Thieme Chemistry Journal Awardees - Where
are They Now? Synthesis of p-Phenylene
Ethynylene Based Macrocycles and Bimacrocycle through Formation
of the Imine Bond

Liu-Gang Wang; Zhan-Ting Li

doi:10.1055/s-0028-1087554

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Synlett 2009(3): 384-389
DOI: 10.1055/s-0028-1087554

LETTER

Thieme Chemistry Journal Awardees - Where are They Now? Synthesis of p-Phenylene Ethynylene Based Macrocycles and Bimacrocycle through Formation of the Imine Bond

Liu-Gang Wang, Zhan-Ting Li*
State Key Laboratory of Bio-Organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: ztli@mail.sioc.ac.cn;

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Publication History

Received 20 October 2008
Publication Date:
21 January 2009 (online)

Abstract
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Abstract

This paper describes the synthesis of three monomacrocycles and one bimacrocycle from two p-phenylene ethynylene frameworks. For two of the monomacrocycles, the two frameworks were linked by an amide unit and the macrocyclization involved the intramolecular formation of one imine bond. For another monomacrocycle and the bimacrocycle, the frameworks contained two and three amino or aldehyde units, respectively, and the macrocyclization involved the intermolecular formation of two and three imine bonds.

Key words

macrocycle - p-phenylene ethynylene - imine - reduction

References and Notes

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11

Analytical Data Compound 12: Pale yellow oil. ^¹H NMR (300 MHz, CDCl₃): δ = 0.82 (t, J = 6.9 Hz, 3 H), 1.09-1.24 (m, 10 H), 1.46 (t, J = 6.6 Hz, 2 H), 1.55 (s, 9 H), 3.78 (t, J = 6.6 Hz, 2 H), 6.86 (d, J = 8.4 Hz, 1 H), 6.97 (t, J = 7.5 Hz, 1 H), 7.28 (d, J = 8.1 Hz, 2 H), 7.39-7.52 (m, 5 H), 7.58 (d, J = 7.5 Hz, 1 H), 7.65 (q, 1 H), 7.80 (d, J = 8.4 Hz, 2 H), 7.96-7.99 (m, 1 H), 8.18 (d, J = 8.4 Hz, 1 H), 8.93 (d, J = 1.5 Hz, 1 H), 9.24 (s, 1 H), 9.86 (s, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 13.9, 22.4, 25.6, 28.1, 28.517, 28.9, 29.0, 31.4, 68.7, 80.6, 83.0, 88.3, 94.0, 96.1, 110.7, 111.3, 115.0, 117.3, 119.1, 121.9, 122.4, 123.5, 127.6, 127.7, 128.9, 129.1, 129.3, 129.7, 130.7, 131.6, 132.7, 133.1, 136.2, 136.9, 137.4, 139.2, 147.7, 152.3, 164.7, 190.9. ESI-MS: m/z 691.2 [M + Na]⁺. ESI-HRMS: m/z calcd for C₄₃H₄₄N₂O₅Na [M + Na]⁺: 691.31424; found: 691.3137.
Compound 22: Pale yellow sticky solid. ^¹H NMR (300 MHz, CDCl₃): δ = 0.83 (t, J = 6.0 Hz, 3 H), 1.22-1.33 (m, 8 H), 1.41-1.48 (m, 2 H), 1.54 (s, 9 H), 1.87 (q, J = .2 Hz, 2 H), 4.10 (t, J = 6.6 Hz, 2 H), 6.90 (d, J = 9.0 Hz, 1 H), 6.98 (t, J = 7.5 Hz, 1 H), 7.31 (td, J ₁ = 7.9 Hz, J ₂ = 1.2 Hz, 1 H), 7.37 (dd, J ₁ = 7.2 Hz, J ₂ = 0.9 Hz, 1 H), 7.49-7.55 (m, 3 H), 7.60 (s, 1 H), 7.65-7.68 (m, 2 H), 7.71-7.74 (t, 2 H), 7.86 (d, J = 7.5 Hz, 1 H), 8.00 (s, 1 H), 8.06 (dd, J ₁ = 6.0 Hz, J ₂ = 3.0 Hz, 1 H), 8.21 (d, J = 11.4 Hz, 1 H), 8.82 (s, 1 H), 9.96 (s,
1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.0, 22.6, 25.9, 28.4, 29.0, 29.2, 29.3, 31.8, 69.2, 80.8, 88.7, 89.3, 92.0, 94,5, 111.4, 112.5, 113.0, 117.7, 119.1, 122.0, 122.0, 123.2, 124.4, 129.5, 129.5, 129.7, 130.0, 130.7, 130.9, 131.4, 133.0, 133.5, 136.6, 136.7, 137.0, 139.8, 152.7, 156.6, 164.5, 191.0. ESI-MS: m/z = 691.2 [M + Na]⁺, 707.1 [M + K]⁺. ESI-HRMS: m/z calcd for C₄₃H₄₄N₂O₅Na [M + Na]⁺: 691.31424; found: 691.3140.
Compound 26: Orange solid; mp 71-72 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.89 (t, J = 6.9 Hz, 3 H), 1.29-1.54 (m, 10 H), 1.87 (q, J = 6.6 Hz, 2 H), 4.12 (t, J = 6.6 Hz, 2 H), 7.00 (d, J = 9.0 Hz, 1 H), 7.44 (td, J ₁ = 7.2 Hz, J ₂ = 1.2 Hz, 1 H), 7.53-7.63 (m, 2 H), 7.70 (dd, J ₁ = 9.0 Hz, J ₂ = 2.4 Hz, 1 H), 7.94 (d, J = 7.5 Hz, 1 H), 8.02 (d, J = 2.1 Hz, 1 H), 10.48 (s, 1 H), 10.61 (s, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.0, 22.6, 25.9, 28.9, 29.1, 29.2, 31.7, 68.9, 84.5, 95.0, 112.8, 114.6, 124.8, 126.6, 127.3, 128.5, 131.7, 133.1, 133.7, 135.7, 138.7, 161.6, 188.8, 191.5. MS (EI): m/z = 362 [M]⁺. Anal. Calcd for C₂₄H₂₆O₃: C, 79.53; H, 7.23. Found: C, 79.49; H, 7.07.
Compound 28: Pale brown solid; mp 96-97 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.89 (t, J = 6.6 Hz, 3 H), 1.29-1.49 (m, 10 H), 1.82 (q, J = 6.9 Hz, 2 H), 3.83 (br, 2 H), 4.00 (t, J = 6.6 Hz, 2 H), 4.25 (br, 2 H), 6.70-6.74 (m, 3 H), 6.88-6.93 (m, 2 H), 7.11 (td, J ₁ = 7.8 Hz, J ₂ = 1.5 Hz, 1 H), 7.33 (d, J = 7.8 Hz, 1 H). ^¹³C NMR (100.4 MHz, CD₃OD): δ = 14.5, 23.8, 27.3, 30.5, 30.6, 33.1, 69.5, 84.7, 96.2, 109.8, 112.3, 115.6, 116.9, 118.6, 118.9, 123.4, 130.2, 132.7, 138.0, 148.8, 149.8. ESI-MS: m/z = 337.1 [M + H]⁺. ESI-HRMS: m/z calcd for C₂₂H₂₉N₂O [M]⁺: 337.22744; found: 337.2283.
Compound 43: Yellow solid; mp 153-154 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.89 (t, J = 6.6 Hz, 3 H), 1.25-1.39 (m,
8 H), 1.45-1.54 (m, 2 H), 1.88 (q, J = 6.6 Hz, 2 H), 4.13 (t, J = 6.6 Hz, 2 H), 7.02 (d, J = 8.7 Hz, 1 H), 7.50 (t, J = 7.8 Hz, 1 H), 7.59-7.68 (m, 3 H), 7.70-7.75 (m, 2 H), 7.97 (d, J = 7.8 Hz, 1 H), 8.03 (d, J = 2.1 Hz, 1 H), 8.10 (d, J = 1.5 Hz, 1 H), 10.48 (s, 1 H), 10.59 (s, 1 H), 10.61 (s, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.5, 22.6, 26.0, 28.9, 29.2, 29.2, 31.7, 69.0, 84.4, 87.8, 94.5, 97.3, 112.9, 114.3, 122.8, 124.9, 125.8, 126.7, 127.6, 129.2, 130.6, 131.9, 133.3, 133.4, 133.8, 135.7, 135.9, 136.2, 138.8, 161.8, 188.7, 190.5, 191.2. Anal. Calcd for C₃₃H₃₀O₄: C, 80.79; H, 6.16. Found: C, 80.63; H, 6.22. MS (MALDI-TOF): m/z = 491.0 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₃₃H₃₁O₄: 491.2217; found: 491.2218.

14

Analytical Data Compound 1: Pale yellow solid; mp 261-262 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.90 (t, J = 6.3 Hz, 3 H), 1.25-1.48 (m, 10 H), 1.83-1.78 (m, 2 H), 4.04 (t, J = 6.6 Hz, 2 H), 6.86 (d, J = 8.4 Hz, 1 H), 7.19-7.29 (m, 2 H), 7.35 (t, J = 7.5 Hz, 1 H), 7.40-7.50 (m, 3 H), 7.55 (d, J = 1.2 Hz, 1 H), 7.58 (s, 1 H), 7.60-7.66 (t, 3 H), 7.74 (s, 1 H), 8.61 (s, 1 H), 8.65 (s, 1 H), 8.68 (d, J = 1.8 Hz, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.1, 22.7, 26.1, 29.1, 29.3, 29.3, 31.7, 68.7, 87.8, 93.7, 111.4, 116.0, 118.3, 118.7, 121.6, 123.9, 125.9, 126.0, 126.4, 127.5, 127.9, 128.4, 128.6, 128.9, 129.8, 130.6, 131.2, 131.9, 132.2, 133.6, 136.8, 149.7, 152.8, 159.5, 166.4. MS (MALDI-TOF): m/z = 551.2 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₃₈H₃₅N₂O₂ [M + H]⁺: 551.2693; found: 551.2704.
Compound 2: Pale yellow solid; mp 270-272 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.87 (t, J = 7.2 Hz, 3 H), 1.25-1.41 (m, 10 H), 1.88 (p, J = 7.5 Hz, 2 H), 4.08 (t, J = 6.9 Hz, 2 H), 6.94 (d, J = 9.0 Hz, 1 H), 7.19-7.25 (m, 2 H), 7.38 (dt, J ₁ = 7.8 Hz, J ₂ = 1.5 Hz, 1 H), 7.52-7.56 (m, 3 H), 7.58-7.60 (m, 2 H), 7.68-7.74 (m, 3 H), 8.27-8.33 (m, 2 H), 8.58 (s,
1 H), 8.73 (s, 1 H), 9.45 (s, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.1, 22.7, 26.0, 29.2, 29.3, 29.4, 31.8, 69.4, 88.2, 91.5, 91.8, 96.3, 100.4, 113.3, 113.6, 117.3, 119.0, 119.3, 122.5, 122.7, 126.2, 126.3, 129.0, 129.1, 129.2, 129.4, 130.9, 131.0, 131.1, 131.4, 131.7, 134.5, 134.8, 137.0, 152.5, 155.9, 158.3, 163.4. MS (MALDI-TOF): m/z = 551.0 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₃₈H₃₅N₂O₂ [M + H]⁺: 551.2693; found: 551.2698. Compound 3: Pale brown solid; mp 226-227 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.89 (t, J = 2.2 Hz, 6 H), 1.26-1.56 (m, 20 H), 1.83 (p, J = 6.6 Hz, 2 H), 1.91 (p, J = 6.6 Hz, 2 H), 4.03 (t, J = 6.6 Hz, 2 H), 4.11 (t, J = 6.6 Hz, 2 H), 6.89 (d, J = 8.7 Hz, 1 H), 6.94 (d, J = 8.4 Hz, 1 H), 7.16-7.24 (m, 2 H), 7.34 (t, J = 8.1 Hz, 1 H), 7.38-7.43 (m, 3 H), 7.51-7.54 (m, 2 H), 7.58 (d, J = 7.8 Hz, 1 H), 7.65 (s, 1 H), 8.27 (t, 1 H), 8.59 (d, J = 1.8 Hz, 1 H), 8.92 (s, 1 H), 9.34 (s, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.1, 22.6, 22.7, 25.9, 26.0, 26.0, 29.0, 29.2, 29.2, 29.3, 29.3, 29.4, 31.7, 31.8, 68.6, 69.3, 85.4, 86.5, 94.1, 95.9, 112.1, 113.3, 115.0, 116.3, 117.4, 119.8, 123.0, 125.1, 125.2, 126.0, 126.7, 128.2, 129.0, 130.4, 130.7, 131.4, 131.7, 132.3, 135.2, 137.0, 141.3, 152.8, 153.7, 154.9, 159.1, 159.1. MS (MADI-TOF): m/z = 663.8 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₄₆H₅₁N₂O₂ [M + H]⁺: 663.3945; found: 663.3945.
Compound 4: Pale yellow solid; mp >320 ˚C. IR (KBr): 2921, 2852, 2204, 1621, 1600, 1589, 1560, 1510, 1472, 1270, 1249, 826, 815, 758, 742 cm^-¹. MS (MALDI): m/z = 889.1 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₆₃H₅₈N₃O₂: 888.4524; found: 888.4528. Anal. Calcd for C₆₃H₅₉N₃O₃˙H₂O: C, 83.50; H, 6.56; N, 4.64. Found: C, 83.28; H, 6.56; N, 4.42. Compound 44: Pale yellow solid; mp 237-239 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.88 (t, J = 6.6 Hz, 3 H), 1.25-1.46 (m, 10 H), 1.79 (t, J = 6.9 Hz, 2 H), 4.02 (t, J = 6.6 Hz, 2 H), 4.36 (d, J = 2.4 Hz, 2 H), 4.87 (br, 1 H), 6.70-6.78 (q, 2 H), 6.86 (d, J = 8.7 Hz, 1 H), 7.22-7.28 (m, 2 H), 7.31-7.34 (m, 2 H), 7.36-7.38 (d, J = 7.2 Hz, 1 H), 7.42-7.50 (q, 3 H), 7.56 (d, J = 6.6 Hz, 1 H), 7.65 (d, J = 7.5 Hz, 1 H), 7.71 (s, 1 H), 7.94 (s, 1 H), 8.41 (s, 1 H). ^¹³C NMR (75.3 MHz, CDCl₃):
δ = 14.1, 22. 7, 26.1, 29.1, 29.3, 29.3, 31.8, 48.2, 68.797, 85.2, 87.0, 93. 7, 95.8, 108.5, 109.9, 111.7, 115.5, 117.0, 121.4, 123.9, 125.2, 126.5, 127.4, 127.6, 128.51, 128.7, 129.3, 129.5, 129.7, 131.0, 132.2, 139.0, 140.2, 149.0, 149.9, 166.7. ESI-MS: m/z 553.2 [M + H]⁺, 575.1 [M + Na]⁺. MS (MALDI-TOF): m/z 553.0 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₃₈H₃₇N₂O₂ [M + H]⁺: 553.2850; found: 553.2863.
Compound 45: White solid; mp 226-227 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 0.89 (t, J = 6.9 Hz, 6 H), 1.26-1.53 (m, 20 H), 1.78-1.89 (m, 4 H), 4.03 (tt, 4 H), 4.44 (d, J = 5.4 Hz, 2 H), 4.61 (t, J = 4.5 Hz, 1 H), 4.64 (d, 2 H), 4.98 (t, J = 4.8 Hz, 1 H), 6.72 (t, 2 H), 6.84 (s, 1 H), 6.87 (s, 1 H), 6.91 (dd, J ₁ = 8.1 Hz, J ₂ = 1.8 Hz, 1 H), 7.17 (d, J = 1.5 Hz, 1 H), 7.21-7.31 (dd, 2 H), 7.34-7.41 (m, 2 H), 7.42-7.28 (t, 2 H), 7.54 (d, J = 6.9 Hz, 1 H), 7.82 (s, 1 H). ^¹³C NMR (100.4 MHz, CDCl₃): δ = 14.1, 22.7, 26.1, 29.2, 29.2, 29.2, 29.3, 29.3, 29.4, 29.7, 31.8, 31.8, 41.1, 46.2, 68.3, 68.5, 83.8, 85.9, 94.7, 96.6, 109.3, 110.3, 110.6, 111.0, 114.3, 115.1, 115.5, 117.1, 120.5, 122.9, 126.4, 127.0, 127.9, 128.4, 129.3, 129.5, 131.3, 131.5, 131.7, 138.2, 140.6, 147.0, 149.1, 156.4. MS (MALDI-TOF): m/z = 667.8 [M + H]⁺. HRMS (MALDI-TOF): m/z calcd for C₄₆H₅₅N₂O₂ [M + H]⁺: 667.4258; found: 667.4273.