19
S1 Supporting Information Available for Synthesis, Reaction, and Optical Properties of Cyclic Oligomers bearing 9,10-Diphenylanthracene Based on an Aromatic Tertiary Amide Unit Ryohei Yamakado, a Shin-ichi Matsuoka, a Masato Suzuki, a Daisuke Takeuchi, b Hyuma Masu, c Isao Azumaya, d and Koji Takagi a * a Department of Materials Science and Engineering, Nagoya Institute of Technology Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan b Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan c Chemical Analysis Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan d Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan Contents 1. Synthesis of C3Aʹ, C4Aʹ, and 2 S2–S3 2. Copy of NMR spectra S4–S13 3. GPC profiles S14 4. MALDI-TOF MS S15–S16 5. UV and fluorescence spectra S17–S19 Electronic Supplementary Material (ESI) for RSC Advances This journal is © The Royal Society of Chemistry 2014

Synthesis, Reaction, and Optical Properties of Cyclic ...Synthesis, Reaction, and Optical Properties of Cyclic Oligomers bearing 9,10-Diphenylanthracene Based on an Aromatic Tertiary

  • Upload
    others

  • View
    6

  • Download
    0

Embed Size (px)

Citation preview

  • S1

    Supporting Information Available for

    Synthesis, Reaction, and Optical Properties of Cyclic Oligomers bearing 9,10-Diphenylanthracene Based on an Aromatic Tertiary Amide Unit Ryohei Yamakado,a Shin-ichi Matsuoka,a Masato Suzuki,a Daisuke Takeuchi,b Hyuma Masu,c Isao Azumaya,d and Koji Takagia* a Department of Materials Science and Engineering, Nagoya Institute of Technology Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan b Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan c Chemical Analysis Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan d Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan

    Contents 1. Synthesis of C3Aʹ, C4Aʹ, and 2 S2–S3 2. Copy of NMR spectra S4–S13 3. GPC profiles S14 4. MALDI-TOF MS S15–S16 5. UV and fluorescence spectra S17–S19

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S2

    Scheme S1. Synthetic route to cyclic aromatic oligomers C3Aʹ and C4Aʹ.

    C3Aʹ Yield, 25%. M.p. >300 ˚C. 1H NMR (δ, 600 MHz, ppm, CDCl3) 7.64 (d, J = 8.0 Hz, 6H), 7.54 (d, J = 8.9 Hz, 6H), 7.47 (d, J = 8.9 Hz, 6H ), 7.41 (d, J = 8.2 Hz, 6H), 7.39–7.36 (12H), 6.94 (m, 6H), 6.89 (m, 6H), 4.21 (t, J = 7.8 Hz, 6H), 1.95 (m, 6H), 1.14 (t, J = 7.7 Hz, 9H). 13C NMR

    (δ, 150 MHz, ppm, CDCl3) 170.5, 143.0, 140.7, 136.8, 136.2, 136.1, 135.9, 131.9, 130.6, 130.0, 129.9, 128.9, 128.1, 126.5, 126.1, 125.5, 125.2, 51.6, 21.2, 11.5.

    C4Aʹ Yield 10%. M.p. >300 ˚C. 1H NMR (δ, 600 MHz, ppm, CDCl3) 7.67 (d, J = 7.9 Hz, 6H), 7.60 (m, 6H), 7.57 (m, 6 H), 7.43 (d, J = 8.3 Hz, 6H), 7.41 (d, J = 8.3 Hz, 6H), 7.35 (d, J = 8.3 Hz, 6H), 7.15 (t, J = 7.0 Hz, 6H), 7.11 (t, J = 7.0 Hz, 6H), 4.17 (t, J = 7.4 Hz, 6H), 1.90 (m, 6H),

    1.57 (m, 6H), 1.13 (t, J = 7.0 Hz, 9H). 13C NMR (δ, 150 MHz, ppm, CDCl3) Not available due to low solubility.

    NPr O

    n

    N COOCH3

    1' C3A' [n = 3 (25 %)]C4A' [n = 4 (10 %]

    LiHMDS (1M THF soln.)

    0 oC

    Pr

    H

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S3

    Scheme S2. Synthetic route to model compound 2. Condition and reagents: i) Benzoylchloride, Pyridine, THF, reflux; (ii) N-Methylaniline, LiHMDS (1 M THF soln.), THF, 0 ˚C.

    6 Compound 1ʹ was prepared as 1. To a solution of 1ʹ (222 mg/ 0.5 mmol) in pyridine (2 mL) and THF (2 mL) was added benzoylchloride (0.08 mL/ 0.6 mmol), and the system was heated to reflux overnight. The reaction mixture was poured into water, and an aqueous phase was extracted with DCM. The combined organic phase was washed with 1 M HCl. After drying over MgSO4, solvents were removed by the rotary evaporator. The crude product was purified by column chromatography (ethyl acetate/DCM = 1/3) to obtain yellow powder (250 mg, 91%).

    M.p. 256–257 ˚C. 1H NMR (δ, 200 MHz, ppm, CDCl3) 8.28 (d, J = 8.6 Hz, 2H), 8.17 (d, J = 8.0 Hz, 2H), 7.71–7.27 (17H), 4.10–3.90 (5H), 1.83 (m, 2H), 1.08 (t, J = 7.0 Hz, 3H). 2 To a THF (5 mL) solution of 6 (250 mg/ 0.45 mmol) and N-methylaniline (0.08 mL/ 0.75 mmol) was added dropwise a 1.0 M THF solution of LiHMDS (1.0 mL), and the system was stirred for 10 h. After saturated aq. NH4Cl was added, an aqueous phase was extracted with DCM. A combined organic phase was dried over MgSO4 and solvents were removed by the rotary evaporator. The resulted solid was recrystallized with CHCl3/hexane to give yellow crystals (140 mg, 50%).

    M.p. 329–330 ˚C. 1H NMR (δ, 200 MHz, ppm, CDCl3) 7.53 (d, J = 7.8 Hz, 2H), 7.51–7.46 (2H), 7.43 (d, J = 7.8 Hz, 2H), 7.37–7.21 (d, J = 7.9 Hz, 2H), 7.20 (d, J = 8.6 Hz, 2H), 4.06 (d, J

    = 6.1 Hz, 2H), 3.61 (s, 3H), 1.07 (t, J = 6.1 Hz, 3H). 13C NMR (δ, 50 MHz, ppm, CDCl3) 170.7, 170.4, 144.9, 140.2, 136.6, 136.2, 131.9, 130.7, 129.5, 129.1, 128.7, 128.1, 127.7, 127.1, 126.7, 125.1, 38.3, 30.3, 21.2, 11.5.

    N COOCH3

    1'

    Pr

    HN COOCH3

    6

    Pr

    O

    Ph

    NPr

    O

    PhN

    O

    CH3Ph

    2

    (i) (ii)

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S4

    2. Copy of NMR spectra

    Figure S1. 1H NMR spectrum of 3 in CDCl3.

    Figure S2. 13C NMR spectrum of 3 in CDCl3.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S5

    Figure S3. 1H NMR spectrum of 4 in CDCl3.

    Figure S4. 13C NMR spectrum of 4 in CDCl3.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S6

    Figure S5. 1H NMR spectrum of 5 in CDCl3.

    Figure S6. 13C NMR spectrum of 5 in CDCl3.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S7

    Figure S7. 1H NMR spectrum of 1 in CDCl3.

    Figure S8. 13C NMR spectrum of 1 in CDCl3.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S8

    Figure S9. 1H NMR spectrum of C3A in CDCl3.

    Figure S10. 13C NMR spectrum of C3A in CDCl3.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S9

    Figure S11. H-H COSY of C3A in CDCl3 (aromatic region).

    Figure S12. ROESY of C3A in CDCl3 (aromatic region).

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S10

    Figure S13. 1H NMR spectrum of C4A in CDCl3.

    Figure S14. H-H COSY of C4A in CDCl3 (aromatic region).

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S11

    Figure S15. 1H NMR spectrum of HC3A in CDCl3.

    Figure S16. H-H COSY of HC3A in CDCl3(aromatic region)

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S12

    Figure S17. Variable-temperature 1H NMR spectra of C3A in CDCl3.

    293 K

    273 K

    253 K

    223 K

    O

    N C8H17

    NC8H17

    O

    NOC8H17

    fg

    f'g'

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S13

    Figure S18. 1H NMR spectrum of 2 in CDCl3.

    Figure S19. 13C NMR spectrum of 2 in CDCl3.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S14

    2. GPC profiles

    Figure S20. GPC (THF) profiles of reaction mixture.

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S15

    3. MALDI-TOF MS

    Figure S21. MALDI-TOF MS of C3A.

    Figure S22. MALDI-TOF MS of C4A.

    1 [1] SP-C05-00-001.tas Description: DPA_C3A_2

    1450

    .728

    1451

    .731

    1452

    .735

    1453

    .739

    1410 1420 1430 1440 1450 1460 1470 1480 1490 m/z0.00

    0.40

    0.80

    1.20

    1.60

    2.00

    2.40

    2.80

    3.20

    3.60

    4.00

    x105

    Inte

    nsi

    ty

    1 [1] SP-G03-00-001.tas Description: C4A

    1933

    .499

    1934

    .503

    1935

    .506

    1900 1910 1920 1930 1940 1950 1960 1970 m/z

    0.00

    0.20

    0.40

    0.60

    0.80

    1.00

    1.20

    1.40

    1.60

    1.80

    2.00

    x104

    Inte

    nsi

    ty

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S16

    Figure S23. MALDI-TOF MS of HC3A.

    1 [1] SP-C03-00-001.tas Description: N_DPA_C3Ak

    1406

    .821

    1407

    .825

    1408

    .829

    1409

    .833

    1384 1388 1392 1396 1400 1404 1408 1412 1416 1420 1424 1428 1432 m/z0.00

    0.40

    0.80

    1.20

    1.60

    2.00

    2.40

    2.80

    3.20

    x105

    Inte

    nsi

    ty

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S17

    4. UV and fluorescence spectra

    Table S1. Detailed absorption and emission peak positions of C3A and 2 in DCM.

    Compound λabs/nm ε/M-1cm-1 λem/nm Φa

    C3A 377 52000 438 0.15 C4A 378 59900 439 0.06

    2 376 14900 425 0.15 a Relative to quinine sulfate with Φfl=0.55 as the standard.

    Figure S24. UV and fluorescence spectra of C3A in Cyclohexane (purple), THF (green), DCM (black), MeCN (orange), and MeOH (red) (10-5 M).

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S18

    Figure S25. UV and fluorescence spectra of C3A (blue line) and C4A (red line) in DCM (solid line, 10-5M) and solid-state (dashed line).

    Figure S26. Solvent-dependent UV spectra of HC3A (10-5 M).

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

  • S19

    Table S2. Detailed absorption and emission peak positions of HC3A in different solvents.

    ET(30)

    /kcal・mol-1

    HC3A

    λabs /nm

    ε

    /M-1cm-1 λem /nm

    Stokes shift /cm-1

    Φa

    /%

    CH 30.9 396 31000 449 2980.8 0.10 Hexane 31.0 395 27000 446 2894.9 0.10 Toluene 33.9 397 32500 464 3637.2 0.10 DOX 36.0 397 29200 472 4002.5 0.16 EtOAc 38.1 395 31700 488 4824.7 0.11 DCM 40.7 397 31300 489 4739.0 0.08 Acetone 42.2 396 31500 509 5606.2 0.09 DMAc 42.9 397 30500 525 6141.3 0.11 DMF 43.2 398 29400 527 6150.3 0.09 DMSO 45.1 399 23000 543 6646.5 0.10

    a Relative to quinine sulfate with Φfl=0.55 as the standard.

    Figure S27. Changes in UV and fluorescence spectra of HC3A in DCM upon the addition of TFA and TEA; HC3A (red solid line), HC3A/TFA = 1/100 (blue solid line), and HC3A/TFA/TEA = 1/100/200 (red broken line).

    Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2014

    /ColorImageDict > /JPEG2000ColorACSImageDict > /JPEG2000ColorImageDict > /AntiAliasGrayImages false /CropGrayImages true /GrayImageMinResolution 150 /GrayImageMinResolutionPolicy /OK /DownsampleGrayImages false /GrayImageDownsampleType /Bicubic /GrayImageResolution 150 /GrayImageDepth 8 /GrayImageMinDownsampleDepth 2 /GrayImageDownsampleThreshold 1.50000 /EncodeGrayImages true /GrayImageFilter /FlateEncode /AutoFilterGrayImages false /GrayImageAutoFilterStrategy /JPEG /GrayACSImageDict > /GrayImageDict > /JPEG2000GrayACSImageDict > /JPEG2000GrayImageDict > /AntiAliasMonoImages false /CropMonoImages true /MonoImageMinResolution 1200 /MonoImageMinResolutionPolicy /OK /DownsampleMonoImages false /MonoImageDownsampleType /Bicubic /MonoImageResolution 1200 /MonoImageDepth -1 /MonoImageDownsampleThreshold 1.50000 /EncodeMonoImages true /MonoImageFilter /FlateEncode /MonoImageDict > /AllowPSXObjects false /CheckCompliance [ /None ] /PDFX1aCheck false /PDFX3Check false /PDFXCompliantPDFOnly false /PDFXNoTrimBoxError true /PDFXTrimBoxToMediaBoxOffset [ 0.00000 0.00000 0.00000 0.00000 ] /PDFXSetBleedBoxToMediaBox true /PDFXBleedBoxToTrimBoxOffset [ 0.00000 0.00000 0.00000 0.00000 ] /PDFXOutputIntentProfile (None) /PDFXOutputConditionIdentifier () /PDFXOutputCondition () /PDFXRegistryName () /PDFXTrapped /False

    /Description >>> setdistillerparams> setpagedevice