표제지
ABSTRACT
목차
ABBREVIATIONS 10
CHAPTER 1. UNSYMMETRICAL BIARYL DERIVATIVES 24
1.1. Introduction 24
1.2. Results and Discussion 29
1.3. Summary 45
1.4. Experimental Details 46
CHAPTER 2. UNSYMMETRICAL TERPHENYL DERIVATIVES 60
2.1. Introduction 60
2.2. Results and Discussion 68
2.3. Summary 81
2.4. Experimental Details 82
CHAPTER 3. NICKEL-CATALYZED COUPLING OF POLYARENESULFONATES WITH ARYL GRIGNARD REAGENTS 102
3.1. Introduction 102
3.2. Results and Discussion 106
3.3. Summary 113
3.4. Experimental Details 114
CHAPTER 4. SYNTHESES OF UNSYMMETRICAL STILBENE AND DISTYRYLARYLENE DERIVATIVES AS BLUE EMITTING MATERIALS FOR ORGANIC LIGHT-EMITTING DIODES 121
4.1. Introduction 121
4.2. Results and Discussion 128
4.2.1. Syntheses and Characterizations of Stilbene Derivatives 128
4.2.2. Syntheses and Characterizations of Distyrylarylene (DSA) Derivatives 152
4.3. Summary 174
4.4. Experimental Details 175
CHAPTER 5. SYNTHESIS OF UNSYMMETRICAL STILBENE DERIVATIVES VIA SOLID-PHASE ORGANIC SYNTHESIS (SPOS) 204
5.1. Introduction 204
5.2. Results and Discussion 209
5.3. Summary 217
5.4. Experimental Details 218
REFERENCES 226
Scheme 1. Transition metal-catalyzed cross-coupling reaction 25
Scheme 2. Cross-coupling of vinylic sulfides with Grignard reagents catalyzed by (PPh3)2NiCl2 25
Scheme 3. Sequential cross-coupling of alkenylthio compounds with Grignard reagents in the presence of nickel-phosphine complex as a catalyst 26
Scheme 4. Cross-coupling of vinylic sulfones with Grignard reagents catalyzed by nickel complex 26
Scheme 5. Cross-coupling of alkyl-and/or aryl sulfones with aryl Grignard reagents in the presence of Ni(0) catalyst 27
Scheme 6. Ni(0)-catalyzed cross-coupling reaction of arenesulfonates 1 with 2 27
Scheme 7. Cross-coupling of 1a with 2a in the presence of dppfNiCl2 29
Scheme 8. Nickel-mediated cross-coupling of unactivated neopentyl iodides with organozincs 29
Scheme 9. Preparation of arenesulfonates 1 using 4 with various sulfonyl chlorides 5 30
Scheme 10. Cross-coupling reaction of 1 with Grignard reagents 2 36
Scheme 11. Ni(0)-catalyzed cross-coupling reaction of arenesulfonates 1 with 2 39
Scheme 12. Cross-coupling of Aryl Tosylates 1h and/or 1i with 2 in the presence of dppfNiCl₂ 43
Scheme 13. The coupling reaction of aryl electrophiles containing sulfur-substituent compounds 9 61
Scheme 14. Typical preparation of symmetric terphenyl derivatives (I) 62
Scheme 15. Typical preparation of symmetric terphenyl deriv. (II) 62
Scheme 16. Typical preparation of symmetric terphenyl deriv. (III) 63
Scheme 17. General preparation of unsymmetrical terphenyl derivatives (I) 63
Scheme 18. General preparation of unsymmetrical terphenyl derivatives (II) 64
Scheme 19. General preparation of unsymmetrical terphenyl derivatives (III) 64
Scheme 20. General preparation of unsymmetrical terphenyl derivatives (IV) 65
Scheme 21. General preparation of unsymmetrical terphenyl derivatives (V) 65
Scheme 22. General preparation of unsymmetrical terphenyl derivatives (VI) 66
Scheme 23. General preparation of unsymmetrical terphenyl derivatives (VII) 67
Scheme 24. Total synthetic route of unsymmetrical terphenyl derivatives 10 using aryl Grignard reagents 2 67
Scheme 25. Preparation of alkyl halobenzenesulfonates 7 68
Scheme 26. Pd(0)-catalyzed cross-coupling of phenylboronic acid with haloarenes with 8 69
Scheme 27. Preparation of neopentyl biphenylsulfonates 9 71
Scheme 28. Synthesis of unsymmetrical terphenyl derivatives 10 76
Scheme 29. Synthesis of four-directional poly(ether-amide) cascade polymers 103
Scheme 30. Synthesis of four-directional amine-terminated dendritic molecules 104
Scheme 31. Cubane and synthesis of xamthene derivative 104
Scheme 32. Synthesis of unsymmetrical terphenyls by using 17c as a core molecule 105
Scheme 33. Preparation of polyarenesulfonates 24 and/or 25a 106
Scheme 34. Ni(0)-catalyzed C-C coupling of polyarenesulfonates 24 and 25 with aryl Grignard reagents 2 108
Scheme 35. Preparation of tetrabromobenzenesulfonylneopentane 25d 110
Scheme 36. Preparation of tetrabiphenylsulfonates 30 110
Scheme 37. Ni(0)-catalyzed C-C coupling of tetrabiphenylsulfonates 30 111
Scheme 38. Synthetic route of unsymmetrical stilbene derivatives 13 from 4-bromobenzenesulfonates 7a 127
Scheme 39. Synthetic route for stilbene compounds 13 from 7a 129
Scheme 40. Preparation of formylbiphenylsulfonates 6 129
Scheme 41. Preparations of stilbenesulfonates 12 131
Scheme 42. Nickel-catalyzed coupling of 12 with aryl Grignard reagents 2 134
Scheme 43. Preparation of diketone 15a using Method A 152
Scheme 44. Preparation of 15a using Method B 153
Scheme 45. Preparation of Activated Nickel Powder 154
Scheme 46. Preparation of 15a using Activated Ni Powder 154
Scheme 47. The conclusions of Method C 155
Scheme 48. Nickel-Phosphine Complex-Catalyzed Homo Coupling of 15 in the presence of Zinc dust (Method B) 155
Scheme 49. Preparations of 22 using thionyl chloride 156
Scheme 50. Preparations of various phosphonates 11 157
Scheme 51. Synthesis of 16 using 11 and diketones 15 159
Scheme 52. Synthesis of 31 from 33 164
Scheme 53. Synthesis of 32 from 31 166
Scheme 54. Ni(0)-catalyzed cross-coupling reaction of polymer-bound arenesulfonate with aryl Grignard reagents 205
Scheme 55. Ni(0)-catalyzed cross-coupling reaction of 12 with 2 in solution phase synthesis 206
Scheme 56. Ni(0)-catalyzed cross-coupling reaction of 29 with 2 in solid-phase synthesis 206
Scheme 57. Preparations of stilbenes 13 in SPOS 209
Scheme 58. Preparations of polymer-bound bromobenzenesulfonate 27 210
Scheme 59. Preparations of polymer-bound formylbiphenylsulfonate 28 212
Scheme 60. Preparations of polymer-bound stilbenesulfonate 29 212
Scheme 61. Ni(0)-catalyzed cross-coupling reaction of 29 with 2 214
Figure 1. Mechanism for dppfNiCl2 catalyzed cross-coupling of sulfonates 1 with aryl Grignard reagents 2 28
Figure 2. Alcohol sources for preparation of alkyloxysulfonyl compounds 30
Figure 3. Typical sulfonyl chloride groups of a sulfonate acceptor 31
Figure 4. Representative unsymmetrical terphenyl derivatives for biological activities 62
Figure 5. The various aryl boronic acids 8 building blocks 72
Figure 6. The change of the reaction time by alkyl group 79
Figure 7. Typical commercial polyols 17 106
Figure 8. polyarenesulfonates 24a, 24b and 25a 106
Figure 9. Two kinds of tetrabiphenylsulfonates 30 111
Figure 10. 4-Nitro-4’-methoxy-trans-stilbene (n = 1) and polyene derivatives containing up to three double bonds 121
Figure 11. Natural and synthetic stilbenoids 122
Figure 12. Structure of OLEDs 124
Figure 13. Typical Emitting Materials for OLEDs 125
Figure 14. U.S. Patent structures 126
Figure 15. Creative structure of distyrylbiphenylarylene (DBA) 16 derivatives 127
Figure 16. Creative structure of distyrylquarterphenylarylene (DQA) 32 derivatives 128
Figure 17. 1H NMR (500 MHz, CDCl3) spectrum of 13a 139
Figure 18. 1H NMR (500 MHz, CDCl3) spectrum of 13i 139
Figure 19. 1H NMR (500 MHz, CDCl3) spectrum of 13q 140
Figure 20. 13C NMR (125 MHz, CDCl3) spectrum of 13q 140
Figure 21. UV-vis maximum wavelength for the change of R substituent (H, 4-Me, 4-tBu, 4-Ph) & fixation of R substituent (H) (13a, 13d, 13g, and 13j) 144
Figure 22. UV-vis maximum wavelength for the change of R2 substituent (H, 4-Me, 4-tBu, 4-Ph) & fixation of R3 substituent (4- Me) (13b, 13e, 13h, and 13k) 144
Figure 23. UV-vis maximum wavelength for the change of R2 substituent (H, 4-Me, 4-tBu, 4-Ph) & fixation of R3 substituent (4-tBu) (13c, 13f, 13i, and 13l) 145
Figure 24. UV-vis maximum wavelength for 13m and 13n 145
Figure 25. UV-vis maximum wavelength for 13o, 13p, 13q, 13r, and 13s 146
Figure 26. PL maximum wavelength for the change of R2 substituent (H, 4-Me, 4-tBu, 4-Ph) & fixation of R3 substituent (H) (13a, 13d, and 13g) 148
Figure 27. PL maximum wavelength for the change of R2 substituent (H, 4-Me, 4-tBu, 4-Ph) & fixation of R3 substituent (4-Me) (13b, 13e, and 13h) 148
Figure 28. PL maximum wavelength for the change of R2 substituent (H, 4-Me, 4-tBu, 4-Ph) & fixation of R3 substituent (4-tBu) (13c, 13f, and 13i) 149
Figure 29. PL maximum wavelength for 13m, 13n, 13o, 13p, and 13q 149
Figure 30. UV-vis absorption (λmax) of 13 151
Figure 31. PL maximum wavelength of 13 151
Figure 32. Various starting material sources for halogenations 156
Figure 33. UV-vis spectra of 16a, 16b, 16c, 16d, 16h, and 16i coated onto the quartz plate using CHCl3 162
Figure 34. PL spectra of DPEBi 16a, PTEBi 16b, PBpEBi 16c, PNEBi 16d, EPEBi 16h, and EBpEBi 16i 162
Figure 35. UV vs. PL λmax values of DBA 16 derivatives 163
Figure 36. UV-vis λmax values of DQA 32 168
Figure 37. Color coordinates in CIE of 13 169
Figure 38. Double-layer-type device 170
Figure 39. Electroluminescence spectra of the Device (I) and Device (II) 171
Figure 40. Voltage vs. current density relationship of the device (I) and Device (II) 172
Figure 41. Current density vs. luminance characteristic relationship of the device (I) and device (II) 172
Figure 42. Color coordinates in CIE in the blue region 173
Figure 43. Solid-phase reaction apparatus 207
Figure 44. Synthesis of the resin 208
Figure 45. Sequential filtration & washing of the resin 208
Figure 46. BT CoreTM resin (0.91 mmol/g, 100-200 mesh) 210
Figure 47. FT-IR data of 26 and 27 211
Figure 48. FT-IR data for of 27 and 28 212
Figure 49. FT-IR data of 28 and 29 213
Figure 50. Shows the progress of the whole reactions monitored by FT-IR analysis of the resin 213
Figure 51. Polymer-bound stilbenesulfonates 29 prepared 214
Table 1. Preparations of Alkyl and Aryl Arenesulfonates 1a 32
Table 2. Effect of Changing Reaction Conditions on the Coupling of 1a with 2aa 34
Table 3. Nickel-catalyzed coupling of neopentyl tosylates 1a and 1b with 2aa 37
Table 4. Nickel-catalyzed coupling of neopentyl arenesulfonates with 2a 40
Table 5. Nickel-catalyzed coupling of aryl tosylates 1h and/or with 2a 43
Table 6. Preparation of neopentyl halobenzenesulfonates 7a 69
Table 7. Cross-coupling reactions between phenylboronic acid and halobenzenes under various reaction conditions 70
Table 8. Coupling reactions of 7 with arylboronic acids 8 73
Table 9. Nickel-catalyzed cross-coupling of 9 with 2 77
Table 10. Reaction of polyarenesulfonates 24 and 25a 107
Table 11. The purpose of using neopentyl polyol 17 108
Table 12. Ni(0)-catalyzed C-C coupling of polyarenesulfonates and 25 109
Table 13. Ni(0)-catalyzed C-C coupling of polyarenesulfonates 112
Table 14. Preparations of formylbiphenylsulfonates 6 130
Table 15. Preparation of stilbenesulfonates 12 132
Table 16. Nickel-catalyzed coupling of 12 with 2 135
Table 17. UV-vis & PL specifications of stilbene derivatives 13 142
Table 18. Preparations of various phosphonates 11 158
Table 19. Synthesis and characterization of new symmetrical blue-emitting materials 16 160
Table 20. PL specifications of new blue-emitting materials 16 164
Table 21. Preparations of 31 by treatment 33 with 11 165
Table 22. Preparations of 32 167
Table 23. Nickel-Catalyzed Coupling of 29 with 2 in SPOS 215