supporting information direct functionalization of bodipy ... · instrument operating at a...

S1

Supporting information

Direct functionalization of BODIPY dyes by oxidative nucleophilic hydrogen substitution at the 3- or 3,5-positions

Volker Leen, Verónica Zaragozí Gonzalvo, Wim M. Deborggraeve, Noël Boens and Wim

Dehaen*

Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F – bus 02404, 3001 Leuven, Belgium

*To whom correspondence should be addressed: [email protected]

Contents

1. Experimental procedures and characterization data S2 2. NMR-analysis of base induced tautomerization S8 3. NMR-spectra of new compounds S14

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

S2

Experimental procedures and characterization data Chemicals where purchased from Acros Organics, and used as received. All reactions were carried out in flame dried glassware, but no special precautions were to taken for the exclusion of moisture. Solvents were not dried prior to use. Oxygen gas was 99.5% pure. 1H and 13C NMR spectra were recorded at room temperature on a Bruker Avance 300 instrument operating at a frequency of 300 MHz for 1H and 75 MHz for 13C. In the case of ambiguous assignments, spectra were run on a Bruker 400 or Bruker 600. 1H NMR spectra in CDCl3 were referenced to tetramethylsilane (0.00 ppm) as an internal standard. 13C NMR spectra in CDCl3 were referenced to the CDCl3 (77.67 ppm) signal. 1H NMR spectra in CD3CN were referenced to CH3CN (1.94 ppm) as an internal standard. 13C NMR spectra in CD3CN were referenced to the CD3CN (118.2 ppm) signal. Mass spectra were recorded on a Hewlett-Packard 5989A mass spectrometer (EI mode and CI mode). High-resolution mass data were obtained with a Kratos MS50TC instrument. Melting points were taken on a Reichert Thermovar and are uncorrected. 19F-NMR were recorded on a Bruker 600 MHz, and referenced to CFCl3. Absorption spectra where recorded on a Perkin Elmer Lambda 40. For the corrected steady-state emission spectra, a SPEX Fluorolog was used. Freshly prepared samples in 1-cm quartz cells were utilized to perform all UV–vis absorption and emission measurements. For the determination of the relative fluorescence quantum yields (Φf) in solution, only dilute solutions with an absorbance below 0.1 at the excitation wavelength of 500 nm were used. Rhodamine 6G (Φf = 0.95)in spectrograde ethanol (Fluka) was used as standard to determine the fluorescence quantum yields. All spectroscopic measurements were done at 20 °C. 8-arylated BODIPY dyes were prepared according to standard literature procedures, through a water based dipyrromethane synthesisi and oxidation and condensation.ii Oxidative substitution: Optimization of reaction protocol:

Table 1: Optimization of oxidative nucleophlic hydrogen substitution with butylamine.

Solvent Oxidizer Reaction Time Yield (%)-a Air 16 h 11

CH3CN O2 5 days 33 THF O2 14 days 16b

DMSO O2 24 h 41 DMF O2 16 h 65 NMP O2 16 h 55 DMF Air 24 h 48 DMF DDQ 48 h 26 DMF PCA 48 h 31 DMF AgPyMnO4 48 h 16

a) Butylamine was used as the solvent; b) Reaction not complete at this stage


S3

Oxidative subsitution: General procedure for amine substitution To a solution of BODIPY 1 (0.5 mmol, 134 mg) in DMF (5ml) is added the corresponding amine (0.55 mmol, 2.1 equiv.). The mixture is flushed with oxygen and stirred at room temperature for the indicated time under an oxygen atmosphere. Subsequently, the solution is poured in diethyl ether (100 ml), washed with saturated aqueous NaHCO3, dried over MgSO4, filtered, and evaporated to dryness. The crude product is purified by filtration over a silica pad with dichloromethane as solvent. 3-(N-Butylamino)-8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 4a

NBF2

N

HN

Red crystals; Mp 120°C; 1H-NMR (CDCl3, 600 MHz): δ 7.47 (m, 6H), 6.93 (d, 1H, J = 5.49 Hz), 6.42 (d, 1H, J = 2.73 Hz), 6.33 (d, 1H, J = 1.83 Hz), 6.32 (s, br, 1H, NH), 6.18 (d, 1H, J = 4.56 Hz), 3.41 (q, 2H, J = 6.39 Hz, J = 13.68 Hz), 1.73 (m, 2H), 1.46 (m, 2H), 0.97 (t, 3H, J = 9.72 Hz); 13C-NMR (CDCl3, 100 MHz): δ 161.9, 136.2, 134.7, 133.5, 132.8, 132.6, 130.9, 130.4, 129.1, 128.2, 119.8, 113.4, 110.4, 44.5, 32.2, 19.8, 13.7; 19F-NMR (CDCl3, 564 MHz): δ -149.50 (q, J = 35 Hz); MS (EI): 339; HRMS: Calculated for C19H20N3BF2: 339.17183, found 339.17353. 3-(N-Dodecylamino)-8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 4b

NBF2

N

NHC12H25

Red oil; 1H-NMR (CDCl3, 300 MHz): δ 7.46 (s, 6H), 6.93 (d, 1H, J = 4.56 Hz), 6.41 (s, 1H), 6.33 (s, 1H), 6.28 (s, br, 1H, NH), 6.18 (d, 1H, J = 5.49 Hz), 3.39 (q, 2H, J = 6.39 Hz, J = 12.78 Hz)), 1.69 (m, 2H), 1.26 (m, 18 H), 0.87 (t, 3H, J = 7.32 Hz); 13C-NMR (CDCl3, 75 MHz): δ 161.9, 136.2, 134.8, 133.5, 132.8, 131.0, 130.4, 129.2, 128.3, 119.9, 113.5, 110.4, 44.9, 32.0, 30.2, 29.7, 29.6, 29.5, 29.4, 29.3, 26.7, 22.8, 14.2; MS (EI): 451; HRMS: Calculated for C27H36N3BF2: 451.2970, found 451.29731. 3-(N-Benzylamino)-8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 4c


S4

NBF2

N

HN

Red solid; Mp 156°C; 1H-NMR (CDCl3, 300 MHz): δ 7.88 (d, 1H, J = 8.22 Hz), 7.43 (m, 10H), 6.9 (d, 1H, J = 4.56 Hz), 6.66 (s, br, 1H, NH), 6.34 (s, 1H), 6.13 (d, 1H, J = 4.6 Hz), 4.61 (d, 1H, J = 6.39 Hz); 13C-NMR (CDCl3, 75 MHz): δ 161.9, 136.7, 136.2, 134.6, 133.9, 133.4, 132.7, 131.7, 130.4, 129.8, 129.3, 129.1, 128.2, 126.9, 120.6, 113.8, 110.3, 48.3; MS (EI): 373; HRMS: Calculated for C22H18N3BF2: 373.1561, found 373.15777. 3-(N-Piperidinyl)-8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 4d

NBF2

N

N

Red crystals; Mp 55°C; 1H-NMR (CDCl3, 300 MHz): δ 7.44 (m, 6H), 6.86 (d, 1H, J = 5.46 Hz), 6.32 (s, 2H), 6.26 (d, 1H, J = 5.49 Hz), 3.90 (d, 4H, J = 4.56 Hz), 1.78 (m, 6H); 13C-NMR (CDCl3, 150 MHz): δ 162.1, 135.7, 135.6, 135.4, 131.9, 131.5, 130.7, 130.5, 128.9, 128.1, 117.9, 113.9, 51.9, 26.5, 24.8; IR (thin film): 2937, 2857; MS (EI): 351; HRMS: Calculated for C20H20N3BF2: 351.17183, found 351.17179. Oxidative subsitution: General procedure for malonate substitution To a solution of BODIPY 1 (0.5 mmol, 134 mg) in DMF (5ml) is added the corresponding malonate (0.55 mmol, 1.1 equiv.), followed by Na2CO3 (1 mmol, 106 mg, 2 equiv.). The mixture is flushed with oxygen and stirred at room temperature for the indicated time under an oxygen atmosphere. Subsequently, the solution is poured in diethyl ether (100 ml), washed with diluted aqueous HCl and brine, dried over MgSO4, filtered, and evaporated to dryness. The crude product is purified by column chromatography (silica, CH2Cl2). Dimethyl 2-(8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacen-3-yl) malonate

NBF2

N

OO

O

O


S5

Orange solid; Mp 138°C; 1H-NMR (CDCl3, 400 MHz): δ 7.88 (s, 1H), 7.58-7.48 (m, 5H), 6.92 (d, 1H, J = 4.28 Hz), 6.88 (d, 1H, J = 4 Hz), 6.68 (d, 1H, J = 4.28 Hz), 6.52 (m, 1H), 5.52 (s, 1H), 3.81 (s, 6H); 13C-NMR (CDCl3, 150 MHz): δ 166.7, 150.5, 147.1, 144.1, 134.9, 133.5, 131.8, 131.5, 130.7, 130.4, 128.4, 119.5, 118.8, 53.3, 51.8; MS (EI): 398; HRMS: Calculated for C20H17N2O4BF2: 398.1249, found 398.12325. Di-t-butyl 2-(8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacen-3-yl) malonate

NBF2

N

OO

O

O

t-Bu

t-Bu

Orange solid; 1H-NMR (CDCl3, 400 MHz): δ 7.86 (s, 1H), 7.58-7.48 (m, 5H), 6.92 (d, 1H, J = 4.28 Hz), 6.85 (d, 1H, J = 3.76 Hz), 6.70 (d, 1H, J = 4.52 Hz), 6.50 (d, 1H, J = 2.52 Hz), 5.30 (s, 1H), 1.50 (s, 18H); 13C-NMR (CDCl3, 100 MHz): δ 165.5, 153.0, 146.6, 143.2, 135.2, 134.7, 133.9, 132.1, 130.8, 130.7, 130.5, 128.5, 119.9, 118.3, 82.9, 54.6, 27.9; MS (EI): 482; HRMS: Calculated for C26H29BF2N2O4: 482.2188, found 482.2194. 3,5-Bis-(di-t-butylmalon-2-yl)-8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene

Orange solid; Mp 178°C; 1H-NMR (CDCl3, 300 MHz): δ 7.53 (m, 5H), 6.84 (d, 2H, J = 4.14 Hz), 6.67 (d, 2H, J = 4.14 Hz), 1.49 (s, 36H); 13C-NMR (CDCl3, 100 MHz): δ 165.5, 151.9, 145.8, 134.7, 133.8, 131.2, 130.5, 128.4, 119.6, 82.8, 54.4, 27.9; MS (EI): 696; HRMS: Calculated for C37H47BF2N2O8: 696.3394, found 696.3394. 3-(Phenacyl)-8-(p-tolyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene

NBF2

NO


S6

To a solution of 8-tolyl-BODIPY (0.5 mmol, 141 mg) in DMF (5ml) is added acetophenone (3g, 1.1 equiv.) followed by potassium bis(trimethylsilyl)amide (KHMDS, 1 mmol, 200 mg, 2 equiv.). The mixture is flushed with oxygen and stirred at room temperature for 6h under an oxygen atmosphere. Subsequently, the dark solution is poured in diethyl ether (100 ml), washed with diluted aqueous HCl and brine, dried over MgSO4, filtered, and evaporated to dryness. The crude product is purified by column chromatography (silica, CH2Cl2). Orange solid; Mp 113-115°C; 1H-NMR (CDCl3, 300 MHz): δ 8.09 (d, 2H, J = 7.32 Hz), 7.99 (s, 1H), 7.61-7.44 (m, 5H), 7.31 (d, 2H, J = 7.74 Hz), 6.94 (d, 1H, J = 3.9 Hz), 6.86 (d, 1H, J = 3.39 Hz), 6.51 (m, 2H), 4.70 (s, 2H), 2.46 (s, 3H); 1H-NMR (CD3CN, 600 MHz): 8.05 (d, 2H, J = 7.14 Hz), 7.83 (s, 1H), 7.66 (t, 1H, J = 7.56 Hz), 7.55 (t, 2H, J = 7.5 Hz), 7.51 (d, 2H, J = 8.28 Hz), 7.38 (d, 2H, J = 7.56 Hz), 7.01 (d, 1H, J = 3.78 Hz), 6.90 (d, 1H, J = 3.36 Hz), 6.56 (m, 2H), 4.75 (s, 2H), 2.45 (s, 3H); 13C-NMR (CD3CN, 100 MHz): δ 195.7, 157.2, 147.2, 142.6, 142.4, 137.4, 136.0, 134.9, 134.4, 133.4, 133.2 ,131.6, 131.5, 131.0, 130.0, 129.7, 129.1, 122.5, 118.8, 39.7, 21.3; 19F-NMR (CDCl3, 565 MHz): δ -144.6 (q, J = 31 Hz) ppm; MS (EI): 400; HRMS: Calculated for C24H19BF2N2O: 400.1559, found 400.15672.

NBF2

NOH

1H-NMR (CD3CN, 600 MHz): 7.89 (m, 2H), 7.81 (d, 1H, J = 5.16 Hz), 7.43 (m, 3H), 7.40 (d, 2H, J = 7.32 Hz), 7.27 (d, 2H, J = 7.38 Hz), 7.11 (s, 1H), 6.74 (d, 1H, J = 5.16 Hz), 6.66 (s, 1H), 6.16 (d, 1H, J = 2.22 Hz), 6.04 (d, 1H, J = 2.16 Hz), 2.40 (s, 3H, Tolyl-CH3) ; 13C-NMR (CD3CN, 150 MHz): δ 185.6, 166.9, 144.0, 138.9, 1138.5, 135.0 134.2, 133.2, 132.0, 131.2, 130.7, 129.6, 129.0, 127.7, 126.7, 126.0, 121.0, 112.2, 111.7, 92.9, 21.2. Ethyl (8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacen-3-yl) phenylacetate

NBF2

NO

O

To a solution of 8-tolyl-BODIPY (0.5 mmol, 134 mg) in DMF (5ml) is added ethyl phenylacetate (90 mg, 1.1 equiv.) followed by NaOtBu (1 mmol, 112 mg, 2 equiv.). The mixture is flushed with oxygen and stirred at room temperature for 6h under an oxygen atmosphere. Subsequently, the dark solution is poured in diethyl ether (100 ml), washed with diluted aqueous HCl and brine, dried over MgSO4, filtered, and evaporated to dryness. The crude product is purified by column chromatography (silica, CH2Cl2).


S7

Orange solid; No crystals obtained; 1H-NMR (CDCl3, 300 MHz): δ 7.84 (s, 1H), 7.47-7.28 (m, 9H), 6.88-6.84 (m, 2H), 6.54 (d, 1H, J = 4.5 Hz), 6.50 (m, 1H), 5.76 (s, 1H), 4.33-4.15 (m, 2H), 2.44 (s, 3H), 1.27 (t, 3H, J = 7.14 Hz); 13C-NMR (CDCl3, 100 MHz): δ 170.6, 158.2, 146.9, 142.4, 141.1, 136.5, 135.2, 134.5, 132.1, 131.1, 130.9, 130.6, 130.3, 129.2, 129.0, 128.7, 127.9, 120.0, 117.9, 61.8, 51.1, 23.5, 14.1; MS (EI): 444; HRMS: Calculated for C26H23BF2N2O2: 444.1821, found 444.1837.


S8

Spectroscopic data

BODIPY Solvent λabs / nm λem /nm νΔ /cm-1 Φf

MeCN 466 530 2591 0.013 MeOH 468 529 2464 0.012 THF 493 533 1522 0.019 4a

Toluene 505 533 1040 0.033 MeCN 502 520 690 0.017 MeOH 503 520 650 0.041 THF 506 523 642 0.064 4e

Toluene 509 526 635 0.14 MeCN 503 521 687 0.03 MeOH 504 520 611 0.040 THF 507 523 603 0.06 4f

Toluene 509 527 671 0.14 MeCN 551 592 1257 0.002 MeOH 569 625 1575 0.022 THF 506 523 642 0.08 4h

Toluene 508 526 674 0.087


S9

NMR-analysis of base induced tautomerization 4h, 1H, 600 MHz, CD3CN, Full spectrum ↓

2.0161

1.0087

1.0071

2.1055

1.9127

2.0373

1.0000

0.9821

1.9831

1.9749

3.0468

Integral

8.0547

8.0428

7.8038

7.6765

7.6639

7.6520

7.5667

7.5542

7.5410

7.5291

7.5153

7.3961

7.3835

7.0172

7.0109

6.9112

6.9056

6.5631

6.5568

4.7527

2.4588

(ppm)

0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.89.29.6

4h, 1H, 600 MHz, CD3CN, Zoom ↓

2.0161

1.0087

1.0071

2.1055

1.9127

2.0373

1.0000

0.9821

1.9831

1.9749

Integral

8.0547

8.0428

7.8038

7.6765

7.6639

7.6520

7.5667

7.5542

7.5410

7.5291

7.5153

7.3961

7.3835

7.0172

7.0109

6.9112

6.9056

6.5631

6.5568

4.7527

(ppm)

4.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.8


S10

4h, 13C , 600 MHz, CD3CN ↓

195.7820

157.2945

147.2752

142.6885

142.4843

137.4965

136.1548

134.9953

134.5286

133.5442

133.2890

131.7212

131.5899

131.0868

130.0877

129.8252

129.1617

122.6134

118.8725

39.8556

21.4286

(ppm)

0102030405060708090100110120130140150160170180190200210

4h, DEPT, 600 MHz, CD3CN ↓

142.5599

134.4001

133.4156

131.5926

130.9655

129.9592

129.6967

129.0331

122.4775

118.7513

39.7198

21.3000

(ppm)

0102030405060708090100110120130140150160170180190200


S11

4h, 1H, 600 MHz, CD3CN + DBU, Full spectrum ↓

2.1115

1.0179

3.0742

1.9939

2.0924

1.0059

1.0146

1.0220

1.0000

0.9887

3.2498

Integral

7.9016

7.8955

7.8894

7.8857

7.8234

7.8148

7.4432

7.4371

7.4334

7.4102

7.3980

7.2819

7.2696

7.1181

6.7416

6.7330

6.6670

6.1707

6.1670

6.0570

6.0534

5.4471

3.4472

3.4399

3.4313

3.3861

3.3763

3.3665

3.1978

3.1893

3.1795

2.5402

2.5316

2.5231

2.4082

1.9473

1.9437

1.9400

1.9351

1.9314

1.9070

1.8972

1.8874

1.8777

1.8679

1.6686

1.6601

1.6112

1.6026

1.5965

(ppm)

0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.89.2

4h, 1H , 600 MHz, CD3CN + DBU, Zoom ↓

2.1115

1.0179

3.0742

1.9939

2.0924

1.0059

1.0146

1.0220

1.0000

0.9887

Integral

7.9016

7.8955

7.8894

7.8857

7.8234

7.8148

7.4432

7.4371

7.4334

7.4102

7.3980

7.2819

7.2696

7.1181

6.7416

6.7330

6.6670

6.1707

6.1670

6.0570

6.0534

5.4471

(ppm)

4.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.8


S12

4h, 13C, 600 MHz, CD3CN + DBU ↓

185.6971

166.9565

161.7864

144.0302

138.9476

138.5393

135.0026

134.2734

133.2890

132.0274

131.2618

130.7440

129.6648

129.0742

127.7251

126.7844

126.0771

121.0018

112.2440

111.7555

92.9055

68.5791

55.1034

49.2186

39.0681

33.6792

29.3696

26.8830

24.2798

21.2608

19.8243

(ppm)

0102030405060708090100110120130140150160170180190200

4h, DEPT , 600 MHz, CD3CN + DBU ↓

131.9739

131.2009

130.6832

129.6040

129.0133

127.6643

126.7163

126.0163

112.1832

111.6946

92.8446

55.0425

49.1578

39.0072

33.6184

29.3088

26.8222

24.2189

21.2000

19.7635

(ppm)

0102030405060708090100110120130140150160170180190


S13

4h, 1H, 600 MHz, CD3CN + DBU + CF3COOD, Full spectrum ↓

1.9739

0.9839

0.9508

1.9118

1.9400

2.1350

1.0000

1.0009

2.0101

0.8541

0.4207

3.0562

Integral

8.0580

8.0458

7.8062

7.6803

7.6681

7.6556

7.5703

7.5572

7.5446

7.5281

7.5150

7.3989

7.3860

7.0202

7.0135

6.9139

6.9078

6.5664

6.5600

4.7573

4.7264

3.5184

3.5104

3.5025

3.4579

3.4484

3.4386

3.2647

3.2556

2.5949

2.5854

2.5777

2.4613

1.9708

1.9614

1.9519

1.9488

1.9442

1.9406

1.7300

1.7215

1.7126

1.7013

1.6930

1.6845

1.6723

1.6631

1.6551

(ppm)

0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.89.2

4h, 1H, 600 MHz, CD3CN + DBU + CF3COOD, Zoom ↓

1.9739

0.9839

0.9508

1.9118

1.9400

2.1350

1.0000

1.0009

2.0101

0.8541

0.4207

Integral

8.0580

8.0458

7.8062

7.6803

7.6681

7.6556

7.5703

7.5572

7.5446

7.5281

7.5150

7.3989

7.3860

7.0202

7.0135

6.9139

6.9078

6.5664

6.5600

4.7573

4.7264

(ppm)

4.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.8


S14

4h, 19F, 600 MHz, CDCl3 ↓

0.0000

-144.6398

-144.6950

-144.7503

-144.8056

(ppm)

-195-185-175-165-155-145-135-125-115-105-95-85-75-65-55-45-35-25-15-551525

-144.6398

-144.6950

-144.7503

-144.8056

(ppm)

-151.5-150.0-148.5-147.0-145.5-144.0-142.5-141.0-139.5

NMR-spectra of new compounds 4a, 1H, 300 MHz, CDCl3 ↓

5.9220

1.0000

0.9118

1.0030

0.8947

0.9402

2.0366

2.1072

2.2275

2.9264

Integral

7.4830

7.4678

7.4617

7.4282

7.2577

6.9472

6.9289

6.4266

6.4175

6.3414

6.3353

6.3231

6.1952

6.1800

3.4492

3.4279

3.4036

3.3823

1.7383

1.7140

1.6927

1.6653

1.6409

1.5587

1.5161

1.4917

1.4674

1.4400

1.4156

1.3913

0.9985

0.9742

0.9498

(ppm)

-0.20.20.61.01.41.82.22.63.03.43.84.24.65.05.45.86.26.67.07.47.88.28.69.09.4


S15

4a, 13C, 400 MHz, CDCl3 ↓

161.9430

136.2194

134.7903

133.5289

132.8143

132.6977

130.9988

130.4228

129.1614

128.2792

119.8431

113.4706

110.4447

44.5680

32.2457

19.8578

13.7550

(ppm)

0102030405060708090100110120130140150160170180

4a, 19F, 600 MHz, CDCl3 ↓

-0.0000

-149.4668

-149.5283

-149.5835

-149.6449

(ppm)

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-1001020

-149.4668

-149.5283

-149.5835

-149.6449

(ppm)

-153.0-152.0-151.0-150.0-149.0-148.0-147.0


S16

4b, 1H, 300 MHz, CDCl3 ↓

5.8728

0.9576

0.9273

0.8668

0.8876

1.0000

1.9480

2.1109

18.795

3.7334

Integral

7.4587

7.4282

7.2547

6.9776

6.9411

6.9259

6.4266

6.4144

6.3322

6.2805

6.1892

6.1709

3.4310

3.4097

3.3884

3.3640

2.2711

1.7170

1.6957

1.6713

1.6470

1.5709

1.4308

1.4095

1.3760

1.2604

0.8981

0.8798

0.8555

-0.0000

(ppm)

0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.6

4b, 13C, 300 MHz, CDCl3 ↓

162.3614

136.6517

135.2505

133.9711

133.3009

133.1486

131.4732

130.8640

129.6151

128.7317

120.3243

113.9273

110.8507

45.3275

32.4727

30.8887

30.7059

30.1576

30.0967

30.0053

29.8834

29.7616

27.1114

23.2428

14.6830

(ppm)

0102030405060708090100110120130140150160170180190


S17

4c, 1H, 400 MHz, CDCl3 ↓

5.9872

5.4964

1.0089

1.0537

0.9634

0.9929

1.0000

2.0184

Integral

7.4766

7.4595

7.3856

7.3673

7.3498

7.3336

7.3208

6.9236

6.9114

6.6470

6.4634

6.4548

6.3476

6.1453

6.1331

4.6395

4.6239

(ppm)

3.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2

4c, 13C, 400 MHz, CDCl3 ↓

161.9940

136.7516

136.2485

134.7028

133.9591

133.4414

132.7852

131.7571

130.4374

129.3072

129.2197

128.3156

128.2427

126.9740

120.6744

113.7841

110.3937

48.3230

(ppm)

0102030405060708090100110120130140150160170180


S18

4d, 1H, 300 MHz, CDCl3 ↓

5.9962

1.0001

1.9738

1.1236

6.1480

Integral

7.4434

7.2547

6.8680

6.8498

6.3231

6.2683

6.2500

5.2911

3.9120

3.8968

1.7779

(ppm)

0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.0

4d, 13C, 300 MHz, CDCl3 ↓

162.1786

135.7379

135.6465

135.4637

131.9301

131.5951

130.7117

130.5594

128.9144

128.1834

117.9787

113.9273

113.3790

52.0596

51.9682

51.9073

26.5022

24.3394

(ppm)

0102030405060708090100110120130140150160170180190


S19

4e, 1H, 400 MHz, CDCl3 ↓

0.9691

5.1471

0.6531

1.2078

0.9520

1.0000

0.9670

6.2128

Integral

7.8874

7.5873

7.5778

7.5703

7.5621

7.5571

7.5420

7.5388

7.5250

7.5086

7.4897

6.9234

6.9127

6.8944

6.8844

6.6905

6.6798

6.5351

6.5288

6.5250

5.5257

3.8172

(ppm)

2.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.89.09.2

4e, 13C, 400 MHz, CDCl3 ↓

166.8434

150.6137

147.2463

144.2317

135.0968

134.9549

133.6749

131.9657

131.6894

130.8930

130.5766

128.5692

119.6162

118.9143

77.5818

77.1600

76.7345

53.4718

51.9299

(ppm)

0102030405060708090100110120130140150160170180190200


S20

4f, 1H, 400 MHz, CDCl3 ↓

1.0000

5.1571

0.9043

1.0039

0.9475

0.9914

0.9664

19.123

Integral

7.8673

7.5885

7.5722

7.5646

7.5527

7.5369

7.5250

7.5086

7.5061

7.4885

7.2588

6.9278

6.9171

6.8592

6.8498

6.7119

6.7006

6.5106

6.5043

5.3086

1.5034

(ppm)

1.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.0

4f, 13C, 400 MHz, CDCl3 ↓

165.5157

153.0841

146.6969

143.2919

135.2423

134.7101

133.9080

132.1290

130.8676

130.7145

130.5978

128.5125

119.9379

118.3412

82.9712

54.6008

27.9876

(ppm)

0102030405060708090100110120130140150160170180


S21

4g, 1H, 300 MHz, CDCl3 ↓

5.8873

2.1109

2.0000

40.661

Integral

7.5307

7.5162

6.8528

6.8390

6.6827

6.6689

5.3037

1.4901

(ppm)

0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.4

4g, 13C, 300 MHz, CDCl3 ↓

165.5634

151.9592

145.8863

134.7840

133.8022

131.2384

130.5475

128.4274

119.6780

82.8439

54.4755

27.9436

(ppm)

0102030405060708090100110120130140150160170180


S22

4i, 1H, 300 MHz, CDCl3 ↓

1.0000

9.2576

2.0456

0.9749

1.0473

1.0141

2.1714

3.0802

3.6511

Integral

7.8539

7.4849

7.4610

7.4259

7.3995

7.3888

7.3838

7.3606

7.3355

7.3085

7.2934

7.2821

7.2507

6.8854

6.8704

6.8572

6.8434

6.5540

6.5390

6.5070

6.5013

6.4938

5.7638

4.3340

4.3108

4.2982

4.2869

4.2744

4.2612

4.2512

4.2373

4.2267

4.2135

4.2016

4.1896

4.1777

4.1539

2.4491

1.2961

1.2723

1.2484

(ppm)

0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8

4i, 13C, 400 MHz, CDCl3 ↓

170.6123

158.2682

146.9230

142.4607

141.1920

136.5620

135.2642

134.5642

132.1581

131.1884

130.6488

130.3280

129.2343

129.0156

128.6948

127.9146

120.0983

117.9984

61.8629

51.1593

21.5494

14.1998

(ppm)

0102030405060708090100110120130140150160170180190

i T. Rohand, E. Dolusic, T. Ngo, W. Maes, W. Dehaen, ARKIVOC, 2007, 10, 307.


S23

ii H. Kee, C. Kirmaier, L. Yu, P. Thamyongkit, W. Youngblood, M. Calder, L. Ramos, B.

Noll, D. Bocian, W. Scheidt, R. Birge, J. Lindsey, D. Holten, J. Phys. Chem. B, 2005, 109, 20433-20443.


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