1

Supporting Information

Efficient Access to Alkynylated Quinalizinones via the Gold(I)-

catalyzed Aminoalkynylation of Alkynes

Popat S. Shinde, Aslam C. Shaikh and Nitin T. Patil*

Table of Contents

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

2. All procedures ............................................................................................................................... 3

2.1 Sonogashira cross-coupling of aryl iodides with alkynes: ............................................................. 3

2.2 Synthesis of 2-alkynylphenylboronic acids: .................................................................................. 3

2.3 Synthesis of 2-methoxy-6-(2(alkynyl)-phenyl) pyridines: ............................................................. 4

2.4 Gold-catalyzed aminoalkynylation reactions: ............................................................................... 5

3. Control experiments ..................................................................................................................... 6

3.1 Control experiment 1: ................................................................................................................... 6

3.2 Control experiment 2: ................................................................................................................... 6

3.3 Control experiment 3: ................................................................................................................... 7

4. Product modifications ................................................................................................................... 7

5. ORTEP diagram: ............................................................................................................................. 9

4. Characterization data: ................................................................................................................. 10

5. 1H NMR and 13C NMR spectra: .................................................................................................... 32

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

2

1. General information

Practical Considerations:

Unless otherwise specified, all reactions were carried out in oven dried vials or reaction

vessels with magnetic stirring under argon atmosphere. The aminoalkynylation reactions

were performed in 2.5 mL glass vials with a PTFE-lined cap and all other reactions for the

preparation of starting materials were performed in round-bottom flasks with rubber septa.

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

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

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

staining in iodine chamber or potassium permanganate solution followed by charring on a hot

plate. Solvents were removed in vacuo 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.

Materials:

Unless otherwise noted, material obtained from commercial suppliers was used without

further purification. Tetrahydrofuran was distilled from Na/benzophenone under an

atmosphere of dry N2. Anhydrous methanol, dichloromethane, dimethylformamide, diethyl

ether, acetonitrile and pet. ether were dried by using standard protocols under N2. The

catalyst AuCl was purchased from Sigma–Aldrich. All deuterated solvents were used as

supplied by Sigma–Aldrich.

Instrumentation:

Melting points are uncorrected and recorded using digital Büchi melting point apparatus B-

540. 1H NMR spectra and

13C NMR spectra were recorded on Bruker AV, 200/400/500,

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), d (doublet), dd (doublet of

doublet), dt (doublet of triplet), t (triplet), quin (quintet), br.s. (broad signal), m (multiplet)…

etc. HRMS (ESI) data were recorded on a Thermo Scientific Q-Exactive, Accela 1250 pump.

Single-crystal data was collected on a Bruker SMART APEX II CCD diffractometer with

graphite-monochromatized (MoK= 0.71073Å) radiation.

3

2. All procedures

2.1 Sonogashira cross-coupling of aryl iodides with alkynes:

All bromoalkynes were prepared by literature known methods1 except S1, S2, S9, S13,

S14 and S16 which were synthesised by slightly modified procedure as described below.

Representative procedure: A suspension of 2-bromoiodobenzene (2 gm, 7.06 mmol),

PdCl2(PPh3)2 (99.2 mg, 0.14 mmol, 2 mol%), CuI (40.2 mg, 0.21 mmol, 3 mol%) in 20 mL

of Et3N was degassed. After 10 min, a solution of phenyl acetylene (0.84 mL, 7.77 mmol, 1.1

eq) in Et3N (3.6 mL) was added dropwise over a period of 5 min via syringe and the reaction

mixture was left to stir for 12 h. After total consumption of the 2-bromoiodobenzene, the

reaction mixture was filtered through celite and extracted with EtOAc (3 × 10 mL). The

organic layer was washed with a saturated solution of NH4Cl (2 × 10 mL), water (2 × 10

mL), dried over Na2SO4 and the solvent was removed under vacuo. The reaction mixture was

purified by flash chromatography on silica gel, (eluent: pet. ether) to give the product 1-

bromo-2-(phenylethynyl) benzene (S1) as a yellow oil (88% yield).

2.2 Synthesis of 2-alkynylphenylboronic acids:

The boronic acids S20, S23, S24, S27 and S30 were synthesized by literature known

methods2 and all others were synthesized by slightly modified procedure as described below.

1 a) M. Kuhn, F. C. Falk, J. Paradies, Org. Lett. 2011, 13, 4100; b) K. Hirano, Y. Inaba, K. Takasu, S. Oishi, Y.

Takemoto, N. Fujii, H. Ohno, J. Org. Chem. 2011, 76, 9068; c) T. Morishita, H. Yoshida, J. Ohshita, Chem.

Commun. 2010, 46, 640. 2 a) R. Guo, K.-N. Li, B. Liu, H.-J. Zhu, Y.-M. Fan, L.-Z. Gong, Chem. Commun. 2014, 50, 5451; b) W.-J. Yoo,

T. V. Q. Nguyen, S. Kobayashi, Angew. Chem., Int. Ed. 2014, 53, 10213; c) C. rner, P. Starkov, T. D.

Sheppard, J. Am. Chem. Soc. 2010, 132, 5968.

4

Representative procedure: In a two-necked round bottom flask, 1.6 M solution of nBuLi in

nhexane (5.5 mL, 8.78 mmol, 1.5 eq) was added dropwise to a solution of 2-phenylethynyl

bromobenzene (S1) (1.5 g, 5.85 mmol) in 45 mL of diethyl ether under N2 atmosphere at -78

°C. The mixture was stirred at -78 °C for 1 h and then at -40 °C for 1 h and then cooled back

to -78 °C and B(OiPr)3 (1.65 g, 8.78 mmol, 1.5 eq) was added dropwise. The mixture was

allowed to warm up gradually to room temperature, while maintaining vigorous stirring for

16 h. Then, the reaction was quenched with 40 mL of 1N HCl for 30 minutes and extracted

with EtOAc (3 x 20 mL). The combined organic solution was dried over Na2SO4 and the

solvent was removed under vacuo. The product was purified by flash chromatography on

silica gel, (eluent: pet. ether/EtOAc) followed by recrystallization from pet. ether to give the

product [2-(phenylethynyl)phenyl]boronic acid (S20) as a white solid (84% yield). Note:

Boronic acids S22 and S25 are obtained in a slightly impure form and therefore used as such

for next reactions.

2.3 Synthesis of 2-methoxy-6-(2(alkynyl)-phenyl) pyridines:

Representative procedure: In a sealed tube 2-bromo-6-methoxypyridine3

(300 mg, 1.59

mmol) and [2-(phenylethynyl)phenyl]boronic acid (S20) (425 mg, 1.91 mmol, 1.2 eq) in

DMF/H2O 1:1 (2 mL) was degassed with N2 for 5 min followed by addition of Na2CO3 (507

mg, 4.78 mmol, 3 eq) under continuous flow of N2, PdCl2(PPh3)2 (55.8 mg, 0.079 mmol, 5

mol%) were added to the reaction mixture under a N2 atmosphere. The reaction mixture was

stirred at 80 °C for 12 h. After total consumption of the starting materials, the reaction

mixture was diluted with NaHCO3 (5 mL) and then the product was extracted with EtOAc (3

× 5 mL). The combined organic layer was dried over Na2SO4 and the solvent was removed

3 P. K. Agarwal, M. Saifuddin, B. Kundu, Tetrahedron 2010, 66, 862.

5

under vacuo. The crude product was purified on a silica gel column using pet. ether/EtOAc as

eluent to afford 2-methoxy-6-[2-(phenylethynyl)-phenyl] pyridine (1a) as a yellow thick

liquid (84% yield).

2.4 Gold-catalyzed aminoalkynylation reactions:

Representative procedure: To a screw-cap vial containing a stir bar were added 2-methoxy-6-

[2-(phenylethynyl)-phenyl] pyridine (1a) (30 mg, 0.10 mmol), TIPS-EBX (2a) (64 mg, 0.15

mmol, 1.5 eq), AuCl (1.1 mg, 5 mol%) and CH3CN:MeOH (1.9:0.1 mL). The reaction vial

was fitted with a cap, evacuated and back filled with N2 and heated at 50 °C for 24 h. The

reaction mixture was allowed to cool at ambient temperature. The reaction mixture was

diluted with EtOAc and wash with NaHCO3 followed by brine. The collective organic layer

dried over Na2SO4 and the solvent was removed under vacuo. The resulting residue was

purified by flash column chromatography on silica gel (eluent: pet. ether/EtOAc) to give the

product 3a as yellow thick liquid (84% yield).

6

3. Control experiments

3.1 Control experiment 1:

To a stirred solution of 2-methoxy-6-[2-{(4-methoxyphenyl)ethynyl}phenyl]pyridine

(1k) (40 mg, 0.126 mmol) in CH3CN:MeOH (1.9:0.1 ml) was added AuCl (1.47 mg, 0.0063

mmol, 5 mol%) at room temperature. The resulting mixture was stirred under temperature 80

°C for 24 h. The reaction mixture was warm to room temperature and evaporated in vacuo.

The residue was purified by flash chromatography on silica gel, (eluent: pet. ether/EtOAc) to

give the product 6-(4-methoxyphenyl)-4H-pyrido [2,1-a]isoquinolin-4-one (8) as a yellow

thick liquid (68% yield).

3.2 Control experiment 2:

To a screw-cap vial containing a stir bar were added 6-(4-methoxyphenyl)-4H-pyrido

[2,1-a]isoquinolin-4-one (8) (30 mg, 0.10 mmol), TIPS-EBX (2a) (64 mg, 0.15 mmol, 1.5

eq), AuCl (1.1 mg, 5 mol%) and CH3CN:MeOH (1.9:0.1 mL). The reaction vial was fitted

with a cap, evacuated and back filled with N2 and heated at 50 °C for 24 h. The reaction

mixture was allowed to cool at ambient temperature. The reaction mixture was diluted with

EtOAc and wash with NaHCO3 followed by brine. The collective organic layer dried over

Na2SO4 and the solvent was removed under vacuo. The resulting residue was purified by

flash column chromatography on silica gel, (eluent: pet. ether/EtOAc) to give the product (9)

as yellow solid (83% yield).

7

3.3 Control experiment 3:

To a stirred solution of 2-methoxy-6-[2-{(4-methoxyphenyl)ethynyl}phenyl]pyridine

(1k) (100 mg, 0.317 mmol) in chlorobenzene (2.5 ml) was added AlCl3 (42 mg, 0.317 mmol,

1.1 eq) at room temperature. The resulting mixture was stirred under reflux for 10 min. The

mixture was quenched with crushed ice at ice bath temperature and partitioned between

EtOAc and aq. HCl. The organic layer was washed with water followed by brine and dried

over Na2SO4 and the solvent was removed under vacuo. The residue was triturated with pet.

ether and dried under reduced pressure 6-(4-chlorophenyl)-2(1H)-pyridinone (10) as a off

white solid (47% yield).

4. Product modifications

a) Desilylation of 3p:

The substrate 3p (50 mg, 0.10 mmol) was dissolved in THF (3 mL) and TBAF (1.0 M

in THF, 0.15 mL, 0.15 mmol) was added slowly at 0 °C. The reaction mixture was stirred for

1 h at room temperature. After complete conversion of starting material reaction mixture was

quenched by addition of water. The reaction mixture was extracted with EtOAc (3 × 5 mL)

and the combined organic layers was washed with brine (10 mL), dried over Na2SO4 and

evaporated in vacuo. The crude product, thus obtained, was purified by column

chromatography (eluent: pet. ether/EtOAc) to afford the terminal alkynes 12 as a yellow thick

liquid (79% yield).

b) Sonogashira reaction of 12 with Iodobenzene:

8

A suspension of iodobenzene (21 mg, 0.10 mmol), PdCl2(PPh3)2 (1.4 mg, 0.002

mmol, 2 mol%), CuI (0.57 mg, 0.003 mmol, 3 mol%) in 1.5 mL of Et3N was degassed. After

10 min, a solution of 12 (36 mg, 0.11 mmol, 1.1 eq) in Et3N (1.5 mL) was added dropwise

over 5 min via syringe and the reaction mixture was heated at 60 °C for 2 h. After total

consumption of the iodobenzene, the reaction mixture was filtered through celite and

extracted with EtOAc (3 × 5 mL). The organic layer was washed with a saturated solution of

NH4Cl (2 × 5 mL), water (2 × 5 mL), dried over Na2SO4 and the solvent was removed under

vacuo. The reaction mixture was purified by flash chromatography on silica gel, (eluent: pet.

ether/ EtOAc) to give the desired product 13 as a yellow thick liquid (81% yield).

c) Click reaction of 12 with benzyl azide:

To a solution of CuSO4.5H2O (5.5 mg, 0.02 mmol, 20 mol%), sodium ascorbate (8.8

mg, 0.04 mmol, 40 mol%) in tBuOH/H2O (1:2 v/v, 2.0 mL) was added a mixture of alkyne 12

(35 mg, 0.11 mmol) and benzyl azide (15 mg, 0.11 mmol, 1 eq) at room temperature. The

resultant mixture was stirred at 60 °C for 1 h. After completion of the reaction, the reaction

mixture was diluted with EtOAc. 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 (eluent, pet. ether/EtOAc) to give the desired product 14 as a yellow solid

(83% yield).

9

5. ORTEP diagram:

Sr.

No

Compound Structure ORTEP Diagram

1

CCDC No 1456690

2

CCDC No 1456691

10

4. Characterization data:

(S2): yellow solid, 74% yield; mp = 110-111 °C; Rf = 0.80 (pet. ether); 1H NMR (400 MHz,

CDCl3) δ = 8.17 - 8.12 (m, 1 H), 7.88 - 7.82 (m, 3 H), 7.70 - 7.60 (m, 3 H), 7.57 - 7.49 (m, 2

H), 7.37 - 7.29 (m, 1 H), 7.24 - 7.16 (m, 1 H); 13

C NMR (100 MHz, CDCl3) δ = 133.2,

132.9, 132.4, 131.6, 129.4, 128.3, 128.0, 127.8, 127.8, 127.0, 126.8, 126.6, 125.7, 125.4,

120.2, 94.3, 88.4; HRMS (ESI) calcd for C18H12Br (M++ H) 307.0117, found 307.0114.

(S9): colourless liquid, 88% yield; Rf = 0.80 (pet. ether); 1H NMR (400 MHz, CDCl3) δ =

7.57 (d, J = 7.8 Hz, 1 H), 7.44 (d, J = 7.3 Hz, 1 H), 7.23 (t, J = 7.6 Hz, 1 H), 7.16 - 7.06 (m, 1

H), 2.38 (d, J = 6.8 Hz, 2 H), 1.92 (d, J = 12.2 Hz, 2 H), 1.76 (d, J = 12.7 Hz, 2 H), 1.69 (d, J

= 12.2 Hz, 2 H), 1.28 (t, J = 12.5 Hz, 2 H), 1.22 - 1.11 (m, 3 H); 13

C NMR (100 MHz,

CDCl3) δ = 133.3, 132.2, 128.5, 126.8, 126.2, 125.4, 94.5, 80.2, 37.4, 32.7, 27.4, 26.3, 26.2;

HRMS (ESI) calcd for C15H18Br (M++ H) 277.0519, found 277.0522.

(S13): yellow liquid, 80% yield; Rf = 0.20 (pet. ether); 1H NMR (400 MHz, CDCl3) δ = 7.67 -

7.55 (m, 2 H), 7.45 - 7.30 (m, 3 H), 6.85 - 6.72 (m, 2 H), 6.52 (d, J = 2.3 Hz, 1 H), 3.83 (s, 6

H); 13

C NMR (100 MHz, CDCl3) δ 160.5, 131.5, 128.3, 124.4, 123.0, 109.2, 101.7, 89.3,

88.9, 55.3; HRMS (ESI) calcd for C16H14O2Br (M++ H) 317.0172, found 317.0168.

11

(S14): yellow liquid, 88% yield; Rf = 0.80 (pet. ether); 1H NMR (400 MHz, CDCl3) δ = 7.66 -

7.61 (m, 2 H), 7.46 - 7.42 (m, 1 H), 7.41 - 7.38 (m, 3 H), 7.21 (d, J = 5.5 Hz, 2 H), 2.49 (s, 3

H); 13

C NMR (100 MHz, CDCl3) δ = 138.7, 132.5, 131.6, 130.7, 130.4, 128.5, 128.4, 128.3,

127.8, 126.7, 125.8, 123.1, 93.4, 88.8, 23.8; HRMS (ESI) calcd for C15H12Br (M++ H)

271.0117, found 271.0116.

(S16): yellow liquid, 99% yield; Rf = 0.70 (pet. ether); 1H NMR (400 MHz, CDCl3) δ = 7.40

(s, 1 H), 7.33 (d, J = 7.9 Hz, 1 H), 7.04 (d, J = 7.9 Hz, 1 H), 6.27 (t, J = 3.8 Hz, 1 H), 2.32 (s,

3 H), 2.29 - 2.25 (m, 2 H), 2.16 (dd, J = 2.7, 5.8 Hz, 2 H), 1.72 - 1.67 (m, 2 H), 1.66 - 1.62

(m, 2 H); 13

C NMR (100 MHz, CDCl3) δ = 139.4, 135.6, 132.8, 132.7, 127.8, 125.1, 122.8,

120.7, 95.1, 85.5, 29.0, 25.8, 22.3, 21.5, 21.0; HRMS (ESI) calcd for C15H16Br (M++ H)

275.0326, found 275.0327.

(S21): white solid, 68% yield; mp = 192-193 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (500 MHz, CDCl3) δ = 8.09 (d, J = 1.8 Hz, 1 H), 8.05 (dd, J = 1.4, 7.3 Hz, 1 H), 7.89 -

7.81 (m, 3 H), 7.68 - 7.63 (m, 1 H), 7.59 (dd, J = 1.8, 8.7 Hz, 1 H), 7.56 - 7.48 (m, 3 H), 7.46

- 7.41 (m, 1 H), 5.95 (s, 2 H); 13

C NMR (125 MHz, CDCl3) δ = 135.7, 133.1, 132.9, 132.6,

131.7, 130.9, 128.4, 128.4, 127.9, 127.8, 127.1, 126.8, 126.7, 119.1, 93.9, 90.0; HRMS (ESI)

calcd for C18H14O2B (M++ H) 273.1081, found 273.1082.

(S26): yellow solid, 77% yield; mp = 81-82 °C; Rf = 0.30 (pet. ether/EtOAc = 90/10); 1H

NMR (500 MHz, CDCl3) δ = 7.98 (d, J = 7.6 Hz, 1 H), 7.48 - 7.45 (m, 1 H), 7.40 (dt, J =

1.5, 7.5 Hz, 1 H), 7.37 - 7.33 (m, 1 H), 6.28 - 6.15 (m, 2 H), 2.74 - 2.60 (m, 1 H), 2.00 - 1.93

12

(m, 2 H), 1.82 - 1.74 (m, 2 H), 1.63 - 1.53 (m, 3 H), 1.44 - 1.35 (m, 3 H); 13

C NMR (125

MHz, CDCl3) δ = 135.4, 132.5, 130.7, 127.6, 127.5, 99.0, 81.7, 32.5, 29.7, 25.7, 24.9;

HRMS (ESI) calcd for C14H18O2B (M++ H) 229.1340, found 229.1344.

(S28): white solid, 27% yield; mp = 90-91 °C; Rf = 0.60 (pet. ether/EtOAc = 80/20);1H NMR

(400 MHz, CDCl3) δ = 8.00 (d, J = 7.3 Hz, 1 H), 7.52 - 7.45 (m, 1 H), 7.44 - 7.33 (m, 2 H),

6.54 (s, 2 H), 2.44 - 2.38 (m, 2 H), 1.89 (d, J = 11.9 Hz, 3 H), 1.77 (d, J = 12.8 Hz, 2 H), 1.73

- 1.52 (m, 3 H), 1.37 - 1.25 (m, 2 H), 1.22 - 1.05 (m, 3 H); 13

C NMR (100 MHz, CDCl3) δ =

135.4, 132.6, 130.7, 127.6, 127.5, 94.1, 82.6, 37.3, 32.7, 27.2, 26.1, 26.0; HRMS (ESI) calcd

for C15H20O2B (M++ H) 243.1551, found 243.15503.

(S29): white solid, 46% yield; mp = 114-115 °C; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H

NMR (500 MHz, CDCl3) δ = 8.06 - 7.99 (m, 1 H), 7.60 (d, J = 7.6 Hz, 1 H), 7.49 - 7.45 (m,

3 H), 7.43 - 7.39 (m, 1 H), 7.21 (d, J = 8.0 Hz, 2 H), 6.03 (s, 2 H), 2.40 (s, 3 H); 13

C NMR

(125 MHz, CDCl3) δ = 139.4, 135.6, 132.5, 131.4, 130.8, 129.4, 128.1, 126.9, 118.8, 93.7,

89.2, 21.6; HRMS (ESI) calcd for C15H14O2B (M++ H) 237.1081, found 237.1081.

(S31): white solid, 46% yield; mp = 115-116 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (500 MHz, CDCl3) δ = 8.03 (dd, J = 1.1, 7.5 Hz, 1 H), 7.62 - 7.58 (m, 1 H), 7.55 (t, J

= 1.5 Hz, 1 H), 7.51 - 7.46 (m, 1 H), 7.46 - 7.41 (m, 2 H), 7.40 - 7.36 (m, 1 H), 7.34 (d, J =

7.6 Hz, 1 H), 5.84 (s, 2 H); 13

C NMR (125 MHz, CDCl3) δ = 135.7, 134.5, 132.7, 131.3,

130.9, 129.8, 129.7, 129.3, 128.7, 126.0, 123.6, 91.9, 90.8; HRMS (ESI) calcd for

C14H11O2B37

Cl (M++ H) 259.0506, found 259.0504.

13

(S32): white solid, 45% yield; mp = 108-109 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (400 MHz, CDCl3) δ = 8.06 - 7.95 (m, 1 H), 7.64 - 7.56 (m, 1 H), 7.47 (dt, J = 1.4, 7.6

Hz, 1 H), 7.42 (dt, J = 1.1, 7.4 Hz, 1 H), 6.70 (d, J = 2.3 Hz, 2 H), 6.52 (t, J = 2.3 Hz, 1 H),

5.92 (s, 2 H), 3.83 (s, 6 H); 13

C NMR (100 MHz, CDCl3) δ = 160.7, 135.6, 132.6, 130.8,

128.4, 126.5, 123.1, 109.3, 102.4, 93.4, 89.2, 55.5; HRMS (ESI) calcd for C16H16O4B (M++

H) 283.1136, found 283.1135.

(S33): white solid, 69% yield; mp = 95-96 °C; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR

(400 MHz, CDCl3) δ = 7.60 - 7.49 (m, 2 H), 7.41 (d, J = 7.6 Hz, 1 H), 7.39 - 7.33 (m, 3 H),

7.33 - 7.28 (m, 1 H), 7.19 (d, J = 7.6 Hz, 1 H), 5.45 (s, 2 H), 2.52 (s, 3 H); 13

C NMR (100

MHz, CDCl3) δ = 142.3, 131.5, 130.1, 129.2, 128.5, 128.4, 125.8, 122.7, 91.8, 90.0, 22.7;

HRMS (ESI) calcd for C15H14O2B (M++ H) 237.1081, found 237.1080.

(S34): white solid, 57% yield; mp = 106-107 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (400 MHz, CDCl3) δ = 7.85 (s, 1 H), 7.58 - 7.53 (m, 2 H), 7.51 (d, J = 7.8 Hz, 1 H),

7.42 - 7.36 (m, 3 H), 7.29 (dd, J = 1.6, 8.5 Hz, 1 H), 6.11 (s, 2 H), 2.41 (s, 3 H); 13

C NMR

(100 MHz, CDCl3) δ = 138.4, 136.3, 132.5, 131.6, 131.5, 128.9, 128.6, 123.6, 122.1, 92.9,

89.9, 21.4; HRMS (ESI) calcd for C15H14O2B (M++ H) 237.1081, found 237.1080.

14

(S35): yellow solid, 59% yield; mp = 102-103 °C; Rf = 0.30 (pet. ether/EtOAc = 90/10); 1H

NMR (400 MHz, CDCl3) δ = 7.80 (s, 1 H), 7.38 (d, J = 7.8 Hz, 1 H), 7.23 (d, J = 7.8 Hz, 1

H), 6.30 - 6.22 (m, 1 H), 6.14 (s, 2 H), 2.38 (s, 3 H), 2.28 - 2.23 (m, 2 H), 2.18 (dd, J = 2.6,

6.0 Hz, 2 H), 1.75 - 1.68 (m, 2 H), 1.67 - 1.61 (m, 2 H); 13

C NMR (100 MHz, CDCl3) δ =

137.8, 136.4, 136.2, 132.3, 131.6, 124.2, 119.8, 94.9, 87.3, 29.0, 25.8, 22.2, 21.3; HRMS

(ESI) calcd for C15H18O2B (M++ H) 241.1394, found 241.1393.

(S36): white solid, 76% yield; mp = 159-160 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (500 MHz, CDCl3) δ = 7.92 (d, J = 7.6 Hz, 1 H), 7.56 (br. s., 2 H), 7.44 (s, 1 H), 7.42

- 7.37 (m, 3 H), 7.24 (d, J = 7.6 Hz, 1 H), 6.01 (br. s., 2 H), 2.40 (s, 3 H); 13

C NMR (125

MHz, CDCl3) δ = 141.3, 136.0, 133.4, 131.9, 131.8, 129.6, 129.3, 128.8, 126.8, 122.2, 93.3,

90.2, 21.6; HRMS (ESI) calcd for C15H14O2B (M++ H) 237.1081, found 237.1080.

(S37): white solid, 72% yield; mp = 122-123 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (400 MHz, CDCl3) δ = 7.96 (d, J = 8.3 Hz, 1 H), 7.63 - 7.51 (m, 3 H), 7.47 - 7.33 (m,

5 H), 6.04 (s, 2 H); 13

C NMR (100 MHz, CDCl3) δ = 137.3, 132.5, 131.9, 129.8, 129.0,

128.9, 128.6, 121.6, 94.8, 88.7; HRMS (ESI) calcd for C14H11O2BCl (M++ H) 257.0535,

found 257.0534.

(S38): white solid, 55% yield; mp = 125-126 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (500 MHz, CDCl3) δ = 7.56 (br. s., 2 H), 7.37 (br. s., 3 H), 7.15 (br. s., 1 H), 6.60 (br.

s., 1 H), 6.12 (br. s., 2 H), 3.91 (br. s., 3 H), 3.89 (br. s., 3 H); 13

C NMR (125 MHz, CDCl3)

15

δ = 161.7, 160.7, 131.4, 128.6, 128.5, 122.5, 110.7, 108.4, 101.4, 96.6, 86.2, 56.0, 55.5;

HRMS (ESI) calcd for C16H16O4B (M++ H) 283.1136, found 283.1135.

(1a): yellow thick liquid, 84% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 7.89 (d, J = 7.8 Hz, 1 H), 7.74 - 7.64 (m, 3 H), 7.51 - 7.38 (m, 4 H), 7.37 -

7.29 (m, 3 H), 6.83 - 6.71 (m, 1 H), 4.05 (s, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.8,

155.1, 142.1, 138.5, 133.6, 131.6, 129.9, 128.7, 128.6, 128.4, 128.3, 123.7, 121.5, 117.3,

109.7, 92.8, 89.8, 53.6; HRMS (ESI) calcd for C20H16NO (M++ H) 286.1226, found

286.1224.

(1b): yellow thick liquid, 80% yield; Rf = 0.60 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.94 (s, 1 H), 7.89 (dd, J = 1.2, 7.6 Hz, 1 H), 7.84 - 7.78 (m, 3 H), 7.75 -

7.70 (m, 2 H), 7.69 (d, J = 0.9 Hz, 1 H), 7.53 - 7.49 (m, 2 H), 7.49 - 7.44 (m, 2 H), 7.41 (d, J

= 1.2 Hz, 1 H), 6.80 (dd, J = 1.1, 7.8 Hz, 1 H), 4.04 (s, 3 H); 13

C NMR (125 MHz, CDCl3) δ

= 163.6, 154.9, 141.9, 138.3, 133.4, 133.0, 132.7, 131.2, 129.7, 128.5, 128.1, 128.0, 128.0,

127.7, 126.6, 126.5, 121.2, 120.8, 117.0, 109.4, 92.9, 89.9, 53.4; HRMS (ESI) calcd for

C24H18NO (M++ H) 336.1383, found 336.1383.

(1c): yellow thick liquid, 77% yield; Rf = 0.60 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 8.67 (t, J = 9.3 Hz, 2 H), 8.21 (d, J = 8.3 Hz, 1 H), 7.98 (s, 1 H), 7.89 -

7.80 (m, 3 H), 7.74 - 7.64 (m, 4 H), 7.64 - 7.54 (m, 2 H), 7.54 - 7.43 (m, 2 H), 6.83 (d, J = 7.8

16

Hz, 1 H), 4.01 (s, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.7, 155.3, 142.2, 138.6, 133.6,

131.7, 131.2, 131.1, 130.2, 130.0, 129.7, 128.6, 128.5, 128.1, 127.4, 127.0, 126.9, 126.9,

122.7, 122.6, 121.6, 119.9, 117.2, 109.5, 93.8, 91.0, 53.4; HRMS (ESI) calcd for C28H20NO

(M++ H) 386.1539, found 386.1540.

(1d): yellow thick liquid, 75% yield; Rf = 0.40 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 7.85 - 7.76 (m, 1 H), 7.65 - 7.59 (m, 2 H), 7.56 - 7.50 (m, 1 H), 7.42 - 7.34

(m, 1 H), 7.34 - 7.28 (m, 1 H), 6.76 - 6.66 (m, 1 H), 4.02 (s, 3 H), 2.42 - 2.33 (m, 2 H), 1.58 -

1.49 (m, 2 H), 1.45 - 1.36 (m, 2 H), 0.95 - 0.86 (m, 3 H); 13

C NMR (100 MHz, CDCl3) δ =

163.5, 155.0, 141.5, 138.1, 133.4, 129.5, 127.8, 127.6, 122.0, 117.0, 109.1, 93.8, 80.2, 53.2,

30.5, 21.9, 19.3, 13.6; HRMS (ESI) calcd for C18H20NO (M++ H) 266.1539, found 266.1539.

(1e): yellow thick liquid, 48% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.80 (dd, J = 1.2, 7.9 Hz, 1 H), 7.63 - 7.58 (m, 2 H), 7.53 (dd, J = 1.2, 7.6

Hz, 1 H), 7.38 (dt, J = 1.2, 7.6 Hz, 1 H), 7.33 - 7.28 (m, 1 H), 6.72 (dd, J = 2.4, 6.7 Hz, 1 H),

4.02 (s, 3 H), 2.37 (t, J = 7.0 Hz, 2 H), 1.57 - 1.48 (m, 2 H), 1.40 - 1.34 (m, 2 H), 1.32 - 1.26

(m, 4 H), 0.89 (t, J = 6.9 Hz, 3 H); 13

C NMR (125 MHz, CDCl3) δ = 163.5, 155.0, 141.5,

138.1, 133.5, 129.5, 127.8, 127.6, 122.0, 117.0, 109.1, 93.9, 80.2, 53.3, 31.4, 28.6, 28.4, 22.5,

19.6, 14.1; HRMS (ESI) calcd for C20H24NO (M++ H) 294.1852, found 294.1852.

(1f): yellow thick liquid, 88% yield; Rf = 0.60 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 7.89 - 7.79 (m, 1 H), 7.68 - 7.56 (m, 2 H), 7.56 - 7.49 (m, 1 H), 7.38 (dt, J

= 1.2, 7.6 Hz, 1 H), 7.33 - 7.28 (m, 1 H), 6.73 (dd, J = 2.0, 7.1 Hz, 1 H), 4.02 (s, 3 H), 2.81

17

(quin, J = 7.2 Hz, 1 H), 2.04 - 1.86 (m, 2 H), 1.76 - 1.55 (m, 6 H); 13

C NMR (100 MHz,

CDCl3) δ = 163.4, 154.9, 141.5, 138.0, 133.3, 129.5, 127.8, 127.6, 122.0, 117.0, 109.0, 98.0,

79.8, 53.2, 33.5, 31.0, 24.9; HRMS (ESI) calcd for C19H20NO (M++ H) 278.1539, found

278.1539.

(1g): yellow thick liquid, 74% yield; Rf = 0.40 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 7.83 (d, J = 7.3 Hz, 1 H), 7.68 - 7.58 (m, 2 H), 7.53 (d, J = 7.3 Hz, 1 H),

7.38 (t, J = 7.6 Hz, 1 H), 7.34 - 7.29 (m, 1 H), 6.72 (d, J = 7.8 Hz, 1 H), 4.02 (s, 3 H), 2.65 -

2.50 (m, 1 H), 1.80 (d, J = 8.3 Hz, 2 H), 1.69 (dd, J = 3.4, 5.9 Hz, 2 H), 1.54 - 1.44 (m, 3 H),

1.37 - 1.30 (m, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.5, 154.9, 141.5, 138.0, 133.4,

129.5, 127.8, 127.6, 122.0, 117.1, 109.1, 97.8, 80.3, 53.2, 32.3, 29.8, 25.9, 24.7; HRMS

(ESI) calcd for C20H22NO (M++ H) 292.1696, found 292.1696.

(1h): yellow solid, 84% yield; mp = 50-51 °C; Rf = 0.40 (pet. ether/EtOAc = 98/02); 1H

NMR (400 MHz, CDCl3) δ = 7.88 - 7.78 (m, 1 H), 7.68 - 7.59 (m, 2 H), 7.58 - 7.50 (m, 1 H),

7.39 (dt, J = 1.3, 7.5 Hz, 1 H), 7.35 - 7.28 (m, 1 H), 6.73 (dd, J = 1.6, 7.2 Hz, 1 H), 6.18 -

5.97 (m, 1 H), 4.02 (s, 3 H), 2.13 (dd, J = 3.7, 5.6 Hz, 4 H), 1.69 - 1.56 (m, 4 H); 13

C NMR

(125 MHz, CDCl3) δ = 163.5, 154.8, 141.4, 138.1, 135.0, 133.2, 129.5, 127.9, 127.9, 121.7,

120.9, 117.0, 109.2, 94.5, 86.8, 53.3, 28.8, 25.7, 22.2, 21.5; HRMS (ESI) calcd for

C20H20NO (M++ H) 290.1539, found 290.1539.

18

(1i): yellow thick liquid, 56% yield; Rf = 0.40 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.81 (dd, J = 1.2, 7.9 Hz, 1 H), 7.67 - 7.58 (m, 2 H), 7.56 (dd, J = 1.2, 7.6

Hz, 1 H), 7.39 (dt, J = 1.4, 7.6 Hz, 1 H), 7.35 - 7.29 (m, 1 H), 6.74 (dd, J = 1.8, 7.0 Hz, 1 H),

4.03 (s, 3 H), 2.28 (d, J = 6.7 Hz, 2 H), 1.81 - 1.65 (m, 5 H), 1.55 - 1.46 (m, 1 H), 1.32 - 1.19

(m, 2 H), 1.15 (tt, J = 3.0, 12.3 Hz, 1 H), 1.04 - 0.94 (m, 2 H); 13

C NMR (125 MHz, CDCl3)

δ = 163.5, 155.0, 141.5, 138.0, 133.4, 129.4, 127.8, 127.6, 122.1, 117.0, 109.0, 92.8, 81.0,

53.2, 37.3, 32.7, 27.4, 26.2, 26.1; HRMS (ESI) calcd for C21H24NO (M++ H) 306.1852,

found 306.1851.

(1j): yellow thick liquid, 75% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 7.84 (dd, J = 1.5, 7.6 Hz, 1 H), 7.68 - 7.59 (m, 3 H), 7.48 - 7.34 (m, 2 H),

7.31 (s, 1 H), 7.25 (s, 1 H), 7.16 - 7.07 (m, 2 H), 6.74 (dd, J = 2.4, 6.6 Hz, 1 H), 4.00 (s, 3 H),

2.35 (s, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.6, 154.9, 141.7, 138.3, 138.2, 133.3,

131.2, 129.6, 129.1, 128.3, 128.0, 121.5, 120.4, 117.0, 109.3, 92.8, 88.8, 53.3, 21.5; HRMS

(ESI) calcd for C21H18NO (M++ H) 300.1383, found 300.1382.

(1k): yellow thick liquid, 80% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (400

MHz, CDCl3) δ = 7.87 (d, J = 7.8 Hz, 1 H), 7.73 - 7.59 (m, 3 H), 7.47 - 7.41 (m, 1 H), 7.41 -

7.32 (m, 3 H), 6.87 (d, J = 8.3 Hz, 2 H), 6.77 (d, J = 7.3 Hz, 1 H), 4.03 (s, 3 H), 3.82 (s, 3 H);

13C NMR (100 MHz, CDCl3) δ = 163.5, 159.5, 154.9, 141.5, 138.2, 133.1, 132.8, 129.6,

128.1, 128.0, 121.5, 117.0, 115.6, 114.0, 109.3, 92.6, 88.2, 55.2, 53.3; HRMS (ESI) calcd for

C21H18NO2 (M++ H) 316.1332, found 316.1331.

19

(1l): yellow solid, 82% yield; mp = 52-53 °C; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR

(400 MHz, CDCl3) δ = 7.94 - 7.85 (m, 1 H), 7.76 - 7.69 (m, 2 H), 7.61 (d, J = 7.3 Hz, 1 H),

7.51 (dt, J = 1.2, 7.6 Hz, 1 H), 7.47 - 7.40 (m, 2 H), 7.36 - 7.32 (m, 1 H), 7.32 - 7.28 (m, 2 H),

6.82 (d, J = 8.3 Hz, 1 H), 4.06 (s, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.6, 154.8,

142.1, 138.3, 134.2, 133.4, 131.1, 129.7, 129.5, 129.5, 128.8, 128.4, 128.0, 125.2, 120.8,

116.9, 109.5, 91.0, 90.7, 53.3; HRMS (ESI) calcd for C20H15NOCl (M++ H) 320.0837, found

320.0837.

(1m): yellow thick liquid, 79% yield; Rf = 0.20 (pet. ether/EtOAc = 95/05); 1H NMR (400

MHz, CDCl3) δ = 7.86 (d, J = 7.7 Hz, 1 H), 7.73 - 7.65 (m, 2 H), 7.64 - 7.58 (m, 1 H), 7.51 -

7.42 (m, 1 H), 7.42 - 7.33 (m, 1 H), 6.77 (d, J = 8.2 Hz, 1 H), 6.58 (d, J = 2.2 Hz, 2 H), 6.47

(t, J = 2.2 Hz, 1 H), 4.03 (s, 3 H), 3.79 (s, 6 H); 13

C NMR (100 MHz, CDCl3) δ = 163.5,

160.5, 154.8, 142.0, 138.2, 133.2, 129.6, 128.5, 128.0, 124.7, 121.1, 116.9, 109.3, 109.1,

101.6, 92.5, 89.1, 55.3, 53.3; HRMS (ESI) calcd for C22H20NO3 (M++ H) 346.1438, found

346.1437.

(1n): yellow thick liquid, 88% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.74 - 7.64 (m, 1 H), 7.49 (br. s., 1 H), 7.31 - 7.23 (m, 5 H), 7.23 - 7.16

(m, 2 H), 7.07 (d, J = 7.0 Hz, 1 H), 6.77 (d, J = 8.2 Hz, 1 H), 3.95 (s, 3 H), 2.27 (s, 3 H); 13

C

20

NMR (125 MHz, CDCl3) δ = 163.6, 156.2, 142.8, 138.4, 136.9, 131.5, 130.7, 129.9, 128.4,

128.2, 127.9, 123.7, 122.8, 118.4, 109.2, 92.3, 89.4, 53.7, 20.7; HRMS (ESI) calcd for

C21H18NO (M++ H) 300.1383, found 300.1384.

(1o): yellow thick liquid, 82% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.71 - 7.65 (m, 2 H), 7.64 - 7.61 (m, 1 H), 7.58 (d, J = 7.9 Hz, 1 H), 7.44 -

7.38 (m, 2 H), 7.37 - 7.30 (m, 3 H), 7.24 - 7.15 (m, 1 H), 6.77 (d, J = 7.9 Hz, 1 H), 4.04 (s, 3

H), 2.46 (s, 3 H); 13

C NMR (125 MHz, CDCl3) δ = 163.6, 155.1, 141.8, 138.7, 138.3, 133.3,

131.3, 130.3, 129.0, 128.3, 128.1, 123.7, 118.4, 117.2, 109.3, 91.9, 89.7, 53.4, 21.6; HRMS

(ESI) calcd for C21H18NO (M++ H) 300.1383, found 300.1384.

(1p): orange thick liquid, 85% yield; Rf = 0.40 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 77.65 - 7.58 (m, 3 H), 7.45 (d, J = 7.9 Hz, 1 H), 7.14 (d, J = 7.9 Hz, 1 H),

6.72 (d, J = 7.9 Hz, 1 H), 6.08 (br. s., 1 H), 4.03 (s, 3 H), 2.42 (s, 3 H), 2.16 - 2.10 (m, 4 H),

1.68 - 1.63 (m, 2 H), 1.62 - 1.57 (m, 2 H); 13

C NMR (125 MHz, CDCl3) δ = 163.5, 155.0,

141.3, 138.1, 138.0, 134.6, 133.1, 130.1, 128.8, 121.0, 118.8, 117.1, 109.0, 93.8, 86.9, 53.3,

28.9, 25.7, 22.3, 21.5; HRMS (ESI) calcd for C21H22NO (M++ H) 304.1696, found 304.1695.

(1q): yellow thick liquid, 75% yield; Rf = 0.20 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.79 (d, J = 7.9 Hz, 1 H), 7.70 - 7.64 (m, 2 H), 7.52 (s, 1 H), 7.46 - 7.41

(m, 2 H), 7.37 - 7.32 (m, 3 H), 7.29 (s, 1 H), 6.76 (d, J = 7.6 Hz, 1 H), 4.03 (s, 3 H), 2.43 (s, 3

H); 13

C NMR (125 MHz, CDCl3) δ = 1163.5, 154.8, 139.1, 138.2, 137.9, 133.8, 131.3,

21

129.6, 129.5, 128.3, 128.1, 123.5, 120.9, 116.8, 109.1, 92.1, 89.7, 53.3, 20.9; HRMS (ESI)

calcd for C21H18NO (M++ H) 300.1383, found 300.1383.

(1r): yellow thick liquid, 61% yield; Rf = 0.50 (pet. ether/EtOAc = 98/02); 1H NMR (500

MHz, CDCl3) δ = 7.82 (d, J = 8.5 Hz, 1 H), 7.70 - 7.61 (m, 3 H), 7.42 (dd, J = 2.0, 6.3 Hz, 3

H), 7.37 - 7.32 (m, 3 H), 6.77 (d, J = 8.2 Hz, 1 H), 4.00 (s, 3 H); 13

C NMR (125 MHz,

CDCl3) δ = 163.6, 153.7, 140.1, 138.4, 133.8, 132.8, 131.4, 131.0, 128.7, 128.6, 128.4,

122.9, 122.7, 116.9, 109.7, 93.6, 88.2, 53.4; HRMS (ESI) calcd for C20H15NOCl (M++ H)

320.0837, found 320.0839.

(1s): yellow thick liquid, 78% yield; Rf = 0.30 (pet. ether/EtOAc = 95/05);1H NMR (500

MHz, CDCl3) δ = 7.69 - 7.63 (m, 1 H), 7.60 (dd, J = 0.9, 7.3 Hz, 1 H), 7.39 - 7.35 (m, 2 H),

7.31 - 7.25 (m, 3 H), 6.97 (d, J = 2.4 Hz, 1 H), 6.76 (dd, J = 0.8, 8.1 Hz, 1 H), 6.53 (d, J = 2.4

Hz, 1 H), 4.00 (s, 3 H), 3.95 (s, 3 H), 3.89 (s, 3 H); 13

C NMR (125 MHz, CDCl3) δ = 163.7,

162.1, 160.7, 155.1, 145.0, 138.4, 131.4, 128.4, 127.9, 124.3, 117.6, 109.8, 106.4, 104.0,

98.6, 96.0, 85.7, 56.4, 55.7, 53.6; HRMS (ESI) calcd for C22H20NO3 (M++ H) 346.1438,

found 346.1439.

(3a): yellow thick liquid, 84% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 8.03 (d, J = 7.3 Hz, 1 H), 7.61 (br. s., 2 H), 7.58 - 7.50 (m, 4 H), 7.47

(t, J = 6.9 Hz, 1 H), 7.21 (t, J = 7.2 Hz, 1 H), 7.08 (d, J = 5.8 Hz, 1 H), 6.60 (d, J = 7.9 Hz, 1

22

H), 6.43 (d, J = 8.9 Hz, 1 H), 1.04 (br. s., 21 H); 13

C NMR (125 MHz, DMSO-d6) δ = 158.3,

143.4, 138.7, 137.6, 136.8, 133.1, 130.7, 129.9, 129.7, 129.5, 129.0, 122.0, 121.3, 119.6,

114.7, 114.5, 106.0, 99.5, 18.4, 10.8; HRMS (ESI) calcd for C30H34NOSi (M++ H) 452.2404,

found 452.2400.

(3b): yellow thick liquid, 81% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 8.22 (s, 1 H), 8.10 (d, J = 8.5 Hz, 1 H), 8.05 (d, J = 7.9 Hz, 2 H), 7.97

(d, J = 7.6 Hz, 1 H), 7.74 (dd, J = 1.5, 8.5 Hz, 1 H), 7.67 - 7.59 (m, 2 H), 7.56 (dd, J = 6.7,

9.2 Hz, 1 H), 7.46 (t, J = 7.6 Hz, 1 H), 7.19 - 7.06 (m, 2 H), 6.67 (d, J = 8.2 Hz, 1 H), 6.46 (d,

J = 8.9 Hz, 1 H), 1.06 (s, 21 H); 13

C NMR (125 MHz, DMSO-d6) δ = 158.4, 143.4, 138.9,

137.7, 134.1, 133.1, 133.1, 132.8, 130.8, 130.1, 129.8, 128.6, 128.3, 127.8, 127.3, 127.0,

121.9, 121.5, 119.6, 114.9, 114.4, 106.1, 99.7, 18.5, 10.8; HRMS (ESI) calcd for

C34H36NOSi (M++ H) 502.2561, found 502.2562.

(3c): yellow thick liquid, 74% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 9.12 (d, J = 8.1 Hz, 1 H), 8.82 (t, J = 9.3 Hz, 2 H), 8.18 (t, J = 9.0 Hz,

2 H), 7.78 (d, J = 7.8 Hz, 1 H), 7.74 - 7.68 (m, 2 H), 7.68 - 7.62 (m, 2 H), 7.60 - 7.54 (m, 2

H), 7.44 (s, 1 H), 7.40 (dd, J = 7.0, 8.9 Hz, 1 H), 7.12 (d, J = 6.6 Hz, 1 H), 5.91 (d, J = 9.0

Hz, 1 H), 1.00 (d, J = 4.4 Hz, 21 H); 13

C NMR (100 MHz, DMSO-d6) δ = 158.7, 144.1,

140.6, 138.8, 137.7, 134.0, 132.1, 131.7, 131.0, 130.7, 130.4, 129.7, 129.2, 127.8, 127.5,

127.3, 126.8, 126.5, 125.3, 124.2, 123.3, 123.2, 122.0, 120.0, 111.4, 107.5, 105.5, 100.7,

18.8, 11.2; HRMS (ESI) calcd for C38H38NOSi (M++ H) 552.2717, found 552.2719.

23

(3d): yellow thick liquid, 59% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, CDCl3) δ = 8.08 (d, J = 8.2 Hz, 1 H), 8.11 (d, J = 7.9 Hz, 1 H), 7.61 (t, J = 7.5 Hz, 1

H), 7.56 - 7.47 (m, 2 H), 7.20 (d, J = 7.3 Hz, 1 H), 6.61 (d, J = 8.9 Hz, 1 H), 3.67 - 3.58 (m, 2

H), 1.75 (quin, J = 7.7 Hz, 2 H), 1.42 - 1.35 (m, 2 H), 1.23 - 1.14 (s, 21 H), 0.92 (t, J = 7.3

Hz, 3 H); 13

C NMR (125 MHz, CDCl3) δ = 163.3, 147.3, 141.6, 137.3, 130.3, 129.7, 128.0,

125.8, 125.8, 123.3, 116.4, 111.2, 101.3, 101.0, 100.1, 33.2, 31.2, 22.9, 18.7, 13.9, 11.4;

HRMS (ESI) calcd for C28H38NOSi (M++ H) 432.2717, found 432.2715.

(3e): yellow thick liquid, 57% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, CDCl3) δ = 8.08 (d, J = 8.2 Hz, 1 H), 8.11 (d, J = 7.9 Hz, 1 H), 7.61 (t, J = 7.5 Hz, 1

H), 7.55 - 7.48 (m, 2 H), 7.20 (d, J = 6.7 Hz, 1 H), 6.66 - 6.55 (m, 1 H), 3.68 - 3.60 (m, 2 H),

1.81 - 1.72 (m, 2 H), 1.41 - 1.33 (m, 2 H), 1.30 - 1.27 (m, 4 H), 1.22 - 1.17 (m, 21 H), 0.86 (t,

J = 6.9 Hz, 3 H); 13

C NMR (125 MHz, CDCl3) δ = 163.3, 147.3, 141.6, 137.3, 130.3, 129.7,

128.0, 125.9, 125.8, 123.3, 116.4, 111.2, 101.3, 101.0, 100.1, 33.4, 31.7, 29.5, 29.1, 22.7,

18.8, 14.0, 11.4; HRMS (ESI) calcd for C30H42NOSi (M++ H) 460.3030, found 460.3028.

(3f): yellow thick liquid, 60% yield; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, CDCl3) δ = 8.17 (d, J = 7.9 Hz, 1 H), 8.05 (d, J = 8.2 Hz, 1 H), 7.58 (t, J = 7.5 Hz, 1

H), 7.55 - 7.45 (m, 2 H), 7.16 (d, J = 7.3 Hz, 1 H), 6.58 (d, J = 8.5 Hz, 1 H), 3.74 (quin, J =

9.5 Hz, 1 H), 2.68 - 2.53 (m, 2 H), 2.17 - 2.06 (m, 2 H), 1.98 - 1.86 (m, 2 H), 1.70 - 1.65 (s, 2

24

H), 1.25 - 1.16 (m, 21 H); 13

C NMR (125 MHz, CDCl3) δ = 164.3, 150.0, 141.8, 137.4,

130.6, 130.2, 128.0, 125.7, 125.5, 123.0, 116.1, 111.2, 105.6, 100.7, 99.5, 44.3, 31.6, 26.1,

18.7, 11.5; HRMS (ESI) calcd for C29H38NOSi (M++ H) 444.2717, found 444.2716.

(3g): yellow thick liquid, 58% yield; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 8.19 (d, J = 7.8 Hz, 1 H), 8.04 (d, J = 8.1 Hz, 1 H), 7.58 (t, J = 7.6 Hz,

1 H), 7.53 - 7.46 (m, 2 H), 7.14 (d, J = 7.1 Hz, 1 H), 6.59 (d, J = 8.8 Hz, 1 H), 3.40 - 3.30 (m,

1 H), 2.73 - 2.62 (m, 2 H), 1.96 (d, J = 12.2 Hz, 2 H), 1.82 (br. s., 2 H), 1.73 - 1.68 (m, 1 H),

1.62 (br. s., 1 H), 1.39 - 1.36 (m, 2 H), 1.25 - 1.18 (m, 21 H); 13

C NMR (100 MHz, DMSO-

d6) δ = 164.4, 151.2, 141.8, 137.3, 130.6, 130.2, 128.0, 125.7, 125.6, 123.0, 116.3, 111.2,

104.9, 101.4, 99.4, 43.4, 29.7, 27.1, 25.6, 18.7, 18.7, 18.3, 11.5; HRMS (ESI) calcd for

C30H40NOSi (M++ H) 458.2874, found 458.2871.

(3h): yellow thick liquid, 67% yield; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 8.20 (d, J = 8.0 Hz, 1 H), 8.15 (d, J = 8.0 Hz, 1 H), 8.06 (d, J = 8.0 Hz,

2 H), 8.04 - 7.95 (m, 2 H), 7.64 (t, J = 7.4 Hz, 1 H), 7.59 - 7.51 (m, 2 H), 7.45 (t, J = 7.4 Hz,

2 H), 7.25 (s, 1 H), 7.24 - 7.13 (m, 2 H), 6.67 (d, J = 8.8 Hz, 1 H), 5.59 (br. s., 1 H), 2.61 (br.

s., 1 H), 2.50 (br. s., 1 H), 2.26 - 2.12 (m, 2 H), 1.87 (br. s., 2 H), 1.69 (br. s., 2 H), 1.19 (s, 21

H); 13

C NMR (125 MHz, DMSO-d6) δ = 162.1, 145.4, 141.9, 137.4, 133.3, 131.9, 130.4,

128.3, 128.0, 126.2, 125.5, 123.4, 116.2, 110.5, 101.3, 100.1, 94.6, 29.7, 25.4, 22.7, 21.8,

18.8, 11.4; HRMS (ESI) calcd for C30H38NOSi (M++ H) 456.2717, found 456.2720.

25

(3i): yellow thick liquid, 62% yield; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, CDCl3) δ = 8.18 - 8.04 (m, 2 H), 7.65 - 7.60 (m, 1 H), 7.57 - 7.49 (m, 2 H), 7.23 - 7.20

(m, 1 H), 6.61 (dd, J = 1.4, 9.0 Hz, 1 H), 3.87 (br. s., 2 H), 1.42 (s, 1 H), 1.22 - 1.19 (s, 21 H),

1.07 (d, J = 8.2 Hz, 5 H), 1.01 - 0.95 (m, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.6,

145.8, 141.4, 137.4, 130.4, 129.5, 128.1, 126.3, 125.8, 123.3, 116.5, 112.3, 101.8, 101.2,

100.1, 39.1, 37.5, 32.8, 29.7, 26.4, 26.1, 18.8, 11.4; HRMS (ESI) calcd for C31H42NOSi

(M++ H) 472.3030, found 472.3026.

(3j): yellow thick liquid, 80% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 8.04 (d, J = 7.8 Hz, 1 H), 7.57 - 7.44 (m, 4 H), 7.37 (d, J = 7.3 Hz, 2

H), 7.23 (br. s., 1 H), 7.07 (d, J = 6.4 Hz, 1 H), 6.72 (d, J = 8.3 Hz, 1 H), 6.42 (d, J = 9.3 Hz,

1 H), 2.43 (s, 3 H), 1.04 (br. s., 21 H); 13

C NMR (100 MHz, DMSO-d6) δ = 158.3, 143.4,

139.3, 138.4, 137.6, 133.8, 133.2, 130.7, 130.1, 130.0, 129.6, 122.0, 121.4, 119.5, 114.7,

114.3, 106.1, 99.5, 21.0, 18.5, 10.8; HRMS (ESI) calcd for C31H36NOSi (M++ H) 466.2561,

found 466.2566.

(3k): yellow solid, 87% yield; mp = 53-54 °C; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H

NMR (400 MHz, DMSO-d6) δ = 8.03 (d, J = 7.8 Hz, 1 H), 7.58 - 7.50 (m, 3 H), 7.47 (t, J =

7.6 Hz, 1 H), 7.26 (t, J = 7.7 Hz, 1 H), 7.12 (d, J = 8.6 Hz, 2 H), 7.07 (d, J = 6.6 Hz, 1 H),

6.78 (d, J = 8.1 Hz, 1 H), 6.41 (d, J = 9.0 Hz, 1 H), 3.87 (s, 3 H), 1.05 (s, 21 H); 13

C NMR

26

(100 MHz, DMSO-d6) δ = 160.4, 158.3, 143.4, 137.9, 137.5, 133.3, 131.5, 130.6, 130.1,

129.5, 128.8, 121.8, 121.3, 119.4, 114.6, 114.5, 114.0, 106.2, 99.4, 55.4, 18.5, 10.8; HRMS

(ESI) calcd for C31H36NO2Si (M++ H) 482.2510, found 482.2508.

(3l): yellow thick liquid, 68% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 8.05 (d, J = 7.6 Hz, 1 H), 7.66 (d, J = 1.5 Hz, 1 H), 7.65 - 7.59 (m, 3

H), 7.55 (dd, J = 6.7, 9.2 Hz, 1 H), 7.51 (t, J = 7.3 Hz, 1 H), 7.31 - 7.24 (m, 1 H), 7.10 (dd, J

= 0.6, 6.7 Hz, 1 H), 6.71 (d, J = 8.2 Hz, 1 H), 6.49 - 6.37 (m, 1 H), 1.07 - 1.02 (m, 21 H); 13

C

NMR (125 MHz, DMSO-d6) δ = 158.3, 143.3, 139.3, 138.9, 137.8, 133.6, 132.8, 130.9,

130.8, 130.2, 130.0, 129.5, 129.3, 128.9, 122.1, 121.5, 119.7, 115.3, 112.4, 105.7, 99.9, 18.4,

10.8; HRMS (ESI) calcd for C30H33NOClSi (M++ H) 486.2014, found 486.2015.

(3m): yellow thick liquid, 71% yield; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 7.97 (br. s., 1 H), 7.53 - 7.39 (m, 2 H), 7.25 (br. s., 1 H), 7.02 (br. s., 1

H), 6.84 (d, J = 8.2 Hz, 1 H), 6.75 (s, 2 H), 6.64 (br. s., 1 H), 6.40 (d, J = 9.2 Hz, 1 H), 3.76

(s, 6 H), 1.04 (s, 21 H); 13

C NMR (125 MHz, DMSO-d6) δ = 160.5, 158.3, 143.4, 139.0,

138.6, 137.4, 133.1, 130.7, 129.9, 129.5, 122.4, 121.1, 119.5, 114.6, 114.2, 107.6, 105.7,

101.6, 99.4, 79.1, 55.2, 18.4, 10.8; HRMS (ESI) calcd for C32H38NO3Si (M++ H) 512.2615,

found 512.2609.

27

(3n): yellow thick liquid, 72% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 7.59 - 7.53 (m, 6 H), 7.28 (d, J = 7.3 Hz, 1 H), 7.09 (t, J = 7.8 Hz, 1

H), 6.94 (d, J = 6.8 Hz, 1 H), 6.52 (d, J = 8.1 Hz, 1 H), 6.44 (d, J = 9.3 Hz, 1 H), 2.60 (s, 3

H), 1.04 (s, 21 H); 13

C NMR (100 MHz, DMSO-d6) δ = 158.5, 143.7, 138.7, 137.7, 137.0,

134.0, 133.8, 131.8, 130.4, 129.9, 129.4, 129.1, 128.7, 119.7, 119.3, 114.5, 114.0, 106.3,

103.1, 20.4, 18.5, 10.8; HRMS (ESI) calcd for C31H36NOSi (M++ H) 466.2561, found

466.2558.

(3o): yellow thick liquid, 70% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 7.83 (s, 1 H), 7.60 - 7.57 (m, 2 H), 7.56 - 7.49 (m, 4 H), 7.04 - 6.99 (m,

2 H), 6.47 (d, J = 8.2 Hz, 1 H), 6.41 (d, J = 9.2 Hz, 1 H), 2.33 (s, 3 H), 1.03 (s, 21 H); 13

C

NMR (125 MHz, DMSO-d6) δ = 177.4, 158.4, 143.5, 139.9, 138.9, 137.6, 136.9, 131.2,

131.0, 130.8, 130.0, 129.4, 129.0, 121.9, 121.3, 119.5, 114.1, 113.6, 106.1, 99.4, 72.7, 21.0,

18.5, 10.8; HRMS (ESI) calcd for C31H36NOSi (M++ H) 466.2561, found 466.2559.

(3p): yellow thick liquid, 77% yield; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 8.07 (d, J = 8.3 Hz, 1 H), 7.91 (s, 1 H), 7.53 - 7.41 (m, 2 H), 7.19 (d, J

= 7.3 Hz, 1 H), 6.55 (d, J = 8.8 Hz, 1 H), 5.57 (br. s., 1 H), 2.59 (br. s., 1 H), 2.51 (s, 3 H),

2.18 (br. s., 2 H), 1.86 (br. s., 2 H), 1.80 (br. s., 1 H), 1.69 (br. s., 1 H), 1.26 (s, 2 H), 1.19 (s,

21 H); 13

C NMR (100 MHz, DMSO-d6) δ = 161.8, 144.6, 141.4, 138.2, 137.1, 136.2, 131.8,

127.7, 126.1, 125.8, 125.1, 123.2, 115.9, 110.2, 101.6, 99.5, 29.1, 25.3, 22.7, 21.8, 21.7, 18.7,

11.4; HRMS (ESI) calcd for C31H40NOSi (M++ H) 470.2874, found 470.2870.

28

(3q): yellow thick liquid, 74% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 7.91 - 7.81 (m, 1 H), 7.62 - 7.50 (m, 5 H), 7.50 - 7.45 (m, 1 H), 7.27

(d, J = 8.3 Hz, 1 H), 7.00 - 6.86 (m, 1 H), 6.44 - 6.30 (m, 2 H), 2.07 (s, 3 H), 1.04 (s, 21 H);

13C NMR (100 MHz, DMSO-d6) δ = 158.3, 143.5, 139.5, 138.7, 137.4, 136.9, 133.4, 130.6,

129.9, 129.3, 128.8, 128.5, 122.4, 121.0, 119.0, 114.5, 114.3, 105.9, 98.8, 21.6, 18.4, 10.8;

HRMS (ESI) calcd for C31H36ONSi (M++ H) 466.2561, found 466.2558.

(3r): yellow thick liquid, 71% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, DMSO-d6) δ = 8.08 (d, J = 8.3 Hz, 1 H), 7.60 (br. s., 5 H), 7.57 - 7.53 (m, 2 H), 7.12

(d, J = 6.4 Hz, 1 H), 6.49 - 6.41 (m, 2 H), 1.04 (s, 21 H); 13

C NMR (100 MHz, DMSO-d6) δ

= 158.4, 142.7, 137.9, 136.8, 134.8, 134.4, 130.1, 129.9, 129.8, 129.4, 123.4, 122.0, 120.0,

116.3, 115.7, 106.0, 100.4, 18.7, 10.9; HRMS (ESI) calcd for C30H33ONClSi (M++ H)

486.2014, found 486.2015.

(3s): yellow thick liquid, 75% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 7.52 - 7.47 (m, 1 H), 7.38 - 7.32 (m, 5 H), 7.29 - 7.27 (m, 1 H), 7.11

(d, J = 6.7 Hz, 1 H), 6.46 (s, 1 H), 6.39 (d, J = 9.2 Hz, 1 H), 3.87 (s, 3 H), 3.07 (s, 3 H), 1.04

(s, 21 H); 13

C NMR (125 MHz, DMSO-d6) δ = 162.4, 158.7, 155.3, 143.7, 140.6, 138.8,

137.5, 136.9, 134.1, 129.4, 127.4, 127.2, 119.8, 114.6, 112.3, 111.8, 107.6, 100.7, 99.9, 96.8,

29

56.0, 55.2, 18.5, 10.9; HRMS (ESI) calcd for C32H38NO3Si (M++ H) 512.2615, found

512.2615.

(11a): yellow thick liquid, 74% yield; Rf = 0.40 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 8.03 (d, J = 7.6 Hz, 1 H), 7.60 - 7.53 (m, 6 H), 7.47 (t, J = 7.3 Hz, 1

H), 7.23 - 7.18 (m, 1 H), 7.09 (dd, J = 0.9, 6.7 Hz, 1 H), 6.55 (d, J = 7.9 Hz, 1 H), 6.46 (dd, J

= 0.9, 9.2 Hz, 1 H), 0.91 (s, 9 H), 0.12 (s, 6 H); 13

C NMR (125 MHz, DMSO-d6) δ = 158.4,

143.4, 139.1, 137.8, 136.6, 133.1, 130.8, 130.0, 130.0, 129.8, 129.6, 129.2, 122.1, 121.4,

119.6, 116.4, 114.2, 105.0, 99.7, 26.0, -4.6; HRMS (ESI) calcd for C27H28NOSi (M++ H)

410.1935, found 410.1934.

(11b): yellow thick liquid, 48% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (500

MHz, DMSO-d6) δ = 8.06 (d, J = 7.6 Hz, 1 H), 7.83 - 7.77 (m, 4 H), 7.72 - 7.66 (m, 2 H),

7.63 - 7.58 (m, 4 H), 7.50 (t, J = 7.5 Hz, 1 H), 7.46 - 7.38 (m, 6 H), 7.23 (t, J = 7.8 Hz, 1 H),

7.13 (d, J = 6.7 Hz, 1 H), 6.59 (d, J = 8.2 Hz, 1 H), 6.53 (d, J = 9.2 Hz, 1 H), 1.01 (s, 9 H);

13C NMR (125 MHz, DMSO-d6) δ = 158.7, 143.5, 139.3, 138.1, 136.7, 135.3, 133.1, 132.6,

131.0, 130.1, 130.0, 129.7, 129.3, 127.9, 122.4, 121.5, 119.8, 113.9, 112.8, 107.7, 100.1,

26.8, 18.3; HRMS (ESI) calcd for C37H32NOSi (M++ H) 534.2248, found 534.2247.

(8): yellow thick liquid, 68% yield; Rf = 0.20 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, CDCl3) δ = 8.22 (d, J = 8.1 Hz, 1 H), 7.65 - 7.58 (m, 3 H), 7.57 - 7.52 (m, 1 H), 7.36 -

30

7.32 (m, 2 H), 7.31 - 7.30 (m, 1 H), 6.97 - 6.92 (m, 2 H), 6.87 (s, 1 H), 6.58 (dd, J = 1.0, 8.8

Hz, 1 H), 3.86 (s, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 162.2, 158.8, 142.6, 138.6, 137.4,

131.3, 130.4, 128.1, 127.1, 126.8, 126.6, 123.5, 119.2, 115.8, 113.2, 99.8, 55.3; HRMS (ESI)

calcd for C20H16NO2 (M++ H) 302.1176, found 302.1174.

(9): yellow solid, 83% yield; mp = 61-62 °C; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR

(500 MHz, CDCl3) δ = 10.09 (d, J = 8.4 Hz, 1 H), 7.72 (d, J = 9.2 Hz, 1 H), 7.62 (d, J = 6.9

Hz, 1 H), 7.59 (s, 1 H), 7.49 - 7.46 (m, 1 H), 7.33 - 7.28 (m, J = 8.4 Hz, 2 H), 6.97 - 6.91 (m,

J = 8.8 Hz, 2 H), 6.89 (s, 1 H), 6.51 (d, J = 9.2 Hz, 1 H), 3.85 (s, 3 H), 1.23 - 1.18 (m, 21 H);

13C NMR (125 MHz, CDCl3) δ = 161.7, 159.1, 144.5, 139.0, 134.2, 134.1, 131.5, 131.0,

130.9, 129.3, 129.2, 127.3, 126.9, 126.7, 126.5, 119.6, 115.5, 113.6, 106.6, 98.1, 97.4, 55.3,

18.8, 11.5; HRMS (ESI) calcd for C31H36NO2Si (M++ H) 482.2510, found 482.2509.

(10): off white solid, 47% yield; mp = 136-137 °C; Rf = 0.20 (pet. ether/EtOAc = 40/60); 1H

NMR (400 MHz, CDCl3) δ = 11.01 (br. s., 1 H), 7.68 - 7.60 (m, 1 H), 7.55 - 7.46 (m, 2 H),

7.43 (d, J = 5.9 Hz, 4 H), 6.85 (d, J = 8.3 Hz, 2 H), 6.57 (d, J = 9.3 Hz, 1 H), 6.51 (d, J = 6.8

Hz, 1 H), 3.80 (s, 3 H); 13

C NMR (100 MHz, CDCl3) δ = 163.7, 160.0, 145.6, 140.9, 134.6,

133.3, 133.2, 129.6, 128.7, 128.5, 121.4, 119.3, 114.4, 114.1, 106.7, 95.2, 85.8, 55.3; HRMS

(ESI) calcd for C20H16NO2 (M++ H) 302.1176, found 302.1172.

31

(12): yellow thick liquid, 79% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, CDCl3) = 7.99 (d, J = 8.3 Hz, 1 H), 7.92 (s, 1 H), 7.51 (t, J = 8.3 Hz, 1 H), 7.44 (d, J

= 7.8 Hz, 1 H), 7.20 (d, J = 7.3 Hz, 1 H), 6.56 (d, J = 8.8 Hz, 1 H), 5.51 (br. s., 1 H), 3.47 (s,

1 H), 2.64 (br. s., 1 H), 2.52 (s, 3 H), 2.19 (br. s., 2 H), 1.85 (br. s., 3 H), 1.69 (br. s., 2 H);

13C NMR (100 MHz, CDCl3) δ = 161.7, 145.5, 141.4, 138.4, 137.2, 136.3, 131.8, 127.4,

125.8, 125.2, 123.3, 116.0, 108.9, 99.5, 85.0, 29.3, 25.4, 22.8, 21.9, 21.8; HRMS (ESI) calcd

for C22H20NO (M++ H) 314.1539, found 314.1539.

(13): yellow thick liquid, 81% yield; Rf = 0.30 (pet. ether/EtOAc = 80/20); 1H NMR (400

MHz, CDCl3) δ = 8.10 (d, J = 8.3 Hz, 1 H), 7.97 (s, 1 H), 7.63 - 7.57 (m, 2 H), 7.56 - 7.47

(m, 2 H), 7.45 - 7.35 (m, 3 H), 7.24 (d, J = 7.3 Hz, 1 H), 6.58 (d, J = 9.3 Hz, 1 H), 5.59 (br. s.,

1 H), 2.69 (br. s., 2 H), 2.54 (s, 3 H), 2.25 (br. s., 2 H), 1.91 (br. s., 3 H), 1.75 (br. s., 1 H);

13C NMR (100 MHz, CDCl3) δ = 161.8, 144.2, 141.4, 138.4, 137.1, 136.6, 131.8, 131.4,

128.5, 128.4, 127.5, 125.9, 125.9, 125.1, 123.4, 115.9, 110.0, 99.6, 97.1, 84.9, 29.5, 25.5,

22.9, 22.1, 21.8; HRMS (ESI) calcd for C28H24NO (M++ H) 390.1852, found 390.1852.

(14): yellow solid, 83% yield; mp = 120-121 °C; Rf = 0.30 (pet. ether/EtOAc = 60/40); 1H

NMR (500 MHz, CDCl3) δ = 7.96 (s, 1 H), 7.42 - 7.31 (m, 6 H), 7.26 - 7.19 (m, 3 H), 6.54

(d, J = 8.7 Hz, 1 H), 5.63 (br. s., 1 H), 5.58 (br. s., 1 H), 5.19 (br. s., 1 H), 2.46 (s, 3 H), 2.02

(d, J = 7.8 Hz, 1 H), 1.94 (br. s., 1 H), 1.66 - 1.45 (m, 4 H), 1.45 - 1.30 (m, 1 H); 13

C NMR

(125 MHz, CDCl3) δ = 162.2, 142.8, 142.2, 140.6, 138.1, 137.1, 135.5, 134.6, 131.5, 129.2,

128.9, 128.8, 128.1, 126.1, 125.9, 125.8, 124.4, 123.4, 115.9, 115.7, 99.5, 54.3, 30.4, 24.9,

22.3, 21.7, 21.5; HRMS (ESI) calcd for C29H27N4O (M++ H) 447.2178, found 447.2179.

32

5. 1H NMR and

13C NMR spectra:

10 9 8 7 6 5 4 3 2 1 0

1.011.082.103.063.111.00

CHLOROFORM-d

8.1

4

7.8

67

.85

7.8

47

.68

7.6

67

.55

7.5

47

.53

7.5

27

.33

7.2

2

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

3.2

31

32.4

41

31.6

41

28.2

91

28.0

31

27.8

21

27.7

61

27.0

31

26.5

7

12

0.1

7

94

.33

88

.36

77

.31

77

.00

76

.68

33

10 9 8 7 6 5 4 3 2 1 0

3.032.012.112.012.032.091.021.001.001.00

CHLOROFORM-d

7.5

87

.56

7.4

57

.43

7.2

57

.23

7.2

17

.14

7.1

27

.10

2.3

92

.37

1.9

31

.90

1.7

81

.75

1.3

21

.28

1.2

01

.19

1.1

81

.16

1.1

3

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

3.2

81

32.2

21

28.5

41

26.8

31

26.1

51

25.4

3

94

.53

80

.18

77

.32

77

.00

76

.69

37

.39

32

.70

27

.37

26

.26

26

.16

34

10 9 8 7 6 5 4 3 2 1 0

5.961.002.022.972.03

CHLOROFORM-d

7.6

17

.60

7.6

07

.59

7.4

07

.39

7.3

87

.38

6.7

86

.77

6.7

66

.53

6.5

2

5.3

0

3.8

3

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

0.4

7

13

1.5

41

28.2

6

12

4.4

41

23.0

0

10

9.2

5

10

1.7

0

89

.35

88

.86

77

.31

77

.00

76

.68

55

.25

35

10 9 8 7 6 5 4 3 2 1 0

3.132.063.011.062.01

CHLOROFORM-d

7.6

57

.64

7.6

37

.62

7.4

37

.40

7.3

97

.39

7.2

27

.20

2.4

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

8.7

41

32.4

51

31.6

21

30.7

41

30.3

71

28.4

81

28.4

01

28.3

21

26.6

81

25.7

91

23.0

7

93

.45

88

.77

77

.32

77

.00

76

.69

23

.79

36

10 9 8 7 6 5 4 3 2 1 0

2.032.082.032.053.031.021.011.010.99

CHLOROFORM-d

7.4

07

.34

7.3

27

.27

7.0

57

.04

6.2

86

.27

6.2

7

2.3

22

.27

2.1

72

.16

2.1

62

.15

1.7

01

.69

1.6

41

.64

1.6

3

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

9.3

51

35.6

01

32.7

91

32.6

51

27.8

21

25.1

41

22.7

51

20.6

9

95

.07

85

.55

77

.26

77

.00

76

.75

29

.02

25

.77

22

.28

21

.49

21

.04

37

10 9 8 7 6 5 4 3 2 1 0

2.011.023.121.051.023.181.001.02

CHLOROFORM-d

8.0

98

.09

7.8

77

.86

7.8

57

.85

7.5

57

.54

7.5

47

.53

7.4

37

.27

5.9

5

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

5.6

71

32.9

31

32.6

21

31.7

11

30.8

61

28.3

81

27.8

81

27.1

41

26.8

31

19.1

0

93

.90

90

.04

77

.31

77

.00

76

.69

38

10 9 8 7 6 5 4 3 2 1 0

3.013.102.072.001.002.011.001.020.880.94

CHLOROFORM-d

7.9

97

.97

7.4

77

.45

7.4

27

.41

7.4

07

.36

7.3

57

.35

6.2

66

.24

6.2

36

.21

2.7

02

.69

2.6

8

1.9

71

.96

1.9

51

.78

1.7

71

.77

1.5

91

.57

1.4

01

.38

1.3

7

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

5.4

41

32.5

11

30.6

81

27.5

71

27.5

0

99

.04

81

.66

77

.25

77

.00

76

.74

32

.48

29

.71

25

.68

24

.89

39

10 9 8 7 6 5 4 3 2 1 0

3.182.412.432.242.462.202.082.201.061.00

CHLOROFORM-d

8.0

17

.99

7.4

97

.47

7.4

37

.41

7.4

17

.39

7.3

77

.35

7.2

76

.54

2.4

32

.41

2.4

01

.91

1.8

81

.79

1.7

61

.68

1.3

21

.29

1.2

01

.14

1.1

11

.08

1.0

5

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

5.4

51

32.6

11

30.6

51

27.5

5

94

.11

82

.58

77

.31

77

.00

76

.69

37

.33

32

.74

27

.16

26

.11

26

.03

40

10 9 8 7 6 5 4 3 2 1 0

3.062.012.031.033.061.021.02

CHLOROFORM-d

8.0

48

.02

7.6

07

.59

7.4

77

.45

7.4

27

.41

7.2

77

.22

7.2

0

6.0

3

2.4

0

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

9.3

91

35.6

21

32.4

71

31.4

41

30.7

91

29.3

71

28.1

41

26.8

81

18.7

7

93

.73

89

.16

77

.26

77

.00

76

.75

21

.55

41

10 9 8 7 6 5 4 3 2 1 0

2.320.991.102.281.241.021.141.13

CHLOROFORM-d

8.0

38

.02

7.5

97

.55

7.4

97

.44

7.4

47

.43

7.3

57

.33

7.2

7

5.8

4

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

5.6

7

13

2.6

91

31.3

41

30.8

71

29.8

51

29.6

61

29.3

41

28.6

71

23.5

6

91

.86

90

.80

77

.26

77

.00

76

.75

42

10 9 8 7 6 5 4 3 2 1 0

6.242.171.042.041.140.971.011.00

CHLOROFORM-d

8.0

28

.00

7.6

17

.61

7.5

97

.47

7.4

37

.42

7.4

17

.27

6.7

16

.70

6.5

36

.52

6.5

25

.92

3.8

3

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

0.7

0

13

5.6

21

32.5

91

30.8

01

28.3

81

26.4

71

23.1

0

10

9.3

0

10

2.4

5

93

.41

89

.22

77

.31

77

.00

76

.68

55

.48

43

10 9 8 7 6 5 4 3 2 1 0

3.002.020.991.082.881.031.99

CHLOROFORM-d

7.5

57

.54

7.5

37

.40

7.3

77

.36

7.3

67

.29

7.1

8

5.4

5

2.5

2

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

14

2.2

91

31.5

11

30.0

81

29.2

51

28.5

01

28.3

91

25.8

31

22.7

2

91

.81

90

.01

77

.31

77

.00

76

.69

22

.70

44

10 9 8 7 6 5 4 3 2 1 0

3.142.041.043.011.032.031.02

CHLOROFORM-d

7.8

5

7.5

57

.54

7.5

27

.50

7.4

07

.40

7.3

97

.39

7.2

7

6.1

1

2.4

1

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

8.3

91

36.3

21

32.5

31

31.6

41

31.4

71

28.8

91

28.5

71

23.6

01

22.0

5

92

.87

89

.91

77

.31

77

.00

76

.69

21

.44

45

10 9 8 7 6 5 4 3 2 1 0

2.132.132.002.073.122.001.051.041.011.02

CHLOROFORM-d

7.8

07

.39

7.3

77

.27

7.2

47

.22

6.2

76

.26

6.1

4

2.3

82

.26

2.2

52

.19

2.1

82

.17

1.7

11

.70

1.6

51

.65

1.6

41

.61

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

7.7

61

36.4

01

36.1

91

32.2

61

31.5

5

12

4.2

2

11

9.8

4

94

.86

87

.35

77

.32

77

.00

76

.69

28

.95

25

.77

22

.17

21

.34

46

10 9 8 7 6 5 4 3 2 1 0

3.082.001.013.131.022.031.00

CHLOROFORM-d

7.9

37

.91

7.5

67

.47

7.4

47

.40

7.3

77

.27

7.2

57

.23

6.0

1

2.4

0

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

14

1.3

31

35.9

61

33.4

11

31.7

81

29.6

11

29.2

61

28.8

51

26.8

31

22.1

7

93

.33

90

.16

77

.00

21

.56

47

10 9 8 7 6 5 4 3 2 1 0

2.004.153.050.94

CHLOROFORM-d

7.9

77

.94

7.5

97

.56

7.5

57

.55

7.4

27

.41

7.4

07

.27

6.0

4

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

13

7.3

41

32.5

01

31.9

31

29.7

51

29.0

01

28.9

51

28.6

01

21.6

5

94

.76

88

.71

77

.64

77

.31

77

.00

48

10 9 8 7 6 5 4 3 2 1 0

3.163.092.001.001.013.292.20

CHLOROFORM-d

7.5

67

.37

7.2

77

.15

6.6

0

6.1

2

3.9

13

.89

180 160 140 120 100 80 60 40 20

CHLOROFORM-d

16

1.6

81

60.7

4

13

1.4

11

28.5

51

28.4

6

12

2.5

5

11

0.7

21

08.3

8

10

1.4

0

96

.62

86

.21

77

.26

77

.00

76

.75

55

.97

55

.50

49

10 9 8 7 6 5 4 3 2 1 0

3.201.003.114.153.091.03

CHLOROFORM-d

7.9

07

.88

7.6

97

.67

7.4

57

.44

7.4

47

.35

7.3

57

.34

7.3

4

6.8

06

.80

4.0

5

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.8

3

15

5.1

01

42.1

11

38.5

31

33.6

01

31.6

01

29.9

21

28.7

51

28.5

91

28.4

51

28.2

71

23.7

41

21.5

11

17.2

71

09.6

6

92

.81

89

.78

77

.64

77

.31

77

.00

53

.58

50

10 9 8 7 6 5 4 3 2 1 0

3.071.011.182.072.191.142.153.191.031.04

CHLOROFORM-d

7.9

47

.82

7.8

07

.79

7.7

27

.70

7.6

97

.51

7.5

07

.49

6.8

16

.80

6.7

9

4.0

4

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

8

15

4.8

71

41.8

91

38.3

21

33.3

81

31.1

51

28.5

31

28.1

21

28.0

41

27.9

81

27.7

31

26.6

31

26.5

31

21.2

51

20.7

61

17.0

41

09.4

3

92

.93

89

.85

77

.25

77

.00

76

.74

53

.35

51

10 9 8 7 6 5 4 3 2 1 0

3.191.022.232.324.243.151.041.002.20

CHLOROFORM-d

8.6

98

.67

8.6

5

7.9

87

.88

7.8

77

.85

7.7

17

.69

7.6

87

.67

7.5

97

.51

7.2

76

.84

6.8

3

4.0

1

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.7

4

15

5.2

71

42.1

51

38.5

61

33.5

61

31.6

81

29.7

11

28.5

31

28.1

11

27.4

11

27.0

31

26.9

31

26.9

01

22.6

71

21.5

61

17.1

71

09.5

2

93

.80

91

.00

77

.32

77

.00

76

.69

53

.40

52

10 9 8 7 6 5 4 3 2 1 0

3.322.262.042.053.110.951.071.271.001.980.99

CHLOROFORM-d

7.8

27

.80

7.6

27

.62

7.6

17

.60

7.5

37

.38

7.3

17

.31

6.7

36

.72

6.7

2

4.0

2

2.4

02

.39

2.3

82

.37

1.5

51

.54

1.5

31

.53

1.5

21

.39

0.9

40

.93

0.9

20

.91

0.9

0

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

8

15

4.9

7

14

1.5

31

38.0

71

33.4

41

29.5

11

27.8

21

27.6

41

22.0

21

16.9

7

10

9.0

7

93

.85

80

.22

77

.31

77

.00

76

.69

53

.23

30

.51

21

.90

19

.26

13

.58

53

10 9 8 7 6 5 4 3 2 1 0

3.104.142.052.142.093.060.971.071.161.002.011.00

CHLOROFORM-d

7.7

97

.62

7.6

07

.52

7.3

87

.38

7.3

17

.30

7.2

76

.73

6.7

26

.71

6.7

1

4.0

2

2.3

82

.37

2.3

61

.55

1.5

41

.52

1.2

91

.29

1.2

81

.28

1.2

70

.91

0.8

90

.88

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

9

15

4.9

7

14

1.5

31

38.0

91

33.4

71

29.5

21

27.8

41

27.6

51

22.0

41

16.9

9

10

9.0

9

93

.94

80

.24

77

.26

77

.00

76

.75

53

.26

31

.37

28

.56

28

.44

22

.54

19

.62

14

.06

54

10 9 8 7 6 5 4 3 2 1 0

6.282.070.963.110.981.081.191.002.041.00

CHLOROFORM-d

7.8

47

.84

7.8

27

.63

7.6

17

.52

7.5

17

.38

7.3

87

.31

6.7

46

.73

6.7

2

4.0

2

2.8

52

.83

2.8

12

.79

2.7

8

1.9

21

.72

1.7

21

.70

1.6

91

.66

1.6

51

.62

1.5

8

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

5

15

4.9

1

14

1.4

81

37.9

71

33.2

71

29.4

81

27.8

11

27.5

91

22.0

3

11

7.0

1

10

9.0

4

97

.99

79

.83

77

.32

77

.00

76

.69

53

.23

33

.48

30

.95

24

.89

55

10 9 8 7 6 5 4 3 2 1 0

3.133.172.242.061.043.141.020.981.301.061.950.96

CHLOROFORM-d

7.8

47

.82

7.6

57

.63

7.6

17

.54

7.5

27

.38

7.3

67

.31

6.7

36

.71

4.0

2

2.5

92

.58

1.7

91

.70

1.6

91

.69

1.5

11

.50

1.4

91

.48

1.3

41

.33

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

8

15

4.9

2

14

1.5

31

37.9

91

33.3

71

29.4

81

27.8

01

27.6

11

22.0

41

17.1

4

10

9.0

6

97

.80

80

.26

77

.32

77

.00

76

.69

53

.23

32

.32

29

.76

25

.89

24

.72

56

10 9 8 7 6 5 4 3 2 1 0

5.094.313.171.000.991.091.031.022.041.02

CHLOROFORM-d

7.8

47

.84

7.8

27

.64

7.6

27

.54

7.5

47

.39

7.3

27

.32

6.7

46

.73

6.7

26

.11

6.1

0

4.0

2

2.1

42

.13

2.1

32

.12

1.6

61

.66

1.6

41

.63

1.6

11

.60

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

5

15

4.8

0

14

1.3

91

38.1

11

35.0

01

33.1

51

29.5

41

27.9

21

21.6

81

20.9

41

17.0

3

10

9.1

6

94

.55

86

.77

77

.31

77

.00

76

.69

53

.27

28

.81

25

.72

22

.25

21

.48

57

10 9 8 7 6 5 4 3 2 1 0

2.021.132.221.055.132.002.981.001.021.001.001.941.01

CHLOROFORM-d

7.8

27

.80

7.6

27

.61

7.5

67

.55

7.3

97

.39

7.3

27

.32

6.7

56

.73

6.7

3

4.0

3

2.2

92

.28

1.7

91

.79

1.7

61

.73

1.7

11

.71

1.2

61

.23

1.0

11

.00

0.9

90

.98

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

5

15

5.0

0

14

1.5

21

38.0

51

33.4

31

29.4

31

27.7

91

27.5

61

22.1

0

11

7.0

1

10

9.0

3

92

.83

81

.00

77

.25

77

.00

76

.74

53

.20

37

.35

32

.66

27

.40

26

.16

26

.08

58

10 9 8 7 6 5 4 3 2 1 0

3.173.101.022.141.100.972.173.071.03

CHLOROFORM-d

7.8

67

.81

7.6

67

.64

7.6

37

.39

7.3

87

.31

7.2

77

.25

7.1

47

.10

6.7

66

.71

4.0

0

2.3

5

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

5

15

4.8

81

41.7

21

38.3

41

38.2

41

33.2

61

31.2

41

29.6

21

29.0

81

28.2

81

27.9

71

21.4

61

20.4

21

17.0

11

09.3

2

92

.76

88

.83

77

.32

77

.00

53

.32

21

.48

59

10 9 8 7 6 5 4 3 2 1 0

3.233.171.052.183.181.103.271.09

CHLOROFORM-d

7.8

87

.86

7.6

87

.66

7.6

57

.44

7.4

07

.37

7.3

56

.88

6.8

66

.78

6.7

6

4.0

3

3.8

2

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

1

15

9.5

4

15

4.9

1

14

1.5

41

38.2

01

33.0

91

32.7

61

29.5

91

28.1

01

27.9

51

21.5

51

16.9

81

15.5

71

13.9

61

09.2

6

92

.57

88

.15

77

.31

77

.00

76

.68

55

.24

53

.29

60

10 9 8 7 6 5 4 3 2 1 0

3.011.012.021.072.011.041.022.021.01

CHLOROFORM-d

7.8

87

.73

7.7

17

.69

7.6

27

.60

7.4

37

.43

7.3

37

.32

7.3

1

6.8

36

.81

4.0

6

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.6

2

15

4.7

51

42.0

81

38.3

11

34.1

61

33.4

11

31.1

41

29.7

01

29.5

41

29.4

51

28.8

31

28.4

01

28.0

41

25.1

91

20.7

51

16.9

11

09.5

1

90

.97

90

.69

77

.31

77

.00

76

.68

53

.33

61

10 9 8 7 6 5 4 3 2 1 0

6.173.061.002.001.011.051.061.002.021.02

CHLOROFORM-d

7.8

77

.85

7.7

07

.68

7.6

67

.62

7.6

07

.46

7.3

96

.78

6.7

66

.59

6.5

86

.47

6.4

7

4.0

3

3.7

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

21

60.4

5

15

4.8

4

14

1.9

61

38.2

11

33.2

31

29.5

71

28.5

11

27.9

61

24.7

11

21.0

61

16.9

51

09.3

31

09.0

6

10

1.5

6

92

.48

89

.06

77

.32

77

.00

76

.68

55

.28

53

.29

62

10.0 9.5 9.0 8.5 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

3.143.140.961.012.005.041.001.01

CHLOROFORM-d

7.6

8

7.2

87

.27

7.2

67

.26

7.2

57

.20

7.1

97

.08

6.7

8

3.9

5

2.2

7

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.6

5

15

6.2

1

14

2.7

61

38.4

21

36.9

01

31.4

91

30.7

01

29.9

51

28.4

11

28.1

91

27.9

11

23.6

61

22.8

41

18.4

11

09.2

4

92

.35

89

.39

77

.51

77

.26

77

.00

53

.70

20

.69

63

10 9 8 7 6 5 4 3 2 1 0

3.013.030.991.183.042.061.051.002.01

CHLOROFORM-d

7.6

87

.67

7.6

37

.59

7.5

87

.41

7.3

37

.32

7.3

27

.20

6.7

86

.76

4.0

4

2.4

6

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

4

15

5.0

01

41.6

81

38.6

21

38.2

21

33.2

51

31.2

41

30.2

41

28.8

91

28.2

71

27.9

81

23.6

31

18.2

91

17.0

9

10

9.1

9

91

.77

89

.61

77

.26

77

.00

76

.75

53

.35

21

.57

64

10 9 8 7 6 5 4 3 2 1 0

2.202.134.143.083.031.031.061.081.063.07

CHLOROFORM-d

7.6

37

.61

7.6

07

.58

7.4

57

.44

7.2

77

.15

7.1

36

.73

6.7

16

.08

4.0

3

2.4

22

.14

2.1

32

.12

1.6

61

.65

1.6

41

.63

1.6

11

.60

1.5

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

7

15

4.9

9

14

1.2

51

38.0

61

37.9

61

34.5

51

33.0

81

30.1

21

28.7

71

21.0

11

18.7

51

17.1

1

10

8.9

8

93

.76

86

.86

77

.25

77

.00

76

.74

53

.29

28

.85

25

.70

22

.26

21

.49

65

10 9 8 7 6 5 4 3 2 1 0

3.113.131.001.013.012.040.982.061.00

CHLOROFORM-d

7.8

07

.78

7.6

87

.66

7.6

67

.52

7.4

47

.43

7.3

57

.34

6.7

76

.75

4.0

3

2.4

3

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.4

7

15

4.8

1

13

9.0

91

38.2

21

37.9

01

33.7

81

31.3

11

29.4

81

28.2

91

28.1

01

23.5

21

20.9

21

16.8

01

09.0

6

92

.12

89

.67

77

.26

77

.00

76

.75

53

.28

20

.93

66

10 9 8 7 6 5 4 3 2 1 0

3.001.003.073.063.011.00

CHLOROFORM-d

7.8

27

.81

7.6

87

.66

7.4

27

.42

7.4

17

.35

7.3

57

.34

6.7

86

.76

4.0

0

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

9

15

3.6

61

40.1

21

38.3

61

33.8

11

32.7

71

31.4

21

30.9

81

28.6

71

28.5

61

28.3

91

22.9

21

22.7

41

16.8

71

09.7

2

93

.56

88

.16

77

.25

77

.00

76

.74

53

.35

67

10 9 8 7 6 5 4 3 2 1 0

3.033.013.001.051.001.023.192.051.011.06

CHLOROFORM-d

7.6

77

.66

7.6

47

.61

7.3

77

.29

7.2

77

.27

6.9

76

.97

6.7

76

.75

6.5

36

.52

4.0

03

.95

3.8

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.7

21

62.0

61

60.7

1

15

5.0

6

14

4.9

9

13

8.4

3

13

1.3

91

28.3

91

27.8

71

24.3

21

17.6

5

10

9.7

81

06.3

91

04.0

0

98

.57

95

.95

85

.68

77

.51

77

.26

77

.00

56

.45

55

.71

53

.58

68

10 9 8 7 6 5 4 3 2 1 0

21.500.951.000.991.021.056.161.00

DMSO-d6

8.0

38

.02

7.6

17

.56

7.5

37

.52

7.4

87

.47

7.2

27

.21

7.0

87

.07

6.6

16

.59

6.4

46

.42

3.3

3

2.5

0

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.3

01

43.3

91

38.7

41

37.5

71

36.8

11

33.0

71

30.7

51

29.9

51

29.6

81

29.5

01

29.0

21

22.0

21

21.3

41

19.5

61

14.6

91

14.4

71

06.0

29

9.5

3

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

18

.41

10

.79

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 6.7 6.6 6.5 6.4

0.951.000.991.021.056.161.00

69

10 9 8 7 6 5 4 3 2 1 0

21.420.971.042.161.251.092.211.151.052.001.071.04

DMSO-d6

8.2

28

.11

8.0

98

.06

8.0

47

.75

7.7

47

.63

7.4

67

.14

7.1

27

.10

6.6

76

.66

6.4

76

.45

3.3

3

2.5

0

1.2

31

.06

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.4

01

43.4

31

38.8

81

37.6

8

13

0.8

11

30.1

41

29.8

11

28.6

31

28.3

21

27.8

41

27.2

91

27.0

31

21.9

01

21.4

61

19.6

31

14.8

81

06.1

49

9.7

1

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

18

.47

10

.84

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 6.7 6.6 6.5 6.4

0.971.042.161.251.092.211.151.052.001.071.04

70

9.0 8.5 8.0 7.5

1.011.040.982.122.092.171.062.032.091.00

10 9 8 7 6 5 4 3 2 1 0

21.550.941.011.040.982.122.092.171.062.032.091.00

DMSO-d69

.13

9.1

18

.85

8.8

28

.18

8.1

67

.77

7.7

27

.70

7.6

97

.67

7.6

57

.58

7.5

67

.44

7.3

87

.13

5.9

25

.90

3.3

4

2.5

0

1.0

00

.99

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.2

61

43.6

01

38.3

71

37.2

71

31.6

41

29.9

21

28.7

21

27.0

71

26.7

91

26.0

21

24.8

31

23.7

21

22.7

81

21.5

21

19.5

31

10.9

01

07.0

71

04.9

81

00.2

1

40

.14

39

.93

39

.72

39

.51

39

.30

39

.10

38

.88

18

.36

10

.76

71

10 9 8 7 6 5 4 3 2 1 0

3.2121.222.142.062.001.001.152.111.082.06

CHLOROFORM-d

8.1

28

.10

8.0

98

.07

7.6

17

.52

7.5

17

.51

7.5

07

.27

7.2

07

.19

6.6

26

.60

3.6

63

.65

3.6

3

1.7

71

.76

1.7

41

.41

1.4

01

.38

1.3

6

1.2

01

.20

0.9

40

.92

0.9

1

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.2

5

14

7.2

5

14

1.5

8

13

7.2

7

13

0.3

31

29.7

31

28.0

21

25.8

41

23.3

31

16.4

41

11.1

91

01.2

81

01.0

51

00.0

9

77

.25

77

.00

76

.74

33

.18

31

.18

22

.88

18

.74

13

.94

11

.38

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 6.7 6.6

1.001.152.111.082.06

72

10 9 8 7 6 5 4 3 2 1 0

3.4021.404.082.302.062.071.021.012.101.062.04

CHLOROFORM-d

8.1

28

.10

8.0

98

.07

7.6

17

.52

7.5

27

.51

7.5

0

7.2

77

.20

7.1

96

.62

6.6

0

3.6

63

.65

3.6

3

1.7

61

.75

1.3

6

1.2

91

.28

1.2

71

.26

1.2

01

.20

0.8

70

.86

0.8

5

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.2

6

14

7.3

11

41.5

91

37.2

71

30.3

31

29.7

41

28.0

11

25.8

61

25.7

71

23.3

41

16.4

51

11.1

61

01.3

11

01.0

21

00.0

9

77

.26

77

.00

76

.75

33

.41

31

.71

29

.49

29

.15

22

.68

18

.75

14

.03

11

.40

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 6.7 6.6

1.021.012.101.062.04

73

10 9 8 7 6 5 4 3 2 1 0

21.232.112.332.172.151.081.001.042.261.091.050.98

CHLOROFORM-d

8.1

88

.16

8.0

68

.04

7.5

87

.57

7.5

47

.52

7.5

07

.48

7.2

77

.16

7.1

56

.59

6.5

7

3.7

73

.76

3.7

43

.72

3.7

02

.63

2.6

02

.58

2.1

32

.12

2.1

12

.11

1.9

41

.92

1.6

91

.68

1.6

71

.21

1.1

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

4.2

6

14

9.9

8

14

1.8

51

37.4

31

30.5

71

30.2

41

27.9

71

25.6

71

25.4

71

23.0

21

16.1

51

11.2

11

05.6

01

00.7

09

9.4

6

77

.26

77

.00

76

.75

44

.34

31

.61

26

.11

18

.68

11

.53

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 6.7 6.6 6.5

1.001.042.261.091.050.98

74

10 9 8 7 6 5 4 3 2 1 0

21.212.001.091.021.982.001.990.991.001.072.131.021.010.99

CHLOROFORM-d

8.2

08

.18

8.0

58

.03

7.6

07

.58

7.5

67

.53

7.5

07

.49

7.2

77

.15

7.1

36

.60

6.5

8

3.3

73

.35

3.3

43

.33

3.3

23

.31

2.6

92

.66

1.9

81

.94

1.8

21

.69

1.4

31

.40

1.3

81

.36

1.2

61

.23

1.2

2

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

4.4

4

15

1.2

3

14

1.8

31

37.3

21

30.5

91

30.1

91

28.0

01

25.7

21

25.6

31

22.9

71

16.3

11

11.2

41

04.9

01

01.3

69

9.4

5

77

.26

77

.00

76

.75

43

.42

29

.71

27

.06

25

.62

18

.74

18

.66

18

.27

11

.51

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 6.7 6.6 6.5

1.001.072.131.021.010.99

75

10 9 8 7 6 5 4 3 2 1 0

21.112.022.032.021.960.900.971.971.042.002.011.002.001.901.011.00

CHLOROFORM-d

8.1

68

.07

8.0

68

.02

8.0

28

.01

7.5

57

.54

7.4

77

.45

7.4

47

.27

7.2

0

6.6

86

.66

5.5

9

2.6

12

.50

2.2

02

.18

1.8

71

.82

1.6

9

1.1

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

2.0

7

14

5.4

31

41.8

61

37.4

11

33.3

41

31.9

21

30.4

01

28.2

91

27.9

91

26.2

21

25.4

81

23.3

71

16.1

71

10.5

01

01.3

31

00.0

7

94

.65

77

.26

77

.00

76

.75

29

.69

25

.36

22

.69

21

.76

18

.77

11

.42

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 6.7

0.971.971.042.002.011.002.001.901.011.00

76

10 9 8 7 6 5 4 3 2 1 0

1.073.025.0321.071.200.942.110.831.182.021.042.00

CHLOROFORM-d

8.1

48

.12

8.1

18

.09

7.6

27

.54

7.5

37

.51

7.2

77

.23

7.2

17

.21

6.6

36

.62

6.6

1

3.8

7

1.4

21

.26

1.2

11

.20

1.0

71

.06

1.0

10

.98

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.5

5

14

5.7

61

41.4

11

37.3

61

30.3

61

29.5

11

28.0

91

26.2

51

25.7

71

23.3

11

16.4

81

12.3

0

10

1.8

01

01.1

51

00.1

5

77

.32

77

.00

76

.69

39

.08

37

.48

32

.75

29

.69

26

.41

26

.10

18

.79

11

.43

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 6.7 6.6 6.5

0.831.182.021.042.00

77

10 9 8 7 6 5 4 3 2 1 0

21.403.150.991.081.061.092.014.051.01

DMSO-d6

8.0

48

.02

7.5

17

.50

7.4

77

.45

7.3

87

.36

7.2

37

.08

7.0

76

.74

6.7

16

.43

6.4

1

3.3

4

2.5

02

.43

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.3

51

43.4

31

39.3

11

38.4

51

37.5

71

33.8

41

33.1

91

30.7

01

30.0

71

30.0

01

29.6

51

21.9

61

21.3

81

19.5

11

14.6

81

14.3

11

06.1

49

9.5

2

40

.14

39

.92

39

.72

39

.51

39

.30

39

.10

38

.88

21

.00

18

.48

10

.84

8.0 7.5 7.0 6.5

0.991.081.061.092.014.051.01

78

10 9 8 7 6 5 4 3 2 1 0

21.123.041.001.001.072.061.091.163.141.03

8.0

48

.02

7.5

67

.54

7.5

37

.50

7.4

77

.26

7.1

37

.11

7.0

87

.06

6.7

96

.77

6.4

26

.40

3.8

7

3.3

3

2.5

0

1.0

5

180 160 140 120 100 80 60 40 20 0

16

0.3

51

58.3

4

14

3.4

31

37.4

71

33.2

81

31.5

31

30.6

01

30.0

81

29.4

91

28.7

61

21.8

31

21.3

41

19.3

61

14.5

71

14.4

51

13.9

81

06.2

29

9.3

8

55

.37

40

.14

39

.93

39

.72

39

.51

39

.30

39

.09

38

.88

18

.46

10

.83

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 6.7 6.6 6.5 6.4 6.3

1.001.001.072.061.091.163.141.03

79

10 9 8 7 6 5 4 3 2 1 0

21.491.001.031.041.161.151.063.081.081.03

DMSO-d6

8.0

58

.04

7.6

57

.65

7.6

27

.61

7.6

07

.58

7.5

07

.27

7.1

06

.71

6.7

06

.45

6.4

56

.43

3.3

2

2.5

0

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.2

71

43.3

3

13

8.8

81

37.7

51

33.6

41

30.9

11

30.8

41

30.1

81

30.0

01

29.5

01

29.3

11

28.9

51

22.0

71

21.4

91

19.7

41

15.2

61

12.4

21

05.6

89

9.8

6

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

18

.40

10

.79

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 6.7 6.6 6.5 6.4

1.001.031.041.161.151.063.081.081.03

80

10 9 8 7 6 5 4 3 2 1 0

21.066.121.001.031.980.960.991.042.081.02

DMSO-d6

7.9

77

.49

7.4

87

.47

7.4

57

.25

7.0

26

.84

6.8

36

.75

6.6

46

.41

6.3

9

3.7

6

3.3

2

2.5

0

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

16

0.5

21

58.2

7

14

3.4

11

38.9

71

38.5

81

37.3

71

33.0

71

30.7

41

29.8

91

29.4

81

22.4

41

21.1

21

19.4

81

14.6

21

14.2

41

07.6

41

05.6

71

01.6

49

9.4

0

79

.13

78

.86

78

.59

55

.24

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

18

.39

10

.79

8.0 7.5 7.0 6.5

1.001.031.980.960.991.042.081.02

81

10 9 8 7 6 5 4 3 2 1 0

21.413.071.001.031.031.051.225.96

DMSO-d6

7.5

97

.57

7.5

67

.55

7.5

47

.53

7.2

77

.08

6.9

56

.93

6.5

36

.51

6.4

56

.43

3.3

3

2.6

02

.50

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.4

61

43.7

41

38.7

21

37.7

11

36.9

61

34.0

31

33.8

11

31.8

21

29.9

51

29.4

51

29.0

81

28.6

81

19.6

91

19.2

81

14.5

31

14.0

11

06.2

61

03.1

3

40

.14

39

.93

39

.72

39

.51

39

.30

39

.10

38

.88

20

.43

18

.45

10

.82

7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4

1.001.031.031.051.225.96

82

10 9 8 7 6 5 4 3 2 1 0

21.033.170.990.991.983.992.011.02

DMSO-d6

7.8

37

.59

7.5

87

.58

7.5

57

.54

7.5

47

.53

7.0

27

.02

7.0

16

.48

6.4

76

.41

6.4

0

3.3

4

2.5

02

.33

1.0

3

180 160 140 120 100 80 60 40 20 0

DMSO-d6

17

7.4

3

15

8.4

11

43.4

91

39.8

71

38.8

91

37.6

31

36.9

31

31.1

61

31.0

51

30.7

71

29.9

91

29.4

51

29.0

31

21.9

31

21.2

61

19.5

51

14.1

41

06.0

8

72

.71

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

20

.99

18

.47

10

.84

7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4

0.990.991.983.992.011.02

83

10 9 8 7 6 5 4 3 2 1 0

21.222.151.982.002.083.021.050.960.951.072.111.001.00

CHLOROFORM-d

8.0

88

.06

7.9

17

.52

7.5

07

.48

7.4

67

.44

7.2

77

.20

7.1

86

.57

6.5

4

5.5

7

2.5

92

.51

2.1

8

1.8

61

.80

1.6

91

.26

1.1

9

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

1.8

3

14

4.6

31

41.3

81

38.2

41

37.1

01

36.2

11

31.7

81

27.7

11

26.0

71

25.8

11

25.1

41

23.2

41

15.8

61

10.1

5

10

1.5

69

9.5

2

77

.32

77

.00

76

.69

29

.14

25

.32

22

.71

21

.77

21

.74

18

.73

11

.37

8.0 7.5 7.0 6.5 6.0 5.5

0.960.951.072.111.001.00

84

10 9 8 7 6 5 4 3 2 1 0

21.083.091.921.071.191.065.071.08

DMSO-d6

7.8

67

.85

7.6

07

.59

7.5

87

.55

7.4

87

.47

7.2

87

.26

6.9

66

.95

6.3

86

.36

6.3

5

3.3

1

2.5

0

2.0

7

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.3

51

43.5

31

39.4

61

38.7

51

37.4

31

36.9

01

30.5

71

29.9

11

29.2

91

28.8

21

28.5

11

22.3

61

20.9

61

19.0

31

14.5

01

14.3

41

05.9

29

8.8

3

79

.19

78

.86

78

.54

40

.14

39

.93

39

.72

39

.51

39

.30

39

.10

38

.88

21

.56

18

.38

10

.79

7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3

1.921.071.191.065.071.08

85

10 9 8 7 6 5 4 3 2 1 0

21.332.001.002.045.051.08

DMSO-d6

8.0

98

.07

7.6

07

.57

7.5

67

.55

7.5

47

.13

7.1

16

.47

6.4

46

.43

3.3

3

2.5

0

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.3

7

14

2.7

31

37.9

21

36.7

91

34.8

11

34.4

51

30.1

41

29.8

81

29.7

51

29.4

41

23.3

81

21.9

71

20.0

31

16.3

41

15.7

21

05.9

61

00.3

8

40

.34

40

.13

39

.92

39

.72

39

.51

39

.30

39

.09

18

.65

10

.90

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 6.7 6.6 6.5 6.4

2.001.002.045.051.08

86

10 9 8 7 6 5 4 3 2 1 0

21.133.003.061.000.981.141.024.991.00

DMSO-d6

7.5

17

.50

7.5

07

.48

7.3

57

.33

7.2

87

.21

7.1

27

.11

6.4

66

.40

6.3

8

3.8

7

3.3

4

3.0

7

2.5

0

1.0

4

180 160 140 120 100 80 60 40 20 0

DMSO-d6

16

2.3

51

58.7

31

55.3

21

43.6

91

40.6

31

38.8

51

37.5

31

36.8

91

34.1

41

29.4

21

27.4

51

27.1

81

19.7

71

14.5

61

12.3

41

11.8

11

07.6

01

00.6

99

9.9

09

6.8

3

55

.97

55

.21

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

18

.50

10

.94

7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4

1.000.981.141.024.991.00

87

10 9 8 7 6 5 4 3 2 1 0

6.079.041.001.021.031.051.106.131.05

DMSO-d6

8.0

48

.03

7.5

87

.57

7.5

67

.55

7.5

47

.47

7.1

07

.08

6.5

66

.54

6.4

76

.47

6.4

6

3.3

4

2.5

0

0.9

1

0.1

2

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.3

81

43.4

41

39.1

01

37.7

51

36.6

01

30.7

81

29.9

81

29.7

81

29.5

61

29.1

81

22.1

21

21.4

01

19.6

11

16.4

11

14.2

11

04.9

99

9.7

0

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

25

.99

-4.5

9

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 6.7 6.6 6.5

1.001.021.031.051.106.131.05

88

10 9 8 7 6 5 4 3 2 1 0

9.101.040.991.091.056.181.264.052.024.031.00

DMSO-d6

8.0

57

.81

7.7

97

.68

7.6

17

.60

7.6

07

.59

7.4

27

.41

7.4

0

7.1

36

.58

6.5

46

.52

3.3

3

2.5

0

1.0

1

180 160 140 120 100 80 60 40 20 0

DMSO-d6

15

8.6

81

43.5

31

39.2

81

38.1

21

35.3

01

33.0

71

32.5

91

30.1

31

30.0

31

29.7

41

29.2

71

27.9

31

22.3

81

21.5

01

19.8

01

13.8

71

12.8

11

07.7

31

00.0

6

40

.01

39

.84

39

.68

39

.51

39

.34

39

.18

39

.01

26

.82

18

.32

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 6.7 6.6 6.5

1.040.991.091.056.181.264.052.024.031.00

89

10 9 8 7 6 5 4 3 2 1 0

3.031.011.042.111.002.001.253.071.02

CHLOROFORM-d

8.2

38

.21

7.6

07

.58

7.3

67

.35

7.3

47

.33

7.3

07

.27

6.9

56

.93

6.8

76

.59

6.5

7

3.8

6

180 160 140 120 100 80 60 40 20

CHLOROFORM-d

16

2.2

41

58.8

5

14

2.6

01

38.6

41

37.3

71

31.3

11

30.3

61

28.1

31

27.1

31

26.7

91

26.6

01

23.5

41

19.1

81

15.8

31

13.2

4

99

.80

77

.32

77

.00

76

.69

55

.28

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 6.7 6.6

1.011.042.111.002.001.253.071.02

90

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

21.083.131.011.122.252.161.011.131.151.081.00

CHLOROFORM-d1

0.1

01

0.0

8

7.7

37

.71

7.6

27

.59

7.4

67

.31

7.2

97

.27

6.9

46

.92

6.8

96

.52

6.5

0

3.8

5

1.2

11

.20

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

1.6

91

59.1

1

14

4.5

51

39.0

41

34.2

21

31.4

81

31.0

21

30.8

7

12

9.1

91

27.2

71

26.9

41

26.7

51

26.5

31

19.5

61

15.5

01

13.5

61

06.5

89

8.1

19

7.4

1

77

.26

77

.00

76

.75

55

.28

18

.77

11

.49

7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5

1.011.122.252.161.011.131.151.08

91

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

3.011.041.022.034.052.081.041.01

CHLOROFORM-d

11

.01

7.6

37

.51

7.4

97

.49

7.4

37

.42

6.8

66

.84

6.5

86

.56

6.5

26

.50

3.8

0

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

3.7

5

15

9.9

7

14

5.5

71

40.8

91

34.6

41

33.2

01

29.5

51

28.6

81

28.4

61

21.4

11

19.3

01

14.3

91

14.1

01

06.7

4

95

.21

85

.75

77

.31

77

.00

76

.68

55

.25

92

10 9 8 7 6 5 4 3 2 1 0

5.062.043.401.041.011.021.001.021.031.041.021.02

CHLOROFORM-d

8.0

07

.98

7.9

27

.54

7.5

17

.49

7.4

57

.43

7.2

77

.21

7.1

96

.57

6.5

5

5.5

1

3.4

7

2.6

42

.52

2.1

9

1.8

51

.69

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

1.6

7

14

5.5

31

41.4

31

38.4

21

37.2

01

36.2

81

31.8

31

27.3

71

25.8

01

25.2

01

23.3

11

15.9

7

10

8.9

3

99

.52

84

.96

78

.69

77

.31

77

.00

76

.68

29

.25

25

.39

22

.76

21

.88

21

.77

93

9 8 7 6 5 4 3 2 1 0

4.162.263.062.070.970.901.232.982.272.001.120.94

CHLOROFORM-d

8.1

18

.09

7.9

77

.60

7.5

87

.58

7.4

77

.41

7.3

9

7.2

77

.25

7.2

36

.60

6.5

7

5.5

9

2.6

92

.54

2.2

52

.18

1.9

11

.75

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

1.7

5

14

4.2

11

41.4

21

38.3

71

37.0

81

36.6

01

31.8

31

31.4

21

28.4

81

27.4

91

25.9

01

25.0

61

23.4

01

15.8

61

10.0

5

99

.60

97

.10

84

.88

77

.32

77

.00

76

.69

29

.51

25

.50

22

.95

22

.15

21

.81

94

10 9 8 7 6 5 4 3 2 1 0

2.254.981.173.220.992.130.993.036.041.01

CHLOROFORM-d

7.9

67

.53

7.5

17

.37

7.3

77

.36

7.3

57

.35

7.2

57

.23

6.5

56

.53

5.6

35

.58

5.1

9

2.4

62

.43

1.5

11

.50

1.4

81

.41

1.4

11

.39

1.3

81

.32

1.2

7

180 160 140 120 100 80 60 40 20 0

CHLOROFORM-d

16

2.1

5

14

2.7

91

42.1

81

38.0

61

37.1

21

35.5

11

31.5

41

29.1

51

28.8

81

28.1

0

12

5.8

61

25.7

71

24.4

31

23.3

61

15.9

51

15.6

7

99

.46

77

.31

77

.00

76

.68

54

.28

30

.36

24

.89

22

.34

21

.71

21

.50