bis(butan-1-one) (3b). Pale yellow oily liquid; Yield
61%; Rf (10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (2.2
equiv of acid chloride and 2.2 equiv of aluminium trichloride used)
(Reaction completion time 4 h at 50°C): IR (Neat, cm−1
) 3345, 3057,
3028, 2962, 2874, 1682, 1602, 1569; 1H NMR (400 MHz, CDCl3) δ
7.90 (d, J = 8.0 Hz, 4H), 7.32 – 7.19 (m, 7H), 7.09 (d, J = 7.2 Hz,
2H), 5.63 (s, 1H), 2.91 (t, J = 7.2 Hz, 4H), 1.78 – 1.70 (m, 4H), 0.99
(t, J = 7.2 Hz, 6H); 13
C NMR (100 MHz, CDCl3) δ 199.80, 148.18, 142.12, 135.46, 129.48, 129.21,
128.54, 128.20, 126.82, 56.57, 40.36, 17.66, 13.80; HRESI-MS (m/z) Calculated for C27H28O2 (M+ +
Na) 407.1987, found (M+ + Na) 407.1987.
1,9-diphenylnonane-1,9-dione (3c).6 Yellow solid; Yield 32 %; Rf (10%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure
(15 equiv of benzene, 1.1 equiv of acid chloride and 2.2 equiv of aluminium
trichloride used) (Reaction completion time 4 h at 50°C): 1H NMR (400 MHz,
CDCl3) δ 7.96 (d, J = 7.6 Hz, 4H), 7.55 (t, J = 7.2 Hz, 2H), 7.46 (t, J = 7.2 Hz,
4H), 2.96 (t, J = 7.2 Hz, 4H), 1.78 – 1.70 (m, 4H), 1.44 – 1.40 (m, 6H).
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1,1'-(5'-(4-butyrylphenyl)-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(butan-1-one) (3d). White solid;
Yield 34%; mp 119 − 122°C; Rf (10% EtOAc/hexane) 0.1.
Prepared as shown in the general experimental procedure (3.3
equiv of acid chloride and 3.3 equiv of aluminium trichloride
used) (reaction completion time 4 h at 50°C): IR (KBr, cm−1
)
3339, 3185, 3054, 2959, 2930, 2871, 1673, 1596, 1562; 1H
NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.4 Hz, 6H), 7.86 (s,
3H), 7.78 (d, J = 8.0 Hz, 6H), 3.0 (t, J = 7.2 Hz, 6H), 1.86 –
1.76 (m, 6H), 1.04 (t, J = 7.2 Hz, 9H); 13
C NMR (100 MHz, CDCl3) δ 199.85, 144.76, 141.50,
136.23, 128.73, 127.39, 125.95, 40.56, 17.76, 13.86; HRESI-MS (m/z) Calculated for C36H36O3 (M+
+ Na) 539.2562, found (M+ + Na) 539.2566.
1-(4-phenoxyphenyl)pentan-1-one (5k). Colourless oily liquid; Yield 52%; Rf (5% EtOAc/hexane)
0.1. Prepared as shown in the general experimental procedure (reaction
completion time 2 h at 50 °C): IR (Neat, cm−1
) 3340, 3065, 2958, 2869, 2608,
2680, 1585, 1489; 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 2H),
7.39 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.2 Hz, 1H), 7.07 (d, J = 8.0 Hz, 2H),
6.99 (d, J = 8.4 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.75 – 1.67 (m, 2H), 1.45 – 1.36 (m, 2H), 0.95 (t, J
= 7.2 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ 199.19, 161.73, 155.54, 131.78, 130.29, 130.01,
124.51, 120.10, 117.29, 38.11, 26.62, 22.49, 13.93. HRESI-MS (m/z) Calculated for C17H18O2 (M+ +
Na) 277.1204, found (M+ + Na) 277.1203.
1-(4-(phenylthio)phenyl)butan-1-one (5l). Pale yellow oily liquid; Yield 53%; Rf (5%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental
procedure (reaction completion time 2 h at 50 °C): IR (Neat, cm−1
) 3221,
3060, 2962, 2873, 2561, 2132, 1680, 1586, 1474; 1H NMR (400 MHz,
CDCl3) δ 7.82 (d, J = 8.0 Hz, 2H), 7.49 – 7.48 (m, 2H), 7.39 – 7.38 (m, 3H),
7.21 (d, J = 8.0 Hz, 2H), 2.88 (t, J = 7.2 Hz, 2H), 1.79 – 1.69 (m, 2H), 0.98 (t, J = 7.2 Hz, 3H). 13
C
NMR (100 MHz, CDCl3) δ 199.40, 144.42, 134.40, 133.72, 132.18, 129.61, 128.67, 128.60, 127.52,
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40.32, 17.77, 13.84; HRESI-MS (m/z) Calculated for C16H16OS (M+ + Na) 279.0820, found (M
+ +
Na) 279.0817.
1-(thiophen-2-yl)butan-1-one (7a).7
Dark brown oily liquid; Yield 84%; Rf
(hexane) 0.2. Prepared as shown in the general experimental procedure (reaction
completion time 6 h at RT): 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 3.6 Hz,
1H), 7.62 (d, J = 4.4 Hz, 1H), 7.12 (t, J = 4.0 Hz, 1H), 2.88 (t, J = 7.2 Hz, 2H), 1.83
– 1.74 (m, 2H), 1.00 (t, J = 7.2 Hz, 3H).
1-(5-methylthiophen-2-yl)butan-1-one (7b). Yellow oily liquid; Yield 83%; Rf (hexane) 0.2.
Prepared as shown in the general experimental procedure (reaction completion
time 6 h at RT): IR (Neat, cm−1
) 3300, 3073, 2963, 2930, 2873, 2737, 1658,
1455; 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 3.6 Hz, 1H), 6.79 (d, J = 3.2
Hz, 1H), 2.81 (t, J = 7.2 Hz, 2H), 2.52 (s, 3H), 1.80 – 1.71 (m, 2H), 0.99 (t, J =
7.2 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ 193.07, 149.28, 142.27, 132.22, 126.58, 40.70, 18.30,
15.91, 13.79; HRESI-MS (m/z) Calculated for C9H12OS (M+ + Na) 191.0507, found (M
+ + Na)
191.0504.
1-(5-bromothiophen-2-yl)butan-1-one (7c). Dark brown oily liquid; Yield 70%; Rf (hexane) 0.2.
Prepared as shown in the general experimental procedure (reaction completion
time 1 h at 50°C): IR (Neat, cm−1
) 3308, 3216, 3094, 2963, 2874, 2730, 2621,
1662, 1522, 1459; 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 3.6 Hz, 1H), 7.09
(d, J = 3.6 Hz, 1H), 2.80 (t, J = 7.2 Hz, 2H), 1.80 – 1.71 (m, 2H), 0.99 (t, J =
7.2 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ 192.26, 145.91, 131.71, 131.11, 122.23, 40.52, 18.04,
13.76. HRESI-MS (m/z) Calculated for C8H9BrOS (M+ + Na) 254.9455, found (M
+ + Na) 254.9455.
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Typical experimental procedure for friedel crafts acylation of arenes, indoles and furan
(starting material synthesis).
To a solution of anhydrous aluminium trichloride (1.1 equiv) in DCE (10 mL) at 0°C was added acid
chloride (1.1 equiv), slowly, the reaction mixture was stirred at 0 °C for 10 min, followed by addition
of a solution of arene in DCE (500 mg – 1g in 10 mL DCE, 1equiv) during 10 min, the reaction
mixture was slowly warmed to 50 °C and allowed to stir at 50 °C for completion of the reaction
(monitored by TLC), the reaction mixture was cooled to 0 °C and quenched with methanol (5 mL)
followed by water (30 mL). The reaction mixture was extracted with ethyl acetate (3 x 20 mL), and
combined organic layer was washed with dilute sodium carbonate solution (25 mL) and finally with
water. The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure.
The crude product was purified on a silica gel column using hexane/EtOAc to get the pure product.
1-(5-methylfuran-2-yl)butan-1-one (7d).8 Pale yellow oily liquid; Yield 25%; Rf (hexane) 0.3.
Prepared as shown in the general experimental procedure (reaction completion
time 4 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.09 (d, J = 3.2 Hz, 1H), 6.14
(d, J = 3.2 Hz, 1H), 2.73 (t, J = 7.2 Hz, 2H), 2.39 (s, 3H), 1.79 – 1.70 (m, 2H),
0.98 (t, J = 7.2 Hz, 3H).
1-(1-methyl-1H-indol-3-yl)butan-1-one (7e). Yellow oily liquid; Yield 62%; Rf (10 %
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure
(reaction completion time 2 h at 50 °C): IR (Neat, cm−1
) 3455, 3107, 3049,
2960, 2931, 2872, 2601, 1642, 1529, 1465; 1H NMR (400 MHz, CDCl3) δ 8.40
– 8.39 (m, 1H), 7.68 (s, 1H), 7.30 – 7.28 (m, 3H), 3.79 (s, 3H), 2.79 (t, J = 7.2
Hz, 2H), 1.84 – 1.75 (m, 2H), 1.01 (t, J = 7.2 Hz, 3H). 13
C NMR (101 MHz, CDCl3) δ 195.81,
137.34, 135.20, 126.23, 123.13, 122.49, 122.36, 116.49, 109.49, 41.75, 33.35, 18.58, 14.01. HRESI-
MS (m/z). Calculated for C13H15NO (M+ + Na) 224.1051, found (M
+ + Na) 224.1055.
1-(1-benzoyl-1H-indol-3-yl)butan-1-one (7f). White solid; Yield 56%; mp 106 − 108°C; Rf (5%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction completion
time 3 h at 50 °C): IR (KBr, cm−1
) 3382, 3307, 3138, 3057, 2960, 2927, 2523, 2321, 2209, 1917,
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1739, 1697, 1663, 1599; 1H NMR (400 MHz, CDCl3) δ 8.41 – 8.38 (m, 1H),
8.24 – 8.21 (m, 1H), 7.93 (s, 1H), 7.79 – 7.77 (m, 2H), 7.67 (t, J = 7.6 Hz,
1H), 7.57 (t, J = 7.6 Hz, 2H), 7.41 – 7.38 (m, 2H), 2.76 (t, J = 7.2 Hz, 2H),
1.80 – 1.71 (m, 2H), 0.97 (t, J = 7.2 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ
196.41, 168.48, 136.37, 133.30, 132.74, 132.70, 129.35, 128.86, 127.55,
125.76, 125.16, 122.53, 121.00, 115.71, 41.79, 17.77, 13.76. HRESI-MS (m/z). Calculated for
C19H17NO2 (M+ + Na) 314.1157, found (M
+ + Na) 314.1157.
1-(1-benzoyl-5-methoxy-1H-indol-3-yl)butan-1-one (7g). White solid; Yield 61%; mp 128 − 130°C;
Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general
experimental procedure (reaction completion time 2 h at 50 °C): IR (KBr,
cm cm−1
) 3383, 3308, 3136, 3057, 3008, 2960, 2898, 2872, 2839, 2164,
1698, 1665, 1609; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.8 Hz,
1H), 7.91 (d, J = 2.4 Hz, 1H), 7.89 (s, 1H), 7.76 (d, J = 7.6 Hz, 2H), 7.68
(t, J = 7.2 Hz, 1H), 7.58 (t, J = 7.6 Hz, 2H), 7.01 (dd, J = 8.8, 2.4 Hz, 1H), 3.90 (s, 3H), 2.75 (t, J =
7.2 Hz, 2H), 1.81 – 1.72 (m, 2H), 0.98 (t, J = 7.6 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ 196.67,
168.30, 157.68, 133.34, 133.07, 132.68, 130.91, 129.34, 128.87, 128.70, 120.81, 116.60, 115.23,
104.27, 55.61, 41.64, 17.79, 13.81. HRESI-MS (m/z) Calculated for C20H19NO3 (M+ + Na)
344.1263, found (M+ + Na) 344.1268.
General procedure for O-benylation of 4- Hydroxy Propiophenone (starting material synthesis).
A mixture of 4-hydroxy propiophenone (500 mg, 1equiv), benzyl bromide (1.5equiv), potassium
carbonate (2 equiv) in acetonitrile (10 mL) was heated at reflux for 12h. After the completion of the
reaction (monitored by TLC), 50 mL water was added and the reaction mixture was extracted with
ethyl acetate (3x20 mL). The combined organic layer was washed with dilute sodium carbonate
solution (25 mL, 5% aqueous) and finally with water. The organic layer was dried over anhydrous
Na2SO4 and concentrated under reduced pressure. The crude product was purified on a silica gel
column using hexane/EtOAc to get the pure product.
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1-(4-(benzyloxy)phenyl)propan-1-one (5f).9 White solid; Yield 81%; Rf (15% EtOAc/hexane) 0.3.
Prepared as shown in the general experimental procedure (reaction
completion time 12 h at 80°C): 1H NMR (400 MHz, CDCl3) δ 7.94
(d, J = 8.4 Hz, 2H), 7.43 – 7.32 (m, 5H), 7.00 (d, J = 8.4 Hz, 2H),
5.12 (s, 2H), 2.94 (q, J = 7.2 Hz, 2H), 1.21 (t, J = 7.2 Hz, 3H).
4'-((4-propionylphenoxy)methyl)-[1,1'-biphenyl]-2-carbonitrile (5g). White solid; Yield 68%; mp
118 − 120°C; Rf (20% EtOAc/hexane) 0.4. Prepared as
shown in the general experimental procedure (reaction
completion time 12 h at 80°C): IR (KBr, cm−1
) 3325,
3058, 2978, 2933, 2870, 2220, 2045, 1670, 1596, 1502,
1476; 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.8 Hz,
2H), 7.77 (d, J = 7.6 Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H), 7.61 – 7.50 (m, 5H), 7.45 (t, J = 7.6 Hz, 1H),
7.03 (d, J = 8.4 Hz, 2H), 5.19 (s, 2H), 2.96 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H). 13
C NMR
(100 MHz, CDCl3) δ 199.41, 162.24, 144.85, 136.79, 133.73, 132.85, 130.28, 130.22, 129.98, 129.04,
127.69, 118.61, 114.46, 111.17, 69.57, 31.38, 8.37. HRESI-MS (m/z) Calculated for C23H19NO2 (M+
+ Na) 364.1313, found (M+ + Na) 364.1314.
1-(4-((4-nitrobenzyl)oxy)phenyl)propan-1-one (5h). Yellow solid; Yield 72%; mp 119 − 122°C; Rf
(20% EtOAc/hexane) 0.4. Prepared as shown in the general
experimental procedure (reaction completion time 12 h at 80°C):
IR (KBr, cm−1
) 3508, 3321, 3043, 2936, 2724, 2445, 2320, 2167,
1670, 1596, 1506; 1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.4
Hz, 2H), 7.97 (d, J = 8.8 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.00
(d, J = 8.4 Hz, 2H), 5.24 (s, 2H), 2.96 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H). 13
C NMR (100
MHz, CDCl3) δ 199.35, 161.62, 147.68, 143.60, 130.72, 130.30, 127.60, 123.89, 114.43, 68.64, 31.45,
8.33. HRESI-MS (m/z) Calculated for C16H15NO4 (M+ + Na) 308.0899, found (M
+ + Na) 308.0898.
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General procedure for O-benzoylation of 4- Hydroxy Propiophenone (starting material
synthesis).
To a solution of 4-hydroxy propiophenone (1equiv, 500 mg) and triethylammine (1.1equiv) in THF
(10 mL) at 0 °C was added benzoyl chloride (1.1equiv) drop wise for 10 min, and allowed reaction
mixture to stir at room temperature for 1 h. After the completion of the reaction (monitored by TLC),
50 mL of water was added and the reaction mixture was extracted with ethyl acetate (3x20 mL). The
combined organic layer was washed with dilute HCl (25 mL, 2N), followed by dilute sodium
carbonate solution (25 mL, 5% aqueous solution) and finally with water. The organic layer was dried
over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified on
a silica gel column using hexane/EtOAc to get the pure product.
4-propionylphenyl benzoate (5i). White solid; Yield 88%; mp 114 − 116°C; Rf (20% EtOAc/hexane)
0.6. Prepared as shown in the general experimental procedure. IR
(KBr, cm−1
) 3342, 3039, 2971, 2930, 2871, 2728, 1727, 1675, 1586;
1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 7.6 Hz, 2H), 8.06 (d, J =
8.4 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.53 (t, J = 7.6 Hz, 2H), 7.33
(d, J = 8.8 Hz, 2H), 3.02 (q, J = 7.2 Hz, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ
199.56, 164.64, 154.47, 134.54, 133.88, 130.22, 129.63, 129.04, 128.65, 121.88, 31.78, 8.20; HRESI-
MS (m/z) Calculated for C16H14O3 (M+ + Na) 277.0841, found (M
+ + Na) 277.0841.
4-propionylphenyl 2-fluorobenzoate (5j). White solid; Yield 90%; mp 68 − 70°C; Rf (20%
EtOAc/hexane) 0.5. Prepared as shown in the general experimental
procedure. IR (KBr, cm−1
) 3345, 2978, 2935, 2874, 2522, 1738,
1678, 1595, 1486; 1H NMR (400 MHz, CDCl3) δ 8.12 – 8.02 (m,
3H), 7.65 – 7.57 (m, 1H), 7.35 – 7.15 (m, 4H), 3.02 (q, J = 7.2 Hz,
2H), 1.24 (t, J = 7.2 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ
199.63, 162.32 (d, J = 260 Hz),162.17 (d, J = 4 Hz), 154.06, 135.59, 135.50, 134.62, 132.70, 132.51,
129.62, 124.20 (d, J = 3.7 Hz), 121.82, 117.55 (d, J = 9 Hz), 117.26 (d, J = 22 Hz), 31.77, 8.17;
HRESI-MS (m/z) Calculated for C16H13O3F (M+ + Na) 295.0746, found (M
+ + Na) 295.0749.
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Typical experimental procedure for α Hydroxylation of aryl ketones
Aryl ketones (100 mg, 0.75 mmol), molecular iodine (0.5 equiv. 0.37 mmol) and TBHP in decane
5.5M (3 equiv. 2.23 mmol) in DMSO (1 mL) were stirred at 80 °C (6-12 h) in a 5ml round bottomed
flask. After the completion of the reaction (monitored by TLC), added water (25 mL) and extracted
with ethylacetate (3x20mL). The combined organic layer was washed with dilute sodium thiosulphate
solution (10 mL, 5% aqueous solution) and water. The combined organic layer was dried over Na2SO4
and concentrated under reduced pressure. The crude product was purified on a silica gel column using
hexane/ EtOAc to get the pure product.
Typical experimental procedure for α-Hydroxylation of aryl di and tri ketones
Aryl ketones (100 mg, 0.75 mmol), molecular iodine (1 equiv. 0.75 mmol) and TBHP in decane 5.5M
(6 equiv. 4.47 mmol) in DMSO (2 mL) were stirred at 80 °C (6-12 h) in a 5ml round bottomed flask.
After the completion of the reaction (monitored by TLC), added water (25 mL) and extracted with
ethylacetate (3x20mL). The combined organic layer was washed with dilute sodium thiosulphate
solution (10 mL, 5% aqueous solution) and water. Organic layer was dried over Na2SO4 and
concentrated under reduced pressure. The crude product was purified on a silica gel column using
hexane/ EtOAc to get the pure product.
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Characterization data
2-hydroxy-1-phenylpropan-1-one (2a):10
Yellow oily; Yield 70% (79 mg); Rf (10% EtOAc/hexane)
0.1. Prepared as shown in the general experimental procedure (reaction
completion time 8 h at 80 °C): IR (Neat, cm−1
) 3459, 3063, 2981, 2933, 1683,
1597, 1578; 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.6 Hz, 2H), 7.63 (t, J
= 7.6 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 5.21 – 5.14 (m, 1H), 3.82 (d, J = 6.4
Hz, 1H), 1.45 (d, J = 6.8 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 202.22,
133.83, 133.17, 128.71, 128.50, 69.17, 22.06; HRESI-MS (m/z) Calculated for C9H10O2 (M+ + Na)
173.0578, found (M+ + Na) 173.0578.
2-hydroxy-1-phenylbutan-1-one (2b):11
Yellow oily liquid; Yield 71% (87 mg); Rf (10%
EtOAc/hexane) 0.1. Prepared as shown in general experimental procedure (reaction completion time 6
h at 80 °C): IR (neat, cm−1
) 3789, 3700, 3472, 3062, 2967, 2931, 2877, 2360,
1677, 1597, 1579; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 7.2 Hz, 2H), 7.62 (t,
J = 7.2 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 5.08 – 5.06 (m, 1H), 2.01 – 1.91 (m,
1H), 1.67 – 1.57 (m, 1H), 0.94 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ
202.10, 133.90, 133.72, 128.84, 128.47, 73.93, 28.81, 8.82; HRESI-MS (m/z) Calculated for
C10H12O2 (M+ + Na) 187.0735, found (M
+ + Na) 187.0733.
2-hydroxy-1-phenylpentan-1-one (2c):12
Yellow oily liquid; Yield 75% (100 mg); Rf (10%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction completion
time 6 h at 80 °C): IR (neat, cm−1
) 3476, 3062, 2960, 2929, 2872, 2173, 1679,
1597, 1579, 1451; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.0 Hz, 2H), 7.62
(t, J = 7.6 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 5.09 (dd, J = 7.2, 3.6 Hz, 1H), 1.86 –
1.79 (m, 1H), 1.57 – 1.51 (m, 2H), 1.49 – 1.40 (m, 1H), 0.92 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 202.14, 133.84, 133.61, 128.79, 128.45, 72.87,
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37.88, 18.17, 13.76; HRESI-MS (m/z) Calculated for C11H14O2 (M+ + Na) 201.0891, found (M
+ +
Na) 201.0892.
2-hydroxy-6-methyl-1-phenylheptan-1-one (2d): Colorless oily liquid; Yield 67% (111 mg); Rf (5%
EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion
time 6 h at 80 °C): IR (neat, cm−1
) 3019, 2954, 1748, 1679, 1401; 1H NMR
(400 MHz, CDCl3) δ 7.91 (d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.51
(t, J = 7.6 Hz, 2H), 5.10 – 5.06 (m, 1H), 3.72 (d, J = 6.4 Hz, 1H), 1.86 –
1.81 (m, 1H), 1.54 – 1.41 (m, 3H), 1.40 – 1.37 (m, 1H), 1.21 – 1.1 (m, 2H),
0.84 (dd, J = 6.4, 4.4 Hz, 6H); 13
C NMR (100 MHz, CDCl3) δ 202.18, 133.87, 133.68, 128.83,
128.48, 73.13, 38.56, 36.11, 27.83, 22.76, 22.59, 22.37; HRESI-MS (m/z) Calculated for C14H20O2
(M+ + Na) 243.1361, found (M
+ + Na) 243.1365.
2-hydroxy-1-phenyldecan-1-one (2e): Colorless oily liquid; Yield 63% (117 mg); Rf (5%
EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion
time 7 h at 80 °C): IR (Neat, cm−1
) 3788, 3699, 3472, 3055, 2925, 2854,
2324, 1726, 1678, 1597, 1449; 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 7.2
Hz, 2H), 7.62 (t, J = 7.6 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 5.09 – 5.06 (m,
1H), 3.69 (d, J = 6.4 Hz, 1H), 1.90 – 1.81 (m, 1H), 1.6 – 1.47 (m, 2H), 1.39 –
1.37 (m, 1H), 1.31 – 1.23 (m, 10H), 0.86 (t, J = 6.4 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 202.19,
133.87, 133.69, 128.83, 128.49, 73.11, 35.87, 31.78, 29.34, 29.32, 29.13, 24.88, 22.59, 14.05;
HRESI-MS (m/z) Calculated for C16H24O2 (M+ + Na) 271.1674, found (M
+ + Na) 271.1674.
1-(4-ethylphenyl)-2-hydroxybutan-1-one (2f): Colorless oily liquid; Yield 76% (109 mg); Rf (10%
EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion
time 9 h at 80 °C): IR (Neat, cm−1
) 3447, 2968, 2935, 2876, 2094, 1675,
1607, 1568; 1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.0 Hz, 2H), 7.32 (d,
J = 8.0 Hz, 2H), 5.04 (dd, J = 6.8, 4.0 Hz, 1H), 3.76 (s, 1H), 2.73 (q, J = 7.6
Hz, 2H), 2.01 – 1.91 (m, 1H), 1.67 – 1.56 (m, 1H), 1.27 (t, J = 7.6 Hz, 3H),
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0.94 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.58, 151.04, 131.28, 128.69, 128.30,
73.76, 28.97, 28.94, 15.03, 8.81; HRESI-MS (m/z) Calculated for C12H16O2 (M+ + Na) 215.1048,
found (M+ + Na) 215.1046.
1-(4-(tert-butyl)phenyl)-2-hydroxybutan-1-one (2g):13
Colorless oily liquid; Yield 71% (117 mg);
Rf (10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 9 h at 80 °C): IR (Neat, cm−1
) 3474, 2963, 2872, 1736,
1674, 1604; 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.4 Hz, 2H), 7.51
(d, J = 8.4 Hz, 2H), 5.05 (dd, J = 6.4, 3.6 Hz, 1H), 3.76 (s, 1H), 2.02 – 1.92
(m, 1H), 1.68 – 1.57 (m, 1H), 1.35 (s, 9H), 0.95 (t, J = 7.6 Hz, 3H); 13
C
NMR (100 MHz, CDCl3) δ 201.52, 157.76, 130.97, 128.43, 125.74, 73.76,
35.16, 30.95, 28.90, 8.83; HRESI-MS (m/z) Calculated for C14H20O2 (M+ + Na) 243.1361, found (M
+
+ Na) 243.1360.
1-(4-(tert-butyl)phenyl)-2-hydroxypentan-1-one (2h): Colorless oily liquid; Yield 67% (118 mg);
Rf (10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 9 h at 80 °C): IR (Neat, cm−1
) 3714, 3477, 2961, 2870,
1950, 1676, 1604, 1563, 1463; 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J =
8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 2H), 5.07 (dd, J = 7.2, 3.2 Hz, 1H), 1.89 –
1.81 (m, 1H), 1.58 – 1.50 (m, 2H), 1.48 – 1.43 (m, 1H), 1.35 (s, 9H), 0.93
(t, J = 7.6 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.67, 157.80, 130.92,
128.49, 125.79, 72.77, 38.12, 35.22, 31.00, 18.27, 13.81; HRESI-MS (m/z) Calculated for C15H22O2
(M+ + Na) 257.1517, found (M+ + Na) 257.1513.
1-(4-decylphenyl)-2-hydroxybutan-1-one (2i): Colorless oily liquid; Yield 73% (167 mg); Rf (5%
EtOAc/Hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion
time 8 h at 80 °C): IR (Neat, cm−1
) 3475, 2923, 2853, 2359, 1675, 1606,
1567; 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 2H), 7.30 (d, J
= 8.0 Hz, 2H), 5.04 (dd, J = 6.8, 4.0 Hz, 1H), 2.67 (t, J = 7.6 Hz, 3H),
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2.01 – 1.91 (m, 1H), 1.67 – 1.58 (m, 3H), 1.31 – 1.25 (m, 14H), 0.94 (t, J = 7.2 Hz, 3H), 0.88 (t, J =
6.8 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.57, 149.88, 131.24, 128.84, 128.62, 73.76, 36.06,
31.85, 31.01, 29.56, 29.51, 29.41, 29.28, 29.24, 28.97, 22.64, 14.08, 8.85; HRESI-MS (m/z)
Calculated for C20H32O2 (M+ + Na) 327.2300, found (M
+ + Na) 327.2300.
1-(4-benzylphenyl)-2-hydroxypentan-1-one (2j): Yellow oily liquid; Yield 62% (124 mg); Rf (10%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction completion
time 8 h at 80 °C): IR (Neat, cm−1
) 3473, 3027, 2958, 2928, 2870, 1948,
1674, 1602, 1568; 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 2H),
7.32 – 7.30 (m, 4H), 7.26 – 7.22 (m, 1H), 7.19 (d, J = 7.2 Hz, 2H), 5.05 –
5.03 (m, 1H), 4.05 (s, 2H), 3.69 (s, 1H), 1.84 – 1.79 (m, 1H), 1.57 – 1.48
(m, 2H), 1.46 – 1.39 (m, 1H), 0.91 (t, J = 7.2 Hz, 3H); 13
C NMR (100
MHz, CDCl3) δ 201.67, 147.82, 139.66, 131.61, 129.32, 128.97, 128.83, 128.67, 126.52, 72.81, 41.95,
38.07, 18.24, 13.80; HRESI-MS (m/z) Calculated for C18H20O2 (M+ + Na) 291.1361, found (M
+ +
Na) 291.1361.
2-hydroxy-1-(5,6,7,8-tetrahydronaphthalen-2-yl)pentan-1-one (2k): Yellow oily liquid; Yield 61%
(106 mg); Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure
(reaction completion time 6 h at 80 °C): IR (Neat, cm−1
) 3328, 2943, 2830,
2497, 2056, 1676, 1450; 1H NMR (400 MHz, CDCl3) δ 7.63 (s, 1H), 7.60 (d, J
= 8.4 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 5.06 – 5.03 (m, 1H), 3.74 (s, 1H), 2.84
– 2.82 (m, 4H), 1.84 – 1.79 (m, 5H), 1.57 – 148 (m, 2H), 1.44 – 1.38 (m,
1H), 0.92 (t, J = 6.8 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.95, 144.24,
137.83, 131.02, 129.50, 129.35, 125.50, 72.69, 38.14, 29.67, 29.31, 22.79, 22.66, 18.14, 13.82;
HRESI-MS (m/z) Calculated for C15H20O2 (M+ + Na) 255.1361, found (M
+ + Na) 255.1361.
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1-(9H-fluoren-2-yl)-2-hydroxybutan-1-one (2l): Dark Yellow solid; (mp. 86-88°C) Yield 60% (114
mg); Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction
completion time 7 h at 80 °C): IR (Neat, cm−1
) 3765, 3455, 3056, 2966,
2932, 2876, 2332, 2079, 1667, 1608; 1H NMR (400 MHz, CDCl3) δ 8.09
(s, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 7.6 Hz, 2H), 7.58 (d, J = 6.8
Hz, 1H), 7.43 – 7.37 (m, 2H), 5.11 (dd, J = 6.0, 4.0 Hz, 1H), 3.94 (s, 2H),
3.83 (s, 1H), 2.05 – 1.95 (m, 1H), 1.72 – 1.61 (m, 1H), 0.97 (t, J = 7.2 Hz,
3H); 13
C NMR (100 MHz, CDCl3) δ 201.69, 147.27, 144.44, 143.44, 140.13, 131.84, 128.30, 127.81,
127.09, 125.23, 125.07, 120.94, 119.83, 73.86, 36.81, 29.04, 8.86; HRESI-MS (m/z) Calculated for
C17H16O2 (M+ + Na) 275.1048, found (M
+ + Na) 275.1048.
2-hydroxy-1-(5'-phenyl-[1,1':3',1''-terphenyl]-4-yl)butan-1-one (2m): Colorless oily liquid; Yield
63% (184 mg); Rf (10% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure
(reaction completion time 12 h at 90 °C): IR (Neat, cm−1
) 3700,
3471, 3057, 3035, 2964, 2927, 2874, 2360, 1952, 1805, 1673, 1598,
1496; 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.0 Hz, 2H), 7.85
– 7.80 (m, 5H), 7.70 (d, J = 7.2 Hz, 4H), 7.50 (t, J = 7.2 Hz, 4H),
7.41 (t, J = 7.2 Hz, 2H), 5.11 (dd, J = 6.8, 4.0 Hz, 1H), 3.75 (s, 1H),
2.07 – 1.97 (m, 1H), 1.71 – 1.60 (m, 1H), 0.98 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 201.60, 146.58, 142.65, 140.71,
132.55, 129.15, 128.92, 127.76, 127.69, 127.31, 126.28, 125.16, 73.97, 28.93, 8.88; HRESI-MS
(m/z) Calculated for C28H24O2 (M+ + Na) 415.1674, found (M
+ + Na) 415.1675.
1-(4-benzhydrylphenyl)-2-hydroxybutan-1-one (2n): Yellow oily liquid;
Yield 63% (156 mg); Rf (10% EtOAc/hexane) 0.3. Prepared as shown in
the general experimental procedure (reaction completion time 6 h at 80
°C): IR (Neat, cm−1
) 3478, 3027, 2922, 2852, 1736, 1676, 1598; 1H NMR
(400 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 2H), 7.32 – 7.21 (m, 8H), 7.10
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(d, J = 7.6 Hz, 4H), 5.60 (s, 1H), 5.01 (dd, J = 6.8, 3.6 Hz, 1H), 3.70 (s, 1H), 1.99 – 1.89 (m, 1H),
1.65 – 1.55 (m, 1H), 0.94 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.55, 150.50, 142.70,
131.77, 129.87, 129.33, 128.59, 128.50, 126.70, 73.86, 56.81, 28.89, 8.91; HRESI-MS (m/z)
Calculated for C23H22O2 (M+ + Na) 353.1517, found (M
+ + Na) 353.1519.
2-hydroxy-1,3-diphenylpropan-1-one (2o):14
Pale yellow solid (mp. 62-65°C); Yield 50% (85 mg);
Rf (5% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction
completion time 10 h at 80 °C): IR (Neat, cm−1
) 3466, 3062, 3029, 2925,
2359, 1682, 1597, 1495; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 7.2 Hz,
2H), 7.63 (t, J = 7.2 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 7.26 – 7.20 (m, 3H),
7.12 (d, J = 6.8 Hz, 2H), 5.34 – 5.31 (m, 1H), 3.72 (s, 1H), 3.19 (dd, J =
14.0, 4.0 Hz, 1H), 2.89 (dd, J = 14.4, 7.2 Hz, 1H); 13
C NMR (100 MHz, CDCl3) δ 200.97, 136.42,
133.96, 133.80, 129.39, 128.90, 128.56, 128.27, 126.76, 73.69, 41.87; HRESI-MS (m/z) Calculated
for C15H14O2 (M+ + Na) 249.0891, found (M
+ + Na) 249.0892.
2-hydroxy-1-(3-(trifluoromethyl)phenyl)propan-1-one (2p): Yellow oily liquid; Yield 59% (97
mg); Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction
completion time 6 h at 80 °C): IR (Neat, cm−1
) 3427, 2925, 2854, 1692, 1612; 1H
NMR (400 MHz, CDCl3) δ 8.20 (s, 1H), 8.11 (d, J = 7.6 Hz, 1H), 7.89 (d, J =
7.6 Hz, 1H), 7.68 (t, J = 7.6 Hz, 1H), 5.20 (q, J = 6.8 Hz, 1H), 3.7 (s, 1H), 1.48
(d, J = 6.8 Hz, 3H). 13
C NMR (100 MHz, CDCl3) δ 201.170, 134.03, 131.61 (q,
2JC-F = 31.6 Hz), 131.70 – 131.69 (m), 130.27 (q,
3JC-F = 3.6 Hz), 129.54, 125.44 (q,
3JC-F = 3.7 Hz),
123.45 (q, 1JC-F = 271 Hz), 69.52, 21.91;
19F NMR (100 MHz, CDCl3) δ -62.96; HRESI-MS (m/z)
Calculated for C10H9F3O2 (M+ + Na) 241.0452, found (M
+ + Na) 241.0449.
1,1'-(5'-phenyl-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(2-hydroxybutan-1-one) (4a): Pale yellow oily
liquid; Yield 45% (161 mg); Rf (20% EtOAc/hexane) 0.1. Prepared as shown in the general
experimental procedure (reaction completion time 8 h at 80 °C): IR (Neat, cm−1
) 3480, 2966, 1675,
1603, 1559, 1457; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.4 Hz, 4H), 7.87 – 7.81 (m, 7H), 7.70
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(d, J = 7.6 Hz, 2H), 7.51 (t, J = 7.2 Hz, 2H), 7.45 – 7.42 (m, 1H), 5.11
(dd, J = 6.4, 3.6 Hz, 2H), 3.72 (s, 2H), 2.05 – 1.98 (m, 2H), 1.72 – 1.64
(m, 2H), 0.99 (t, J = 7.2 Hz, 6H); 13
C NMR (100 MHz, CDCl3) δ
201.58, 146.14, 143.01, 141.08, 140.34, 132.79, 129.21, 129.01, 128.00,
127.71, 127.29, 126.28, 125.18, 74.00, 28.91, 8.87; HRESI-MS (m/z)
Calculated for C32H30O4 (M+ + Na) 501.2042, found (M
+ + Na)
501.2036.
1,1'-((phenylmethylene)bis(4,1-phenylene))bis(2-hydroxybutan-1-one) (4b): Pale yellow oily
liquid; Yield 47% (147 mg); Rf (20% EtOAc/hexane) 0.2. Prepared as shown in the general
experimental procedure (reaction completion time 8 h at 80 °C): IR
(Neat, cm−1
) 3855, 3395, 2918, 2851, 2364, 2345, 1676, 1420; 1H NMR
(400 MHz, CDCl3) δ 7.87 (d, J = 8.0 Hz, 4H), 7.36 – 7.28 (m, 3H), 7.25
(d, J = 8.0 Hz, 4H), 7.09 (d, J = 7.6 Hz, 2H), 5.66 (s, 1H), 5.02 (dd, J =
6.4, 3.6 Hz, 2H), 3.68 (s, 2H), 2.0 – 1.90 (m, 2H), 1.66 – 1.55 (m, 2H),
0.95 (t, J = 7.2 Hz, 6H); 13
C NMR (100 MHz, CDCl3) δ 201.48, 149.20,
141.61, 132.17, 129.82, 129.26, 128.78, 128.76, 127.16, 73.92, 56.79, 28.86, 8.91; HRESI-MS (m/z)
Calculated for C27H28O4 (M+ + Na) 439.1885, found (M
+ + Na) 439.1884.
2-hydroxy-1,9-diphenylnonane-1,9-dione (4ca): Pale yellow oily liquid; Yield 42 % (102 mg); Rf
(20% EtOAc/hexane) 0.5. Prepared as shown in the general experimental procedure (reaction
completion time 5.5 h at 80 °C): IR (Neat, cm−1
) 3474, 3062, 3020, 2928,
2855, 1677, 1597, 1449; 1H NMR (400 MHz, CDCl3) δ 7.99 – 7.90 (m, 4H),
7.62 (t, J = 7.2 Hz, 1H), 7.57 – 7.43 (m, 5H), 5.08 (dd, J = 6.8, 3.2 Hz, 1H),
3.68 (s, 1H), 2.93 (t, J = 7.2 Hz, 2H), 1.90 – 1.84 (m, 1H), 1.72 – 1.68 (m,
2H), 1.56 – 1.49 (m, 2H), 1.36 – 1.25 (m, 5H); 13
C NMR (100 MHz, CDCl3) δ
202.07, 200.38, 136.94, 133.89, 133.58, 132.84, 128.83, 128.49, 128.46,
127.96, 73.00, 38.41, 35.76, 29.14, 29.07, 24.75, 24.10; HRESI-MS (m/z) Calculated for C21H24O3
(M+ + Na) 347.1623, found (M
+ + Na) 347.1623.
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2,8-dihydroxy-1,9-diphenylnonane-1,9-dione (4cb): Pale yellow oily liquid; Yield 25% (64 mg); Rf
(20% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction
completion time 5.5 h at 80 °C): IR (Neat, cm−1
) 3470, 2927, 2856, 1679,
1597, 1449, 1406; 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 7.6 Hz, 4H),
7.62 (t, J = 7.6 Hz, 2H), 7.50 (t, J = 7.6 Hz, 4H), 5.06 – 5.02 (m, 2H), 3.67 (s,
2H), 1.86 – 1.80 (m, 2H), 1.55 – 1.45 (m, 4H), 1.42 – 1.23 (m, 4H); 13
C
NMR (100 MHz, CDCl3) δ 202.02, 133.93, 133.56, 128.85, 128.46, 72.97,
72.90, 35.70, 35.59, 29.03, 28.88, 24.75, 24.58; HRESI-MS (m/z)
Calculated for C21H24O4 (M+ + Na) 363.1572, found (M
+ + Na) 363.1569.
1,1'-(5'-(4-(2-hydroxybutanoyl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(butan-1-one) (4d):
Yellow oily liquid: Yield 25% (99 mg); Rf (20% EtOAc/hexane) 0.5. Prepared as shown in the general
experimental procedure (reaction completion time 5 h at 80 °C): IR (Neat, cm−1
) 3722, 3482, 3018,
2927, 2360, 1676, 1599, 1212; 1H NMR (400 MHz, CDCl3) δ
8.10 (d, J = 8.4 Hz, 4H), 8.06 (d, J = 8.0 Hz, 2H), 7.88 (s, 1H),
7.81 (s, 2H), 7.83 (d, J = 8.0 Hz, 2H), 7.79 (d, J = 8.4 Hz,
4H), 5.14 – 5.10 (m, 1H), 3.74 (d, J = 6.4 Hz, 1H), 3.01 (t, J =
7.2 Hz, 4H), 2.05 – 1.99 (m, 1H), 1.86 – 1.77 (m, 4H), 1.72 –
1.66 (m, 1H), 1.04 (t, J = 7.6 Hz, 6H), 0.99 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 201.59, 199.94, 145.99,
144.72, 141.69, 141.26, 136.35, 132.89, 129.24, 128.81, 127.75, 127.45, 126.30, 126.03, 74.02, 40.63,
28.92, 17.81, 13.90, 8.87; HRESI-MS (m/z) Calculated for C36H36O4 (M+ + Na) 555.2511, found (M
+
+ Na) 555.2514.
1-(4-bromophenyl)-2-hydroxypropan-1-one (6a):15
Yellow oily liquid;
Yield 70% (120 mg); Rf (10% EtOAc/hexane) 0.2. Prepared as shown in the
general experimental procedure (reaction completion time 8 h at 80 °C): IR
(Neat, cm−1
) 3454, 3090, 2932, 2981, 1686, 1586, 1567; 1H NMR (400 MHz,
CDCl3) δ 7.80 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 5.12 (q, J = 6.8 Hz, 1H), 3.73 (s, 1H),
Yogesh and Prabhu/Organic Chemistry/IISc
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1.44 (d, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.37, 132.20, 132.00, 130.04, 129.21,
69.26, 22.12; HRESI-MS (m/z) Calculated for C9H9BrO2 (M+ + Na) 250.9684, found (M
+ + Na)
250.9689.
1-(3-bromophenyl)-2-hydroxypropan-1-one (6b):16
Yellow oily liquid; Yield 70% (119 mg); Rf
(10% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction
completion time 6 h at 80 °C): IR (Neat, cm−1
) 3437, 3065, 2982, 2932, 1727,
1688, 1556; 1H NMR (400 MHz, CDCl3) δ 8.07 (s, 1H), 7.84 (d, J = 8.0 Hz,
1H), 7.75 (d, J = 7.6 Hz, 1H), 7.39 (t, J = 8.0Hz, 1H), 5.12 (q, J = 7.2 Hz, 1H),
3.71 (s, 1H), 1.45 (d, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.14,
136.74, 135.10, 131.54, 130.38, 127.06, 123.17, 69.41, 22.03; HRESI-MS (m/z) Calculated for
C9H9BrO2 (M+ + Na) 250.9684, found (M
+ + Na) 250.9680.
1-(4-chlorophenyl)-2-hydroxypropan-1-one (6c):17
Yellow oily liquid; Yield 68% (94 mg); Rf (10%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure
(reaction completion time 8 h at 80 °C): IR (Neat, cm−1
) 3457, 3071, 2982,
2933, 1686, 1591, 1570; 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.4 Hz,
2H), 7.49 (d, J = 8.4 Hz, 2H), 5.12 (q, J = 7.2 Hz, 1H), 1.45 (d, J = 7.2 Hz,
3H); 13
C NMR (100 MHz, CDCl3) δ 201.16, 140.45, 131.59, 129.98, 129.20,
69.26, 22.13; HRESI-MS (m/z) Calculated for C9H9ClO2 (M+ + Na) 207.0189, found (M
+ + Na))
207.0185.
1-(3-chlorophenyl)-2-hydroxypropan-1-one (6d):18
Colorless oily liquid; Yield 68% (94 mg); Rf
(10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction
completion time 6 h at 80 °C): IR (Neat, cm−1
) 3454, 3070, 2983, 2933, 1690,
1572; 1H NMR (400 MHz, CDCl3) δ 7.91 (s, 1H), 7.80 (d, J = 7.6 Hz, 1H),
7.60 (d, J = 7.6 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H), 5.12 (q, J = 6.8 Hz, 1H),
1.45 (d, J = 6.8 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.23, 135.22,
134.90, 133.84, 130.16, 128.62, 126.63, 69.45, 22.04; HRESI-MS (m/z)
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Calculated for C9H9ClO2 (M+ + Na) 207.0189, found (M
+ + Na) 207.0190.
1-(3-fluorophenyl)-2-hydroxypropan-1-one (6e):16
Yellow oily liquid; Yield 60% (76 mg); Rf (10%
EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction completion
time 6 h at 80 °C): IR (Neat, cm−1
) 3436, 3075, 2983, 2934, 1693, 1588; 1H
NMR (400 MHz, CDCl3) δ 7.71 (d, J = 7.6 Hz, 1H), 7.63 (d, J = 9.2 Hz, 1H),
7.50 (dd, J = 13.6, 7.6 Hz, 1H), 7.35 – 7.31 (m, 1H), 5.13 (q, J = 6.8 Hz, 1H),
3.68 (s 1H), 1.46 (d, J = 6.8 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 201.24,
162.80 (d, J = 247 Hz), 135.36 (d, J = 6 Hz), 130.58 (d, J = 8 Hz), 124.33 (d, J
= 3 Hz), 121.00 (d, J = 21 Hz), 115.39 (d, J = 22 Hz), 69.50, 22.08. HRESI-MS (m/z) Calculated for
C9H9FO2 (M+ + Na) 191.0484, found (M
+ + Na) 191.0480.
1-(4-(benzyloxy)phenyl)-2-hydroxypropan-1-one (6f): Yellow solid; (mp. 93-96°C) Yield 72%
(138 mg); Rf (20% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure
(reaction completion time 7 h at 80 °C): IR (KBr, cm−1
) 3472, 3028, 2934,
2872, 2493, 1894, 1724, 1659, 1596, 1563, 1505. 1H NMR (400 MHz,
CDCl3) δ 7.91 (d, J = 8.4 Hz, 2H), 7.43 – 7.34 (m, 5H), 7.04 (d, J = 8.8 Hz,
2H), 5.13 (s, 2H), 5.09 (q, J = 7.2 Hz, 1H), 3.90 (s, 1H), 1.43 (d, J = 6.8 Hz,
3H); 13
C NMR (100 MHz, CDCl3) δ 200.61, 163.25, 135.87, 130.99, 128.69,
128.30, 127.43, 126.18, 114.86, 70.19, 68.84, 22.58; HRESI-MS (m/z) Calculated for C16H16O3 (M+
+ Na) 279.0997, found (M+ + Na) 279.0995.
4'-((4-(2-hydroxypropanoyl)phenoxy)methyl)-[1,1'-biphenyl]-2-carbonitrile (6g): Yellow solid;
(mp. 130-132°C) Yield 74% (199 mg); Rf (30% EtOAc/hexane) 0.2.
Prepared as shown in the general experimental procedure (reaction
completion time 8 h at 80 °C): IR (KBr, cm−1
) 3470, 3060, 2977, 2923,
2503, 2363, 2218, 2084, 1837, 1658, 1598, 1568, 1512; 1H NMR (400
MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 2H), 7.77 (d, J = 7.2 Hz, 1H), 7.67 –
7.50 (m, 6H), 7.46 (t, J = 7.6 Hz, 1H), 7.07 (d, J = 8.4 Hz, 2H), 5.20 (s, 2H),
Yogesh and Prabhu/Organic Chemistry/IISc
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5.11 (q, J = 6.8 Hz, 1H), 1.45 (d, J = 6.8 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 200.56, 163.05,
144.72, 138.02, 136.43, 133.69, 132.84, 131.00, 129.92, 129.04, 127.68, 127.65, 126.25, 118.57,
114.81, 111.07, 69.65, 68.80, 22.52; HRESI-MS (m/z) Calculated for C23H19NO3 (M+ + Na)
380.1263, found (M+ + Na) 380.1263.
2-hydroxy-1-(4-((4-nitrobenzyl)oxy)phenyl)propan-1-one (6h): Yellow solid; (mp. 110-113°C)
Yield 64% (144 mg); Rf (30% EtOAc/hexane) 0.3. Prepared as shown in the general experimental
procedure (reaction completion time 6 h at 80 °C): IR (KBr, cm−1
) 3709,
3417, 3077, 2973, 2929, 2362, 1976, 1671, 1598, 1568, 1511, 1341; 1H
NMR (400 MHz, CDCl3) δ 8.27 (d, J = 8.8 Hz, 2H), 7.94 (d, J = 8.8 Hz,
2H), 7.62 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 8.8 Hz, 2H), 5.26 (s, 2H), 5.11 (q,
J = 6.8 Hz, 1H), 3.86 (s, 1H), 1.45 (d, J = 7.2 Hz, 3H); 13
C NMR (100 MHz,
CDCl3) δ 200.55, 162.42, 147.62, 143.26, 131.04, 127.59, 126.69, 123.84,
114.76, 68.85, 68.68, 22.44; HRESI-MS (m/z) Calculated for C16H15NO5 (M+ + Na) 324.0848, found
(M+ + Na) 324.0846.
4-(2-hydroxypropanoyl)phenyl benzoate (6i): White solid; (mp. 80-83°C) Yield 74% (150 mg); Rf
(20% EtOAc/hexane) 0.5. Prepared as shown in the general experimental procedure (reaction
completion time 8 h at 80 °C): IR (KBr, cm−1
) 3387, 3065, 2978, 2926,
2856, 2668, 1921, 1730, 1677, 1593, 1503; 1H NMR (400 MHz, CDCl3) δ
8.20 (d, J = 7.2 Hz, 2H), 8.02 (d, J = 8.8 Hz, 2H), 7.66 (t, J = 7.2 Hz, 1H),
7.53 (t, J = 7.6 Hz, 2H), 7.38 (d, J = 8.8 Hz, 2H), 5.17 (q, J = 6.8 Hz, 1H),
3.85 (d, J = 6.0 Hz, 1H), 1.47 (d, J = 7.2 Hz, 3H); 13
C NMR (100 MHz,
CDCl3) δ 201.09, 164.46, 155.25, 134.01, 130.81, 130.34, 130.23, 128.81,
128.68, 122.27, 69.26, 22.27; HRESI-MS (m/z) Calculated for C16H14O4 (M+ + Na) 293.0790, found
(M+ + Na) 293.0792.
4-(2-hydroxypropanoyl)phenyl 2-fluorobenzoate (6j): Pale yellow solid; (mp. 88-91°C) Yield 71%
(154 mg); Rf (30% EtOAc/hexane) 0.4. Prepared as shown in the general experimental procedure
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(reaction completion time 8 h at 80 °C): IR (KBr, cm−1
) 3743, 3466, 3075,
2980, 2925, 2851, 2186, 2075, 1980, 1744, 1680, 1598; 1H NMR (400
MHz, CDCl3) δ 8.11 (dt, J = 7.2, 1.2 Hz, 1H), 8.03 (d, J = 8.8 Hz, 2H), 7.67
– 7.61 (m, 1H), 7.40 (d, J = 8.8 Hz, 2H), 7.31 (t, J = 7.6 Hz, 1H), 7.26 –
7.21 (m, 1H), 5.17 (q, J = 6.8 Hz, 1H), 3.74 (s, 1H), 1.48 (d, J = 6.8 Hz,
3H); 13
C NMR (100 MHz, CDCl3) δ 201.10, 162.01 (d, J = 260 Hz), 162.01
(d, J = 4 Hz), 154.85, 135.75, 132.54, 130.96, 130.35, 124.26 (d, J = 4 Hz), 122.25, 117.42, 117.38 (d,
J = 9 Hz), 69.28, 22.26; HRESI-MS (m/z) Calculated for C16H13FO4 (M+ + Na) 311.0696, found (M
+
+ Na) 311.0701.
2-hydroxy-1-(4-phenoxyphenyl)pentan-1-one (6k): Pale yellow oily liquid; Yield 64% (130 mg); Rf
(10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction
completion time 6 h at 80 °C): IR (Neat, cm−1
) 3474, 3062, 2959, 2931,
2871, 2366, 2043, 1674, 1584; 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J =
8.8 Hz, 2H), 7.42 (t, J = 8.0 Hz, 2H), 7.23 (t, J = 7.2 Hz, 1H), 7.10 (d, J =
8.0 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 5.03 (dd, J = 8.0, 3.2 Hz, 1H), 3.71
(s, 1H), 1.85 – 1.80 (m, 1H), 1.56 – 1.51 (m, 2H), 1.49 – 1.40 (m, 1H),
0.93 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 200.51, 162.76, 155.01, 130.85, 130.12,
127.90, 124.94, 120.42, 117.26, 72.61, 38.22, 18.24, 13.82; HRESI-MS (m/z) Calculated for
C17H18O3 (M+ + Na) 293.1154, found (M
+ + Na) 293.1159.
2-hydroxy-1-(4-(phenylthio)phenyl)butan-1-one (6l): Pale yellow oily liquid; Yield 64% (131 mg);
Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction
completion time 6 h at 80 °C): IR (Neat, cm−1
) 3469, 3059, 2967, 2930,
2874, 2123, 1911, 1672, 1585; 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J =
8.4 Hz, 2H), 7.54 – 7.52 (m, 2H), 7.43 – 7.26 (m, 3H), 7.19 (d, J = 8.4 Hz,
2H), 4.97 (dd, J = 6.4, 3.6 Hz, 1H), 3.71 (s, 1H), 1.95 – 1.87 (m, 1H), 1.64
– 1.53 (m, 1H), 0.92 (t, J = 7.6 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ
Yogesh and Prabhu/Organic Chemistry/IISc
29
200.85, 146.66, 134.38, 131.09, 130.51, 129.76, 129.15, 128.96, 126.89, 73.70, 28.91, 8.82; HRESI-
MS (m/z) Calculated for C16H16O2S (M+ + Na) 295.0769, found (M
+ + Na) 295.0770.
2-hydroxy-1-(thiophen-2-yl)butan-1-one (8a): Yellow oily liquid; Yield 56% (71 mg); Rf (10%
EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction completion
time 12 h at 90 °C): IR (Neat, cm−1
) 3449, 3091, 2967, 2932, 2876, 2014, 1735,
1652, 1513; 1H NMR (400 MHz, CDCl3) δ 7.77 (dd, J = 3.6, 0.8 Hz, 1H), 7.74
(dd, J = 4.0, 0.8 Hz, 1H), 7.20 – 7.17 (m, 1H), 4.87 (dd, J = 6.8, 4.0 Hz, 1H),
3.55 (s, 1H), 2.07 – 1.97 (m, 1H), 1.79 – 1.68 (m, 1H), 0.99 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 194.48, 139.86, 134.65, 132.86, 128.31, 74.81, 29.80, 8.90; HRESI-
MS (m/z) Calculated for C8H10O2S (M+ + Na) 193.0299, found (M
+ + Na) 193.0297.
2-hydroxy-1-(5-methylthiophen-2-yl)butan-1-one (8b): Yellow oily liquid; Yield 65% (90 mg); Rf
(10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 9 h at 90 °C): IR (Neat, cm−1
) 3788, 3700, 3660, 3468, 2967,
2926, 2360, 1650; 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 4.0 Hz, 1H),
6.85 (d, J = 4.0 Hz, 1H), 4.81 (dd, J = 6.8, 3.6 Hz, 1H), 2.56 (s, 3H), 2.04 –
1.94 (m, 1H), 1.77 – 1.68 (m, 1H), 0.98 (t, J = 7.2 Hz, 3H); 13
C NMR (100
MHz, CDCl3) δ 193.90, 150.96, 137.58, 133.52, 127.02, 74.42, 29.97, 15.98, 8.90; HRESI-MS (m/z)
Calculated for C9H12O2S (M+ + Na) 207.0456, found (M
+ + Na) 207.0455.
1-(5-bromothiophen-2-yl)-2-hydroxybutan-1-one (8c): Yellow oily liquid; Yield 60% (111 mg); Rf
(10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 9 h at 90 °C): IR (Neat, cm−1
) 3439, 3095, 2966, 2926,
2852, 2552, 2182, 2163, 1737, 1656, 1597; 1H NMR (400 MHz, CDCl3) δ
7.51 (d, J = 4.0 Hz, 1H), 7.15 (d, J = 4.0 Hz, 1H), 4.78 (dd, J = 7.2, 4.0 Hz,
1H), 3.44 (s, 1H), 2.03 – 1.93 (m, 1H), 1.77 – 1.66 (m, 1H), 0.98 (t, J = 7.2
Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 193.42, 141.31, 133.11, 131.39, 123.94, 74.67, 29.70, 8.91;
HRESI-MS (m/z) Calculated for C8H9BrO2S (M+ + Na) 270.9404, found (M
+ + Na) 270.9404.
Yogesh and Prabhu/Organic Chemistry/IISc
30
2-hydroxy-1-(5-methylfuran-2-yl)butan-1-one (8d): Colourless oily
liquid; Yield 45% (51 mg); Rf (10% EtOAc/hexane) 0.1. Prepared as
shown in the general experimental procedure (reaction completion time 8 h
at 90 °C): IR (Neat, cm−1
) 3673, 3451, 3121, 2967, 2929, 2877, 2358,
1993, 1661, 1513; 1H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 3.6 Hz, 1H), 6.22 (d, J = 3.6 Hz, 1H),
4.75 (dd, J = 6.8, 4.0 Hz, 1H), 3.54 (s, 1H), 2.42 (s, 3H), 2.02 – 1.92 (m, 1H), 1.76 – 1.65 (m, 1H),
0.98 (t, J = 7.6 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 189.55, 158.67, 148.92, 120.86, 109.29,
73.91, 29.00, 14.06, 8.88; HRESI-MS (m/z) Calculated for C9H12O3 (M+ + Na) 191.0684, found (M
+
+ Na) 191.0684.
2-hydroxy-1-(1-methyl-1H-indol-3-yl)butan-1-one (8e): Brown solid; (mp. 81-84°C) Yield 46%
(75 mg); Rf (30% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure
(reaction completion time 9 h at 90 °C): IR (KBr, cm−1
) 3462, 2924, 2868,
2360, 1632, 1528, 1462, 1354; 1H NMR (400 MHz, CDCl3) δ 8.32 – 8.30
(m, 1H), 7.73 (s, 1H), 7.35 – 7.32 (m, 3H), 4.78 (dd, J = 6.8, 3.6 Hz, 1H),
3.85 (s, 3H), 3.26 (s, 1H), 2.04 – 1.94 (m, 1H), 1.76 – 1.66 (m, 1H), 0.99 (t, J
= 7.6 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 195.90, 137.26, 135.58,
126.30, 123.65, 122.93, 122.30, 112.39, 109.84, 74.36, 33.65, 30.33, 9.03; HRESI-MS (m/z)
Calculated for C13H15NO2 (M+ + Na) 240.1000, found (M
+ + Na) 240.1001.
1-(1-benzoyl-1H-indol-3-yl)-2-hydroxybutan-1-one (8f): Brown oily liquid; Yield 52% (120 mg);
Rf (20% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction
completion time 8 h at 90 °C): IR (Neat, cm−1
) 3373, 2930, 2846, 2159,
1920, 1697, 1659, 1541; 1H NMR (400 MHz, CDCl3) δ 8.34 – 8.31 (m,
1H), 8.25 – 8.21 (m, 1H), 8.00 (s, 1H), 7.77 (d, J = 7.2 Hz, 2H), 7.71 (t, J =
7.2 Hz, 1H), 7.60 (t, J = 7.6 Hz, 2H), 7.47 – 7.42 (m, 2H), 4.74 – 4.72 (m,
1H), 3.70 (d, J = 5.6 Hz, 1H), 1.98 – 1.91 (m, 1H), 1.74 – 1.65 (m, 1H),
0.95 (t, J = 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 197.53, 168.41,
136.28, 133.39, 133.17, 132.98, 129.53, 129.02, 127.36, 126.23, 125.52, 122.32, 117.23, 115.86,
Yogesh and Prabhu/Organic Chemistry/IISc
31
74.93, 29.76, 8.83; HRESI-MS (m/z) Calculated for C19H17NO3 (M+ + Na) 330.1106, found (M
+ +
Na) 330.1105.
1-(1-benzoyl-5-methoxy-1H-indol-3-yl)-2-hydroxybutan-1-one (8g): Brown oily liquid; Yield 64%
(162 mg); Rf (20% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure
(reaction completion time 11 h at 90 °C): IR (Neat, cm−1
) 3470, 2966,
2935, 2836, 2076, 1697, 1658, 1537, 1475, 1451; 1H NMR (400 MHz,
CDCl3) δ 8.13 (d, J = 9.2 Hz, 1H), 7.95 (s, 1H), 7.82 (d, J = 2.4 Hz, 1H),
7.76 (d, J = 7.2 Hz, 2H), 7.70 (t, J = 7.2 Hz, 1H), 7.59 (t, J = 7.6 Hz,
2H), 7.04 (dd, J = 9.2, 2.8 Hz, 1H), 4.70 (dd, J = 6.4, 4.0 Hz, 1H), 3.92
(s, 3H), 3.69 (s, 1H), 1.99 – 1.89 (m, 1H), 1.73 – 1.63 (m, 1H), 0.95 (t, J
= 7.2 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ 197.60, 168.19, 157.87, 133.69, 133.05, 132.95,
130.74, 129.46, 128.97, 128.52, 116.92, 116.69, 115.52, 104.12, 74.81, 55.67, 29.89, , 8.85; HRESI-
MS (m/z) Calculated for C20H19NO4 (M+ + Na) 360.1212, found (M
+ + Na) 360.1212.
Yogesh and Prabhu/Organic Chemistry/IISc
32
References
1. W.-B. Sheng, Q. Jiang, W.-P. Luo and C.-C. Guo, J. Org. Chem., 2013, 78, 5691-5693.
2. E. Rothstein and W. G. Schofield, J. Chem. Soc., 1965, 4566-4576.
3. R. Lin, F. Chen and N. Jiao, Org. Lett., 2012, 14, 4158-4161.
4. R. Takagi, N. Igata, K. Yamamoto and S. Kojima, J. Mol. Catal. A: Chem., 2010, 321, 71-76.
5. F. Wu, W. Lu, Q. Qian, Q. Ren and H. Gong, Org. Lett., 2012, 14, 3044-3047.
6. M. Nakamura, M. Miki and T. Majima, J. Chem. Soc. Perkin Trans., 1 2000, 415–420.
7. R. Lerebours, A. Camacho-Soto and C. Wolf, J. Org. Chem., 2005, 70, 8601-8604.
8. S. Scholz, H. Marschall-Weyerstahl and P. Weyerstahl, Liebigs Ann. Chem., 1985, 1935-1950.
9. Ž. Hodnik, L. Peterlin Mašič, T. Tomašić, D. Smodiš, C. D’Amore, S. Fiorucci and D. Kikelj, J.
Med. Chem., 2014, 57, 4819-4833.
10. M. Uchiyama, S. Furumoto, M. Saito, Y. Kondo and T. Sakamoto, J. Am. Chem. Soc., 1997,
119, 11425-11433.
11. A. S. Patil, D.-L. Mo, H.-Y. Wang, D. S. Mueller and L. L. Anderson, . Angew. Chem., Int. Ed.,
2012, 51, 7799-7803.
12. M. Koprowski, J. Łuczak and E. Krawczyk, Tetrahedron, 2006, 62, 12363-12374.
13. C. K. Jang, S. H. Kim and J.-Y. Jaung, Porphyrins Phthalocyanines, 2010, 14, 531-539.
14. A. Clerici and O. Porta, J. Org. Chem., 1993, 58, 2889-2893.
15. T. J. Houghton, K. S. E. Tanaka, T. Kang, E. Dietrich, Y. Lafontaine, D. Delorme, S. S. Ferreira,
F. Viens, F. F. Arhin, I. Sarmiento, D. Lehoux, I. Fadhil, K. Laquerre, J. Liu, V. Ostiguy, H.
Poirier, G. Moeck, T. R. Parr and A. R. Far, J. Med. Chem., 2008, 51, 6955-6969.
16. A. S. Demir, Ö. Şeşenoglu, E. Eren, B. Hosrik, M. Pohl, E. Janzen, D. Kolter, R. Feldmann, P.
Dünkelmann and M. Müller, Adv. Synth. Catal., 2002, 344, 96-103.
17. M. Y. Jin, S. M. Kim, H. Han, D. H. Ryu and J. W. Yang, Org. Lett., 2011, 13, 880-883.
18. G. W. Amarante, M. Cavallaro and F. Coelho, J. Braz. Chem. Soc., 2011, 22, 1568-1584.
Yogesh and Prabhu/Organic Chemistry/IISc
33
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
-0.0
00
0.9
82
1.0
00
1.0
19
1.2
38
1.2
57
1.2
76
1.7
19
1.7
38
1.7
56
1.7
74
1.7
93
1.8
11
2.6
74
2.6
93
2.7
12
2.7
31
2.9
06
2.9
24
2.9
42
7.2
67
7.2
87
7.8
81
7.9
01
3.1
80
3.1
42
2.1
09
2.1
49
2.1
02
2.0
99
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
34
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
92
15.1
95
17.8
54
28.8
86
40.4
06
76.6
83
77.0
01
77.3
19
128.0
00
128.2
42
134.8
10
149.7
38
200.1
31
Yogesh and Prabhu/Organic Chemistry/IISc
35
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.8
60
0.8
77
0.8
94
0.9
81
1.0
00
1.0
18
1.2
56
1.3
01
1.3
12
1.5
85
1.6
03
1.6
21
1.6
39
1.6
57
1.7
18
1.7
37
1.7
55
1.7
74
1.7
92
1.8
10
2.6
29
2.6
49
2.6
68
2.9
03
2.9
21
2.9
39
7.2
42
7.2
61
7.8
68
7.8
89
3.1
23
3.1
39
14.7
67
2.2
58
2.0
82
2.0
58
2.0
53
2.1
20
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
36
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.9
00
14.0
87
17.8
55
22.6
57
29.2
42
29.2
96
29.4
33
29.5
35
29.5
72
31.1
14
31.8
71
35.9
53
40.3
99
76.6
83
77.0
01
77.3
18
128.1
57
128.5
42
134.8
01
148.5
29
200.1
09
Yogesh and Prabhu/Organic Chemistry/IISc
37
10 9 8 7 6 5 4 3 2 1 0 ppm
0.9
19
0.9
37
0.9
55
1.3
44
1.3
62
1.3
80
1.3
99
1.4
18
1.4
35
1.6
61
1.6
80
1.6
98
1.7
18
1.7
36
2.8
97
2.9
15
2.9
34
4.0
11
7.1
57
7.1
76
7.2
05
7.2
23
7.2
48
7.2
68
7.2
85
7.3
04
7.8
67
7.8
87
3.2
44
2.1
87
2.2
74
2.0
75
2.0
00
2.3
61
5.1
85
2.0
13
Yogesh and Prabhu/Organic Chemistry/IISc
38
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.9
01
22.4
40
26.4
87
38.1
99
41.8
19
76.6
83
77.0
00
77.3
18
126.3
27
128.3
26
128.3
83
128.5
57
128.8
78
129.0
17
135.1
00
140.0
32
146.4
53
200.1
37
Yogesh and Prabhu/Organic Chemistry/IISc
39
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
27
0.9
45
0.9
64
1.3
53
1.3
71
1.3
89
1.4
08
1.4
26
1.4
45
1.6
65
1.6
84
1.7
03
1.7
21
1.7
40
1.8
06
2.7
96
2.8
06
2.8
98
2.9
16
2.9
35
7.1
08
7.1
29
7.2
52
7.6
56
7.6
65
3.1
42
2.2
02
2.2
94
4.0
79
4.0
73
2.0
42
1.0
00
1.8
92
Yogesh and Prabhu/Organic Chemistry/IISc
40
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
99
22.4
59
22.7
92
22.9
27
26.6
23
29.3
35
29.5
40
38.1
56
76.6
83
77.0
01
77.3
19
125.1
10
128.8
86
129.2
02
134.5
55
137.2
98
142.8
02
200.5
22
Yogesh and Prabhu/Organic Chemistry/IISc
41
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.0
11
1.0
30
1.0
48
1.6
73
1.7
57
1.7
75
1.7
94
1.8
12
1.8
30
1.8
49
2.9
71
2.9
89
3.0
08
3.9
31
7.2
50
7.3
43
7.3
61
7.3
82
7.4
04
7.4
22
7.5
61
7.5
79
7.8
00
7.8
19
7.8
36
7.9
86
8.0
05
8.1
32
3.0
98
2.0
64
2.0
51
2.0
68
2.0
38
1.0
26
2.0
34
1.0
35
1.0
00
7.47.67.88.08.2 ppm
7.250
7.343
7.361
7.382
7.404
7.422
7.561
7.579
7.800
7.819
7.836
7.986
8.005
8.132
2.038
1.026
2.034
1.035
1.000
Yogesh and Prabhu/Organic Chemistry/IISc
42
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.9
27
17.9
53
36.8
59
40.6
31
76.6
82
77.0
00
77.3
18
119.5
97
120.7
87
124.6
69
125.2
00
126.9
94
127.3
66
127.8
94
135.5
17
140.5
01
143.2
44
144.4
33
146.1
50
200.2
76
125130135140145 ppm
119.597
120.787
124.669
125.200
126.994
127.366
127.894
135.517
140.501
143.244
144.433
146.150
Yogesh and Prabhu/Organic Chemistry/IISc
43
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.0
09
1.0
28
1.0
46
1.7
56
1.7
75
1.7
93
1.8
11
1.8
30
1.8
48
2.9
58
2.9
76
2.9
94
7.2
22
7.3
71
7.3
90
7.4
08
7.4
57
7.4
76
7.4
95
7.6
72
7.6
91
7.7
52
7.7
72
7.7
85
7.8
13
8.0
47
8.0
67
3.0
77
2.0
58
2.0
23
2.0
77
4.0
62
4.0
62
5.0
62
2.0
00
7.47.67.88.0 ppm
7.222
7.371
7.390
7.408
7.457
7.476
7.495
7.672
7.691
7.752
7.772
7.785
7.813
8.047
8.067
2.077
4.062
4.062
5.062
2.000
Yogesh and Prabhu/Organic Chemistry/IISc
44
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
97
17.7
98
40.5
52
76.6
83
77.0
00
77.3
18
125.1
24
125.9
74
127.2
98
127.3
71
127.6
73
128.6
65
128.8
70
135.9
74
140.7
98
142.5
28
145.3
71
199.9
51
Yogesh and Prabhu/Organic Chemistry/IISc
45
10 9 8 7 6 5 4 3 2 1 0 ppm
0.9
58
0.9
76
0.9
95
1.6
98
1.7
17
1.7
36
1.7
54
1.7
72
1.7
91
2.8
71
2.8
89
2.9
08
5.5
77
7.0
81
7.0
99
7.1
89
7.2
08
7.2
23
7.2
54
7.2
73
7.2
91
7.8
62
7.8
82
3.0
48
2.1
42
2.0
00
1.0
31
4.1
02
4.0
10
4.1
84
1.9
71
Yogesh and Prabhu/Organic Chemistry/IISc
46
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
32
17.6
95
40.3
59
56.6
73
76.6
81
76.9
99
77.3
17
126.5
20
128.0
80
128.3
81
129.2
86
129.5
42
135.2
19
142.9
39
149.1
32
199.8
89
Yogesh and Prabhu/Organic Chemistry/IISc
47
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.0
14
1.0
33
1.0
51
1.7
60
1.7
79
1.7
97
1.8
16
1.8
34
1.8
52
2.9
67
2.9
86
3.0
04
7.2
46
7.3
90
7.4
07
7.4
26
7.4
71
7.4
90
7.5
08
7.6
72
7.6
90
7.7
53
7.7
73
7.8
00
7.8
26
8.0
58
8.0
78
6.0
66
4.1
09
4.0
01
1.0
74
2.1
62
2.0
53
7.0
31
4.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
48
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
68
17.7
64
40.5
42
76.6
83
77.0
00
77.3
18
125.0
95
125.9
38
127.2
67
127.3
60
127.8
24
128.6
87
128.9
16
136.0
88
140.4
95
141.2
36
142.7
43
145.0
38
199.8
75
Yogesh and Prabhu/Organic Chemistry/IISc
49
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
01
0.9
60
0.9
68
0.9
87
1.0
05
1.7
08
1.7
27
1.7
46
1.7
64
1.7
82
2.8
94
2.9
12
2.9
30
5.6
35
7.0
79
7.0
97
7.1
90
7.2
10
7.2
42
7.2
58
7.2
85
7.3
03
7.3
21
7.8
88
7.9
08
6.3
20
4.2
21
4.2
07
1.0
42
2.1
11
7.1
82
4.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
50
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.7
98
17.6
56
40.3
64
56.5
75
76.6
82
77.0
00
77.3
18
126.8
17
128.1
96
128.5
40
129.2
05
129.4
76
135.4
55
142.1
18
148.1
77
199.8
04
Yogesh and Prabhu/Organic Chemistry/IISc
51
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.0
20
1.0
39
1.0
57
1.7
68
1.7
86
1.8
04
1.8
22
1.8
41
1.8
59
2.9
82
3.0
01
3.0
19
7.2
66
7.7
69
7.7
89
7.8
58
8.0
76
8.0
97
9.2
32
6.3
86
6.2
54
6.0
00
3.0
61
6.0
51
Yogesh and Prabhu/Organic Chemistry/IISc
52
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
62
17.7
57
40.5
62
76.6
83
77.0
00
77.3
18
125.9
50
127.3
88
128.7
34
136.2
26
141.5
00
144.7
55
199.8
51
Yogesh and Prabhu/Organic Chemistry/IISc
53
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.1
97
1.2
15
1.2
33
2.9
31
2.9
49
2.9
67
2.9
86
5.1
89
7.0
22
7.0
43
7.2
60
7.4
36
7.4
54
7.4
73
7.5
06
7.5
26
7.5
46
7.5
66
7.5
88
7.6
08
7.6
34
7.6
53
7.6
72
7.7
61
7.7
80
7.9
58
7.9
80
3.0
65
2.0
39
2.0
35
2.0
00
1.0
34
5.1
26
1.0
39
1.0
28
2.0
21
7.57.67.77.87.98.0 ppm
7.436
7.454
7.473
7.506
7.526
7.546
7.566
7.588
7.608
7.634
7.653
7.672
7.761
7.780
7.958
7.980
1.034
5.126
1.039
1.028
2.021
Yogesh and Prabhu/Organic Chemistry/IISc
54
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
8.3
71
31.3
84
69.5
74
76.6
83
77.0
00
77.3
18
111.1
66
114.4
58
118.6
14
127.6
89
129.0
42
129.9
82
130.2
23
130.2
80
132.8
54
133.7
34
136.7
90
137.9
64
144.8
52
162.2
44
199.4
13
128130132134136138140142144 ppm
127.689
129.042
129.982
130.223
130.280
132.854
133.734
136.790
137.964
144.852
Yogesh and Prabhu/Organic Chemistry/IISc
55
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.1
97
1.2
15
1.2
33
2.9
33
2.9
51
2.9
70
2.9
88
5.2
44
6.9
95
7.0
16
7.2
68
7.6
08
7.6
29
7.9
57
7.9
79
8.2
51
8.2
72
3.1
05
2.0
39
2.0
37
2.0
08
2.0
00
2.0
10
2.0
01
Yogesh and Prabhu/Organic Chemistry/IISc
56
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
8.3
32
31.4
46
68.6
45
76.6
83
77.0
00
77.3
18
114.4
29
123.8
86
127.6
01
130.2
96
130.7
24
143.6
03
147.6
79
161.6
18
199.3
45
Yogesh and Prabhu/Organic Chemistry/IISc
57
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.2
27
1.2
45
1.2
63
2.9
94
3.0
12
3.0
30
3.0
48
7.2
61
7.3
16
7.3
38
7.5
10
7.5
29
7.5
48
7.6
43
7.6
61
7.6
80
8.0
51
8.0
72
8.1
99
8.2
18
3.0
42
2.0
23
2.0
13
2.0
67
1.0
16
2.0
48
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
58
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
8.2
04
31.7
81
76.6
82
77.0
00
77.3
18
121.8
76
128.6
49
129.0
38
129.6
32
130.2
21
133.8
82
134.5
45
154.4
68
164.6
41
199.5
63
Yogesh and Prabhu/Organic Chemistry/IISc
59
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
1.2
27
1.2
45
1.2
63
2.9
97
3.0
15
3.0
33
3.0
51
7.1
52
7.1
76
7.2
04
7.2
27
7.2
52
7.2
65
7.2
76
7.2
95
7.3
14
7.3
33
7.3
54
7.5
77
7.6
06
7.6
21
7.6
36
7.6
53
8.0
20
8.0
51
8.0
72
8.0
90
8.1
09
8.1
28
2.8
84
1.9
02
4.1
46
1.0
54
3.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
60
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
8.1
72
31.7
73
76.6
83
77.0
00
77.3
18
117.1
47
117.3
68
117.5
03
117.5
94
121.8
23
124.1
83
124.2
22
129.6
21
132.5
12
132.6
96
134.6
23
135.4
99
135.5
92
154.0
65
161.0
18
162.1
45
162.1
85
163.6
21
199.6
26
Yogesh and Prabhu/Organic Chemistry/IISc
61
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.9
32
0.9
51
0.9
69
1.3
60
1.3
78
1.3
97
1.4
16
1.4
34
1.4
53
1.6
77
1.6
96
1.7
14
1.7
33
1.7
52
2.9
03
2.9
21
2.9
40
6.9
85
7.0
06
7.0
57
7.0
77
7.1
75
7.1
93
7.2
11
7.2
58
7.3
72
7.3
91
7.4
11
7.9
33
7.9
54
3.2
07
2.1
34
2.0
68
2.0
76
2.3
04
2.0
66
1.0
60
2.0
74
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
62
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.9
26
22.4
91
26.6
21
38.1
13
76.6
83
77.0
00
77.3
18
117.2
91
120.0
96
124.5
15
130.0
06
130.2
89
131.7
77
155.5
40
161.7
34
199.1
89
Yogesh and Prabhu/Organic Chemistry/IISc
63
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
64
0.9
82
1.0
01
1.6
95
1.7
15
1.7
34
1.7
52
1.7
70
1.7
88
2.8
58
2.8
77
2.8
95
7.1
98
7.2
18
7.3
82
7.3
94
7.4
80
7.4
90
7.8
12
7.8
32
3.0
94
2.3
41
1.9
65
2.2
82
3.0
79
2.0
01
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
64
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
40
17.7
73
40.3
19
76.6
83
77.0
00
77.3
18
127.5
19
128.5
99
128.6
68
129.6
07
132.1
80
133.7
22
134.3
96
144.4
22
199.3
99
Yogesh and Prabhu/Organic Chemistry/IISc
65
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
70
0.9
89
1.0
07
1.8
90
2.5
24
2.7
90
2.8
09
2.8
27
6.7
83
6.7
91
7.2
81
7.5
17
7.5
26
3.1
16
2.0
67
3.0
69
2.0
63
1.0
00
1.0
05
Yogesh and Prabhu/Organic Chemistry/IISc
66
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.7
95
15.9
10
18.3
05
40.7
03
76.6
83
77.0
01
77.3
19
126.5
79
132.2
19
142.2
65
149.2
79
193.0
74
Yogesh and Prabhu/Organic Chemistry/IISc
67
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
74
0.9
93
1.0
11
1.7
12
1.7
30
1.7
48
1.7
66
1.7
85
1.8
03
2.7
85
2.8
03
2.8
21
7.0
88
7.0
97
7.4
35
7.4
44
3.1
75
2.2
17
2.0
95
1.0
00
1.0
11
Yogesh and Prabhu/Organic Chemistry/IISc
68
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.7
60
18.0
36
40.5
16
76.6
82
77.0
00
77.3
18
122.2
35
131.1
08
131.7
07
145.9
05
192.2
64
Yogesh and Prabhu/Organic Chemistry/IISc
69
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.0
00
1.0
19
1.0
37
1.7
48
1.7
67
1.7
85
1.8
04
1.8
22
1.8
41
1.8
59
2.8
01
2.8
20
2.8
38
3.8
45
7.2
58
7.2
87
7.3
02
7.3
07
7.3
19
7.3
30
7.3
44
7.7
20
8.3
86
8.3
94
8.4
07
3.0
87
2.1
67
2.0
73
3.1
16
3.0
90
1.0
09
1.0
00
7.47.67.88.08.28.4 ppm
7.258
7.287
7.302
7.307
7.319
7.330
7.344
7.720
8.386
8.394
8.407
3.090
1.009
1.000
Yogesh and Prabhu/Organic Chemistry/IISc
70
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
14.0
15
18.5
79
33.3
49
41.7
49
76.6
83
77.0
00
77.3
18
109.4
94
116.4
91
122.3
55
122.4
86
123.1
34
126.2
29
135.1
98
137.3
41
195.8
13
Yogesh and Prabhu/Organic Chemistry/IISc
71
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
54
0.9
72
0.9
91
1.7
11
1.7
29
1.7
48
1.7
66
1.7
84
1.8
02
2.7
41
2.7
59
2.7
77
7.2
55
7.3
85
7.3
94
7.3
99
7.4
07
7.5
56
7.5
75
7.5
94
7.6
55
7.6
73
7.6
92
7.7
53
7.7
71
7.9
27
8.2
15
8.2
23
8.2
37
8.3
83
8.3
90
8.3
98
8.4
05
3.0
74
2.0
18
2.0
45
2.0
09
2.0
87
1.1
69
2.1
02
1.0
70
0.9
71
1.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
72
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.7
64
17.7
68
41.7
94
76.6
83
77.0
01
77.3
19
115.7
12
121.0
05
122.5
27
125.1
65
125.7
62
127.5
47
128.8
58
129.3
48
132.7
01
132.7
39
133.2
97
136.3
70
168.4
80
196.4
14
Yogesh and Prabhu/Organic Chemistry/IISc
73
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
63
0.9
82
1.0
00
1.7
20
1.7
38
1.7
56
1.7
75
1.7
93
1.8
11
2.7
39
2.7
57
2.7
75
3.9
03
6.9
94
7.0
00
7.0
16
7.0
22
7.2
66
7.5
64
7.5
83
7.6
02
7.6
61
7.6
79
7.6
98
7.7
53
7.7
72
7.8
89
7.9
10
7.9
15
8.1
21
8.1
44
3.0
96
2.2
45
2.0
59
3.0
98
1.0
00
2.0
26
1.0
75
2.0
15
0.9
46
1.0
35
1.0
10
7.47.67.88.08.2 ppm
7.266
7.564
7.583
7.602
7.661
7.679
7.698
7.753
7.772
7.889
7.910
7.915
8.121
8.144
2.026
1.075
2.015
0.946
1.035
1.010
Yogesh and Prabhu/Organic Chemistry/IISc
74
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.8
11
17.7
86
41.6
39
55.6
07
76.6
82
77.0
00
77.3
19
104.2
68
115.2
34
116.5
98
120.8
13
128.7
01
128.8
72
129.3
36
130.9
14
132.6
75
133.0
65
133.3
39
157.6
79
168.3
03
196.6
66
Yogesh and Prabhu/Organic Chemistry/IISc
75
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.4
49
1.4
66
3.8
10
3.8
26
5.1
38
5.1
55
5.1
72
5.1
89
5.2
06
7.2
70
7.4
91
7.5
10
7.5
29
7.6
09
7.6
27
7.6
45
7.9
25
7.9
44
3.0
45
0.9
45
1.0
10
2.0
07
1.0
00
2.0
06
Yogesh and Prabhu/Organic Chemistry/IISc
76
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
22.0
61
69.1
72
76.6
80
76.9
99
77.3
17
128.5
00
128.7
06
133.1
71
133.8
25
202.2
23
Yogesh and Prabhu/Organic Chemistry/IISc
77
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
-0.0
00
0.9
25
0.9
44
0.9
62
1.5
65
1.5
83
1.6
01
1.6
19
1.6
37
1.6
54
1.6
73
1.9
10
1.9
19
1.9
29
1.9
38
1.9
47
1.9
56
1.9
64
1.9
74
1.9
82
1.9
92
2.0
01
2.0
11
5.0
55
5.0
64
5.0
72
5.0
81
7.2
68
7.4
86
7.5
05
7.5
24
7.6
05
7.6
23
7.6
42
7.9
09
7.9
27
3.1
16
1.0
66
1.0
76
1.0
00
2.0
69
1.0
25
2.0
45
Yogesh and Prabhu/Organic Chemistry/IISc
78
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
2
28.8
1
73.9
3
76.6
8
77.0
0
77.3
2
128.4
7
128.8
4
133.7
2
133.9
0
202.1
0
Yogesh and Prabhu/Organic Chemistry/IISc
79
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
00
0.9
18
0.9
36
1.4
00
1.4
18
1.4
25
1.4
36
1.4
45
1.4
52
1.4
63
1.4
71
1.4
88
1.5
11
1.5
20
1.5
31
1.5
41
1.5
52
1.5
59
1.5
71
1.5
76
1.7
98
1.8
07
1.8
15
1.8
28
1.8
35
1.8
51
1.8
61
5.0
80
5.0
89
5.0
98
5.1
06
7.2
79
7.4
84
7.5
03
7.5
22
7.6
01
7.6
20
7.6
38
7.9
06
7.9
26
3.1
44
1.0
83
2.1
50
1.0
34
1.0
06
2.1
00
1.0
15
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
80
220 200 180 160 140 120 100 80 60 40 20 0 ppm
13.7
6
18.1
7
37.8
8
72.8
7
76.6
8
77.0
0
77.3
2
128.4
5
128.7
9
133.6
1
133.8
4
202.1
4
Yogesh and Prabhu/Organic Chemistry/IISc
81
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.8
26
0.8
37
0.8
42
0.8
54
1.1
12
1.1
19
1.1
28
1.1
36
1.1
43
1.1
51
1.1
68
1.1
77
1.1
81
1.1
88
1.1
93
1.2
06
1.3
71
1.3
80
1.3
85
1.3
96
1.4
11
1.4
22
1.4
68
1.4
84
1.5
00
1.5
07
1.5
17
1.5
26
1.5
35
1.5
45
1.8
10
1.8
18
1.8
31
1.8
37
1.8
44
1.8
57
1.8
65
3.7
08
3.7
24
5.0
60
5.0
77
5.0
85
5.1
01
7.2
68
7.4
87
7.5
06
7.5
25
7.6
03
7.6
22
7.6
40
7.9
05
7.9
24
6.0
64
2.1
69
1.2
36
3.0
99
1.0
57
0.9
67
1.0
24
2.0
48
1.0
08
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
82
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.3
7
22.5
9
22.7
6
27.8
3
36.1
1
38.5
6
73.1
3
76.6
8
77.0
0
77.3
2
128.4
8
128.8
3
133.6
8
133.8
7
202.1
8
Yogesh and Prabhu/Organic Chemistry/IISc
83
-18 7 6 5 4 3 2 1 0 ppm
0.0
00
0.8
43
0.8
61
0.8
77
1.2
30
1.2
71
1.2
89
1.3
08
1.3
68
1.3
79
1.3
89
1.4
69
1.4
86
1.4
94
1.5
10
1.5
27
1.5
38
1.5
48
1.5
58
1.5
98
1.8
13
1.8
31
1.8
39
1.8
53
1.8
77
1.8
85
1.8
95
3.6
84
3.7
00
5.0
56
5.0
73
5.0
80
5.0
89
7.2
62
7.4
88
7.5
07
7.5
26
7.6
05
7.6
23
7.6
42
7.9
05
7.9
23
3.1
81
10.6
86
1.1
74
2.0
97
1.0
34
0.9
03
1.0
13
2.0
37
1.0
06
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
84
220 200 180 160 140 120 100 80 60 40 20 0 ppm
14.0
5
22.5
9
24.8
8
29.1
3
29.3
2
29.3
4
31.7
8
35.8
7
73.1
1
76.6
8
77.0
0
77.3
2
128.4
9
128.8
3
133.6
9
133.8
7
202.1
9
Yogesh and Prabhu/Organic Chemistry/IISc
85
8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.9
21
0.9
39
0.9
58
1.2
52
1.2
71
1.2
90
1.5
63
1.5
81
1.5
99
1.6
16
1.6
34
1.6
52
1.6
70
1.9
06
1.9
16
1.9
25
1.9
34
1.9
43
1.9
53
1.9
60
1.9
70
1.9
79
1.9
88
1.9
98
2.0
07
2.6
96
2.7
15
2.7
34
2.7
53
3.7
66
5.0
29
5.0
39
5.0
46
5.0
56
7.2
72
7.3
10
7.3
30
7.8
37
7.8
57
3.1
96
3.3
35
1.1
62
1.0
88
2.1
81
0.7
74
1.0
00
2.0
24
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
86
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
1
15.0
3
28.9
4
28.9
7
73.7
6
76.6
8
77.0
0
77.3
2
128.3
0
128.6
9
131.2
8
151.0
4
201.5
8
Yogesh and Prabhu/Organic Chemistry/IISc
87
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
27
0.9
46
0.9
64
1.3
51
1.5
68
1.5
86
1.6
04
1.6
21
1.6
39
1.6
57
1.6
75
1.9
17
1.9
26
1.9
36
1.9
45
1.9
54
1.9
63
1.9
71
1.9
81
1.9
90
1.9
99
2.0
08
2.0
18
3.7
59
5.0
34
5.0
43
5.0
50
5.0
59
7.2
69
7.5
00
7.5
21
7.8
52
7.8
73
3.2
41
9.3
62
1.1
43
1.1
06
0.9
09
1.0
49
2.0
08
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
88
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
3
28.9
0
30.9
5
35.1
6
73.7
6
76.6
8
77.0
0
77.3
2
125.7
4
128.4
3
130.9
7
157.7
6
201.5
2
Yogesh and Prabhu/Organic Chemistry/IISc
89
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
12
0.9
29
0.9
47
1.3
55
1.4
31
1.4
47
1.4
55
1.4
72
1.4
85
1.5
09
1.5
17
1.5
40
1.5
57
1.5
79
1.8
17
1.8
45
1.8
91
5.0
53
5.0
60
5.0
70
5.0
78
7.2
64
7.5
03
7.5
24
7.8
50
7.8
71
3.2
43
9.7
14
1.2
61
2.3
16
1.0
26
1.0
15
2.0
59
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
90
220 200 180 160 140 120 100 80 60 40 20 0 ppm
13.8
1
18.2
7
31.0
0
35.2
2
38.1
2
72.7
7
76.6
8
77.0
0
77.3
2
125.7
9
128.4
9
130.9
2
157.8
0
201.6
7
Yogesh and Prabhu/Organic Chemistry/IISc
91
-19 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.8
60
0.8
77
0.8
93
0.9
23
0.9
42
0.9
60
1.2
58
1.3
11
1.5
79
1.5
97
1.6
15
1.6
32
1.6
50
1.6
68
1.9
07
1.9
17
1.9
26
1.9
35
1.9
44
1.9
54
1.9
62
1.9
71
1.9
80
1.9
89
1.9
98
2.0
08
2.6
50
2.6
70
2.6
89
5.0
24
5.0
34
5.0
41
5.0
51
7.2
68
7.2
86
7.3
06
7.8
26
7.8
46
3.1
43
3.0
96
14.8
44
3.0
55
1.0
14
2.0
58
1.0
00
1.9
54
1.9
70
Yogesh and Prabhu/Organic Chemistry/IISc
92
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
5
14.0
8
22.6
4
28.9
7
29.2
4
29.2
8
29.4
1
29.5
1
29.5
6
31.0
1
31.8
5
36.0
6
73.7
6
76.6
8
77.0
0
77.3
2
128.6
2
128.8
4
131.2
4
149.8
8
201.5
7
Yogesh and Prabhu/Organic Chemistry/IISc
93
10 9 8 7 6 5 4 3 2 1 0 ppm
0.9
12
0.9
30
1.2
69
1.3
91
1.4
10
1.4
27
1.4
35
1.4
52
1.4
64
1.4
89
1.4
98
1.5
10
1.5
20
1.5
37
1.5
56
1.5
75
1.7
90
1.8
18
1.8
43
3.6
93
4.0
49
5.0
30
5.0
37
5.0
46
5.0
53
7.1
83
7.2
01
7.2
37
7.2
58
7.3
03
7.3
17
7.3
23
7.8
28
7.8
48
3.1
21
1.1
87
2.1
63
1.0
38
0.8
07
2.1
09
1.0
30
2.1
32
1.3
14
4.1
68
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
94
220 200 180 160 140 120 100 80 60 40 20 0 ppm
13.8
0
18.2
4
38.0
7
41.9
5
72.8
1
76.6
8
77.0
0
77.3
2
126.5
2
128.6
7
128.8
3
128.9
7
129.3
2
131.6
1
139.6
6
147.8
2
201.6
7
Yogesh and Prabhu/Organic Chemistry/IISc
95
9 8 7 6 5 4 3 2 1 0 ppm
0.8
98
0.9
16
0.9
33
1.3
79
1.3
98
1.4
04
1.4
17
1.4
23
1.4
42
1.4
78
1.5
03
1.5
11
1.5
30
1.5
40
1.5
49
1.5
74
1.7
98
1.8
28
1.8
44
2.8
27
2.8
43
3.7
30
5.0
35
5.0
43
5.0
51
5.0
59
7.1
60
7.1
80
7.2
65
7.5
94
7.6
15
7.6
29
3.1
76
1.1
72
2.0
44
5.4
07
4.4
47
0.7
55
1.0
36
1.0
64
1.0
00
1.0
01
Yogesh and Prabhu/Organic Chemistry/IISc
96
220 200 180 160 140 120 100 80 60 40 20 0 ppm
13.8
2
18.1
4
22.6
6
22.7
9
29.3
1
29.6
7
38.1
4
72.6
9
76.6
8
77.0
0
77.3
2
125.5
0
129.3
5
129.5
0
131.0
2
137.8
3
144.2
4
201.9
5
Yogesh and Prabhu/Organic Chemistry/IISc
97
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
53
0.9
71
0.9
90
1.6
11
1.6
28
1.6
46
1.6
64
1.6
82
1.6
99
1.7
17
1.9
51
1.9
69
1.9
78
1.9
87
1.9
96
2.0
03
2.0
14
2.0
22
2.0
32
2.0
50
3.8
25
3.9
37
5.0
99
5.1
08
5.1
13
5.1
23
7.2
53
7.3
67
7.3
84
7.4
00
7.4
15
7.4
33
7.5
70
7.5
87
7.8
23
7.8
42
7.9
25
7.9
45
8.0
85
3.0
48
1.0
56
1.0
68
0.7
01
2.0
72
1.0
00
2.0
34
1.0
19
2.0
27
1.0
05
0.9
79
Yogesh and Prabhu/Organic Chemistry/IISc
98
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
6
29.0
4
36.8
1
73.8
6
76.6
8
77.0
0
77.3
2
119.8
3
120.9
4
125.0
7
125.2
3
127.0
9
127.8
1
128.3
0
131.8
4
140.1
3
143.4
4
144.4
4
147.2
7
201.6
9
Yogesh and Prabhu/Organic Chemistry/IISc
99
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
64
0.9
82
1.0
01
1.5
95
1.6
25
1.6
43
1.6
61
1.6
79
1.6
96
1.7
14
1.9
65
1.9
75
1.9
84
1.9
93
2.0
02
2.0
12
2.0
19
2.0
29
2.0
38
2.0
47
2.0
56
2.0
66
3.7
47
5.1
01
5.1
11
5.1
18
5.1
28
7.2
55
7.3
95
7.4
13
7.4
32
7.4
80
7.4
99
7.5
17
7.6
91
7.7
09
7.8
04
7.8
07
7.8
16
7.8
37
7.8
46
7.8
49
8.0
23
8.0
43
3.0
14
1.2
66
1.0
59
0.7
70
1.0
00
2.0
88
4.1
34
4.1
41
5.0
78
2.0
49
Yogesh and Prabhu/Organic Chemistry/IISc
100
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
8
28.9
3
73.9
7
76.6
8
77.0
0
77.3
2
125.1
6
126.2
8
127.3
1
127.6
9
127.7
6
128.9
2
129.1
5
132.5
5
140.7
1
142.6
5
146.5
8
201.6
0
Yogesh and Prabhu/Organic Chemistry/IISc
101
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
19
0.9
38
0.9
56
1.5
45
1.5
63
1.5
81
1.5
98
1.6
16
1.6
34
1.6
52
1.8
97
1.9
06
1.9
15
1.9
24
1.9
34
1.9
43
1.9
50
1.9
60
1.9
69
1.9
78
1.9
88
3.6
80
4.9
96
5.0
05
5.0
13
5.0
22
5.5
98
7.0
92
7.1
11
7.2
18
7.2
39
7.2
55
7.2
60
7.2
83
7.3
02
7.3
20
7.8
27
7.8
47
3.0
38
1.0
70
1.0
42
0.8
13
1.0
16
1.0
18
4.1
34
8.2
60
2.0
00
7.07.27.47.67.8 ppm
7.092
7.111
7.218
7.239
7.255
7.260
7.283
7.302
7.320
7.827
7.847
4.134
8.260
2.000
Yogesh and Prabhu/Organic Chemistry/IISc
102
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
8.9
08
28.8
91
56.8
15
73.8
64
76.6
83
77.0
01
77.3
19
126.6
99
128.5
01
128.5
95
129.3
26
129.8
74
131.7
65
142.6
96
150.5
03
201.5
45
Yogesh and Prabhu/Organic Chemistry/IISc
103
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
2.8
67
2.8
84
2.9
02
2.9
20
3.1
67
3.1
78
3.2
03
3.2
13
3.7
20
5.3
18
5.3
29
5.3
43
7.1
10
7.1
26
7.2
04
7.2
17
7.2
21
7.2
29
7.2
47
7.2
64
7.4
87
7.5
06
7.5
25
7.6
08
7.6
27
7.6
45
7.9
11
7.9
29
1.0
43
1.0
47
0.8
81
1.0
40
2.0
00
3.0
73
2.0
93
1.0
15
2.0
39
Yogesh and Prabhu/Organic Chemistry/IISc
104
220 200 180 160 140 120 100 80 60 40 20 0 ppm
41.8
7
73.6
9
76.6
8
77.0
0
77.3
2
126.7
6
128.2
7
128.5
6
128.9
0
129.3
9
133.8
0
133.9
6
136.4
2
200.9
7
Yogesh and Prabhu/Organic Chemistry/IISc
105
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
1.4
65
1.4
82
3.6
99
5.1
64
5.1
81
5.1
99
5.2
16
7.2
73
7.6
53
7.6
73
7.6
92
7.8
78
7.8
97
8.1
02
8.1
21
8.2
00
3.2
29
0.9
35
1.0
53
1.0
53
1.0
36
1.0
25
1.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
106
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.9
10
69.5
23
76.6
82
77.0
01
77.3
18
119
.383
122
.095
124
.804
125
.378
125
.419
125
.456
125
.494
127
.511
129
.545
130
.221
130
.257
130
.293
130
.329
131
.127
131
.442
131
.689
131
.700
131
.780
132
.098
134
.028
201
.171
122124126128130132134 ppm
119.383
122.095
124.804
125.378
125.419
125.456
125.494
127.511
129.545
130.221
130.257
130.293
130.329
131.127
131.442
131.689
131.700
131.780
132.098
134.028
Yogesh and Prabhu/Organic Chemistry/IISc
107
-160-140-120-100-80-60-40-200 ppm
-62.9
62
Yogesh and Prabhu/Organic Chemistry/IISc
108
10 9 8 7 6 5 4 3 2 1 ppm
0.0
00
0.9
67
0.9
85
1.0
03
1.6
44
1.6
62
1.6
80
1.6
98
1.7
16
1.9
84
1.9
94
2.0
02
2.0
12
2.0
19
2.0
29
2.0
38
2.0
47
3.7
22
5.1
04
5.1
13
5.1
20
5.1
29
7.2
60
7.4
17
7.4
34
7.4
52
7.4
95
7.5
14
7.5
32
7.6
90
7.7
09
7.8
18
7.8
38
7.8
70
8.0
36
8.0
57
6.1
52
2.3
67
2.0
88
1.5
17
1.9
76
1.0
52
2.0
03
2.0
04
7.0
00
4.0
15
7.27.47.67.88.08.2 ppm7.260
7.417
7.434
7.452
7.495
7.514
7.532
7.690
7.709
7.818
7.838
7.870
8.036
8.057
1.052
2.003
2.004
7.000
4.015
Yogesh and Prabhu/Organic Chemistry/IISc
109
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
8.8
68
28.9
09
74.0
00
76.6
82
77.0
00
77.3
17
125.1
77
126.2
84
127.2
94
127.7
07
128.0
02
129.0
10
129.2
08
132.7
90
140.3
38
141.0
80
143.0
11
146.1
43
201.5
83
Yogesh and Prabhu/Organic Chemistry/IISc
110
10 9 8 7 6 5 4 3 2 1 0 ppm
0.9
27
0.9
46
0.9
64
1.5
54
1.5
71
1.5
89
1.6
07
1.6
25
1.6
43
1.6
61
1.9
05
1.9
15
1.9
23
1.9
33
1.9
42
1.9
51
1.9
59
1.9
68
1.9
77
1.9
86
2.0
05
3.7
02
5.0
09
5.0
19
5.0
24
5.0
32
5.6
60
7.0
89
7.1
07
7.2
37
7.2
58
7.2
80
7.2
98
7.3
19
7.3
38
7.3
55
7.8
58
7.8
78
6.0
85
2.1
10
2.0
67
1.9
47
2.0
18
1.0
09
2.0
48
4.2
30
3.0
33
4.0
00
7.27.4 ppm
7.089
7.107
7.237
7.258
7.280
7.298
7.319
7.338
7.355
2.048
4.230
3.033
Yogesh and Prabhu/Organic Chemistry/IISc
111
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
8.9
09
28.8
58
56.7
89
73.9
16
76.6
82
77.0
00
77.3
17
127.1
56
128.7
67
128.7
84
129.2
59
129.8
23
132.1
66
141.6
06
149.1
95
201.4
84
128130132 ppm
127.156
128.767
128.784
129.259
129.823
132.166
Yogesh and Prabhu/Organic Chemistry/IISc
112
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.2
54
1.3
04
1.3
49
1.3
61
1.4
27
1.4
95
1.5
23
1.5
39
1.5
58
1.5
63
1.6
88
1.7
05
1.7
22
1.8
43
1.8
52
1.8
68
1.8
88
1.8
96
2.9
16
2.9
34
2.9
52
3.6
83
5.0
65
5.0
73
5.0
82
5.0
90
7.2
63
7.4
34
7.4
53
7.4
72
7.4
88
7.5
06
7.5
26
7.5
52
7.5
70
7.6
03
7.6
21
7.6
40
7.9
02
7.9
21
7.9
29
7.9
31
7.9
50
7.9
70
7.9
90
5.4
65
2.4
03
2.2
23
1.2
09
1.8
78
0.8
31
1.0
31
5.1
24
1.1
23
4.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
113
220 200 180 160 140 120 100 80 60 40 20 0 ppm
24.1
0
24.7
5
29.0
7
29.1
4
35.7
6
38.4
1
73.0
0
76.6
8
77.0
0
77.3
2
127.9
6
128.4
6
128.4
9
128.8
3
132.8
4
133.5
8
133.8
9
136.9
4
200.3
8
202.0
7
Yogesh and Prabhu/Organic Chemistry/IISc
114
-18 7 6 5 4 3 2 1 0 ppm
-0.0
00
1.2
30
1.2
43
1.2
54
1.2
76
1.2
94
1.3
10
1.3
30
1.3
38
1.3
47
1.3
56
1.3
73
1.4
01
1.4
25
1.4
52
1.4
82
1.4
95
1.5
04
1.5
23
1.5
39
1.5
47
1.8
00
1.8
09
1.8
25
1.8
31
1.8
53
1.8
63
3.1
78
3.6
74
4.3
94
4.3
95
5.0
25
5.0
37
5.0
44
5.0
51
5.0
63
7.2
70
7.4
76
7.4
95
7.5
15
7.5
99
7.6
19
7.6
38
7.8
78
7.8
97
4.2
83
4.2
47
2.0
69
1.5
84
2.0
43
4.0
53
2.0
00
3.9
99
Yogesh and Prabhu/Organic Chemistry/IISc
115
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
24.5
83
24.7
53
28.8
82
29.0
28
35.5
90
35.6
97
72.9
02
72.9
67
76.6
81
76.9
99
77.3
17
128.4
56
128.8
51
133.5
56
133.9
31
202.0
23
Yogesh and Prabhu/Organic Chemistry/IISc
116
-0.58.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
-0.0
00
0.9
67
0.9
85
1.0
04
1.0
25
1.0
44
1.0
62
1.6
64
1.6
82
1.7
00
1.7
18
1.7
35
1.7
75
1.7
93
1.8
11
1.8
29
1.8
48
1.8
66
1.9
87
1.9
96
2.0
05
2.0
14
2.0
22
2.0
32
2.0
50
2.9
94
3.0
12
3.0
30
3.7
29
3.7
45
5.1
02
5.1
17
5.1
27
5.1
43
7.2
64
7.7
80
7.8
01
7.8
20
7.8
40
7.8
71
7.8
88
8.0
45
8.0
65
8.0
88
8.1
09
3.2
55
6.0
56
1.3
69
4.0
02
1.1
92
4.0
21
1.0
69
1.0
58
4.0
00
2.2
73
2.1
33
1.1
09
2.1
71
4.0
33
7.98.08.1 ppm
7.780
7.801
7.820
7.840
7.871
7.888
8.045
8.065
8.088
8.109
4.000
2.273
2.133
1.109
2.171
4.033
Yogesh and Prabhu/Organic Chemistry/IISc
117
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
8.8
72
13.8
99
17.8
06
28.9
15
40.6
29
74.0
22
76.6
81
76.9
99
77.3
17
126.0
26
126.3
00
127.4
48
127.7
48
128.8
10
129.2
41
132.8
91
136.3
54
141.2
61
141.6
90
144.7
21
145.9
87
199.9
39
201.5
85
Yogesh and Prabhu/Organic Chemistry/IISc
118
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
1.4
34
1.4
52
3.7
25
5.0
90
5.1
07
5.1
25
5.1
42
7.2
77
7.6
44
7.6
65
7.7
88
7.8
09
3.1
92
0.8
54
1.0
34
2.0
00
2.0
25
Yogesh and Prabhu/Organic Chemistry/IISc
119
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.1
2
69.2
6
76.6
8
77.0
0
77.3
2
129.2
1
130.0
4
132.0
0
132.2
0
201.3
7
Yogesh and Prabhu/Organic Chemistry/IISc
120
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.4
42
1.4
60
3.7
06
5.0
93
5.1
11
5.1
28
5.1
46
7.2
79
7.3
73
7.3
93
7.4
13
7.7
37
7.7
56
7.8
29
7.8
49
8.0
67
3.2
23
0.8
92
1.0
30
1.0
22
1.0
00
1.0
32
1.0
02
Yogesh and Prabhu/Organic Chemistry/IISc
121
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.0
3
69.4
1
76.6
8
77.0
0
77.3
2
123.1
7
127.0
6
130.3
8
131.5
4
135.1
0
136.7
4
201.1
4
Yogesh and Prabhu/Organic Chemistry/IISc
122
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
01
1.4
38
1.4
56
5.0
98
5.1
15
5.1
33
5.1
51
7.2
80
7.4
76
7.4
97
7.8
69
7.8
90
3.1
45
1.0
24
2.0
00
2.0
13
Yogesh and Prabhu/Organic Chemistry/IISc
123
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.1
3
69.2
6
76.6
8
77.0
0
77.3
2
129.2
0
129.9
8
131.5
9
140.4
5
201.1
6
Yogesh and Prabhu/Organic Chemistry/IISc
124
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.4
45
1.4
62
5.0
98
5.1
15
5.1
33
5.1
50
7.2
78
7.4
38
7.4
58
7.4
78
7.5
85
7.6
04
7.7
87
7.8
06
7.9
11
3.1
21
1.0
21
1.0
19
1.0
00
1.0
19
1.0
07
Yogesh and Prabhu/Organic Chemistry/IISc
125
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
22.0
4
69.4
5
76.6
8
77.0
0
77.3
2
126.6
3
128.6
2
130.1
6
133.8
4
134.9
0
135.2
2
201.2
3
Yogesh and Prabhu/Organic Chemistry/IISc
126
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.4
52
1.4
69
3.6
87
5.1
01
5.1
18
5.1
36
5.1
53
7.2
76
7.3
12
7.3
29
7.3
49
7.4
74
7.4
93
7.5
08
7.5
27
7.6
21
7.6
44
7.6
97
7.7
16
3.2
06
0.8
14
1.0
17
1.0
00
1.0
16
1.0
22
1.0
01
Yogesh and Prabhu/Organic Chemistry/IISc
127
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.0
8
69.5
0
76.6
8
77.0
0
77.3
2
115.2
8
115.5
0
120.9
0
121.1
1
124.3
1
124.3
4
130.5
4
130.6
2
135.3
3
135.3
9
161.5
7
164.0
4
201.2
4
Yogesh and Prabhu/Organic Chemistry/IISc
128
9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
1.4
28
1.4
45
3.8
99
5.0
72
5.0
89
5.1
07
5.1
32
7.0
25
7.0
47
7.2
53
7.3
43
7.3
60
7.3
78
7.3
96
7.4
15
7.4
34
7.8
98
7.9
19
3.0
90
0.8
46
1.0
36
2.0
19
2.0
00
5.1
17
2.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
129
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.5
8
68.8
4
70.1
9
76.6
8
77.0
0
77.3
2
114.8
6
126.1
8
127.4
3
128.3
0
128.6
9
130.9
9
135.8
7
163.2
5
200.6
1
Yogesh and Prabhu/Organic Chemistry/IISc
130
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.4
41
1.4
58
5.0
86
5.1
03
5.1
20
5.1
37
5.2
05
7.0
63
7.0
84
7.2
67
7.4
57
7.4
76
7.5
08
7.5
27
7.5
46
7.5
66
7.5
95
7.6
14
7.6
37
7.6
56
7.6
75
7.7
61
7.7
79
7.9
28
7.9
49
2.9
59
1.0
08
2.0
13
2.0
00
1.0
73
6.6
28
1.1
46
2.0
02
Yogesh and Prabhu/Organic Chemistry/IISc
131
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.5
2
68.8
0
69.6
5
76.6
8
77.0
0
77.3
2
111.0
7
114.8
1
118.5
7
126.2
5
127.6
5
127.6
8
129.0
4
129.9
2
131.0
0
132.8
4
133.6
9
136.4
3
138.0
2
144.7
2
163.0
5
200.5
6
Yogesh and Prabhu/Organic Chemistry/IISc
132
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
1.4
40
1.4
58
5.0
84
5.1
01
5.1
19
5.1
36
5.2
63
7.0
41
7.0
63
7.2
66
7.6
12
7.6
33
7.9
33
7.9
55
8.2
65
8.2
87
3.0
01
1.0
15
2.0
41
2.0
37
2.1
92
2.0
00
2.0
44
Yogesh and Prabhu/Organic Chemistry/IISc
133
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.4
4
68.6
8
68.8
5
76.6
8
77.0
0
77.3
2
114.7
6
123.8
4
126.6
9
127.5
9
131.0
4
143.2
6
147.6
2
162.4
2
200.5
5
Yogesh and Prabhu/Organic Chemistry/IISc
134
10 9 8 7 6 5 4 3 2 1 ppm
0.0
00
1.4
64
1.4
82
3.8
43
3.8
58
5.1
47
5.1
63
5.1
79
5.1
96
7.2
76
7.3
71
7.3
93
7.5
08
7.5
27
7.5
47
7.6
45
7.6
64
7.6
82
8.0
15
8.0
37
8.1
95
8.2
13
3.0
91
0.9
84
1.0
23
2.0
18
2.0
30
1.0
00
2.0
22
2.0
15
Yogesh and Prabhu/Organic Chemistry/IISc
135
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.2
7
69.2
6
76.6
8
77.0
0
77.3
2
122.2
7
128.6
8
128.8
1
130.2
3
130.3
4
130.8
1
134.0
1
155.2
5
164.4
6
201.0
9
Yogesh and Prabhu/Organic Chemistry/IISc
136
10 9 8 7 6 5 4 3 2 1 ppm
-0.0
00
1.4
74
1.4
91
3.7
36
5.1
42
5.1
59
5.1
77
5.1
94
7.2
15
7.2
37
7.2
41
7.2
63
7.2
87
7.3
06
7.3
25
7.3
94
7.4
16
7.6
16
7.6
20
7.6
28
7.6
34
7.6
36
7.6
50
7.6
59
7.6
67
7.6
71
8.0
23
8.0
45
8.0
92
8.0
96
8.1
11
8.1
14
8.1
29
8.1
33
3.0
12
0.7
73
1.0
04
1.1
60
1.0
63
2.0
17
1.0
00
2.0
29
1.0
51
Yogesh and Prabhu/Organic Chemistry/IISc
137
220 200 180 160 140 120 100 80 60 40 20 0 ppm
22.2
6
69.2
8
76.6
8
77.0
0
77.3
2
117.2
0
117.3
3
117.4
2
122.2
5
124.2
4
124.2
8
130.3
5
130.9
6
132.5
4
135.6
6
135.7
5
154.8
5
161.0
6
161.9
9
162.0
3
163.6
6
201.1
0
Yogesh and Prabhu/Organic Chemistry/IISc
138
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.9
11
0.9
28
0.9
46
1.4
05
1.4
25
1.4
31
1.4
49
1.4
69
1.4
75
1.4
88
1.5
18
1.5
38
1.5
57
1.5
83
1.8
02
1.8
10
1.8
29
1.8
55
3.7
11
5.0
18
5.0
24
5.0
34
5.0
41
7.0
14
7.0
36
7.0
85
7.1
05
7.2
13
7.2
32
7.2
51
7.2
63
7.4
01
7.4
20
7.4
40
7.8
91
7.9
13
3.1
52
1.2
38
2.1
54
1.0
92
0.8
24
1.0
00
2.0
76
2.0
05
1.0
80
2.0
26
2.0
40
Yogesh and Prabhu/Organic Chemistry/IISc
139
220 200 180 160 140 120 100 80 60 40 20 0 ppm
13.8
2
18.2
4
38.2
2
72.6
1
76.6
8
77.0
0
77.3
2
117.2
6
120.4
2
124.9
4
127.9
0
130.1
2
130.8
5
155.0
1
162.7
6
200.5
1
Yogesh and Prabhu/Organic Chemistry/IISc
140
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
01
0.9
03
0.9
22
0.9
40
1.5
30
1.5
48
1.5
66
1.5
83
1.6
01
1.6
19
1.6
37
1.8
71
1.8
81
1.8
90
1.9
00
1.9
09
1.9
18
1.9
26
1.9
35
1.9
44
1.9
54
3.7
11
4.9
62
4.9
71
4.9
78
4.9
87
7.1
83
7.2
04
7.2
65
7.4
18
7.4
25
7.4
33
7.5
19
7.5
25
7.5
30
7.5
33
7.5
42
7.7
56
7.7
77
3.0
97
1.0
67
1.1
04
0.8
84
1.0
04
2.0
44
3.0
31
2.0
00
2.0
23
Yogesh and Prabhu/Organic Chemistry/IISc
141
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
2
28.9
1
73.7
0
76.6
8
77.0
0
77.3
2
126.8
9
128.9
6
129.1
5
129.7
6
130.5
1
131.0
9
134.3
8
146.6
6
200.8
5
Yogesh and Prabhu/Organic Chemistry/IISc
142
9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.9
71
0.9
90
1.0
08
1.6
85
1.7
03
1.7
21
1.7
38
1.7
56
1.7
74
1.7
92
1.9
70
1.9
80
1.9
88
1.9
98
2.0
07
2.0
17
2.0
24
2.0
34
2.0
42
2.0
52
2.0
61
2.0
71
3.5
54
4.8
59
4.8
69
4.8
76
4.8
86
7.1
76
7.1
85
7.1
87
7.1
97
7.2
75
7.7
30
7.7
32
7.7
42
7.7
44
7.7
64
7.7
66
7.7
73
7.7
75
3.1
42
1.2
07
1.0
83
0.8
70
1.0
11
1.0
12
1.0
00
1.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
143
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.9
0
29.8
0
74.8
1
76.6
8
77.0
0
77.3
2
128.3
1
132.8
6
134.6
5
139.8
6
194.4
8
Yogesh and Prabhu/Organic Chemistry/IISc
144
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
57
0.9
76
0.9
94
1.6
77
1.6
95
1.7
13
1.7
31
1.7
48
1.7
67
1.9
39
1.9
48
1.9
57
1.9
67
1.9
76
1.9
85
1.9
93
2.0
02
2.0
11
2.0
21
2.0
29
2.0
39
2.5
64
4.7
97
4.8
06
4.8
14
4.8
24
6.8
45
6.8
54
7.2
75
7.5
77
7.5
87
3.0
47
1.0
42
1.0
53
3.0
63
1.0
00
1.0
13
1.0
11
Yogesh and Prabhu/Organic Chemistry/IISc
145
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.9
0
15.9
8
29.9
7
74.4
2
76.6
8
77.0
0
77.3
2
127.0
2
133.5
2
137.5
8
150.9
6
193.9
0
Yogesh and Prabhu/Organic Chemistry/IISc
146
9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
65
0.9
83
1.0
02
1.6
60
1.6
78
1.6
96
1.7
14
1.7
32
1.7
50
1.7
68
1.9
30
1.9
40
1.9
49
1.9
59
1.9
67
1.9
77
1.9
84
1.9
94
2.0
02
2.0
13
2.0
21
2.0
31
3.4
38
4.7
63
4.7
73
4.7
81
4.7
90
7.1
45
7.1
55
7.2
77
7.5
08
7.5
18
3.2
59
1.1
95
1.1
72
0.9
18
1.0
00
1.0
17
1.0
11
Yogesh and Prabhu/Organic Chemistry/IISc
147
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.9
1
29.7
0
74.6
7
76.6
8
77.0
0
77.3
2
123.9
4
131.3
9
133.1
1
141.3
1
193.4
2
Yogesh and Prabhu/Organic Chemistry/IISc
148
9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.9
57
0.9
76
0.9
94
1.6
49
1.6
67
1.6
85
1.7
02
1.7
20
1.7
38
1.7
56
1.9
22
1.9
32
1.9
41
1.9
51
1.9
59
1.9
69
1.9
76
1.9
86
1.9
95
2.0
05
2.0
13
2.0
23
2.4
23
3.5
45
4.7
40
4.7
50
4.7
58
4.7
68
6.2
15
6.2
24
7.2
22
7.2
31
7.2
87
3.1
94
1.1
37
1.1
53
3.1
72
0.8
72
1.0
08
1.0
02
1.0
00
Yogesh and Prabhu/Organic Chemistry/IISc
149
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
8
14.0
6
29.0
0
73.9
1
76.6
8
77.0
0
77.3
2
109.2
9
120.8
6
148.9
2
158.6
7
189.5
5
Yogesh and Prabhu/Organic Chemistry/IISc
150
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
01
0.9
69
0.9
88
1.0
06
1.6
56
1.6
74
1.6
92
1.7
27
1.7
45
1.7
64
1.9
39
1.9
58
1.9
67
1.9
76
1.9
86
1.9
93
2.0
03
2.0
11
2.0
21
2.0
39
3.2
56
3.8
49
4.7
65
4.7
74
4.7
82
4.7
91
7.3
23
7.3
31
7.3
48
7.7
31
8.2
99
8.3
07
8.3
20
3.0
37
1.0
42
1.1
03
1.1
99
3.0
42
0.9
87
3.1
73
1.0
55
1.0
01
Yogesh and Prabhu/Organic Chemistry/IISc
151
220 200 180 160 140 120 100 80 60 40 20 0 ppm
9.0
3
30.3
3
33.6
5
74.3
6
76.6
8
77.0
0
77.3
2
109.8
4
112.3
9
122.3
0
122.9
3
123.6
5
126.3
0
135.5
8
137.2
6
195.9
0
Yogesh and Prabhu/Organic Chemistry/IISc
152
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0
00
0.9
28
0.9
47
0.9
65
1.6
47
1.6
64
1.6
82
1.7
00
1.7
18
1.7
35
1.9
09
1.9
17
1.9
27
1.9
36
1.9
46
1.9
52
1.9
63
1.9
71
1.9
81
3.6
92
3.7
06
4.7
32
4.7
42
7.2
59
7.4
27
7.4
37
7.4
45
7.4
52
7.4
60
7.4
70
7.5
77
7.5
96
7.6
15
7.6
90
7.7
09
7.7
27
7.7
60
7.7
78
8.0
03
8.2
12
8.2
22
8.2
29
8.2
37
8.2
45
8.2
54
8.3
07
8.3
16
8.3
24
8.3
31
8.3
39
8.3
48
3.0
13
1.2
08
1.0
53
0.9
58
1.0
00
2.1
26
2.1
62
1.1
14
2.0
81
1.0
27
1.0
25
1.0
40
7.67.88.08.28.4 ppm
7.427
7.437
7.445
7.452
7.460
7.470
7.577
7.596
7.615
7.690
7.709
7.727
7.760
7.778
8.003
8.212
8.222
8.229
8.237
8.245
8.254
8.307
8.316
8.324
8.331
8.339
8.348
2.126
2.162
1.114
2.081
1.027
1.025
1.040
Yogesh and Prabhu/Organic Chemistry/IISc
153
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
3
29.7
6
74.9
3
76.6
8
77.0
0
77.3
2
115.8
6
117.2
3
122.3
2
125.5
2
126.2
3
127.3
6
129.0
2
129.5
3
132.9
8
133.1
7
133.3
9
136.2
8
168.4
1
197.5
3
Yogesh and Prabhu/Organic Chemistry/IISc
154
9 8 7 6 5 4 3 2 1 0 ppm
-0.0
00
0.9
28
0.9
47
0.9
65
1.6
26
1.6
44
1.6
62
1.6
79
1.6
97
1.7
15
1.7
33
1.8
90
1.9
01
1.9
09
1.9
19
1.9
27
1.9
38
1.9
44
1.9
55
1.9
62
1.9
73
1.9
81
1.9
92
3.6
86
3.9
17
4.6
89
4.6
99
4.7
05
4.7
15
7.0
26
7.0
32
7.0
48
7.0
55
7.2
66
7.5
72
7.5
90
7.6
10
7.6
82
7.7
01
7.7
19
7.7
49
7.7
67
7.8
16
7.8
22
7.9
47
8.1
16
8.1
39
3.0
06
1.1
46
1.1
45
0.9
43
3.0
49
1.0
07
1.0
94
2.1
33
1.1
26
2.0
36
1.0
46
1.0
38
1.0
00
7.07.27.47.67.88.08.2 ppm
7.026
7.032
7.048
7.055
7.266
7.572
7.590
7.610
7.682
7.701
7.719
7.749
7.767
7.816
7.822
7.947
8.116
8.139
1.094
2.133
1.126
2.036
1.046
1.038
1.000
Yogesh and Prabhu/Organic Chemistry/IISc
155
220 200 180 160 140 120 100 80 60 40 20 0 ppm
8.8
5
29.8
9
55.6
7
74.8
1
76.6
8
77.0
0
77.3
2
104.1
2
115.5
2
116.6
9
116.9
2
128.5
2
128.9
7
129.4
6
130.7
4
132.9
5
133.0
5
133.6
9
157.8
7
168.1
9
197.6
0