Supporting Information A Facile Strategy for …Manjur O. Akram, Saibal Bera and Nitin T. Patil*...

1

Supporting Information

A Facile Strategy for Accessing 3-Alkynylchromones through

Gold-Catalyzed Alkynylation/Cyclization of o-

Hydroxyarylenaminones

Manjur O. Akram, Saibal Bera and Nitin T. Patil*

Contents

1. General information ................................................................................................................ 2

1.1 Practical considerations .................................................................................................... 2

1.2 Instrumentation................................................................................................................. 2

1.3 Materials ........................................................................................................................... 2

2. General procedures ................................................................................................................. 3

2.1 Preparation of substituted o-hydroxy acetophenones....................................................... 3

2.2 General procedure for the synthesis of o-hydroxyarylenaminones .................................. 8

2.3 Procedure for the synthesis of 3-alkynyl chromones (3)................................................ 17

2.4 Procedure for synthetic transformations ........................................................................ 27

3. X-ray crystallography ........................................................................................................... 30

4. NMR Data ............................................................................................................................. 31

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2016

http://onlinelibrary.wiley.com/doi/10.1002/anie.201600840/full

2

1. General information

1.1 Practical considerations

All reactions were carried out in oven dried vials or reaction vessels with magnetic

stirring under argon atmosphere, unless otherwise specified. Dried solvents and liquid reagents

were transferred by oven-dried syringes or hypodermic syringe cooled to ambient temperature in

a desiccators. All experiments were monitored by analytical thin layer chromatography (TLC).

TLC was performed on pre-coated silica gel plates. After elution, plate was visualized under UV

illumination at 254 nm for UV active materials. Further visualization was achieved by staining

KMnO4 and charring on a hot plate. Solvents were removed in vacuum and heated with a water

bath at 35 °C. Silica gel finer than 200 mesh was used for flash column chromatography.

Columns were packed as slurry of silica gel in pet ether and equilibrated with the appropriate

solvent mixture prior to use. The compounds were loaded neat or as a concentrated solution

using the appropriate solvent system. The elution was assisted by applying pressure with an air

pump.

1.2 Instrumentation

Melting points are uncorrected and recorded using digital Büchi Melting Point Apparatus

B-540. 1H NMR and

13C NMR spectra were recorded on Bruker AV, 400/500, JEOL 400 MHz

spectrometers in appropriate solvents using TMS as internal standard or the solvent signals as

secondary standards and the chemical shifts are shown in δ scales. Multiplicities of 1H NMR

signals are designated as s (singlet), br. s (broad singlet), d (doublet), dd (doublet of doublet),

ddd (doublet of doublet of doublet), t (triplet), q (quartet), m (multiplet)… etc. HRMS (ESI) data

were recorded on a Thermo Scientific Q-Exactive, Accela 1250 pump. Single-crystal data was

collected on a Super Nova Dual source X-ray Diffractometer system (Agilent Technologies)

equipped with CCD area detector.

1.3 Materials

Unless otherwise noted, materials obtained from commercial suppliers were used without

further purification. THF was distilled from Na/benzophenone under an atmosphere of dry N2.

DCE, toluene, chloroform, DCM were dried using standard protocol under N2. Gold and silver

salts were purchased from Sigma-Aldrich and stored under inert atmosphere.

3

2. General procedures

2.1 Preparation of substituted o-hydroxy acetophenones

Compounds S1, S2, S3, S4, S5, S6, S7 have been used from commercial sources. Substituted

o-hydroxy acetophenones S8, S9, S10, S11, S12, S13, S14, S15, S16 and S25 have been synthesized using

literature known methods.1 Compounds S17, S18, S19, S20, S21, S22, S23 and S24 were not exist in

the literature and those were synthesized by the following literature known procedures.

Synthesis of compound S17

Compound S17 was prepared by using literature known procedure.2 A solution of 5-bromo-2-

hydroxyacetophenone (S12) (215 mg, 1.00 mmol, 1 equiv) in 10 mL anhydrous DMF was mixed

with of copper cyanide (98 mg, 1.10 mmol, 1.1 equiv) and the resulting mixture was heated for

24 h at 160 °C. The reaction mixture was cooled to room temperature and mixed with ether and

mixture was filtered through celite. The filtrate was concentrated and purified by flash column

chromatography with silica using pet. ether/EtOAc as eluent to afford compound S17.

1 (a) R. Murashige, Y. Hayashi, S. Ohmori, A. Torii, Y. Aizu, Y. Muto, Y. Murai, Y. Oda, M. Hashimoto,

Tetrahedron 2011, 67, 641-649. (b) S. L.-F. Chan, K.-H. Low, C. Yang, S. H.-F. Cheung, C.-M. Che, Chem. Eur. J.

2011, 17, 4709-4714. 2 A. V. Nizovtsev, A. Scheurer, B. Kosog, F. W. Heinemann, K. Meyer, Eur. J. Inorg. Chem. 2013, 2538-2548.

4

Rf: 0.60 (pet. ether/EtOAc = 80/20); 111 mg, Yield: 69%; Physical appearance: Reddish solid;

M. P.: 171 °C; 1H NMR: (500 MHz, CDCl3) = 12.69 (s, 1 H), 8.09 (d, J = 2.3 Hz, 1 H), 7.70

(d, J = 8.8 Hz, 1 H), 7.05 (d, J = 8.8 Hz, 1 H), 2.67 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) =

203.6, 165.3, 138.7, 135.7, 120.0, 119.7, 118.1, 102.6 , 26.6; HRMS: calcd 162.0550 for

C9H8NO2 [M+H]+ found 162.0550.


Compound S17 was prepared by using literature known procedure.3 A 50 mL oven-dried

round bottom flask was evacuated and back-filled with argon and charged with Compound S11

(262 mg, 1.00 mmol), thiophen-2-ylboronic acid (254 mg, 2.00 mmol), K2CO3 (552 mg, 4

mmol), degassed THF (25 mL), and Pd(PPh3)4 (92 mg, 0.08 mmol) were added. The reaction

mixture was stirred at 60 ºC for 10h. The reaction profile was monitored by TLC. The reaction

mixture was cooled to room temperature and mixed with ether and the mixture was filtered

through celite. The filtrate was concentrated and purified by flash column chromatography

through silica using pet. ether/EtOAc as eluent to yield compound S18.

Rf: 0.60 (pet. ether/EtOAc = 95/05); 191 mg, Yield: 88%; Physical appearance: Yellow solid;

M. P.: 53 °C; 1H NMR: (500 MHz, CDCl3) = 12.31 (s, 1 H), 7.90 (d, J = 2.3 Hz, 1 H), 7.69

(dd, J = 2.3, 8.8 Hz, 1 H), 7.31 - 7.24 (m, 1 H), 7.22 (dd, J = 1.0, 3.6 Hz, 1 H), 7.09 (dd, J = 3.6,

5.1 Hz, 1 H), 7.00 (d, J = 8.8 Hz, 1 H), 2.67 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 204.3,

161.7, 142.9, 134.1, 128.0, 127.7, 125.6, 124.3, 122.6, 119.5, 118.8, 26.5; HRMS: calcd

218.0396 for C12H10O2S [M+H]+ found 218.0397.

3 Y. Xie, Y. Liu, G. Gong, A. Rinderspacher, S. X. Deng, D. H. Smith, U. Toebben, E. Tzilianos, L. Branden, D.

Vidovic, C. Chung, S. Schurer, L. Tautz, D. W. Landry, Bioorg. Med. Chem. Lett. 2008, 18, 2840-2844.

5


Compound S19 was prepared by using literature known procedure.3 A 50 mL oven-dried

round bottom flask was evacuated and back-filled with argon and charged with compound S4

(262 mg, 1.00 mmol), benzofuran-2-ylboronic acid (322 mg, 2.00 mmol), K2CO3 (552 mg, 4

mmol), degassed THF (25 mL), and Pd(PPh3)4 (92 mg, 0.08 mmol) were added. The reaction

mixture was stirred at 60 ºC for 12h. The reaction profile was monitored by TLC. The reaction

mixture was cooled to room temperature and mixed with ether. The mixture was filtered through

celite and the filtrate was concentrated and purified by flash column chromatography with silica

gel using pet. ether/EtOAc as eluent to afford compound S19.


M. P.: 134 °C; 1H NMR: (500 MHz, CDCl3) = 12.45 (s, 1 H), 8.19 - 8.12 (m, 1 H), 7.86 (dd, J

= 1.9, 8.8 Hz, 1 H), 7.60 - 7.55 (m, 1 H), 7.55 - 7.49 (m, 1 H), 7.30 (dt, J = 1.3, 7.7 Hz, 1 H),

7.28 - 7.22 (m, 1 H), 7.04 (d, J = 8.4 Hz, 1 H), 6.87 (s, 1 H), 2.69 (s, 3 H); 13

C NMR: (125 MHz,

CDCl3) = 204.5, 162.5, 154.6, 154.6, 132.8, 129.1, 126.7, 124.1, 123.0, 121.7, 120.7, 119.5,

119.0, 110.9, 100.2, 26.6; HRMS: calcd 252.0781 for C16H12O3 [M]+ found 252.0781.

Synthesis of compounds S20

Compound S20 was prepared by using literature known procedure.4 In a 30 mL sealed tube, a

solution of 1-(2-hydroxy-5-iodophenyl)ethan-1-one (S4) (262 mg, 1.00 mmol), Pd(PPh3)2Cl2 (14

mg, 0.02 mmol) and CuI (3.8 mg, 0.02 mmol) in dry Et3N/THF (10 mL, 1:1) was degassed. After

10 min, 1-heptyne (290 µL, 1.10 mmol) was added slowly and mixture was left to stir for 12 h.

After completion of reaction (as monitored by TLC) the reaction mixture was filtered through a

celite pad. The organic layer was evaporated under reduced pressure and the resulting crude

mixture was purified by silica gel column chromatography using pet. ether/EtOAc as eluent.

4 S. H. Lee, Y. B. Kwon, C. M. Yoon, Synth. Commun. 2009, 39, 4069-4078.

6

Rf: 0.60 (pet. ether/EtOAc = 98/02); 177 mg, Yield: 86%; Physical appearance: Yellow liquid;

1H NMR: (500 MHz, CDCl3) δ = 12.29 (s, 1 H), 7.79 (s, 1 H), 7.49 (d, J = 8.8 Hz, 1 H), 6.91 (d,

J = 8.8 Hz, 1 H), 2.63 (s, 3 H), 2.40 (t, J = 7.1 Hz, 2 H), 1.66 - 1.58 (m, 2 H), 1.47 - 1.33 (m, 4

H), 0.93 (t, J = 7.1 Hz, 3 H); 13

C NMR: (125 MHz, CDCl3) δ = 204.2, 161.7, 139.4, 133.8,

119.4, 118.6, 114.9, 89.4, 79.2, 31.2, 28.5, 26.7, 22.2, 19.3, 14.0; HRMS: (ESI) calcd 210.0925

for 231.1380 C15H19O2 [M+H]+ found 231.1380.

Synthesis of compounds S21

Compound S20 was prepared by using literature known procedure.4 In a 50 mL round bottom

flask, a solution of 1-(2-hydroxy-5-iodophenyl)ethan-1-one (S4) (524 mg, 2.00 mmol),

Pd(PPh3)2Cl2 (28 mg, 0.04 mmol) and CuI (7.6 mg, 0.04 mmol) in dry Et3N/THF (20 mL, 1:1)

was degassed. After 10 min, trimethylsilylacetylene (313 µL, 2.20 mmol) was added slowly and

mixture was left to stir for 12 h. After completion of reaction (as monitored by TLC) the reaction

mixture was filtered through a celite pad. The organic layer was evaporated under reduced

pressure and the resulting crude mixture was purified by silica gel column chromatography using

pet. ether/ EtOAc as eluent.

Rf: 0.50 (pet. ether/EtOAc = 98/02); 366 mg, Yield: 79%; Physical appearance: Yellow liquid;

1H NMR: (500 MHz, CDCl3) δ = 12.37 (s, 1 H), 7.86 (d, J = 1.9 Hz, 1 H), 7.55 (dd, J = 2.1, 8.6

Hz, 1 H), 6.91 (d, J = 8.8 Hz, 1 H), 2.64 (s, 3 H), 0.26 (s, 9 H); 13

C NMR: (125 MHz, CDCl3) δ

= 204.1, 162.4, 139.6, 134.5, 119.4, 118.7, 113.9, 103.8, 93.1, 26.6, -0.1; HRMS: (ESI) calcd

233.0992 for C13H16O2Si [M]+ found 233.0994.


Compound S19 (323 mg,1.0 mmol) was dissolved in dry THF, cooled to 0 °C, then 1equiv

1(M) TBAF (1 mL, 1.0 mmol) was slowly added, stirred for 1h. After completion of the reaction

(as monitored by TLC) water was added, the combined organic layer was washed with brine,

7

dried over Na2SO4 and the resulting residue was purified by column chromatography (silica gel,

pet. ether/EtOAc) to give the desired products S22.


M. P.: 105 °C; 1H NMR: (500 MHz, CDCl3) δ = 12.39 (s, 1 H), 7.90 (s, 1 H), 7.57 (d, J = 8.5

Hz, 1 H), 6.94 (d, J = 9.2 Hz, 1 H), 3.03 (s, 1 H), 2.64 (s, 3 H); 13


= 204.0, 162.6, 139.6, 134.8, 119.4, 118.8, 112.8, 82.4, 76.3, 26.6; HRMS: (ESI) calcd

160.0591 for C10H8O2 [M+H]+ found 160.0591.


Compound S22 (107 mg, 0.60 mmol) was taken in a 30 mL sealed tube, AcOH/H2O (10 mL,

1:1) was added, followed by AgBF4 (12 mg, 0.06 mmol, 0.1 equiv). The reaction mixture was

heated at 80 °C for 12 h. After completion of reaction, acetic acid was quenched by NaHCO3.

The combined organic layer was washed with brine, dried over Na2SO4 and the resulting residue

was purified by column chromatography (silica gel, pet. ether/EtOAc) to give the desired product

S23.

Rf: 0.50 (pet. ether/EtOAc = 80/20); 90 mg, Yield: 84%; Physical appearance: White solid; M.

P.: 136 °C; 1H NMR: (500 MHz, CDCl3) δ = 12.67 (s, 1 H), 8.42 (s, 1 H), 8.05 (d, J = 8.5 Hz, 1

H), 7.01 (d, J = 8.5 Hz, 1 H), 2.70 (s, 3 H), 2.58 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) δ =

204.7, 195.6, 166.0, 136.2, 131.8, 128.6, 119.1, 118.5, 26.6, 26.2; HRMS: (ESI) calcd 178.2070

for C10H10O3 [M+H]+ found 178.2061.

Synthesis of 1-(5-benzoyl-2-hydroxyphenyl)ethan-1-one (S24)

1

Compound S20 was prepared by Fries rearrangement of o-hydroxyacetophenone. To a cooled

(0 °C) solution of o-hydroxy acetophenone (1.09 g, 8 mmol) in a 30 mL sealed tube, was added

triflic acid (15 mL) followed by slow addition of benzoyl chloride (0.9 mL, 8 mmol) over 10 min

5 Z.-W. Chen, D.-N. Ye, Y.-P. Qian, M. Ye, L.-X. Liu, Tetrahedron 2013, 69, 6116-6120.

8

under N2 atmosphere. The reaction was kept at room temperature for 12h. The reaction mixture

was allowed to cool to 0 °C and quenched with ice-cold water. The reaction mixture was diluted

with EtOAc (20 mL). The organic layer was washed two times with 2(N) HCl. Then the organic

layer was washed thoroughly with saturated sodium bicarbonate solution and dried over Na2SO4.

The solvent was removed under reduced pressure and resulting residue was purified by column

chromatography (silica gel, pet. ether/EtOAc) to afford S24.

Rf: 0.50 (pet. ether/EtOAc = 90/10); 326 mg, Yield: 17%; Physical appearance: Pale brown

solid; M. P.: 85 °C; 1H NMR: (500 MHz, CDCl3) = 12.68 (br. s., 1 H), 8.32 (d, J = 1.9 Hz, 1

H), 7.91 (dd, J = 2.3, 8.8 Hz, 1 H), 7.78 - 7.68 (m, 2 H), 7.61 - 7.54 (m, 1 H), 7.51 - 7.45 (m, 2

H), 7.00 (d, J = 8.8 Hz, 1 H), 2.64 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 204.6, 194.3,

165.6, 137.9, 137.4, 133.7, 132.2, 129.5, 128.4, 128.3, 119.0, 118.2, 26.5; HRMS: (ESI) calcd

241.0859 for C15H13O3 [M+H]+ found 241.0855.

2.2 General procedure for the synthesis of o-hydroxyarylenaminones

An oven dried sealed tube equipped with a stirring bar, filled with ketones (0.5 mmol),

followed by of N,N-Dimethylformamide dimethyl acetal (DMF-DMA) (2.0 mmol) in toluene (5

mL). The reaction was allowed to stir at 80 °C for 6-8h until the complete conversion of starting

material as monitored by TLC. The reaction mixture was then concentrated and was purified by

flash column chromatography (silica gel, pet. ether/EtOAc) to afford the desired products 1.

Compounds 1i, 1v, 1z were used as such for next step, without further purification.

9

Characterization data

Compound 1a: Rf: 0.30 (pet. ether/EtOAc = 70/30); 87 mg, Yield: 91%; Physical appearance:

Yellow solid; M. P.: 130 °C; 1H NMR: (500 MHz, CDCl3) = 13.98 (s, 1 H), 7.87 (d, J = 12.2

Hz, 1 H), 7.70 (dd, J = 1.1, 8.0 Hz, 1 H), 7.41 - 7.30 (m, 1 H), 7.03 - 6.87 (m, 1 H), 6.87 - 6.71

(m, 1 H), 5.77 (d, J = 12.2 Hz, 1 H), 3.17 (br. s., 3 H), 2.95 (br. s., 3 H); 13

C NMR: (125 MHz,

CDCl3) = 191.4, 162.9, 154.7, 133.9, 128.2, 120.3, 118.1, 117.9, 90.0, 45.3, 37.3; HRMS:

(ESI) calcd 192.1019 for C11H13NO2 [M+H]+ found 192.1021.

Compound 1b: Rf: 0.40 (pet. ether/EtOAc = 70/30); 91 mg, Yield: 89%; Physical appearance:


Hz, 1 H), 7.47 (s, 1 H), 7.16 (d, J = 8.4 Hz, 1 H), 6.83 (d, J = 8.4 Hz, 1 H), 5.76 (d, J = 12.2 Hz,

1 H), 3.16 (br. s., 3 H), 2.96 (br. s., 3 H), 2.29 (s, 3 H); 13


10

191.4, 160.7, 154.6, 134.8, 128.1, 126.8, 119.9, 117.8, 90.0, 45.3, 37.4, 20.6; HRMS: (ESI)

calcd 206.1176 for C12H15NO2 [M+H]+ found 206.1178.

Compound 1c: Rf: 0.40 (pet. ether/EtOAc = 70/30); 94 mg, Yield: 90%; Physical appearance:

Brown solid; M. P.: 144 °C; 1H NMR: (500 MHz, CDCl3) = 13.67 (s, 1 H), 7.89 (d, J = 11.8

Hz, 1 H), 7.35 (dd, J = 3.1, 9.5 Hz, 1 H), 7.07 (dt, J = 3.1, 8.6 Hz, 1 H), 6.87 (dd, J = 4.8, 9.0 Hz,

1 H), 5.65 (d, J = 12.2 Hz, 1 H), 3.20 (s, 3 H), 2.97 (s, 3 H); 13


190.2, 158.9, 155.6-153.7 (d, J = 12.2 Hz), 155.2, 121.1-120.9 (d, J = 12.2 Hz), 120.1-120.0 (d, J

= 5.7 Hz), 119.1-119.0 (d, J = 7.6 Hz), 113.5-113.3 (d, J = 23.8 Hz), 89.7, 45.5, 37.4; HRMS:

(ESI) calcd 210.0925 for C11H12FNO2 [M+H]+ found 210.0916.

Compound 1d: Rf: 0.40 (pet. ether/EtOAc = 70/30); 105 mg, Yield: 94%; Physical

appearance: Yellow solid; M. P.: 142 °C; 1H NMR: (500 MHz, CDCl3) = 13.93 (s, 1 H),

7.89 (d, J = 12.2 Hz, 1 H), 7.63 (d, J = 2.3 Hz, 1 H), 7.29 (dd, J = 2.7, 8.8 Hz, 1 H), 6.88 (d, J =

8.8 Hz, 1 H), 5.68 (d, J = 11.8 Hz, 1 H), 3.21 (s, 3 H), 2.99 (s, 3 H); 13

C NMR: (125 MHz,

CDCl3) = 190.1, 161.4, 155.2, 133.6, 127.5, 122.5, 121.1, 119.7, 89.7 , 45.5, 37.5; HRMS:

(ESI) calcd 226.0629 for C11H13O2NCl [M+H]+ found 226.0633.

Compound 1e: Rf: 0.40 (pet. ether/EtOAc = 70/30); 148 mg, Yield: 94%; Physical appearance:


Hz, 1 H), 7.88 (d, J = 11.8 Hz, 1 H), 7.57 (dd, J = 1.5, 8.8 Hz, 1 H), 6.71 (d, J = 8.8 Hz, 1 H),

5.65 (d, J = 12.2 Hz, 1 H), 3.20 (s, 3 H), 2.99 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 189.8,

162.6, 155.3, 142.1, 136.5, 122.6, 120.7, 89.6, 79.0, 45.5, 37.6; HRMS: (ESI) calcd 317.9985

for C11H13O2NI [M+H]+ found 317.9986.

11

Compound 1f: Rf: 0.40 (pet. ether/EtOAc = 70/30); 124 mg, Yield: 92%; Physical appearance:


Hz, 1 H), 7.77 (d, J = 2.7 Hz, 1 H), 7.41 (dd, J = 2.3, 8.8 Hz, 1 H), 6.83 (d, J = 8.8 Hz, 1 H), 5.67

(d, J = 12.2 Hz, 1 H), 3.21 (s, 3 H), 2.99 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 190.0,

161.9, 155.3, 136.4, 130.5, 121.7, 120.1, 109.5, 89.7, 45.5, 37.6; HRMS: (ESI) calcd 270.0124

for C11H13O2NBr [M+H]+ found 270.0129.

Compound 1g: Rf: 0.30 (pet. ether/EtOAc = 40/60); 66 mg, Yield: 64%; Physical appearance:

Yellow solid; M. P.: 205 °C: ; 1H NMR: (500 MHz, DMSO-d6) = 13.23 (s, 1 H), 8.28 (br. s.,

1 H), 7.76 (d, J = 11.8 Hz, 1 H), 7.09 (br. s., 1 H), 6.90 - 6.73 (m, 1 H), 6.65 (d, J = 8.8 Hz, 1 H),

5.63 (d, J = 12.2 Hz, 1 H), 3.12 (br. s., 3 H), 2.88 (br. s., 3 H); 13


= 190.6, 155.3, 154.2, 148.1, 121.9, 119.7, 117.7, 113.2, 89.6, 44.9, 36.9; HRMS: (ESI) calcd

208.0968 for C11H14O3N [M+H]+ found 208.0970.

Compound 1h: Rf: 0.40 (pet. ether/EtOAc = 60/40); 93 mg, Yield: 85%; Physical appearance:


Hz, 1 H), 7.24 - 7.15 (m, 1 H), 7.00 (dd, J = 2.4, 8.8 Hz, 1 H), 6.88 (d, J = 8.8 Hz, 1 H), 5.71 (d,

J = 12.2 Hz, 1 H), 3.80 (s, 3 H), 3.18 (br. s., 3 H), 2.96 (br. s., 3 H); 13

C NMR: (125 MHz,

CDCl3) δ = 191.0, 157.0, 154.8, 151.2, 120.6, 120.1, 118.6, 112.7, 90.0, 56.1, 45.4, 37.4;

HRMS: (ESI) calcd 222.1125 for C12H16O3N [M+H]+ found 222.1126.

12

Compound 1i: The compound 1i was found to be unstable and used as such without further

purification.

Compound 1j: Rf: 0.30 (pet. ether/EtOAc = 70/30); 103 mg, Yield: 70%; Physical appearance:

Reddish solid; M. P.: 142 °C; 1H NMR: (500 MHz, CDCl3) = 14.81 (br. s., 1 H), 8.36 (br. s.,

1 H), 7.94 (d, J = 12.2 Hz, 1 H), 7.86 - 7.64 (m, 3 H), 7.64 - 7.53 (m, 1 H), 7.53 - 7.39 (m, 2 H),

6.95 (d, J = 8.5 Hz, 1 H), 5.81 (d, J = 11.6 Hz, 1 H), 3.22 (br. s., 3 H), 2.99 (br. s., 3 H); 13

C

NMR: (125 MHz, CDCl3) = 195.2, 190.8, 167.1, 155.4, 138.1, 136.2, 131.9, 131.2, 129.6,

128.2, 127.4, 120.0, 117.8, 89.7, 45.6, 37.6; HRMS: (ESI) calcd 296.1281 for C18H18O3N

[M+H]+ found 296.1283.

Compound 1k: Rf: 0.30 (pet. ether/EtOAc = 60/40); 90 mg, Yield: 77%; Physical appearance:

Yellow solid; M. P.: 112 °C; 1H NMR: (500 MHz, CDCl3) = 14.80 (br. s., 1 H), 8.35 (br. s., 1

H), 7.90 (br. s., 2 H), 6.91 (br. s., 1 H), 5.82 (d, J = 11.8 Hz, 1 H), 3.19 (br. s., 3 H), 2.99 (br. s.,

3 H), 2.54 (br. s., 3 H); 13

C NMR: (125 MHz, CDCl3) = 196.4, 190.7, 167.3, 155.4, 134.2,

129.1, 127.6, 119.7, 118.0, 89.5, 45.5, 37.6, 26.2; HRMS: (ESI) calcd 234.1125 for C13H16O3N

[M+H]+ found 234.1125.

Compound 1l: Rf: 0.30 (pet. ether/EtOAc = 70/30); 96 mg, Yield: 89%; Physical appearance:

Yellow solid; M. P.: 176 °C; 1H NMR: (500 MHz, CDCl3) = 8.04 - 7.96 (m, 1 H), 7.93 (d, J =

11.6 Hz, 1 H), 7.55 (d, J = 8.5 Hz, 1 H), 6.95 (d, J = 8.5 Hz, 1 H), 5.68 (d, J = 12.2 Hz, 1 H),

3.24 (s, 3 H), 3.02 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) δ = 189.3, 166.6, 155.7, 136.3,

133.2, 120.5, 119.5, 119.2, 100.9, 89.2, 45.7, 37.6; HRMS: (ESI) calcd 217.0972 for

C12H13O2N2 [M+H]+ found 217.0972.

13

Compound 1m: Rf: 0.30 (pet. ether/EtOAc = 60/40); 99 mg, Yield: 84%; Physical appearance:

Yellow solid; M. P.: 188 °C; 1H NMR: (500 MHz, CDCl3) = 15.23 (s, 1 H), 8.65 - 8.60 (m, 1

H), 8.22 (dd, J = 2.3, 8.8 Hz, 1 H), 7.98 (d, J = 11.8 Hz, 1 H), 6.98 (d, J = 9.2 Hz, 1 H), 5.79 (d,

J = 11.8 Hz, 1 H), 3.27 (s, 3 H), 3.07 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 189.4, 168.8,

156.0, 138.8, 128.8, 124.7, 119.1, 119.0, 89.1, 45.8, 37.8; HRMS: (ESI) calcd 237.0870 for

C11H13O4N2 [M+H]+ found 237.0870.

Compound 1n: Rf: 0.40 (pet. ether/EtOAc = 70/30); 86 mg, Yield: 84%; Physical appearance:

Greenish-yellow solid; M. P.: 129 °C; 1H NMR: (500 MHz, CDCl3) = 14.04 - 13.90 (m, 1 H),

7.85 (d, J = 12.2 Hz, 1 H), 7.58 (d, J = 8.4 Hz, 1 H), 6.74 (s, 1 H), 6.63 (d, J = 8.0 Hz, 1 H), 5.74

(d, J = 12.2 Hz, 1 H), 3.16 (br. s., 3 H), 2.95 (br. s., 3 H), 2.32 (s, 3 H); 13

C NMR: (125 MHz,

CDCl3) = 191.2, 163.0, 154.4, 145.0, 128.1, 119.2, 118.3, 117.8, 89.9, 45.2, 37.3, 21.7;


Compound 1o: Rf: 0.40 (pet. ether/EtOAc = 60/40); 78 mg, Yield: 71%; Physical appearance:


Hz, 1 H), 7.61 (d, J = 9.2 Hz, 1 H), 6.41 (d, J = 2.3 Hz, 1 H), 6.38 (dd, J = 2.3, 8.8 Hz, 1 H), 5.67

(d, J = 12.2 Hz, 1 H), 3.81 (s, 3 H), 3.16 (br. s., 3 H), 2.94 (br. s., 3 H); 13

C NMR: (125 MHz,

CDCl3) = 190.5, 165.5, 164.3, 154.0, 129.7, 113.8, 106.3, 101.0, 89.7, 55.3, 45.2, 37.3;


14

Compound 1p: Rf: 0.40 (pet. ether/EtOAc = 70/30); 92 mg, Yield: 88%; Physical appearance:

Yellow solid; M. P.: 134 °C; 1H NMR: (500 MHz, CDCl3) = 14.47 - 14.42 (m, 1 H), 7.87 (d,

J = 11.8 Hz, 1 H), 7.70 - 7.65 (m, 1 H), 6.60 (d, J = 10.7 Hz, 1 H), 6.57 - 6.46 (m, 1 H), 5.67 (d,

J = 11.8 Hz, 1 H), 3.19 (br. s., 3 H), 2.97 (br. s., 3 H); 13

C NMR: (125 MHz, CDCl3) = 190.4,

167.0-165.0 (d, J = 252.7 Hz), 165.4-165.2 (d, J = 13.4 Hz), 154.7, 130.2-130.1 (d, J = 11.4 Hz),

117.0 (d, J = 2.9 Hz), 105.8-105.7 (d, J = 21.9 Hz), 104.7-104.5 (d, J = 22.9 Hz), 89.7, 45.4,

37.4; HRMS: (ESI) calcd 210.0925 for C11H13O2NF [M+H]+ found 210.0917.

Compound 1q: Rf: 0.30 (pet. ether/EtOAc = 80/20); 101 mg, Yield: 92%; Physical

appearance: Golden-yellow solid; M. P.: 126 °C; 1H NMR: (500 MHz, CDCl3) = 14.04 (s, 1

H), 7.86 (d, J = 12.2 Hz, 1 H), 7.34 (s, 1 H), 7.07 (s, 1 H), 5.78 (d, J = 12.2 Hz, 1 H), 3.16 (br. s.,

3 H), 2.96 (br. s., 3 H), 2.24 (s, 3 H), 2.27 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 191.8,

159.2, 154.5, 135.9, 126.6, 126.0, 125.6, 119.1, 90.2, 45.2, 37.4, 20.6, 15.6; HRMS: (ESI) calcd

220.1332 for C13H18O2N [M+H]+ found 220.1322.

Compound 1r: Rf: 0.30 (pet. ether/EtOAc = 80/20); 110 mg, Yield: 85%; Physical


7.91 (d, J = 11.7 Hz, 1 H), 7.54 (d, J = 2.0 Hz, 1 H), 7.42 (d, J = 2.0 Hz, 1 H), 5.63 (d, J = 12.2

Hz, 1 H), 3.22 (s, 3 H), 3.00 (s, 3 H); 13

C NMR: (125 MHz, CDCl3) = 189.2, 157.6, 155.9,

133.1, 126.1, 123.2, 122.0, 121.5, 89.4, 45.7, 37.6; HRMS: (ESI) calcd 260.0240 for

C11H12O2NCl2 [M+H]+ found 260.0228.

15

Compound 1s: Rf: 0.30 (pet. ether/EtOAc = 40/60); 65 mg, Yield: 61%; Physical appearance:


Hz, 1 H), 7.84 (s, 1 H), 7.45 (d, J = 8.4 Hz, 1 H), 6.87 (d, J = 8.4 Hz, 1 H), 5.72 (d, J = 11.8 Hz,

1 H), 3.18 (br. s., 3 H), 3.00 (s, 1 H), 2.96 (br. s., 3 H); 13

C NMR: (125 MHz, CDCl3) = 190.4,

163.5, 155.1, 137.2, 132.4, 120.1, 118.5, 111.3, 89.6, 83.6, 75.3, 45.4, 37.5; HRMS: (ESI) calcd

216.1019 for C13H14O2N [M+H]+ found 216.1019.

Compound 1t: Rf: 0.30 (pet. ether/EtOAc = 70/30); 119 mg, Yield: 83%; Physical appearance:

Yellow solid; M. P.: 193 °C; 1H NMR: (500 MHz, CDCl3) = 14.30 (br. s., 1 H), 7.87 (d, J =

11.8 Hz, 1 H), 7.81 (br. s., 1 H), 7.44 (d, J = 8.8 Hz, 1 H), 6.85 (d, J = 8.4 Hz, 1 H), 5.74 (d, J =

12.2 Hz, 1 H), 3.18 (br. s., 3 H), 2.98 (br. s., 3 H), 0.25 (br. s., 9 H); 13

C NMR: (125 MHz,

CDCl3) = 190.5, 163.4, 155.1, 137.3, 132.1, 120.0, 118.4, 112.5, 105.1, 91.9, 89.8, 45.4, 37.5,

0.0; HRMS: (ESI) calcd 288.1414 for C16H22O2NSi [M+H]+ found 288.1414.

Compound 1u: Rf: 0.30 (pet. ether/EtOAc = 80/20); 130 mg, Yield: 91%; Physical


7.88 (d, J = 11.7 Hz, 1 H), 7.74 (s, 1 H), 7.38 (d, J = 8.8 Hz, 1 H), 6.85 (d, J = 8.3 Hz, 1 H), 5.75

(d, J = 12.2 Hz, 1 H), 3.19 (s, 3 H), 2.98 (s, 3 H), 2.39 (t, J = 7.1 Hz, 2 H), 1.61 (quin, J = 7.2 Hz,

2 H), 1.49 - 1.32 (m, 4 H), 0.93 (t, J = 7.1 Hz, 3 H); 13

C NMR: (125 MHz, CDCl3) = 190.7,

162.5, 155.0, 137.0, 131.4, 120.0, 118.3, 113.5, 89.9, 88.3, 80.1, 45.4, 37.5, 31.2, 28.6, 22.2,

19.3, 14.0; HRMS: (ESI) calcd 286.1802 for C18H24O2N [M+H]+ found 286.1801.

Compound 1v: The compound 1v was found to be unstable and used as such without further

purification.

16

Compound 1w: Rf: 0.30 (pet. ether/EtOAc = 70/30); 113 mg, Yield: 94%; Physical

appearance: Brown solid; M. P.: 171 °C; 1H NMR: (500 MHz, CDCl3) = 15.98 (s, 1 H), 8.46

(d, J = 8.4 Hz, 1 H), 7.90 (d, J = 12.2 Hz, 1 H), 7.74 (d, J = 8.0 Hz, 1 H), 7.67 (d, J = 9.2 Hz, 1

H), 7.59 - 7.53 (m, 1 H), 7.52 - 7.46 (m, 1 H), 7.22 (d, J = 8.8 Hz, 1 H), 5.81 (d, J = 11.8 Hz, 1

H), 3.13 (br. s., 3 H), 2.93 (br. s., 3 H); 13

C NMR: (125 MHz, CDCl3) = 191.2, 162.5, 154.5,

136.4, 128.7, 127.1, 125.9, 125.2, 123.9, 117.0, 113.1, 90.1, 45.3, 37.3; HRMS: (ESI) calcd

242.1176 for C15H16O2N [M+H]+ found 242.1165.

Compound 1x: Rf: 0.30 (pet. ether/EtOAc = 70/30); 114 mg, Yield: 84%; Physical

appearance: Yellow solid; M. P.: 120 °C; 1H NMR: (500 MHz, CDCl3) = 14.09 (br. s., 1 H),

7.90 (d, J = 12.2 Hz, 1 H), 7.88 (d, J = 2.3 Hz, 1 H), 7.60 (dd, J = 2.1, 8.6 Hz, 1 H), 7.26 - 7.15

(m, 2 H), 7.06 (dd, J = 3.8, 5.0 Hz, 1 H), 6.96 (d, J = 8.8 Hz, 1 H), 5.80 (d, J = 12.2 Hz, 1 H),

3.18 (br. s., 3 H), 2.98 (br. s., 3 H); 13

C NMR: (125 MHz, CDCl3) = 191.0, 162.6, 155.0,

144.2, 131.9, 127.9, 125.7, 124.7, 123.7, 122.2, 120.3, 118.6, 89.8, 45.4, 37.4; HRMS: (ESI)

calcd 274.0896 for C15H16O2N [M+H]+ found 274.0882.

Compound 1y: Rf: 0.30 (pet. ether/EtOAc = 70/30); 136 mg, Yield: 89%; Physical

appearance: Yellow solid; M. P.: 175 °C; 1H NMR: (500 MHz, CDCl3) = 14.36 (br. s., 1 H),

8.17 (d, J = 1.9 Hz, 1 H), 7.93 (d, J = 12.2 Hz, 1 H), 7.81 (dd, J = 2.1, 8.6 Hz, 1 H), 7.60 - 7.48

(m, 2 H), 7.29 - 7.19 (m, 2 H), 7.02 (d, J = 8.4 Hz, 1 H), 6.89 (s, 1 H), 5.88 (d, J = 12.2 Hz, 1 H),

3.19 (br. s., 3 H), 3.02 (br. s., 3 H); 13

C NMR: (125 MHz, CDCl3) = 190.9, 163.6, 155.8,

17

155.2, 154.6, 130.7, 129.4, 124.6, 123.7, 122.8, 120.7, 120.5, 120.2, 118.8, 110.9, 99.5, 89.8,

45.4, 37.6; HRMS: (ESI) calcd 308.1281 for C19H18O3N [M+H]+ found 308.1265.

Compound 1z: The compound 1z was found to be unstable and used as such without further

purification.

Compound 8: Rf: 0.30 (pet. ether/EtOAc = 40/60); 70 mg, Yield: 81%; Physical appearance:

Yellow solid; M. P.: 89 °C; 1H NMR: (500 MHz, CDCl3) δ= 7.88 (d, J = 6.5 Hz, 2 H), 7.78

(dd, J = 2.1, 10.1 Hz, 1 H), 7.48 - 7.34 (m, 3 H), 5.75 - 5.63 (m, 1 H), 3.10 (br. s., 3 H), 2.89 (br.

s., 3 H); 13

C NMR: (125 MHz, CDCl3) δ = 188.5, 154.1, 140.4, 130.7, 128.0, 127.4, 44.9, 37.2;

HRMS: (ESI) calcd 176.1070 for C11H14ON [M+H]+ found 176.1061.

2.3 Procedure for the synthesis of 3-alkynyl chromones (3):

An oven dried sealed tube equipped with a stirring bar, filled with argon o-

hydroxyarylenaminones (0.2 mmol, 1.0 equiv), TIPS-EBX (0.24 mmol, 1.2 equiv), AuCl (5 mol

%), dry DCE (2.0 mL) were added under a stream of argon flow in the reaction vessel. The

reaction was allowed to stir at room temperature for 12h until and unless noted in the specific

examples. The reaction mixture was then concentrated and resulting residue was purified by

column chromatography (silica gel, pet. ether/EtOAc) to give the desired products 3 (33-96%

yield).

Characterization Data:


Brown liquid; 1H NMR: (500 MHz, CDCl3) δ = 8.25 (dd, J = 1.5, 8.0 Hz, 1 H), 8.18 (s, 1 H),

7.68 (ddd, J = 1.5, 7.2, 8.5 Hz, 1 H), 7.46 (d, J = 8.4 Hz, 1 H), 7.44 - 7.40 (m, 1 H), 1.16 (s, 21

18

H); 13

C NMR: (125 MHz, CDCl3) δ = 175.4, 158.4, 155.9, 133.8, 126.1, 125.7, 123.7, 118.1,

111.6, 97.8, 96.6, 18.6, 11.2; HRMS: (ESI) calcd 327.1775 for C20H27O2Si [M+H]+ found

327.1759.

Compound 3a was synthesized in large scale in decent yield. An oven dried 2-neck round bottom

flask was equipped with a stirring bar, filled with argon o-hydroxyphenylenaminone (0.764 g, 4

mmol, 1.0 equiv), TIPS-EBX (2.05g, 4.8 mmol, 1.2 equiv), AuCl (46 mg, 5 mol%), dry DCE

(40.0 mL) were added under a stream of argon flow in the reaction vessel. The reaction was

allowed to stir at room temperature for 12 h. The reaction mixture was then concentrated and

resulting residue was purified by column chromatography (silica gel, pet. ether/EtOAc) to give

the desired products 3a in 83% yield (1.08 g).


White solid; M. P.: 94 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.14 (s, 1 H), 8.03 - 7.97 (m, 1 H),

7.46 (dd, J = 2.1, 8.6 Hz, 1 H), 7.34 (d, J = 8.4 Hz, 1 H), 2.44 (s, 3 H), 1.15 (s, 21 H); 13

C NMR:

(125 MHz, CDCl3) δ = 175.5, 158.3, 154.2, 135.7, 135.0, 125.4, 123.3, 117.9, 111.3, 97.5, 96.8,

21.0, 18.6, 11.2; HRMS: (ESI) calcd 341.1931for C21H29O2Si [M+H]+ found 341.1909.

Compound 3c: Rf: 0.50 (pet. ether/EtOAc = 95/05); 58 mg, Yield: 84%; Physical appearance:

White solid; M. P.: 95 °C; 1H NMR: (500MHz, CDCl3) δ = 8.18 (s, 1 H), 7.87 (dd, J = 3.1, 8.4

Hz, 1 H), 7.48 (dd, J = 4.2, 9.2 Hz, 1 H), 7.40 (dt, J = 3.1, 8.4 Hz, 1 H), 1.15 (s, 21 H); 13

C

NMR: (125MHz, CDCl3) δ = 174.7, 160.7-158.7 (d, J = 247.0 Hz), 158.5, 152.1, 124.9-124.8

(d, J = 7.6 Hz), 122.2-122.0 (d, J = 25.8 Hz), 120.4-120.3 (d, J = 7.6 Hz), 111.1-110.9 (d, J =

23.8 Hz), 111.0, 98.3, 96.1, 18.6, 11.2; HRMS: (ESI) calcd 345.1681 for C12H13O2N2 (M++ H)

found 345.1675.

19

Compound 3d: Rf: 0.50 (pet. ether/EtOAc = 95/05); 66 mg, Yield: 91%; Physical appearance:

Pale yellow solid; M. P.: 91 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.19 (d, J = 2.7 Hz, 1 H),

8.17 (s, 1 H), 7.61 (dd, J = 2.5, 9.0 Hz, 1 H), 7.42 (d, J = 8.8 Hz, 1 H), 1.16 - 1.14 (m, 21 H); 13

C

NMR: (125 MHz, CDCl3) δ = 174.3, 158.4, 1514.2, 134.1, 131.6, 125.5, 124.5, 119.9, 111.7,

98.5, 96.0, 18.6, 11.2; HRMS: (ESI) calcd 361.1385 for C20H26O2ClSi [M+H]+ found 361.1382.

Compound 3e: Rf: 0.40 (pet. ether/EtOAc = 98/02); 79 mg, Yield: 87%; Physical appearance:

Pale yellow solid; M. P.: 92 °C; 1H NMR: (400 MHz, CDCl3) δ = 8.55 (d, J = 2.0 Hz, 1 H),

8.16 (s, 1 H), 7.92 (dd, J = 2.4, 8.8 Hz, 1 H), 7.22 (d, J = 8.8 Hz, 1 H), 1.15 (s, 21 H); 13

C NMR:

(100 MHz, CDCl3) δ = 173.9, 158.4, 155.3, 142.4, 135.0, 125.2, 120.2, 111.9, 98.6, 96.0, 89.5,

18.6, 11.2; HRMS: (ESI) calcd 453.0741 for C20H26O2ISi [M+H]+ found 453.0732.

Compound 3f: Rf: 0.40 (pet. ether/EtOAc = 98/02); 75 mg, Yield: 92%; Physical appearance:

White solid; M. P.: 88 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.36 (d, J = 2.7 Hz, 1 H), 8.17 (s, 1

H), 7.75 (dd, J = 2.5, 9.0 Hz, 1 H), 7.36 (d, J = 8.8 Hz, 1 H), 1.15 (s, 21 H); 13

C NMR: (125

MHz, CDCl3) δ = 174.1, 158.4, 154.6, 136.8, 128.7, 124.9, 120.1, 119.1, 111.8, 98.6, 96.0, 18.6,

11.2; HRMS: (ESI) calcd 405.0880 for C20H26O2BrSi [M+H]+ found 405.0877.

Compound 3g: Rf: 0.50 (pet. ether/EtOAc = 80/20); 51 mg, Yield: 76%; Physical appearance:

White solid; M. P.: 137 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.21 (s, 1 H), 8.05 (d, J = 2.7 Hz,

1 H), 7.73 (br. s., 1 H), 7.39 (d, J = 9.2 Hz, 1 H), 7.29 (dd, J = 3.1, 9.2 Hz, 1 H), 1.16 (s, 21 H);

20

13C NMR: (125 MHz, CDCl3) δ = 176.5, 158.8, 154.9, 150.5, 124.1, 123.9, 119.5, 110.4, 109.5,

97.7, 96.4, 18.6, 11.2; HRMS: (ESI) calcd 343.1724 for C20H27O3Si [M+H] +

found 343.1717.

Compound 3h: Rf: 0.50 (pet. ether/EtOAc = 90/10); 58 mg, Yield: 82%; Physical appearance:

White solid; M. P.: 101 °C; 1H NMR: (400 MHz, CDCl3) δ = 8.17 (s, 1 H), 7.68 - 7.53 (m, 1

H), 7.39 (d, J = 8.8 Hz, 1 H), 7.28 - 7.22 (m, 1 H), 3.88 (s, 3 H), 1.16 (s, 21 H); 13

C NMR: (100

MHz, CDCl3) δ = 175.4, 158.1, 157.2, 150.7, 124.3, 123.9, 119.6, 110.7, 105.0, 97.6, 96.8,

55.9, 18.6, 11.2; HRMS: (ESI) calcd 357.1880 for C21H29O3Si [M+H]+ found 357.1879.

Compound 3i: Rf: 0.60 (pet. ether/EtOAc = 95/05); 52 mg, Yield: 65%; Physical appearance:

White solid; M. P.: 85 °C; 1H NMR: (500MHz, CDCl3) δ = 8.47 (d, J = 2.3 Hz, 1 H), 8.20 (s, 1

H), 7.92 (dd, J = 2.1, 8.6 Hz, 1 H), 7.64 (d, J = 7.6 Hz, 2 H), 7.53 (d, J = 8.8 Hz, 1 H), 7.48 (t, J

= 7.6 Hz, 2 H), 7.43 - 7.37 (m, 1 H), 1.17 (s, 21 H); 13

C NMR: (125MHz, CDCl3) δ = 175.5,

158.3, 155.3, 139.1, 138.8, 132.7, 129.0, 128.0, 127.1, 123.9, 123.8, 118.7, 111.6, 98.0, 96.6,

18.6, 11.2; HRMS: (ESI) calcd 403.2088 for C12H13O2N2 (M++ H) found 403.2065.

Compound 3j: Rf: 0.40 (pet. ether/EtOAc = 95/05); 61 mg, Yield: 71%; Physical appearance:

Reddish brown solid; M. P.: 103 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.59 (d, J = 2.3 Hz, 1 H),

8.26 (dd, J = 2.3, 8.8 Hz, 1 H), 8.22 (s, 1 H), 7.79 (dd, J = 1.3, 8.2 Hz, 2 H), 7.65 - 7.60 (m, 2 H),

7.53 - 7.48 (m, 2 H), 1.16 - 1.14 (m, 21 H); 13

C NMR: (125 MHz, CDCl3) δ = 194.7, 175.0,

158.3, 158.0, 136.8, 134.8, 132.9, 129.9, 129.1, 128.6, 122.8, 119.1, 112.3, 99.0, 95.8, 18.6,

11.2; HRMS: (ESI) calcd 431.2037 for C27H31O3Si [M+H]+ found 431.2039.

21

Compound 3k: Rf: 0.50 (pet. ether/EtOAc = 90/10); 47 mg, Yield: 64%; Physical appearance:

White solid; M. P.: 93 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.79 (d, J = 1.9 Hz, 1 H), 8.34 -

8.28 (m, 1 H), 8.20 (s, 1 H), 7.53 (d, J = 8.8 Hz, 1 H), 2.68 (s, 3 H), 1.16 (s, 21 H); 13

C NMR:

(125 MHz, CDCl3) δ = 196.2, 175.0, 158.3, 158.3, 134.3, 132.9, 127.6, 123.1, 119.0, 112.2,

99.1, 95.7, 26.6, 18.6, 11.2; HRMS: (ESI) calcd 369.1880 for C22H29O3Si [M+H]+ found

369.1878.

Compound 3l: Rf: 0.55 (pet. ether/EtOAc = 95/05); 23 mg, Yield: 33%; Physical appearance:

White solid; M. P.: 113 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.56 (d, J = 2.3 Hz, 1 H), 8.20 (s,

1 H), 7.90 (dd, J = 1.9, 8.8 Hz, 1 H), 7.59 (d, J = 8.8 Hz, 1 H), 1.16 - 1.14 (m, 21 H); 13

C NMR:

(125 MHz, CDCl3) δ = 173.6, 158.4, 157.5, 136.1, 131.8, 124.0, 119.9, 117.3, 112.7, 110.0,

99.8, 95.2, 18.6, 11.2; HRMS: (ESI) calcd 352.1727 for C21H26O2NSi [M+H]+ found 352.1717.

Compound 3l′: Hydration product 3l′ was obtained alongwith with 3l.

Rf: 0.50 (pet. ether/EtOAc = 95/05); 15 mg, Yield: 21%; Physical appearance: White solid; M.

P.: 152 °C; 1H NMR: (500 MHz, CDCl3) δ = 10.54 (s, 1 H), 8.57 (d, J = 1.9 Hz, 1 H), 7.93 (dd,

J = 2.1, 8.6 Hz, 1 H), 7.48 (d, J = 8.8 Hz, 1 H), 1.23 - 1.16 (m, 3 H), 1.10 - 1.07 (m, 18 H); 13

C

NMR: (125 MHz, CDCl3) δ = 190.2, 180.5, 175.5, 157.0, 136.8, 131.5, 124.5, 119.1, 117.2,

116.0, 110.2, 19.0, 18.4, 11.9; HRMS: (ESI) calcd 370.1833 for C21H28O3NSi [M+H]+ found

370.1823.

22

Compound 3m: Rf: 0.60 (pet. ether/EtOAc = 90/10); 36 mg, Yield: 49%; Physical appearance:

White solid; M. P.: 110 °C; 1H NMR: (500 MHz, CDCl3) δ = 9.12 (d, J = 2.7 Hz, 1 H), 8.51

(dd, J = 2.7, 9.2 Hz, 1 H), 8.22 (s, 1 H), 7.63 (d, J = 9.2 Hz, 1 H), 1.17 - 1.15 (m, 21 H); 13

C

NMR: (125 MHz, CDCl3) δ = 173.9, 158.6, 158.3, 145.1, 128.2, 123.7, 122.9, 120.0, 112.5,

100.2, 95.0, 18.6, 11.2; HRMS: (ESI) calcd 372.1626 for C20H26O4NSi [M+H]+ found

372.1627.

Compound 3n: Rf: 0.50 (pet. ether/EtOAc = 98/02); 58 mg, Yield: 85%; Physical appearance:

Brown solid; M. P.: 84 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.18 - 8.08 (m, 2 H), 7.26 - 7.17

(m, 2 H), 2.48 (s, 3 H), 1.15 (s, 21 H); 13

C NMR: (125 MHz, CDCl3) δ = 175.3, 158.2, 156.0,

145.3, 127.2, 125.9, 121.5, 117.9, 111.5, 97.5, 96.8, 21.8, 18.6, 11.3; HRMS: (ESI) calcd

341.1931 for C21H29O2Si [M+H]+ found 341.1930.

Compound 3o: Rf: 0.50 (pet. ether/EtOAc = 95/05); 58 mg, Yield: 81%; Physical appearance:

White solid; M. P.: 76 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.14 (d, J = 9.2 Hz, 1 H), 8.11 (s, 1

H), 7.03 - 6.93 (m, 1 H), 6.83 (br. s., 1 H), 3.90 (s, 3 H), 1.15 (s, 21 H); 13

C NMR: (125 MHz,

CDCl3) δ = 174.7, 164.1, 158.0, 157.6, 127.5, 117.5, 114.9, 111.5, 100.4, 97.5, 96.7, 55.8, 18.6,

11.2; HRMS: (ESI) calcd 357.1880 for C21H29O3Si [M+H]+ found 357.1881.

Compound 3p: Rf: 0.60 (pet. ether/EtOAc = 98/02); 60 mg, Yield: 87%; Physical appearance:

Yellow liquid; 1H NMR: (500MHz, CDCl3) δ = = 8.30 - 8.21 (m, 1 H), 8.15 (br. s., 1 H), 7.14

(d, J = 8.4 Hz, 2 H), 1.15 (br. s., 21 H); 13

C NMR: (125MHz, CDCl3) δ = 174.5, 166.6-164.6

(d, J = 256.5 Hz), 158.4, 156.9-156.8 (d, J = 13.4 Hz), 128.8-128.7 (d, J = 11.4 Hz), 120.5,

23

114.6-114.4 (d, J = 22.9 Hz), 111.9, 105.0-104.8 (d, J = 25.8 Hz), 98.4, 96.0, 18.6, 11.2; HRMS:

(ESI) calcd 345.1681 for C12H13O2N2 (M++ H) found 345.1679.

Compound 3q: Rf: 0.50 (pet. ether/EtOAc = 98/02); 63 mg, Yield: 89%; Physical appearance:

White solid; M. P.: 126 °C; 1H NMR: (400 MHz, CDCl3) δ = 8.19 (s, 1 H), 7.84 (s, 1 H), 7.31

(s, 1 H), 2.42 (s, 3 H), 2.40 (s, 3 H), 1.15 (s, 21 H); 13

C NMR: (100 MHz, CDCl3) δ = 175.8,

158.1, 152.7, 136.1, 135.1, 127.2, 123.3, 123.0, 111.1, 97.3, 97.0, 20.9, 18.6, 15.3, 11.2; HRMS:

(ESI) calcd 355.2088 for C22H31O2Si [M+H]+ found 355.2086.

Compound 3r: Rf: 0.40 (pet. ether/EtOAc = 98/02); 66 mg, Yield: 84%; Physical appearance:

White solid; M. P.: 83 °C; 1H NMR: (500 MHz, CDCl3) δ =

1H NMR (500MHz

,CHLOROFORM-d) = 8.23 (s, 1 H), 8.11 (d, J = 2.3 Hz, 1 H), 7.72 (d, J = 2.3 Hz, 1 H), 1.15

(s, 21 H); 13

C NMR: (125 MHz, CDCl3) δ = 173.7, 158.2, 150.3, 134.1, 131.4, 125.4, 124.5,

124.2, 112.1, 99.5, 95.4, 18.6, 11.2; HRMS: (ESI) calcd 395.0995 for C20H25O2Cl2Si [M+H]+

found 395.0995.

Compound 3s: Rf: 0.60 (pet. ether/EtOAc = 95/05); 33 mg, Yield: 47%; Physical appearance:

White solid; M. P.: 99 °C; 1H NMR: (500MHz, CDCl3) δ = 88.36 (d, J = 1.9 Hz, 1 H), 8.16 (s,

1 H), 7.74 (dd, J = 1.9, 8.8 Hz, 1 H), 7.42 (d, J = 8.8 Hz, 1 H), 3.15 (s, 1 H), 1.15 (s, 21 H); 13

C

NMR: (125MHz, CDCl3) δ = 174.5, 158.3, 155.5, 137.0, 130.2, 123.5, 120.0, 118.6, 111.9,

98.4, 96.1, 81.8, 78.6, 18.6, 11.2; HRMS: (ESI) calcd 351.1775 for C12H13O2N2 (M++ H) found

351.1777.

24

Compound 3t: Rf: 0.60 (pet. ether/EtOAc = 98/02); 64 mg, Yield: 76%; Physical appearance:

Yellow liquid; 1H NMR: (500 MHz, CDCl3) δ = 8.32 (d, J = 1.9 Hz, 1 H), 8.14 (s, 1 H), 7.70

(dd, J = 2.1, 8.6 Hz, 1 H), 7.38 (d, J = 8.8 Hz, 1 H), 1.15 (s, 21 H), 0.27 (s, 9 H); 13

C NMR: (125

MHz, CDCl3) δ = 174.5, 158.3, 155.3, 136.8, 129.9, 123.5, 121.1, 118.4, 111.8, 103.0, 98.3,

96.2, 96.0, 18.6, 11.2, -0.2; HRMS: (ESI) calcd 423.2170 for C25H35O2Si2 [M+H]+ found

423.2162.

Compound 3u: Rf: 0.70 (pet. ether/EtOAc = 98/02); 75 mg, Yield: 89%; Physical appearance:

Yellow liquid; 1H NMR: (400 MHz, CDCl3) δ = 8.23 (d, J = 2.0 Hz, 1 H), 8.14 (s, 1 H), 7.63

(dd, J = 2.0, 8.8 Hz, 1 H), 7.36 (d, J = 8.3 Hz, 1 H), 2.41 (t, J = 7.1 Hz, 2 H), 1.47 - 1.33 (m, 4

H), 0.93 (t, J = 7.1 Hz, 3 H); 13

C NMR: (100 MHz, CDCl3) δ = 174.7, 158.2, 154.8, 136.7,

129.0, 123.5, 122.1, 118.2, 111.6, 98.0, 96.4, 92.1, 79.0, 31.1, 28.2, 22.2, 19.3, 18.6, 14.0, 11.2;

HRMS: (ESI) calcd 420.6781 for C27H37O2Si [M+H]+ found 420.6780.

Compound 3v: Rf: 0.60 (pet. ether/EtOAc = 98/02); 48 mg, Yield: 64%; Physical appearance:

White solid; M. P.: 94 °C; 1H NMR: (500MHz, CDCl3) δ = 10.07 (d, J = 8.4 Hz, 1 H), 8.22 (s,

1 H), 8.08 (d, J = 9.2 Hz, 1 H), 7.90 (d, J = 8.0 Hz, 1 H), 7.78 - 7.72 (m, 1 H), 7.63 (t, J = 7.4 Hz,

1 H), 7.49 (d, J = 9.2 Hz, 1 H), 1.19 (s, 21 H); 13

C NMR: (125MHz, CDCl3) δ = 176.9, 157.1,

156.2, 135.7, 130.7, 130.4, 129.5, 128.2, 127.4, 126.9, 117.4, 117.1, 114.2, 98.0, 97.0, 18.7,

11.3; HRMS: (ESI) calcd 377.1931 for C12H13O2N2 (M++ H) found 377.1915.

25

Compound 3w: Rf: 0.60 (pet. ether/EtOAc = 98/02); 61 mg, Yield: 81%; Physical appearance:

Pale yellow liquid solid; M. P.: 109 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.45 (d, J = 8.0 Hz, 1

H), 8.36 (s, 1 H), 8.17 (d, J = 8.8 Hz, 1 H), 7.93 (d, J = 8.0 Hz, 1 H), 7.78 (d, J = 8.8 Hz, 1 H),

7.75 - 7.65 (m, 2 H), 1.18 (s, 21 H); 13

C NMR: (125 MHz, CDCl3) δ = 175.3, 157.6, 153.3,

135.8, 129.5, 128.1, 127.3, 125.8, 123.8, 122.2, 120.8, 120.0, 112.9, 98.5, 96.5, 18.7, 11.2;

HRMS: (ESI) calcd 377.1931 for C24H29O2Si [M+H]+ found 377.1906.

Compound 3x: Rf: 0.40 (pet. ether/EtOAc = 95/05); 56 mg, Yield: 68%; Physical appearance:

White solid; M. P.: 169 °C; 1H NMR: (400 MHz, CDCl3) δ = 8.42 (d, J = 2.4 Hz, 1 H), 8.14 (s,

1 H), 7.87 (dd, J = 2.1, 8.9 Hz, 1 H), 7.44 (d, J = 9.2 Hz, 1 H), 7.37 (d, J = 3.1 Hz, 1 H), 7.32 (d,

J = 4.9 Hz, 1 H), 7.09 (dd, J = 3.7, 4.9 Hz, 1 H), 1.17 (s, 21 H); 13


= 175.2, 158.2, 154.9, 142.1, 132.2, 131.3, 128.3, 125.9, 124.1, 123.8, 122.1, 118.8, 111.5, 98.1,

96.4, 18.6, 11.2; HRMS: (ESI) calcd 409.1652 for C24H29O2SSi [M+H]+ found 409.1625.

Compound 3y: Rf: 0.40 (pet. ether/EtOAc = 95/05); 71 mg, Yield: 79%; Physical appearance:

White solid; M. P.: 205 °C; 1H NMR: (400 MHz, CDCl3) δ = 8.67 (s, 1 H), 8.23 - 8.03 (m, 2

H), 7.60 (d, J = 7.8 Hz, 1 H), 7.52 (dd, J = 2.2, 8.1 Hz, 2 H), 7.35 - 7.28 (m, 1 H), 7.28 - 7.21 (m,

1 H), 7.09 (s, 1 H), 1.18 (s, 21 H); 13

C NMR: (100 MHz, CDCl3) δ = 175.1, 158.2, 155.5,

155.0, 153.8, 130.1, 128.9, 128.3, 124.8, 123.8, 123.2, 122.0, 121.2, 118.9, 111.7, 111.3, 102.6,

98.3, 96.4, 18.6, 11.2; HRMS: (ESI) calcd 443.2037 for C28H31O3Si [M+H]+ found 443.2038.

Compound 3z: Rf: 0.45 (pet. ether/EtOAc = 95/05); 28 mg, Yield: 37% (over two steps);

Physical appearance: White solid; M. P.: 97 °C; 1H NMR: (200 MHz, CDCl3) δ = 8.28 (s, 1

H), 8.11 - 8.01 (m, 1 H), 7.91 (dd, J = 1.5, 6.9 Hz, 1 H), 7.57 (m, 2 H), 1.17 (s, 21 H); 13

C NMR:

26

(125 MHz, CDCl3) δ = 172.0, 156.9, 153.3, 147.0, 139.4, 129.1, 125.4, 123.8, 122.0, 113.4,

111.0, 99.7, 95.7, 18.6, 11.2; HRMS: (ESI) calcd 383.1496 for C22H27O2SSi [M+H]+ found

383.1496.

Compound 3z′: Hydration product 3z′ was obtained alongwith 3z.

Rf: 0.40 (pet. ether/EtOAc = 95/05); 20 mg, Yield: 25% (over two steps); Physical appearance:

White solid; M. P.: 139 °C; 1H NMR: (500 MHz, CDCl3) δ = 10.63 (s, 1 H), 7.99 (d, J = 8.0

Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7.64 - 7.60 (m, 1 H), 7.58 - 7.54 (m, 1 H), 3.22 (s, 2 H), 1.27

- 1.20 (m, 3 H), 1.12 (d, J = 7.2 Hz, 18 H); 13

C NMR: (125 MHz, CDCl3) δ = 190.9, 178.6,

174.4, 152.7, 139.7, 129.1, 128.6, 125.6, 125.0, 124.0, 121.6, 116.4, 18.5, 17.9, 11.8; HRMS:

(ESI) calcd 401.1601 for C22H29O3SSi [M+H]+ found 401.1595.


White solid; M. P.: 91 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.25 (dd, J = 1.9, 8.0 Hz, 1 H),

8.17 (s, 1 H), 7.68 (ddd, J = 1.5, 7.1, 8.6 Hz, 1 H), 7.46 (d, J = 8.4 Hz, 1 H), 7.44 - 7.41 (m, 1 H),

1.02 (s, 9 H), 0.21 (s, 6 H); 13

C NMR: (125 MHz, CDCl3) δ = 175.3, 158.6, 155.9, 133.9, 126.2,

125.7, 123.7, 118.2, 111.4, 99.6, 95.3, 26.1, 16.7, -4.7; HRMS: (ESI) calcd 285.1305 for

C17H21O2Si [M+H]+ found 285.1305.


White solid; M. P.: 131 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.30 (dd, J = 1.5, 8.0 Hz, 1 H),

8.28 (s, 1 H), 7.93 - 7.89 (m, 4 H), 7.70 (ddd, J = 1.9, 7.1, 8.6 Hz, 1 H), 7.48 (d, J = 8.4 Hz, 1 H),

7.47 - 7.44 (m, 1 H), 7.44 - 7.41 (m, 6 H), 1.20 (s, 9 H); 13


27

175.3, 158.8, 155.9, 135.7, 134.0, 132.9, 129.5, 127.7, 126.1, 125.8, 123.7, 118.2, 111.3, 98.9,

96.6, 27.1, 18.7; HRMS: (ESI) calcd 409.1618 for C27H25O2Si [M+H]+ found 409.1615.

Compound 9: Compound 9 was found to be highly unstable. Rf: 0.50 (pet. ether/EtOAc =

50/50); 50 mg, Yield: 68%; Physical appearance: Yellow liquid; 1H NMR: (500 MHz, CDCl3)

δ = 7.71 - 7.58 (m, 3 H), 7.28 - 7.16 (m, 3 H), 3.47 (br. s., 3 H), 3.07 (br. s., 3 H), 0.83 (s, 21 H);

13C NMR: (125 MHz, CDCl3) δ = 194.8, 156.1, 140.3, 130.0, 128.5, 127.4, 105.0, 98.1, 91.0,

47.4, 38S.5, 18.5, 11.4; HRMS: (ESI) calcd 356.2404 for C22H34ONSi [M+H]+ found 356.2400.

2.4 Procedure for synthetic transformations

a) Procedure for synthesis of 3-ethynyl-4H-chromen-4-one (10)

Entry Reagent Additives

(1 equiv)

Temp Time (h) Yield (%)

1 K2CO3 - rt 3 -

2 TBAF - 0 °C 1 -

3 TBAF HF.py 0 °C 12 -

4 TBAF CF3SO3H 0 °C – rt 6 trace

5 TBAF MsOH 0 °C – rt 6 -

6 TBAF TsOH 0 °C – rt 6 -

7 TBAF CH3COOH 0 °C – rt 6 trace

8 TBAF CF3COOH 0 °C – rt 6 trace

9 TBAF CSA 0 °C – rt 3 79

28

To a stirred solution of 3a (978 mg, 3.00 mmole) and CSA (696 mg, 3.00 mmole) in THF (15

mL) was added TBAF (1.0 M in THF, 3.3 mL, 3.30 mmol) at 0 °C. The reaction mixture was

stirred for 3h at room temperature. The mixture was quenched by addition of water, extracted

with EtOAc (3 × 5 mL) and the combined organic layer was evaporated in vacuo. Obtained

crude product was purified by column chromatography (silica gel, pet. ether/EtOAc) to afford

10.

Rf: 0.40 (pet. ether/EtOAc = 80/20); 403 mg, Yield: 79%; Physical appearance: White solid;

M. P.: 123 °C; 1H NMR: (500 MHz, CDCl3) δ = 8.29 - 8.25 (m, 1 H), 8.20 (s, 1 H), 7.70 (ddd, J

= 1.5, 7.1, 8.6 Hz, 1 H), 7.49 - 7.43 (m, 2 H), 3.29 (s, 1 H); 13


175.4, 159.0, 155.9, 134.1, 126.2, 125.9, 123.5, 118.2, 110.3, 83.2, 74.0; HRMS: (ESI) calcd

171.0441 for C11H7O2 [M+H]+ found 171.0433.

c) Procedure for synthesis of triazole 11

To a solution of CuSO4.5H2O (10.0 mg, 0.04 mmol), sodium ascorbate (15.8 mg, 0.08 mmol),

in tBuOH/H2O (1:1 v/v, 2.0 mL) was added a mixture of alkyne 10 (40 mg, 0.22 mmol) and

benzyl azide (30 mg, 0.22 mmol) at room temperature. The resultant mixture was stirred for 1 h.

Then CH2Cl2 (5 mL) was added to dissolve the crude product. The organic layer was washed

with H2O followed by brine, dried over Na2SO4 and evaporated in vacuo. The crude product was

purified by a column chromatography (silica gel, pet. ether/EtOAc) to give triazole 11.



= 1.5, 7.1, 8.6 Hz, 1 H), 7.49 - 7.43 (m, 2 H), 3.29 (s, 1 H); 13


175.4, 159.0, 155.9, 134.1, 126.2, 125.9, 123.5, 118.2, 110.3, 83.2, 74.0; HRMS: (ESI) calcd

304.1081 for C18H14O2N3 [M+H]+ found 304.1081.

b) Procedure for synthesis of internal alkyne 12

29

To a stirred solution of iodobenzene (40 mg, 0.20 mmol), PdCl2(PPh3)2 (2.8 mg, 0.004 mmol,

2 mol %), CuI (1.15 mg, 0.006 mmol, 3 mol%) in dry THF:NEt3 (5:1, 2 mL) was added 10 (35

mg, 0.20 mmol). The mixture was stirred at room temperature for 2h. After completion of the

reaction, the reaction mixture was filtered through celite pad and evaporated in vacuo. The crude

product was purified by column chromatography (silica gel, pet. ether/EtOAc) to give the desired

product 12.



= 1.5, 7.1, 8.6 Hz, 1 H), 7.49 - 7.43 (m, 2 H), 3.29 (s, 1 H); 13

C NMR: (125MHz, CDCl3) δ =

175.4, 159.0, 155.9, 134.1, 126.2, 125.9, 123.5, 118.2, 110.3, 83.2, 74.0; HRMS: (ESI) calcd

247.0754 for C17H11O2 [M+H]+ found 247.0744.

d) Procedure for synthesis of 3-(benzofuran-2-yl)-chromone 13

To a stirred solution of 2-iodophenol (40 mg, 0.20 mmol), PdCl2(PPh3)2 (2.8 mg, 0.004mmol,

2 mol %), CuI (1.15 mg, 0.006 mmol, 3 mol%) in dry THF:NEt3 (5:1, 2 mL) was added 10 (35

mg, 0.20 mmol). The mixture was stirred at 60 °C for 12h. After completion of the reaction, the

reaction mixture was filtered through celite pad and evaporated in vacuo. The crude product was

purified by column chromatography (silica gel, pet. ether/EtOAc) to give the desired a product

13.



= 1.5, 7.1, 8.6 Hz, 1 H), 7.49 - 7.43 (m, 2 H), 3.29 (s, 1 H); 13


175.4, 159.0, 155.9, 134.1, 126.2, 125.9, 123.5, 118.2, 110.3, 83.2, 74.0; HRMS: (ESI) calcd

263.0703 for C17H11O3 [M+H]+ found 263.0696.

30

e) Procedure for synthesis of 3-cyanochromone 146

An oven-dried screw cap reaction tube was charged with a magnetic stir-bar, 10 (0.5 mmol),

tBuONO (1.0 mmol, 103 mg, 119 µL) and 2-picoline-N-oxide (1.0 mmol, 109 mg) under N2

atmosphere. Then, 2 mL of dry THF was added using syringe at the end. The reaction mixture

was stirred vigorously on a preheated oil bath at 70 °C for 12h (monitored by TLC). After

evaporation of the solvent, the crude product was purified by column chromatography (silica gel,

pet. ether/EtOAc) to give the desired a product 14.



= 1.5, 7.1, 8.6 Hz, 1 H), 7.49 - 7.43 (m, 2 H), 3.29 (s, 1 H); 13


175.4, 159.0, 155.9, 134.1, 126.2, 125.9, 123.5, 118.2, 110.3, 83.2, 74.0; HRMS: (ESI) calcd

172.0393 for C10H6NO2 [M+H]+ found 172.0385.

3. X-ray crystallography

Compound Structure ORTEP Diagram

CCDC 1498524

6 Dutta, U.; Lupton, D. W.; Maity, D. Org. Lett. 2016, 18, 860-863.

31

4. NMR Data

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0

Chemical Shif t (ppm)

3.0

9

1.0

0

1.0

0

1.0

1

0.9

6

CHLOROFORM-d

12

.69

8.0

97

.70

7.6

97

.27

7.0

67

.04

2.6

7

-0.0

2

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

3.5

6

16

5.3

5

13

8.6

81

35

.72

11

9.9

61

19

.73

11

8.0

6

10

2.6

1

77

.26

77

.00

76

.75

26

.56

32

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

4

1.0

0

1.0

0

1.0

0

0.9

8

1.0

1

1.0

0

0.9

3

CHLOROFORM-d

12

.31

7.8

9

7.2

87

.27

7.2

27

.22

7.1

07

.09

7.0

97

.01

6.9

9

2.6

7

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.3

0

16

1.6

7

14

2.9

31

34

.07

12

7.9

91

27

.66

12

5.6

51

24

.28

12

2.5

61

19

.51

11

8.8

5

77

.26

77

.00

76

.75

26

.50

33

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

3

1.0

0

1.0

0

1.0

6

1.0

3

1.0

0

0.9

9

1.0

1

1.0

0

0.9

2

CHLOROFORM-d

12

.45

8.1

6

7.5

67

.53

7.5

27

.52

7.3

07

.27

7.2

57

.04

7.0

36

.87

2.6

9

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.4

5

16

2.5

3

15

4.5

7

13

2.8

21

29

.12

12

6.7

21

24

.13

12

3.0

21

21

.70

12

0.7

11

19

.50

11

8.9

51

10

.94

10

0.2

1

77

.26

77

.00

76

.75

26

.62

34

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

4.0

52

.11

2.0

0

3.0

4

0.9

9

1.0

0

0.9

9

0.9

9

CHLOROFORM-d

12

.29

7.7

97

.50

7.4

87

.27

6.9

26

.90

2.6

32

.41

2.4

02

.38

1.6

21

.60

1.4

41

.42

1.4

00

.95

0.9

40

.92

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.1

9

16

1.6

8

13

9.3

8

13

3.8

1

11

9.4

01

18

.56

11

4.8

7

89

.37

79

.18

77

.32

77

.00

76

.69

31

.15

28

.45

26

.66

22

.23

19

.29

13

.99

35

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


9.0

0

3.0

5

1.0

1

1.0

2

1.0

0

0.9

5

CHLOROFORM-d

12

.37

7.8

67

.56

7.5

47

.27

6.9

26

.90

2.6

42

.63

0.2

6

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.1

0

16

2.4

1

13

9.6

0

13

4.5

4

11

9.3

51

18

.67

11

3.9

0

10

3.7

9

93

.13

77

.26

77

.00

76

.74

26

.65

-0.0

6

36

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

4

0.9

0

0.9

8

0.9

8

1.0

0

0.8

8

CHLOROFORM-d

12

.39

7.9

07

.58

7.5

67

.27

6.9

56

.93

3.0

3

2.6

4

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.0

3

16

2.6

0

13

9.5

9

13

4.7

7

11

9.4

31

18

.82

11

2.7

5

82

.45

77

.31

77

.00

76

.69

76

.26

26

.62

37

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

3.0

0

0.9

7

1.0

0

1.0

1

0.9

0

CHLOROFORM-d

12

.67

8.4

28

.06

8.0

4

7.2

77

.02

7.0

0

2.7

02

.58

-0.0

2

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.7

5

19

5.6

4

16

5.9

6

13

6.2

51

31

.77

12

8.5

61

19

.12

11

8.5

0

77

.32

77

.00

76

.69

26

.65

26

.21

38

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

2

1.0

0

1.9

9

1.0

1

1.9

7

1.0

0

0.9

9

0.9

1

CHLOROFORM-d

12

.68

8.3

28

.32

7.9

27

.90

7.7

47

.73

7.7

27

.58

7.5

07

.48

7.0

17

.00

2.6

4

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

20

4.5

8

19

4.3

1

16

5.6

1

13

7.9

41

37

.37

13

3.7

41

32

.25

12

9.5

01

28

.39

12

8.3

01

19

.03

11

8.1

6

77

.26

77

.00

76

.75

26

.53

39

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

0

3.0

5

1.0

8

1.0

1

0.9

4

1.0

0

1.0

6

1.0

1

0.9

3

CHLOROFORM-d

13

.98

7.8

87

.86

7.7

07

.69

7.6

97

.35

6.9

46

.92

6.9

26

.83

6.8

2

5.7

85

.76

3.1

72

.95

0.0

0

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

19

1.4

1

16

2.8

8

15

4.7

0

13

3.8

8

12

8.1

8

12

0.2

61

18.1

31

17.9

3

89

.96

77

.25

77

.00

76

.74

45

.32

37

.34

40

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

4

3.0

6

3.0

5

1.0

4

0.9

5

0.9

9

1.0

6

1.0

0

1.0

2

CHLOROFORM-d

13

.75

7.8

67

.84

7.4

77

.27

7.1

77

.15

6.8

46

.83

5.7

75

.75

3.1

62

.96

2.2

9

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

1.4

1

16

0.6

5

15

4.6

1

13

4.8

2

12

8.0

91

26

.83

11

9.8

71

17

.83

89

.98

77

.26

77

.00

76

.74

45

.26

37

.36

20

.58

41

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

33

.07

1.0

5

1.0

0

1.0

3

1.0

6

1.0

4

1.0

1

CHLOROFORM-d

13

.67

7.9

07

.88

7.3

67

.35

7.3

37

.08

7.0

76

.89

6.8

86

.87

6.8

65

.66

5.6

4

3.2

02

.97

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

19

0.1

8

15

8.8

91

55

.58

15

5.1

51

53

.70

12

1.0

71

20

.89

12

0.0

51

20

.01

11

9.0

81

19

.02

11

3.4

71

13

.28

89

.70

77

.25

77

.00

76

.74

45

.45

37

.44

42

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

2.9

7

0.9

9

0.9

2

0.9

0

0.9

5

0.9

6

0.9

0

CHLOROFORM-d

13

.93

7.9

17

.88

7.6

37

.30

7.2

97

.27

7.2

76

.89

6.8

7

5.6

95

.67

3.2

12

.99

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.0

6

16

1.4

3

15

5.2

5

13

3.5

81

27

.54

12

2.4

71

21

.06

11

9.6

7

89

.67

77

.26

77

.00

76

.75

45

.50

37

.54

43

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

13

.02

1.0

0

1.0

0

1.0

0

1.0

1

1.0

0

1.0

1

CHLOROFORM-d

14

.02

7.9

37

.89

7.8

67

.58

7.5

67

.27

6.7

26

.71

5.6

65

.64

3.2

02

.99

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

18

9.7

9

16

2.5

6

15

5.2

6

14

2.0

7

13

6.5

5

12

2.5

51

20

.66

89

.64

78

.96

77

.25

77

.00

76

.74

45

.50

37

.57

44

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

2

3.0

1

1.0

4

0.9

6

0.9

6

1.0

2

1.0

0

0.9

6

CHLOROFORM-d

13

.97

7.9

07

.88

7.7

77

.42

7.4

17

.27

6.8

46

.82

5.6

85

.66

3.2

12

.99

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

18

9.9

6

16

1.9

0

15

5.2

8

13

6.3

8

13

0.5

2

12

1.7

11

20

.15

10

9.5

4

89

.67

77

.26

77

.00

76

.75

45

.51

37

.57

45

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0

3.0

1

3.0

1

1.0

1

0.9

5

1.0

0

1.0

0

1.0

3

0.9

9

0.9

8

DMSO-d6

13

.23

8.2

87

.77

7.7

57

.38

7.0

96

.85

6.8

46

.83

6.6

56

.64

5.6

55

.62

3.1

22

.88

2.7

32

.50

200 180 160 140 120 100 80 60 40 20 0

DMSO-d6CHLOROFORM-d

19

0.5

8

15

5.3

31

54

.23

14

8.0

8

12

1.8

61

19

.67

11

7.6

91

13

.23

89

.60

77

.25

77

.00

76

.74

44

.89

40

.08

39

.92

39

.75

39

.58

39

.41

39

.24

39

.08

36

.91

46

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

43

.01

3.0

1

1.0

1

0.9

4

1.0

0

1.0

1

1.0

0

0.9

7

CHLOROFORM-d

13

.41

7.8

97

.86

7.2

77

.19

7.1

97

.00

6.9

96

.98

6.8

96

.87

5.7

35

.70

3.8

0

3.1

82

.96

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

1.0

4

15

7.0

41

54

.84

15

1.2

1

12

0.6

11

20

.15

11

8.6

31

12

.66

89

.99

77

.32

77

.00

76

.69

56

.10

45

.37

37

.40

47

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

0

3.0

1

1.0

0

0.9

6

1.9

6

1.0

0

2.9

4

1.0

1

1.0

0

0.9

3

CHLOROFORM-d

14

.81

8.3

67

.92

7.7

97

.77

7.7

57

.59

7.5

67

.51

7.4

97

.47

6.9

66

.94

5.8

35

.80

3.2

22

.99

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

5.2

11

90

.75

16

7.1

4

15

5.3

9

13

8.1

41

36

.22

13

1.9

21

31

.24

12

9.6

41

28

.21

12

7.4

31

19

.96

11

7.7

8

89

.70

77

.26

77

.00

76

.75

45

.56

37

.63

48

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

3.0

4

3.0

5

1.0

0

0.9

5

2.0

0

1.0

3

0.9

4

CHLOROFORM-d

14

.80

8.3

5

7.9

0

7.2

7

6.9

1

5.8

35

.81

3.1

92

.99

2.5

4

-0.0

3

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

6.3

9

19

0.7

0

16

7.2

7

15

5.4

0

13

4.1

61

29

.10

12

7.5

91

19

.71

11

8.0

3

89

.51

77

.26

77

.00

76

.75

45

.51

37

.61

26

.21

49

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

7

3.0

8

1.0

4

1.0

0

0.9

4

1.0

3

1.0

3

0.6

4

CHLOROFORM-d

14

.74

7.9

97

.99

7.9

47

.91

7.5

67

.54

7.2

76

.96

6.9

45

.70

5.6

7

3.2

43

.02

-0.0

1

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

18

9.2

7

16

6.6

2

15

5.7

5

13

6.3

31

33

.18

12

0.5

41

19

.55

11

9.2

2

10

0.9

4

89

.19

77

.31

77

.00

76

.68

45

.66

37

.64

50

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

5

3.0

2

1.0

2

1.0

1

1.0

5

1.0

0

1.0

8

0.9

9

CHLOROFORM-d

15

.23

8.6

28

.23

8.2

28

.21

7.9

97

.97

7.2

76

.98

6.9

7

5.8

05

.78

3.2

73

.07

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

18

9.3

9

16

8.8

3

15

6.0

4

13

8.8

1

12

8.8

41

24

.68

11

9.1

31

19

.00

89

.13

77

.25

77

.00

76

.74

45

.79

37

.84

51

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

3.0

1

3.0

7

1.0

2

1.0

0

0.9

1

1.0

3

0.9

6

0.9

4

CHLOROFORM-d

13

.98

7.8

67

.84

7.5

97

.57

7.2

7

6.7

46

.64

6.6

25

.76

5.7

3

3.1

62

.95

2.3

2

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

1.2

2

16

2.9

7

15

4.3

7

14

5.0

2

12

8.0

9

11

9.1

71

18

.29

11

7.8

4

89

.92

77

.25

77

.00

76

.74

45

.25

37

.31

21

.66

52

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

7

3.0

4

3.0

1

1.0

6

1.0

0

0.9

4

1.0

61

.00

0.9

8

CHLOROFORM-d

14

.49

7.8

47

.82

7.6

27

.60

7.2

7

6.4

16

.39

6.3

86

.37

6.3

75

.69

5.6

6

3.8

1

3.1

62

.94

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.5

5

16

5.5

11

64

.29

15

3.9

7

12

9.6

6

11

3.8

3

10

6.3

4

10

0.9

9

89

.74

77

.26

77

.00

76

.75

55

.31

45

.23

37

.27

53

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

9

3.0

8

1.0

8

1.0

0

0.9

1

1.0

4

1.0

0

1.0

1

CHLOROFORM-d

14

.45

14

.45

7.8

87

.86

7.6

97

.68

7.6

67

.27

6.6

26

.59

6.5

46

.53

6.5

26

.50

5.6

85

.65

3.1

92

.97

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.3

9

16

7.0

41

65

.35

16

5.2

51

65

.03

15

4.7

5

13

0.1

71

30

.08

11

7.0

5

10

5.8

51

05

.67

10

4.6

61

04

.48

89

.69

77

.25

77

.00

76

.74

45

.40

37

.38

54

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


6.0

2

3.0

0

2.9

9

1.0

3

0.9

9

1.0

1

0.9

9

0.9

1

CHLOROFORM-d

14

.04

7.8

77

.84

7.3

47

.27

7.0

7

5.8

05

.77

3.1

62

.96

2.2

72

.24

0.0

1

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

1.7

8

15

9.1

6

15

4.4

7

13

5.8

61

26

.60

12

6.0

01

25

.61

11

9.0

7

90

.24

77

.32

77

.00

76

.69

45

.24

37

.35

20

.60

15

.59

55

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

0

3.0

0

1.0

0

0.9

1

1.0

0

1.0

0

1.0

0

CHLOROFORM-d

14

.92

7.9

27

.89

7.5

37

.43

7.4

27

.27

5.6

45

.61

3.2

23

.00

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

18

9.1

9

15

7.5

91

55

.87

13

3.1

0

12

6.0

71

23

.23

12

2.0

01

21

.52

89

.39

77

.32

77

.00

76

.69

45

.67

37

.63

56

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

2

1.0

1

3.0

3

1.0

7

1.0

2

0.9

9

1.0

7

1.0

3

1.0

1

CHLOROFORM-d

14

.30

7.8

87

.86

7.8

47

.46

7.4

47

.27

6.8

86

.86

5.7

35

.71

3.1

83

.00

2.9

6

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.3

6

16

3.5

2

15

5.1

4

13

7.1

8

13

2.3

7

12

0.0

71

18

.49

11

1.3

5

89

.65

83

.60

77

.25

77

.00

76

.74

75

.27

45

.44

37

.47

57

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


9.0

0

3.0

33

.06

1.0

6

1.0

1

1.0

0

1.0

2

1.0

5

1.0

1

CHLOROFORM-d

14

.30

7.8

87

.86

7.8

17

.45

7.4

37

.27

6.8

66

.84

5.7

55

.73

3.1

82

.98

0.2

5

220 200 180 160 140 120 100 80 60 40 20 0 -20


CHLOROFORM-d

19

0.4

7

16

3.3

9

15

5.1

0

13

7.2

91

32

.06

11

9.9

71

18

.38

11

2.4

8

10

5.0

7

91

.87

89

.78

77

.25

77

.00

76

.74

45

.42

37

.53

0.0

2

58

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

4.0

9

2.1

4

2.0

3

3.0

0

3.0

3

1.0

3

1.0

0

1.0

0

1.0

1

1.0

0

0.9

8

CHLOROFORM-d

14

.13

7.8

97

.86

7.7

47

.39

7.3

77

.27

6.8

66

.84

5.7

65

.73

3.1

92

.98

2.4

12

.39

2.3

71

.61

1.6

01

.43

1.4

21

.37

0.9

40

.93

0.9

1

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.7

4

16

2.5

4

15

4.9

6

13

6.9

7

13

1.4

1

12

0.0

11

18

.31

11

3.4

9

89

.89

88

.26

80

.10

77

.31

77

.00

76

.68

45

.41

37

.48

31

.16

28

.58

22

.22

19

.35

13

.98

59

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

2

3.0

5

1.0

5

1.0

2

1.0

3

1.0

0

1.0

2

1.0

3

1.0

3

1.0

0

1.0

4CHLOROFORM-d

15

.98

8.4

78

.45

7.9

17

.89

7.7

57

.73

7.6

87

.66

7.5

67

.49

7.2

37

.21

5.8

25

.80

3.1

32

.93

0.0

2

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

1.1

7

16

2.5

1

15

4.4

7

13

6.4

11

28

.65

12

7.1

31

25

.90

12

5.1

71

23

.93

11

6.9

71

13

.13

90

.13

77

.25

77

.00

76

.74

45

.26

37

.29

60

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

4

3.0

1

1.0

1

1.0

0

1.0

3

2.0

0

1.0

0

1.0

3

1.0

8

1.0

1

CHLOROFORM-d

14

.09

7.9

17

.89

7.8

87

.23

7.2

27

.20

7.1

97

.07

7.0

66

.97

6.9

55

.81

5.7

8

3.1

82

.98

0.0

1

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.9

9

16

2.5

8

15

5.0

3

14

4.1

81

31

.87

12

7.8

81

25

.74

12

4.7

31

23

.74

12

2.1

81

20

.29

11

8.6

3

89

.77

77

.26

77

.00

76

.75

45

.39

37

.44

61

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0


3.0

1

3.0

1

1.0

2

0.9

7

0.9

6

2.1

3

1.9

7

1.0

0

1.0

0

1.0

2

0.9

9

CHLOROFORM-d

14

.36

8.1

77

.94

7.9

27

.80

7.5

57

.52

7.5

17

.26

7.2

27

.03

7.0

16

.89

5.8

95

.87

3.1

93

.02

0.0

2

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.9

5

16

3.5

81

55

.78

15

5.1

71

54

.56

13

0.6

81

29

.43

12

4.6

11

23

.68

12

2.8

41

20

.71

12

0.5

21

20

.25

11

8.7

91

10

.85

99

.53

89

.83

77

.25

77

.00

76

.74

45

.42

37

.55

62

11 10 9 8 7 6 5 4 3 2 1 0


3.0

3

3.0

2

1.0

5

3.0

0

1.0

0

2.0

1

CHLOROFORM-d

7.8

97

.88

7.7

67

.43

7.4

27

.41

7.4

17

.40

7.3

97

.38

5.7

15

.71

5.6

95

.68

3.1

02

.89

-0.0

1

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

18

8.5

0

15

4.1

1

14

0.4

4

13

0.7

41

27

.99

12

7.3

5

77

.25

77

.00

76

.75

44

.85

37

.16

63

11 10 9 8 7 6 5 4 3 2 1 0


21

.01

1.0

4

0.9

9

1.0

2

0.9

0

0.9

9

CHLOROFORM-d

8.2

58

.24

8.2

48

.18

7.6

87

.66

7.4

77

.45

7.4

47

.42

7.2

7

1.1

6

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.4

4

15

8.4

21

55

.91

13

3.8

5

12

6.1

51

25

.68

12

3.6

91

18

.15

11

1.6

2

97

.76

96

.56

77

.25

77

.00

76

.74

18

.64

11

.24

8.25 8.20 8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40

1.0

4

0.9

9

1.0

2

0.9

0

0.9

9

64

11 10 9 8 7 6 5 4 3 2 1 0


21

.00

3.0

1

1.0

0

1.0

1

1.0

0

0.9

5

CHLOROFORM-d

8.1

48

.00

7.4

77

.47

7.4

67

.45

7.3

47

.33

7.2

7

2.4

4

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.4

7

15

8.3

01

54

.16

13

5.6

91

35

.04

12

5.3

81

23

.31

11

7.8

7

11

1.3

2

97

.47

96

.81

77

.25

77

.00

76

.74

20

.95

18

.62

11

.23

8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35

1.0

3

1.0

8

1.0

2

1.0

2

65

11 10 9 8 7 6 5 4 3 2 1 0

21

.13

1.0

3

1.0

2

1.0

1

0.9

7

CHLOROFORM-d

8.1

87

.88

7.8

87

.87

7.8

67

.49

7.4

87

.47

7.4

07

.40

7.2

7

1.1

5

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

17

4.7

2

16

0.6

81

58

.72

15

8.4

61

52

.13

12

4.9

01

24

.84

12

2.2

21

22

.02

12

0.3

31

11

.09

11

1.0

21

10

.90

98

.30

96

.09

77

.25

77

.00

76

.74

18

.62

11

.21

8.20 8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35

1.0

3

1.0

2

1.0

1

0.9

7

66

11 10 9 8 7 6 5 4 3 2 1 0


21

.02

1.0

1

0.9

9

0.9

0

0.9

9

CHLOROFORM-d

8.1

98

.18

8.1

77

.62

7.6

27

.60

7.4

37

.42

7.2

7

1.1

51

.14

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.2

7

15

8.4

11

54

.18

13

4.0

81

31

.62

12

5.4

71

24

.53

11

9.9

2

11

1.6

6

98

.52

95

.96

77

.25

77

.00

76

.74

18

.60

11

.18

8.20 8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40

1.0

1

0.9

9

0.9

0

0.9

9

67

11 10 9 8 7 6 5 4 3 2 1 0


21

.00

1.0

8

1.0

5

1.0

2

1.0

0

CHLOROFORM-d

8.5

68

.55

8.1

67

.94

7.9

37

.92

7.9

17

.27

7.2

37

.21

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

3.9

0

15

8.3

61

55

.30

14

2.4

0

13

5.0

1

12

5.1

7

12

0.2

0

11

1.8

9

98

.62

96

.00

89

.55

77

.31

77

.00

76

.68

18

.60

11

.19

8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2

1.0

8

1.0

5

1.0

2

1.0

0

68

11 10 9 8 7 6 5 4 3 2 1 0


21

.10

1.0

0

1.0

1

0.9

6

0.9

5

CHLOROFORM-d

8.3

68

.35

8.1

77

.76

7.7

67

.74

7.7

47

.37

7.3

57

.27

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.1

1

15

8.3

91

54

.65

13

6.8

4

12

8.7

31

24

.93

12

0.1

31

19

.11

11

1.8

1

98

.62

95

.98

77

.26

77

.00

76

.75

18

.62

11

.21

8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

1.0

0

1.0

1

0.9

6

0.9

5

69

11 10 9 8 7 6 5 4 3 2 1 0


21

.07

1.0

0

0.9

6

0.9

6

1.0

0

0.8

7

CHLOROFORM-d

8.2

18

.05

8.0

57

.73

7.4

07

.39

7.3

07

.30

7.2

87

.28

7.2

7

1.1

6

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

6.5

2

15

8.8

51

54

.90

15

0.4

5

12

4.1

31

23

.89

11

9.5

3

11

0.4

41

09

.53

97

.66

96

.41

77

.25

77

.00

76

.74

18

.65

11

.24

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3

1.0

1

1.0

1

1.0

4

1.0

3

0.9

0

70

11 10 9 8 7 6 5 4 3 2 1 0


21

.09

3.0

3

1.0

2

1.0

1

1.0

1

0.9

2

CHLOROFORM-d

8.1

77

.61

7.6

07

.40

7.3

87

.27

7.2

67

.25

3.8

8

1.1

6

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.4

3

15

8.0

91

57

.19

15

0.7

2

12

4.2

61

23

.89

11

9.5

8

11

0.6

7

10

5.0

39

7.6

09

6.7

5

77

.31

77

.00

76

.68

55

.87

18

.62

11

.22

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2

1.0

2

1.0

1

1.0

1

0.9

2

71

11 10 9 8 7 6 5 4 3 2 1 0

21

.02

1.0

0

2.0

0

1.0

0

2.0

0

1.0

0

0.8

8

0.9

3

CHLOROFORM-d

8.4

78

.47

8.2

07

.91

7.6

57

.64

7.5

47

.53

7.4

97

.48

7.4

67

.40

1.1

7

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

17

5.5

1

15

8.3

41

55

.27

13

9.0

71

38

.83

13

2.6

91

29

.01

12

7.9

71

27

.13

12

3.8

81

23

.79

11

8.6

71

11

.60

97

.99

96

.57

77

.25

77

.00

76

.74

18

.65

11

.24

8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

1.0

0

2.0

0

1.0

0

2.0

0

1.0

0

0.8

8

0.9

3

72

11 10 9 8 7 6 5 4 3 2 1 0


21

.07

2.0

9

2.0

8

1.9

9

0.9

8

1.0

4

1.0

0

CHLOROFORM-d

8.5

98

.26

8.2

58

.22

7.8

07

.80

7.7

87

.78

7.6

27

.60

7.5

27

.50

7.2

7

1.1

51

.15

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

4.7

4

17

4.9

6

15

8.3

21

57

.98

13

6.8

41

34

.77

13

2.8

91

29

.92

12

9.1

21

28

.57

12

2.7

61

19

.08

11

2.2

8

99

.02

95

.77

77

.25

77

.00

76

.74

18

.60

11

.19

8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5

2.0

9

2.0

8

1.9

9

0.9

8

1.0

4

1.0

0

73

11 10 9 8 7 6 5 4 3 2 1 0


21

.00

3.0

1

1.0

0

0.9

0

1.0

0

1.0

0

CHLOROFORM-d

8.7

98

.79

8.3

28

.31

8.3

08

.30

8.2

07

.54

7.5

37

.27

2.6

8

1.1

6

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

6.1

8

17

4.9

9

15

8.3

1

13

4.3

31

32

.89

12

7.5

71

23

.08

11

9.0

3

11

2.2

2

99

.14

95

.74

77

.25

77

.00

76

.74

26

.57

18

.60

11

.19

8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

1.0

0

0.9

0

1.0

0

1.0

0

74

11 10 9 8 7 6 5 4 3 2 1 0


21

.01

1.0

1

1.0

0

0.9

0

0.8

6

CHLOROFORM-d

8.5

68

.20

7.9

17

.91

7.8

97

.89

7.5

97

.58

7.2

7

1.1

51

.15

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

3.5

6

15

8.3

91

57

.54

13

6.1

11

31

.78

12

4.0

31

19

.94

11

7.3

11

12

.70

11

0.0

0

99

.83

95

.15

77

.26

77

.00

76

.75

18

.60

11

.18

8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6

1.0

1

1.0

0

0.9

0

0.8

6

75

11 10 9 8 7 6 5 4 3 2 1 0


18

.10

3.1

1

1.0

1

1.0

0

0.8

5

0.8

5

CHLOROFORM-d

10

.54

8.5

77

.94

7.9

37

.92

7.9

27

.49

7.4

77

.27

1.2

31

.21

1.2

01

.19

1.1

81

.17

1.0

91

.08

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.1

9

18

0.5

3

17

5.5

5

15

7.0

1

13

6.8

3

13

1.4

6

12

4.4

61

19

.06

11

7.2

11

15

.97

11

0.2

4

77

.26

77

.00

76

.75

19

.03

18

.39

11

.92

8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

1.0

1

1.0

0

0.8

5

76

11 10 9 8 7 6 5 4 3 2 1 0


21

.01

1.0

0

0.9

4

1.0

0

0.8

8

CHLOROFORM-d

9.1

29

.12

8.5

28

.52

8.5

18

.50

8.2

2

7.6

47

.62

7.2

7

1.1

61

.15

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

3.9

0

15

8.5

91

58

.31

14

5.0

8

12

8.1

71

23

.74

12

2.9

21

20

.03

11

2.5

4

10

0.1

8

95

.00

77

.25

77

.00

76

.74

18

.60

11

.19

9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6

1.0

0

0.9

4

1.0

0

0.8

8

77

11 10 9 8 7 6 5 4 3 2 1 0


21

.12

3.0

3

2.0

2

1.9

3

CHLOROFORM-d

8.1

38

.13

8.1

17

.27

7.2

47

.22

2.4

8

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.3

2

15

8.2

31

56

.04

14

5.2

9

12

7.1

91

25

.89

12

1.4

51

17

.86

11

1.4

9

97

.50

96

.78

77

.26

77

.00

76

.75

21

.79

18

.65

11

.25

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2

2.0

2

1.9

3

78

11 10 9 8 7 6 5 4 3 2 1 0


21

.25

3.0

1

0.9

81

.00

0.8

6

0.9

9

CHLOROFORM-d

8.1

58

.13

8.1

1

7.2

76

.98

6.9

86

.97

6.8

3

3.9

0

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.7

4

16

4.1

4

15

8.0

41

57

.63

12

7.5

4

11

7.5

41

14

.89

11

1.5

0

10

0.3

89

7.4

99

6.7

4

77

.25

77

.00

76

.74

55

.83

18

.64

11

.23

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8

0.9

8

1.0

0

0.8

6

0.9

9

79

11 10 9 8 7 6 5 4 3 2 1 0


21

.20

2.0

0

0.9

0

1.0

0

CHLOROFORM-d

8.2

78

.26

8.1

5

7.2

77

.15

7.1

3

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.4

6

16

6.6

31

64

.59

15

8.4

31

56

.88

15

6.7

8

12

8.7

91

28

.70

12

0.5

41

14

.62

11

4.4

41

11

.86

10

4.9

91

04

.79

98

.35

96

.01

77

.25

77

.00

76

.74

18

.61

11

.20

8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1

2.0

0

0.9

0

1.0

0

80

11 10 9 8 7 6 5 4 3 2 1 0


21

.02

3.0

2

3.0

4

1.0

1

1.0

1

0.9

6

CHLOROFORM-d

8.1

9

7.8

4

7.3

17

.27

2.4

22

.40

1.1

5

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.8

1

15

8.1

1

15

2.7

2

13

6.1

21

35

.09

12

7.2

41

23

.26

12

2.9

7

11

1.0

6

97

.31

97

.01

77

.31

77

.00

76

.68

20

.90

18

.63

15

.34

11

.24

81

11 10 9 8 7 6 5 4 3 2 1 0

21

.08

0.9

9

0.9

9

0.9

9

CHLOROFORM-d

8.2

38

.11

8.1

17

.72

7.7

27

.27

1.1

51

.15

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

17

3.6

5

15

8.1

7

15

0.2

9

13

4.0

61

31

.37

12

5.3

81

24

.49

12

4.2

4

11

2.0

7

99

.54

95

.35

77

.25

77

.00

76

.74

18

.60

11

.20

8.25 8.20 8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65

0.9

9

0.9

9

0.9

9

82

11 10 9 8 7 6 5 4 3 2 1 0

21

.09

0.9

6

0.9

9

1.0

0

0.8

9

0.9

1

CHLOROFORM-d

8.3

68

.35

8.1

67

.75

7.7

47

.73

7.7

37

.43

7.4

17

.27

3.1

5

1.1

5

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

17

4.5

1

15

8.3

21

55

.53

13

6.9

9

13

0.1

71

23

.55

12

0.0

21

18

.56

11

1.9

1

98

.43

96

.11

81

.76

78

.60

77

.26

77

.00

76

.75

18

.63

11

.22

8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

0.9

9

1.0

0

0.8

9

0.9

1

83

11 10 9 8 7 6 5 4 3 2 1 0


9.0

7

21

.28

1.0

1

1.0

1

1.0

0

0.8

8

CHLOROFORM-d

8.3

28

.32

8.1

47

.71

7.6

9

7.3

97

.37

7.2

7

1.1

5

0.2

7

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.5

3

15

8.2

61

55

.30

13

6.7

9

12

9.9

21

23

.47

12

1.0

81

18

.35

11

1.8

2

10

2.9

89

8.2

99

6.2

59

6.0

4

77

.25

77

.00

76

.74

18

.62

11

.23

-0.2

0

8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

1.0

1

1.0

1

1.0

0

0.8

8

84

11 10 9 8 7 6 5 4 3 2 1 0

3.0

2

21

.21

4.1

1

2.0

9

2.0

4

1.0

1

1.0

0

0.9

4

0.8

7

CHLOROFORM-d

8.2

48

.23

8.1

47

.65

7.6

47

.63

7.6

27

.37

7.3

57

.27

2.4

32

.41

2.3

9

1.4

41

.44

1.4

21

.40

1.3

91

.37

1.3

50

.95

0.9

30

.91

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.7

1

15

8.2

31

54

.81

13

6.6

8

12

9.0

51

23

.48

12

2.1

21

18

.22

11

1.6

5

98

.01

96

.41

92

.13

78

.95

77

.31

77

.00

76

.69

31

.06

28

.24

22

.20

19

.33

18

.63

13

.96

11

.23

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3

1.0

1

1.0

0

0.9

4

0.8

7

85

11 10 9 8 7 6 5 4 3 2 1 0

21

.04

0.9

7

1.0

0

1.0

0

1.0

0

1.0

0

0.8

6

0.9

3

CHLOROFORM-d

10

.08

10

.06

8.2

28

.09

8.0

77

.91

7.8

97

.76

7.7

47

.63

7.5

07

.48

7.2

7

1.1

9

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

17

6.9

3

15

7.1

21

56

.24

13

5.7

41

30

.73

13

0.3

81

29

.45

12

8.1

51

27

.44

12

6.8

71

17

.36

11

7.1

01

14

.22

97

.97

96

.97

77

.26

77

.00

76

.75

86

11 10 9 8 7 6 5 4 3 2 1 0

21

.00

2.0

6

1.0

7

1.0

3

1.0

0

0.9

1

0.9

9

CHLOROFORM-d

8.4

58

.44

8.3

68

.18

8.1

77

.94

7.9

27

.78

7.7

77

.72

7.6

77

.27

1.1

8

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.2

7

15

7.6

01

53

.33

13

5.8

31

29

.48

12

8.1

31

27

.32

12

5.8

01

23

.78

12

2.1

61

20

.85

12

0.0

31

12

.91

98

.50

96

.52

77

.25

77

.00

76

.74

18

.65

11

.24

8.45 8.40 8.35 8.30 8.25 8.20 8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65

2.0

6

1.0

7

1.0

3

1.0

0

0.9

1

0.9

9

87

11 10 9 8 7 6 5 4 3 2 1 0

21

.02

1.0

0

1.0

3

1.0

2

1.0

0

1.0

3

0.9

3

0.9

6

CHLOROFORM-d

8.4

28

.41

8.1

47

.88

7.8

67

.45

7.4

37

.37

7.3

77

.33

7.3

17

.27

7.0

9

1.1

7

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.2

1

15

8.1

81

54

.94

14

2.1

11

32

.19

13

1.3

01

28

.27

12

5.8

61

24

.09

12

3.7

71

22

.15

11

8.8

11

11

.49

98

.08

96

.42

77

.31

77

.00

76

.68

18

.60

11

.19

8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0

1.0

0

1.0

3

1.0

2

1.0

0

1.0

3

0.9

3

0.9

6

88

11 10 9 8 7 6 5 4 3 2 1 0

21

.00

1.0

1

1.2

4

1.0

4

2.0

0

1.0

2

1.9

3

0.9

6

CHLOROFORM-d

8.6

78

.15

8.1

48

.12

7.6

17

.59

7.5

37

.51

7.5

07

.32

7.2

77

.25

7.0

9

1.1

8

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.1

4

15

8.2

11

55

.53

15

4.9

91

53

.83

13

0.1

11

28

.89

12

8.2

71

24

.83

12

3.8

41

23

.17

12

2.0

31

21

.19

11

8.8

61

11

.68

11

1.2

51

02

.58

98

.33

96

.36

77

.31

77

.00

76

.68

18

.63

11

.24

8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0

1.0

1

1.2

4

1.0

4

2.0

0

1.0

2

1.9

3

0.9

6

89

11 10 9 8 7 6 5 4 3 2 1 0


21

.03

2.2

5

1.0

0

1.0

0

1.0

0

CHLOROFORM-d

8.2

88

.05

7.9

37

.93

7.8

97

.61

7.6

07

.57

7.5

77

.54

7.5

37

.27

1.1

7

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

2.0

3

15

6.9

41

53

.31

14

7.0

2

13

9.4

3

12

9.1

21

25

.41

12

3.8

41

21

.97

11

3.4

11

11

.00

99

.68

95

.75

77

.25

77

.00

76

.74

18

.64

11

.24

8.30 8.25 8.20 8.15 8.10 8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50

2.2

5

1.0

0

1.0

0

1.0

0

90

11 10 9 8 7 6 5 4 3 2 1 0


18

.09

3.2

1

2.1

4

1.0

9

1.0

7

1.0

5

1.0

6

0.9

0

CHLOROFORM-d

10

.63

8.0

07

.98

7.9

57

.93

7.6

27

.60

7.5

77

.57

7.5

6

7.2

7

3.2

2

1.2

71

.26

1.2

41

.23

1.2

31

.21

1.1

21

.11

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

0.9

3

17

8.6

51

74

.36

15

2.6

5

13

9.7

41

29

.11

12

8.6

21

25

.65

12

5.0

21

24

.01

12

1.5

61

16

.44

77

.25

77

.00

76

.74

18

.47

17

.90

11

.78

8.05 8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50

1.0

9

1.0

7

1.0

5

1.0

6

91

11 10 9 8 7 6 5 4 3 2 1 0

6.0

1

9.0

0

1.0

4

0.9

50

.98

0.8

6

0.9

9

CHLOROFORM-d

8.2

58

.24

8.2

48

.17

7.6

87

.66

7.4

77

.45

7.4

47

.44

7.4

37

.27

1.0

2

0.2

1

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.3

5

15

8.6

01

55

.90

13

3.9

21

26

.19

12

5.7

41

23

.65

11

8.1

71

11

.41

99

.55

95

.31

77

.26

77

.00

76

.75

26

.12

16

.70

-4.7

0

8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

1.0

4

0.9

5

0.9

8

0.8

6

0.9

9

92

11 10 9 8 7 6 5 4 3 2 1 0


9.0

1

5.9

9

0.9

8

0.9

9

1.0

1

4.0

5

0.9

1

1.0

1

CHLOROFORM-d

8.2

87

.92

7.9

17

.91

7.9

07

.70

7.4

97

.45

7.4

47

.43

7.4

2

1.2

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.3

3

15

8.8

21

55

.89

13

5.6

71

34

.01

13

2.9

01

29

.55

12

7.7

51

26

.11

12

5.8

31

23

.66

11

8.2

21

11

.31

98

.86

96

.57

77

.25

77

.00

76

.74

27

.09

18

.72

8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4

5.9

9

0.9

8

0.9

9

1.0

1

4.0

5

0.9

1

1.0

1

93

11 10 9 8 7 6 5 4 3 2 1 0

20

.87

3.0

1

3.0

0

3.1

1

3.0

0

CHLOROFORM-d

7.6

87

.67

7.6

47

.63

7.6

27

.25

7.2

47

.23

7.2

17

.17

3.4

7

3.0

7

0.8

3

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

19

4.7

6

15

6.1

1

14

0.2

9

13

0.0

41

28

.46

12

7.3

8

10

5.0

4

98

.10

91

.04

77

.26

77

.00

76

.75

47

.39

38

.45

18

.53

11

.39

94

11 10 9 8 7 6 5 4 3 2 1 0


0.9

4

2.0

4

1.0

3

0.9

4

1.0

0

CHLOROFORM-d

8.2

88

.28

8.2

68

.26

8.2

07

.70

7.7

07

.48

7.4

77

.46

7.4

47

.27

3.2

9

0.0

0

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

5.3

6

15

8.9

61

55

.92

13

4.1

41

26

.23

12

5.8

61

23

.49

11

8.1

9

11

0.2

6

83

.24

77

.25

77

.00

76

.74

73

.99

95

11 10 9 8 7 6 5 4 3 2 1 0


2.0

3

4.3

5

1.0

0

1.0

0

0.9

9

1.0

00

.93

0.8

8

CHLOROFORM-d

9.0

28

.47

8.2

78

.25

7.6

77

.54

7.4

37

.40

7.3

87

.36

7.3

47

.33

7.3

2

5.5

9

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.9

1

15

5.9

51

53

.33

13

9.0

51

34

.55

13

3.7

01

29

.06

12

8.6

81

28

.09

12

5.8

61

25

.42

12

3.9

01

23

.48

11

8.2

81

15

.73

77

.31

77

.00

76

.68

54

.21

96

11 10 9 8 7 6 5 4 3 2 1 0


3.0

0

2.0

3

2.0

0

1.0

0

0.9

1

0.9

6

CHLOROFORM-d

8.2

98

.28

8.2

47

.58

7.5

87

.57

7.5

77

.57

7.3

57

.35

7.3

47

.27

200 180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

17

5.2

8

15

7.8

51

55

.89

13

3.9

41

31

.77

12

8.6

01

28

.24

12

6.1

91

25

.70

12

3.5

21

22

.62

11

8.1

61

11

.36

94

.98

79

.47

77

.25

77

.00

76

.74

97

11 10 9 8 7 6 5 4 3 2 1 0


1.0

1

1.0

4

2.0

5

1.0

0

1.0

1

1.0

2

0.9

6

1.0

0

0.9

5

CHLOROFORM-d

8.7

4

7.8

27

.65

7.6

37

.56

7.5

47

.50

7.4

87

.31

7.2

77

.25

1.5

9

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

4.1

7

15

5.7

81

53

.61

15

2.9

61

47

.50

13

3.7

91

29

.16

12

6.2

51

25

.56

12

4.8

01

24

.06

12

2.9

81

21

.42

11

8.2

21

15

.89

11

0.6

91

07

.76

77

.26

77

.00

76

.75

98

11 10 9 8 7 6 5 4 3 2 1 0


2.0

4

1.0

2

1.0

0

0.9

4

CHLOROFORM-d

8.4

48

.26

8.2

58

.24

8.2

47

.80

7.7

97

.78

7.5

77

.55

7.5

47

.27

200 180 160 140 120 100 80 60 40 20 0


CHLOROFORM-d

17

2.3

5

16

2.1

2

15

5.7

4

13

5.3

21

27

.12

12

6.1

91

23

.33

11

8.5

1

11

2.1

6

10

2.9

4

77

.25

77

.00

76

.74

Supporting Information A Facile Strategy for …Manjur O. Akram, Saibal Bera and Nitin T. Patil*...

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Transcript of Supporting Information A Facile Strategy for …Manjur O. Akram, Saibal Bera and Nitin T. Patil*...